Silicon-Organic Oligomers and Polymers With Inorganic and Organic-Inorganic Main Chains (Polymer Science and Technology)

POLYMER SCIENCE AND TECHNOLOGY

SILICON-ORGANIC OLIGOMERS AND POLYMERS WITH INORGANIC AND ORGANIC-INORGANIC MAIN CHAINS

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POLYMER SCIENCE AND TECHNOLOGY

SILICON-ORGANIC OLIGOMERS AND POLYMERS WITH INORGANIC AND ORGANIC-INORGANIC MAIN CHAINS

NODAR LEKISHVILI VICTOR KOPYLOV AND

GENNADY ZAIKOV

Nova Science Publishers, Inc. New York

Copyright © 2010 by Nova Science Publishers, Inc. All rights reserved. No part of this book may be reproduced, stored in a retrieval system or transmitted in any form or by any means: electronic, electrostatic, magnetic, tape, mechanical photocopying, recording or otherwise without the written permission of the Publisher. For permission to use material from this book please contact us: Telephone 631-231-7269; Fax 631-231-8175 Web Site: http://www.novapublishers.com NOTICE TO THE READER The Publisher has taken reasonable care in the preparation of this book, but makes no expressed or implied warranty of any kind and assumes no responsibility for any errors or omissions. No liability is assumed for incidental or consequential damages in connection with or arising out of information contained in this book. The Publisher shall not be liable for any special, consequential, or exemplary damages resulting, in whole or in part, from the readers’ use of, or reliance upon, this material. Independent verification should be sought for any data, advice or recommendations contained in this book. In addition, no responsibility is assumed by the publisher for any injury and/or damage to persons or property arising from any methods, products, instructions, ideas or otherwise contained in this publication. This publication is designed to provide accurate and authoritative information with regard to the subject matter covered herein. It is sold with the clear understanding that the Publisher is not engaged in rendering legal or any other professional services. If legal or any other expert assistance is required, the services of a competent person should be sought. FROM A DECLARATION OF PARTICIPANTS JOINTLY ADOPTED BY A COMMITTEE OF THE AMERICAN BAR ASSOCIATION AND A COMMITTEE OF PUBLISHERS. LIBRARY OF CONGRESS CATALOGING-IN-PUBLICATION DATA Lekishvili, N. Silicon-organic oligomers and polymers with inorganic and organic-inorganic main chains / Nodar Lekishvili, Victor Kopylov, Gennady Zaikov. p. cm. Includes bibliographical references and index. ISBN 978-1-62100-522-3 (eBook) 1. Silicon polymers. 2. Organosilicon compounds. I. Kopylov, Victor, 1950- II. Zaikov, Gennadii Efremovich. III. Title. QD383.S54.L45 2009 547'.7--dc22 2010001175

Published by Nova Science Publishers, Inc. Ô New York

CONTENTS   Preface

ix 

Introduction

xi 

Chapter 1

Chapter 2

Development of the Chemistry of Polyfunctional Siliconorganic Compounds with Organic-inorganic Main Chains

1 

Polymers Containing Silicon-nitrogen and Silicon-oxigen Bonds

9 

2.1. A Combined Polymerization Condensation Process – A Nontraditional Method of Synthesis of Siliconorganic Polymers with Inorganic and Organic-Inorganic Main Chains of Macromolecules 2.2. New Type Si–N Containing Polymers with OrganicInorganic Main Chains Chapter 3

Chapter 4

Synthesis of Elementorganic Soluble Polyimides Based on Silicon-organic Carbocyclic Dianhydrides, Organoelement and Heterocyclic Diamines Organosilicon Oligophenylenes on the Base of some Diethynylsilanes and Diethynylsiloxanes

9 78

95 

111 

vi

Contents

Chapter 5

Organosilicon Carbofunctional Polymers with Organic-inorganic Main Chains Based on Organosilicon Oligoepoxides

5.1. Synthesis and Use Oligoorganosiloxane Polyfunctional Modifiers Containing hydroxy and Amino Groups 5.2. Synthesis and Use of Carbofunctional Organosiloxane Co-oligomers Based on Monoepoxydisiloxane 5.3. Oligosiloxaneepoxides with Regular Side Epoxy Groups Based on Oligohydride Siloxanes 5.4. Siliconorganic Polyepoxides with Organic-Inorganic Main Chains of Macromolecules Modified with Chelates Chapter 6

The Traditional and Nontraditional Application Areas of the Described above Polymers with Inorganic and Organo-inorganic Main Chains

6.1. Use of Carbofunctional Polymers with Terminal Epoxi Groups 6.2. Antibiocorrosive Covers Based on Carbofunctional Oligoisiloxanes with Side Methacrylic Groups and Biological Active Organic-inorganic Complex Compounds 6.3. Modification of Properties of Rubber Compositions and Vulcanizates Prepared on the Basis of All-hydrocarbon Elastomers by Polyorganosilazasyloxyarylenes 6.4. Physical and Chemical Modification of Oligomethylsiloxanes by Polyorganosilaza Siloxiarylenes in the Treatment Process 6.5. Modification of Polycarbonate by Polyorganosilazasiloxiarylenes

123 

123  140  145  152 

159  159

165

190

192

198 

References

203 

Index

217 

PREFACE “The progress is a replacement of one problems with the others” Joke with a large part of truth “The main indication of the talent is that the person knows what he wants” Pyotr L. Kapitsa 1980, Moscow, USSR

Polymer material science – is a science about creation of polymer materials, their processing, research of their properties (including degradation, stabilization and combustion), search new ways of application and utilization of the wastes. Man kind produced polymers as much as cast iron, steel, and color metals all together (500,000,000 m3/yr) if we will calculate production of polymers not by weight (in tons), but by volume (cubic meters). It’s important, that worldwide growth of manufacturing of polymers exceeds a growth of metals. One ca say, that mankind lived in Stone Age, then in Bronze and Iron ages and now is in Polymer Age. What’s next? Perhaps the age of nanocomposites and transition on the renewable resources. One more circumstance. Soon of all, we should not expect in future multitoll manufacturing of new polymers (creation of new low-ton manufacturing will take place and there will be several of them). Progress in creation of multi-ton new polymeric materials we should seek on the way of creation polymeric blends, polymeric composites and, in particular, nanocomposites. But we should expect more and more mini-toll manufacturing new polymers (very expensive) and we really see this situation in the world. First of all it is polymer materials for very low and very high exploitation temperature. Silicon-organic polymers are the most important kind of polymers for production of these materials. Such materials are very important

x

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

for solving of problems of assimilation of cosmos and for construction of new machines. Now the scientists try to make modification of these polymers (particularly with inorganic and organic-inorganic chains). It is very perspective way for innovations in this field. The book “Silicon-organic oligomers and polymers with inorganic and organic-inorganic main chains” is collecting the information about synthesis, properties and applications of these kind of polymers and materials on the base of these polymers. The editor and contributors will be happy to receive comments from the readers which we can take in account in future in our research. Prof. Gennady E. Zaikov N.M.Emanuel Institute of Biochemical Physics Russian Academy of Sciences Moscow, Russia [email protected] Prof. Riszard M. Kozlowski Institute for Engineering of Polymers Materials and Dyes Torun, Poland [email protected]

INTRODUCTION Most developed Si−N containing oligomers and polymers are silazaneorganic oligomers and polymers − one of the applicable siliconorganic polyfunctional compounds with inorganic-organic main chains [1-20]. They are using for production of various important technical compositions and materials with specific properties: polymer varnishes and coatings, waterrepellents, polymer ceramics and silicon-nitride fibers, etc. They also successfully used in nanotechnology and as modifiers of the other organic and elementorganic oligomers, polymers and materials on their basis. Among them, by thermal, adhesive, thermomechanical and radiation-stable properties distinguish oligomers and polymers containing various heteroatoms, arylene and heteroarylene fragments in the macrochains [15-20]. In the literature are described practically important and technologically justified four methods for obtaining polyfunctional siliconorganic polymers with organic - inorganic main chains [21-23]: •

•

• • • • •

The polymerization polycondensation method of heterocycles containing silicon-nitrogen heterocycles _ organocyclosilazane and organocyclosiloxanes with arylene and heteroarylene diaminse and bisphenols; The catalytic polymerization condesation of organosiloxane heterocycles with various difunctional organosilicon and other compounds containing hydroxy groups; The co-oligomerization of siliconorganic heterocycles with siliconorganic difunctional compounds; α,ω-dihydridooligoorganosiloxanes polycombination with polyfunctional divinyl and dialyl compounds; The priority of the first method is stipulated according to the following features [21], mainly: The ability of carring out of the reaction without catalysts; The possibility of removing completely of side-product without any additional special experimental procedures;

xii

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov • • • • • •

The relatively high yield of the obtaining polymers; The experimental simplicity of the procedure; The easiness of providing the control of the reaction; The ability to vary the properties of the obtaining polymers; The relative availability of the initial silazane monomers the preparation of which is easy; The ability of modifying the properties of various commercial organic and element-organic materials through application a small amount of the obtained polymers.

The second method according to the technological simplicity is similar to the first one. In this method production of side-products is excluded. The priority of the third method is the simplicity and availability. The fourth method allows at low temperatures to synthesize the polyfunctional polymers, with applicable perspective in modern techniques, containing simultaneously Si-N-, Si−N-, Si−O- and N−H-groups with linear macro chain regular structure. In practice the abovementioned methods are applied for obtaining the siliconorganic polymers with specific features and are considered as nontraditional method for synthesizing of heterochain siliconorganics. The authors have analizeded a lot of scientific works of well-known authors of these fields and oun experimental results. In there study it is shown that the described methods are experimentally simple and available, thus allowing to obtain different type siliconorganic polymers. In the monograph according to the modern achievements are discussed the kinetics and mechanisms of hydride polyaddition and polymeriztion polycondensation reactions. Based on this simultaneously Si–N- and Si–O- groups obtained through the hydride polyaddition and polymerization polycondensation reactions, for production of new nonmetal materials, mainly, high stable polymeric composites, protective surfaces, antibiocorrasion surfaces, nano-hibrydes and nano materials for organic-inorganic support production and for features modification of polyfunctional synthetic industrial materials. This will encourage the development of chemistry and physics of nontraditional synthetic materiare explained the influence of structure and reactionabilty of initial monomers on the direction of reaction, on the structure of polymers and feature.

Chapter 1

DEVELOPMENT OF THE CHEMISTRY OF POLYFUNCTIONAL SILICONORGANIC COMPOUNDS WITH ORGANIC-INORGANIC MAIN CHAINS Heterochain organosilicon polymers of various composition and structure have found wide practical application in different areas of human activities and are commercially manufactured. Due to the great importance of the polymers for new advanced materials creation a lot of researchers of academy and corporate laboratories are engaged in the development of various synthetic methods and study of chemical bond nature in the polymers. There are a few basic kinds of polymer structures that attract a lot of attention, namely: polycarbosilanes, polyorganosilazanes, polyorganosiloxanes as well as compounds containing above polymers fragments. Until recently polycarbosilanes have not found wide practical application and attracted most attention as theoretical study objects and development of organosilicon compounds synthesis methods. They may have linear, branched, cyclic or polycyclic structures. Basic polycarbosilane chains consist of silicon atoms and bifunctional organic groups linking silicon atoms together. At the beginning of 1970s polycarbosilanes served the basis for silicon carbide ceramics and high-impact high modulus ceramic fiber synthesis methods development [24, 25]. Polycarbosilanes (PCS) allow obtaining heatand oxidation-resistant high-impact silicon carbide fibers and ceramics through melt and solution processing with the following thermochemical

2

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

treatment. They are widely used in constructional materials for aircraft, space and other technologies where extreme conditions are employed [26]. 1 3

R

R

|

|

[−Si − (C)n −]m |

|

R2

R4

R1 - R4 = Alk, Ar, H etc; (С)n = –CH2–, –CH2–CH2–, (–CH2– )n (n>3), –CH=CH–, –C≡C–, –CH2–C≡C–CH2 –, arylenes, xylylenes etc. Polyorganpsilazanes – compounds containing alternating structural fragment with ≡Si-N= bond. Most commonly polyorganosilazanes are produced by organochlorosilane interaction with ammonia (ammonolysis reaction). Low-molecular compounds are produced at triorganochlorosilane and diorganochlorosilane ammonolysis. The only exception is methyldichlorosilane for which formation of linear polymer of X-[(Me)(H)SiN(H)]nX kind where n~ 50, and Х – group –NH2, is supposed. However, we may not exclude cyclobranched polymers production due to structural fragments forming with trisilylated nitrogen atom - N(SiMeH-)3. Cyclobranched organosilazane resins of [RSi(NH)(3-a)/2(NH2)n]m general formula were obtained by organotrichlorosilane ammonolysis. At co-ammonolysis of organochlorosilane mixtures whose average functionality is above two, polyorganosilazane resins of various composition and structure and containing highly reactive ≡Si-NH2 groups were also produced. When heated the resins may condense by groups ≡Si-NH2 with cross linked polyorganosilazanes production. High-molecular cyclobranched polyorganosilazanes containing uncommon cyclodisilazane fragments were obtained through hexamethylcyclotri- or octamethylcyclotetrasilazane interaction with methylphenylsilane [27]:

Development of the Chemistry…

a R2SiNH

n

+ b R'R''SiH2

kat - H2

R R R' Si N N Si Si R'' R R

3

m

Polyorganosilazanes demonstrate high reactivity by ≡Si-N= bond at interaction with water, polyorganosiloxane silanol groups and hydroxyl groups on organic and inorganic materials surfaces. It allows their efficient practical use as water-repellent agents, cross-linking agents for polyorganosiloxane resins and for protective coatings on various materials surfaces. Some polyorganosiloxanes are produced commercially. Synthesis of combined silicon carbide – silicon nitride ceramics through polyorganosilazane pyrolysis has been investigated [28]. Researchers pay maximum attention to polyorganosiloxanes whose polymer chain involves alternating ≡Si-O- bonds. Along with siloxanes bond there are 1 ÷ 3 organic substituents at silicon related to actually all organic compounds classes. Organosiloxanes amount to above 99% of all heterochain organosilicon polymers manufacturing. Organosiloxanes are distinguished by the properties of particular interest: chemical and physical stability, oxidationand thermal resistance, low surface tension, relatively slight viscosity change at temperature or shear velocity modifications, good operational parameters at low temperature, water repellency and high compressibility. In nature silicon exists in the form of oxygen compounds only, as silicon dioxide or silicates having polymeric identity as a rule. Polymeric skeleton of these compounds is made of orthosilicic acid Si(O-)4 residues. Organosiloxanes for the most part reduplicate silicate structure peculiarities. There are the following main kinds of organosiloxane structure fragments: Si(O-)4 (Q), RSi(O-)3 (T), R2Si(O-)2 (D), R3SiO- (M). The combination of presented structure fragments determines entire organosiloxanes diversity. Polysilicic acid esters that may be represented in general by a formula {(RO0,5)m(SiO2)}n, where RO – alkoxy-group are the simplest organosiloxanes including Q structures only. Said products physical state varies from liquid to solid ones. At presenrt diethyl ether of orthosilicic and polysilicic acids are in commercial production. They are widely used as initial agents for the production of organosiloxane polymers of various structures.

4

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

QM resins {(Ме3SiO0,5)m(SiO2)}n that may be obtained by alkali silicate interaction with Me3SiCl are organosiloxanes, including M and Q structures. Organosiloxanes (R3SiO0,5)8[Si8O16] including polyhedral cluster SiO2 are produced through silicate [Si8O20]8- solution reaction with R3SiCl [29-34] were obtained by means of Q and D structure fragments combination.

Cross organosiloxanes

and spiran ones

Development of the Chemistry…

5

Organosiloxanes containing RSi(O-)3 (T) structure fragments are called organosilsesquioxanes and they are organosiloxane resins base. Silsesquioxanes are most commonly produced by hydrolytic condensation of RSiX3, where Х – readily hydrolysable group.

H2O RSiX3

[ RSi(OH)aO(3-a)/2]m Solvent

[ RSiO1,5]n -H2O

Depending on synthetic conditions said compounds molecule structure may represent ladder-like

three dimensional polyhedral cluster including three-, tetra-, penta- and hexasiloxane cycles

or branched dendrimer structure.

6

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

Branched organosesquioxanes may also include ladder and threedimensional polycyclic ring structure fragments [35-40]. Linear polydiorganosiloxanes combine M and D structural fragments 1 2 3 4 5 1 2 3 R R R SiO(R R SiO)nSiR R R . Linear organosiloxanes, containing acyclic, aromatic, trifluoroalkyl substituents are widely used as fluids whose viscosity may vary from 6/5.10-4 up to 600 poise. Silicone fluids are widely used as release agents for molds thanks to their low surface tension and lubricating capacity. Physiologic inertness of silicone fluids allows their use in medicine and cosmetics. Thermal resistance and minimum viscosity change at temperature modifying allows silicone fluid employment as coolants for electric systems, hydraulic fluids and heat-transfer agents. High resistivity constant and low dielectric losses combined with environmental stability enable their usage as dielectric liquids in mains transformers and fluid-filled condensers for electric and electronic systems. Thanks to high compressibility factor they are employed in mechanics as liquid springs. Linear polyorganosiloxanes, containing hydroxyl, alkoxyl, vinyl, Si-H groups at the end or in the chain, are widely used as rubbers for siloxanes rubber compositions. Curing ability within a wide temperature range and unique properties typical for silicones make them indispensable in household, engineering and industry.

Development of the Chemistry… Initial reagent

Protection removal z

y

o

x

x x

z

i

x

z z

o

o z

The initial branching centre

z

o

z

x z

j

x

x o

o x

o

x x

i, j x

x

o

x

x

x

o

1

o x

o

o x

o

x

x i, j

x x

x

x

o

o x

o o

x

x

x

x, y, z - functional groups

2 o

o x

x

o

1

o

x o

o

o

x

x

x

o

x x

x

i, j

x x x

x x xx x x o o o x x x o o o o x o o x o o o x x o x o o xx x o o o o o o x x o o 1 x x o o o 2 x x o o o 3o x x o o o o x o o x o o x x o o o o x x xx xx x x x x x x x

o

o

o

o

x

o

o

o

x

x

o

o

x x

o

o

x

x

o

x

x

7

x

xx

o o

o

Generation:

n=1

n=2

n=3

n=4

Nx:

6

12

24

48

Nx = 3*2n - number of end groups

Synthesis method for branched polyorganosiloxanes having no closedchain – dendrimers, in their structure has been developed recently. Dendrimer synthesis is performed in such a way, that there would be neither growing branch linking together nor molecules association with each other. In the same way the branches of a single tree or tops of standing side-by-side trees never grow together. «Building» of such molecules is conducted according to prescheduled plan, for example using reacting groups of three types (А, B and C) that must meet the requirements of specific logic design: Each group is not able to react with similar one (А does not react with А etc.), groups А and B can interact but each of them cannot react with C, group C should have the opportunity to transform to group A at a given time. Polymerization is performed according to the strategy «protection – protection removal», that is used at Nucleic Acids and Protein Synthesis with preset amino acids and nucleotides sequence. The first polymerization stage results in free groups forming on “branches” ends. Each group is able to react with two additional monomers, thus a dendrimer of the first generation is produced. Such consecutive steps may amount to finite quantity, as at a given time a tight pack from monomers is produced, that prevents further polymerization proceeding. Thus, in [41] dendrimer synthesis of formula MeSi{OSiMe{-OSiMe{-OSiMe{-OSiMe(OEt)2}2}2}2}3 is described. On the first stage MeSiCl3 interacts with NaOSiMe(OEt)2 then the obtained product is treated by SOCl2 and ethoxy group is replaced with Cl. The produced chlorosiloxane reacts with NaOSiMe(OEt)2. After fourfold reaction dendrimer with 46 silicon atoms is obtained. Just imagine – dendrimer of the ninth generation should consist of as many as 3069 monomers, and such molecule diameter amounts to ~10 nm [42, 43]. Today researchers have learned to retain metal ions on dendrimer surfaces by means of chelate groups. Due to contacting “branches” of the branched molecule, intracavities are formed where various small molecules not

8

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

chemically bonded with dendrimer may be present. Various pharmaceuticals may be introduced in these cavities thus providing their durable therapeutic action. The dendrimers may also hold substances with a radioactive marker; this may be used for various disease diagnostics. Organosiloxanes having functional groups at silicon or in an organic substituent are able to interact with organic polymers producing hybrid compounds containing both organic and inorganic polymer chains [44]. There are three basic types of polymers with organic-inorganic molecule chains. Branched polyorganosiloxane – polyester block copolymers set when heated with the formation of cross-linked polymeric matrix. They are produced by co-condensation through the interaction of polyfunctional organosiloxane resin silanol groups with polyester resin functional groups. Property combination of organosilicon and organic polymers allows their efficient use as paintwork material components. They are produced by all leading organosilicon polymers manufactures. Graft polyorganosiloxane – polyester block copolymers contain linear polyorganosiloxane chain and graft polyoxyalkylene blocks. Considered block copolymers demonstrate the properties of highly efficient surfactants in aqueous and organic media. They are widely used in various areas and have become indispensable as foam stabilizers in polyurethane foam production. Fast development of heterochain organosilicon polymers application areas results in the fact that most achievements have been patented. But patents do not include detailed analysis of the obtained results thus thwarting progress in this area. Therefore there is a need in further detailed study of synthesis methods and property investigations of these polymers.

Chapter 2

POLYMERS CONTAINING SILICONNITROGEN AND SILICON-OXIGEN BONDS 2.1. A COMBINED POLYMERIZATION CONDENSATION PROCESS – A NONTRADITIONAL METHOD OF SYNTHESIS OF SILICONORGANIC POLYMERS WITH INORGANIC AND ORGANIC-INORGANIC MAIN CHAINS OF MACROMOLECULES It is known from the literature that the allotment arylen, heteroarylen and other hard fragments into the main chain of polyorganosiloxanes leads to improvment of their heetresistance, and thermal and radioation stability, mechanical, tribological and other characteristics [45]. As we would be awaited analogical modification of the properties of silazane, siloxsazane- and carbosiloxane oligomers and polymers would be existing [46]. By the combined polymerization condensation method one can sinthesized polyfunctional oligomers and polymers with the regular liner structures of their molecules containing simultaneously Si−N-, Si−O- and N−H groups [47]. The aforemantion polymers attracted the attantion of scientists and technologs as modifiers leads to purposeful regulation of the properties of various industrial organic and organoelemnt polymers [48].

10

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

2.1.1. Polymerization-polycondesation of Silicon-nitrogen Containing Heterocycles with Various Diamines and Aromatic Diols For industrial purpose siliconorganic polymers as a rule produce by using traditional methods of synthesis – hydrolitic polcondensation of organochlorosilanes and polymerization of organosiloxane heterocycles of polymers manufactured by these methods characterized with the complex interesting properties. But in many cases they have a low radiation and mechanical stability, low addhesion to metallic and other surfases, etc. Besides it is not posible to reach the variety of the macromolecular disign. Eighties and nineties of the last sentury the usage of the non-traditional mathods of sinthesis of siliconorganic polymers has stimulate the synthesis of siliconorganic polymers contaned various organic and organic-inorganic fragments in macromolecular main chains [49]: • • • • • • • • •

Polyorganosiloxanes and polyorganosiloxiarylenes; polysiloxisilarylenes; polyorganosilazasiloxiarylenes; polyorganosiloxaazanarylenes da -silazasiloqsiarilenebi; polyorganosilazasiloxiheteroarylens; polyorganosilazasiloxicarbonats and -siloxicarbonates; polyorganoboricsiloxanes; polyorganosilazasiloxanes with liner, cycloliner and polycycle structure of makromolecules; polyorganocarbosiloxiarylenes, etc.

The first efforts aimed at obtaining polymers with inorganic and organoinorganic molecule chains using combined polymerization and condensation processes were published in the 60s. While studying trans-amination of octamethylcyclotetrasilazane with diaminobenzidine in 1963 we found [49] that when the reaction mixture was heated above the melting point of benzidine (>120°C), the reaction not only opening a silazane cycle, but also releasing ammonia and gradually increasing viscosity by the following scheme:

Polymers Containing Silicon-nitrogen and Silicon-oxigen Bonds Me2Si n

NH

HN Me2Si

Si2Me NH

NH

+

2n H2N

NH2

Si2Me

Me Si

11

Me NH

Si

Me

+

NH

NH

2n NH3

n

Me

Scheme 2.1.

The resultant solid polymer with ηred.=0.215 is soluble in chloroform, dimenthyl-formamide, aniline, pyridine. In the same year Zhinkin et al. demonstrated [50] that a similar polymerization-condensation scheme occurred in a reaction between organocyclosilazanes and aliphatic diamines (Scheme 2), the reaction mixture being heated up to 160-200°C:

n [Me2SiNH]3

+

1,5n H2N(CH2)mNH2

SiMe2

N

- n NH3

SiMe2

(CH2)m SiMe2

N

N (CH2)m

n-1

SiMe2

N

where m=2-6; n=8-10. Scheme 2.2.

A catalytic amount (0.1-1%) of ammonium sulphate accelerates the reaction by more than an order of magnitude. Reduction of diamine basicity (elongation of the hydrocarbon fragment between the amino-groups) enhances the catalyst action upon the reaction rate. Elliot and Breed [51] used aromatic diols instead of diamines in a reaction with organocyclosilazanes to achieve polymerization-condensation. It was shown that with an equimolar ratio of the initial reagents the reaction was

12

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

conducted quite intensely both in bulk, and in solvent (toluene, benzene, and xylene) releasing ammonia and forming high-molecular compounds with Si–N links in a chain:

n [RR/SiNH]3

+

n HO

X

OH

- (n-1) NH3

H2N (SiRR/NH)2SiRR/-O-X-O

n

R = R/ = alkyl, aryl; R = R/; X =

H

,

,

Me C

,

,

CH2

Me

Scheme 2.3.

Boiling of synthesized organosilazaoxyarylene polymers with ethyl alcohol for one hour does not lead to any noticeable reduction of viscosity, and their destruction starts only at 350-400°C. An increase of the molar fraction of the original aromatic diol to 1:3 induces complete replacement of the NH-groups in a polymer chain with residues of the aromatic diol, thereby producing relatively low-molecular products of the siloxyarylene structure [52]: n [RR/SiNH]3 + 3n HO

X

OH

H 2N

SiRR/-O-X-O

n

H + (3n-1) NH3

n = 20 : 25; R = Me, R/ = Ph; R = R/ = Me, Ph; X =

Scheme 2.4.

An investigation of reaction of organic diols of different structures with organo-cyclosilazanes of different cycle sizes and different nature of organic radicals at silicon atoms was aimed at clearing up the effect of diol and organocyclosilazane structures upon the polymerization-condensation process (Table 2.1) [53, 54]. The reaction of dialkyl-, methylphenyl- and diphenylcyclosilazanes with dioxynaphthalenes and polycyclic bisphenols of the card

Polymers Containing Silicon-nitrogen and Silicon-oxigen Bonds

13

type proceeded in bulk until the ammonia isolation stops. With an equimolar ratio of the reagents the reaction proceeds as follows: m (RR/SiNH)n

+ m HO

X

OH

(SiRR/NH)p SiRR/-O-X-O

X=

,

,

- (n - p) NH3

m

C

,

.

C

.

Scheme 2.5.

The reaction rate, the viscosity and yield of the polymers formed depend considerably on the diol and organocyclosilazane structures (Table 2.1), while toe completeness of the reaction on the reagents ratio. In all the cases in the initial stage of the reaction the kinetic curves of ammonia isolation (Figures 2.1 and 2.2) reveal an induction period, its length growing with the radical volume on the silicon atom. At the initial stage of the reaction the induction period seems to depend on the establishment of a stationary concentration of the transition complex3 which then decays in the following way [22]: R/

R

R/

R

Si HN R Si R/

Si NH Si

NH

+

R R

HO

X

HN

OH

R Si R/

/

H N

H

Si NH R R /

O

(A) R H 2N

Si R/

R NH

2

Si

O

X

OH

R/

where X – the residue of the aromatic diols. Scheme 2.6.

(B)

X

OH

14

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

Figure 2.1. Dependence of emount of separated ammonia on time in the reaction of 1,5- dihydroxinaphtalin with [RRSiNH]3 (1M:1M) (Tible 1): 1.-R=R’=Me; 2.- R=Me; R’=n-Bu; 3.- R=R’=Et; 4.- R=Me, R’=Ph; 5.- R=Me, R’=C8H17.

The resultant compound I attack the new molecule of the cycle, forming a similar complex which then either undergoes decay or starts a condensation reaction with the new diol molecule. Consequently, the growth of a polymer chain is due both to the polymerization reaction of cyclic silazane proceeding with its opening and to condensation of the end amine and hydroxyl groups. The hydroxyl group can attack not only cyclic compounds, but also linear sections of a silazane-group containing chain, thus leading to the statistical distribution of structural units in a macromolecular chain. As it is evident from Table 2.1, conversion over ammonia, in some cases, exceeds the one calculated from the quantity of the original diol. When conversion over ammonia was less than one mole on mole of the initial diol, the reaction had been continuing up to 1.03-1.05 moles of NH3 on one mole of the diol. The polymers transformed into insoluble, infusible state. These facts demonstrated, that not only the reaction of chain increase occurs, but also the reaction of trans- aminationtakes place due to the interaction of NH-groups, being formed during the process of chain increase, with ≡Si–NH–Si≡ groups presenting into the system. It causes formation of branching and retina macromolecules with trisilylamino groups at the knots of branching [22]: Si

NH

Scheme 2.7.

Si

+

N2H

Si

ΝΗ3

Si

N Si

Si

Table 2.1. Polysilazasiloxiarilens based on polycyclic bisphenols and aromatic diols [RR/ SiNH]3

Reaction

diols R − R

tempera-

/

Reaction time, hrs

ture,0C 1. Me Me 2. Me* Me*

HO

OH

3. Me Ph 4. Ph

Ph

Separate ammonia, %

130

0,52

101

130

0,6

100

140

1,0

106 84

170-180

Formula of the elementary rings of polymers

Yield of Polymers, % 89

(S iM e 2 -N H ) 2 -S iM e 2 -O

O

5. Me Me

HO

6. Me* Me* 7. Me Ph 8. Ph

OH

Ph

9. Me n.-Bu

130

2,0

100

130

0,5

91

140

0,6

97

1,2

81

2,2

101

160-170 180

0,5 10. Et Et HO 11. Me n.-C8H17

OH C

12. Me Me

13. Me Me 14. Me Ph 15. Ph

Ph

HO

OH C

.

(S iM e 2 -N H ) 2 -S iM e 2 -O O S iR R / -N H -S iR R / -O

-

0,82

27

73

0,32

-

-

1,01

10

-

0,69

-

90

0,50

30

74

0,23

-

83

0,58

-

0,60

13

0,45

25 42

101

180

1,0

100

89

0,81

130

1,5

100

81

0,80

O

C

0,40

140-150

1,2

97

91

130-150

2,0

98

96

170-180

3,0

94

S iR R / -N H -S iR R / -O

O C

.

C

8

0,8

O

0

0,75

180

(S iM e 2 -N H ) 2 -S iM e 2 -O

Tgam. in

1,29

O

S iR R / -N H -S iR R / -O

ηsp(1% solution Toluene)

0,34

36 -

95

56

96.5

63

-

Table 2.2. Rate constants of model reaction of the combined polymerization-condensation process

Si−N-containing heterocycles

k1, 2

k3

k5

k6

Me2 Me2SiOSiOSiMe2 NH

1,20

20,31

0,68

0,94

0,20

10,12

1,04

0,94

0,05

13,19

1,10

0,90

Me2Si

(CH2)3 NH

SiMe2

Me2 Me2 Me2SiOSiOSiOSiMe2 NH

Table 2.3. Conditions of the polymerization condesation of organocyclosilazans with α,ω-dihydroxipolyorganosiloxanes

#

Initial monomers cyclosilazane diol

Treac. C

0

6

[(Me2SiNH)2(Me2SiO)2] HO[Me2SiO]3H 80 [(Me2SiNH)2(Me2SiO)2] HO[Me2SiO]10H 150160 [(Me2SiNH)2(Me2SiO)2] HO[Me2SiO]15H 150160 [(Me2SiNH)2(Me2SiO)2] HO[Me2SiO]55H 180190 [Me(Et)SiNH]3 HO[Me2SiO]15H 150160 [C6H13Si(NH)1,5]6 [PhSiO(OH)]4 101*

7

[C6H13Si(NH)1,5]6

1 2 3 4 5

[PhSiO(OH)]4

150200

React. amount of time, sepa-rated hrs NH3, % ηsp.

Tg, 0 C C

Data of the elemental analysis Found, % Calculated, % H Si N C H Si N

2,80 3,20

86 72

32,59 8,35 0,25 _ 0,33 -100 _

37,74 _ _ _

32,46 8,36 _ _

37,95 2,70 _ _

4,70

91

0,50 -123 38,60 8,20

37,74 1,21

32,49 8,13

37,86 0,99

37,43

40,48 8,16

37,91 0,32

_

_

10,00 87 2,50

89,5

0,68

39,92 7,94

0,27 -68

_

_

_

_

_

_

14-15 93,7

0,10 +90 54,32 7,94

20,83 6,36

55,33 8,14

21,58 7,53

14,00 78

0,13 -100 54,44 7,98

21,20 7,08

55,33 8,14

21,58 17,53

18

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

The model reactions of some of Si−N containing heterocycles with phenol (at the ratio 1:2) were studied and the kinetic curves of isolation of ammonia were obtained for investigating the principal CPC process. Considering the above mentioned experimental data the mechanism of the reaction was described by system of differential equations. Several versions of the mechanisms, were calculated with the aim of choosing the most probable one. The simplest mechanism comprising the stage of the opening of cycles over Si−N bond and of further heterofunctional condensation of the formed NH2groups with hydroxygroups did not lead to any satisfactory approximation for solving the extreme problem. At the given precision of the experiment the most satisfactory result from the point of view of minimization of average deviation (Figure 2.2) is the following mechanism [22]:

Si a

Si

NH + HOPh

H

Si

(1)

a

Si

N H O Ph

(2)

Si

NH2

a Si

OPh

(A) SiNH2 + HOPh PhOH + ΝΗ3 ( 2

(3)

(4)

_

PhO (NH4)+ (5)

Si)2NH + H2NSi SiNH2

(6)

SiHOPh + ΝΗ3

Si

NH

(B)

Si)3N + ΝΗ3

( Si

+ ΝΗ3

Scheme 2.8.

The velocity constants of the elementary stages were determined (Table 2.2) by minimizing the average deviation of the points of the experimental curve from the theoretical function for separation of ammonia. The formation of transition complex has been established by 1H-NMR method. The process of transamination (stage 5) was established using 1HNMR-, UV-spectra and chromatography analysis. The compound of the following structure was shown to form [22]:

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

19

Scheme 2.9.

The kinetic data reveal (Table 2.2) that the limiting stage is the formation of a transition complex (A) and the reaction of the cyclic silazane opening giving rise to the induction period of the reaction. However, the observed induction period (Figure 2.1) can be seemingly due to ammonia binding (reaction 4). Besides, the resultant nucleophilic particles (B) may act as an effective catalyst in the condensation reactions. When diols are used reactions (2) and (3) are definitive at the chain growth stage. A simultaneous side reaction (5) is possible, also catalyzed by nucleophilic molecules (B), thus leading to macromolecular chain branching and eventually to polymer structure formation. Indeed, when a polymer mass is subjected to prolonged heating up to 180-200°C, the polymers change to a non-melting and insoluble state. Most of the resultant polymers are hard rubber-like substances; their elastic properties depend on the size of the organosilicon fragment in the elementary link of a macromolecular chain and the nature of the organic radicals on the silicon atom. Polymers of the highest viscosity ([η] = 0.75-0.87 dl/g) and satisfactory elastic properties were obtained on the basis of hexamethylcyclotrisilazane and dioxynaphthalcne with 1:1 ratio. Methylphenyl- and diphenylcyclosilazanes form polymers with higher temperatures of vitrification (Table 2.1). In the case of organocyclosilazanes with large aliphatic radicals at silicon atoms highly viscous liquids are formed. It is noteworthy that the importance of the exchange reactions in the process of polymerization-condensation increases with the growth of the diol molar fragment in the original mixture. With a three-fold excess of diol the reaction produces fragile vitreous materials; in such a case, just as in Reference 10, the products form contain an elementary link solids which does not contain silazane groups and which arc a high molecular weight ηsp= 0.090.13). Polymers based on diorganocyclosilazane and aromatic diols are readily soluble in benzene, toluene, chloroform, but insoluble in saturated hydrocarbons.

20

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

Figure 2.3. 'H NMR spectrum of the trans-isomer of [MePhSiNH]3

ª Figure 2.4. 'H NMR spectrum of the mixture of the trans-isomer of [MePhSiNH]3 and phenol after mixed of the initial compounds at 4th (a) and 45th (b) min.

The character of polymer thermomechanical curves depends on the ratio of ilie original compounds, the volume of radicals at silicon atoms and the nature of the aromatic diol. When the permanently applied load is increased (from 30 to 100' the highly elastic area vanishes and Tvit of the polymers drops significantly; meanwhile, with [–SiRR'–0–X–0–]n,-type polymers, i.e.,

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

21

polymers without any silazane groups in chains, there is no elastic area on the curves and the polymers demonstrate comparatively high temperatures of vitrification (Tvit = + 38- + 93°C). According to the thermogravimetric data, mass losses, as low as 2-5% was observed in polymers obtained from hexamethylcyclotrisilazane and aromatic diol at an equimolar ratio and at 400°C. A polymerization-polycondensation process can be carried out by using siliconorganic diols [54, 55]. Thus, a reaction of diorganocyclosilazanes with a three-four-fold molar excess of dihydroxydiphenylsilane yielded polyorganosiloxanes with a high content of diphenylsiloxy links.in a polymer chains:

Scheme 2.10.

Figure 2.5. 'H NMR spectrum of the mixture of the trans-isomer of [MePhSiNH]3 and phenol after mixed of the initial compounds at 429 min.

22

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

Figure 2.6. Dependence of chemical shipts of hydroxy groups protons on time in mixture of the phenol and trans isomer of [MePhSiNH]3 at their verious molar ratio: 1.0,5:1; 2.- 0,65:1; 3.- 1:0,5.

The polymers obtained are of interest as bonds to be used in the formation of composite materials with high thermal and irradiation stability. Curious results have been recently obtained [55] in a study of a reaction between α,ω dihydroxypolydimethyl(methylvinyl)siloxanes and dimethylcyclosilazanes. The reaction also proceeded easily, in mass, with isolation of gas ammonia, according to the polymerization-polycondensation mechanism with ammonia isolation: Me x H

O

Si

Me m-1

O

Si

Me

Vi

Me P

O

H

O

Si Me

Scheme 2.11.

y

Me

Me -(x-n) ΝΗ3

OH + x [Me2SiNH]n

Si

Me m

O

Si Vi

Me P

O Si Me

OH z x-y

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

23

Therefore, the molecular mass of polymethyl(methylvinyl)siloxanes increases forming high-molecular elastomers ([η]=1.4-1.8dl/g). The optimal conditions of the process require a reaction temperature 175oC and diol-tohexamethylcyclotrisilazane ratio 1:2. the lower the temperature, the slower the reaction rate; meanwhile, at higher temperatures the polymer formed has an insufficient MM because hexamethylcyclotrisilazane boils out before it has time to complete the reaction with diol (the trimer Tb.p. is 180oC); the duration of this process is ditrectly related to the original α,ω- dihydropolydimethyl(methylvinyl)siloxanes MM. The characteristic viscosity in toluene observed in the diol condensation product at MM =6000 was 0.5 dl/g after 10 hours, while at MM =30,000 it was 1.6 dl/g after the same period of treatment. The physical and chemical characteristics of rubber obtained from synthesized polymers and subject to thermal ageing are superior to those of rubber obtained from industrial rubber polydimethyl(siloxane, since the rubber obtained by polymerization polycondensation of dihydroxypolydimethyl (methylvinyl)siloxanes with dimethylcyclosilazanes without acid or alkaline catalysts, is naturally free of the latter which usually deteriorate the thermal stability of rubber. The reactions of tetramethyltetraphenethlcyclotetrasilazane with dihydroxydiphenylsilane and 1,3-dihydroxytetraphenyldisiloxane were studied [55] at the molar ratio 1:1. The processes proceed via a polymerization mechanism releasing ammonia and forming a corresponding polyorganosilazaoxanes by the scheme: n[(CH3C6H5)2SiNH]4+nHO[(C6H5)2SiO]mH → → H2N{CH3(C6H5)SiNH]3(CH3C6H5)SiO[(C6H5)2SiO}mH, where m = 0 or 1 The reaction does not proceed even at 130-140o C, when it is carried out in an aromatic solvent (toluene, ditolylmethane) due to high hydrolytic stability of cyclosilazane with phenethyl radical attached to the silicon atom, while in bulk the reaction begins at 70o C achieving the maximum of conversion in terms of isolating ammonia (80-98%) in the range of 110-120o C. At temperatures hegher than this, the conversion of ammonia reduces. Especially it is noticeable in the case of the nitrogen content in the polymer, after it is placed under reduced pressure due to replacing of silazanic bonds by siloxanic ones.

24

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

2

Me

2

O SiO

Me

Me

Si

NH 2

Me

1,5

80

78

79

-

170180

2,5

85

100

82

-

210220

4,0

90

102

89

0,3

ηred

150160 12

Me

32

C10H13 Me

C10H13 Me

Me

Si

NH

Me

Si

O SiO

C10H13 Me

C10H13 Si

Si

NH

Yield of the polymers, %

Si

Amount of the separated NH3, % Tg,, 0C

C10H13 Me

C10H13

Reaction temperature, 0C

The structure polymer elemental ring

Reaction time, hrs

Table 2.4. The conditions of the reaction of tris(tricyclodecenilmethyl)cyclotrisilazan with α.ω-dihydroxioligodimethylsiloxane and some properties of the obtaining polymers

O SiO Me

72

Investigation of the kinetics of the reaction monitors the process to be characterized by the induction period achieving 30 min in case of the reaction with dihydroxydiphenylsilane at 98oC, while increasing the temperature above 130oC, it diminishes to 3min. Mn of the polymers is of the order of 6.0 6.7·104. Gel-chromatograpic analysis demonstrates sufficiently narrow distribution of MM in the polymers. Combined polymerizatoin-condensation reaction of tris(tricyclodecenylmethyl)cyclotrisolazane with the oligodimethylsiloxanes (m = 12, 35 and 72) at molar ratio 1:1 [56- 58] was also investigated. It was established that conditions of the reaction, Tg,, yield and specific viscosity of the polymers, depend on the length of siloxane chain of α,ω-dihydroxythemethyldisiloxane (Table 2.4). As it is evident from Table 2.4, increasing the extent of polymerization of the oligomer, temperature and the duration of the reaction also increase as well

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

25

the degree of conversion in terms of ammonia and the yield of polyorganosilazasiloxanes, while their vitrification temperature decreases. The polymerization polycondensation method turned out to be a sufficiently universal one for synthesizing polymers with inorganic and organo-inorganic macromolecular chains of various composition and structure, because it can employ organocyclosilazanes as well as organocyclo-silsesquiazanes, mixed organocyclosiloxazanes, organocyclosiloxanes and organocyclosilsesquioxanes as the initial cyclic compound, which can readily entrain comparatively low reactionable different organic and organosilicon diols into polymerization polycondensation reaction. Keeping in mind the dependence of the polymerization-polycondensation reaction on the structure and reactability of the original organosilicon heterocycles and diols, an investigation [59, 60] was carried out into the interaction of polycyclic organocyclosilsesquiazanes with α,ω-dihydroxydimethylsiloxanes, dihydroxy-diphenylsilane and tetrahydroxytetraphenylcyclotetrasiloxane (tetrol). Interaction of pentamethylhexaethyltricyclohexasilpentazane of the following structute [59] Et HN Me Et

Me

Me

Si

Si N

Et

Et NH Me Si Si Si Et N N Si Me Et

(I)

Scheme 2.12.

with α,ω-dihydroxyoligodimethylsiloxanes (n=10.42) and dihydroxydiphenylsilane in bulk at 170-180o C and at an equimolar ratio of reagents hes shown thet the reaction goes on according to a matched polymerization polycondensation scheme with ammonia isolation, however forming structured polymers. Meanwhile, although of organocyclosilazanes and diols, it does not exceed 50% when diols react with a tricyclic compound I. In the latter case the initial stage of the reaction shows along induction period and as low growth of MM within the first 3-6hours. Here, just as in case of organocyclosilazanes, a silazane cycle opens initially along the Si–NH–Si link to form a Si–O link and

26

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

NH2 -group which starts a condensation reaction with the hydroxyl group of another diol molecule (Scheme 2.13). Since a tri-cyclic compound contains two reaction centres in different cycles and each chemical event of opening a silazane ring gives rise to a new, more reactive NH2-group, there immediately appears a possibility of forming a branched oligomer with subsequent structurization. The reaction is slow one, limited by the stage of cycle openings. Only a prolonged heating of the reaction is a slow one, limited by the stage of cycle openings. Only a prolonged heating of the reaction at 220oC and higher can facilitate an 85% conversion in terms of ammonia and 85-86% of the gel-fraction content (up to 60% in case of dihydroxydiphenylsilane). In contrast to the reaction of tricyclic compound I with organosilicon diols a three-dimensional polymerization polycondensation of cyclosilsesquiazane (T6) with α,ω-dihydro- xyoligodimethylsiloxanes (n=42) proceeds at a much higher rate. A great number of branching centres, 8 of them, in complex molecule of cyclosilsesquiazane (T6) ensures structurization of the system within 2 hours at 150oC and 10 min at 180oC. The polymerizaition-polycondesation reaction of complex cyclosilsesquiazane systems with organo-silicon diols proceeding up to gelformation, yields viscous, soluble liquids which after structurization form rubber-like substances, the vitrification temperatureof shift to the negative temperature region and the elasticity modulus decreases with a longer siloxane chain [59]: Si

Si HN Si N

NH

Si

Si

Si

+

HO

R

OH

Si

SiO

ROH

N

HN

Si

Si N

NH

Si NH

Si

( III )

OH

Si

NH 2

Si

Si N

(I)

OR

N

HN

N

Scheme 2.13.

Si

Si

N

Si

N

( II )

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

27

Figure 2.7. Dependence of the emount of separated ammonia, specific viscosity (till gellation process) and gel fraction (%) on time in reaction of the pentamethylhexaethyltricyklohexasilpentazan with the α,ω-dihydroxidiphenylsilan in mass.

Table 2.5. Some characterizing parameters of polymerization condensation of Me5Et6Si6NH3(NH)2 with siliconorganic diols and polymers based on them Molar ratio Treact., Time of gelof iinitial 0C formation, monomers hrs 1 HOSi(Ph)2 1 : 1 140- 3.7 OH 150 2.1 2 1 : 8.0 _”_ 2.5-2.6 3 HOSi(Ph)2 1 : 1 170OH 175 4 HO[Si(Me)2 1 : 1 180 8.0-8.5 5 O]10H 1:1 170- 6.0-6.5 180 HO[Si(Me)2 O]42H HO[Si(Me)2 O]40H # Diol

Amount ηsp. of (max.) separated NH3, % 47 0.120 38 0.088 33 0.056

40 39

NH3 Tg, Gel0 , C fraqtion % , % 80.7 20 60 89.3 _ 78 80.9 -10 86

0.520 58- -35 79 0.500 59 _ _ 52.0

28

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov C6H13 Si HN

H13C6

H13C6

NH

HO

Si

NH Si C6H13 C6H13 Si HN NH NH NH Si

Si

NH

C6H13 H2N

Si

NH

Si

C6H13

C6H13

Si

Si

NH

NH

C6H13

Si

O

NH NH

C6H13

Ph Si

C6H13

Ph

-(2x-1)NH3

Ph

Ph O

Si

O

H

O

O Si

OH

Si

Ph

O

Si

O O

Si

Ph

OH

Si

O HO

C6H13

O

Si

x

+

NH

HN H2N

Ph

Ph

NH

O

Si Ph

O

H x

Scheme 2.14.

An increase of functionality of the original hydroxyl-containing organosilicon compound from 2 to 4 in a polymerization polycondensation reaction does not lead to any increase in the threedimensional process rate and in the gel-fraction output. thus, the reaction of cyclo- silsesquiazane T6 with tetrolproceeds under the same conditions (170-180oC, reagents ration 1:1) in block within 15 hours with a 70% conversion in terms of ammonia and ~ 15% gel-fraction output. The reaction rate is much higher in a 40% dioxane solution: at 95-100oC the conversion in terms of ammonia reaches 93% within 15 hours, forming soluble products. Under cooling the solution precipitates crystalline substances (7-8%) with Tm = 220-250oC, which are a mixture of octa- and decaphenylsilsesquiazanes T8 and T10. these products being isolated and the solution removed, a polymer was obtained, its formation proceeds in the following way [59]: However, an incomplete ammonia release and presence of comparatively large number of functional groups evidence for some defects in the structure and a low viscosity value (ηred ≈ 0.1) at MM = 218000 and asymmetry coefficient z ≈leads to a branched structure of macro- molecules. The polymer is an amorphous powder with Tvit ~ 100 oC, showing no region of high-elastic state. Therefore, in this case polymerization polycondensation is accompanic by a cyclization processes and yields a branched polymer wich cyclolinear fragments in a macromolecule. Owing to the different reactivity of Si–N and Si–O bonds with respect to hydroxyl- containing compounds, research was

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

29

carried out [60, 61] to investigate polymerization polycondensation of mixed cyclosilazasiloxanes, viz, organospirobicyclosilazasiloxanes with organic, carborane and arganosilicon biols of different structures. The reaction of organospirobicyclosilazasiloxane (I) with the diols in bulk or in solution at an equimolar cycle-to-diol ratio proceeding up to a complete ceasing of ammonia release appeared in an ideal case to be going on as [62]: The nature of original diol influences greatly the course of this reaction, the structure and properties of the resulting products (Table 2.6). As the data of Table 5 show, the polymerization polycondensation of α,ωdihydroxyoligo- dimethylsiloxanes (n=25) with I in bulk an of diphenylpropane with I, both in bilk and in toluene, yields mainly insoluble products. When 1,2-bis(hydroxymethyl)carborane reats with I, a vitreous polymer, readily soluble in benzene and toluene; while when N,N'-bis(hydroxyldimethylsilyl) tetramethylcyclodisilazane reacts with I, a soluble oligomer is formed: however, the conversion in terms of ammonia is not high either in bulk or in solution. The differences in the behavior of the organic, carborane and organosilicon diols of different structures in the reaction with organospirobicyclosilazasiloxane can be explained by differences in the behavior of nucleophilic molecules resulting from a side reaction between diol hydroxyl groups and the released ammonia (p. 20), which catalyses the further process of polymerization-condensation.

x O

Me

Ph2 Si O Si O Ph2

NH

Si

O NH Si Me Ph

Si

Me H2N

Ph

Si Ph

x HO

+

Me O

Si Ph

NH

Si

O

O

O

Ph2 Si

Si Ph2 O

Scheme 2.15.

R OH

R

O

H x

-(x-1)NH3

30

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

Me HO

Si

O

T,0C

Reaction conditions

Diol

τ hrs Emount of the evaluated Gel- fraction, %

Table 2.6. Reaction of Organospyrobiscyclosilazane with verious diols

In mass 180

5.0

70

66

OH

In mass 150 110

6.5 3.5

86 90

73 31

CH2OH

Toluene 110

4.5

99

H 25

Me

Me C

HO

Me HOH2C

CH CH O B10H10

HO

Si Me

_

Me2 Si

Me N

Si Me2

_

Me N

Si Me

OH

In mass 140200

4.0

48

Toluene 110

9.5

40

A lower acidity of carborane diol causes a leftward shift of an equilibrium reaction which forms a nucleophilic molecule, and owing to a low concentration of nucleophilic molecules the siloxane cycle opens at an insignificant rate; however, the reaction of cycle opening with silazane groups and condensation of OH-and NH2 - groups is more complete (99% conversion in terms of ammonia), thus forming a soluble polymer of a linear of weakly branched structure. The concentration of nucleophilic molecules that can open a siloxane cycle is higher in the reaction of silazasiloxane bicycle with dimethylsiloxane and aromatic diols due to rightward shift of the side reaction and to a less complete reaction resulting from a comparatively rapid formation of a branched and partial network polymer. Therefore, the experimental data prove the decisive role of the diol nature and bicyclosilazasiloxane siloxane cycle activity in the formation of structurized products.

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

31

An interesting reaction is observed during polymerization polycondensation of bicycle silazasiloxane with N,N'-bis(hydroxyl-dimethylsilyl)tetramethylcyclodisilazane. The reaction begins with opening silazane groups in the bicycle and condensation of formed terminal NH2 -groups with diol hydroxyl grups. However, as soon as ammonia appears in the reaction system, an anion regrouping of cyclosilazane begins at a noticeable speed and with the cycle expansion (Scheme 2.17). This results in the hydroxyl group concentration dropping and the reaction is less speedy and less complete, while the resultant polymers are of alower MM. A similar re-grouping of cyclodisilazane accompanied by the cycle expansion and cyclosilazasiloxane formation had been reported earlier by Andrianov et al. In a study of polymerization condensation of N,N'-bis(hydroxymethylsilyl tetramethylcyclodisilane with dimethylcyclosiloxanes in the prrsence of tetramethylammonium siloxanediolate [63]:

Scheme 2.17.

The polymers reported [64] are of high thermaloxidative stability. Their mass losses start at 350oC and the basic destruction occurs at temperatures above 400oC. Zhdanov et al. [65] investigated the interaction of α,ω-siloxanediols with organospiro- cyclosilazanes (SC) of a new type with following structures: Here, two main processes are observed to proceed at 130- 140 oC an opening of interior cycles occurs and the formation of oligomers with the SC structural fragments regularly arranged over the chai8n takes place: at 180-190 o C elastic polyorganosiloxanes (RP) of regular structure are obtained. The formation of RP is predetermined by the opening of cyclotrisiloxanic

32

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

fragments and by the polymerization-exchange processes with the contribution of the nucleophilic particles type of O-[NH4]+ formed on the endings of the polymer chain, increasing the concentration (molar ratio) of isolating ammonia NH3, due to heterofunctional polycondensation:

O

Si

NH

Si

Si O Me2

O

R/

R

Me2 Si O

NH

Si

NH

Si O Me2

Si

Si

NH

NH

O

Si O Me2

R/

R

Me2 Si O

NH ,

O O

Me2 Si O , Si Me2

O

Si R

Me2 Si O

R/

R Si

NH

Si

NH

NH

Si

NH

R

Me2 Si O

NH

Si Si O NH Me2

Si NH

Si

O O

R/

Me2 Si O Si Me2

Me2 Si O , Si Me2

O O

Si

R/

O

O SiMe2

Me2 Si O where

R = Me, R/ =Me, Vin.

Scheme 2.18.

Si NH2 + HO

NH3 + HO

Si

Si

-NH3

Si O

Si

+ NH4 O Si

Scheme 2.19.

It was established that there is no requirement for initiators of ionic polymerization [67]. On the basis of the determination of gel-fraction by the method of equilibrium swelling it was demonbstrated that the density of crosslinking, together of R P essentially depends on the initial ratio of SC-siloxandiol and achieves its maximum at a ratio corresponding to one: one of the components [65].

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

33

2.1.2. Catalitic Polymerization Condensation of Organocyclosiloxanes Although the polymerization polycondensation of organocyclosilazanes and organocyclo- silazoxanes with organic and organosilicon diols proceeds actively enough with out any anionic initiators owing to the releasing ammonia capable of reacting with diol hidroxyl groups to form nucleophilic molecules which catalyze the further process, the reaction of organocyclosiloxanes and diols is impossible without anion initiators. A reaction of octamethylcyclotetrasiloxane (D4) with 1,4-bis(hydroxyldimethylsilyl)phenylene was studied and proved that D4 entrains diol into polymerization polycondansation only in the presence of an anion initiator (potassium oxide), producing copolymers with linear macromolecular chains [66, 67]: Me2Si O O Me2Si

SiMe2 O

O

HO

+

x.n HO

SiMe2

Me

Me

Si Me

Si O H Me

Me

Me

Me

Si Me

Si O Me

Si O Me

n

KOH -(x-1)H2O

H 4

x

Scheme 2.20.

The reaction was carried out in solution at 150o C and at cycle-to-diol ratios 1:1, 1:4 and 1:10. By fractionating the resulting polymers their copolymer composition was confirmed. Copolymers precipitated from benzene solution by methanol copolymers were, as a rule, white amorphous powders with 1.5. They are soluble in aromatic hydrocarbons, ether, CCl4, but insoluble in the methyl and ethyl alcohols. Comparatively weekly reactive organic and organosilicon diols are entrained into the polymerization polycondensation reaction with organocyclosiloxanes in the presence of nucleophilic initiators at the exchange reaction between the diol hydroxyl group proton and the initiator cation; and since the diol concentration is large as compared with the initiator

34

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

concentration, there occurs a transfer of active as compared with the initiator concentration, there occurs a transfer of active centers into diols which leads to further reaction. The high rates of proton-cation exchange and the formation of silanolate associates with silanol were shown experimentally in a study of a model system of sodium trimethylsilanol-teimethylsilanolate by 1H NMR and 13C NMR spectroscopy. Within this a rapid exchange reaction of hydroxyl of hydroxyl proton to sodium cation goes on [68]: Me3Si*OH

+

Me3Si*ONa

Me3SiONa

+

, ,, Me3SiOH

averaging the position of trimethylsilyl signals in the 1H NMR spectrum. It is that high rate of proton- top cation exchange reaction that contributes to an active diol entrainment into a reaction with organocyclosiloxanes. The reactions of polymerization-condensation of cis-1,3,5,-methyl-1,3,5triphenyl-cyclo-trisiloxane (cis-A3) with tetrakis-(3,5,7- triphenyltrisil-oxano-7hydroxy)-silane (TMPS) and -titan (TMPS-Ti) have been studied to obtain polymethylphenylsiloxanes with macromolecules of star-like structure. The reaction were carried out in bulk at 105oC in the presence of initiator methylsilanolate of potassium under an argon atmosphere, at the molar ratio of original-methylsilanolate of potassium under an argon atmosphere, at the molar ratio of original reagents: cis-A3 to TmPS-Si/TMPS-Ti=60:1. This process can be illustrated by the following scheme [69]:

∋

(OSiMePh)3

4

+

Initiat.

4n MePhSiO

HO (SiMePhO)m HO (SiMePhO)l

3

∋

(OSiMePh)pOH (OSiMePh)zOH

where ,

∋ = Si, Ti, m+ l + p + z = 4n, n = 45+60.

Scheme 2.21.

The distinctive feature of the reaction is that it proceeds with velocity. An increase of ηsp of the product of CPC occurs in the first 5-10 of the reaction (the conversion of cycle reaches ~ 90% in 10 min ) and practically entirely finishes after one hour.

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

35

The investigation of hydrodynamical properties as well as certain molecular parameters demonstrates that molecules of the polymer, formed via the reaction between cis-A3 and TMPS-Si are of tertiary functional star-like structure with one canter of branching on a molecule; meanwhile, the polymer obtained from the reaction of cis-A3 with TMCS-Ti has number of branching higher than one. Hence its MM is essentially decreased. Considering that the partial rearrangement of a six-member cycle into an eight-member one takes place in the process of anionic polymerization hindering the control of the course of the reaction over the amount of the cycle retained. These investigations substantiated that there is formed of low MM during the reaction of cis-A3 with TMPS-Ti. In a solution its molecules behave as semi-permeable claws. For the reaction of cis-A3 with TMPS-Ti, the presence of the Ti- atom in the molecule of the latter seems to be of considerable importable bue to its ability as an initiator. The formation of the polymer with low MM in the case of TMPS-Ti, when the content of the latter is not great, demonstrates that cutting of the polymer occurs due to consumption of the Ti- containing component [70]. This suggestion can be substantiated by the data from Reference 32, where the reactions of tetramethylcyclotetrasiloxane (D4) with boric acid as well as with its ethers were studied. It is revealed that, in the absence of initiator, the reaction at 1350C in bulk proceeds, via the combined polymerization-condensation method in compliance with the scheme [71]:

where R=R'=H, C4H9: R=H, R'=C6H5. Scheme 2.22.

It is evident that boric acid and its ethers be considered as initiators. A detailed study [71] was aimed at the kinetics and mechanism of polymerization polycondensation of methylphenylcyclotrisiloxane (a mixture

36

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

of cis- and trans- isomers) (A3) with diethyleneglyol (DEG) in the presence of a nucleophilic initiator − 1,5-dipotassiumoxytrimethyltriphenyltrisiloxane (DPTS). As the kinetics of this reaction showed, both of the reagents react completely under conditions that exclude any possibility of water formation (60oC, in toluene solution), while the rate of consumption of A3 (up to 70% conversion) is of the first order both in terms of the cycle and the initiator (WA3=KA3[A3]·[DPTS]o). Considering the experimental results, the following reaction mechanism was suggested: (SiR2O)nK

+

HO

R/

HO

R/

OK + [R2SiO]3

HO

R/

(OSiR2)3

HO

R/

OK +

OH

k2

OK + [R2SiO]3

(OSiR2)m

k1

(SiR2O)n OH + KO

k-1 R/

HO

k3

k4 k-4

(OSiR2)3

(1)

OH

(2)

OK

HO

R/

(OSiR2)n+3

HO

R/

OSiR2

+ KO

R/

(SiR2O)n

(3)

OK

(OSiR2)m-n-1

+

(4)

Scheme 2.23.

Thus, DEG reacts at the expense of rapid exchange between the diol hydroxyl group proton and the initiator group cation (stage I), enabling diol to take an active part in organosiloxane cycle opening reaction. When this reaction goes on in boiling toluene, it is accompanied by water isolation at the expense of condensation of silanol groups that form during polymerization polycondensation of A3 with DEG in the presence of DPTS, as initiator [72]: According to the above scheme, at the first stage of the reaction, diol reacts with the cycle in the presence of the initiator, forming alkoxysiloxane. The formed end hydroxyl groups condense releasing water and forming newsiloxane links (stage 2). At the same time a reaction can proceed, via a diol with a linear siloxane chain, yielding alkoxysiloxane and siloxanol (stage 3) which is capable of condensation and forming water (stage 4). The water released in the course of

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

37

the above reaction can react over the Si-O-C- link to produce siloxanol and alkoxylosiloxane (stage 5) [72]. [R2SiO]n +

SiR2OH

R/

HO

+

HO

inic.

R/

O

R/

OH

(2)

+ H2O

R2SiOR/OH + R2SiOSiR2O

+ H2O

(1)

(SiR2O)n H

R2SiOSiR2O

HOSiR2

R2SiOR/OSiR2

HO

SiR2O + HO

R2SiOSiR2O R2SiOH +

OH

HO

+ H2O

R2SiOH + HO R/ OSiR2

SiR2O

(3)

(4)

(5)

Scheme 2.24.

The above reaction stages are reversible and the system's equilibrium, as well as the equilibrium composition will be depended significantly on the reagents. The role of each reaction will change in the course of the reaction with respect to the reagents ratio and a constant concentration of the DPTS initiator (10.4·10-4 mol/l). Indeed, the rate of water isolation at initial stage and the amount of weather released within the time interval (10 hours) depends significantly on the reagents ratio in the reaction mixture (Figure 4). It is clear from Figure 4 that maximal conversion (95%) in terms of water released after 10 hours of the reaction, is observed at the cycle-to-diol ratio 6:1 (curve 4); minimal limit conversion in terms of the released water (62%), at 1:1 (curve 5). Meanwhile, as the above scheme shows, the rate of water formation in relation to the cycle: diol ratio should pass through the maximum. Figure 5 represents the relation of the time required for 30, 50 and 60% conversion of the hydroxyl group to the molar ratio of A3 to DEG, showing that the rate of water formation crosses the maximum, with the maximal speed of water isolation at the cycle-to-diol ratio 2:1-4.5:1. A study of the kinetic curves of the hydroxyl group conversion to 50 60%, the rate of water release in time is subject to a second-order equation and is liner with relation to time. The water release rate in relation to the second-order equation is quite understandable considering the equation of water release during silanol group interaction (stage 2) and alkoxyl and silane group interaction (stage 5) in the reverse reaction.

38

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

Figure 2.8. H2O release vs. time of reaction of A3 and DEG at the A3- to-DEG: 3:1(1),2:1(2), 5:1 (3), 6:1(4),1:1(5), 1:2 (6).

Figure 2.9. The time required to reach the given OH-group concentration in the reaction vs. A3-to-DEG molar ratio at 30% (1), 50%(2), 60%(3), conversion.

Considering the sharp drop of the polymer MM and the reaction rate constant (KA3) caused by the water concentration increase in the reaction system it appeared interesting to study the kinetics of water release during polymerization polycondensation of various organocyclosiloxanes (A3, D4), hexamethylcyclotrisiloxane (D3) and tetramethyltetravinylcyclotetra- siloxane (Dvi4)/ with DEG in the presence of KOH or DPTS [72]. Investigation have proved that the water isolation rate is highly influenced by the cycle stress and the nature of organic substitutes on the silicon atom (Figure 2.7), the water isolation rate being in all cases subject to the second-

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

39

order equation (Figure 2.8); the initiator concentration, however, seems to be unimportant (see Figure 2.9). The polymerization polycondensation reaction of organocyclosiloxanes with α,ω-di- hydroxyoligodiorganosiloxanes was used to obtain organosilicon block-copolymers [72]. The block-copolymers obtained from polymerization polycondensation reaction of organocyclosiloxanes with diols are of a great practical importance in the creation of heat-resistant lubricants, thermoplastic data carriers, heatresistant coating compounds; etc. Hence, it can be concluded that the combined process of polymerization and polycondensation is at present underlying the formation of macromolecules of many polymers with inorganic and organoinorganic molecular chains [72].

Figure 2.10. 1/C-1/Co for OH groups vs. reaction time at the A3 -to-DEG molar ratios: 3:1 (1), 2:1(2), 5:1(3), 6:1(4), 1:1(5), 1:2(6).

Figure 2.11. H2O release vs. time in the reaction of DEG with As (1), D4vi (2), D4 (3), D3 (4) at KOH concentration 12•10-3 mol/l and at cycle-to-diol molar ratio 1:1.

40

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

Figure 2.12. 1/C-1/Co for the OH -groups vs. time of reaction of DEG with D4vi (1), D4 (2), A3 (3), D3(4).

Figure 2.13. H2O release vs. time of reaction of A3 with DEG at KOH [MePhSiO]3K concentration 5.2• 10-4 (∆); 10.4• 10-4 (.); 52•10-4(O); •10-4(x) mol/l.

Taking into account, that the large number of polymers with organoinorganic and inorganic macrochains is synthesized by the method of

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

41

combined polymerization-condensation, the interest the combined processes of polymerization and poly- condensation should increase in the near future [72].

2.1.3. Synthesis and Properties of Polyorganosilazasiloxiheteroarylens and Polyorganosilazasiloxiazoarylens It is known that incorporation of arylene groups into the main chain of polyorganosiloxanes leads to improvement of their thermal and mechanical properties [73]. It was expected that the analogous properties modification should take place in case of synthesis of the multifunctional polysilazasiloxyheteroarylenes and azoarylenes [74-75]. To obtain the polymers with the aforementioned structures the method of combined polymerizationcondensation of silicon-nitrogen-containing heterocycles with heteroarylene and azoarylene bisphenols was used [74, 76]. As in the case of silazasiloxyarilen polymers the choice of this method was justified by a row of the specific features, what gives the method clear advantages compared with the other methods of synthesis of the organosilicon polymers with the organic-inorganic main chains [75]. As the silicon-nitrogen-containing heterocycles, the reaction-able organocyclotrisilazanes with different organic radicals at the silicon atom were used: [R′R′′SiNH]3, [R′=R′=CH3, R′=CH3, R′′= CH=CH2, C10H13, (dicyclopentadienyl), C6H5] [75]. As the initial heteroarylene and the azoarylene bisphenols, the compounds, obtained transformation of corresponding diamines according to the reaction scheme shown below (Scheme 2.24), were used. The obtained bisphenols are colored crystalline substances with a high melting point (>1800C). The bisphenols composition and structure were estimated by using the elemental analysis and the IR and UV-spectroscopy [75]: in the IR-spectra, the absorbency bands corresponding to the imideazole cycles (1425-1450cm-1) were found along with the absorbency bands corresponding to the OH-groups (3600-3500cm-1). The band corresponding to the NH2-group (3400-3300cm-1), in the IR spectra was not found. In the UV-spectra of the bisphenols type II (See Scheme 2.24), the λmax=345-360 nm characteristic to the –N=N-groups were found [74, 76].

42

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov H2N

R

+NaNO2

NH2

X-N2+

N2+X-

R

N

N

R

HO

OH

C6H5OH

II

HO

I , tO

R

N

OH

N

X

X

where N R =

N

C

C NH

NH

N C

(X=H), NH

N C

( X = H , OCH3 ) , NH

N

N

N

N

O

Si (CH3 ) ( C6H5 )

N

N

N

N

where x is the “residue” of the sulfuric acid, y = H or OCH3 Scheme 2.24.

The structure and some properties of synthesized bisphenols are setting in the Table 1.

Table 2.7. HYield and some characteristics of heteroarylen and –azoarylen bisphenols

1.

2.

Yield m.p.., 0 , C %

Formula

№

N

HO

N

N

O

HO

N

N

CH2

N

N

N

CH3O

3.

HO

OH

OH

OCH3 N

N

N C

N

N

Νexp. %,

Μcalc./Μdet ΟΗexp (By determ of ΟΗgroups)

80

183-184 11,53

8,2

410/419

78

205206

12,26

8,3

408/409

87

180181

16,90

6,8

__

89

262

12,21

__

__

91

268

19,13

__

__

OH

NH

N

4.

HO

OH

C NH

5.

N HO

N

N

C NH

N

N

OH

Table 2.8. Conditions of synthesis and some properties of polyorganoheteroarylens and –azoarylens

Table 2.9. The data of the elemental analyses of polydimethylsilazasiloxiarilens till and after destruction Found, % №

I

Till destructin, % / After destructin, %

Formula of elementary link of polymer

Me Me Me SiNHSiNHSiO Me Me Me

C

Si

C / Si

52,98 48,23

23,24 25,4

2,28 1,90

60,43 55,05

17,77 20,19

3,90 2,86

58,58 52,83

18,35 20,96

3,13 2,54

O

II

III

Me Me Me Me SiOSiNHSiOSiO Me Me Me Me

Me Me Me Me SiOSiNHSiOSiO Me Me Me Me

C

O

CH3 C CH3

O

Table 2.10. The data of thermal and thermooxidative destruction of poliorganosilazasiloxanes and silazasilseskvioxanes №

Elementary link of polymer

The medium

1

2

Me Me Si O Si NH Me Me

I

Me

Me SiO Me 17

N Si NH Si Me

Temp. of destruct ion on 50%, 0 C 6 500 490

Eeffect kJ/mo l.

7 100 85

8 _ _

He Air

400 310

475 440

530 _

75 42

238.4 60.2

Et Me Et Si NH Si

II

Temp. of destruct ion on 10%, 0 C 5 380 380

Loss of the mass, %

3 He Air

Temp. of the bigining of destruct ion, 0C 4 280 220

Et Et

Me Si

N

Et

Me SiO SiO Me Et Me 10

Hex

III

Si

NH

NH NH

Hex

V

VI

Hex

Si

Si

NH

NH

Si

IV

Hex

Si Hex

O

NH Si

NH

Hex

Me SiO Me 4

Ph

Ph Si

O

O

340 290

410 410

_ 670

43 51

69,0 25,5

He Air

325 310

370 420

410 570

93 71

_ _

He Air

360 330

410 430

475 580

87 76

24,0 15,5

He Air

380 370

465 490

510 640

76 69

29,7 19,4

O

O O

Si

He Air

Si

O

Ph

Si

O

Ph

O

Me Me Si O Si NH Me Me

Me SiO Me 2

Me Me Si O Si NH Ph Ph

Me SiO Ph 2

O

O

Table 2.10. Continued

VI I

Me Me Si O Si NH Me Me

VI II

Me Si NH Me

Me SiO Me

Me Si NH Me

Me SiO Me

IX

XI

Me Si NH Me

Me SiO Me

Me SiO Me

O

C

He Air

390 360

450 470

500 630

74 61

He Air

260 390

500 510

625 610

84 63

He

280

475

560

84

He

350

400

490

74

O

O

C

O

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

49

The general reaction scheme of the combined polymerizing of organocyclotrisilazanes with hetero- and azoarilene bisphenols analogous to the reaction with the “simple” aromatic diols (resorcin, “dian”, naphtholdiols) can be represented as shown in Scheme 2 below.

n [R'R''SiNH]3 + nHO−R−OH→ −{[(R'R'')SiNH]2SiORO}n− + (2n+1) NH3 where:

RI = RII = CH3 , RI = CH3 , RII = C6H5 , −CH=CH2 N R=

C

(1)

NH N N

N

C NH

N

N

N

(2)

N

C

C NH

NH

Scheme 2.25.

To obtain the polymerizing condensation process basic regularities, the reaction was conducted both in oil and in the amide aproton solvents (N,Nmethylpyrrolidone) in the media of dry argon. The reaction in the volume intensely occurs at 150-1600C. In solvents, the reaction temperature is close to the solvents boiling temperatures. The choice of a certain temperature regime for the reaction is mainly based on the structure of the organic radical at the silicon atom. For example, the polymerizing condensation of trimethyltriphenylcyclotrisilazane with bis- phenols was conducted at 160-1800C. In the case of conducting the reaction in the volume, the complete homogenization of the reaction mass is observed after the quantitative separation of ammonia. It should be noted that the chain composition of the preparing polymers (based on the Si content, %) are slightly different if the reaction is conducted in the volume or in the solution. In particular, for the polymer based on [CH3(C6H5)SiNH]3 and heteroarylen bisphenol (1) (See Scheme 1), the silicon content of polymer obtained at the reaction in the volume is 11.2%. What is lower compared with the silicon content of the polymer obtained in solution N,N’-dimethylformamid (13.1%). This can be possibly connected with the

50

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

statistical process of substitution of the residual bisphenol in the forming macrochains of the polysilazane polymer on the SiNHSi bonds simultaneously with the molecular mass increase of the polymerizing condensation product:

R

R

R

Si NH Si NHSi Ι

R

Ι

R

O R

RΙ

. . . + HO

R OH

Ι

R

R Si

O

O R O

R

R

Si NH

Si

RΙ

RΙ

O R O

-NH3

...

Scheme 2.26.

The possibility of occurring of the side of the residual bisphenol in the polysilazane chain substitution is confirmed by formation of polymers close on structure to the polysiloxyhetero- arylene and azoarylene structures obtained at interaction of organocyclotrisilazanes with bisphenol tri-mole excess [75]: n/3[CH3R’SiNH]3 + n HO–R–OH→ H2N⌠Si(CH3)R–O–R–O⌡nH + (2n1)NH3, where R’=CH3, R is the Bisphenol “residue” Scheme 2.27.

However, the 100%-substitution of the “residual” voluminous and stiffchain bisphenols does not occur what was confirmed by the IR-spectra: the weak absorbency bands in the area 930-940cm-1 corresponding to the SiNSi groups were found [75]. At conducting the reaction of organocyclotrisilazanes with bisphenols (in the volume), it was found that in the same experiment conditions and with the same bisphenol, the reaction rate (based on NH3 separation) depends on the nature of the organic radical, and its maximal value was observed in the case of hexamethylcyclotrisilazane (Figure 2.14).

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

51

Figure 2.14. Dependence of the ammonia amount separated on time, t, in the following reactions (1:1 ratio), temperature 1600C. 1. [(CH3)2SiNH]3 +BBisphenol-2; 2. [(CH3)( C6H5)2SiNH]3 + Bisphenol-2; 3. [(CH3)( C6H5)2SiNH]3 + Bisphenol--1 (1:1) (Table 2.8).

This is, probably, the result of not only the small volume of the methyl radicals at Si-atom but also of the electron-acceptor effect of the phenyl groups. The last effect causes the strengthening of the conjunction of the silicon d-electrons with the nitrogen pi-electrons what would increase the strength of the Si–N-bond toward the influence of the bisphenol hydroxylgroups. It should be noted that for this particular reaction, the existence of the induction period is observed (Figure 2.16). Its longevity depends, basically, on the volume and the electron nature of the organic frame around the siliconatom. The analogous phenomenon is observed in case of the combined polymerisation condensation of organocyclotrisilazanes with the “sample” aromatic diols and probably, it is connected with formation of the temporary complex type A (p.20) [46] and its consecutive decomposition on the linear oligomers with the end groups NH2- and -OH. Further on, the groups interact either with the organosiliconheterocycle or with themselves or with bisphenol with separating ammonia (Scheme 2.27) [75]. Based on the IR-spectra, the conductance of the branching reaction, the formation of the trisilazane substituted nitrogen atom, which may be formed in the reaction of the NH2-end groups of the intermediate oligomeric products with the NH-groups of the propagating chain, does not occur [75].

52

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

Figure 2.15. Quantum-chemical calculations of distribution of the particular charges on the atoms in the molecule of Bisphenol A and Bisphenol B.

An interesting experimental fact was observed at conducting the reaction of the hexa- methylcyclotrisilazane with heteroarylene bisphenols having different structure. In particular, at forming polymers at interaction of [CH3(C6H5)SiNH]3 with Bisphenol B, the character of the intrinsic viscosity increase in the process is significantly is different. In the case of the reaction with Bisphenol B the viscosity increase occurs more uniformly. This can be probably explained by the different reaction ability of the OH-groups of Bisphenol A (by the distribution of the particular charges on the corresponding carbon atoms, see Figure 2.15). By the analysis of the obtained data and also in accordance with the model reaction, the system of differential equations was prepared. The system describes the certain mechanism of the investigating reaction. Based on the theoretical calculations [22, 76], several possible reaction mechanisms were suggested to choose from. At the given preciseness of the experiment, the most satisfying (the minimal average deviation) (Figure 2.16) is the mechanism corresponding to the scheme 2.9. The reaction trans-amination is less probable due to the low intermediate concentration of the Si-NH2-groups and the higher activation energy, Ea compared with the reaction of the hetero-functional polycondensation [75]. It should be noted that it is possible some deviation from the “ideal” scheme of the reaction of bisphenol with SiNHSi-bonds of the propagating chain. However, to take this into account is very difficult at solving the calculation tasks.

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

53

Figure 2.16. Comparison of ‘the theoretical curve (solid line) and the experimental date (points) of the dependency of the separated ammonia on the time of reaction, τ of [(CH3)(C6H5)SiHH]3 + Bisphenol B (1:1).

Figure 2.17. Thermomecanical curves of the following polymers:

2,3,4,5-

(Me2SiO)m O

n where: 2-m=48, 3- m=25, 4- m=3, 5- m=1

54

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

The obtained polymers are ones soluble in aproton solvents, glassy solids, resin-like or powder-like products having ηsp = 0.17-0.28dl/g and the yield 8994.5% (according to the separating ammonia).

2.1.4. Thermomechanical Properties and Thermostability of Polymers Containing Simultaneously Si-N and Si-O Groups Thermostability [77-79] and thermomechanical properties [78] and of silazasiloxyarylene polymers are considered in close details in the literary sources. Character of thermomechanical curves (Figures 2.17-2.20) depends on the ratio of initial monomers, on the volume of organic radicals at silicon atoms, and on the nature of aromatic diols. Under condition of permanent load acting upon polymer sample, when load increases from 30 to 100 grams, area of highly elastic (elastomeric) deformation disappears on the thermomechanical curve and glazing temperature (Tg) decreases significantly [78].

Figure 2.18. Thermomecanical curves of the following polymers:

1,2,3

1. R =

SiMe2OSiMe2NHSiMe2OSiMe2ORO

; 2. R =

;

n

3. R =

where:

C

; .

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

55

Figure 2.19. Thermomecanical curves of the following polymers:

1. Et2SiNHSiEt2O

;

O

n 2. [Me(Bu)SiNH] SiMe(Bu)O 2

O

n 3. [Me(Ph)SiNH] 2 SiMe(Ph)O O

;

; n

Area of high elasticity doesn’t appear on the thermomechanical curve in case of polymers of siloxyarylene type ([-SiR(R)–O–X–O-]) and they are characterized by relatively high glazing temperature (Tg = + 38÷930C) (Figure 4.1-4.4) in comparison with polyorganosiloxanes [78]. More high glazing temperature is distinctive for polyorganosilazasyloxyarylenes, that should be connected with comparatively strong interaction between chains (in comparison with siloxyarylenes) because of the existence of N-H bonds in the macromolecules. As expected, trimethyltriphenyl- and hexaphenylcyclotrisilazanes form polymers with more high glazing temperature (Table 2.9), in comparison with polymers synthesized on the basis of hexamethylcyclotrisilazanes, and that is caused by content of hard phenyl radicals bonded with silicon atoms in macromolecules [77].

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Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

Figure 2.20. Thermomecanical curves of the following polymers:

1. (Me2)SiOSi(Me2)NMeSi(Me2)OSi(Me2)O

;

O

n 2. (Me2)SiOSi(Me2)NHSi(Me2)OSi(Me2)O

;

O

n 3. Me(Ph)SiOSiMe(Ph)NHSiMe(Ph)OSiMe(Ph)O

;

O

n

Polyorganosilazasyloxyarylenes containing flexible aliphatic radicals bonded with silicon atoms are characterized with most low glazing temperature among synthesized polymers and they represent very viscous liquids [78]. Studies of thermal and thermal-oxidative destruction of synthesized polymers carried out by thermogravimetric, differential-thermal (Figures 2.212.24) and chromatographical analysis show that thermal properties of polymers are basically determined by the structure of appropriate cyclosilazane (Table 2.9, Table 2.10). As it seen from table 2.9 data, by insertion of NH-groups and aromatic groups in the polyorganosiloxanes macrochain temperature range of destruction shifts by 10-50°C towards the

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

57

more high temperatures, that is connected by essential change of polysiloxanes destruction mechanism [77]. Besides, existence of aromatic groups, as well as of branches in the polymers macrochain has a significant impact on the run of deep stage of destruction and causes the weight increase of non-volatile part of researched objects (Figure 2.21). It is known that during high temperature destruction of siloxane polymers two competitive processes – depolymerization of basic chain and structurization of macromolecule – run, and they occurs with removal or oxidation of organic groups binded with silicon atoms (Table 2.9)]. Destruction of polydimethylsiloxane (siliconorganic polymer widely used in the industry) in the inert area or in the vacuum basically runs by depolymerization mechanism, at the expense of ionic admixtures or by means of hydroxylic groups, which may be a part of polymers, or else may form during the destruction process [77, 78]. It was found out that insertion of silazane and siloxyarylene groups in the siloxane chain significantly increases the thermal stability of poly-methylsioxane [77].

Fugure 2.21. DTA curves of the polymers I, II and VII (Table 2.9).

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Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

Study of polydimethylsilazasiloxiarylenes thermal destruction shows that these polymers differ by high stability and completely destruct only at 600620°C temperatures (in the inert gas area) (Figures 2.23-2.25). Existence of small quantities of branched trisilylaminogroup in the macrochain does not inhibit complete destruction of polymers [77]. It should be noted that in case of SiNHSi-groups containing polymers, centers of branching similar to above-mentioned may form during destruction process at the expense of the following reaction (Scheme 2.28) [79]: O Si

O NH

O Si

+ CH3

Si O

O Si CH4

O N

O Si

Si O

Scheme 2.28.

Figure 2.22. DTA corves of the polymers I, II, III and 6 (Table 2.10) in the Helium area.

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

59

Thermal stability of received polymers increases in comparison with polydimethylsiloxane, and that shows itself by the shift of temperature range of destruction basic process towards the higher temperatures. Destruction of bonds containing of the tertiary nitrogen atoms, existing in the polymers macro-chains or originated during destruction process possibly runs as result of current reactions between these groups and HO-groups (Scheme 2.29) [79]: ≡SiNHSi≡ + HO–Si≡ → ≡Si– O–Si≡ + ≡SiNH2 ≡SiNH2 + HO–Si≡ → ≡Si– O–Si≡ + NH3 (≡Si)3N + HO–Si≡ → (≡Si)2NH + ≡Si– O–Si≡ Scheme 2.29.

Influence of (≡Si)2NH and (≡Si)3NH groups on the thermal and thermaloxidative stability of polyorganosilazasyloxyarylenes is studied, which content in the polyorganosilazasyloxyarylenes macrochain is much more than in the polyorganosilazasyloxyarylenes synthesized by the method of combined polymerizational polycondensation (with plenty of diols). It was established by thermogravimetric analysis that the initial temperature range of thermodestruction process is to 400-480°C for II polymer (Table 4.2), while range of thermal-oxidative destruction is 310-440°C; for III polymer, it is 340-410°С, in the inert gas area and 290-410°C in the air, respectively. Destruction process for both polymers runs with more intensity in the 470-520°C temperature range and is characterized by high activation energy in the inert area]. Quantity of non-volatile part of these polymers significantly increases at more high temperatures and exceeds the similar data of other polymers, given in table (Table 4.1). Weight loss is 1-2% in the temperature range 140-300°C. This fact is probably connected with functional groups participation in the current condensation process, which is followed by separation of volatile accompanied products. Initial temperature of destruction of polymers containing arylene groups depends on the content of NH-group in the elementary ring. For example, in case of VIII and IX polymers (Table 2.10), which contain two NH-groups in the elementary ring weight loss begins at 260-280°C under destruction conditions, at the same time, for IV, V, VI, VII and X polymers (Table 2.10), which don’t contain any NH-groups in the macromolecules elementary rings or else contain only one NH-group, initial temperature range of weight loss is 325-390°C [77, 78].

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Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

Endothermal and exothermal effects are revealed on the thermograms of II and VIII polymers (Figure 2.21), which probably are connected with postcondensation processes in the functional groups and with separation of volatile products, or else (in case of II polymer) with ring expansion at the expense of possible rearrangement reaction [79]. By the rise of temperature exothermal effect with clearly defined peaks at 4900C, 5300C and 5800C becomes apparent, and it corresponds with basic process of polymer destruction. As to polyorganosilazasyloxyarylenes destruction, its basic exothermal effect is revealed at 3750C and 4650C temperatures, and that proves that shift of basic exothermal effect towards high temperatures takes place (in comparison with polydimethylsiloxanes) due to insertion of (≡Si)3N, (≡Si)2NH groups or simultaneous insertion of aromatic and NH-groups in the siloxane chain [79]. It is a clear evidence of the stabilizing effect of above-mentioned groups during destruction processes.

Figure 2.23.Curves of the TGA VII and VIII(Table 2.10) in the air

Figure 2.24. Curves of the TGA VII and VIII(Table 2.10) in the Helium

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

61

More strong stabilizing effect of NH-groups is revealed in case of polymers, elementary rings of which contain two or more such groups. According to TGA data mass loss, both in inert gas area, and in the air is equal to 20-25% in the temperature range 300-400° and 300-500°C, respectively [2]. Proceeding from the data calculated according methyl groups content in the elementary ring of IV, V, VII and X polymers (Table 2.10) we can assume that in the given temperature range polymer structurization process simultaneously runs along with removal of this group [77]. For the confirmation of above mentioned idea thermodestruction process of VII, VIII and X polymers was studied (in the air, T=400ºC) (Tables 2.9 and 2.10) [77]. Change of C/Si ratio before destruction and after it was selected as a criterion of estimation of oxygenized or separated methyl groups. As it seen from table 2.9, C/Si ratio significantly changes, and that proves the separation of methyl group located near silicon atom. Study of thermal destruction of IV and V polymers (table 2.10) in the air, at 450°C (along with analysis of gas products) allows us to prove above mentioned idea, since methane and hydrogen were the main gas products of thermal destruction. Decrease of intensity of corresponding absorption bands (805-815 cm-1 1260-1270 cm-1 and 2910-2965 cm-1) of methyl and C-H group after destruction, under testing condition are revealed in the infrared spectrum of the same polymers samples, while absorption bands (950-960sm-1) more characteristic for (≡SiN)3N groups become more intensive [77]. Thus, for all studied polymers the separations of organic groups from silicon atoms of main chain and structurization of macrochain are the main processes in the given temperature range. Above 500550°C temperatures, destruction process takes place, which completes with intensive destruction (desintegration) of basic chain of macromolecules. The rate of polymer desintegration and weight of solid residue significantly depends on the content of SiNHSi-group in the elementary ring of polyorganosilazasyloxiarylene, and on the destruction conditions (Table 2.10; Figures 2.24-2.25). The investigation of the thermo-oxidative destruction (TGA, DTA) of the polysilazasiloxiarylens showed that their thermo-oxidative stability is higher than the organo-silicon polymers (See Figure -s 4.6-4.8). As it is seen, the lowest weight losses are observed for polymers based on trimethyltriphenylcyclotrisilazane with heteroarylene bisphenols (1:1). The last fact can be explained not only by the stabilizing effect of the electron-acceptor phenyl groups influence on the SiNHSi and SiOCcp bonds but also by the cross linking reaction of the polysilazane chains caused by subtracting the phenylgroups from Si and forming the intermediate cross-linked structures at

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Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

extension. This leads to enhancing of the thermo-oxidative destruction temperature. This assumption is confirmed by the DTA data. Thus, in the temperature interval 340-3500C, there is an exothermic peak corresponding to the subtraction of the phenyl groups (the mass loss is less than 20-25%).

2.1.5. Synthesis and Properties of Polysilazasiloxycarbonates Polycarbonates (PC) are well-known hetero-chain polymers. They used in the optical and other industry branches. Despite the many valuable properties they are difficult to processes. In the end products, they show high internal stresses, what limits the areas of their application. These deficiencies can be overcome by using the modified PC with organo-inorganic main chain polymers, which combine the good optical and elastic properties with a high thermal stability. One of the first representatives of PC, modified by the silicon-organic compounds, was probably, the polycarbonate-siloxanes obtained by the methods described in the works [79-80]. In the literature, there are modified PC, synthesized by interaction of a .o-dichloroligodimethylsiloxane with the excess of Bisphenol A in solution in presence of tert-amines as HCI acceptor, and with consecutive reaction with phosgene [79]. To obtain polysilicon-carbonates, dihydroxyoligoarylcarbonates, synthesized by telomerization of cyclic carbonates by diphenols, were also used [80]. As the result of such modification, the copolymers with a high enough molecular mass (Mn-=3.6·IO4) were prepared. The copolymers were able to form the optically transparent films. The PC modification by small additives of polyorganosilazasiloxyarylenes was also described [80]. To chemically modify the polycarbonate chains, we used the reaction of the polymerization polycondensation of diorganocyclosilazanes with oligocarbonate diols (OCD). Cyclosilazane with trieyclodecenyl radical at the silicon atom (l,3,5-trimethyl-l,3,5-tris (tricycledecenylcyclotrisilazane – C10H13) was prepared for the first time by us by using the reaction of ammonolysis of the corresponding dichlorosilane [81]. By selecting the silicon-nitrogen-containing hetero-cycles as the initial monomers for the mentioned above polymer synthesis method, we have chosen them based on their high reactivity and the availability of organocyclosilazanes. We have also taken into account the opportunity to quantitative removal the reaction mixture of the side product of the polymerization polycondensation reaction - ammonia without any special additives. Besides, the opportunity to conduct the reaction in the mass (in the dry and purified

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

63

from oxygen nitrogen or Ar) with other silicon-organic monomers (for example, diorganodichlorosilanes) allows minimizing the number of compounds participating in the reaction. This is very important for preparing the polymeric materials of the optical application [81]. For comparison, the reaction was also conducted in CHCl3, which well dissolves OCD. In the both cases, the equimolar ratio of the initial compounds was used (see Table 2.11). As the oligocarbonate diols, we used OCD based on Bisphenol A with molecu'ar masses 2.260(n=8, OCD-8), 3.280 (n=12, OCD-12), and 4.290 (n=16, OCD-16). OCD reacts with organocyclosila7-anes according to the general scheme [82]:

X HO

Me

O

Me

C

OCO

C Me

Me

H O

Me

O

Me

C

OCO

C

Me

Me

/ OH + X (RRSiNH)m n

CH3

R

NH3 + O Si NH Si m-1 x n CH3 R/ + (n-1) NH3

Where: R=CH3, CH=CH2; C6H5, C10H13; k=3.4; Scheme 2.30.

Depart from the reaction oforganocyclosilazanes with the aromatic Bisphenol A, the reaction with OCD in the mass occurs at higher temperatures. The reaction rate (Figure 2.25) and the physical state and the properties of obtained polymers (Table 2.11) depend, basically, on the nature of the organic radicals at Si and OCD. In all cases, the polymers based on organocyclosilazanes, including 1,3,5-trimethyl-1,3,5-tris(tricyclodecenyl)cyclotrisilazane are solids well-dissolved in chloroform, have limited solubility in aromatic hydrocarbons, and are insoluble in alcohols and in the saturated hydrocarbons. After the solvent removal, on the metal (steel) and glass surfaces, the optically transparent in the visible part of the spectra films are formed (Figure 2.26) [82].

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Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

Figure 2.25. Curves of ammonia separation in time at interaction of organocyclosilazanes with )CD-8 (im mass): 1. [Me2SiNH3]-OCD8; 2.-[MePhSiNH]3OCD-8; 3.-[Me2ViNH]3-OCD-8 (Table 1).

Figure 2.26. The UV-visible spectrum of the polymer-6 (Table 1).

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

65

Table 2.11.Polycondensation of organocyclosilazanes with oligocarbonatediols Organocyclo OCD, m - silazan

ηmax.** dl/g

1 [Me3SiNH]3

8

In mass

130-140

Reac -tion time, hrs 0,8

2 [MeViSiNH]3

_”_

In mass

140-150

1.8

0.91

0,25

3 [MePhSiNH]3

_”_

In mass

170-180

1,6

0,88

0,45

4 [Me3SiNH]3

12

In mass

190-200

2,5

0.78

0,33

[Me3SiNH]3

16

In mass

220

3.0

0,71

0,22

6 [MeTsSiNH]3

8

In mass

150-160

2.0

0.80

0.10

7 [Me3SiNH]3 8 [MePhSiNH]3

_”_ _”_

15%CHCl3 15%CHCl3

60 60

26 26

1,02 0,42

0,72 0,62

#

5

Reaction conditions

Reaction temp.,0C

NH3/ Cycl mol/ mol 0,98

0,30

* Me–methil; Ts-tricyclodecenil; Vi-vinyl;PPh-phenil: ** In CHCl3, T=298K.

The maximal transparency was found at λ= 550-670 nm (Figure 2.27). At treble-molar excess of diol (Scheme 2.30) compared with cyclosilazane, the glass-like brittle products of the siloxyarylenecarbonate structure with a relatively small molecular mass are formed (Table 2.11). Apparently, as it was noted in works [8,12], there is a quantitative substitution of NH-groups in the polymer chain by the diol fractions in the course of formation of silazasiloxy-arylenecarbonate intermediate macromolecular chains according to the general reaction scheme: The composition and structure of the obtained polymers (Table 2.11) were determined based on the elemental analysis, UV (Figure 2) and IR-spectra. In the IR spectra, together of absorbency bands related to Si–CH3 (1420 cm-1) Si– C6H5 cm-1 (1440 cm-1), Si–CH=CH2, CH3, C6H5, CH=CH2, C6H5, CHalk, CHvin, CHar and NH (1270 cm-1, 1620 cm-1, 810 cm-1, 1595 cm-1, 2970 cm-1, 3050 cm-1, 3100 cm-1, 1580 cm-1 and 3340 cm-1, correspondingly) the following absorbency bands were also found: at 915-923 cm-1 (for the Si–NH–Si bonds) and at 998-1000 cm-1 (for the Si−O−Car bonds). It has to be noted that in the spectra of polymers based on OCD-8, obtained in mass at elevated temperatures at equal molar ratio of the initial compounds (Table 2.11),

66

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

extremely weak absorbency bands at 957-963 cm-1, related with the tretsilyl groups, were found [81]. It was interesting to investigate the effect of the specific tricyclodecenyl radical at the Si atom in the cycle and the nature of dihydroxy components (Bisphenol A and OCD) on the kinetics (Figure 2.28, Table 2.12) and the mechanism of the polymerization polycondensation [82]. Taking into account the kinetic calculation performed by us before for the model systems (organocyclosilazane-phenol) [22], and also some experimental results (for example, existence of the induction period on the kinetic curves, ability to structure formation of polymer at elevated temperatures, high yield of NH3) for the mentioned above systems, we studied several variants, describing the possible mechanism of the polymerization condensation of [CH3(R)SiNH]3 with OCD and Bisphenol A [82]. The simplest mechanism, including the stage of the heterocycle opening on the Si-N bond and the consecutive hetero-functional polycondensation of the intermediate end ≡SiNH; and HO-X-... groups, does not lead to any satisfactory approximation at the extreme task solution. The consecutive incorporation of the elementary stages, indicated below, and the calculation of each of the assumable mechanisms has shown that at the given preciseness of the experiment, the most acceptable from the point of view of minimizing of the average deviation (Figure 2.27) are the combination of the following stages, including along with the basic stages of formation of the intermediate complex and its decomposition on oligomers with the end groups Si-NH2 and HO-(k1,2)) [82]: • The stage of heterofunctional condensation of the end Si−NH2 with the HO-groups of the intermediate oligomers (diol) (k3), • The stage of equilibrium ... –R–OH + NH3 ↔ –R–ONH4 (k4); • The stage of the tert-silyl group formation (branching) (k5); • The stage of the transamination. Table 2.12. Reaction rate constants of polymerization polycondensation of trimethyltridecenylcyclotrisilazane with the OCD-8 Initial compounds

k1,2

k3

k5

k6

[MeTsSiNH]3 +

4.6835

7.745

0.1804

0.4720

OCD -8 (1:1)

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

67

Figure 2.27. The change of the characteristic viscosity of the polymerization condensation product in the reaction of [(CH3)2SiNH]3 with OCD-8 in mass at their equimolar ratio, temperature 1400C.

The stages can occur in the conditions of the reaction, in particular, at high temperature, in the mass (Table 2.11). The constants of the elementary stages of the polymerization polycondensation were calculated according to the method, described in the works [81,82]. In the calculations, the amount of separating ammonia was taken in the molar fractions. The analysis of the rate constant of the elementary stages calculation results showed that as in the case of the model system [46], the lowest rate constant in the both cases- [CH3(R)SiNH]3 + Bisphenol A (1) and [CH3(R)SiNH]3 + OCD-8 (2) - is for the stage of the tert-silyl group formation. The rate constant of the stage (k5) for the system (2) is approximately four times lower compared with the one for the system [(CH3)2SiNH]3 +OCD-8, and it is 1.961•10-1min-1. The structure of the organic radical at Si atom affects the value of k1,2 [82]. The character of the viscosity change in time (Figure 2.28) and also the careful analysis of the IR-spectra of the products of the polymerization

68

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

polycondensation of [CH3(R)SiNH]3 with OCD in mass, determined in the course of the reaction, confirm the more complicated character of the reaction compared with the reactions of organocyclosilazanes with the relatively simple diols, such as “Bisphenol A”. In the IR-spectra of polymers 1 and 6 (Table 2.11) obtained in the course of the process at 160-1800C the weak absorbency bands with the maximum at 2285 cm-1. The bands are characteristic for the isocyanate group. The bands disappear after certain conversion (60-70% based on the separated ammonia). This allows us to assume that not all of the NH2 groups, which appear on the beginning stages of the reaction by the heterocycles opening, enter in the condensation with HO-groups of oligocarbonate diols and the intermediate oligomers. However, some of the NH2-groups interact with the ester bond of the oligocarbonate macrochain according to the scheme 2.31 [80, 82]: O

O Si

NH2 +

OCNH Si

OCO

+ HO

(1)

O OCNH Si

Si

NCO + HO

(2)

Scheme 2.31.

and it with the further transformation urethan groups into oligomer with the end isocyanate groups (the fractionation of the polymer macrochain), which can react again with HO- and H,N groups of the products, forming in the course of the reaction. This will provide also the system viscosity rise (Figure 2.27). However, this is very difficult to take into account at the calculation of the polymerization polycondensation mechanism. The occurrence of the mentioned above side reactions of the polycarbonatesilazane blocks fragmentation is also confirmed along with the IR-spectroscopy by the relatively low values of (he molecular masses (MM) of the polymers (Table 2.11, ηch values), obtained in mass at elevated temperatures compared with MM of the polymers obtained in chloroform. The thermomechanical properties and the thermooxidative stability of the synthesized polymers have been investigated. As it is seen from tlie thermomechanical curves in Figure 28, their glass transition temperatures are shifted towards the lower temperatures compared with the ones of the non-modified

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

69

polycarbonate. The Tg depends on the hetero-cycle structure and the length of the OCD chain. The thermooxidative stability of the synthesized polymers was studied by the methods of DTA and TGA (Fig. 2.29).

Figure 2.28. Thermomechanical curves of the polymers: 1.- polymer 1; 2.-polymer obtained from [(CH3)2SiNH]4 and OCD-8 (1:1); 3.- polymer 6; 4.- polymer 5; 5.polymer 3 (Table 1). The heating rate- 4-50C/min, load = lOOg.

Figure 2.29. The TGA curves of polymers: 1.- polymer 3; 2.- polymer 5; 3. -polymer obtained from CH3(Ts)SiNH and OCD-8 (1:1); 4.-polymer 6 (Table 1.1). Air, heating rate =50C/min.

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Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

It is seen from the TGA curves that the modified polycarbonates show high enough thermooxidative stability. The basic process of the thermooxidative destruction occurs above 400-4500C and the temperature interval of the destruction shifts towards right on the abscissa with the Si-NH groups content in the macrochains of polycarbonatesilazane increase. The polymer with the siloxyarylenecarbonate structure shows also the high enough thermooxidative stability for this class of polymers. Thus, the TGA data show that the mentioned polymer has the mass loss at 3200C less than 3-4% (Figure 2.29, curve 3)

Figure 2.30. Kinetical corves of the isolation of the ammonia during the polycondensation OCSD with TMTPhCTS (in mass, at 1800C) (Table 2.12).

The data of the Wade Angle X-ray analysis confirm the one-phase and amorphous structure of the modified polycarbonates [82]. The interest researches are carried out in the direction of the synthesis of polycarbonatesilazasiloxiarylene block-copolymers containing silazane, siloxane and carbonate fragments simultianeoasly [79, 83]. For the obtaining such polymers the combine polymerization condensation process organocyclosilazanes with oligocarbonatesiloxane diols (OCSD) with polyblock structure of the main chain have been used (Table 2.12) [79]. The molecular masses of the polymers formed undergo changes to the reverse conversion in terms of ammonia depending upon the length of the

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

71

siloxane part of OCSD macromolecule elementary link; this occurring at a high concentration of functional groups, i.e., the amount of released ammonia exceeds its rated value at low m-values in OCSD. Both these data and the IR analysis data (absorption bands appearing with the maximum of 2285cm-1 which is typical of the NCO - groups) indicate that the reaction of OCSD and cyclic silazane is ambiguous and the macromolecule structure comprises also isocyanate groups, like in schemes 1 and 2. The equilibrium of reaction 2 will shift rightwards if the OCSD hydroxyl groups react with the silazane link not only in a cycle, but also in a linear chain: The latter reaction proceeds more readily at a higher hydroxyl-group concentration, i.e., at a lower m-value in OCSD, and in the presence of an anion-type catalyst which forms as a result of reaction between the hydroxyl groups and the released ammonia (Andrianov, Lekishvili et al.) [22]: At high m-values, the rate of reaction between hydroxyl groups and silazane links an linear chain (reaction 3) is significantly lower, the Si-NCOgroup forming reaction equilibrium (reaction 2) is shifted left wars; hence, higher MM of the and polymers are achieved. The branching and binding mechanism in reacting system can be shown schematically as: Thus, the scheme of PCSS formation seems to be an ideal one, because the resulting block-copolymers, containing not only polycarbonate and silazasiloxane blocks, but also urethane groups in a chain, have branched macromolecular structure. In the table 2.13 there given some data for synthesized polymers in consider of the relation of siloxane and polycarbonate blocks [79]. Table 2.13. Properties of the polymers obtained by interaction OCSD with TMTPhTS in dependence on the siloxane block length

#

Methylsiloxane linkes’ mumber

1

2

Containing of the PCblock in the PCSS main chain, % 69

2 3 4 5 6

12 18 30 60 120

57,5 49 39 24 14

The ield of the PCSS, %

ηch.,dl/g

86

0,43

76 74 74 70 69

0,62 0,66 1,10 1,50 1,65

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Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

There was shoed that the data of the elemental analysis correspond with the probability formulae of the polymers’ elementary ring (Scheme 2.32).

Figure 2.31. Change of the values ofv the specific viscosity of the reaction product during the polycondensation OCSD with TMTPhCTS (in mass, at 1800C) (Table 2.12). Me

Me x H

O Si

C

O

m

Me

O OCO

Me

Ph

Me O Si OH m n Ph

C n-1

Me

+

+ x [MePhSiNH]3 -(n-1) ΝΗ 3 Me

Me O Si Ph

O

m

C Me

Me

O OCO

n-1

Me O

C

Si

Me

n = 14, 24, 39, 49, 57, 69, m = 3, 6, 9, 15, 30, 60;

Scheme 2.32.

...

Ph Me

sadac

O

m

...

Si Ph

Me NH

2

Si Ph

NH2 , x

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

Si

OH

Si

[MePhSiNH]3

+

Si O

Si

NH

Si O

Si 2

Si

O

Si

Si

NH 2

NH2

+

NH

(1)

NH2 + HO Si

NH

Si 2

O Si

+

NH3

(2)

Si OH

73

Si

+

O

H2N

Si

(3)

Si

O

Si Si

NCO +

NH

Si Si

NH

C

Si N

(5)

CO

Scheme 2.33.

As it seen from Figure 2.33, quantity of evoluted NH3 depends on the length of siloxane components of OKSD. When the length of siloxane components is small, quantity of evoluted NH3 is more than calculated quantity, while when length of siloxane components’ chain increases, conversion of NH3 reduces to 0,8-0,9 mole per each 1 mole of initial cycle. Molecular mass of resulting polymers changes by inverse relation, during the conversion, according to dependency on the length of siloxane block of macromolecule’s elementary ring (Figure 2.31). Also noteworthy is the fact that at reaction temperatures reactive system reveals certain inclination to the process of structurization (cross-linking). This tendency reveals with high degree in those polymers, in which content of siloxane components is high. Polymer with m = 60 transforms into non-fusible insoluble state within 14 hours after the beginning of reaction [83]. Reaction of simultaneous polymerization polycondensation of trimethyltriphenilcyclotrisilazane (TMTPCTS) from OKSD is carried out in the mass, at 180°C, until full termination of ammonia evolution [83]. In the course of reaction curves of time dependence of evoluted NH3 and reduced viscosity is shown on the figures 2.31 and 2.32. Intensity of absorption band distinctive for OCN-group in the IR spectrum of the polymer, with maximum of 2285cm-1, reduces rapidly depending on the m magnitude. When m = 15, this band is almost invisible in the spectrum.

74

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

During variation of m from zero to 3, intensity of this band reduces twice. In the course of considered reaction the formation of isocyanate group runs by the same way, as it occurs during the polycondensation reaction (3 and 4) of OKD and organocyclosilazane (Scheme 2.33). In the reaction 4 balances will be displaced to the right in the case when the group interreacts not only with the bond of Si-N cycle, but also with the Si-N bond of chain’s linear section. According to the reaction (5), for small magnitude of m the rate of reaction is high enough, and that increases the conversion of NH3 and content of lateral OCN-group in the polymer. When magnitude of m increases, reaction mixture is more saturated with organosiloxane components. But when rate of reaction (5) decreases, balance in the reaction (4) displaces to the left, and as a result we receive final product with big molecular mass and with high content of lateral groups. Quantity of evoluted ammonia (%), in comparison with theoretical is fewer, since the part of nitrogen atoms migrates in the urethan bonds [79, 83]. Polymer formed as a result of reaction may become branched and “sewed” at the expense of the reaction of interamination. According to experimental data, the inclination to the structurization process, during increase of siloxane components’ length, as well as simultaneous reducing of concentration of NHand NH2 groups testifies the low specific part of this reaction. More suitable is to represent the possible mechanism of branching reaction in the following form [79]: It is also possible to represent the mechanism of reaction in the form of other such reactions, which are specific and distinctive only for compound containing urethan groups [83]. Rate of reaction (6) and its specific part in the total process is getting bigger, when molar ratio of these groups is close to stoichiometric. Thus, the system is close to this ratio for high magnitudes of m, during increase of concentration of urethan groups. Some physical-chemical properties of received polycarbonatesilazasiloxanes are studied [79]. Results of electron-microscopic research confirm that received polymers represent two-phase system, with established molar ratio of carbonatesilazane and siloxane components [79, 83]. It was established that against the background of continuous matrices there is chaotic disposition of aggregates, which are close to spheric by their form, and that is typical for two-phase polyblock systems [83]. Also noteworthy is the fact that spheric aggregates have large size (50-60cm), which significantly exceeds the size which is distinctive for block polymers and doesn’t correlate with the contour length of neither carbonate, nor sylozane components. Wide-angle X-ray

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

75

graphical studies also confirm the two-phase construction of received PCSS (with carbonate and siloxane blocks) [79]. For certain ratio of initial components, interpretation of the results obtained by X-ray-graphical methods involves some problems. The point is that the magnitude 2θ = 2.97.10-1rad (d = 0,5 nm) corresponds to basic diffraction maximum of amorphous siloxane block, at the same time 2θ = 3.67.10-1rad (d = 0,42nm) corresponds to the second diffraction maximum of polymethylphenilsiloxane. Since all these maximums are wide enough, their partial covering is presumable. Typical diffractogram of PS (57.5% of PC) is shown on Figure 2.32. Basic diffraction maximum, which is distinctive for siloxane (2θ = 1.75.10-1rad, d = 0.8 nm) and carbonate (2θ-2.97.10-1rad, d=0,5nm) components of amorphous block-copolymer are clearly seen on the diffractogram (Figure 2.33). Similar diffractograms will be received for all sinthezised PCSS. The values of interplanar distance, which are received on the basis of duffractograms, are given below. It is also determined, that for PCSS, which contains 49% and more percent of PC, such diffraction maximums are characteristic, which are in good correlation with carbonate (0,5 nm) and siloxane (0,83nm) blocks. Existence of these maximums on the diffractogram allow us to conclude, that PCSS, in which content of PC exceeds 49%, will have two-phase structure [79]. It is quite difficult to make clear conclusion about phase state of such PCSS, in which the content of PC is less than 49%, because of the fact, that basic diffraction maximum, which is characteristic for PC, is not seen on the diffractogram. It is possible that it is covered by the second diffraction maximum of polysiloxane component or doesn’t exist at all. Displacement of the second diffraction maximum confirms detection of basic maximum of PC, which is revealed for PCSS containing 39% of polycarbonate fragments [79]. By further increase of the concentration of polycarbonatesiloxane component location of maximum remains unchangeable (d = 0.83 nm) (Table 2.13). At the same time corresponding diffraction maximum of PC-component is revealed better [79]. It was determined on the basis of considered data that change of PCSS phase state should occur in case of 40-50% content of PC. It was also determined that for more than 50% content of PC continuous matrix is constructed from fragments enriched by carbonate components [79].

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Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

Figure 2.32. The X-ray patern (difractogram) of the synthesized PCSS with the containing 57.5% polycarbonate block.

Table 2.13. PC molar ratio, % Interplanar distance, corresponded to the first d1 and second d2 difraction maximums, nm: d1

0

14

24

39

49

57,5

69

100

0,83

0,80

0,74

0,73

0,83

0,83

0,83

-

d2

0,42

0,41

0,42

0,45

0,51

0,51

0,52

0,50

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

77

Figure 2.33. The dependence of the glass-transition temperature of the synthesized PCSS on the inserve of the molecular mass of the siloxane block.

Dependence of temperature of glazing of synthesized PCSS, which is determined by thermomechanical method, upon the inverse value of molecular mass of siloxane component is given on the Figure 2.33 [83]. As it seen from the Figure 2.34, a polymer glass temperature (Tg) raises by increase of PC content in the copolymer. Within 50% content of PC, or in the same range, where qualitative changes of diffractogram character take place, it is revealed the klinked curve of dependence of glazing temperature upon the inverse value of molecular mass, that fact testifies the abrupt changes of polymer’s appropriate state.

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Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

2.2. NEW TYPE SI–N CONTAINING POLYMERS WITH ORGANIC-INORGANIC MAIN CHAINS During the last years synthesis of heterochain silicon-organic monomers and polymers (silazane, siloxane-arylene, carbosilazane, epoxide, etc.), containing aromatic groups with unsaturated radicals of allyl and vinyl types, have been attracting particular attention [84, 85]. To obtain the polymers with such structure, the classical method of the polyhydrosilylation revealed new possibilities [86]. The range of unsaturated monomers used for reaction of polyhydrosilylation increased [87-89]. The use of unsaturated monomers of the new type, distinguished from the standard divinyl monomers, required elaboration of a non-traditional approach to this reaction [90]. On another hand, the synthesis of the polymers with the aforementioned structure is of interest for modification of properties of some important industrial polymers, such as polycarbonate, phenolformaldehide gums, rubbers based on carbochain and siliconorganic elastomers, etc. They may be also used in combination with some other organic and element-organic polymers (for example with polyepoxides) as the substrates for nanohybrids [91, 92]. For the synthesis of new dialyl silazane monomers the condensation method has been used and for the synthesis of the polymers based on them the polyhydrosilylation method was applied. The cyclotrisilazanes were synthesized by the ammonolysis of corresponding dichlorine silanes [93]. α,ωoligodimethyldihydridsiloxanes were synthesized by the methods described in ref 93. 1,3-tetramethyldisiloxane was obtained by hydrolysis of dimethylchlorinesilane [93]. 1,5-trimethyltriphenyltrisiloxane has been synthesized by reduction of 1,5-dichlorine-1,3,5-trimethyltriphenyltrisiloxane with LiAlH4 [93]. 1,5-tetramethyl-3,3-diphenyltrisiloxane was obtained via interaction of (Me)2SiHCl with diphenylsilandiol [90]. We have conducted polyhydrosilylation reactions of α,ω-dihydrooligoorganosiloxanes and 1,4-bis(dimetylsilyl)benzene with dialylsilazanes (DAS) in the presence of Speier’s catalyst (0.1 mole solution of H2PtCl6·6H2O in isopropanol) in dry toluene and in mass [89]. The initial diallylsilazanes were synthesized via reaction of commercial organocyclo silazanes (hexametylcyclotrisilazane, methylphenylcyclotrisilazane and methylvinylcyclotrisilazane) with orto-allylphenol (o-AP) and 4allyl-2-methoxyphenol (Evg.), in dry Argon. The reactions proceeded easily in mass at 60-800C according to the following scheme:

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

[CH3(R)SiNH]n+2HO-Ar-CH2-CH=CH2

79

to > − NH 3

, where R = CH3, CH=CH2, C6H5, Ar = phenylene, methoxiphenylene, n=3. Scheme 2.33.

Above we reported that in reactions of cyclosilazanes with alylphenols the induction period is significant. This fact was explained by formation of a transition complex (A) that later decomposes and produces a linear allylsilazane with terminal amino-groups (B).Then B is believed to react with another allylphenol molecule generated from DAS as follow:

Scheme 2.34.

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Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

We have used a simple model system of phenol with organocyclosilazanes [see above, chapter 2.] to determine feasible mechanism of the reaction. We believe that the reaction involves a more complicated mechanism. Alongside with the stages of obtaining the transition complex and of opening silazane cycle, there may take place two side processes: formation of trisilylated nitrogen atom due to interaction of the terminal amino group of intermediate aminoallylphenoxisilazanes with Si–NH–Si groups of silazane heterocycles, and the stage of trans- amination. In fact, we have suggested the following reaction: ~ Si_NH2+H2N_ Si~

~ Si_ NHN_ Si~ +NH3

A comparison of a theoretical curve of formation of ammonia and experimental kinetical data on the reaction of phenol with organocyclosilazane in mass confirmed the feasibility of the reaction mechanism we have proposed (Figure 2.35).

Figure 2.34. Comparison of the theoretical curve of separation of ammonia with the experimental data of the interaction of phenol with n

Based on those results of calculations of rate constants of the elementary stages [22] we can now show that the limiting stage of the reaction is formation of the transition complex (A) giving rise to the induction period [p. 20], and opening of silazane cycle. Returning to the rate constants of the main

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

81

and side stages (Table 1) of the reaction, we now conclude that the probability of the side stages of formation of trisilylated nitrogen atom and transamination is low. In real systems, the reaction of branching of linear silazane chain due to interactions of terminal amino group of intermediate aminoallylphenoxysilazanes with Si–NH–Si groups of DAS would take place only at relatively high temperature. In conditions of the reaction (scheme 2), formation of triallylsilazane was not found. Thus, in the IR spectra of the reaction products the maximum of the absorption related to the trisilylated nytrigen atom was not observed. We note that carring out the reaction of hexametylcyclosilazane with allylphenols in the molar ratio 1:6 leads to formation of bis(allylphenyloxi)dimethylsilane according to the following scheme: orto-allylphenol + [(CH3]2SiNH]3 CH2-CH=CH2

H2N[(CH3)2SiNH]2(CH3)2SiO-Ar-

Scheme 2.35.

The resultant products are slightly viscous, optically transparent (in visible region of the spectra), soluble in typical organic solvents (benzene, toluene, acetone, etc.) and practically insoluble in water. The composition and structure of the obtained bis(allylphenoxi)diorganosilazanes and silanes were confirmed, before based on the data of elemental and IR spectral analysis [88]. The IR spectra of all samples were obtained with SPECORD and UR-20 spectrophotometers, from KBr pellets, while the NMR 1H spectra were obtained with AM-360 instrument at the operating frequency of 360 MHz. All spectra were obtained by using CDCl3 as solvent and an internal standard. The

82

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

Perkin-Elmer DSC-7 differential scanning calorimeter was used to determine DTA and the thermal (phase) transition temperatures were read at the maximum of the endothermic or exothermic peaks. Heating and cooling scanning rates were 100C/min. The column set comprised 103 and 104 Å Ultrastyragel columns. Wide-angle X-ray diffractograms were obtained with DRON-2 instrument. Cu Kα was measured without a filter; the angular velocity of the motor was ω ≈ 20 / min We have found in the IR spectra maxima of absorption related to Si–NH– Si and Si–O–Si, Si–O–C groups (915-925 cm-1, 990-1000 cm-1 and 1060-1080 cm-1). Also there are maxima of the absorption related to Si–CH3, CH2=CH, Si–C6H5 and benzene link (1250 cm-1, 1430 cm-1, 1445 cm-1, 1620-1630 cm-1, 1600-1605 cm-1 respectively) [88, 94]. IR spectra of bis(allylphenyloxi)dimethylsilane (Scheme 4) did not reveal the maximum of the absorption related to Si–NH–Si groups [88, 94]. As we have noted in ref. 89, our method of manufacturing diallylsilazanes is easily performed and has some noteworthy positive technological features for a practical viewpoint: • • •

The reaction is carried out in the absence of solvents and catalysts; Removal of side products is not difficult; Control of the process is simple due to determination of the gaseous ammonia.

Polyhydrosilylation reactions of 1,4-bis(dimethylsilyl)benzene and α,ωdihydroligoorganosiloxanes with dilsilazanes so synthesized can be represented by the following general scheme:

CH 3 (CH 2) 3

R

(CH 2) 3

Si R'

CH 3 Rx

Si R'

n

,

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

83

, where Rx= O, C6H4, O[Si(CH3 )2 O]m, (m=6,11), CH3(C6H5)SiO, Si(C6H5)2, R = R1= CH3; R= CH3, R1 = CH=CH2, C6H5; R1 = CH3, C6H5; n>>1. Scheme 2.36.

Figure 2.35. Conversion of Si−H group in time for hydrosilylation reaction of α,ω-dihydrooligoorganosiloxanes and 1,4-bis(dimethylsilyl)benzene with diallylsilazanes: 1.VII; 2. - VI; 3.- III; 4.- II; 5.- V; 6.- IV (Table 1).

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Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

We have determined active hydrogen in Si−H groups several times as before [95]. Influence of the structure of dihydride monomers on the reaction rate, yield and properties of obtained polymers has been thus evaluated. The results are presented in Table 2.14 and in Figure 2.36. Based on kinetic curves in Figure 2.35 of Si−H groups conversion, the reaction rate constants have been determined Table 2.14. The total reaction order equals to 2. Products of polyhydrosilylation reaction are optically transparent viscous liquids or elastic gums soluble in ordinary organic solvents (toluene, CHCl3, etc.). Composition and structure of polysilazanes so produced were from elemental IR and NMR 1H spectral analyses. In IR spectra (Figure 2.36) we have found the maximums of absorption (915-925 cm-1, 990-1000 cm-1, 10201060 cm-1, 1250 cm-1, 1410 cm-1, 1430 cm-1, 1445 cm-1, 1600-1605 cm-1), related to Si−NH−Si, Si−O−Si, Si−O−Car, Si−CH2, Si−CH3, Si−C6H5, and benzene link, correspondingly (Scheme 4). Results of elemental analysis (for example, Si(I),%, calc./found.=17.01/16.08; Si(VIII),%, calc./found = 17.84/17.09, etc., where the index numbers I and VIII the numbers of polymers in the Table 2.14) correspond to the structures of the products obtained in agreement with the reaction scheme 2.36.

I

H

Si CH3

O

Si CH3

H

333 12

96.6

0.17

The polyaddition reaction rate constants k•10-3, l•mol-1•s-1

CH3

CH3

ηsp***

α,ω-dihydrideoligoorgano#** siloxanes and 1,4-bis(dimethylsillyl)benzene

Reaction temperature,K Duration of reaction, hrs The yield of products of the reactions

Table 2.14. Conditions of hydrosilylation reaction of 1,4bis(dimethylsilyl)benzene and α,ω-dihydrooligoorganosiloxanes with diallylsilazanes (DAS)*, the yield and values of specific viscosities of synthesized polymers (in toluene)

Did not determ.

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

85

333 II

III

H

Si

O

Si

IV

V

VI

H

H

H

VII H

Si

CH3

CH3

CH3 O

CH3

CH3

Si

O

CH3

CH3 H

Si CH3

0.13 4.33

333 12

91.7

0.22 3.97

333 12

96.2

0.15 2.38

333 12

94.6

0.11 1.54

343 12

93.4

0.12

CH3

Si 11

H

CH3

Si

H

Si

O

CH3

C8H17

VIII

Si C6H5

O

96.4

CH3

C6H5

Si

6

O

CH3

H 333 12

CH3

Si

CH 3

0.21 2.78

333

Si

O

CH3

Si

97.0

CH3

Si

O

12

CH3

CH3

CH3

0.10 2.29

H

Si

O

C6H5

CH3

85.5

CH3

C6H5

CH3

10

C6H5

H

C8H17

C6H5 O Si C6H5

CH3 O Si CH3

H

Did not determ.

* CH2=CH_CH2_Ar_O[(CH3)2SiNH]2(CH3)2SiO_Ar_CH2_ CH=CH2; where Ar= C6H4 (VIII); Ar= CH3OC6H4 (I-VII) (Scheme 2);

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Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

** The Latin numerals in the leftmost column identify both the monomers and their polymers *** 1% solution in toluene. 100 95 90 85

65

701.70

70

3555.61

75

1411.10

1602.72

80

917.78

55

1455.95

%T

60

50 45

25 20

795.47

1031.94

30

1093.09

2956.29

1513.02

35

1256.17

40

15 10 4000

3500

3000

2500

2000

Wavenumbers (cm-1)

Figure 2.36. IR spectrum of the polymer III (Table 2.14).

log(ΔANB)

1500

1000

500

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

87

Figure 2.37. Dependence of k value for hydrosilylation reaction rate constants on decimal logarithm of determinants of pseudo-ANB-matrices in the series of α,ω-dihydrooligoorganosiloxanes (Table 2.14).

We observe the singlet signals with chemical shifts within the range of δ ≈ 0.03 _ 0.44 ppm for protons in methyl group of ≡Si−CH3 in NMR 1H spectra of the synthesized polymers (there illustrated the data for IV and VI - Table 2.14). We also observe two signals with centers of chemical shifts at 1.28 ppm and 1.62 ppm which correspond to methylene protons in Si_CH2 groups. There are also multiplet signals with chemical shifts in the range of δ ≈ 6.6 - 7.5 ppm corresponding to protons of phenyl groups in the NMR 1H spectra. Further, we have observed the signals with chemical shifts in the range of δ ≈ 5.1 _ 5.2 ppm corresponding to protons in NH-groups in NMR 1H spectra. The triplet signals with center of chemical shifts at 0.81 ppm correspond to methine protons in Si_ СH(CH3) groups [94]. Thus, our (elemental and spectral analysis and product solubility results) exclude homopolymerization of diallylsilazanes under the conditions of polyhydrosilylation reaction. To evaluate relative reactivity of dihydrosiloxanes (determination of the rank of their relative reactivity in polyhydrosilylation reaction), we have used an algebraic-chemical method based on so called pseudo-ANB-matrices. This is the first time this method has been used for these type reactions. This is a modified version of adjacency matrices [96] and we take into account the nature (structure) of organic radicals R and R1 at the silicon atoms of the dihydride siloxanes. Gverdsiteli and coworkers have demonstrated that log(ΔANB) is a convenient index for quantitative structure-property relations [94]. Here ΔANB is the corresponding correlation equation has the following form: k=alg(ΔANB)+b (1) k is a rate constant for polyhydro- silylation reaction; the determinant of pseudo-ANB-matrices; a and b – slope and intercept, which are calculated by method of least-squares: a=6,792•10-3, b=3,083•10-3. The correlation coefficient r=0.9788 (Figure 2.37). As noted in earlier works [97], polyhydrosilylation reaction of dihydrosiloxanes with α,ω-divinyloligoorganosiloxanes proceeds according to the Scheme 4 given above. However, recent publications [89, 98] show that both α and β adducts (Products of the hydride addition reaction according to antiMarkownikov and Markownikov rule) are obtained (see scheme 2.37 below).

88

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov CH3 CH2

R

CH2 + H

CH

OSi (CH3)3

Si

CH3 CH3 I CH2

CH2

R

Si

CH2

OSi (CH3)3

CH3 CH3 II

CH2

R

CH

Si

CH3

CH3

CH3 R= CH3O

Si

CH3

OSi (CH3)3

CH3 NH

Si

CH3

Scheme 2.37.

Quantum-chemical calculations of heats of formation of the model systems (Scheme 2.37), which are highly similar to the actual structures, have confirmed that polyhydrosilylation reaction proceeded according to the aforementioned two concurrent directions: As a method of quantum-chemical calculation, we used AM1 method [99], the computation keywords used in this study were the following: EF GNORM=0.100 MMOK GEO-OK AM1. For simplicity, preliminary geometry optimization of the investigated species was performed by using molecular mechanics (MM2 force field [100]. We have thus calculated the enthalpies of formation ΔHform for the reaction model products. The results show that formation of the α-adduct (I) (ΔHIform = – 1068 kJ/mol) is slightly more probable than that of the β-adduct (II) for the product with the structure II, ΔHIIform= – 1056 kJ/mol. We have shown [89] in that both I and II products are actually obtained. Signals for

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

89

chemical shifts at δ=0.81-0.82 and δ=1.61-1.63 ppm correspond to β (II) and α (I) adducts (Scheme 5) in NMR 1H spectra of really obtained polysilazanes (Figures 2.38a and 2.38b).

125 Figure 2.38a. 1H NMR specter of the polymer IV (Table 2.14).

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Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

Figure 2.38b. 1H NMR specterum of the polymer VI (Table 1).

In case of the polyhydrosilylation reaction of dihydrosiloxanes with DAS (Scheme 2) dehydrocondensation reaction due to the interaction of NH-groups of di- and intermediate oligosilazanes with Si–H groups of dihydrosiloxanes might also proceed along with the main processes, obtaining trisilylated nitrogen atoms. To determine which process, dehydrocondensation or polyaddition is more probable, we have calculated basic energetic parameters of model systems. For this purpose we have selected structures pertaining to actual reaction products reported before: R'

R'

H3C Si

O

H3C

N Si

H3C ′=

R

Si

CH3

C H2

H C

(III) CH2

CH3

,

where R=OCH3, R CH3; Scheme 2.38.

In spite of the fact that formation of model systems containing the trisilylated nitrogen atom is thermodynamically possible (ΔHIIIform.= –929 kJ), we have found before [89] that formation of hydrogen does not occur. At the same time, IR spectra of products of this reaction do not show a maximum of absorption for trisilylated nitrogen atoms (950-960 cm-1). Evidently, it is favorable for dihydrosiloxanes to attract terminal allyl groups rather than NH-groups bonded to silicon atoms, surrounded with organic radicals under the conditions of polyhydrosilylation reactions. That leads to formation of macromolecules with linear structure (Scheme 2.39). To evaluate structures of the products, we have performed Wade Engle Xray diffractometry. Several diffratograms are displayed in Figure 2.39 and show that we are dealing with amorphous substances. We have also performed differential scanning calorimetry (DSC) on our products. The DSC traces are shown in Figure 2.40. Only glass transition T peaks are seen; no melting confirms the X-ray results. There is no crystallinity in our products.

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

Figure 2.39. Diffractograms of polymers: 1 = II; 2 = IV; 3 = V (Table 2.14).

91

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Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

Figure 2.40. (Continued)

Figure 2.40. DSC curves of polymers: II (a), VI (b), IV (c) (Table 2.14).

Polymers Containing Silicon-Nitrogen and Silicon-Oxygen Bonds

93

Further, we have evaluated the thermal stability of our products by thermogravimetric analysis (TGA) and differential thermal analysis. The results are displayed in figure 2.41. The thermal stability of our polymers exceeds that of polydimethylcarbosiloxanes containing terminal functional groups. This fact may be explained by formation of intermediate stable crosslinked macromolecules from reaction of N–H groups of polysilazanes with H2N–Si groups of linear oligomers at high temperature (210-2300C in the open air); such oligomers may be obtained via hydrolysis of Si–NH–Si bonds by air moisture. Intensive thermal degradation of our polymers begins only above 3500C. From the TGA curve (Figure 2.41), we have calculated the activation energies (Ea) for thermal degradation. The calculated Ea = 64 kJ/mol exceeds the correspond parameter (52-54 kJ/mol) for polydimethylcarbosiloxanes with terminal functional groups. Synthesized by us diallylsilazanes and polymers based on them were used for modification of properties of some industrial polymer composites based on polymers with functional groups.

Figure 2.41. DTA (a) and TGA (b) corves for polymer VIII (Table 1).

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Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

We have obtained that adding 5-10 % of polyorganosilazanes to an adhesive containing vinyldimethylacetilenylcarbinol increases thermal stability of the composite by 25-300C. The optical transparency of thin films of 100 μm thickness was unaffected. We have obtained satisfactory results by modification of properties of phenolform-aldehyde resin (PFRs) composites with our diallylsilazanes. Thus, addition of diallylsilazanes (1-3 mass %) has improved some properties of hardened PFR (Table 2.15). their important physical and mechanical properties of the composites have remained unchanged. We have also performed some investigations of our synthesized oligomers and polymers in combination with phenolformaldehyde resin. They were successfully used as a binding component for polymer/graphite electroconducting composites. Our ECCs can be recommen-ded for making electrodes and for making chemical (fuel) sources of electrical energy. Table 2.15. Some physical and mechanical properties of the modified phenolform aldehide resin composite #*

Electrical conductivity, ρ, om.cm

Strength on pressure, σ, MPa

Strength on winding, σ, MPa

I II1% III 1% III 3% IV 3%

53,28 49,23

21,22 21,22

19,80 12,00

Specific percussive viscosity, kg. cm/cm2 2,76 2,40

49,63

27,16

18,50

2,45

49,50

56,59

16,90

2,27

51,67

41,58

26,20

2,75

* I – without modifiers (Scheme 1); II – diallylsilazane based on 4-allyl-2-methoxyphenol:hexamethylcyclotrisilazane (2:1); III – diallylsilazane based on 4-allyl-2methoxyphenol:trimethyltriphenylcyclotrisilazane (2:1); IV – diallylsilazane based on 4-allyl-2-methoxyphenol:hexamethylcyclotetrasilazane (2:1).

Chapter 3

SYNTHESIS OF ELEMENTORGANIC SOLUBLE POLYIMIDES BASED ON SILICON-ORGANIC CARBOCYCLIC DIANHYDRIDES, ORGANOELEMENT AND HETEROCYCLIC DIAMINES Rapid growth of industry requires creation of polymeric composite materials of new generation. It became necessary not only to obtain high quality materials, but also the preservation of their properties for a long service time [21-23]. It this respect, the heterochain polymers, containing arylene and heteroarylene fragments, plays a very important role. Among such polymers, a special place belongs to polymides both from a commercial and technical point of view. Despite the fact that there is a large enough assortment both of polymides and the corresponding monomers, the creation of a low cost raw base and also improvement of some very important properties (solubility, process-ability, high level of the internal stresses in composite materials, etc. [101-111]), are still a problem. Besides, some procedures of the synthesis of the known polyimides have features, which need to be improved. Among them:

96

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

Scheme 3.1.

•

•

•

Preparation of polyimides with high thermal, electrical, mechanical, etc. properties is currently achieved only by using the exotic monomers; The use of the relatively accessible monomers leads to formation of polymers with the low-molecular weigth, low mechanical, for example, stress-strain properties; The obtained polymers with an interesting structure have low solubility and difficult process-ability.

The search for new monomers for PI synthesis with the necessary and improved properties is still the actual problem. As the initial fluorine-containing dianhydride, the dianhydride, containing dinaphthyldiketone groups, DAN has been chosen (Scheme 3.1) [111]. The used diamines were: 5(6)-amino-2(n-aminophenyl)benzimidazol (DAM) [111] (Scheme 3.1) and 4,4-diamino-3,3-dinitrodiphenylenhexafluoropropane (DAM). The identification of the mentioned above compounds was conducted based on their melting temperatures and the IR-spectra [111]. The synthesis of polyamide acids (PAA) was carried out in aproton solvents − dimethylformamide (DMFA), N-methylpyrolidone (N-MP), and dimethylsulfoxide (DMSO). The concentration of solutions was 5-15%, the mole ratio of monomers was 1:1.

Synthesis of Elementorganic Soluble Polyimides…

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Figure 3.1. The DSC curves of the fluorine-containing polyamide acid.

Scheme 3.2.

The temperature increase from 30 C reduces the intrinsic viscosities of PAA (η=0.14-0.25 dl/g). This is probably related with the splitting of the amide bonds of the PAA by water, separated at the polycondensation. As the catalyst in this case are the protons of the carboxyl groups of PAA, located in the ortho-position toward the amide groups. The formation of a relatively low molecular weight polymers is probably related with the occurrence of the reaction in the diluted solutions, what is caused by the limited solubility of the initial monomers in the mentioned above available polar solvents. By using the DSC and DTA analysis methods (Thermogravimetric and differential-thermal analysis (TGA and DTA) was per-formed on a derivatograph (Paulic, Paulic & Erdey) at the speed of the heating

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10Kmin-1.) the reaction of heterocyclic condensation of the polyamide acid, separated from solution and dried under the reduced pressure has been investigated. On the DTA curve of synthesized polyamide acid, taken in the inert media (dry argon), there are several endothermic and exothermic peaks. The endothermic peak at 2050C corresponds to the PAA melting. The exothermic peak in the interval 270-2900C with the maximum at 2850C corresponds to the reaction of heterocyclization with the water separation and formation of the amide cycles (Scheme 3.1). The analogous temperature interval is observed on the DSC curve (Figure 3.1). This is confirmed by the data of the gas-liquid chromatography (GLC), and by the IR-spectrometrical analysis. In the IR-spectra (IR spectra were obtained from KBr pellets, using UR-20 (Karl Zeis®) spectrophotometers and a Nicollet Nexus 470 machine with MCTB detector). of polymers along with the absorbency bands at 14201450cm, and at 1500-1600cm-1, characteristic for the benzimidazol and arylene (naphtylene and phenylene) groups, there are absorbency bands at 1660cm-1, 1350cm-1, 1170cm-1 and 1780-1730cm-1, which relates to the following groups –(O)C–Ar–C(O)–, C–F, and imide groups, correspondingly [111]. The mass of water, separated on the heterocyclization stage, is approximately equal to the mass loss at 300-3500C. On the TGA curve of the polyamide acid, what is 75-80% of the whole water mass (GLC, Chromatography analysis of original reagents and the reaction products were performed by using the device LKhM-80 (Russia), type 2 (the column 3000 x 4 mm, the head – “Chromosorb W, the phase-5 mass % SE-30, and gas-carrier-helium), and at heating of the polymer till 4000C, it changes insignificantly.thai confirms the assumption that at the reaction conditions (heating in argon medium), there is a partial imidization of PAA. Indeed, in the IR-spectrum of PI, the appearance of the weak absorbency bands in the area 1680-1550 cm confirms the existence of noncyclized fragments in the polyamide acid macrochain. This is, probably, caused by realization of the unfavorable conformations for hetero-cyclocondensation on the first stage of their formation [102]. The more detail study of the problem requires to conduct the absolutely independent theoretical and experimental investigations of large enough volume and application of the methods of vibrational and NMR spectroscopy (NMR spectra were obtained with anAM360 (Brucker®) instrument at an operating frequency of 360 MHz using CDCl3 as a solvent and tetramethylsilane as an internal standard) along with the fine structure analysis. However, the obtained by us experimental data [the

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structure defects, incomplete cyclization, specifics of the diffactograms of the samples-small amounts of reflexes (Figure 3.2, Wide-angle X-ray diffractograms have been obtained by DRON-2 instrument (“Burevestnik”, Petersburg, Russia). Cu Kα was measured without a filter; the motor angular velocity was ω ≈ 2 deg.min-1), and others] and the published calculations in this aspect provide the opportunity to make anassumption that at PAA formation along with the favorable for cuclization structure, there is formation of unfavorable conformations [111]. This can be probably assisted by not only formation of the stable PAA complexes with the molecules of the used aproton polar solvents (dimethylformamide, N-methylpyrrolidone), but also by the strong enough intermolecular interaction (for example, formation of hydrogen bonds). The phenomenon plays a very significant role in the process of the favorable conformation at the macromolecules cyclization. In this case, there is the realization of two types of isomers (Figure 3.3): favorable for cyclization, a (para) and unfavorable, b (meta): Based on this, at the PAA cyclization and with polyimide formation, the important role plays the length of the stiff fragment in the elementary chain (amount of the stiff nuclei-phenylenes, naphthylenes, imidazole cycles), what affects significantly the molecule mobility. Because of this, the 100%cyclization of PAA with such structures is not possible due to the fact that the transformation of such stiff macromolecule fragments in the real systems to obtain the isomer a (Figure 3.3) with the maximally closely located groups NH and -COOH [111] is impossible. The wide-angle diffractograms of the synthesized polymers are characterized by a diffusion maximum in the interval 2θ=22-24, and also by hardly visible maxima in the intervals 14-15, and a very small shoulder in the interval 9.5 -10. The first wide-angle maximum is located at 2θ=23.5 (d=3.785 Ǻ). Based on the character and number of reflexes of the diagrams, it can be concluded that the obtained polyimides are amorphous substances. They are characterized by low mobility of the macromolecular chains, which is caused by existences of massive and stiff naphthylene and amidazole fragments, which provide a layered structure to polymers [110, 111, 113-115]. The second wide-angle maximum at 2θ = 23.5 on the diffractograms corresponds to the distance between the layers. The real structure of macromolecules is more defective than it was shown on the chain model: it was determined only the so-called “near order” in the character of the structure units packing, where there is a very low portion of the highly ordered formations in a polymer and

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which is determined on the diffractograms by the ratio of the area under the shoulder (2θ = 9.5) to the area of the amorphous portion (Fig.3.2).

Figure 3.2. Diffractogram of polyimids based on fluorinecontaining dianhydride and benzimidazole diamine.

HO

O

O

CF3

O

O

C

C

C

C

C

CF3 Ar

HN

HO

C

C

O

O

O

O

CF3

O

O

C

C

C

C

C

O

Ar

CF3 C

C

HN

HN

Ar NH

(a)

OH

OH O

(b)

Ar

Figure 3.3. Isomers (a) and (b) of the basic structure chains of the fluorine-containing polyamide acid.

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The data, obtained from the wide-angle diffractograms of the mentioned above polymers, are confirmed by the data published for analogous systems, which were tested by using the small angle X-ray diffraction method [112, 116]. Because the binary PI are characterized by the relatively limited solubility in a narrow assortment of solvents (DMFA, DMSO, N-methylpyrrolidone, concentrated H2SO4, CHCl3: PhOH) [113-115], we tried to prepare such ternary polymers, the consecutive treatment of which would improve their solubility and also the physical-mechanical properties. For this purpose, as a third monomer, polycarbocyclic dianhydride (Scheme 3.3) [113, 117, 118] was used. To prevent the obtained polymer, structurization process caused by splitting of the unsaturated bonds of the carbocyclic dianhydride at high temperatures, the polycyclocondensation of the polyamide acid, obtained on thefirst stage in conditions analogous to the binary polymer, was conducted without its precipitation from the reaction media, but by slow distillation at 84900C from the azeotropic mixture of toluene and water, separated at imidization according to Scheme 3.3. O

O R/

C

O

C

nm O

//

O C

C

C

C

O + n(m+k) H2N-R -NH2 + nk O C

C O

O

O HN

C

HO O

C

R/

NH

C

OH

O /

N

N

R//

C

where, R =

O

CF3

O

C

C

C

CF3 m, k < n; m + k = 1

Scheme 3.3.

C

NH

HO O

C

C

OH

O

C

C

C

C

, R// =

O

C

N HN

N

R// -H2O

k n

O

m O

O

/

C

N

C

O

HN

O

C

R

C

R//

m

O

O

O

O

C

-H2O

O

O

O

O

R// k n

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In the case of ternary polymers, as in case of the binary ones, the complete imidization of PAA can not by achieved, what is confirmed existence of weak absorbency bands of the amide bonds at 1680-1550 cm-1 in the IR-spectra of the and reaction products. By using the methods of thermogravimetric and differential thermal analysis at studying the thermooxidative stability of the obtained polymers, it was established that sample mass of the synthesized polymers practically does not change at heating till 450-5000C. The intense polymer thermooxidative destruction occurs at 550-6000C The relatively high thermooxidative stability of the ternary polymers is probably due to the structurization processes, taking place at high temperature with participation of the unsaturated bonds of the blocks of carbocyclic dianhydride and air oxygen. This could provide additional polymer thermostabilization. The determined thermomechanical properties of the ternary polymers were very interesting. It was established that at heating of the unfilled polymer tablets (samples) till 5000C at load p=1MPa, the sample deformation was insignificant (η=3.5%); at load p = 5MPa, the deformation value was only 3540%, what indicates on the very valuable temperature properties of the polymer. To investigate the effect of the substituents on the stability of the polyamide acids and their ability to cyclization, we investigated the reaction of fluorine-containing dianhydride with 4,4’-dinitrodiphenyl-2,2-hexafluoropropane. The reaction can be represented as shown in Scheme 3.4. The reaction product, obtained on the stage I of PAA, after precipitation and during, is a yellow powder with η=0.14dl/g. On the curves of DTA of PAA, there are two endothermic peaks at 1050C and 2000C and an exothermic peak at 3150C. The peak at 2000C corresponds to the melting temperature of the polyamide acid, and the peak at 2150C – to the process of polyheterocyclization (Figure 3.4). The polyheterocyclization temperature increase is undoubtedly related with the existence of polar dinitro groups- NO- in the ortho position toward amino groups. The polar groups create a high enough steric hindrance and at the same time provide a negative electron-accepting effect on the nitrogen atom of the NH-group with delocalization of n-electrons. The mass loss of polymer sample at 3150C on the TGA curve corresponds to the water mass, separated at the hetero-cyclization reaction. Besides, it is not excluded that at temperatures above 400 C, the reaction of decarboxylation also takes place. The last assumption is supported by the relatively high mass loss value (-10%) what is more than expected as the result of the heterocyclization process (5%).

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The assumption is also confirmed by the investigating the reaction of PAA hetero-cyclization at 4000C in the inert medium (argon) by using the gas-liquid chromatography method. In this case, it was found that along with water, there is separation of CO2. O

O

CF3

O

O

C

C

C

C

C

n O

O + n H2N-Ar-NH2

CF3 C

C

(DAMN )

O

(DANF6)

O

O

O

CF3

O

O

C

C

C

C

C

HN Ar

C

C

OH

O

O

O

NH2

CF3

O

CF3

O

O

C

C

C

C N

CF3

t0 -H2O

n

Ar

C O

n

CF3 where, Ar = O2N

C CF3

NO2

Scheme 3.4.

Figure 3.4. The DTA curve of polyamide acid, obtained based on fluoro-containing dianhydride and diamiine.

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The composition and structure of PAA were confirmed by the data of elemental analysis and IR-spectroscopy. In the IR-spectrum of polyamide acid (1480 cm-1, 1600 cm-1, 3100-3000 cm-1, 1710-1720 cm-1) and NO-group (1350 cm), it was observed the absorbence bands characteristic for the amide-groups (1550 cm-1 1680 cm-1, 3300 cm-1), and aiso the hydroxyl group of carboxyl group (3200 cm-1). However, at separation of the formed product, the existence of the absorbence bands for the amide groups at 720-725 cm-1, 1380 cm-1, 1735 cm-1, 1790 cm-1 was found [110, 111]. By using the thermooxidative thermogravimetric analysis, it was established that the obtained polymer has enough high stability - the mass loss in air at 400-4500C is less than 10-15%. We have reported above that aromatic, heterocyclic and organo-element compounds – dianhydrides of tetracarbonic acids and diamines are usually used to obtain thermostable polyimides. For this purpose also are used carbocyclic dianhydrides containing double bonds obtained from some of petroleum products [113]. Despite the use of wide range of dianhydrides, only few of them are practically available. This communication relates to synthesis of silicon-containing polyimides with silarylene fragments in chains based on carbocyclic dianhydride (DAN) obtained from maleic anhydride and aromatic hydrocarbons (C–H) according to the method described in Ref. 113, and silicon-organic diamine – 4,4´diaminmethylphenylsilane (DAM) [112] (Scheme3.5). It was expected that the obtained polymers would have such practically important properties as high adhesion, heat and thermal stability, good processability, etc. Besides, the existence in polyimides macrochains of reaction-able unsaturated bonds gives the opportunity of their further chemical modification to improve processability, solubility, impact strength, flameretardance, cross-linking at article production, and etc. The synthesis of polyimides was carried out according to the well known method of polyheterocyclic condensation of fluorine-containing polymers – polyamide acids (PAA) both through the stage of their separation and hightemperature polyheterocyclic condensation of PAA (1 stage) [114] and through the stage without PAA separation from solution in presence of cycling complexes [115]. The polyimide formation reaction can be represented by a scheme shown on the right. The reaction of high temperature polyheterocyclic condensation of PAA (in vacuum at P = 0.5-1.0 mm Hg, in dry Ar) and corresponding model reaction of DAN + anyline (1:2) were investigated by DSC, DTA and IR spectroscopic analysis methods.

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O

O C

R

C

n O C

C O (DAN)

NH2

I

R/

O

(DAM) O

O HN

Si

O + n H2N

R

C

C

NH

Si

HO C O

C

OH

R/

II -2 nH2O

O

n

O

O C

C

C

C

N O (DAN)

O

R N

Si R/ n

Scheme 3.5.

The found exothermal peaks at 270-2800C on the PAA (R=CH3, R=C6H5) DSC corves correspond to the reaction of heterocyclic condensation leading to formation of imide cycles and liberation of water. The IR spectra and composition (Si %) of films and powders of PAA heated to 3000C (in vacuum or in Ar) indicate that the heterocyclic reaction occurs through formation of PAA what is characteristic also for model systems and other analogous systems [101]. It should be noted that the heterocyclization of model system goes practically completely at lower temperature (2500C). The temperature increase above 3800C leads to liberation of small amount of CO as a result of partial decarboxylization of the non-cycled fragments of PAA which at elevated temperatures can be a compatible process to polycyclic condensation. Besides, it is difficult to explain without any doubt the reason of limited solubility of hightemperature polyheterocyclic condensation product (PPC). This, probably, can be related both with strong interchain interaction of the obtained PPC and with cross-linking of formed branched structures on the 1st stage of reaction

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with participation of the basic and intermediate functional groups (- CO-NH-, COOH) or double bonds of DAN. Based on these considerations, the polyheterocyclic condensation was conducted in the presence of cyclizing agents, and in particular, pyridine and acetic anhydride (1:1) without separation of prepolymer (PAA) from solution. In both cases, the stage of PAA formation proceeds in analogous conditions (25-400C) in aprotonic polar solvents (DMFA-dimethylform-amide-, DMSOdimethylsulphoxide or DMFA/DMSO blend, 2:1) in Ar media at equimolar (1:1) ratio of original monomers. In this case, the homogeneity of the reaction mixture is not disturbed both at incorporation of DAN and after the reaction is completed. It should be noted that the value of the specific viscosity of PAA depends on the order of DAN addition to DAM, on solution concentration, and on the way of reaction completion on the 1st stage. The best solvent was found to be the DMFA/DMSO mixture (2:1) in which the concentration of PAA was 15-20% higher than for PAA obtained in DMFA. It is possible that the reduced values of the specific viscosity of prepolymers (η = 0.11-0.16 dl/g) are caused by conducting the reaction in relatively diluted solutions (10-15 mass %) due to limited solution of monomers in the used solvents. There are differences in ηsp values of the soluble PPC obtained either by the 1st method (soluble fraction) or by the 2nd method. In particular, the ηsp of (PPC) < ηsp of (PPC), which is probably, caused not only by formation of chaotically branched macromolecules due to the side reactions with participation of NH and COOH groups of PAA and the bonds of DAN groups, but also by hydrolysis reaction of prepolymer amide bonds in the presence of carboxyl groups located in ortho-position to the amide bond [111]. Some differences in softening temperatures of PPC obtained by I and II methods were also found. This may by relate to the different state of polyheterocyclization of obtained PAA in presence of cycling agents (II) or by heat cyclization (IR spectroscopy, internal standard) [110, 112]. The composition and structure of synthesized PAA and PPC were confirmed by elemental composition (Si, %) and IR spectroscopy of polymers. In the IR spectra of PPC the absorbency bands were found in the areas of 1780 cm-1, 1735 cm-1, 1720 cm-1, 1380 cm-1, 720 cm-1, 1430-1450 cm-1, and 1590 cm-1, related to the imide cycles and silarylene groups correspondingly which confirm the suggested structure. The found in IR spectra low-intensity absorbence maximas at 1680 cm-1 and 1550 cm-1 can be related to the amide groups of non cyclized PPC fragments.

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According to the DTA and DTG analysis (air, up to 4000C) the PPC show only small mass loss, and at the temperature interval 450-5000C the mass loss is less than 15-20%. That can be probably explained not only by the formation of thermostable polycyclic structures with silarylene fragments, but also by cross-linking (high temperature) through the double bonds of dianhydride residue of PPC (see scheme) leading to additional thermo-stabilization of the synthesized polymers. It should be noted that the intense thermo-oxidative destruction of PPC is observed above 5500C that is confirmed by the appeareance of corresponding strong peaks on DTA-spectra in the temperature interval. Further we discuss the data on the synthesis of thermostable polymers based on fluorine-containing diketodianhydrides (DANF6) [113] and siliconorganic diamines (DAMSi) [112]. O

O

CF3

O

O

C

C

C

C

C

n O

O + n H2N-Ar-NH2

CF3 C

C

O

(DADF3 )

O

O

O

CF3

O

O

C

C

C

C

C

HN Ar

C

C

OH

O

O

O

NH2

CF3

O

CF3

O

O

C

C

C

C

n

N Ar

CF3 C O CH3 where, Ar =

Si C6H5

Scheme 3.6.

n

t0 -H2O

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Synthesis of polyimide (PI) with the aforementioned structure we carried out by a direct method of polyheterocyclocondensation in aprotonic solutions via forming polyamide acids (PAA) and its subsequent cyclisation (without its isolation from the solution) in the presence of the cyclisation complex (pyridine complex with acetic anhydride), as well as via isolation of PAA which was precipitated in methanol [1:10] and its subsequent thermocycling in Ar or in vacuum. The reaction with generation of polyimide proceeded by the following scheme: The synthesis of PI in the presence of the cyclisation complex in solutions was carried out by the following procedure: DAN parceled out into small particles was added by continuous stirring with 10-15% solution of DAM (reaction continued in argon which was purified from oxygen). After addition of DAN, the reaction mixture was stirred for 6-8 hrs at 40-50 C, then 3-fold excess of the cycling complex representing the cycling agent was introduced and the reaction mixture was heated for 8-10 hours at the solvent boiling temperature. The obtained product was precipitated from the solution with the abundant water, extracted by acetone and dried in vacuum at 1000C. It should be noted that the reaction occurred at the homogeneous phase after 2.5-3 hrs by subsequent complete addition of DAN in the reactor. At the same time, the effect of the solvents on the yield of the polymer was detected. Some of the polymers with higher MM than that of the others are formed in DMFA. This fact can be explained by a partial inhibition effect of NMP on the PAA chain lengthening. The high temperature heterocyclization reaction with the formed intermediate product such as PAA was investigated by the methods of DSC, DTA and IR spectroscopy. The DSC thermogram of PAA was obtained at 204000C; endo- and exothermal peaks were observed on it. The exothermal peaks at 280-2900C are characteristic of the heterocyclization reaction of PAA with water isolation which was established by the GLC method [110]. The composition of the synthesized polymers was confirmed by IR spectra and elemental analysis data. In the IR spectra of PI there were detected absorption bands in the range of 1780-1750 cm-1, 1380 cm-1 and 720 cm-1 for imide cycles. The synthesized PAA (η = 0.12- 0.18 dl/g) were dissolved in DMFA, in TCE and in DMSO at room temperature. The polymer forms thin collred transparent films from its solution. It should be noted that the relatively higher solubility of the synthesized PI obtained via the first method probably can be

Synthesis of Elementorganic Soluble Polyimides…

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explained by softer polycyclocondensation conditions in the presence of the cycling complex. By DTG and DTA data of PI with heating of the polymer films in air up to 0 480 C significant weight loss was not observed. Intensive thermooxidizing decomposition occurs at 560-6000C according to the condition of isothermal behaviour. There was not practically detected PI weight loss at 3000C for 72 hrs, and the 1-2% weight loss in this reaction (by heating of PI ) is equal to the amount of water isolated during further heterocyclization via interaction of the released groups of NH and COOH of PAA. Various composite materials (antioxidative covers, varnishes, etc.) based on the obtained PPC have been developed.

Chapter 4

ORGANOSILICON OLIGOPHENYLENES ON THE BASE OF SOME DIETHYNYLSILANES AND DIETHYNYLSILOXANES The siliconorganic polymers, obtained by the introduction of siliconcontaining fragments into the oligophenylenes chain during the process of their synthesis from diethynyldiphenylsilane and their mixture with phenylacetylene are described in the literature [119,120]. The investigation of the other method of incorporation of silicon-organic fragments into the oligophenylenes chain via the reaction of hydrosilylation has also been carried out. This reaction is not very convenient because the oligomers must contain a sufficient number of active multiple bonds capable of addition of hydridsilanes and hydridsiloxanes. The method based on the reaction of polyaddition of a,ωoligoorganodihydrosiloxanes to acetylene groups of oligophenylenic chain is more interesting and leads to chemical modification of the above mentioned oligomers [121]. The method of co-polycyclotrimerization of diethynylsilanes seems to be more technological [122], but the data about the synthesis and the general regularities of the formation of these polymers and their properties are extremely restricted. The present work is dedicated to the study of the reaction of polycyclotrimerization of silanes and -siloxanes, containing the acetylene groups at silicon atoms, their copolycyclotrimerization with phenylacetylene (PA) and para-diethynylbenzene (P-DEB) as well as of the properties of the obtained siliconorganic oligophenylenes (SOOP). For the initial siliconorganic monomers we used ditolyldiethynyl-silane (DTDES), diphenyldiethynylsilane (DPDES), l,4-bis-(dimethylethynylsilyl)

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ben zene (DESB) and 1,3-diethynyltetraphenyldisilioxane (DETPDS). They were obtained via the interaction of the lotsich reactive with corresponding diclorsilanes [122-124]: The polycyclotrimerization of siliconorganic diethynyl derivatives were carried out in presence of catalyst of the Ziegler-Natta type Al(iso-C4H9)3TiCl4 in the toluene-hexane solution at the temperature of 15-20°C in Argon medium. The solid powder-like products were slightly yellow-orange colored. Their yield was between 60-97 p.c. (Table 4.I). The extent of polycylcotrimerization was determined by measuring the integral intensities of vas (– C≡CH) and vas (–C6,H5). Their yield and structure depend on the nature of the organic groups at silicon atoms (Scheme 4.1, Table I) and onthe structure of the initial siliconorganic diethynyl compound. The high yield and the relatively low unsaturation of the oligophenylenes based on DTDES, are attributed to a high degree of the cyclotrimerization process completion due to the presence of electron-donor aliphatic (e.g., methyl) relatively low unsaturation of the oligophenylenes based on DTDES, are attributed to a high degree of the cyclotrimerization process completion due to the presence of electron-donor aliphatic (e.g., methyl).substituents in /wra-position of benzene groups. This leads to the increase of the electronic density on the acetylene groups, the opening of triple (–C≡C–) bonds and thus, facilitates the formation of aromatic cycles [125]. The different situation is observed in the case of monomers with the spatial radicals at the silicon atoms, where the formation of benzene cycles is hindered. Therefore, the reaction products have relatively low yield and are characterized by high unsaturation (Table 4.I). The extent of process of cyclotrimerization and the yield of the obtained siliconorganic oligophenylenes are higher in the case of 1,4bis(dimethylethynylsilyl)benzene (Table 4.1). Note that the values of specific viscosity of products having approximately equal molecular weights, differ from each other. This reflects the formation of the chain of macromolecules with different lengths and degrees of branching. We also established the dependence of solubility of the products of polycyclotrimerization on the structure of the initial monomers (Table 4.1). The structure and the composition of the above-mentioned siliconorganic oligophenylenes were determined from the data of the elemental and IR spectral analyses. The appearance and the increase of the integral intensities of absorption maxima in the region of 812-820 cm-1 with the simultaneous decrease of the integral intensities of i/as of C—H bonds in monosubstituted

Organosilicon Oligophenylenes on the Base…

113

ethynyl groups (−C≡C−H, 3300 cm-1) manifests the formation of trisubstituted benzene cycles [126, 127].

Scheme 4.1.

Table 4.1. The propertoes and the yield of the oligophenylenes besed on diethinylsilane The initial diethynyl silanes

Yield, %

Solubility in benzene, toluene and CHCl3

Unsaturation

DPDES

60

Part. soluble

0.081

DPDES

97

Part. soluble

0.030

DESB

88

unsoluble

0.014

The data of elemental analysis, % is found / is calaulated C H Si 82.12 5.53 11.67 82.75 5.17 12.06 82.53 6.47 10.49 83.07 6.15 10.77 68.82 7.51 22.45 69.42 7.44 23.14

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Scheme 4.2.

The obtained results do not allow us to determine with certainty the precise structure of the obtained oligophenylenes; nevertheless it can present the most probable scheme of the polycyclotrimerization: As the data given in Table 4.2 reveal, completely soluble polymers are obtained in polycyclo- trimerization of DETPDS, while at the same reaction of DEB the process should be carried out in the presence of PA with the PA ratio to DEB not less than 1.5:1.0 [128]. The formation of soluble products of the polycyclotrimerization of DETPDS depends on the probability of the formation of the cyclic fragments due to the presence of flexible siloxanic bonds between ethynylic groups of the initial monomer. This was confirmed by the IR spectra of the obtained polymers. The spectra demonstrate that in the process of polycyclotrimerization the ethynylic groups entirely disappear with the simultaneous indication on the absorption regions of 810 cm-1, characteristic for trisubstituted products of benzene. The formation of the soluble and fusible products is also confirmed by their thermo- mechanicalcurves (Figure 4.1). The light orange and pink products completely insoluble in benzene, toluene and chloroform are obtained (yield 63-90%) via the polycyclotrimerization of the above-mentioned diethynylsilanes with phenylacetylene (PA) (Tables 4.2 and 4.3) [129]. According to Table III in case of cyclotrimerization ofDPDES and DTDES with PA, the higher the fraction of PA in

Organosilicon Oligophenylenes on the Base…

115

initial mixture of the monomers, the lower is the unsaturation of the product of the reaction. Molecular masses (M.M.) of the co-polymers of DTDES with PA are higher than those of the co-polymers on the base of DPDES and PA at the same proportions of the initial monomers (4820 and 3960 at the molar ratio 1:1; 6450 and 4280 at the molar ratio 1:2 correspondingly). It should be noted that the co-polymers based on DESB and PA have no unsaturation. This suggests the formation of cyclic fragments during the copolycyclotrimerization, which are derived by the "hinging" of bonds —C— Si—C6H4—Si—C— in initial silicon-organic monomers [129]. This explains the formation of the co-polymers with relatively low-molecular masses (Table 4.3).

Figure 4.1. Thermomechanical curves of (co)polymers DETPDS:DEB:PA: 1) 1:0:0; 2) 1:0.1:0; 3) 1:0.5; 5) 1:1:1; 6) The product of co-polycyclotrimerization DEB:PA (1:1).

At the same time the unsaturation of the co-polymer based on DTDES and PA at the proportion of 1:2 is less in comparision with that of the co-polymer of DPDES with PA of the same ratio. This also indicates the high reactivity of DTDES in process of polycyclotrimeri-zation with PA and explains the high extent of this reaction. The following absorption maxima are found in the IR spectra of the products of co-polycyclotrimerization: 800 cm-1, 810 cm-1 and 820 cm-1 (mono-, di- and trisubstituted benzene groups), 1260 cm-1 (vas, Si(CH3)2) and also 1419 cm-1, (vas of Si─C6H5), 2980 cm-1 (vas CH in alk. group) for co-

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polymers based on DESB, etc. The decrease or the complete disappearance of the absorption maxima VC—H associated with monosubstituted acetylene groups and the increase of the intensity at 3030 cm-1 (H─Car) are also observed. On the basis of these results the process of the formation of the copolymers of DES and PA can be expressed with the following general scheme: Table 4.2. The ratio of the initial monomers and some properties of the co-polymers on the basis of DETPDS Polymer No 1 2 3 4 5 6 7 8

Molar ratio DETPDS: DEB: PA 1: 0 : 0 1 : 0.1 : 0 1 : 0.75 : 0 1: 0 : 0.5 1: 0.5 : 0.5 1:1:1 1 : 1 : 0.5 0 : 1 : 1.5

Yield, % 75.00 65.09 63.60 84.25 53. 36 71.80 75.97 65.0

Solubility in benzene, toluene and chloroform Soluble Part. soluble (93%) Part. soluble (93%) Soluble Soluble Soluble Soluble Soluble

Unsaturation of copolymers 0 1: 35 1 : 12.5 0 1 : 13.5 1 : 12.5 1 : 22.9 1: 10

M.M 2930 5520 1440

nHC≡C—R—C≡CH + mHC≡C—C6H5 →

Scheme 4.3.

In order to decrease the possibilities of the formation ofmacrocycles during the co-polymerization and to increase the ability of structuring the siliconorganic oligophenylenes, para-diethynyl benzene having a harder structure than DESB was incorporated into the initial mixture. The three fold co-polymerization was carried out at the above described conditions with different proportions of the initial monomers. After precipitation of the soluble products of the reaction in ethanol the yellow colored amorphous products were isolated. The conditions of the synthesis and some of properties of the

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117

products of the (co)polycyclotrimerization are given in Tables 4.3 and 4. As these data show, the co-polymers with the high yield are obtained by means of these reactions. The solubility of SOOP depends on the molar ratio of the initial monomers. Elevating the fraction of the diethynyl components in the initial mixture the products insoluble in the ordinary organic solvents are formed (Table 4.4, exper.1 and 2). On the contrary, the increase of the phenylacetylene fraction in the initial mixture of the monomers leads to the formation of partially or completely soluble products (exper 3 and 5, Tab. 4.4). At the same time molecular masses of soluble oligophenylenes determined by ebullioscopy in chloroform are not high (MM ~ 3480). The thermomechanical properties of the synthesized (co)polymers have been investigated (Kargin scale, P=l00g). The analysis of thermomechanical curves of SOOP demonstrated that the oligophe-nylene on the base of DTDES has a well defined region of ductility in the temperature interval of 150-250°C on the curve achieving the relative deformation ~70%. In the temperature region of 220-250°C, the oligophenylene undergo the process of hardening (structuring). At temperatures up to 300°C there are insignificant differences in the characteristics of the thermomechanical curves of SOOP based on DESB. Introduce of disiloxanic fragments into the oligophenylenic chain causes the relative deformation to be increase (Figure 4.1). The study of thermomechanical curves of co-polycyclotrimers shows, that they are typical for polymers with the low molecular mass (Figure 4.2), which completely melt in the vicinity of 160- 165°C. The co-polymers based on the DTDES and PA melt at lower temperatures (Tmelt = 130°C - curve 4 and Tmelt = 115°C - curve 5, Figure 4.2) than in case of co-polymers obtained from DPDES and PA at the same molar ratios of the initial monomers (Tmelt = 120 ÷160°C, curves 2 and 3, Figure 4.2). Note that by enhancing the fraction of PA in the initial mixture of monomers the melting temperature of the co-polymers is reduced (Figurer 4.2, curves 1, 2, 3 for the co-polymers of DPDES: PA and curves 4, 5 for the co-polymers of DTDES: PA correspondingly). The study of thermoxydative destruction of synthesized SOOP (Figures 4.3, 4.4 and 4.5) shows that the thermooxydative stability of co-polymers depends on the structure of the initial silicon-organic diacetylenes and on their molar ratio in the monomer mixture (in case of co-polymerization, figure 4.4 and figure 4.5). From Figures 4 and 5 we see that the thermo- oxydative destruction of the polycyclo- trimers based on diethynylsilanes and -siloxane starts at 320-325°C, while it takes place at 365°C and 380°C for the double

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and threefold co-polymers. The highest intensity of mass loss takes place in the region of 430-550°C and 490-620°C for the "double" and "threefold" copolymers respectively (Figure 4.4 and Figure 4.5). Table 4.3. The ratio of initial monomers and some properties of the of the copolymers based on siliconorganic diacetylenes and phenylacetylene No.

The mole ratio of initial monomers

Yield, %*

Unsaturation

Molec. mass**

1

1 : 0.5 (DPDES: PA)

35.0

0.043

Did not determ.

2

1 : 1(DPDES: PA)

70.0

0.041

3960

84.57 86.22

5.75 5.38

9.01 8.32

3

1: 2(DPDES: PA)

55.2

0.030

4280

4

1:1(DPDES: PA)

89.8

0.040

4820

85.67 88.07 84.64 86.19

5.73 5.58 6.13 6.08

7.61 6.41 6.69 7.73

5

1: 2 (DPDES: PA) 82.5

0.0

6450

86.74 87.17 74.24 76.74 77.62 78.98

6.57 6.05 7.84 6.97 7.33 6.83

7.28 6.78 17.00 16.27 14.95 14.17

6

1:1(DPDES: PA)

63.0

0.0

2150

7

1:1.5(DPDES: PA)

72.3

0.0

2380

The data of elemental analysis, Founded/Calculated C H Si 5.71 10.33 83.37 5.33 9.89 84.80

Figure 4.2. Thermomechanical curves of siliconorganic co=oligophenylenes: 1,2, 3) – DPDES: PA 1) 1:0.5; 2) 1:1; 3) 1:2; 4, 5) – DTDES:PA 4) 1:1; 5) 1:2.

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119

Table 4.4. Yield and some properties of the three - fold co-oligophenylenes on the basis DESB, p -DEB and PA No.

The molar ratio of the Yield, Solubility in initial monomers %* C6H6, C6H5-CH3 DESB: p-DEB: PA and CHCl3

Unsaturation

Molecular mass

1

1: 2: 0

70

unsolul.

0.122

2

1:2 : 0

69

_"

0.106

Did not determ. _"

3

1: 2 : 2

94

part.sol.

0.101

_"

4

1: 1: 1

70

part.sol.

0.080

_"

5

1:1 : 2

71

part.sol

0.073

3480

Figure 4.3. The curves of the T.G.A. of siliconorganic co=oligophenylenes based on DTDES and PA at the different molar ratios: 1) 1:2; 2) 1:1; 3) 1:0.5 (in the air).

At the same time the temperature intervale of complete destruction depends on the degree of conversion and the level of unsaturation of the products of (co)polycyclotrimerization [129].

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Figure 4.4. The curves of T.G.A. of siliconorganic co-polyphenylenes based on DESB, p-DEB and PA at the theirs different molar ratios: 1) 1:0:1; 2) 1:0:1.5; 3) 1:1:1; 4) 1:2:2.

Figure 4.5. Use temperature range of co-oligophenylenes: a) DETPDS:DEB:PA (1:1:0.5); b) DEB:PA (1:1.5).

In order to estimate the affect of the chemical structure of the co-polymers on their heat-resistance, the efficiency range of the synthesized three-fold copolymers was determined. Interesting results were obtained for the copolymers based on DETPDS : DEB : FA. As it is evident from Figure 4.5, the efficiency range of these co-polymers is higher than that of organic copolymers based on DEB: PA [131]. The synthesized oligophenylenes can be used for manufacture of thermostable polymeric composites, hardening without evolution of volative compounds.

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We have developed procedure to prepare organo-silicon oligophenylenes (OSOP) which includes the following steps: 1. Hydrosilylation of the technical diethynyl benzene by dimethylchlorosilane [130]. The formula describing chemical reaction is shown below: C CH HC

C

CH HSi(CH3)2Cl

+

H2PtCl6

HC

CH Si(CH3)2Cl

C

2. Hydrolytic condensation of the hydrosilylation reaction product: CH HC

CH

+H2O

Si(CH3)2Cl

-HCl

C

CH HC

Si(CH3)2OSi(CH3)2

CH

CH

CH C

C

CH

3. Catalytic (cobaltocen) polycyclotrimerization of the hydrolytic condensation reaction product: n HC

C

RI

C

CH

... C

CH

CH

CH

and RII = C6H4C2H5.

Scheme 4.4.

mHC

RI

RI

RI =

+

C

... ,

RI

Cat

RII

where:

RII

Si(CH3)2

CH

CH

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It was shown that on the first step the mono-addition reaction products have more complicated chemical composition and can consist of at least two isomers formed by addition of dimethylchlorosylyl group to α- and β- carbon atom of ethynyl groups. However, such compositionof original monomers of OSOP does not affect significantly on the solubility and processing of the obtained oligophenylenes. The last ones are light-yellow amorphous powders with molecular mass 1,600-2,750 soluble in aromatic and chlorinated hydrocarbons. The softening temperature of the OSOP is in the range 1051600C. The thermo-oxidative destruction of the OSOP starts at 4000C. The average specific impact viscosity of these unsaturated systems is 0.34 kg.cm/cm2 (5 measurements for each case). The average bending strength of thye systems is 49 kg/cm2 (four samples). The elongation at breac is about 100% (this parameter for analogous organic compounds obtained by cocyclotrimerization is less than 80%). The composition and structure of the obtained OSOP compounds were determined based on the elemental and IR analysis. In the IR-spectra the following absorbency bands were found: 700cm-1 and 760cm-1 (characteristic for mono-substituted benzene rings), at 830cm-1 and 880cm-1 (characteristic for 1, 2, 4,-; 1,4; and 1,3,5-substituted benzene rings) and also absorbency bands for bonds >C=C< at 970cm-1 and 1405cm-1; for bonds Si–O–Si at 1020-1080cm-1; for Si–CH3 at 1260cm-1;Car–H at 3030cm-1; ≡C–H characteristic forthe residual ethynyl groups at 3300 cm-1. The unsaturation of OSOP compounds according to the IR-spectra is 0.190.22 (by using the procedure of internal standard). The thermoreactive composite materials based on the obtained organosilicon oligophenylenes have been developed [130]. In the present time we are developing the silicon containing oligophenylene-hetero-arylenes by using the described above procedure.

Chapter 5

ORGANOSILICON CARBOFUNCTIONAL POLYMERS WITH ORGANIC-INORGANIC MAIN CHAINS BASED ON ORGANOSILICON OLIGOEPOXIDES 5.1. SYNTHESIS AND USE OLIGOORGANOSILOXANE POLYFUNCTIONAL MODIFIERS CONTAINING HYDROXY AND AMINO GROUPS For the further development of modern industry and techniques it is necessary to create polymer materials with the given complex of outstanding qualitative characteristics such as high thermo-oxidative and radiation stability, heat resistance, hydrophobility, superb tribological and insulating properties, etc. The fulfillment of these tasks is possible by widening and improving the synthetic direction of polymer chemistry also via modification exist industrial polymer materials. It is still actually to use of organosilicon polyfunctional oligomers and polymers for modification of carbochain elastomers, organic poyepoxide and phenol-formaldehyde resins, polycarbonate, etc. widely used in many areas of techniques and industry [131133]. It contributed to create new rubbers, hydrophobic and insulating materials, electro-conductive polymer composites, anticorossion and antibiocorrosion covers, hermetics and glues, etc, with high mechanical, antifriction and friction properties and thermal stability, keep-able their characteristics at long time. Carbofunctional organosilicon oligomers and polymers, especially organosilicon epoxides and aminalcohols based on them are often used as

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modifier agents [132]. They also are used as the intermediate products in the synthesis of oligomers and polymers with organic-inorganic molecular chains [124]. During the last decades, carbofunctional siliconorganic oligomers based on oligoepoxides attract the particular attention for manufacturing various polyfunctional cooligomers with organic-inorganic main chains [133]. One of the successful methods for synthesis of oligoorganoepoxysiloxanes with terminal epoxy groups and aminalcohols based on them is the reaction of cooligomerization of organoepoxysiloxanes and their aminalcohol derivatives with organocyclosiloxanes [134]. For this purpose, octamethylcyclotetrasiloxane is used more often than any other organocyclosiloxanes [135]. It was shown that, the products of interaction of oligoorganodiepoxysiloxanes with organic amines – aminohydroxyoligosiloxanes were used for modification of properties of some of rubber compositions based on isoprene and butadiene elastomers. By addition of a little amount of aforementioned polyfunctional organosilicon oilgomers to rubber compositions the physical and mechanical properties of vulcanized one have been improved [136]. They also can be used in combination with some other organic polyepoxides (PE) and organoelement (fluorinecontaining polymers) as one of the components for inorganic-organic nanohybrids [91, 92]. It is known from the literature that change of the widely used anti-aging agents for tire industry such as “Diaphen FP” (N-Phenyl-N′-isopropyl-pphenylendiamine), “Diaphen B” (N-1,3-dimethylbutil-N-phenyl-p-phenylendiamine, acetoneanyl P or their combinations by the aforementioned modifiers leads to considerable improvement of the durability of rubber manu-factures [137]. Thus, research into new carbofunctional siliconorganic oligomers as modifiers of industrial polymer composites and as intermediates in the creation of new thermal-stable synthetic materials has not declined and requires further development.

5.1.1. Synthesis of Aminohydroxysiloxanes Based on Carbofunctional Oligosiloxanes with Terminal and Side Epoxy Groups We have synthesized new silicon-organic polyfunctional oligosiloxanes with terminal and side epoxy groups and aminohydroxysiloxanes based on them [138]. For obtaining the organo-siloxane aminohydroxysiloxanes, as the

Organosilicon Carbofunctional Polymers…

125

initial compounds we used organosilicon diepoxide described by the scheme 5.1.

Scheme 5.1. Silicon-organic diepoxide.

The epoxides with side epoxygroups we synthesized according to the scheme 5.2 [139]. The oligomer 2 was obtained at 900C in Ar media in presence of the sulfocationit catalyst CU-23 [132] (the side low molecular dimethylcyclosiloxanes were removed in vacuum, p=0.27 kPa, at temperature 120-1300C).

Scheme 5.2. General scheme of the hydrosilylation reaction of the oligohydridsiloxane with the allylglicidil.

The given values of n and m of the oligomer 2 were obtained by choice of the corresponding conditions of the reaction and the molar ratio of organocyclosiloxanes and epoxy-siloxanes [140]. Based on the NMR 1H spectra of the oligomer 2, the ratios of Si–H and dimethylsiloxy groups were established. By using the ratios and taking into account the oligo-mers MM the values of n and m were determined (n≈5, m≈25) [140].

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The oligosiloxaneepoxide – oligomer 3 (Scheme 5.2, Table 5.1) we obtained at tempera-ture 800C in presence of the Speier’s catalyst (a solution of H2PtCl6 in dry isopropanol). The study of the oligomer 2 and oligomer 3 (Scheme 5.1) by GPC method (The GPC method was performed on the liquid gel-penetring chromatograph “Knauer”, column Lichosorb Si-60 and Si-300, toluene or methylethyl ketone, 1 l/min) showed that for these oligomers the unimodal (monomodal) MM distribution is characterized (Figure 5.1). There were not observed the anomalous changes of MMD of the resultant product of hydrosilylation reaction (oligomer 2) that excluded any type of side reactions in the choised conditions [140]. The resultant products are slightly viscous, optically transparent (in visual area of the spectra) liquids soluble in usual organic solvents (benzene, toluene, acetone, etc.) and practically insoluble in water. IR spectra were obtained from KBr pellets, using UR-20 (Karl Zeis®) spectrophotometers and a Nicollet Nexus 470 machine with MCTB detector. NMR spectra were obtained with an AM-360 (Brucker®) instrument at an operating frequency of 360 MHz using CDCl3 as a solvent and tetramethylsilane as an internal standard.

w eluent, ml Figure 5.1. The GPC curves for oligomer 2 (a) and oligomer 3 (b).

In the IR spectra the maximums of the absorption related to Si–O–Si, Si– Me, C–O–C and to epoxy groups (1060-1080 cm-1, 990-1000 cm-1, 1160cm-1, 1250 cm-1, 1430 cm-1, 920 cm-1), correspondingly, have been found. The composition and structure of the obtaining compounds were confirmed based on the data of elemental, functional, IR and NMR spectral analysis (Table 5.1) [140].

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127

In the NMR 1H spectra of the oligomer 3 there was found the resonance signals with the chemical shifts in range of 0.5, 1.5, and 3.4 ppm for protons H(2)-H(5), correspondingly, confirmed the obtaining of the Si–CH2 and – CH2–CH2-fragments [33, 132]. At the same time, the signals with chemical shifts 5.5 ppm and 6.0 ppm related to protons of Si–H, CH2= and CH= groups (AGE), disappeared. The signals with chemical shifts 2.6 ppm and 3.1 ppm are related to protons of the epoxy group. In the NMR 13C (method INERT) spectra of the oligomer 3 one can observe the positive signal with chemical shift 51 ppm which is related to protons of the CH2-group of the epoxy groups, while the signal related to the –CH– group of the epoxy group (c.s. 44.5 ppm) underwent inversion (Figure 5.2 a). The NMR 13C spectrum (HETCOR) of the oligomer 3 is given below (Figure 5.2 b). Table 5.1. Some data on the synthesized oligosiloxane epoxides MM, Ebul.

k . 10-2 *** min. -1*

15,34/15,47

360**

–

7,18/7,46

29,75/31,09

020

–

2,86/3,06

18,75/19,92

3045

1,46

Oligomer

Yield, %

Epoxygroup, % Found Calc.

1

62

23,81/23,76

3

60

4

84

*

Si, % Found Calc.

4

93

2,97/3,06

19,51/19,92

2890

2,40

5

82

2,47/2,71

16,15/17,66

3480

4,31

5*

90

2,63/2,71

17,23/17,66

3250

7,68

4

/

95

1,45/1,56

19,10/20,25

5920

–

5

/

92

1,27/1,36

16,85/17,81

6700

–

** Criosc. *** Rate constants of co-oligomer.

The content of the active hydrogen in Si–H (experimental – 0.18%, theoretical – 0.22%) confirm that the hidrosilylation process is not carried out completely (until 100 p.c.). The observation in the IR spectra of compound 3 of the weak maximums of the absorption at 2100-2110 cm-1 indicates on the existence of an insignificant amount of the residual Si–H groups [140]. We carried out the cooligomerization of compound 1 (Scheme 5.1) with 1,3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane (A3) and 1,3,5-trimethyl-1,3,5trifluoropropylcyclotrisiloxane (F3) to obtain oligoorganosiloxane diepoxides

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with phenyl and fluoroalkyl radicals at the silicon atoms. The reaction was condacted in presence of the initiator STMA (5·10-2 mol/l) at 800C. As the result of the reaction, the oligomers of the following structure were obtained:

(a)

δ, ppm

(b)

δ, ppm Figure 5.2. NMR 13С spectra (method INERT) (a) and HETCOR (b) of the oligomer 3 (Scheme 1.2).

Organosilicon Carbofunctional Polymers…

129

, where: R=C6H5-, n≈20 (4,4*); n≈40 (4/); R=CF3CH2CH2-, n≈20 (5,5*); n≈40 (5/); (4* and 5*were obtained in the presence of 1.0 mass % of DMFA). Scheme 5.3. Product of the co-ologomerization of the oligomer 1 with various cyclotetrasiloxane (A3 and F3)

Figure 5.3. Dependence of the value of specific viscosity of cooligomerization products of diepoxy compound 1 with A3 (1) and F3 (2), correspondingly, without the addition (a), and with addition of 1 wt % DMFA (b) (n≈20).

Figure 5.4. Dependence of the organocyclosiloxane conversion, S, on time at cooligomerization of oligomer 1 with A3 (1) and F3 (2) without additive (a) and with addition of 1 mass % DMFA (b) (n≈20).

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Figure 5.5. Change of MMD of the products of the cooligomerization of A3 with oligomer I (Initiar STMA) in presence of DMFA 1 mass. %; n=40; the reaction time is 0.5 hr (1), 1 hr (2), and 3 hrs (3)

From the figure 5.3 it is evident that the corves of dependence of the value of specific viscosity ηsp on the time have an extreme character: in the begining, the ηsp increases and reaches the maximal value for 30-40 min at the organosiloxane conversion of 94-95% (Figure 5.4), the value is kept constant for 4.5 hrs for the oligomer 4, and 6.0 hrs for the oligomer 5. After that, the ηsp decreases till certain constant value (Figure 5.3a). It was found that the activity of STMA is increased in the presence of small amount (1 mass %) of dimethylformamide (DMFA) (Figure 5.3b). The study of the cooligomerization reaction of A3 with oligomer 1 in presence of DMFA by the GPC showed that the bimodal MM distribution in the reaction mixture is characteristic for the whole course of the process (Figore 5.5). One maximum corresponds to the low molecular methylphenylcyclosiloxanes and the initial diepoxy compound 1. In the course of the reaction, the maximum decreases. The second maximum corresponded to the cooligomerization products, in the course of the reaction increase. The ratio of Mw/Mn for the cooligomeric component is approximately equal 2 both in the course of the reaction and at the reaction end. For example, for the oligomer 4/, Mw = 12.686, Mn = 5.920. This is characteristic for the products of the equilibrium cooligomerization reactions of organocyclosiloxanes at the significant input of the interchain interaction as it was found by us earlier in case of cooligomerization of D4 with diepoxy compound 1 (Scheme 5.1). Based on the GPC

Organosilicon Carbofunctional Polymers…

131

data of the reaction products of A3 with diepoxy compound 1 it was established that at using a small addition (1 mass %) of the polar solvent like DMFA the content of the low molecular products is 7-12%, while at conducting the cooligomerization reaction without the additive, the content is higher, 16-18%. We carried out the reactions of diepoxy compound 1 with hexylamine (HA), cyclohexylamine (CHA), piperidine (PP), and piperazine (PAz) (Table 5.2, oligomers 6-9):

Scheme 5.4. General scheme of the interaction of oligomer 1 with various amines.

Table 5.2. Yield, MM values, and the elemental analysis data of organosilicon oligomeric aminoalcohols (3, 6-14) Oligomer №

Yield, MM Si, % % Criosc. Found

6

90

580

9,85 10,02

7

86

570

10,10

Calc.

N, %

Oligomer

Found № Calc. 4,52 10 4,96

Yield, MM % Ebul.

Found Calc.

26,04 26,45

1,72 2,06

26,30 26,49 Didn’t 26,42 deter 26,77

1,75 2,06

3450 3400

4,65 5,26

11

84

N, %

Found Calc.

88

9,95

Si, %

8

92

570

10,48 10,52

4,80 5,28

12

86

9

91

540

10,59 10,48

10,22 10,48

13

90

3500

26,15 27,09

1,82 2,11

–

–

–

14

85

3475

26,28 27,00

3,92 4,22

–

–

1,91 2,09

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It was established that interaction of oligomer 1 with the aforementioned amines, when the amines are in excess, results in formation of the corresponding products of the α-attachments. It is in a good accordance with the results of the spectroscopic investigations of the obtained organosilicon aminoalcohol structures [ ], shown below (compounds 7 and 8): 13 12 11 10 9 8 7 6 5 4 3 2 [CH3CH2CH2CH2CH2CH2N(H)CH2CH(OH)CH2OCH2CH2CH2SiMe2]O

(6)

(7)

(8)

(9) Scheme 5.5. The structures of the aminohydroxyoligosiloxanes.

The course of the reaction was controlled by the disappearance of the resonance signals of the epoxy group protons (c.s. 2.4 ppm and 2.9 ppm) in the NMR 1H spectra. The composition and structure of the organosilicon aminoalcohols were determined based on the elemental and functional analysis (Table 5.2), IR and NMR spectra (Tables 5.3a and 1.3b). The determined experimentally content of the titrated nitrogen corresponded to its calculated values (Table 5.2). By interaction of HA, CHA, PP and PAz with oligomer 3 the corresponding aminohydro-xysiloxanes are formed with a high yield (85-90%) (Scheme 5.6 a):

Organosilicon Carbofunctional Polymers…

133

+amine↓

, 13 12 11 10 9 8 where: n≈5, m≈25 R’=CH3CH2CH2CH2CH2CH2–, R=H (10);

Scheme 5.6a. General scheme of the interaction of oligomer 3 with various amines.

In case of the cooligomerization of oligomer 9 with D4, A3 and F3 the corresponding aminohydroxysiloxanes are obtaining according to the general reaction Scheme 6.6 b):

+PAz ↓

+OCS ↓↑

, where: R=Me, n≈18 (15,15*), n≈38 (16,16*); R=C6H5, n≈18 (17,17*), n≈38 (18); R=CF3CH2CH2-, n≈18 (19,19*), n≈38 (20); OCS=D4, A3 and F3; (16*, 17* and 19* are formed in the presence of DMFA 1 mass %). Scheme 5.6b. General scheme of the cooligomerization of aminohydroxysiloxanes with various organocyclosiloxanes.

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By the comparison of the data of NMR COSY, HECTOR 2D spectra (Figure 5.6a and Figure. 5.6b) NMR 13C (method INERT) (Figure 1.6 c) with the data of the monoresonance of NMR 1H and NMR 13C (Tables 5.3a and 5.3b, Figure 5.7), it is possible to determine the structure of the synthesized oligosiloxane aminalcohols with a sufficient accuracy (Scheme 1.4) To illustrate the use of the aforementioned methods we discuss the structure determi-nation of oligomers 6 and 7. The existence of the hexyl and cyclohexyl groups [signals with c.s. 13.5 ppm, 23-30 ppm and 25-32 ppm (NMR 13C), the signals with c.s. 0.8-1.8 ppm (NMR 1H)], related to –CH2 groups at the silicon atom, also the hydrogen and carbon atoms, connected with nitrogen atoms (signals with c.s. 1.8 ppm and 4.48 ppm), confirms the reliability of the assumed above structures. Besides, the NMR 13C spectrum (INERT method) (Figure 5.6c) showed both positive signals for the methylene groups (Table 5.3b) and the inverted, for the methin (6) groups, which, in turn, are easily detected in the experiment HECTOR at c.s. 66.7-66.9 ppm. It can be considered as the additional data for the identification of the synthesized compounds [141].

(a ) δ, ppm

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135

(b) δ, ppm Figure 5.6. (Continued)

(c) δ, ppm Figure 5.6. NMR 13С (method INERT) (a) NMR COSY (b) and HETCOR (c) of the oligomer 9 (Scheme 1.5).

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(d) δ, ppm Figure 5.7. NMR 13C spectrum of the oligomer 9 (Scheme 1.5).

Table 5.3a. Parameters of NMR 1H spectra of oligomers 6-14* (solvent CDCl3) Oligomer H(2) 6 0.5 7 0.5 8 0.5 9 0.5 10 0.5 11 0.5 12 0.5 13 0.5 14 0.5

Chemical shift, δH* (ppm)* for H H(3) H(4) H(5) H(6) H(7) H(8) H(13) 1.5 3.2 3.4 3.5 2.58 1.4 0.9 1.6 3.2 3.3 3.1 2.58 2.3 1.6 3.2 3.3 3.0 2.58 2.3 -1.6 3.2 3.2 3.1 2.58 2.2 -1.4 3.1 3.2 3.4 2.58 1.4 1.6 3.0 3.1 3.3 2.58 2.3 0.85 1.5 3.0 3.3 3.1 3.60 3.0 -1.6 2.8 3.0 2.9 2.58 2.5 -1.6 2.9 3.0 3.0 2.58 2.5 --

OH 3.9 3.6 3.7 3.7 3.8 3.6 4.2 3.7 3.6

NH 2.21 2.21 2.20 2.10 2.10 2.00 2.75 2.20 2.10

* δH (ppm):H(9)-H(12)–0.9-1.5(6,10); H(9)-H(11)-0.8-1.8(7,11);H(9)-H(10)-1.5-1.63 (8,13); H(9)-1.6-1.65 (9,14). H(9)-H(11) –6.6-7.2 (12). H(9)-H(12) –0.9-1.5.

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Table 5.3b. Parameters of NMR 13C spectra of oligomers 6-14 (solvent CDCl3)

С(2)

С(3)

Chemical shift δС (ppm)* for С С(4) С(5) С(6) С(7)

13.8 14.0 13.7 13.6 14.0 14.0 14.5 13.7 13.6

23.7 23.5 23.5 23.5 23.2 23.5 23.5 23.5 23.5

72.0 73.3 73.1 72.9 71.8 72.4 73.5 72.9 73.3

Oligomer

6 7 8 9 10 11 12 13 14

74.0 74.3 74.2 74.3 74.3 74.5 74.3 74.5 74.5

68.0 66.9 68.0 67.8 68.5 67.2 69.8 67.8 67.6

57.5 57.8 57.7 57.8 61.0 57.2 58.0 57.5 57.6

С(8)

С(13)

32.1 47.8 47.5 47.7 31.6 47.2 47.2 47.5 47.5

13.4 ------13.6 ---------

* δC(ppm.):C(9)-C(12) –23.6-30.0(6,10); C(9)-C(11)-25.0-32.0(7,11);C(8)-C(11)118.2--147.6; C(9)-C(10)-26.5-28.5 (8,13); C(9)-27.8-28.2 (9,14); Si-CH3 δ 0,10.15.

The structure of oligomers 10-14 was established analogously to the structures of oligomers 6-14 (Tables 5.3a and 5.3b, and Table 5.4). Table 5.4. Some properties of the organosilicon aminohydroxyoligosiloxanes and co-oligomerization reaction rate constants Oligomer №

n

15 15* 16 17 17* 18 19 19* 20

20 20 40 20 20 40 20 20 40

ηsp 0,031 0,029 0,044 0,043 0,041 0,064 0,045 0,043 0,070

My* 2081 1882 3538 3416 3179 6241 3660 3416 7149

MM Ebul.

N, %

2150 1950 3655 3385 3350 6150 3615 3500 7225

2,65/3,00 2,80/3,00 1,45/1,67 1,65/1,88 1,67/1,88 0,61/0,98 1,48/1,67 1,49/1,67 0,57/0,87

k, min-1

Found Calc.

5 . 10-3 6 . 10-2 – 7,8 . 10-3 15 . 10-3 – – – –

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In the IR spectra of the synthesized aminohydroxyoligosiloxanes the maximum of the absorption (920 cm-1) related to the epoxide groups are absent. In the spectra, it was found the maximums of absorption of the valent vibrations for NH/OH groups (3400-3300cm-1, 4300cm-1). Maximums of absorption of the deformational vibrations of the NH-groups are also found in the area 1570-1620 cm-1. Maximums of absorption at 1100 cm-1 and 1250 cm-1 belong to the valent vibrations of C–N groups in the residues of PPaz, HA and aniline, correspondingly. In IR spectra maximums of absorption at 1260 cm-1, 800 cm-1, 1430-1450 -1 cm , 1270 cm-1 relate to Si–Me, Si-C6H5 (oligomers 4,4*, 4/; 17,17*, 18); C–F (5,5*, 5/, 19,19*, 20). In the IR spectra we also found maximums of absorption at 1115-1120 cm-1 and 1060-1080 cm-1 relate to the C-O-C and Si-O-Si groups, correspondingly [132]. In the IR-spectra of compounds 8,9 and 13,14 along with the maximums of absorption related to Si-Me, C–O–C, Si–O–Si and HO-groups, it was also found the maximums of absorption of the intermediate intensity at 1120 cm-1 related to the valent vibrations of C–N groups of the tertiary nitrogen (oligomers 8, 9, 13 and 14). The out-of-plane deformational vibrations and the deformational vibrations at 740 cm-1 and 690 cm-1, correspondingly, indicate the existence of the single-substituted benzol ring in the oligomer 12. In the IR spectra of oligomers 8 and 13, the absorbency bands characteristic to νNH (1640-1620 cm-1) are absent. In the IR spectra of all synthesized compounds, it was found the absorbency bands at 2900-3100 related to the valent vibrations of the bonds C–H in the alkyl and aryl (phenyl) groups [140]. The obtained data confirm the occurrence of the reaction of amines with oligoepoxy- organosiloxanes, at their significant excess, according to the schemes 2 and 3 with formation of corresponding aminalcohols (6-14). The cooligomerization of D4, A3 and F3 with aminohydroxysiloxanes 9 occurs in conditions of these organocyclosiloxanes with oligomer 1. In this case, the change of ηsp in time has also an extreme character (Figure 5.8a and Figure 5.9a), and the maximal value of ηsp is achieved for 6-8 hrs at the cycles’ conversion 88-92% (Figure 5.9a). At carring out the reaction in presence of DMFA 1 mass % (initiator STMA), the maximal value of the specific viscosity of the reaction mass is achieved for 2.0-2.5 hrs at the maximal conversion of OCS 92-95% (Figure 5.8b and Figure 5.9b). By comparison of the rate constants [140] of the reactions of formation of cooligomers 4 and 4* (Table 5.1) and of cooligomers 15, 15*and 17, 17* (Table 5.4) in presence of DMFA with the situation when the latter (DMFA) is absent, it is clear that in presence of DMFA, the rate constant is significantly

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higher. The fact that molecular mass values of the cooligomer (determined after the careful removal of the law molecular components in vacuum) (Table 1.4) obtained in the absence of DMFA is relatively high, shows that, in these conditions, the process apparently does not reach the equilibrium state. The stage limiting the reaction rate is the failure of the Si–O–Si bond in the initial oligomer [140].

Figure 5.8. Dependence of the specific viscosity of product of cooligomerization of oligomer 9 with A3 (I) and F3 (2) without additive (a) and in presence of DMFA 1 mass. % (b) on time, n=18 (Scheme 5.1).

Figure 5.9. Dependence of the conversion of cooligomerization of oligomer 9 with A3 (I) and F3 (2) without additive (a) and in presence of DMFA 1 mass. % (b) on time, n=18 (Scheme 1.1).

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The synthesised aminohydroxysiloxanes (oligomers 6, 9 and 19) (Schemes 5.5 and 5.6) were investigated as the rubber compound property modifiers. The tested compounds were based on the carbochain elastomers, in particular, synthetic cis-1,4-polyisoprene (SCI-3). The rubber compound had the following composition (in mass parts): SCI-3 -100, technical carbon (carbon black) “P-514”-40.0, sulful-1.2, sulfonamide - 0.75, ZnO – 5.0, “PN6” – 9.0 cumarone-indene resin – 3.0, stearic acid – 2.0, protective wax – 1.0, diaphen “FP”-2.0, modifier 0.5-1.5. The rubber compounds were prepared on the laboratory roll-millat the roll temperature 80±30C. The curing was performed in press at 1430C. The incorporation of oligomeric aminoalcohols 6 into the rubber compound based on SCI-3 (0.5-1.5 mass parts) affects the viscous flow character of the composition (ηm = 39-37 rel. units compared with 45 rel. units for yhe original compound at the additive content 0.5 mass parts, and 33-32 rel. units at the additive content of 1.2 mass parts). The used modifiers also improved such important mechanical and expluatative properties as tensile strength (from 14.6 till 17.0-17.6 MPa), modulus at 300% elongation, f300 (from 4.4 till 5.4 MPa) and heat aging resistance. This is the effect of the inter-structure plasticization. The analogous effect was also found at the use of other silicon-nitrogen containing oligomers, in particular, organosilazasil-oxyarylene ones [142]. The obtained data allow us to assume that the used compounds relate to the group of the so-called multifunctional modifiers. Based on the preliminary investigations, it should be noted that the synthesized oligosilicon aminohydroxysiloxanes with the low n (for example, oligomers 7, 8, 9, Scheme 5.5) can show the bactericidal activity toward some bacteria and the actinomycetes, in particular, Bacillus subtilis, Actinomyces griseus, etc.

5.2. SYNTHESIS AND USE OF CARBOFUNCTIONAL ORGANOSILOXANE CO-OLIGOMERS BASED ON MONOEPOXYDISILOXANE As initial compounds we selected monoorganosilicon epoxides obtaining by hydrosililation of hydrosiloxanes with allylglicidile ether (AGE) in presence of Speir’s catalyst (solution of 10-1 mole H2PtCl6 in isopropyl alcohol) according to the following scheme:

Organosilicon Carbofunctional Polymers…

141

Scheme 5.7.

Organosilicon oligomeric monoepoxides we have been synthesized by catalytic co-oligomerization of various organocyclosiloxanes (for example, octamethylcyclotetrasiloxane (D4, etc.) with (CH3)3Si__O__Si(CH3)2X in accordance with the general reaction scheme 5.8 [143]. The co-oligomerization of the (3-glicidyloxipropylne)tamethyldisiloxane (GPDS) with D4 we carried out at 800С, in presence of the initiator – α,ωbis(tetramethylammoia)oligodimethyl- silanoliat (STMA) with 1% DMF. As it is shown on the Figure 5.2.1a, the value of the specific viscosity (ηsp) of cooligomerization products increase and reaches the maximal during 25-30 min. In this time, conversion of the reaction mixture is 92-95% (by cyclosiloxane, GLC − the chromatography analysis of original reagents and the reaction products were performed by using the device LKhM-80M (Russia), type 2 (the column 3000 x 4 mm, the head – “Chromosorb W, the phase-5 mass % SE-30, and gas-carrier-helium).

Scheme 5.2.8.

The character of the curves ηsp = f(τ) (absence of the maximum on the curves) and the reaching to equilibrium value of ηsp (Figure 5.1) until reaching the maximal conversion by D4 (92-95%) shows that GPDS and D4 have the same reaction abilities [1143].

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The co-oligomerization of (3-methacryloil dioxypropyl-pentamethyldisiloxane (MMPDS) with D4 we have carried out at 600С, in toluene, in presence of initiator sulfocationit gum “CU-23” and stabilizer of radical polymerization. (0.5 weight % of hydroquinone on the100 mass weight of the used metacrylate-siloxane). It was established that the changing ηsp of the product of co-oligomerization in time and conversion of D4 are in simbat dependence [143]. Structures and compositions of the synthesized compounds were established by elemental analysis, and by IR spectral data [ ]. In the IR spectra there were the following absorption maximums: C=C (1610 см-1, 1420 см-1), Si__O__Si, Si__CH3, C__O__C (1090 см-1,1160 см-1 и 800 см-1, 1250 см-1, 11101115 см-1), and epoxy-group (938 см-1) [139]. The content of epoxy- group we have been determined by epoxy number (Table 5.5). The value of n (Scheme 5.8) we have determined using molecular masses of synthesized co-oligomers (Tible 5.2.5). Values of reaction rate constants and some properties of synthesized cooligomers (1-6) are given in the Table 5.2.5.

Figure. 5.2.10. The dependence of the value of the specific viscosity of products of cooligomerization GPDS with D4 on the time in presence of STMA with 1% ДМФА at 800С: 1- n ≈ 13; 2- n ≈ 28; 3- n ≈ 44 (Scheme 5.2).

By the radical co-polymerization (in presence of Benzoil peroxide, at 650С) of the oligomer 4 (Table 5.2.5) with MMA, in molar ratio of initial monomers 1:1(7a), 1:5(7b) и 1:10(7c), we have synthesized their co-polymers. Investigation of reaction products showed that in all cases of co-poly-

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merizatiion the process was carried out with obtaining of amorphous structures [143]. Their glass temperatures are lower than the one for polymethylmethacrylate (PMMA) [143]. Mechanical properties of synthesized copolymers (for example, bending strength, specific impact elasticity) depend on the length of the siloxane fragments. They are worsen appreciably at the appointed number of Si–O-links (in our case, n=44) (Table 5.2.6). Using DTA and TGA analyses methods we studied the termooxidative stability of synthesized co-oligomers. It was established that the mass loss of co-oligomers (Figure 5.2.2, Table 5.2.7) decrease in the following line: Oligomer-4< Oligomer.-5< Oligomer.-6. By the lengthening of the siloxane chain it was observed regular decreasing mass loss of oligomers 4-6 (Figure 5.2.2, Table 5.2.7). As it is shown in Table 5.2.7, synthesized co-oligomers have sufficient termooxidative stability until 3000C. The intensive decomposition of investigated oligomers proceeds higher, then 4000С. Table 5.2.5. Conditions of the synthesis and some physical-mechanical characteristics for oilgomers 1-6 Olig The retio of the initial ocompounds, моль mer Д4 ГПДС ММПДС

MY* The specific viscosity, ηуд

1 2 3 4 5 6

0.022 0.034 0.044 0.023 0.036 0.046

0.030 0.035 0.050 0.030 0.035 0.050

0.010 0.005 0.005 -

0.010 0.005 0.005

1238 2304 3538 1324 2610 3784

k, min-1 Content of the epoxi group, % 9.9x10-2 3.44 1.81 8.6x10-2 1.22 5.7x10-3 4.1x10-3 -

Content of the vinyl group, %

2.05 1.02 0.71

* Ebuloscopy.

It is known from the literature that majority of epoxide resins are the liquids with high viscosity what make difficult their procceding and use. The hardened epoxides have low elasticity and the process of their hardening is exotermic. These shortcomings can be overcome by addition to epoxide resins some siliconorganic oligomers [144-147]. We have investigated the influence of GPDS and of the oligomer 1 on properties of epoxide resin “ED-20”. As a hardening agent we used BF3 (50%solution in diethylenglicole) with the diamindiphenylmethane (DDM) – 5÷15 weight part on 100 weight part “ED-20” (epoxide number, 21.43). It was

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established that the viscosity of the ED-20 in presence of 10÷15 % modifiers (until hardening) was decreased six-eight-fold. Main physical-mechanical characteristics of modified epoxides after hardening was not worsted (Table 5.2.8). Table 5.2.6. Mass loss of oligomers 4-6 at the termooxidative destruction Co-oligomers

bending strength kg/cm2

7а 7b 7c ММА-ММPDS

1550 950 880 1890

Specific impact elasticity kg.cm/cm2 8.4 7.9 5.9 11.5

1

2

100

200

300

3

400 500 600

Figure 5.2.11. DTA curves for the oligomers 4(1), 5 (2) и 6 (3) (Table 5.3).

Table 5.7. Mass loss of oligomers 4-6 at the termooxidative destruction Cologomer 4 5 6

2000С 2.5 2.4 2.2

3000С 7.5 7.4 4.4

Mass loss of the simples, % 3500С 4000С 4500С 17.2 29.8 57.1 16.5 28.5 54.9 8.9 12.6 23.7

5000С 78.8 76.9 46.8

5500С 89.5 86.9 78.0

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Table 5.2.8. Physical-Chemical and dielectrical charactyeristics for modired epoxide compsites The Initial Modifier bending resin agent, g/ strength, on100 kg/сm2 m.p.. ED-20

Relative Dielectrical . lengthening penetrability, at the breakup, e %

Tangence of the angle of the diel. loss потерь, tgd

Specific volume electrical resistance Оm.sm

4.7х1013 4.9х1013 Didn’t determ 5.1х1013 Didn’t determ -‘’The obtained results permit us to suppose that the synthesized modifiers can be used as active diluents for high-viscous epoxide resins using for creation hydrophobic and thermal stable hermetics and covers. They can be also used for manufacturing caulking compounds and penetrating-type composites for radioelectronics and electrotecnics. ED-20 GPDS

5 10 15 Oligomer 5 1 10 15

370 450 440 400 430 420 390

6.3 6.5 7.0 7.0 7.3 8.0 9.0

3.2 3.3/5.5 3.4/6.2 3.6/8.1 3.4/6.6 3.4/6.2 3.6/7.3

0.017 0.019 Didn’tdeterm. 0.024 0.018 Didn’t determ 0.023

5.3. OLIGOSILOXANEEPOXIDES WITH REGULAR SIDE EPOXY GROUPS BASED ON OLIGOHYDRIDE SILOXANES The object of this chapter is to synthesis and transformation of siliconorganic oligo-epoxides diallyl ester of the glycerol bearing glycidile groups at the tertiary carbon atom [144]. Carbofunctional siliconorganic oligomers based on epoxides attract the particular attention for manufacturing several polyfunctional cooligomers with organic-inorganic main chains [144]. One of the useful methods for synthesis of carbofunctional siliconorganic oligomers with terminal and side epoxy groups is the reaction of catalytic cooligomerization of low molecular siliconorganic epoxides with organocyclosiloxanes [145]: For this purpose the octametylcyclotetrasiloxane more then other cycles is used [145]. There are also described in literature the reactions of cooligomerization of siliconorganic oligomers with terminal epoxy groups with the other cyclosiloxanes, for example with 1,3,5-tri-methyl-1,3,5-trifluoropropylcyclotri-

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siloxane and 1,3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane in presence several catalysts [144]. Products of interaction of the aforementioned epoxides with organic amines were used for modification of properties of some rubber compositions based on isoprene and butadiene elastomers. By addition of a little amount of above mentioned polyfunctional silicon-organic oligomers to rubber compositions physical and mechanical properties of vulcanized one have been improved [147]. They also used in combination with some other organic (PE) and inorganic (fluorocontaining) polymers as one of the components for nanohybrids and effective modifiers of properties of some important industrial polymers and polymer composites (organic polyepoxides, rubbers based on carbochain elastomers, phenollformaldehide resins, etc.) [148]. So the elaboration of new carbofunctional siliconorganic oligomers as modifier agents for industrial polymer composites has not decline of actuality and require the further development. Polyhydride addition (polyhydrosilylation) method has been used for the synthesis of polyepoxides. α,ω-dihydrooligodimethylsiloxanes were synthesized by the methods described in ref. 93. 1,3-dihydrotetramethyldisiloxane has been obtained by hydrolysis of dimethylchlorosilane [93]. 1,5-dihydro-1,3,5-trimethyl-1,3,5-triphenyltrisiloxane has been synthesized by reduction of 1,5-dichloro-1,3,5-trimethyl-1,3,5triphenyltrisiloxane with LiAlH4 [93]. 1,5-dihydro-1,5-tetramethyl-3,3diphenyltrisiloxane has been obtained via interaction of (Me)2SiHCl with diphenylsilandiol [89]. The cooligomerization reaction does not secure the obtaining of macromolecules with the regular stucture. For the synthesis of siliconorganic polyepoxides (PEP) with side epoxy groups with the regular stucture of macromolecules we have used the hydrosilylation reaction of α,ω-dihydrideoligoorganosiloxanes and 1,4-bis(dimetylsilyl)benzene with the diallyl ether of the glycerol bearing glycidile groups at the tertiary carbon atom (DAE) described by formula [146]:

Polyhydrosilylation reactions of 1,4-bis(dimethylsilyl)benzene and α,ωdihydrideoligoorganosiloxanes with DAE were carried out in mass and in dry

Organosilicon Carbofunctional Polymers…

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toluene, in the presence of Speier’s (Sp) catalyst (the solution of H2PtCl6 in isopropyl alcohol). The reaction may be presented according to general scheme 5.9. Preliminarily we had studied the following model reaction: (CH3)3SiOSi(CH3)2H + DAE. Heating of the corresponding reaction mixture in the temperature range of 333-353K, in the absence of Speier’s catalyst, showed that the polymerization of DAE or other changes of the structures of the initial compounds did not take place. There did not observe any changes in the IR, NMR 1H and NMR 13C of initial compounds. Content of the double bond of the allyl group and active Hydrogen of the Si–H bond did not change either [145]. CH3

CH3 n CH2

CH

CH2

R

CH2

CH2 +

CH

Si

nH

Si

RX

R

(CH2)3

R

(CH2)3

Si

CH3 RX

R

where

RX = O, C6H4, OSi(C6H5)2O, O[Si(CH3)2O] m R X = OSi(CH3)(C6H5)O, R= O

Sp

R

CH3 Sp

H

Si R

n

(m= 6, 11, 27, 36);

, R = CH3

R = C6H5 CH2

CH O

CH2 CH2

O CH2

CH O

Scheme 5.3.1. The general scheme of the polyhydrosilylation 1,4-bis(dimethylsilyl) benzene and α,ω-dihydrooligoorganosiloxanes.

The process was controlled by determination of hydrogen in Si–H groups for several times [94]. The influence of the structure of monomers with terminal Si–H groups on the reaction rate, yield and on some properties of the obtained polymers has been studied (Table 5.3.1, Figure 5.3.2). By handling the kinetic curves (Figure 5.3.) of Si–H group’s conversion, the reaction rate constants have been determined (Table 5.9). The total reaction order equals to 2.

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The products of the polyhydrosilylation reaction (Table 5.9) are optically transparent viscous liquids or elastic gums (ηsp = 0.26÷0.40) soluble in the toluene, dimethylsulfoxide, N,N′-dimethylformamide, CHCl3, etc. The composition and structure of synthesized polyepoxides were established based on data of elemental, IR, NMR 1H and NMR 13C spectral analyses. FTIR spectra were obtained, from KBr pellets, on UR-20 spectrophotometers (“Karl Zeis”) and on a Nicolet Nexus 470 machine with MCTB detector. NMR 1H and NMR 13C spectra were obtained with AM-360 (“BRUKER”) instrument at the operating frequency of 360 MHz. All NMR 1H and NMR 13C spectra were obtained using CDCl3 as a solvent and an internal standard TMS. The elemental analysis of the obtained compounds was carried out according to the methods described in ref 145.

Figure 5.3.1. Kinetical curves of the hydrosilylation reaction of 1,4-bis(dimethylsilyl)-benzene and α,ω-dihydrideoligoorganosiloxanes with

Organosilicon Carbofunctional Polymers…

149

: 1.- IX; 2.-V; 3.-VIII; 4.- IV 5.- II; 6.-VII; 7.- VI (Table 5.3.1).

In IR spectra were found the maximums of the absorption (990-1000 cm-1, 1020-1060 cm-1, 1250 cm-1, 1410 cm-1, 1430 cm-1, 1445 cm-1, 1600-1605 cm-1) related to Si–O–Si, Si–O–Car, Si–CH2, Si–CH3, Si–C6H5, correspondingly (Scheme 5.3.1). The maximum of the absorption at 918-920 cm-1 is related to epoxy groups []. In NMR 1H spectra of synthesized polymers (Table 5.3.1) one can observe the singlet signals with chemical shifts within the range of δ ≈ 0.05_ 0.44 ppm for protons in methyl group of ≡Si–CH3. In NMR 1H spectra one can also observe two signals with center of chemical shifts at 1.20 ppm and 1.60 ppm, which correspond to methylene protons in Si–CH2 groups. Triplet signals with center of chemical shifts at 0.84 ppm correspond to the methine protons in Si– СH(CH3) _ groups. Multiplet signals with chemical shifts within the range of δ ≈ 7.5-7.6 ppm correspond to the protons of phenyl groups. Signals with chemical shifts δ = 2.7 and δ = 3.2 ppm are related to protons of the epoxy group. In the NMR 13C spectra one can observe the signal with chemical shift 12.60 ppm of carbon nucleas of methylene group in Si–CH2 fragment of ≡Si– CH2–CH2–CH2–O– [145]. The data of elemental and spectral analysis and solubility of the resultant products exclude homopolymerization of DAE under the conditions of the polyhydrosilyation relaction [146]. In according to the classic researches of the polyhydrosilylation reaction of α,ω-dihydrooligodimethylsiloxanes with α,ω-divinyloligo-dimethylsiloxanes are carrying out according to the above given general scheme (Scheme 5.3.1) [146]. At the same time, some other publications informed that both α and β adducts (Products of the hydride addition reaction according to antiMarkovnikov and Markovnikov rule) are obtained [97, 146]. Quantum-chemical calculations of model systems (Scheme 5.3.2) have confirmed the probability of the passing of the polyhydrosilylation reaction according to above mentioned two concurrent directions:

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Nodar Lekishvili, Victor Kopylov and Gennady Zaikov CH3 +H

CH3

Si

Si

O

CH3

CH3

CH3

CH3

CH3 I

H2C

CH

CH2

O

H2C

CH2

CH O

CH2

O

(CH2)3 Si

HC

CH2

O

CH3

Si

CH3

CH3

O

CH3 II

H2C

CH

H2C

O

CH2

HC

O

CH2

O

CH2

CH2 HC

HC CH2

Si

CH3 O

Si

CH3 CH3

CH3

CH3

O

Scheme 5.3.2. Model systems for quantum-chemical calculations for confirmation of hydrosilylation reaction direction.

I

343

10

80.1

0.19

_

II

343

10

96.5

0.22

2.04

1,4-bis(dimethylsilyl)-benzene and α,ω-dihydrooligoorganosiloxanes

Duration of reaction

ηsp*

#

Reaction temperature,K

The yield of products of the reactions

Polyaddition reaction rate constants k•10-3,l•mol-1•s-

Table 5.3.1. Conditions of hydrosilylation reaction of 1,4-bis(dimethylsilyl)benzene and α,ω-dihydredeoligoorganosiloxanes with DAE, volues of reaction rate constants, yield and specific viscosity (1% solution in toluene) of ynthesized polymers

Organosilicon Carbofunctional Polymers…

III

343

151

10

79.2

0.20

_

10

98.7

0.26

1.67

343 IV

V

343

10

97.8

0.31

1.33

VI

343

10

95.9

0.34

3.85

VII

343

10

97.4

0.40

2.50

343

10

95.6

0.41

1.60

343

10

93.7

0.45

1.17

VIII

IX

As a method of quantum-chemical calculation, we used AM1 method; MM2 method was applied to perform optimization of geometry of adducts [98, 99]. The calculation of the heat of formation (ΔHform) of reaction products showed that slightly more probable is the formation of the α-adduct (I) (ΔHIform = –1225.58 kJ/mol) than of the β-adduct (II) (for the product with the structure II, ΔHIIform= – 1211.96 kJ/mol). Due real reactions the both I and II products are obtained. In NMR 'H spectra of real polyhydrosilylation reaction

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products (Table 5.3.1) one can observe the signals with chemical shifts δ=0.84 and δ=1.20, which correspond to β (II) and α (I) adducts (Scheme 5.9) [89].

5.4. SILICONORGANIC POLYEPOXIDES WITH ORGANICINORGANIC MAIN CHAINS OF MACROMOLECULES MODIFIED WITH CHELATES It is known from the literature that the introduction of rigid fragments into main chains of polyorganosiloxanes and polyorganocarbosiloxanes leads to increase of their thermal- and heat resistant stability [21-23]. The modification of the main chain of synthesized PEP was carried out by using the third monomer component, Cu-helates, containing the allyl groups (DAC): CH3 O CH2

CH

CH2

CH2

O O

M

CH

CH2

O CH3

(M = Cu) Scheme 5.4.1. The chelates containing Cu.

Aforementioned chelates have been synthesized by interaction of the salt of corresponding metals with the 4-allyl-2-methoxyphenol (L) in wateralcohol solution at pH=8 according to the general scheme:

Scheme 5.4.2. Reaction scheme for the obtaining of chelates.

Organosilicon Carbofunctional Polymers…

153

Based on data of elemental (Complexonmetry, Table 5.4.1), functional and FTIR spectra analyses the composition and structure of synthesized chelates have been established. In IR spectra (Table 5.4.2) there were found maximums of absorption (1270 cm-1 1660 cm-1, 820-835 cm-1, 1600-1602cm-1, 1000-1010 cm-1, 1380 cm-1, 2890-2950cm-1) related to C–O–Ar, to vinyl group of the allyl group and substituted benzine linkes, also to C–H groups in alkens and alkans, correspondingly [146]. In IR spectra the maximum of absorption for H–O-group is absent. Maximums of absorption, within the range of 428462cm-1, related to M–O bonds in coordination compounds [146]. We also synthesized chelates containing Fe, Mn and Co [146] Polyhydrosilylation ractions of α,ω-dihydrideoligoorganosiloxanes and 1,4-bis(dimethylsylil)- benzene with DAE and DAC were carried out (in presence of Speier’s catalyst) in two stages according to the general scheme 5.4.3. Table 5.4.2. Data of the complexonmetric analysis for synthesized chelates Chelates L-Cu-L

H

Found, % C M

H

5,55

63,04

5,83

14,24

Calculated, % C M 62,99

14,4

* L-ligand.

Table 5.4.3. Maximums of absorption for synthesized chelates Maximums of absorption, cm-1 δas δas δs ν(MO) ν ν ν Chelates ν (C=C) (CH) (CH) (C"C) (C−O−C) (CH3) (CH3) coordin. L−Cu−L 1635

3020

910

1606

1041

1458

1373

455

* L-ligand.

Terpolymers are colored elastic gum-like or hard products. Their solubility in ordinary organic solvents (benzene, toluene, acetone, etc.) is limited in consider with non-modified (with chelates) polymers. They solved better in CCl4 and practically insoluble in hexane, heptane and water. In FTIR spectra of terpolymers along with the maximums of absorption 1020-1060 cm-1, 1250 cm-1, 1410 cm-1, 1430 cm-1, 1445 cm-1, 1600-1605 cm-1, 990-1000 cm-1, 820-835 cm-1, and 938 cm-1 related to Si–O–Si, Si–CH2, Si– CH3, Si–C6H5, C–O–Ar groups, substituted benzine linkes and epoxy groups,

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correspondingly (Scheme 5.6). In IR spectra Maximums of absorption related to M–O bonds (Table 5.4.4) were also found.

Scheme 5.4.3. Polyhydrosilylation reaction scheme for α,ω-dihydrooligoorganosiloxanes and 1,4-bis(dimethylsylil)benzene to DAE and DAC.

Wide angle X-ray scattering (WAXS, Figure 5.4.1), Differential Scanning Calorimetric (DSC) (Figure 5.4.2), DTA and TGA (Figure 5.4.3) methods, synthesized polymers have been investigated. Wide-angle X-ray scanerring (WAXS) diffractograms have been obtained by DRON-2 instrument (“Burevestnik”, Saint Petersburg, Russia). Cu Kα was measured without a filter; the motor angular velocity was ω ≈ 2 deg.min-1. Differential scanning calorimetric (DSC) study was performed on a Perkin-Elmer DSC-7 apparatus. Thermal transitions including glass transition temperatures Tg were taken as the middle point of the falls.10 [89, 97]. The heating and cooling scanning rates were 10K.min-1. The column set comprised 103 and 104 Å Ultrastyragel columns.

Organosilicon Carbofunctional Polymers…

Figure 5.4.1. X-Ray patterns for polymers: curve 1.- II; curve 2.- V; curve 3.- IV; curve 4.- VII (Table 5.9).

(a)

(b) Figure 5.4.2. (Continued)

155

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Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

(c)

(d)

Organosilicon Carbofunctional Polymers…

157

(e) Figure 5.4.2. DSC curves for the polymers: a.-I; b.- III; c-IV; d.-V; e.- Polymer V modified with Mn-containing chelate (Table 1) [146].

It was established (by WAXS and DSC methods) that they are amorphous substances (Figures 5.4.1 and 5.4.2). On DSC curves (Figure 5.4.2) one can see endothermic transitions corresponding to the glass transition temperatures (Tg). It was shown that introduction of rigid chelate fragments into the main chain of silicon-organic polyepoxides increases glass transition temperatures. Thermogravimetric and differential-thermal analysis (TGA and DTA, figures 5.4.3a, b, c) was performed on a Derivatograph (“Paulic, Paulic & Erdey”) at heating rate 10K.min-1. The investigations showed that the synthesized polymers could be successfully used as modifiers of industrial organic polyepoxides for creation of thermally stable and hydrophobic polymer glue, coating and composite materials [147-156]. Based on the synthesized siliconorganic polyepoxides as substrates (in presence of hardening agent) and 0.1-1.0 ℅ biologically active arsenic (scheme 5.4.3a) and thienyl-containing organometallic compounds (Scheme 5,14b), new polyfunctional antibiocorrosional covers with control terms of actions have been elaborated [148].

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(a)

(b)

(c) Figure 5.4.3. DTA and TGA curves for the polymers: a. - IV; b.-V; c. – Polymer IV modified with Mn-containing chelate [146].

Chapter 6

THE TRADITIONAL AND NONTRADITIONAL APPLICATION AREAS OF THE DESCRIBED ABOVE POLYMERS WITH INORGANIC AND ORGANO-INORGANIC MAIN CHAINS 6.1. USE OF CARBOFUNCTIONAL POLYMERS WITH TERMINAL EPOXI GROUPS 6.1.1. Ammohydroxysiloxanes with Terminal Double Bonds for Rubber Composites and Solidifiers of Epoxy Resins Reaction of epoxysiloxanes (a) and diepoxysiloxanes (b) with allylamine was carried out analogically as it is described in the Scheme 6.1: The compound E (Scheme 6.1) was placed in a quadruple neck flask at room temperature. The calculated amount of amine in alcohol solution was added to the flask drop-by-drop. The mixture was heated to 45-500C and the synthesis was continued till completion of the reaction. The solvent and the unreacted compounds were removed by vacuumizing at 60°C and residual pressure of 266 Pa. The characteristics of the obtained aminohidroxyepoxides (21 and 22) are given in the table 6.1.

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a)

(E) +allylmine ↓

(AE)

(DE)

b) +allylamine ↓

(ADE), where X is the rsidue of the allylamine. Scheme 6.1. General scheme of the interaction of EP with allylamine.

l,3-Bis[3-(2-hydroxy-3-allylaminopropoxy)propyl]tetramethyldisiloxane (23) and 1,3-Bis-{3[-2-hydroxy-3-(dimethylbuthylaminoethylamine) propoxy]propyltetramethyldisiloxane (24) were obtained according to procedure described in ref.149. The elemental composition and MM of synthesized compounds correlated with the calculated ones [150]. Table 6.1. Synthesized allylaminohydroxysiloxanes, their yield and coefficient of the refraction Yield, %

nD20

(3-Allylaminopropanol-2oxypropyl)tetramethyldisiloxane

96

1.4412

Bis[(propanol-2oxypropyl)tetramethyldisiloxane]allylamine

97

1.4478

№

allylaminohydroxysiloxanes

21 22

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161

Table 6.2. Rate constants k1 and k2 of reactions of compound EP with allylamine (Calculations were performed according to [149]) A

I:A

[P1]

[P2]

I0

A0

CH2=CH– CH2NH2

1:4 1:1 2:1

93 65 5

7 35 95

0.4 0.7 0.7

1.68 0.66 0.37

k1 k2 xl0-1 I/(mol x sec) 12.2 3.63 12.2 3.63 12.2 3.63

The reaction of compound E with allylamine was performed at molar ratio of original regents 1:1, 1:4 and 2:1. It was found that in the reaction products were compounds both mono-additions (IV) and di-addition (V): (Here and further in the text the numbering of the carbon atoms in mono- and di-addition products is the same).

Scheme 6.2. Structures of products of the interaction of the allylamine with the EP.

In theTable 6.2.there are given the parameters of 13C NMR spectra of compounds EP, DEP (Scheme 2.1), 21-23. The signals corresponding to C(8)C(12) of compounds 21-23 are witnessing the reaction occurring to the scheme 6.2. Table 6.3. Parameters of NMR 13C spectra of ontained compounds 21-23. (Solvent in CDCl3) Compounds 21 22 23

C(1) 2.0 2.0 -

C(2) 0.3 0.3 0.8

Chemical shift δC, ( ppm) for atoms C(4) C(5) C(6) C(7) C(8) C(9) 14.5 23.6 74.1 74.2 69.1 52.5 14.5 23.6 74.4 73.7 68.8 52.0 14.6 23.9 74.3 73.6 68.9 52.4

C(11) 137.4 135.9 137.2

C(12) 115.5 117.3 115.8

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In a general view, the reaction between allylamine and compound E (Scheme 1.1) can be described as a two-step process occurring according to Eqs (1) and (2) and the reaction with allylamine (A) with compound E occurs as a one-step process according to Eq (1): A + E → P1

(1)

P1 + E → P2

(2)

where: A - allylamine, P1 and P2 - the reaction products. The values of k1 and k2 are given in Table 6.2. For the parallel-consecutive two-steps reaction [151], the ratio of the first to second step process rate constants x were calculated. From the ratio x = k1/k2 the values of constant k were calculated (Table 6.2). In the IR spectra of synthesized compounds there is no maximums of absorbtions 3060 and 915 cm-1 corresponding to epoxy group. However, an intensive peak at 3400 cm-1 appears. This band corresponds to OH/NH groups. It was shown earlier, that during cooligomerization of organo-cyclosiloxanes with carbo-functional disiloxanes in presence of DMFA the rate of siloxane ring opening is increasing and the content of low molecular products and linear short-chain oligomer reduces at achieving the approximate constant value of ηin [144]. The cooligomerization of octamethylcyclotetrasiloxane (D4) with compound 23 and compound 24 we carried out with addition of DMFA according to the following scheme: [RR′NCH2(OH)CH2O(CH2)3Si(CH3)2]O + [(CH3)2SiO]4 → RR′NCH2CH(OH)CH2O(CH2)3Si(CH3)2JO[Si(CH3)O]nSi(CH3)2(CH2)3OC H2CH(OH)CH2NRR′, where: n=40, R= CH2=CH–CH2–, R′ = H (25); R=R′ = (CH3)2C=N(CH2)2 (26). Scheme 6.3. Scheme of the interaction of octamethylcyclotetrasiloxane with l,3-Bis[3(2 hydroxy-3-allylaminopropoxy)propyl]tetramethyldisiloxane (23) and 1,3-Bis-{3[-2hydroxy-3-(dimethylbuthylaminoethylamine)propoxy]propyl}tetramethyldisiloxane (24)

The Traditional and Nontraditional Application Areas…

163

Table 6.4. Composition and properties of co-oligomerized compounds 25* Compo- Initial [η] und compounds 25 *

D4 23

MM** Calcul. Found.

0.041 3288

4600

ηin

N, %

OH, %

Calcul. Found Calcul. Found 0.041 0.85

0.91

1.03

1.14

Co-olgomensation was performed in presence of initiator STMA (0.1 mass % and DMFA-1.0 mass %. **Calculaled according to ref. 24.

At cooligomerization of D4 with compound 23 and compound 24 initiated by STMA with addition of DMFA at 80 0C the conversion of D4 reaches the maximum (94-96 %) for 3.5 and 2 hrs correspondingly. The rate of D4 consumption till the conversion of 50-60 % can be described by the first order equation and is equal to 8.5, 2.77 and 7.2 x 1O-4/sec correspondingly. It must noted that at the cooligomerization of D4 with compound 23 the ηm reaches maximum value after 3.5 hrs and keeps the level for more than 40 hrs. The molecular mass, hydroxyl group content and content of titrated nitrogen were determined for compound 23 after removal of the low molecular components. The MM was determined by the ebullioscopy method. The increased MM value of compound 25 could be connected with presence of oligomeric alcohols forming by the reaction of the secondary end amino groups. The advantage of synthesized organosilicone compounds with amino groups on molecule ends was shown before [140]. However, when we used nphenylene diamine derivatives (n-PDA) polymerized by dihydroquinoline (DHQ) or their combinations it was found their significant volatilization and leaching front compounds. Besides, they have an ability to initiate heat aging destruction of cured rubbers at high temperatures. Rubber compounds based on non-polar unsaturated elastomers of general type were prepared in an internal mixer (volume 2 liters) in two stages. The discharging temperature of the first stage was 145-1500C. Mixing time was 4 min. Some of synthesized compounds with terminal double bonds were incorporated into rubber mix together with curing agents on roll-mill at 60650C for 8 min. The sample curing was done in a steam press at 143±10C for 45 min. The sample tests were performed at room temperature both original samples and samples after heat aging at 1000C for 96 hrs. We have found that incorporation of compounds 23 and 25 into isoprene rubber com-pound significantly improves tensile and fatigue properties and heat aging resistance (Table 6.4).

164

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov Table 6.4. Physical properties of vulcanized composites containing compounds 23 and 25

Parameters Mod. at 300% elongation, MPa: at room temp. Tensile Strength MPa: - at room temp. - after heat aging* Elongation at break, % - at room temp. - after heat aging* Fatigue life, cycles** *

Control compound

Compounds 28 9.0

4.4

26 5.1

14.6 9.5

16.3 14.4

22.9 18.3

660 350 136.8

690 511 219.7

545 370 185.9

Heat aging conditions: 100 0C, 96 hrs. Repeated stretching at ε=100% after sample aging at 100°C for 96 hrs.

**

It is seen that tensile strength of compounds modified with aminohydroxysiloxanes is much higher compared with control compound without any modifier. Especially, this is noticeable after heat aging. The tensile strength retention after heat aging for modified compounds is in a range of 80 to 88% compared with 65% for control compound. The same picture is with elongation at break. The parameter retention after heat aging for modified compounds is 68 to 78% while it is only 53% for the control compound. Fatigue life is one of the most important properties at tire compounds. We can see from data in Table 2.4 a significant advantage (1.4 to 1.8 times) of the modified compounds over the control compound on the property. We have found another application for the modifiers-coating of commercial buildings floors. The coating was prepared in the following way: a block-copolymer of ethylene oxide and propylene was added to water, the mixture was stirred until copolymer was dissolved completely. Then, the epoxydiene resin, ED-20 was added to the obtained solution. The mixture was dispersed by stirring at 1000-1500 rev./min for 15-20 min. To the obtained emulsion the modifier compounds were added immediately before the acoating application. The last ones undergo numerous washing with water and different cleaning products. To increase the hydrophobicity of the floors and their resistance to synthetic cleaning products (SCP), the compounds 23 and 26 were added to a polymer composition of the floor coating (ED-20, active diluent – glycidyl ethers of the higher isomeric acids, keto-imine solidifier).

The Traditional and Nontraditional Application Areas…

165

The coating test results are shown in table 2.5. It is seen that the new compositions are characterized by higher hydrophobicity, lesser water absorption and enhanced resistance to action of the SCP. At the same time, the strength properties of the new composition are the same as the ones of the control composition without modifiers. Some physical and mechanical properties of the vulcanized based on “SCI-3”, shown in Table 6.5, confirmed the fact that such kind of modification leads to improving of their most valuable properties, in particular, including fatigue life and resistance to the heat aging [see the analogical systems, ref. 153]. Table 6.5. The floor coating test results Property

Control coating

23

Modifer agent 26

Emulshion stability. Mo

32

32

32

Composition Life, hrs

10

10

10

Sodification time, hrs

24

24

24

Impact strength, N/m - original - after immersion in SCP Flex strengh, mxlO3

5 0,5

5 5

5 5

- original - after immersion in SCP Wettability, 1/sm

1 1 4

1 1 8

1 1 10

Adhesion, rel.units

1

1

1

Wetting angle, deg.

53

78

93

Water absorpt, 24 hr,%

2.5

1.1

1.4

Appearence after immersion in SCP

Dull

Same

Same

6.2. ANTIBIOCORROSIVE COVERS BASED ON CARBOFUNCTIONAL OLIGOISILOXANES WITH SIDE METHACRYLIC GROUPS AND BIOLOGICAL ACTIVE ORGANIC-INORGANIC COMPLEX COMPOUNDS During the first decade of the 21st century a wide assortment of synthetic and natural polymeric materials were produced. At the same time, there appeared various aggressive microorganisms, which can destruct these

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materials [157]. The actions of microorganisms on polymers are influenced by two different processes: a) deterioration and degradation of polymers, which serve as a native substance for growth of the microorganisms (direct action); b) influence of metabolic products of the microorganisms. Losses caused by destruction of natural and synthetic materials with micromycets reach enormous amounts and constitute annually milliards of dollars (indirect action) [158]. One of the ways to protect the synthetic materials from the action of microrganisms is a creation of novel polymer covers with high bioactivity by modification of various polyfunctional adhesive polymer matrixes with biologically active compounds [159]. Use of natural and synthetic biological active compounds as modificating additives unable to firm fixation in polymer matrix. Such polymers are characterized not only by contact [fungistatic] action, as the first ones, but could dosilly extract biological active compounds to environment. The latter is an important factor for guaranteed human protection during its long stay in a closed space [160]. In many regions of the world some diseases of agricultural plants, caused by various phytopathogenic microorganisms, are widely circulated. For example tumors, halles and nodes are formed as a result of intensive division of affected cells of meristem plant tissues. Roots’ and fruit-trees cancers are provoked by - А. tunefacicus; cancer of root crops, beets is provoked by X. campestris pv. beticols etc. These diseases distractively damage plants and significantly decrease harvesting efficiency. They also deteriorate the quality of a grape, water-melons, melons and other agricultural plants [161]. Therefore, synthesis of new compounds as plants’ protectors with high biologically activities, as well as conservators and compounds for antibiocorrosive covers of various natural, synthetic and artificial materials is extremely significant and requires further developments [162]. Antibiocorrosive covers contain two components – biologically active compound and polymer matrix, where the biologically active compound is dropped. Some polyfunctional hetero-chained organic polymers, such are polyurethane elastomers, polyurethane-acrylates, ionomers, etc., has been successfully used as a matrix for creation of antibiocorrosive covers [163]. The polymer matrix for the antibiocorrosive covers may be also obtained based on polyepoxide resins in mass in presence of the active diluents [114]. The use of the organic polyepoxide resins “ED-20” and “ED-26” for creation of the matrix for antibiocorrosive covers did not give the satisfactory results. The obtained covers cracked during the exploitation and turn yellow.

The Traditional and Nontraditional Application Areas…

167

To modify the aforementioned coating material we used silicon-organic oligomers with fluorinealkyl radicals at silicon atoms. These oligomers we obtained by hydrosilylation oligoorganohydridesiloxane (MF-1)14 with perfluorinealkylacrylate (12FA) [165] by formula CH2=CH– C(O)OCH2(CF2)5CF2H in presence of Speier’s catalyst (0.1 mole solution of H2PtCl6 in iso-propanole): nMe3SiO[i-(MeHSi)a(Me2SiO)b(MePhSiO)c]mSiMe3+ mb CH2 = CHC(O)OCH2(CF2)5CF2H Me3SiO[MeSiO)a(MeSiO)b(MePhSiO)]mSiMe3 CH2CH2C(O)OCH2(CF2)5CF2H where: a = 0.3, b = 0.4, c = 0.3; m = 10

Scheme 6.2.1.

In the IR spectra of synthesized compounds together with absorption bands related to SiOSi, SiCH3, SiC6H5, CH3, C6H5 groups(1040-1090 cm-1, 1425 cm-1, 1440 cm-1, 1330 cm-1, 2970 cm-1, 1605 cm-1, 3080 cm-1) there were found absorption bands related to H2C=C (in acrylic groups), C=O (in ester groups) and C–F group (in CF2 groups) (1640 cm-1, 1720 cm-1, 1330 cm-1) [166]. In IR spectra there was also observed a week maximum of absorption related to Si–H group confirmed non-complete (100%) conversion of Si–H groups. The addition of the fluorine-containing oligomers to the composites based on “ED-20” and “ED-26” results the diluent effect, improvement of hydrophobic properties and thermal-stability but the hardening of the aforementioned oligomers, in conditions of their application, is difficult. To make easier of the hardening process of silicon-organic modifiers we have synthesized the new fluorine-containing carbofunctional oligoorganosiloxane with methacrylic groups at silicon atoms (MF-1-AMA-F3) by two stages according to the following scheme: On the first stage we synthesized the comb-type oligosiloxane with side allylmethacrylate fragment (Scheme 2) by the hydrosilylation of the MFA-1 with AMA. The process was controlled by determination of the content of active Si–H groups’ in oligoorganohydridesiloxane in time by the method described in ref. 10. The corresponding kinetic curves were created (Figure 6.2.1). Based on the obtained kinetic curves the reaction rate constant have been determined (k=0.13•10- l.mol-1c-1, T=70°C). The total reaction order equals to 2. In Figure 6.2.1a is shown that hydrosilylation reaction proceeds

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rapidly during the 1-1.5 hours and then slows down. The reaction proceeds at 70°C with conversion about 74-%. The arising of the reaction temperature on 20°C the conversion of the active Si–H groups increased till 80% (Figure 6.2.1).

I. Me3SiO[(Me2SiO)a(SiMeO)b(SiMePhO)c]mSiMe3 H + mb CH2 = CH

CH2

O(O)C

C = CH2 CH3

Me3SiO[(Me2SiO)a(SiMeO)b(SiMePhO)c]mSiMe3 (CH2)3O(O)C

C = CH2 CH3

II. Me3SiO[(Me2SiO)a(SiMeO)b(SiMePhO)c]mSiMe3 (CH2)3O(O)C + nF3

C = CH2 CH3

Me Me3SiO[(Me2SiO)a SiO (SiMeO)b(SiMePhO)c]mSiMe3 R 3n(CH2)3

O(O)C

C = CH2 , CH3

where

R = CH2CH2CF3 a=0.3, b=0.4, c=0.3; m≈10

Scheme 6.2.2. General reaction scheme of obtaining of the oligomer MF-1-AMA-F3.

The Traditional and Nontraditional Application Areas…

169

The synthesized oligomer is viscous liquids soluble in acetone, dioxane, benzene and toluene. The structure and composition of the synthesized oligomer were established by elemental analysis, FTIR and NMR spectral data. IR spectra were obtained from KBr pellets, using UR-20 (Karl Zeis®) spectrophotometers and a Nicollet Nexus 470 machine with MCTB detector. NMR spectra were obtained with an AM-360 (Brucker®) instrument at an operating frequency of 360 MHz NMR spectra were obtained with an AM-400 (Brucker®) and Talsa BS-467 instrument at an operating frequency of 400 MHz using CDCl3 as a solvent and tetramethylsilane as an internal standard [168].

Figure 6.2.1. Dependence of the conversion of Si−H group (a) and reciprocal value of the concentration (b) on time (1.- 700C; 2.- 800C; 3.- 900C) during the reaction of MF-1 with AMA.

Figure 6.2.2. IR spectrum of adduct obtained from the interaction of MF-1 and AMA.

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In the FTIR spectrum (Figure 2) together with the absorption bands (10401080 cm-1, 1440 cm-1, 1450 cm-1, 2930 cm-1, 2970 cm-1, 1605 cm-1) related to Si−O−Si, Si−CH3, Si−C6H5, CH2, CH3 and C6H5 groups, correspondingly, the absorption bands related to C=O, C−O−C and H2C=C groups (1735 cm-1, 1160 cm-1, 1650 cm-1) have been observed. In the IR spectrum was not observed an absorption band for Si–H group. In the 1H NMR spectrum of the hydrosilylation product (Figure 5a) there were identified the resonance signals with chemical shifts 1.92 ppm, 5.40 ppm and 6.99 ppm, related to the protons of the following group:

5.40 ppm H 6.00 ppm

H

C

C CH3 1.92 ppm

In the spectrum one can also observe the resonance signals of phenyl protons with chemical shifts in the range of 7.0-7.6 ppm. There were also observed resonance signals with chemical shifts 1.2 ppm of the methylene groups, 1.1 ppm of the methyl groups and multiplet resonance signal in the range of 4-1.8 ppm related to the methine group. These data confirm a formation of the fragment CH2−CH2 (α) and CH3−CH (β) of feasible derivation of Markovnikov and anti-Markovnikov addition products (Figure 6.2.3a). In the 13C NMR spectrum (Figure 6.2.3b) of the same sample one can observe the presence of the resonance signal with the chemical shift 65.75 ppm related to the protons of the OCH2 group and the resonance signal with the chemical shift 17.71 ppm related to the fragment of CH3 that indicates formation of both (Markovnikov and anti-Markovnikov) products: 21.61 ppm Si

CH2 12.63 ppm

CH2 CH2

O , 18.60 ppm CH3

65.75 ppm

28.95 ppm CH CH2 O 65.75 ppm Si

In the 13C NMR spectrum of the obtained oligomer we have identified four type Si–CH3-contained groups, this is once again proves the presence of α and β adducts (Markovnikov and anti-Markovnikov) [89, 97, 146]. By the ratio of integral intensity of correspond resonance signals we determined the ratio of α and β adducts (39.13 : 60.87).

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171

We have performed calculations by the semiempirical AM1 method for modeling reaction between of oligomethylphenylhydrosiloxane (MF-1) to AMA using software Chem3D [98]. Quantum-chemical calculations were performed on PC with AMD processor with the built-in coprocessor by using Mopac2000 and CS Chem3D Ultra, v8. We gave the following key-words to guide each computation: EF GNORM=0.100 MMOK GEO-OK AM1 MULLIK LET DDMIN=0.0 GNORM=0.1 GEO-OK. 0.82 ppm CH3 CH3

Si CH3

,

0.51 ppm CH3 Si CH2

,

0.15 ppm

1.33 ppm CH3

CH3 Si

,

CH

CH3

Si C6H5

Such calculations for polymethylhydrosiloxane and AMA are not doable since the software does not produce reliable results for systems with more than 100 atoms. Necessarily, numerical values for the model reaction will be different than for the polymers studied experimentally, but they will provide better understanding of the experimental results (Scheme 6.2.3). We consider the hydrosilylation of (CH3)3SiOSi(CH3)(H)SiOSi(C6H5) (CH3)2 with AMA in view of the anti-Markovnikov and Markovnikov rules. According to the model reactions compounds I and II will be obtained (Scheme 6.2.3). The hydrosilylation reaction is considered through the following model reaction:

Figure 6.2.3a. 1H NMR spectrum of adduct of oligomethyl-phenylhydridsiloxane and allylmetacrylate.

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Figure 6.2.3b. 13C NMR spectrum of adduct of oligomethylphenylhydridsiloxane and allylmetacrylate.

(CH3)3SiOSi(CH3)(H)SiOSi(C6H5)(CH3)2 + + CH2=CH–CH2–O–C(O)–C(CH3)=CH2 → β (I) and α (II) adducts CH3 CH3

Si

O CH3

CH3

Si

CH3 C6H5

Si

O

CH3 H + H2 C

CH

CH2 O

C

C

CH2

O

CH3

The activation energy of α-adduct is ΔΔΗ# = 124.8 kJ/mole (RSiC = 2.30 Å), and for β adduct is ΔΔΗ#=114.4 kJ/mole (RSiC = 2.25 Å). In the both cases the combination process is exothermic (ΔΔΗ = -199.3 kJ/mole and ΔΔΗ = 191.2 kJ/mole respectively). The low value of activation energy of β-product indicates the superiority of performing the reaction in this direction. We compare ∆Hf values for compounds of addition taking into account Figures 6.2.4 and 6.2.5. Clearly, hydrosilylation reaction of (CH3)3SiOSi(CH3)(H) SiOSi(C6H5)(CH3)2 to AMA is energetically more favorable according to the anti-Markovnikov rule behind to Markovnikov rule. This result is in good agreement with NMR spectral data.

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CH3 CH3 I

Si

O CH3

CH3

Si

CH3 C6H5

Si

CH3 (CH2)3 O

C

C

CH2

O

O

CH3 CH3 CH3 II C6 H 5

Si

O

CH3

CH3

CH3

Si

Si

O

CH3 CH CH3

CH2 O

C

C

CH2

O

CH3 Scheme 6.2.3. Model system for the calculation of ΔΔΗ# and ΔΔΗ for products of hydrosilylation of MF-1 with AMA.

Figure 6.2.4. Dependence of enthalpy (ΔΗ) on the reaction coordinate (RSiC) for αadduct.

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Figure 6.2.5. Dependence of enthalpy (ΔΗ) on the reaction coordinate (RSiC) for βadduct.

On the second stage we have carried out the catalytic cooligomerization reaction of obtained methacrylate with trimethyltri(trifluorinepropylene) cyclotrisiloxane (in toluene, at 80°C), in the presence of sulfocationit “CU 23“(copolymer of divinylbenzene with styrene – 1.5-2.0 mass %) and hydroquinone (inhibitor, 1.0 mass %). Investigation of the corresponding model reaction (Scheme 4) by CLC method has shown that it is characterized by the establishment of the equilibrium at the room temperature (25°C) during 8 hours. The conversion of the hexametyldisiloxane (HMDS) reaches 50% [169]. By an increase of the temperature till 70°C, the time of the establishment of the equilibrium decrease till 3 hrs. [CH2=C(CH3)-COO(CH2)3 Si(CH3)2] 2O + [(CH3)2Si]2O 2 CH2=C(CH3)-COO(CH2)3 Si(CH3)2-O-Si(CH3)3 Scheme 6.2.4. General scheme of the model reaction.

The value of the specific viscosity of the product of co-oligomerization depends on the molar ratio of MF-1–AMA and cyclosiloxane (Tible 6.2.1) and on the reaction temperature. The corves of dependence of the value of specific viscosity ηsp on the time (Figure 6.2.1.) have an extreme character: in the

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175

beginning, during 2.5-3 hours, the ηsp reaches the maximal value (conversion of the organosiloxane – 80-85%); then it decreases (during 3.0-3.5 hrs) until a certain constant value (Figure 6.2.6, Table 6.2.1).

Figure 6.2.1. Dependence of the value of specific viscosity of co-oligomerization products of MF-1-AMA with F3 (1) at the 800C at the varius molar ratio of initial components: 1.- 1:4; 2.-1:6

Table 6.2.1. The reaction conditions of co-oligomerization of MF-AMA and F3, and some characteristics of reaction products #

Initial substances molar ratio MF-AMA F3

T,°C

Duration of the reaction, hr

ηspec.

Mη*

1 2

1 1

80 80

6 6

0.035 0.028

2523 1784

4 6

1,515. . * Mη = [η 5000]

It must be noted that the value of the specific viscosity of the product of co-oligomerization, in comparison to analogical systems [164], is increasing slowly, which may be connected with the increasing of the spatial (steric) factor at the silicon atoms in MF-1-AMA.

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The obtained co-polymers are colorless transparent or white viscous products soluble in ordinary organic solvents (toluene, dimethylformamide). The composition and structure of synthesized co-oligomers we established by elemental analysis and IR spectra. In the IR spectrum we abserved the absorption bands (1040-1080 cm-1, 1440 cm-1, 1450 cm-1, 1720 cm-1, 1645 cm-1, 2970 cm-1, 1600 cm-1) belonging to Si–O–Si, Si–CH3, Si–C6H5, C=O, C=C, CH3, C6H5 groups. The absorption bands (1170 cm-1, 1270 cm-1) related to CF(CF3) groups were also observed 7. For the synthesized oligomers, we have carried out wide-angle X-ray scattering (WAXS) analysis. Wide-angle X-ray diffractograms have been obtained by DRON-2 instrument (“Burevestnik”, Petersburg, Russia). Cu Kα was measured without a filter; the motor angular velocity was ω ≈ 2 deg.min-1. Figure 6.3.2 shows that the oligomers are amorphous one-phase systems. Diffraction patterns display two maxima. First 2Θ0 ≈ 10.5 corresponds to the maximum of the inter-chain distance d1 ≈ 8.85Ǻ, while the second (2Θ0 ≈ 21) corresponds to d2 ≈ 4.33Ǻ, which characterizes both intra-molecular and interchain interactions 19. By differential-scanning calorimetric (DSC) studies we determined that synthesized oligomers are amorphous one-phase systems (Figure 6.2.3). From analysis of DCS curves it is shown that the incorporation of perfluoromethacrylic radical in the chain of oligomethylphenylsiloxane (MF-1) modified with allylmethacrylate results to the rise of the transition temperature (Tg) on 19°C.

Figure 6.2.2. Wide-angle X-ray patterns of synthesized oligomers: MF-AMA/F3 (1:6), 2. MF-AMA (1:1), 3. MF-1-13FA (1:1).

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177

We studied the thermal-oxidative stability of the synthesized organosiloxane by DTA and TGA analysis methods. Thermogravimetric and differential-thermal analysis (TGA and DTA) was performed on a derivatograph (Paulic, Paulic & Erdey) at the speed of the heating 10Kmin-1. We established that their destruction is starting at 280-290°C. The intensive destruction process proceeds above 450°C. We manufactured antibiocorrosive covers based on the synthesized bioactive compounds, dropped into the aforementioned polymer matrix, for goods from different materials. As biologically active compounds for antibiocorrosive polymer covers and protectors we have synthesized adamantane-containing nitroanilides and new cadmium complex compounds based on them [166]. While selecting nitroanilides and complex-compounds we foresaw their biologically activity and able to form dipole-dipole and hydride bonds with the polymeric matrix. In order to select of these compounds we also considered the availability of their synthesis and possibility of their perspective wide commercialization.

Figure 6.2.3. DSC curves of oligomers: 1. MF-AMA (1:1); 2. MF-1- AMA-F3 (1:1).

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Adamantane-containing (Ad) nitroanilides we synthesized in two stages according to a scheme 6.2.5: O2N

OH NO2

O I.

OH

X

+

Fe / NH4Cl, H2O

arom. solv.

O3 HN

X = Br, OH.

O (a)

O

/

NH2

O

R COCl

NH

O

R/

C

R/ = CH3 (III); R/ = 1-Ad (IV); R/ = Ph (V); R/ = CH2Ph (VI).

R/ O

NO2

R

Fe / NH4Cl, H2O arom. solv.

R/ O

NH2

AdCOCl

R/ O R

R

(b)

NHCO

R = H: R/ = CH3 (I); R/ = C2H5 (II); R = Cl, R/ = y-ClC6H4 (VII).

(A) II.

R/

NHCOR//

O R

HNO3 CH3COOH

R/

NHCOR//

O R

I-VII

NO2

VIII-XIV

R=H, R/=CH3, R//=Ad (VIII); R=H, R/=C2H5, R//=Ad (IX); R=H, R/=Ad,

R//=CH3 (X); R=H, R/=Ad, R//=Ad (XI); R=H, R/=Ad, R//=Ph (XII); R=H, R/=Ad, R//=CH2Ph (XIII); R=Cl, R/=y-ClC6H4, R//=Ad (XIV).

(B) Scheme 6.2.5. Synthesis some adamantane-containing anilides and nitroanilides.

Adamantane-containing anilides were synthesized by the following method: to the benzene solutions of hydrochlorides of initial amines [170] and basic agents (triethylamine, NaHCO3 or NaOH) were added drop-wise benzene solution of the chloroanhydride of various carbonic acids (adamantane-1carboxylic acid, acetic acid, benzoic acid or phenylacetic acid, correspondingly). The mixture was heated and stirred during 1.5-3 hrs. The precipitated

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179

crystals were separated by filtration and washed with H2O; they were dried and physical constants of obtained compounds were determined. The nitroanilides were synthesized by the analogically method [166]: to the solution of adamantane-containing anilides in acetic anhydride and acetic acid was added drop-wise 56-58% HNO3. The mixture was cooled on 5-100C and stirred during 0.5-2 hrs. The reaction mixture was dismissing (by pour out on ice water). The precipitated crystals were separated by filtration and washed with H2O; they were dried and physical constants of obtained compounds were determined. The composition and structures of synthesized compounds (Schemes 6.2.5) were established by using IR and NMR spectral data (Figure 6.2.6a and Figure 6.2.6b, Figure 6.2.6a and Figure 6.2.6b). In the FTIR spectra of obtained compounds we have observed the absorption bands for the next groups: νas N–H (3430-3130cm-1), νas C–H of aromatic rings (3120-3030 cm-1),νasC–H of adamantyl group (2910-2830cm-1), νas>C=O (1670-1640 cm-1), δ N–H, C–N (1540-1500 and 1360-1330 cm-1) and NO2 (1330-1350 cm-1), also νas C–O–C (1270-1230 cm-1). In 1H NMR spectra of the synthesized compounds (III-XVI, Schemes 2.2.4) one can observe singlet signals with chemical shifts within the range 9.01-10.07 ppm for the protons in the NH groups. In spectra we could also observe quartet signals with chemical shifts at 7.30-7.94 ppm, which correspondes to the four protons in phenyl groups. Multiple signals with chemical shifts at 1.57-2.01 ppm correspond to the 15 protons in adamantyl groups. Singlet signals with chemical shifts within the range 3.71-3.83 ppm correspondes to the three protons in the methyl groups (VII, XIV). Singlet signal with chemical shifts 3.60 ppm is attributed to protons of the methylene group (V). In 1H NMR spectra of the synthesized adamantanecontaining nitroanilides (X-XVI) we can observe dublet signals with chemical shifts within the range 7.46-7.51 ppm for the protons C(3)H; the protons C(2)H and C(5)H one can observe in the form of two dublet signals with chemical shifts within the range 7.29-7.65 ppm. Constant of spin-spin interaction J = 2.8 what confirms the substitution of nitro-group in 2-position. In 13C NMR spectra one can observe a signal with a four chemical shifts at 27.6-40.7 ppm typical for adamantyl group, the chemical shifts within the range 55.0 ppm are belonged to the carbon atom of CH3 group (VII); the signals with chemical shifts within the range 165.17-175.57 ppm are corresponded to the carbon atom of C=O groups; the signals with chemical shifts within the range 113.37-155.73 ppm related to the carbon atoms of phenyl groups.

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The synthesized compounds are stable on air white powders insoluble in water and in n-hexane. They are dissolved in chloroform, DMFA, acetone and ethanol [170, 171].

Figure 6.2.5a. IR spectrum of 4-methoxy-N-(1-adamantoyl)anilide.

Figure 6.2.5b. IR spectrum of 4-methoxy-N-(1-adamantoyl)-2-nitroanilide.

The Traditional and Nontraditional Application Areas…

Figure 6.2.6a. 1H NMR spectrum of 4-methoxy-N-(1-adamantoyl)anilide.

Figure 6.2.6b. 1H NMR spectrum of 4-methoxy-N-(1-adamantoyl)-2-nitroanilide.

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For establishment of the direction of the nitration reaction (Scheme 6.2.5) we carried out the quantum-chemical calculations of two probable nitroanilides (Scheme 2.6.6, I and II). As the initial anilides contain several feasible reaction centers we performed series of quantum-chemical calculations to establish the direction of the reaction of nitration (Scheme 6.2.6). Quantum-chemical calculations were performed by CS MOPAC (Chem3D Ultra-version 8.03, method AM1 Austin Model 1) [98]. We also have calculated the heat of formations (enthalpy, ΔHf) and reaction heat effects (ΔHreac.) for probable reaction products. As a model reaction we selected the nitration of 4-(p-chlorophenoxy)-3-chloro-N-(1-adamantoyl)anilide (AH): O Cl O O

Cl

NH

C

O

NH Cl

HNO3

I

NO2 NO2

(b)

Cl

(a)

Cl

O

C

NH

O C

Cl II

Scheme 6.2.6. The model system of nitration of 4-(p-chlorophenoxy)-3-chloro-N-(1adamantoyl)anilide.

The quantum-chemical calculations show that in benzene ring (a) (Scheme 6) the value of effective charges at C(2) and C(6) carbon atom are -0.23315 and -0.20288, correspondingly. During the reaction of nitration the NO2+ group attacks C(2) carbon atom. The results of the calculation show that formation of the product I (ΔHf = -175.60 kJ/mole) is slightly more probable than the product II (Sceme 6.8) (ΔHf = -166.90 kJ/mole)(for the initial anilide [4-(pchlorophenoxy)-3-chloro-N-(1-adamantoyl)anilide] ΔHf = -220.16 kJ/mole). The calculated activation energy of the obtained nitroanilides shows that the minimal activation energy (71.2 kJ/mole) corresponds to nitroanilide obtained by nitration in 2-position (ring a). For position 6 activation energy is 100.8 kJ/mole (Scheme 6.8). We have established that the reaction of nitration of benzene ring (b) has lower probability than the reaction of nitration of benzene ring (a). Activation energies for identical positions in benzene ring (b) are 98.4 kJ/mole and 104.7 kJ/mole, correspondingly. Reaction of nitration in this position takes place

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183

only in rigid condition in comparison with reaction of nitration of benzene ring (a). The synthesized nitroanilides we used as the ligands for manufacturing of the cadmium complex compounds [167]:

where, R = CH3, R/ = J (XV), R = CH3, R/ =Br (XVI); R = C2H5, R/ = J (XVII), R = C2H5, R/ = Br (XVIII). Scheme 6.2.6. General reaction scheme of the synthesis of Cd complex compounds with adamantane-containing nitroanilide ligands.

The composition and structures of synthesized compounds were established based on the data of elemental analysis and FTIR spectra (Figure 6.2.7). In the FTIR spectra together with the following absorption bands – 3448, 3371 (NH), 3090 (CH, Ar), 2928, 2850 (CH, Ad), 1689 (C=O), 1342 (NO), 1265, 1242 (C-O-C), we have observed the absorption bands related to bromate ion (νas 779-810 cm-1) and iodat-ion (νas 745-750 cm-1). In the infrared spectra of the synthesized complex compounds the characteristic frequency υas for nitro groups (1342 cm-1) is splitting on two absorption bands: 1504 cm-1 and 1311 cm-1. We also have abserved the shift of the CO-group absorption band on 10-40 cm-1. That confirms a combination of nitro groups with inorganic (metal-containing) fragments. By using of differential-thermal (DTA) and TGA analysis (Figure 6.2.8) methods we have established that starting destruction process of the obtained complex compounds (Scheme 6.2.5, XIX) proceeds in interval 165-400oC, with 58.4% loss of mass (organic fragments; theoreticaly: 58.7%). The thermolysis of inorganic fragments of the complex proceeds difficultly. Particulary, in the temperatural interval 400-460°C mass loss is 16.6% what corresponds to remuving of the I2O5 (theoreticaly: 16.4%). The endothermic peak at 580°C corresponds to the obtaining of the CdO with the mass loss 9.5% (theoreticaly: 10.0 %).

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Figure 6.2.7a. IR spectra of the 4-methoxi-N-(1-adamantoil)-2-nitroanilide.

Figure 6.2.7b. IR spectra of the bromatocadmiate of 4-methoxi-N-(1-adamantoil)-2.

According the aforementioned process we can suppose that the thermolysis of the investigated samples proceeds from the following summary general scheme:

The Traditional and Nontraditional Application Areas…

RO

NH C

Cd(R/O3)2]

400-4600C - R/2O5

CdO

5800C

...

..

.

O

165-4000C

185

NO2 . . . Cd(R/O3)2

Scheme 6.2.7. General scheme of the thermolysis of Cd-complexes based on adamantane-containing nitroanilides.

Figure 6.2.8 Corves of DTA (a) and TGA (b) analysis of the complex compound based on diiodatocadmiat of the 4-ethoxy-2-nitro-N-(1-adamantoyl)anilide.

We have tested the bactericidal and fungicidal activity of synthesized nitroanilides (Scheme 6.2.5, XV and XVI) and complex compounds XVIII, XIX and XX (Scheme 6.8) [172-177]. To this target we have applied the test-

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microorganisms – Pectobacterium aroideae, Fusarium arenaceum, Autinomyces Griseus and Fusarium proliferate. Bactericidal and fungicidal properties were determined according to the method described in ref. 172. The test results showed that synthesized compounds XVIII and XIX (Scheme 6.2.5) have revealed selected bactericidal properties and have suppressed the development of research cultures. The compounds XVIII and XIX have a relatively high activity towards the bacterium Pectobacterium aroideae, which strikes the melons and gourds and provoke rot. In a case of compound XVIII at concentration 0.01 g/l, the zone of inhibition was 4 mm, correspondingly, whereas for compound XIX, at concentration 0.01 g/l, the zone of inhibition was 7 mm. The compound XX is inactive taword to aforementioned microorganisms, although have reveal weak antifungicidal activity with respect to Fusarium arenaceum, which destroys some synthetic carbo-chain polymers. For this compound, at concentration 0.1 g/l, zone of inhibition was 0.2 cm. For the compound XVIII, at concentrations 1, 0.1 and 0.01 g/l, zone of inhibition toward a same bacterium zone of inhibition was 1 mm. Compounds XVIII and XIX, at concentration 0.01 g/l, have a sufficiently good activity (zone of inhibition were 1 mm and 0.3 mm, correspondingly) towards Pectobacterium aroideae and Act. Griseus. It must note that the bioactivity of the initial nitroanilides is less than bioactivity of their complex compounds. For example, in case of Fusarium arenaceum, zone of inhibition for 4-(p-chlorophenoxy)-2-nitro-3-chloro-N-(1adamantoyl)anilide at concentration 0.1 g/l (Scheme 6.2.5, XVI) was 1 mm. The antibiocorrosive covers prepared by the following way: to bioactive substances (≤ 3 %) and oligoorganosiloxane MF-AMA (modifier for matrix compound ≤ 10 %) in composition with the “ED-26” (matrix) have been added the hardening agent – hexamethylenediamine (≤ 5 %). The mixture was stirred till obtaining homogenous mass. Later, the produced thin layers on the surface of the selected material (lead, plastic, etc.) were holding on the air for 24-48 hours at room temperature. After hardening, there was produced homogenous, smooth, thick mechanically stable protective layer. It has to be noted that the produced compositions are available and their production is technologically simple. The basic properties of protective layers (homogeneity, viscosity, compatibility of polymer matrix components with bioactive compounds), physical and chemical characteristics (water absorption ≤ 0.2 %), and adhesion strength ≥ 4.0 MPa) are in compliance with the compositions of protective layers of objective types.

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187

Table 6.2.2 Some properties of synthesized nitroanilids and IR and NMR spectral data #

m.p.., C

0

RfHexane : diethyl ether, 1:1 0,5

IR spectra, ν, cm-1

3330(N-H), 3100, 3030 (C-H arom.), 2908, 2845 (CH Ad), 1650 (C=O), 1210 (C-O-C). 3390(N-H),3050(C-H arom.), 2908, 2845 (CH Ad),1650 (C=O).

1

H NMR (DMSOD6)

C NMR (DMSOD6)

δ = 10.18 (s, 1 H), 7.94 (d, J = 7.0 Hz, 2 H), 7.67 (d, J = 8.8 Hz, 2 H), 7.58 (t, J = 7.1 Hz, 1 H), 7.52 (dd, J = 7.0 Hz, 2 H), 6.94 (d, J = 8.8 Hz, 2 H), 2.13 (s, 3 H), 1.79 (m, 6 H), 1.57 (m, 6 H)

δ=165.2, 149.3, 135.0, 134.8, 131.3, 128.2, 127.5, 124.5, 120.9, 76.7, 42.2, 35.5, 30.1 δ=168.6, 148.9, 136.0, 134.9, 128.9, 128.2, 126.4, 124.6, 119.5, 76.6, 43.2, 42.2, 35.5, 30.1 δ=175.5, 148.8, 135.0, 124.3, 120.7, 76.5, 42.2, 40.7, 38.3, 35.9, 35.5, 30.1, 27.6 δ=175.4, 155.0, 132.3, 121.8, 113.4, 55.0, 40.6, 38.3, 36.0, 27.6

III

165168

IV

160

0,41

V

181182

0,53

3290 (N-H), 3030 (C-H arom.), 2908, 2845 (CH Ad),1650 (C=O).

δ = 10.07 (s, 1 H), 7.48 (d, J = 8.8 Hz, 2 H), 7.33 (m, 4 H), 7.24 (m, 1 H), 6.87 (d, J = 8.8 Hz, 2 H), 3.60 (s, 2 H), 2.10 (s, 3 H), 1.75 (m, 6 H), 1.55 (m, 6 H)

VI

240241

0,77

3420 (NH), 2950, 2930, 2850 (Ad), 1670 (C=O), 1210, 1050 (CO-C).

VII

178179

0,6

3290 (NH), 3050 (C-H arom.), 1640 (C=O), 1230,1035 (C-O-C).

δ = 9.01 (s, 1 H), 7.52 (d, J = 8.9 Hz, 2 H), 6.85 (d, J = 8.8 Hz, 2 H), 2.12 (s, 3 H), 2.01 (s, 3 H), 1.89 (m, 6 H), 1.76 (m, 6 H), 1.70 (m, 6 H), 1.56 (m, 6 H) δ = 8.95 (s, 1 H), 7.52 (d, J = 9.1 Hz, 2 H), 6.84 (d, J = 9.1 Hz, 2 H), 3.71 (s, 3 H), 2.01 (s, 3 H), 1.89 (m, 6 H), 1.70 (s, 6 H)

13

188

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov Table 6.2.2. Continued

#

m.p.., C

0

RfHexane : diethyl ether, 1:1 0,4

VIII

206207

IX

176177

0,45

X

119122

0,42

XI

151153

0,8

XII

127130

0,65

XIII

172174

0,86

XIV

134135

0,65

IR spectra, ν, cm-1

3290 (NH), 3050 (C-H arom.), 2930, 2908, 2834 (C2H5, Ad), 1640 (C=O), 1230,1035(CO-C) 3290 (N-H), 3030 (C-H arom.), 2908, 2845 (CH Ad),1650 (C=O), 1530 (Cl),1250 (C-OC). 3090 (C-H arom.), 2916, 2854 (CH, Ad),1650 (C=O),1350 (N-O), 1250 (C-O-C). 3447 (N-H); 3090 (C-H arom.), 2915, 2854 (CH, Ad), 1681(C=O), 1342 (N-O), 1265, 1234 (C-O-C). 3317 (N-H); 3108, 3070 (C-H arom.), 2908, 2854 (CH, Ad), 1697 (C=O),1334 (NO), 1272, 1234 (C-OC). 3448, 3371 (N-H), 3090 (C-H arom.), 2928, 2850 (CH, Ad), 1689 (C=O), 1342 (NO), 1265, 1242 (C-OC).

3278 (N-H), 3090 (C-H arom.), 2908, 2846 (CH, Ad),1650 (C=O), 1581, 1350 (N-O), 1288, 1249 (C-O-C).

1

H NMR (DMSOD6)

13 C NMR (DMSOD6)

δ = 9.75 (s, 1 H), 7.75 (d, J = 8.8 Hz, 1 H), 7.51 (d, J = 2.6 Hz, 1 H), 7.34 (dd, J = 8.8, 2.6 Hz, 1 H), 2.15 (s, 3 H), 2.03 (s, 3 H), 1.76 (m, 24 H)

δ=211.1, 175.8, 130.4, 128.0, 125.8, 120.0, 78.6, 41.9, 40.6, 38.4, 38.1, 35.9, 35.9, 35.3, 30.1, 27.4, 27.3 δ=175.6, 155.7, 142.8, 127.3, 125.0, 120.3, 108.8, 55.9, 40.5, 38.2, 35.9, 27.5

δ = 9.62 (s, 1 H), 7.65 (d, J = 9.0 Hz, 1 H), 7.49 (d, J = 3.0 Hz, 1 H), 7.30 (dd, J = 9.0, 3.0 Hz, 1 H), 3.83 (s, 3 H), 2.02 (s, 3 H), 1.88 (m, 6 H), 1.70 (m, 6 H)

The Traditional and Nontraditional Application Areas… XV

133135

0,73

3379 (N-H); 3090 (C-H arom.), 2930, 2908, 2854 (C2H5, Ad); 1650 (C=O); 1581, 1350 (NO); 1280,1056 (C-OC).

XXVI

168170

0,91

3290 (N-H), 3030 (C-H arom.), 2908, 2845 (CH Ad),1650 (C=O), 1530 (Cl), 1342 (N-O), 1250 (C-O-C).

δ = 9.61 (s, 1 H), 7.65 (d, J = 9.0 Hz, 1 H), 7.46 (d, J = 2.9 Hz, 1 H), 7.29 (dd, J = 9.0, 2.9 Hz, 1 H), 4.10 (d, J = 6.9 Hz, 2 H), 2.02 (s, 3 H), 1.88 (m, 6 H), 1.70 (m, 6 H), 1.34 (t, J = 6.9 Hz, 3 H)

189 δ=175.6, 155.0, 142.7, 127.2, 124.9, 120.7, 109.3, 64.0, 40.5, 38.2, 35.9, 27.5, 14.3

The created composites may be recommended as: a) protective covers with multivectorial application (film materials and impregnating compositions) stable to biocorrosion; b) materials with antimycotic properties for prophylaxis and treatment of mycosis; c) c) biologically active polymer materials for protection of archaelogical and museum exhibits; and d) for human protection during its contact with microorganisms. Preliminary investigations have shown that the synthesized compounds have also a real perspective to be utilized as accessible antioxidants towards the cancer. Table 6.2.3. Chemorheological properties of the elastomers with 0.5 weight ratio (numerator) or 1.5 weight ratio (denominator) POSA

Compo- ηxv., sition in conventional unites Without 43 addition POSA- 40/31 1 POSA- 40/29 2

τ

Δτ Min.

18 18/17

7

n, when K, Ỳ=const, kПa·c MПa·c

n, when n Ỳ=05с-1 MПa·c

83

710

80/72 6/5 18/17,5 6/5 80/70

125

0,27

120/108 700/680 0.27/0.24 124/100 708/663 0.27/0.25

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Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

6.3. MODIFICATION OF PROPERTIES OF RUBBER COMPOSITIONS AND VULCANIZATES PREPARED ON THE BASIS OF ALL-HYDROCARBON ELASTOMERS BY POLYORGANOSILAZASYLOXYARYLENES Use of various organic and organoelemental compounds for modification of properties of resin compositions and appropriate vulcanizates, prepared on the basis of carbonchain rubber resin (caoutchouc) is described in the literature [178]. N. Lekishvili, A. Bukanov, et al. used polyorganosilazasyloxyarylenes (POSA) as modifiers of above mentioned systems, which were obtained by them in the mass, by interacting organic cyclic silazane with Bisphenol-A [179].

Scheme 6.3.1.

It is known that aminocompounds have a specific impact on the character of structural modifications of elastomers at high temperatures. Study of impact of small additions of POSA on the chemoreological properties of resin composites and on the physical and mechanical characteristics of appropriate vulcanizates has become the subject of special interest. Resin compositions compound (m. fraction per 100 m. fraction of rubber resin) was the same: cis-isoprene rubber resin SKI-3 – 100, sulphur – 2.5, sulfonamide c – 100, zinc oxide – 5, diaphene fp (antiageing agent) – 2.0, technical carbon dg-100 – 30.0, POSA – 0.5 and 1.5; composition has been prepared on the roll mills, at temperature 80±3°C, while vulcanization were carried out in the press arrangement, at 143°C. Resin compositions viscosity and vulcanization properties were estimated by means of rotation viscometer at 120°C, while shearing rate was γ = 1.2s-1. Reological characteristics

The Traditional and Nontraditional Application Areas…

191

(effective viscosity and liquidity index) were determined by capillary viscometer [180]. Time change of effective viscosity of samples, containing POSA (according to Mun) is shown on the Figure In table 1 the data are given, which confirm viscosity and vulcanization (chemo-reological) changes in resin compositions during insertion of various amount of POSA. In particular, plasticizing effect of additions in the wide range of shearing rate takes place. Insertion of POSA also has an influence on the character of composition liquidity, strengthens appearance of non-Newton properties. Thus, similar to previously described silicon-organic compounds POSA is characterized by molecular plasticization. As it seen from table 6.3.1, POSA accelerates vulcanization processes in resin compositions, that is associated with existence of active Si−NH2-groups in its molecule [181], intermediate concentration of which may increase at the expense of hydrolysis of SI-NH-bonds of polyorganosilazasiloxiarylenes by air damp. Results given in table 6.3.1 confirm that insertion of small additions of POSA in the above-mentioned resin compositions significantly improves the complex of physical and mechanical, and dynamic properties, which are distinctive for them [181, 153].

Figure 6.3.2. Change of viscosity of the rubber compositions (by Moony) in the time: 1. - Without the modifier agent; 2.-, 3. - In presence of 1.5 weight ratio of POSA-1 and POSA-2, correspondingly.

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Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

There are weak absorption bands of vulcanized compositions in the IR spectrum (in 830, 947-950 and 1060-1080 sm-1 ranges), which are distinctive for Si−CH3, Si−NH−Si and Si−O−Si bonds, respectively [181]. On the basis of these data it was determined that during vulcanization process POSA interacts chemically with unsaturated molecules of “SCI-3”. It is possible to suppose, that polar macromolecular fragments generated at this time increase the total level of physical interactions in the vulcanization network. As a result, additional weak bonds are arisen. Such bonds fission much faster during deformation than cross bonds (atomic bridges) or chemical bonds of rubber basic chain, which causes reduction of local tensions and lowering of elastomers’ macrochains orientation toward direction of deformation. Thus, it is possible to consider POSA as modifyer of polyfunctional action of resin compositions and their vulcanized products. Table 6.3.1 Physical, mechanical and dinamic properties of elastomeric composition, contained 0.5 weight ratio (numerator) or 1.5 weight ratio of the POSA (denominator) Compo- Mod.at the sition 200%elongation, MPa

Conventional strength at the elongation, MPa,

Relative strength at the break, %

Hardness By SHORI, conventional units

Coefficient of the thermal aging (800, 48 hrs)

Without 2,15 addition POSA-1 2,25/2,30 POSA-2 2,20/2,25

23,0

760

54

0,90

The endurance at the multiple deformation (700, 20/100%), thousend cycles 87,00

28,2/25,6 28,9/26,8

750/810 53/52 830/780 50/51

0,86/0,82 0,87/0,81

126/274 120/230

6.4. PHYSICAL AND CHEMICAL MODIFICATION OF OLIGOMETHYLSILOXANES BY POLYORGANOSILAZA SILOXIARYLENES IN THE TREATMENT PROCESS Oligomethylsiloxane with divergent structure (OMS) has a wide application as press-materials binding oligomer. Its solidification process is longstanding, runs at high temperatures and needs additional heat treatment.

The Traditional and Nontraditional Application Areas…

193

At the same time, products prepared on its basis often don’t meet the requirements which are imposed to them under service conditions [182]. There are literary data about solidification of OMS by various polyorganosiloxanes [182], which accelerate this process, but don’t improve their physical and mechanical properties. These studies are basically carried out towards the OMS treatment, and therefore, attention is paid to the regulation of structure and to the properties of obtained materials. By taking into consideration the peculiarities of OMS chemical structure (existence of tension cycling fragments and marginal hydroxyl group), polyorganosilazasiloxiarylenes (0.1-1 mass.%) were used for regulation of solidification processes and properties of branched PMS (Scheme 6.1) [182]. The depth of structurization in the presense of polyorganosilazasiloxiarylenes was determined by various methods, which was caused by difficulty of solidification quality control [183].

Scheme 6.4.1

As it seen from extraction data (Figure 6.14) OMS solidification quality depends on the temperature of solidification and chemical structure of polyorganosilazasiloxiarylenes added to it. Structurization process runs more completely in polyorganosilazasiloxiarylenes case, silicon atoms of which are bonded with methyl groups of small size. Because of it, process of space structure formation accelerates significantly [183]. Thermomechanical study data give us a complete idea of the density of space (three-dimensional) network, formed during OMS solidification. As it seen from Figure 6.4.2, insertion of polyorganosilazasiloxiarylenes in OMS composition decreases sample deformation and raises glazing temperature in comparison with initial PMS [182].

194

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

(a)

(b) Figure 6.4.1a,b. The dependence of the extracted compounds mass on the the composition hardening time T=423 K (a) and T=443 K (b) for non-modified OMS (1) and OMS modified by polyorganosilazasiloxiarylenes (1%): 2.- R=R′ = C 6H5; 3.R=R′ = C4H9; 4.- R=R′ = C2H5; 5.- R=R′ = CH3.

Studies show, that increase of solidified OMS space network density takes place in the presence of sylazane modifiers, which is confirmed by determination of deformation heat stability according to Wick [183]. Deformation heat stability increases along with increase of amount of added polyorganosilazasiloxiarylenes and it is determined by nature of organic radicals bonded with silicon atoms in the addition. It was also confirmed that heat resistance of polymer-compositions reduces by increase of volume of organic groups bonded with silicon atoms in the modifier agent (Table 6.4.1).

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195

Temperature range, in which the process of OMS structurization runs intensively, was determined by thermographic studies. As it seen from experimental data, structurization temperature is basically depended on the quantity and chemical nature of modifiers (Figure 6.4.2).

N Figure 6.4.2. Thermomecanical curves for non-modified OMS (1) and OMS modified by polyorganosilazasiloxiarylenes (2-13). 2_0.1%; 6_0.5%; 10_1%_C6H5 3_0.1%; 7_0.5%; 11_1%_C4H9 4_0.1%; 8_0.5%; 12_1%_C2H5 5_0.1%; 9_0.5%; 13_1%_CH3

The process of product formation is especially important, along with necessary completion of chemical reaction of network polymer formation during the treatment of plastic materials prepared on the basis of received siliconorganic compounds. Whole complex of physical and chemical properties of received materials and their stability during product’s operational process depend on the quality of completion of the structurization reaction (Figures 6.4.3 and 6.4.4). Completion of solidification reactions and rate of their performing, in its turn, is determined by reaction capability of the substrate and by chemical nature of polyfunctional modifier agent [178]. Researches carried out for determination of polyorganosilazasiloxyarylenes impact on the OMS structurization and properties of received composites show that process of OMS structurization significantly accelerates at their presence, that is connected by their interaction with SiNHSi-groups of silanols group modifier (Scheme 6.4.2). In the authors opinion, nucleophilic particle ≡Si−ONH4 formed by interaction with ammonia excreted by ≡Si−OH

196

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

groups accelerates the process of hydroxyl groups homocondensation, that, finally, assists formation of space network structure [22]. At the same time OMS solidification temperature decreases and density of space network created as a result of solidification increases that are connected by the alloying effect, caused by insertion of small amount of additions, their placement on the surface of structure elements and formation of polymer systems with high dynamic properties [182].

Figure 6.4.3 Thermomechanical carves of non-modified OMS (1) and OMS modified by polyorganosilazasiloxyarylene additives (2.- R=R′ = C2H5; 3.- R=R′ = C6H5).

Figure 6.4.4. Dependence of the heatresistance of the OMS on the amount of polyorganosilazasiloxyarilene additives (Scheme 7.1): 1. _ R=R′ = C6H5; 2. _ R=R′ = C4H9; 3, _ R=R′ = C2H5; 4, _ R=R′ =CH3.U.

The Traditional and Nontraditional Application Areas…

197

Figure 6.4.5. Dependence of the temperature of the structurization on the amount of polyorganosilazasiloxyarilene additives (Scheme 7.1): 1.- R=R′ = CH3;; 2.- R=R′ = C2H5;3.- R=R′ = C4H9; 4.- R=R′ = C6H5.

OH

+

OH

+

Si

OH

+

NH3

Si

OH

+

HO

Scheme 6.4.2.

NH

Si

+

O Si

H2N Si

+

O Si

Si

H2N Si

(2)

NH3

(3)

+

Si O NH4

Si

Si

(1)

O

Si

+

H2O

(4)

198

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

Figure 6.4.6. Dependence of velue of residual tension for non-modified OMS (1) and OMS modified by polyorganosilazasiloxiarylenes on their amount and the structure of the radicals at silicon atoms: 1.- R=R′ = CH3; 2.- R=R′ = C2H5; 3.- R=R′ = C4H9; 4.- R=R′ = C6H5.

6.5. MODIFICATION OF POLYCARBONATE BY POLYORGANOSILAZASILOXIARYLENES Polycarbonates (macrolon, diphlone and others) are characterized by high physical and chemical properties and are widely used for preparation of constructional products. Treatment of polycarbonates by high efficiency method is complicated by necessity of high viscosity of their melts, as well as by necessity of maintenance of high temperatures during its treatment in the narrow temperature range. In the products, manufactured from polycarbonates, it is indicated a high level of residual internal stresses, as a rule, which is caused by chain rigidity and low rate of relaxation processes. This fact causes cracking of products manufactured from polycarbonate in the treatment process, and because of it their use is limited [184].

Table 6.4.1. Modification of the oligimethylsiloxane by polyorganosilazasiloxyarilenes Hardening degree, %

Composition

#

1

(OMS) [CH3SiO1,5]n

2

OMS*) + 0,5% [Si(CH3)2- NH]2Si(CH3)2O

38 86

Compression strength kG/cm2

Strength

180

477

250

240

880

_

950

60

860

72

1050

54

Deformation thermal stability 5kG/cm2

kG/cm2

O n 3

4

5

OMS + 2,0% [Si(CH3)2 NH]2Si(CH3)2O

OMS + 2,0% [CH3SiC6H5NH]2Si(CH3)(C6H5)O

93 340

O n

84 330

OMS + 2,0% [(CH3)Si(C4H9)NH]2Si(CH3)(C4H9)O

O n

88 320

O n 40

OMS + 2,0% [Si(CH3)2-NH]2Si(CH3)2O

280

6

.

O n

82

915

200

Nodar Lekishvili, Victor Kopylov and Gennady Zaikov

Well known polycarbonate-siloxane elastomers represent polycarbonates copolymers with polyorganoiloxanes [185]. Main defect of such elastomers is their low heat stability, and very low mechanical solidity, in comparison with common polycarbonates. Polymeric composition manufactured on the basis of polycarbonates contains aromatic polycarbonates and polyorganosiloxanes with various viscosities – polydimethylsiloxane and polymethylphenilsiloxane [180]. Polycarbonate dissolved in methylene chloride is added to liquid organosiloxanes. Films (webs) are taken from the formed solution. Compositions received by this method are characterized by low liquidity, while during their exploitation at high temperatures their mechanical solidity reduces. For the purposes of increase of above-mentioned compositions liquidity and their mechanical solidity polyorganosilazasiloxiarylenes are used as modifiers instead of polyorganosiloxanes, and molecular mass of the first ones may vary from 100 thousand to 200 thousand [184]. Polyorganosilazasiloxiarylenes (0.1-3 m.n.) used for the same purposes are capable to penetrate not-reversibly into disordered areas of polycarbonates supramolecular structure, don’t initiate their swelling or opening and increase shear capacity of structural units. This fact provides acceleration of relaxation processes and lowers the level of residual stress in the product [184]. It is established, that insertion of alloying additions doesn’t require any special accommodating, doesn’t complicate technology of polycarbonates receiving and allows to improve polymers treatment capacity, reduces treatment temperature by 30-60°C. Polycarbonates (PC), obtained on the basis of diphenylolpropane and phosgene (which are manufactured with molecular mass from 25000 to 45000) are used for receiving of given composition. Well known antioxidants - tri-p-nonylphenylphosphates and other polyphosphates, e.g. polytiodiphenylenphenylphosphinates or stilbenes are used as stabilizers [185]. As it seen from table 6.5.1, insertion of certain amount of polyorganosilazasiloxiarylenes as alloying additions in polycarbonate increases its liquidity 2-7 times, at the same time, limit value of solidity during tension and given limit value of extension coefficient during bruise are maintained for a long period of time, in the ageing process at 120°C, while non-modified polycarbonates have no such capacity.

The Traditional and Nontraditional Application Areas…

201

Table 6.5.1 Properties of the modified polycarbonate based on bisphenol A Composition

Polycarbonate (PC) PC + 5% Fluoroplast

Melting index, Imelt.

Change of strength characteristics ρ, during of ageing, σ kG/cm2 /ε 106 hz Before After 5 After 10 After 30 ageing days days days

1

605/80

2

567/91

635/70 630/50 580/85 555/71

535/30

tgδ,

E,

6

10 hz kV. mm

3.1 . 1016 0.008

23.5

515/50

.

4.5 10

16

0.0092 21.2

.

16

0.0076 24.0

PC +1 %[Me2SiOMe2 SiNHSiMe2OSiMe2ORO]n

8

631/93

646/93 640/95

630/80

4.4 10

PC + 1 % [MeEtSiNHMe EtSiOR′O]n

3

620/100 602/95 612/86

560/81

-

PC + 1 % [Me2SiOMe2 SiORO]n

8

628/99

639/88 636/62

626/60

2.2 . 1016 0.0078 23.0

PC + 1 % [Me2SiOMe2 SiOR′O]n

2

600/102 610/88 606/80

602/78

2.4 . 1016 0.0072 23.3

PC + 1 % [Me2SiO]48 R′O]n

4

560/72

603/70 602/66

560/52

4.1 . 1016 0.0095 22.5

PC + 1 % [MeButSiNHMe ButSiOR′O]n

3

665/93

650/90 648/80

632/80

2.3 . 1016 0.0090 21.0

-

-

It is established by the studies that index of polycarbonates melting (Imelt.) raises with increase of alloying addition content in the composition, at the same time its solidity characteristics worsen. Polycarbonate modification with above-mentioned alloying additions allows manufacturing such polymeric compositions, good technological properties of which are combined with increased indices of solidity. A composition prepared by this method has the wide use for producing of reinforcing constructions, electric and radiotechnical details and others [184]. Manufacturing of above-mentioned details from pure polycarbonate is complicated because of high viscosity of its melts and, respectively, because of low liquidity, that fact necessitates increase of melt’s temperature. In this case, as a rule, cracking of products manufactured from polycarbonates, as well as polymers destruction and high level of residual stress are mentioned. Polycarbonates treatment capacity improves, its liquidity increases and treatment temperature lowers by 40-60°C [185] by insertion of silazasiloxiarylene alloying additions, and that makes the application of these technology.

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INDEX A  absorption, 61, 71, 73, 81, 82, 84, 90, 108,  112, 114, 115, 126, 127, 138, 142, 149,  153, 165, 167, 170, 176, 179, 183, 186,  192  acceptor, 62  accuracy, 134  acetic acid, 179  acetone, 81, 108, 126, 153, 169, 180  acetylene, 111, 112, 116  acid, 3, 23, 35, 42, 97, 98, 100, 101, 102,  103, 104, 140, 179  acidity, 30  actinomycetes, 140  activation, 52, 59, 93, 173, 183  activation energy, 52, 59, 173, 183  active centers, 34  adamantane, 177, 179, 180, 183, 185  additives, 62, 166, 196, 197  adducts, 87, 89, 149, 151, 170, 172  adhesion, 104, 186  adhesion strength, 186  age, ix  ageing, 23, 201  agent, 108, 143, 145, 157, 165, 186, 190,  191, 194, 195  agents, 3, 6, 106, 124, 146, 163, 179 

aggregates, 74  aging, 124, 140, 163, 164, 165, 192  agricultural, 166  air, 59, 61, 93, 102, 104, 107, 109, 119, 180,  186, 191  alcohol, 140, 147, 152, 159  alcohols, 63, 163  Alcohols, 213  alkali, 3  alkaline, 23  allylamine, 159, 160, 161, 162  amide, 49, 97, 98, 102, 104, 106  amine, 14, 159  amines, 62, 124, 131, 132, 133, 138, 146,  179  amino, 7, 11, 79, 80, 81, 96, 102, 163  amino acid, 7  amino acids, 7  amino groups, 102, 163  amino‐groups, 11, 79  aminohydroxysiloxanes, 124, 133, 138, 140,  164  ammonium, 11  ammonium sulphate, 11  amorphous, 28, 33, 70, 75, 90, 99, 116, 122,  143, 157, 176  Amsterdam, 204, 209  angular velocity, 82, 99, 154, 176  aniline, 11, 138 

218

Index

anomalous, 126  application, ix, xii, 1, 8, 62, 63, 98, 164, 167,  189, 192, 202  argon, 34, 49, 98, 103, 108  aromatic hydrocarbons, 33, 63, 104  aromatic rings, 179  arsenic, 157  Asian, 214  assimilation, x  asymmetry, 28  atmosphere, 34  atoms, 1, 7, 12, 19, 20, 52, 54, 55, 56, 57,  59, 61, 74, 87, 90, 111, 112, 128, 134,  161, 167, 171, 176, 180, 193, 194, 198  attacks, 183  availability, xii, 62, 177  averaging, 34 

B  Bacillus, 140  Bacillus subtilis, 140  bacteria, 140  bacterium, 186  basicity, 11  behavior, 29  bending, 122, 143, 144, 145  benzene, 12, 19, 29, 33, 78, 81, 82, 83, 84,  112, 113, 114, 115, 116, 121, 122, 126,  146, 147, 148, 150, 153, 154, 169, 179,  182, 183  binding, 19, 71, 94, 192  bioactive compounds, 177, 186  biocompatibility, 213  biologically active compounds, 166, 177  bisphenol, 49, 50, 51, 52, 201  bisphenols, xi, 12, 15, 41, 42, 43, 49, 50, 52,  61  block polymers, 74  blocks, 8, 68, 71, 75, 102  boiling, 36, 49, 108  boils, 23 

bonds, 3, 22, 23, 28, 50, 52, 55, 59, 61, 65,  74, 93, 97, 101, 102, 104, 106, 111, 112,  114, 115, 122, 138, 153, 154, 177, 191,  192  boric acid, 35  branching, 14, 19, 26, 35, 51, 58, 66, 71, 74,  81, 112  buildings, 164  butadiene, 124, 146 

C  cadmium, 177, 183  cancer, 166, 189  capillary, 191  carbide, 1, 3  carbon, 52, 122, 134, 140, 145, 146, 149,  161, 180, 182, 190  carbon atoms, 52, 134, 161, 180  carbonates, 62  carbonic acids, 179  carboxyl, 97, 104, 106  carboxyl groups, 97, 106  carrier, 98, 141  catalyst, 11, 19, 71, 78, 97, 112, 125, 126,  140, 147, 153, 167  cation, 33, 34, 36  cavities, 8  ceramic, 1  ceramics, xi, 1, 3  chain branching, 19  chain rigidity, 200  characteristic viscosity, 23, 67  chelates, 152, 153  chemical bonds, 192  chemical composition, 122  chemical properties, 74, 195, 200  chloride, 200  chlorinated hydrocarbons, 122  chloroform, 11, 19, 63, 68, 114, 116, 117,  180  chromatography, 18, 141 

Index chromatography analysis, 18, 141  Cincinnati, 209  cis, 34, 35, 36, 140, 190  classes, 3  classical, 78  cleaning, 164  Co, 39, 40, 140, 144, 152, 163  CO2, 103  coatings, xi  combustion, ix  commercialization, 177  communication, 104  compatibility, 186  competitive process, 57  compliance, 35, 186  components, 8, 32, 66, 73, 74, 75, 117, 124,  139, 146, 163, 166, 186  composites, 94, 145, 164, 167, 189, 190,  195, 204  compressibility, 3, 6  computation, 88, 171  concentration, 13, 30, 31, 32, 33, 37, 38, 39,  40, 52, 71, 74, 75, 96, 106, 169, 186, 191  condensation, 4, 8, 9, 10, 11, 14, 16, 19, 23,  24, 26, 27, 29, 30, 31, 34, 35, 36, 41, 49,  51, 59, 60, 66, 67, 68, 70, 78, 98, 104,  105, 106, 121  conductance, 51  conductive, 123  conductivity, 94  Congress, iv, 206, 213  construction, x, 75  constructional materials, 1  consumption, 35, 36, 163  control, xii, 35, 157, 164, 165  conversion, 14, 23, 25, 26, 28, 29, 30, 34,  36, 37, 38, 68, 70, 73, 74, 84, 119, 129,  130, 138, 139, 141, 142, 147, 163, 167,  168, 169, 175  cooligomerization, 124, 127, 129, 130, 133,  138, 139, 142, 145, 146, 162, 163, 174  cooling, 28, 82, 154  copolymer, 33, 75, 77, 164, 174 

219

copolymers, 8, 33, 39, 62, 70, 71, 116, 118,  200  correlation, 75, 87  correlation coefficient, 87  cosmetics, 6  covering, 75  CPC, 18, 34  cracking, 200, 202  crops, 166  crystalline, 28, 41  crystallinity, 90  crystals, 179, 204  curing, 140, 163  cycles, 5, 18, 26, 31, 41, 62, 68, 98, 99, 105,  106, 108, 112, 113, 138, 145, 164, 192  cycling, 104, 106, 108, 109, 193  cyclohexyl, 134 

D  decay, 14  decomposition, 51, 66, 109, 143  defects, 28, 99  deformation, 54, 102, 117, 192, 193, 194  degradation, ix, 93, 166  dehydrocondensation, 90  delocalization, 102  dendrimers, 7, 8  density, 32, 112, 193, 196  depolymerization, 57  derivatives, 112, 124, 163  destruction, 12, 31, 45, 46, 56, 57, 58, 59,  60, 61, 62, 70, 117, 119, 144, 163, 166,  177, 184, 202  destruction processes, 60  detection, 75  deviation, 18, 52, 66  diamines, 11, 41, 96, 104, 107  dianhydrides, 104, 210  differential equations, 18, 52  differential scanning, 82, 90  differential scanning calorimeter, 82 

220

Index

differential scanning calorimetry, 90  diffraction, 75  diffusion, 99  difractogram, 76  diluent, 164, 167  dimethylformamide, 96, 99, 130, 148, 176  dimethylsulfoxide, 96, 148  dimethylsulphoxide, 106  diphenylolpropane, 201  dipole, 177  direct action, 166  diseases, 166  disposition, 74  distillation, 101  distribution, 14, 24, 52, 126, 130  diversity, 3  division, 166  DMF, 141  DMFA, 96, 101, 106, 108, 129, 130, 131,  133, 138, 139, 162, 163, 180  donor, 112  double bonds, 104, 106, 107, 163  DSC, 82, 90, 92, 97, 104, 105, 108, 154, 157,  176, 178  DSC method, 157  DTA curve, 57, 98, 103, 144  ductility, 117  durability, 124  duration, 23, 24 

E  elaboration, 78, 146  elasticity, 26, 55, 143, 144  elasticity modulus, 26  elastomers, 23, 78, 123, 124, 140, 146, 166,  189, 190, 192, 200  electrical resistance, 145  electrodes, 94  electron, 51, 61, 74, 102, 112  electronic systems, 6  electrons, 51, 102 

elongation, 11, 122, 140, 164, 192  employment, 6  endothermic, 82, 98, 102, 157, 184  endurance, 192  energetic parameters, 90  energy, 94, 173, 183  environment, 166, 213  epoxides, 123, 125, 127, 140, 143, 144, 145,  146  epoxy, 124, 125, 126, 127, 132, 142, 145,  146, 149, 153, 162  epoxy groups, 124, 126, 127, 145, 146, 149,  153  equilibrium, 30, 32, 37, 66, 71, 130, 139,  141, 175  equilibrium state, 139  ester, 68, 145, 167  esters, 3  ethanol, 116, 180  ethers, 35, 164  ethyl alcohol, 12, 33  ethylene, 164  ethylene oxide, 164  evolution, 73, 120  exothermic peaks, 82, 98  expert, iv  exploitation, ix, 166, 200  extraction, 193 

F  failure, 139  fatigue, 163, 165  fiber, 1  fibers, xi, 1  film, 189  films, 62, 63, 105, 108  filtration, 179  first generation, 7  fission, 192  fixation, 166  flow, 140 

Index fluid, 6  fluorine, 96, 97, 100, 102, 104, 107, 167  formaldehyde, 123  formamide, 11  fractionation, 68  fragmentation, 68  France, 203  friction, 123  fuel, 94  fulfillment, 123  functional analysis, 132  fungicidal, 185  Fusarium, 186 

G  gas, 22, 58, 59, 61, 98, 103, 141  gel, 26, 27, 28, 32, 126  gel‐fraction, 26, 28, 32  generation, 7, 95, 108  Georgia, 207, 208, 210, 211, 212, 214  Germany, 212, 213  glass, 63, 65, 68, 77, 90, 143, 154, 157  glass transition, 68, 90, 154, 157  glass transition temperature, 68, 154, 157  GLC method, 108  glycerol, 145, 146  graphite, 94  grouping, 31  growth, ix, 14, 19, 25, 95, 166  gums, 84, 148 

H  handling, 147  hardening process, 167  harvesting, 166  heat, 1, 6, 39, 104, 106, 120, 123, 140, 151,  152, 163, 164, 165, 182, 192, 194, 200  heat aging, 140, 163, 164, 165  heating, 19, 26, 69, 97, 98, 102, 109, 154,  157, 177 

221

heating rate, 69, 157  helium, 98, 141  heptane, 153  heterocycles, xi, 10, 18, 25, 41, 80  heterofunctional condensation, 18, 66  hexane, 112, 153, 180  high temperature, 21, 57, 59, 60, 67, 81, 93,  101, 102, 104, 107, 108, 163, 190, 192,  200  high‐molecular compounds, 12  Holland, 204  homogeneity, 106, 186  homogenous, 186  homopolymerization, 149  household, 6  human, 1, 166, 189  hybrid, 8  hydraulic fluids, 6  hydride, xii, 87, 149, 177  hydro, 19, 33, 63, 104, 122  hydrocarbon, 11, 190, 209  hydrogen, 61, 84, 90, 99, 127, 134, 147  hydrogen bonds, 99  hydrolysis, 78, 93, 106, 146, 191  hydrolytic stability, 23  hydrophobic, 123, 145, 157, 167  hydrophobic properties, 167  hydrophobicity, 164  hydroquinone, 142, 175  hydrosilylation, 83, 84, 87, 111, 121, 125,  126, 146, 148, 150, 167, 170, 171, 173  hydroxyl, 3, 6, 14, 26, 28, 29, 31, 33, 34, 36,  37, 71, 104, 163, 193, 196  hydroxyl groups, 3, 14, 29, 36, 71, 196 

I  ice, 179  identification, 96, 134, 212  identity, 3  imidization, 98, 101, 102  immersion, 165 

222

Index

impact strength, 104  inactive, 186  index numbers, 84  indication, ix, 114  indices, 202  induction, 13, 19, 24, 25, 51, 66, 79, 80  induction period, 13, 19, 24, 25, 51, 66, 79,  80  industrial, xii, 9, 10, 23, 78, 93, 123, 124,  146, 157, 206, 213  industry, 6, 57, 62, 95, 123, 124  inert, 57, 58, 59, 61, 98, 103  inertness, 6  infrared, 61, 183  inhibition, 108, 186  inhibitor, 175  initial reagents, 11  injury, iv  inorganic, x, xi, xii, 1, 3, 8, 10, 25, 39, 40, 41,  62, 123, 124, 145, 146, 159, 165, 183,  184, 206, 213  insertion, 56, 57, 60, 191, 193, 196, 200,  201, 202  interaction, 2, 3, 8, 14, 25, 31, 37, 50, 52,  62, 64, 71, 78, 80, 90, 99, 105, 109, 112,  124, 130, 131, 132, 133, 146, 152, 160,  161, 162, 169, 180, 195  interactions, 81, 176, 192  intermolecular, 99  interval, 37, 62, 70, 98, 99, 107, 117, 184  intrinsic, 52, 97  intrinsic viscosity, 52  inversion, 127  ionic, 32, 57  ionic polymerization, 32  ions, 7  IR spectra, 41, 65, 81, 82, 84, 90, 98, 105,  106, 108, 112, 114, 115, 126, 127, 138,  142, 149, 153, 154, 162, 167, 169, 176,  184, 187, 188  IR spectroscopy, 106, 108  iron, ix  irradiation, 22 

Iisolation, 13, 18, 22, 25, 36, 37, 38, 70, 108  isomeric acids, 164  isomers, 36, 99, 122  isoprene, 124, 146, 163, 190  isothermal, 109  Italy, 213 

K  kinetic curves, 13, 18, 37, 66, 84, 147, 167  kinetics, xii, 24, 35, 38, 66  knots, 14 

L  law, 139  leaching, 163  liberation, 105  ligand, 153  ligands, 183  linear, xii, 1, 2, 8, 14, 30, 33, 36, 51, 71, 74,  79, 81, 90, 93, 162  links, 12, 21, 36, 71, 143  liquid chromatography, 98, 103  liquidity, 191, 200, 201, 202  liquids, 6, 19, 26, 56, 84, 126, 143, 148, 169  long period, 201  longevity, 51  losses, 6, 21, 31, 61  low molecular weight, 97  low temperatures, xii  low‐intensity, 106  lubricants, 39 

M  machines, x  macromolecular chains, 25, 33, 65, 99  macromolecules, 14, 34, 39, 55, 59, 61, 90,  93, 99, 106, 112, 146  magnetic, iv  maintenance, 200 

Index manufacturing, ix, 3, 82, 124, 145, 183, 202  Markovnikov rule, 149, 171, 173  mass loss, 21, 31, 61, 62, 70, 98, 102, 104,  107, 118, 143, 184  Matrices, 209  matrix, 8, 75, 166, 177, 186  mechanical properties, 41, 94, 101, 124,  146, 165, 193  media, 8, 49, 98, 101, 106, 125  medicine, 6  melons, 166, 186  melt, 1, 117, 202  melting, 10, 19, 41, 90, 96, 98, 102, 117,  201  melting temperature, 96, 102, 117  melts, 200, 202  Mendeleev, 203, 206  meristem, 166  metabolic, 166  metal ions, 7  metals, ix, 152  methane, 61  methanol, 33, 108  methine group, 170  methyl group, 61, 87, 149, 170, 180, 193  methyl groups, 61, 170, 180, 193  methylene, 87, 134, 149, 170, 180, 200  methylene chloride, 200  methylene group, 134, 149, 170, 180  micromycetes, 213  microorganisms, 165, 166, 186, 189  mobility, 99  model system, 34, 66, 67, 80, 88, 90, 105,  149, 182  modeling, 171  modulus, 1, 140  moisture, 93  molar ratio, 22, 23, 24, 32, 34, 37, 38, 39,  65, 74, 76, 81, 115, 117, 119, 120, 125,  142, 161, 175, 176  molar ratios, 39, 117, 119, 120  mole, 14, 50, 73, 78, 96, 118, 140, 167, 173,  183 

223

molecular mass, 23, 50, 62, 65, 68, 70, 74,  77, 115, 117, 122, 139, 142, 163, 200,  201  molecular weight, 19, 97, 112  molecules, 7, 9, 19, 28, 29, 30, 33, 35, 99,  192  monomer, 101, 114, 117, 152  monomers, xii, 7, 17, 27, 54, 62, 78, 84, 86,  95, 96, 97, 106, 111, 112, 115, 116, 117,  118, 119, 122, 142, 147  morphology, 214  Moscow, ix, x, 203, 206, 207, 208, 210, 211,  212, 214  mycology, 213 

N  nanocomposites, ix  nanotechnology, xi  nation, 134  National Academy of Sciences, 206  natural, 165, 166  neck, 159  network, 30, 192, 193, 194, 195, 196  network density, 194  New York, iii, iv, 203, 206, 208, 209, 213  Newton, 191  nitride, xi, 3, 204  nitrogen, xi, 2, 9, 10, 23, 41, 51, 59, 62, 74,  80, 81, 90, 102, 132, 134, 138, 140, 163  nodes, 166  non‐polar unsaturated elastomers, 163  n‐phenylene diamine derivatives, 163  nuclei, 99  nucleophilic initiators, 33  nucleotides, 7 

O  OH/NH groups, 162  OH‐groups, 41, 52  oil, 49 

224

Index

oligomer, 24, 26, 29, 68, 125, 126, 127, 128,  129, 130, 131, 132, 133, 135, 136, 138,  139, 142, 143, 162, 168, 169, 170, 192  oligomeric, 51, 131, 140, 141, 163  oligomeric products, 51  oligomerization, 141, 142  oligomers, x, xi, 9, 31, 51, 66, 68, 93, 94,  111, 123, 124, 126, 128, 131, 134, 136,  137, 138, 140, 142, 143, 144, 145, 146,  167, 176, 177, 178, 206, 209  optical, 62, 63, 94  optimization, 88, 151  organ, 157  organic C, 95, 214  organic compounds, 3, 62, 122, 191, 212  organic polymers, ix, 8, 78, 166  organic solvent, 81, 84, 117, 126, 153, 176  organic solvents, 84, 117, 126, 153  organocyclosiloxanes, xi, 25, 33, 34, 38, 39,  124, 125, 130, 133, 138, 141, 145  organometallic, 157  Organometallic, 203, 206  orientation, 192  oxidation, 1, 3, 57  oxidative, 56, 59, 61, 107, 122, 123, 177  oxidative destruction, 56, 59, 61, 107, 122  oxide, 33, 164, 190  oxygen, 3, 63, 102, 108 

P  PAA formation, 99, 106  parallel‐consecutive two‐steps reaction,  162  parameter, 93, 122, 164  particles, 19, 32, 108  patents, 8  penetrability, 145  permit, 145  peroxide, 142  petroleum, 104  petroleum products, 104 

pharmaceuticals, 8  phenol, 18, 20, 21, 22, 66, 80, 123  phenolformaldehide gums, 78  physical and mechanical properties, 94,  124, 146, 165, 193  physical interaction, 192  physics, xii  plants, 166  plastic, 186, 195  plasticization, 140, 191  Poland, x  polar groups, 102  polyamide, 96, 97, 98, 100, 101, 102, 103,  104, 108  polyamide acid, 96, 97, 98, 100, 101, 102,  103, 104, 108  polycarbonate, 62, 69, 71, 75, 76, 78, 123,  200, 201, 202  polycarbonates, 70, 200, 201  polycarbosilanes, 1  polycondensation, xi, xii, 21, 22, 23, 25, 26,  28, 29, 31, 32, 33, 35, 36, 38, 39, 52, 59,  62, 66, 67, 68, 70, 72, 73, 74, 97  polycondensation process, 21  polydimethylsiloxane, 57, 59, 200  polyester, 8  polyheteroarylenes, 210  polyimide, 99, 104, 108  polyimides, 95, 96, 99, 104, 210  polyisoprene, 140  polymer chains, 8, 21  polymer composites, 93, 123, 124, 146  polymer destruction, 60  polymer films, 109  polymer materials, ix, 123, 189  polymer matrix, 166, 177, 186  polymer structure, 1, 19  polymer synthesis, 62  polymer systems, 196  polymeric blends, ix  polymeric composites, ix, xii, 120  polymeric materials, ix, 63, 165  polymerization mechanism, 23 

Index polymethylmethacrylate, 143  polyorganocarbosiloxanes, 152  polyorganosiloxanes, 1, 3, 6, 7, 9, 21, 31,  41, 55, 56, 152, 193, 200  polyphosphates, 201  polysiloxanes, 57  polyurethane, 8, 166, 213  polyurethane foam, 8, 213  polyurethanes, 214  Portugal, 208  potassium, 33, 34  powder, 28, 54, 102, 112  powders, 33, 105, 122, 180  precipitation, 101, 102, 116  prepolymer, 106  pressure, 23, 94, 98, 159  probability, 72, 81, 114, 149, 183  production, ix, xi, xii, 2, 3, 8, 104, 186  property, iv, 8, 87, 140, 164  prophylaxis, 189  propylene, 164  protection, 7, 166, 189  protective coating, 3  protons, 22, 87, 97, 127, 132, 149, 170,  179, 180  pseudo, 87  pyrolysis, 3 

Q  quality control, 193  quantum, 88, 150, 151, 182  quantum‐chemical calculations, 150, 182 

R  radiation, xi, 10, 123  radical polymerization, 142  radio, 202  Raman, 209 

225

range, 6, 23, 56, 59, 61, 77, 78, 87, 104,  108, 120, 122, 127, 147, 149, 153, 164,  170, 179, 180, 191, 195, 200  reaction center, 182  reaction mechanism, 36, 52, 80  reaction order, 84, 147, 167  reaction rate, 11, 13, 23, 28, 38, 50, 63, 84,  87, 137, 139, 142, 147, 150, 167  reaction rate constants, 84, 87, 137, 142,  147, 150  reaction temperature, 23, 49, 73, 168, 175  reaction time, 39, 130  reactivity, 3, 28, 62, 87, 115, 207  reagents, 13, 25, 28, 34, 36, 37, 98, 141  reflexes, 99  regular, xii, 9, 31, 143, 146  regulation, 9, 193  relaxation, 200, 204  relaxation process, 200  relaxation processes, 200  reliability, 134  renewable resource, ix  Republican, 209  residues, 3, 12, 138  resin, 8, 54, 94, 140, 143, 145, 164, 190,  191, 192  resins, 2, 3, 4, 123, 143, 145, 146, 166  resistance, 3, 6, 104, 120, 123, 140, 145,  163, 164, 165, 194  resistivity, 6  resources, ix  retention, 164  retina, 14  rigidity, 200  rings, 59, 61, 122  room temperature, 108, 159, 163, 175, 186  RP, 31  rubber, 6, 19, 23, 26, 124, 140, 146, 163,  190, 191, 192  Rubber, 159, 163  rubber compounds, 140  rubbers, 6, 78, 123, 146, 163  Russia, x, 98, 141, 154, 176, 203, 207 

226

Index

Russian, x, 203, 207, 210, 211, 212, 214  Russian Academy of Sciences, x 

S  salt, 152  sample, 51, 54, 102, 163, 164, 170, 193  saturated hydrocarbons, 19, 63  scattering, 154, 176, 213  SCP, 164, 165  SE, 98, 141  search, ix, 96  selecting, 62, 177  separation, 18, 49, 50, 59, 60, 61, 64, 80,  98, 103, 104, 106  services, iv  shear, 3, 200  shoulder, 99  signals, 34, 87, 127, 132, 134, 149, 152,  161, 170, 179, 180  silane, 34, 37, 111  silanol groups, 3, 8, 36  silicate, 3  silicates, 3  silicon dioxide, 3  siloxane, 23, 24, 26, 30, 36, 38, 57, 60, 62,  70, 71, 73, 74, 75, 77, 78, 117, 124, 142,  143, 162, 209  skeleton, 3  sodium, 34  software, 171  solidification, 192, 193, 195, 196  solidification processes, 193  solubility, 63, 87, 95, 96, 97, 101, 104, 105,  108, 112, 117, 122, 149, 153  solvent, 12, 23, 63, 81, 98, 106, 108, 126,  131, 136, 137, 148, 159, 169  solvents, 49, 54, 82, 96, 97, 99, 101, 106,  108  Soviet Union, 207, 212  spatial, 112, 176  species, 88 

specter, 89  spectral analysis, 81, 87, 126, 149  spectroscopy, 34, 41, 98  spectrum, 20, 21, 34, 61, 64, 73, 86, 98,  104, 127, 134, 136, 169, 170, 171, 172,  176, 180, 181, 182, 192, 213  speed, 31, 37, 97, 177  spin, 180  springs, 6  stability, 3, 6, 9, 10, 22, 23, 31, 57, 58, 59,  61, 62, 69, 93, 94, 102, 104, 117, 123,  143, 152, 165, 167, 177, 194, 195, 200  stabilization, ix, 107  stabilizers, 8, 201  stages, 18, 37, 66, 67, 68, 80, 153, 163, 167,  178  steel, ix, 63  steric, 102, 176  stilbenes, 201  strain, 96  strength, 51, 122, 140, 143, 144, 145, 164,  165, 186, 192, 201  stress, 38, 96, 200, 202  stretching, 164  strikes, 186  strong interaction, 55  structural modifications, 190  structure formation, 66, 193  structuring, 116, 117  styrene, 174  substances, 8, 19, 26, 28, 41, 90, 99, 157,  176, 186  substitutes, 38  substitution, 50, 65, 180  substrates, 78, 157  subtraction, 62  sulfonamide, 140, 190  sulfuric acid, 42  sulphur, 190  superiority, 173  supramolecular, 200  surface tension, 3, 6  surfactants, 8 

Index swelling, 32, 200  synthesis, x, 1, 7, 8, 10, 41, 44, 62, 70, 78,  95, 96, 104, 107, 108, 111, 116, 124,  143, 145, 146, 159, 166, 177, 183, 209,  211  synthetic cleaning products, 164  synthetic rubbers, 212 

T  talent, ix  technical carbon, 140, 190  tensile, 140, 163, 164  tensile strength, 140, 164  tension, 193, 198, 201  TGA, 61, 69, 93, 97, 98, 102, 143, 154, 157,  158, 177, 184, 185  thermal aging, 192  thermal analysis, 93, 97, 102, 157, 177  thermal degradation, 93  thermal destruction, 58, 61  thermal properties, 56  thermal resistance, 3  thermal stability, 23, 57, 62, 93, 94, 104,  123  thermodestruction, 59, 61  thermograms, 60  thermogravimetric, 21, 56, 59, 93, 102, 104  thermogravimetric analysis, 59, 93, 104  thermolysis, 184, 185  thermo‐mechanical, 68  thermomechanical method, 77  thermooxidative destruction, 46, 70, 102  thermooxidative stability, 68, 102  thermoplastic, 39  thermostabilization, 102  thermostable polymers, 107, 210  thin film, 94  thin films, 94  three‐dimensional, 6, 26, 193 

227

toluene, 12, 19, 23, 29, 36, 78, 81, 84, 86,  101, 112, 113, 114, 116, 126, 142, 147,  148, 150, 153, 169, 174, 176  trans, 10, 14, 20, 21, 22, 36, 52, 80  transfer, 34  transformation, 41, 68, 99, 145  transition, ix, 13, 18, 19, 77, 79, 80, 82, 157,  176  transition temperature, 68, 77, 82, 154,  157, 176  transitions, 154, 157  transparency, 65, 94  transparent, 62, 63, 81, 84, 108, 126, 148,  176  trees, 7, 166  tribological, 9, 123  trimer, 23  tumors, 166  two‐dimensional, 212, 213 

U  Ukraine, 206, 208, 213  urethane, 71 

V  vacuum, 57, 104, 105, 108, 125, 139  values, 68, 71, 72, 75, 84, 106, 112, 125,  131, 132, 139, 162, 171, 173  variation, 74  velocity, 3, 18, 34, 82, 99, 154, 176  viscosity, 3, 6, 10, 12, 13, 19, 24, 27, 28, 52,  67, 68, 72, 73, 94, 106, 112, 122, 129,  130, 138, 139, 141, 142, 143, 144, 150,  175, 176, 186, 190, 191, 200, 202  visible, 63, 81, 99  visual area, 126  vitreous, 19, 29  vitreous polymer, 29  vitrification, 19, 21, 25, 26  vitrification temperature, 25, 26 

228

Index

volatilization, 163  vulcanizates, 190  vulcanization, 190, 191, 192 

W  water, xi, 3, 36, 37, 38, 81, 97, 98, 101, 102,  105, 108, 109, 126, 152, 153, 164, 166,  179, 180, 186  water absorption, 165, 186  weight loss, 59, 61, 109  weight ratio, 189, 191, 192 

X  X‐ray analysis, 70  X‐ray diffraction, 101  xylene, 12 

Y  yield, xii, 13, 24, 25, 54, 66, 84, 108, 112,  113, 114, 117, 132, 147, 150, 160 

Z  zinc, 190  zinc oxide, 190