Polypropylene Handbook: Polymerization, Characterization, Properties, Processing, Applications

Contents Part I . PoIypmpylene: The Material ................... ..: 1 Introduction ....................................

................................... ...........................

,

Edwurd P . I k n rr. ~ Jr

1.1 Scope ................................................................................................. 1.2 Chemistry ............................................................................................ 1.3 History ............................................................................................... 1.3.1 Before Ziegler and Nana............................. ... ................................. t 3 . 2 Ziepler .................... . ................................................................ 1.3.3 Nam .......................................................................................... 1.4 Commercial Significance.......................................................................... General References ......................................................................................

2 Catalysts and Polymerizations....................................................................... E . A l b k u ri. O: Giannini G. Collino L. Nu& ti. L. Rescotti

.

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2.1 I n d u c t i o n ........................ , . .............................................................. 2.2 History and Development of Stereospecific Catalysts .................................. ... 2.2.1 First Generation CataIysts ................................................................. 2.2.2 Second Generation Catalysts .............................................................. 2 2 . 3 Third Generation Cata1lrst.s ............................................................ 2.2.4 Fourth Generation Catalysts ............................................................... 2.2.5 Fifth Generation Catalysts ................................................................. 2.2.6 Metallocenes-S ixth Generation Catalysts.............................................. 2.3 Catalysts: Synthesis, Chemistry, Structure...................................................... 2.3.1 Heterogeneous Catalysts ................................................................... 2.3.1.1 First Generation TiCl, CataIysts ................................................ 2.3. 1 . 1.1 Synthesis and Structure .................... 2.3.1.1.2 Aluminum Metal Reduction ......................................... 2.3.1.1.3 Aluminum Alkyl Reduction ......................................... 2.3.1.1.4 Polymerization Perfomance ......................................... 2.3.1.2 Second Generation TiC13 Catalysts ............................................. 2.3.1.2.1 Synthesis and Structure............................................... 2.3.1.2.2 Folymerization Performance .........................................

.,.....

..*.....,....A,..

2.3.1.3 MgC12-Supported Catalysts ...................................................... 2.3.1.3.1 Preparation Methods .................................................. 2.3.1.3.2 Structure-of MgC12.................................................... 2.3.1 3 . 3 Catalyst Chemistry .................................................... 2.3.1.3.4 Catalyst Structure...................................................... 2.3.1.3.5 Cocatalyst Chemistry .................................................

2.3.1..3.6 Catalyst-Cocatalyst Interactions....................... ,,........... , 2.3.1.3.7 Catalyst Composition .................................................

.

2.3.2.3.8 Ti Oxidation State ..................................................... 2.3.1.3.9 Polymerizatian Performance ......................................... 2.3.1.3.10 Lewis Base Effects ...................................... ,....... .... 2.3.1.3.I I Effcct of Catalyst Composition and Stmctun: ...................

xii

Contents /

. ............................................... . . ...

2.3.2 Homogeneous Catalysts.................

2.3.2. I Introduction ................... .. ....*........‘............................ 2.3.2.2 Development and History ........................................................

2.3.2.3 Mcblloccne Catalysts ............................................................ 2.3.2.3.1 Stmcture ................................................................ 2.3.2.3.2 Cocatalysz ......................................................... 2.3.2.3.3 Catalyst Activation .................................................... 2.3 .2.3.4 lsospecific Catalysts................ ........ . ........................ 2.3.2.3.5 Syndiospecific Catalysts .............................................. 2.3-2.2.6 Aspecific Catalysts .................................................... 2.3.2.3.1 Catalysts for Elastorneric Polypropylene................ ..... 2.3.2.3.8 Other Homogeneous Catalysts .................... ....... ....*... 2.3 .2.3.9 Supponed Metallocene Catalysts ................................... 2.4 Mechanism of Propyfene Polymerization ....................................................... 2.4.1 The Active Metal--C&n Bond............................ . . ......................... 2.4.2 Insenion Mode and Regloselectivity..................................................... 2.4.3 Stereochemistry of the Insertion Reaction .............................................. 2.4.4 Steric Control of Monomesic Unit Insenion ............................................ 2.4.5 Catalytic Site Models .................... . . ............................................. 2.4.5.1 TiCI, Catalysts .......... . . ..... .............................................. 2.4.5.2 .MgC12-Supported Catalysts...................................................... 2.4.5.2.1 Stereoregulating Effect of the Lewis Bases........................ 2.4.5.3 Homogeneous Catalysts .......................................................... 2.4.5.3.1 Metallocene S d m e n y and Polymer Stereochemiq ........... 2.4.5.3.2 Aspecific Catalysts .................................................... 2.4.5.3.3 lsospecific Catalysts................................................... 2.4.5.3.4 Syndiospecific Catalysts.............................................. 2.5 Polymerization Kinetics .......................................................................... 2.5.1 l n e t i c Models .............................................................................. 2.5.2 Catalyst Concentration..................................................................... 2.5.3 Cocatalyst Concentration .................................................................. 2.5.4 Monomer Concenttation ................................................................... 2.5.5 Hydrogen Concentration. .................................................................. 2.5 -6 Temperature.................................................................................. 2.5.7 Polymerization Time ............................................................... 2.5.8 Polymerization Medium ................................................................... 2.5.9 Number of Active Centers and Value of Propagation Rate Consrant ............... 2.5.10 The Rate Determining Step .............................................................. 2.5.11 Active Site Heterogeneity ................................................................ 2.5.12 Chain Termination ........................................................................ 2.5.1 3 Replication and Polymer Morphology ................................................. 2.6 Copolymerization .................................................................................. 2.6.1 Enrroduction .................................................................................. . . 2.6.2 Statist~cai(Random) Copolymenmt~on .................................................. 2.6.2.1 Catalyst A c t i ~ i ................................................................... v 2.6.2.1 Reactivity Ratios and C o ~ o l p c Composition s .............................. 2.6.3 Scqucntial Copolymcriza~ion........ , . .................................................. 2.6.3.1 Kinctics and Catalyst hlorphology ............................................. 2.6.3.2 Ruhbcr Molccuinr Stnlcrurc ......................... .. ................... 2.6.4 Comparison Bcrivccn Homogcnmus and I-Icterogcncous Catalysts. ................ 2.6.4.1 Calalyst Aciivity ................................................................... 2.6.4.2 Composition Dis?riburion :u~dRcactivily Rar ios .............................

. . .

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. ...

2.6.4.3 Scqucntial Copo1ymrriz;tdon .................................................. 97 Rcfcrcnccs ................................................................................................ 9H 3 Structure and blorpholo~y........................................................................... Rrpr ..I. Plrillips . hfi~b11ad D. W ~ l k r ~ n:~ i r

3.1 Introduction ......................................................................................... 3.1 . 1 Building Blocks af PP bIorphology. ..................................................... 3.1.2 Crystallinity and Stcreoregulrlriry......................................................... 3.1.3 Relat~onshipof Morpholo~yto Structure, Processing, and Propemrs .............. 3.2 Morpholou,y of a-Form Isonctic PP ............................................................. 3.2.1 Crystallographic Symmetry ......................... .. ........*..*......-.........-3.2.2 Lamellar Morphology ........................ ..-- ........................................... 3.2.3 Spherulitic Morpholo~y.................................................................... 3.2.4 Melting Behavior ................... . ...................................................... 3.2.4. I Equilibrium Melting Point ........................... .....-- .................... 3.2.4.2 Multiple Endothems ............................................................. 3.2.4.3 Summary ........................................................................... 3.2.5 Crystallization Kinetics and biorphology Development .............................. 3.2.5.1 Isothermal CrystalIization: Regime Analysis .................................. 3.2.5.2 Isothermal Crystallitarion: Isotactic PPlAtactic PP Blends ................. 3.2.5.3 Isothcmal Crystallization: Isotactic PPlRubber Blends ..................... 3.3 Polymorphic Foms of Isotactic PP .............................................................. 3.3.1 B-Fom ........................................................................................ 3.3.1.1 Crystallographic Symmetry ...................................................... 3.3.1.2 Lamellar Morphology .................... ............................*..**.*..*.. 3.3-1.3 Spherulitic Morphology .......................................................... 3.3.1.4 Melting Behavior .................................................................. I 3.3.1.5 Crystallization KineticslMorphoIogy Development .......................... 3.3.2 pFom ........................................................................................ 3.3.2.1 CrystalIographic Symmetry ..................................................... 3.3.2.2 Lamellar/Spherulitic Morphology............................................... ................................... 3.3.2.3 Melting Behavior. ...................... 3.3-2.4 CsystalEization Kinetics S f M Morpholagy Development .................... 3.3.3 Mesomorphic (~mectic)Form ............................................................ 3.3.3.1 Crystallographic Symmetry ...................................................... 3.3.3.2 Lamellar Morphology ............................................................ 3.3.3.3 Melting Behavior ....................... . ... ...................................

.. ..

-

3.3.3.4 MorphoIogy Development ....................................................... 3.4 Morphology of Syndiotacric PP ................................................................. ....-.*......-. 3.4.1 Crystallographic Symmetry ...................................... 3.4.2 Lamellar Morphology ...................................................................... 3.4.3 Spherulitic Morphology.................................................................... 3.4.4 Melting Behavior ........................................................................... 3.4.5 CrystallizatiodMorphology Dwelopment .............................................. 3.5 Morphology of Rubber-Modified PP ............................................................ 3,5.1 Rubber Modification ....................................................................... 3.5.2 Morphology .................................................................................. 3.5.3 Viscosity Ratio .............................................................................. 3.5.4 Processing.................................................................................... 3 - 5 5 Crystallinity in the Rubber Phw ........................................................ 3.5.6 High Alloy Copolyrncrs....................................................................

. .

113

.... ........................................ 3.6 Injection Molded Homopolymer.............. ............................................................. 3.6.1 Injection Molding Process 3.6.2 Mamrnorphology .......................................................................... 3.6.3 Morphology Hicsarchy ..................................................................... 3.6.4 ShvnrrelProcessin~Mo'ph0106yIpropetty Relations ................................. 3.7 Concluding Commcnts ............................................................................ References ................................................................................................

. Role of Additives in PP ...........................................................................

Ronald F Bechq

4.1

k.sier l? J Burton. Stephen E Amos

PP Oxidation and Degmchtion................................................. . . . ...................................................................................... 4.2.1 In~t~at~on

4.2 Mechanism of

4.2.2 Propagation .................................................................................. 4.2.3 Branching .................................................................................... 4.2.4 Ternmation .................................................................................. 4.2.5 Chain Scission ....................... ...................................... 4.3 Stabilizing PP ....................................................................................... 4.3.1 Primary Antioxidants. ...................................................................... ................................ 4.3.1. l Hindered Phenols ............................... , 4.3.1.2 Hindered Amines.................................................................. 4.3.2 Secondary Antioxidants.................................................................... :............. 4.3-3 Effects of Flame Retardants ................................................. .................................... 4.3.4 Effects of Fillers ................................. 4.4 Other Additives ..................................................................................... ............................................. 4.4.1 Acid Scavengers ...................... . . . . 4.4.2 Nuclearing Agents .......................................................................... 4.4.3 Peroxides ..................................................................................... 4.4.4 Slip Agents .................................................................................. 4.4.5 Antiblocking Agents .......................................................................

.................

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.

177 178

178 179 t79 180 181 182 183 183 184

186 18% 189

190 190

190

192 193 194 195 4.4.6 Antistats ...................................................................................... 4.4.6.1 hzernal Antistats .................................................................. 195 4.4.6.2 ExtemaI Antistats ................................................................. 196 4.4.7 Mold Release Agents ...................................................................... 196 197 4.4.8 . Pigments ................................. . . .. . 4.4.9 Fluorescent Whitening Agents ............................................................ 197 198 4.4.10 Metal Chelators............................................................................ 4.4.1 1 Lubricants .................................................................................. 198 4.4.12 Biocides.................................................................................... 198 4.5 Addirivc Requirements for Resin Suppliers .................................................... 198 4.6 Additive Rcqtiiremcnts for Specific Markers................................................... 199 4.6.1 Fihcfi ......................................................................................... 199 4.6.1.1 Disposable Iicms .................................................................. 199 4.0.1.2 Catpct and Upl~olslcry............................................................ ZOO 3.11.2 Films ................ . ..... . . . ........................................................... 200 4.0.3 Mcdical Applications....................................................................... ,302 4.6.3.1 Chc~nistryand S~ahilizationof Imdiated PP ................................. 203 205 4.h.4 Au~omori!jc .................................................................................. 4.6.4.1 Wndcrthc tlood ................................................................... 205 4.6.4.1 Eslcrior ......................... ............................................... 205

,.

4.h.4.3 lnlcrior .............................................................................. 206

. ............... . . ... 206

4.6.5 Housc\mrcs .........................

4.6.6Co~tstruction.................................................................................

4.7 Tcstit~g............................................................................................... 4.7.1 PmcessorMcltStability.................................... ........................ 4.7.2 Long-Term Heat Aging (LTHA) ..................... . . . . .............................. 4.7.3 UV Stability ................................................................................. 4.3.4 Radiation Resistance ..................................................................... Rcfcrcnccs ................................................................................................

..

207

207

207 208 208 208 209

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&

5 Compounded

Polypropylene Products .............................................................

211

5.1 Introduction ......................................................................................... 5.2 Technical Issues .................................................................................... .................................................. 5.2.1 Composition ........................ . . .

.....................*............ 5.2.2 Compounding Process ................................. . 5.2.3 Particle Dispersion .......................................................................... 5.2.4 Interface ...................................................................................... 5.2.5 Crystallization ............................................................................... 5.3 Principles of Rubber Thghening ................................................................ 5.3.1 Mechanisms .................................................................................. 5.3.2 Elastomer Characteristics ................................... ... ................*......-5.4 Impact-Modified PP ................. ..\ ................. 5.4.1 Performance ................................................................................. 5.5 Thermoplastic Olefins ............................................................................. 5.5. I EPR Blends .................................................................................. 5.5.1, I Morphology ........................................................................ 5.5.1.2 Properties ........................................................................... 5.5.2 Ternary BIends of PP, PE,and EPR .................................................... 5.5.3 In-Reactor Thermoplastic Olefins ........................................................ 5.5.4 Performance of TPOs ...................................................................... 5.6 Therrnoplstic Vulcanizates ........ , . ........ . ................................................. ................................................................... 5.6.1 Dynamic Vulcanization .......................................................... 5.6.2 Morphology .................. . . . 5.6,3 Performance ................................................................................ 5.7 Filled and Reinforced PP .................. ....... ............................................. ........................................................................... 5.7.1. Mineral-Filled PP 5.7.1.1 Talc-Filled PP ...................................................................... 5.7.1 -2 CaIcium Carbonate-Filled PP .................................................... 5.7.2 Reinforced PP ............................................................................... 5.7.2.1 Mica-Reinforced PP .............................................................. 5.7.2.2 Glass-Reinforced PP .............................................................. 5.8 Flame Retardant PP ................................................................................ References ................................................................................................

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6 End-Use Properties .......................,,............................................................ Drrrio Del Ducu. Edwurd P Moore. Jr 6.1 Introduction ..............................

...................................................... . .

6.2 Typical End-Usc Properties of Unoriented PF ................................................. 6.3 Influences on End-Use Propenics................................................................ 6.3.1 Homopolymers ..............................................................................

237

237 237 240 240

xvi

Contents 6.3.2 Random Copolymers ....................................................................... 6.3.3 Impact (Hctmophasic) Capolymcrs ....................... ........................ .......................... 6.3.3.1 Blush Resistance ................................. 6.3.4 High Alloy Copolymm ................................................................... 6.4 Properties of Oriented PP ......................................................................... 6.5 Property Measurements and Relationships ..................................................... 6.5.1 Tacticity ..................................... .............................................. 6.5.2 Molecular Weight ........................................................................... 6.5.3 Molecrular Weight Distribution ............................ 6.5.4 Crystal 1inity.................................................................................. 6.5.5 Impact Strength ............................................................................. 6.5.6 Optical Properties...........................................................................

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References ................................................................................................

Part TI . Polypropylene: The Business .............................

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7 Introduction t o PP Business ......................................................................... Edward P Moore. Jr. Gregory A . h s o n

7.1 S t r u m of the Business.......................................................................... 7.1.1 Business Growth ............................................................................

7.1.2 hocess ....................... . . . .......................................................... 7.1.2.1 Third and Fourth Generation Catalysts ........................ :............... 7.1.3 Producers..................................................................................... 7.1.3.1 Specialization...................................................................... 7.1.4 Monomer Supply ........................................................................... ...

7.1.5 Economics ................................................................................... 7.1.6 ConventionaI PP Products ................................................................. 7.1.6.1 Properties ........................................................................... 7.1.6.2 Applications ........................................................................ .. 7.1.7 Donmtream Integration ................... . ..... . , .... . . ........................... 7.1.8 Recent Devclopment ....................................................................... 7.1.8. I Later Fourth Generation Catalysts .............................................. 7.1.8.2 High Alloy Copolymers .......................................................... 7.1.8.2.1 Properties ............................................................... 7.1.8.2.2 Applications ............................................................ 7.1.8.3 High Melt Strength PP ........................................................... 7.1.8.5.1 Definition ............................................................... 7.1.8.3.2 Propcnies ............................................................... 7.1.8.3.3 Applications ............................................................ 7.7 Paten! Rights ....................................................................................... 7.3 Eniironmennl C o n c m s ........................................................................... 7.3.1 Rcc!.cling ......................... . ....................................................... 7.3. l .I Recycling FP ................................................................... 7.3.1 Od~crAppro;lchcs. .......................................................................... 7.3.2.1 Lifc C!.clr: Analysis ............................................................... 7.3 .2.2 Source Rcdr~crion................................................................. ' 7 ' 7.3.-.> Landfill ............................................................................. 7.3 .2.4 Incinc~ttion and Energy Rcco~lcry.............................................. 7.3.3 summ.!ry ..................................................................................... ?

1

ltcfcrcnoc~................................................................................................

8 Manufattu ring .......................................................................................... Richard B. i+ir*hr.r.trrun.Riulrrrrd 7: EA?Nvir

8. 1 Early Procusscs .................... . , . ...... ....... ...................................... 8.2 Cumnt Proccsscs .................................................................................. 8.3 Monomcr ............................................................................................ 8.4 PoIyt~crFinishing .................................................................................. 3.5 Prorcss Environmental Issues .................................................................... Rc Fcrcnccs ................................................................................................ 9 Fabrication Processes.................................................................................. & L ~ \ V U JP~ .\!t?(>f

r. Jr

9.1 Introduction ......................................................................................... 9.1.1 Introduction to Extrusion Processes...................................................... 9.1.1.1 Extrusion ........ , .................................................................. 9.1.1.2 Quenching .......................................................................... 9.1.1.3 Reheating ........................................................................... 9.1.1,4 Coextrusion ........................................................................ 9.1.1.5 Health, Safety, and Environmental Issues.............. ................. ........................... 9.1.1.5.1 Health . . . . ... . ...... 9.1.1.5.2 Safety ................................................................... 9.I 1S.3 Environment............................................................ 9.1.2 tnmduction to Orientation ................................................................ 9.1 .2.1 Trpes of Orientation .............................................................. 9.1.2.2 The Orientation Process .......................................................... 9.1.2.3 Properties of Oriented Articles .................................................. 9.1.2.4 Measurement of Orientation .....................................................

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9.2 Exmsion ko&sses ................................................................................ 9.2.I Fibek ......................................................................................... 9.2.1.1 Melt Blown Fibers ...................... . . ...................................... 9.2.1.2 Spunbonded Fibers., .............................................................. 9.2.1.3 Conventional Fine Denier PP Fibers ........................................... 9.2. t .4 Continuous Filament Fibers ............ ...... ................................. 9.2.1.5 Bulked Continuous Filament ..................................................... 9.2.1.6 Staple Fibers ....................... . . ............................................ 9.2. I .7 Monofilaments..................................................................... 9.2.1.8 SlitTape ............................................................................ 9.2.1.9 Strapping ...........................................................................

9.2.1 -10 Decorative Ribbon ............................................................... 9.2.2 Oriented Films............................................................................... 9.2.2.1 Tubular Biaxially Oriented Film ................... ..... ............. ............-9.2.2.2 .Tentered BiaxialIy Oriented Film ............................. . . 9.2.2.3 Polymer Selection ..................................... 9.2.3 Unoriented Products ........................................................................ 9.2.3.1 Chill Roll Cast Film .............................................................. 9.2.3.2 Water Quenched Blown Film.. .................................................. 9.2.3.3 Air Quenched Blown Film ....................................................... 9.2.3.4 Shect ........................................ . . . . . ............ 9.2.3.4.1 Thcnnofoming ........................................................ 9.2.3.4.2Solid Phase Pressure Forming ....................................... 9.2.3.4.3 Mcll Forming ....,...................#................................ 9.2.3.5 Extrusion Coating.. ...............................................................

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xviii

Contents

9.2.3.6 Othm Extrusions ................................................................... 9.2.3.6.1 Profilesand Pipe ..................... ........... .............. 9.2.3.6.2 Wire and Cable Coating .............................................. 9.2.3.6.3 Cormgated Board ..................................................... 9.2.3.6.4 Foamed Sheet .......................................................... 9.3 Injection Molding .................................................................................. 9.3.1 Product Design ............................................................................... 9.3,2 Mold Design .............................................................................. ................................................... 9.3.3 Mdding Cycle ..................... 9.3.3.1 Mold Fill ........................................................................... 9.3.3.2 Mold Pack .......................................................................... 9.3.3.3 Hold ................................................................................. 9.3.3.4 Cooling ............................................................................. 9.3.3.5 Screw R e c w q ................................................................... 9.3.3.6 Ejection ............................................................................. 9.3.4 Resin Selection.............................................................................. 9.3.5 Thin Wall Injection Molding .............. ....,.. ..... ............................. 9.3.6 Special Molding Processes ................................................................ 9.3.dl Gas Assist Molding ............................................................... 9.3.6.2 Structuml Foam Molding ......................................................... 9.4 Blow Molding ...................................................................................... 9.4.1 Extrusion Blow Molding .................................................................. 9.4.2 Injection Blow MoIding .................... . . ............................................ 9.4.3 injection Stretch Blow Molding .......................................................... 9.5 Other Processes..................................................................................... 9.5.1 Compression Molding...................................................................... 9.5.2 Foamed Bead Molding.. ............ . . . . ............................................... References ................................................................................................ ; . .

10 Applications ..................................... . . ..................................................... Charles G. OeneI 10.1 The Evolution ..................................................................................... 10.2 Fibers ............................................................................................... 10.2.1 Carpets ....................................................................................

10.3

10.2.2 Slit Tape ................................................................................... 10.2.3 Nonwoven fabrics ....................................................................... 10.2.4 Apparel .................................................................................... 10.2.5 Cordage ................................................................................... . . 10.7.6 h m m g ..................................................................................... Injcctinn MoIdcd Cansu~ncrProducrs ......................................................... 10.3. l .LLppliances ................................................................................ 10.3.2 Gsnenl Consurtlcr Products ............................................................ 10.3.2 hledical Applications.................................................................... 1 O.j.3 Rigid Packaging.......................................................................... 10.3.5 T~mspertalion............................................................................ 5 1 inrcrior Uses ................................................................... 10.3.5.2 Esrcrior Uscs .................................................................. Film ............................................................................................... 10.4.1 Bia~iullyOricntcd Film ................................................................. -. 10.4.2 Untlricnrcd l-dm .......................................................................... Wirc and Cable... ................................................................................. Mis~cllnntnus..................................................................................... 1'1

10.4

10.S 10.6

Contcnts

xix

.................. . .

11 Rcgulutiuns and Approvals ...........................

.

Crrrlterint E Rtrk . Richurti T LehrIlir

I 1. I ~nnoducti~rn ........................................................................................ 11.2 H ~ l l t dCotn~nunication.......................................................................... 11.2. t hl;lzsrial Safcty Data Sheets (LISDSs) ................................................ 11.2.2 PP md PP Copolymcts ................................................................. 1 1.3 Chcmiczll Rc~istntion............................................................................ 11.3.1 Tosic Substances Control Act (TSCA)-- t'nitcd States ............................ I I .j b 2 European invcnltory of Existing Chtmical Suhsrances (EINECS)/Europran Lisl of New Chemical S~ubst~ncccs (ELINCSI ....................................... l 1.3.3 Domestic Substances List (DSL)and Nondomestic Substances List (NDSL) Cmada.....................................................................................

1 1.4 Food Contact ...................................................................................... ll.3.1 United States: Food and Drug Administration (FDA) .............................. . .......................................... 1 1.4.1.1 FDA Petitions ..................... I I .4. 1.2 FDA Regulations for PP Homopolymers and Copolymers ............. 1 1.4.1.3 Title 2 1, Part 177.152Q-Olefin Polyners Regulation .................. 11.5.1.4 Food Types..................................................................... 11.4.2 Canada: Health and Welfare Depament-Health Protection Branch (HPB) ... 1 1.3.3 European Union .......................................................................... 11.4.3.1 PP and PP Copolymers ...................................................... 1 1A 3 . 2 Additives ....................................................................... 11.4.3.3 Certification far Food Contact Compliance ............................... 1 1.4.4 Japan: Japan Hygienic Olefin and Styrene Plastics Association (JHOSPA) ..... 1 1.4.5 Australia.................. .,..... . .................................................... 11.5 Potable Water ...................................................................................... 1 1.6 Medical Applications ............................................................................. 1 1.7 Fire and Electrical Safety Certifications....................................................... 11.7.1 Flammability.............................................................................. 11.7.1.1 Horizontal Bum

(94HB).....................................................

1 1.7.1.2 20-mm Vertical Burn (94V0,94V1,94V2) ............................... 11.7.1.3 125-rnm Vertical Bum (94-5VA, 94-5VB) ................................ 11.7.2 Short-Term Property Evaluations ...................................................... 11.7.3 Long-Term Property Evaluations ...................................................... .................................................... 1 I .8 Customer Specifications ................... , References ................................................................................................

Part JII . Polypropylene: The Future . .......................... , . . . , .

.

....

12 Specialty Types and Developments ................................................................. Edwrd t? ,Moore. Jr 12.1 Introduction ........................................................................................ 12.2 Meallocene Catalysts ............................................................................ 12.2.1 Technology ................................................................................ 12.2.2 Isoractic PP ...............................................................................

12.2.3 Syndiotactic PP .......................................................................... 12.2.4 Commcrcialization ....................................................................... 12.3 Nonolefinic Alloy Copolymers ................................................................. 12.4 Summary ...........................................................................................

References ................................................................................................

Contributors Alhizzari, Enrico, Monte11 Italia S,p,A., G.Natta Research Center, P.le Doncgani 12,41000 Ferrara, Italy

Amos, Skphen E., 3M Company, 521 5 Logan Ave. South, Minneapolis, MN 554 19-1021, USA Becker; Ronald E Montell USA, Fnc., R & D Center, 912 Appleton Rd., Elkton MD 2 1 921, USABwrni, Omar M.,Monte11 USA, Inc., 2727 Alliance Dr,,Lansing, MI 48915, USA Burton, Lester

EX,Montell USA, Inc., Ft & D Center, 912 Appleton Rd., Elktan, M D 21921, USA

Collina, Gimni, Monte11 ltalia S.p.A., G.Natta Research Center, P.le Donegani 12,41000 Femra, Italy

Del Duca, Datio, Morltell Italia S.p.A., G.Natta Research Center,Ple Donegani I2,41000Femra, Italy Dwyer; Stephen M., Monte11 USA, hc.2727 Alliance Dr., Lansing, MI 48910: USA Giannifii, Umberto, Montell Italia S.p.A.,

G. Natta Research Center, Ple Donegani 12,41000 Ferrara,

Italy Larson, Gregory A., Netherlands

LeNoir; Richard 5961. USA

onte tell PoIyolehs, P.O. Box 625, Hoeksteen 2130 AP, Woofddorp, The

Z,Montell USA,

Inc.,

R & D Center, 800 Greenbank Rd.,W~lmington,DE 19808

Liebeman, Richard B., Montell USA, Inc., R & D Center, 9 12 Appleton Rd., Elkton, M D 21 921, USA Moore, Edward I?. Montell USA, Inc. (retired), 7 18 Cheltenham Road, W i l m i n p , DE 19808, USA Noristi. Lucinno, Montell Italia S.p.A., G.Natta Research Center,

Donegani 17.4 I000 Ferrara, Italy

.

Oertel, Charles G.,Montell USA, Inc. [retired), 1000 Oriente Ave., WiIrninston. DE 19807, USA Phillips, Roger A., Montell USA, Inc., R & D Center, 912 Appletan Rd., Elbon. MD 21 921, USA

Resconi, Luigi, Montell Italia S.p.A., G.Nana Research Center, Ple Donegani 12.41000 Fenam, Italy Ruiz, Carl~erineE.. Allied-Signal Corp.. 101 Columbia Rd., Morristown, NJ 07961, USA

Shlc, Chicl~ong,Mantell USA. lnc.. 2727 Alliance Dr., Lansing, MI 48910,US.4 M,blkoulic:. MicFtoel D.,Montell US.4. lnc.. R & D Center, 9 12 Appleton Rd.. Elkton. M D 2 192 1, USA

Subject Index

Ah initio ca[cuIations 83 Acid scavengers 190 Actlvatcd MgCI? 13. 22, 44 Activation energy for polymerization 78, 83 Activat~onof metallocene catalysts 45 Active center modcis 74 in TiCI2 catalysts 61-64 in MgCll-supponed catalysts 29, 65-69 in metallocene catalysts 69-73 Active centers 61, YO

Aluminum trihydnte I 8 8 America[ National Standanls Institute (ANSI) 382 American Saciety for Test Methods (ASTM) 396 ArnocolChisso process 3 7

concenmtion 80 deactivation 75, 79 formation 48,56 heterogeneity 84 selective site poisoning 67 Addipol process 300 Adhesive tape 376 Adserptior! of monomer 74 o f aluminum alkyls 75 Air quenched blown film (AQRF) 331 Al-Alkoxides 33 . AIC13 12, id,91 AIEtz Br I8 AIEt,CI 12, 18, 36, 57, 58, 78, 82, 84, 90,

syndiotactic PP 147 &,-orz transition 120 &a! hmsition 136 y-or innsition 140 Antiblocking agents 194,I'QI Antimony oxide 188

91 A I R 2 18

AlEtCl? 20 AIR3 18, 19,29,31-36,4842, 73-77, 82,86, 90, 91 Ali-Bu3 29, 32, 48, 75, 82, 90 Alkoxysilanes as external donors 13, 3 7-42 reaction with AIR3 33-33 Alkylphthalates 13, 28, 38, 44

AlkyI radicals 203 Allyl radicals 203 Alumina as support 12, 54, 54 Aluminum alkyl cocatalysts I I , 18, 29, 75 Aluminum alkyls as cocatalysts, effect of f 8, 75 reaction with catalysts 33-36 reaction with Lewis bases 29-33

Annealing

isothermal thickenins I26 mesomorphic-z transition 143 multiple melting 126

Antioxidants primary 183 secondary 186 Antistatic agents 195 Apparel 354 Appliances 358

Approach to business 261 Aromatic acid esters as internal donors J3,27,34 as external donors 13,34,37 65 reaction with AIR3 2S.33 Aspecific catalysts 52, 70 Association Francaise de Normalisation

( P J N O R ) , France 395 Atactic PP 4, 12,52 Atactic PP removal 13, 287

Aufbau reactian 7 Automotive applications 368 Avrami analysis isotacticlatactic blends 2 31 a-form 129 Y-~O~TII

141

Axialites 122

Barrier 241 BASF process 292

Bathes 277,3r5R B(Chf 513 48

Bcnzoic acid esters 13, 27, 34, 37, 65 Bcnzoxamles 19 7 Biaxially oriented PP (BOPP) film 325,371 opaque 328,3 74 properties 250 Bimetallic mechanism 61 Blend thermodynamics 131 Block copoiymets 92 Blush resistance 220, 248 Blow molding 345 injection 346 injection sixetch 347 Blowing agents 34.5 Body side molding 205 Borates I88 BoronAcompound, for metallocenes 48 Bottles 366 Branching S British Standards Associati~n(BSA) 385 Bulked continuous filaments (BCF) 319 Bumper fascia 205, 371 1-Bmene copolymerization 90, 244 Calcium cahnate-filled PP 227 Canadian Standards Association (CSA) 395 Capacitor film 312, 328, 3 75 Capacity, production 258 Car seats, children 360 Carbon monoxide reaction with metal-carbon bond 56 labeled, acrive certers determination with 81 Carpet backing 351 Carpeting 330 Catalloy prnccss 249,271 Caralyst activation 48 fragmentation 86.87 morphoiogy 17. 18, 2 3 , 8 6 4 7 shapc ,'0,,"3 surf;ice m a and porosiry 29. 64.87. 92 Catn tyst gcncrmons first I?. 15 sucond 12.20, -7.59 third 12, 22, ?fill fourth I.?. 2150 iillh 13 sixth Id

Catalyst residues 13, 259,287 Certification protocol 3&1 Chain end groups 5 6 5 7 Chain scission 181 Chain rclmination reactions 84-85 Chemical abstract services (CAS) 384 Chemical Manufacturers Association (CMA) 382 Chemical resistance 239 Chill roll cast film 328 Chisso process 297 Clarifiers 190,244 Clatity 239,366 Closures 365 Cocatalysts 29, 75 aluminum alkyls / I , I& Cocontinuous phases 249 Coextmsion 307 Cornonomer distribution 90, 97, 405 Compact staple spinning process 321 Complex formation 31, 33 Compounding equipment 212 Compression molding 347 Compression set 222 Continuous filament fibers 318 Controlled rheology PP 192, 317 Coofers 361 Copolymerization 89 random 90-91,244

-

sequential 92-94,245-249 reactivity ratios in 90, 96 Copolymers "block*' 92 high alloy 249, 271, 306. 331 impact (or heteraphasic) 5, 92,212,2 1 7. 245

nonolefinic a l l q 4(37 random 5 , YO, 244 Corda~c356 Comgarcd board 338, 377 Corona trcatmcnt of film ,702 Cosscc mcchanisrn 61, 62. 71 CoupIrng a g n t sillinc 214. tttanatc 227 C1'TtClr 55 Cp2T~Clr61 Crystalli~~~ty 7, 166, 215. ,730, -752 injrct ion moldings 166 polymorpllism 134

rubber phasc 1.58 * tacticity effcct on 114, 12rS Crystallite sizc TiCI3 16, 18, 20 MgClz 26, 29 Crystallization, and kinetics of 4, 214 Avrami analysis 129 blend therrnod>nmics 131 crystallization temperature, effect on 139

fold surfacc: encyy 125 isotactidatactic blends 131 melt orientation Ed5 metalloccne-based iPP 404 malecular weight. emct on 13 1 nonlinear growh 132 nucleaaon theory. 129 secondary crystallization 318 syndiotactic PP 148 tacticity, e f f i t on 131 work for chain folding 131, 148 ~ - f ~129m

p-form 137 )t-fom 141 Customer relationships 261

DEAC, see AlEt,CI Deactivation of catalyst 7 8 4 Decorative ribbon '324, 377 Defects in polymer chain regioirregularities 4, 57-58, 404 stereoimgularities 4, 6 0 4 1 Degradation mechanism 178 branching 179 initiation 178 propagation 179 termination 180 Dehydrogenation of propane 263 Dcnsity 252 amorphous 126 crystalline (9-form) 126 Density functional method 83 Dialkytphthalates, see phthalic acid esters Diapcrs 354, 376 Diatomaceous earth 194 Dic dnwdown 305 Diclcctsic strength 312 Dicthcr donors 13, 28, 35, 42, 76 Dicthylaluminumchloride,see AIEttCZ DiITusiorl of monomer 78, 87

Dilucnt 287 Dircctivcs. Europsnn Utlir~tl3(02 Dishwshur linct 358 Dispersion 213, 2177 Distcavl thiodipropionrltc (DSTDP) 186 Domcstic Subsmccs List (DSL), Canada 385 Dnwdown surge 305 Dmg Miutcr Filc (DMF)N S DuPont Co. 275 Dynamic vulcanization 22:

EADC. see AlEtCl? Eastman process 238 ES (Ethyl benzoate) 1 3 , 3 . 38, 44 Elastomeric polypropylene. From metallocenes 53 Electron beam radiation 203 Electron donon intemaI 13, 26, 29, 42 external 13, 29, 41, 42 reaction with cocatalyst 29-33 Electron spin resonance (ESR) 26, 36 End-use regulations in f d contact 387 Enviwnmental concerns, PP processes 300 Enviw nmental Protection Agency (EPA) 384 Et Paso process 293 Erucamide 201 Ethylaluminumdichloride, see AIEKIZ Ethylanisate 29 Ethylbenzoate, see EB Ethylene crackers 262 Ethylene-propylene copolymers 5, 90, 94, 218, 244

Ethylene-propylene rubber (EPR) 216, 220, 245 Ethylene-pmpylene-diene monomer (EPDM) rubber 216 European Union directives 382 monomers d~rective 39 I European Inventor)l of Existing Chemical Substances (€IN ECS) 385 European List of New ChemicaI Sustances

(ELMCS) 385 Expanding universe model of particlc growth 8 7 Exterior trim 370 Extractablcs, for food contact applications 245 Extrusion coating 336

414

Index

FDA regulations 387 conditions of use 389 cooking 387 noncmking 387 Fmcing 356 Fender liners 371 Fibers 350 propmies 250 Filtration 287 Flame retardant PP 188, 232 Foamed bead molding 348 Foamed sheet 338 Fold surface energy I24 melting, effect on 125 nucleation theoq 129 syndiotactic PP 149 tacticity, effect on 131 a-form 131 fi-form i 37 Food cantact 206 Food and Drug Administration (FDA) 386 Food packagmg 365 Free radicals 178

Gamma radiation 203 Garden xools 361 Gas assist moI&ng 344 Gas fading 184, ,700 Gas phase process ,792 Geogrjds 356 Geotextiles 353

Glass fiber-reinforced PP 214,229 Glass mansition temperature of elastomer 216 GMS (glycerol monostearate) 195 Grafl~ny,:I?. 229 Granule 24Y. J 3 I . -749

I lafr~c~ccncs 4(I Ii:tndcdncss J t Ii~Iopc~lotcJ FRs 189 ! I;~rdncss2.;:. ,741 I lnrtrcc-l'nck c:~l~ul:rt~ot~s 71, h'3 Itnzitrd Comrnlu~ir;~t~on Strutdard

( I IAZTOhl) .;A'? 1 1 [)PI! r~ddfrion ,','I]

I l e , ~ d - f r ~ - ~l ;instbrt li ion of rilorlonlcr 4

Health Protection Branch (HPB), Canada 389 Heat-sealable films 244 Heat-setting process 311 Helix 4, 119 Hercules Powder Company 7, 275, 350 Heterophasic copolymers 5, 92,2 12, 2 17 Hexane diluent 287 1-Hexene copolymerization 90 High alloy copolymers 249,271, 306, 331 High melt strength PP 273,306,335-339,346 Higher alphaalefin copalymers 405 Hsrnont 9 Hindered amines 184 Hindered phenols 183 "Hivalloy " process 407 Hoechst 7, 9, 275 Homogeneous catalysts 45 Homopolymers 5 Hydrogen effects 7677 Hydroperoxides 178 Health, safety, and environmental issues 308 Hypol process 294

Impact copolymers 212,217 Impact strength 149, 151, 158,237,253,311 Incinemtion 279 Infrared spectroscopy of catalysts 28, 31, 35 Injection blow molding 346 Injection molding 165, 219, 340, 267 polymorphism 167 process parameters, effect on 1.50, IS4,J62, 168 rubber modification 154 skin-core smcture 165 thin wail 343 Injection stretch blow mald~ng347 In-process s[abilij!x:r 177 Insertion mccl~anisrn.nlononlcr 5'6.HI chain cnd control 59 chain rnigralory 70 chain sklp back 61 cnanltomarphic s ~ l ccanttal 59 luscnioti rcactlon act i\-;~tion cncrgy 83 n.giosclccl!vity Srj stcrcochcmiary 5h' stcric canlml 59 lt~tt.ri;~:,lcial sdlicsion 214, ,716, 22Y I ~ l ~ ~ r f btcnsir~n ~ i i ~ l 16.5

Index

Fntcrior trim JdY Intcmarionnt Elcctrnzcchnical Commission (IEC) 396 [ntcrnariorual Standards Organization (!SO)396 lmdiatcrd PP stiibilization 203 [sotactic 1ndc.u (11) 12, 38, 222 Isotacticiry 4, I l j . 11 7, 132, 240, 250 Japan Hygienic Olttin and Styrene Plastics Association (JHOSPA) 392

Kaminsky. W. 46. 49 Kinetics of polymeriz3tion 74

Larnellae 113, 114 crosshatching 120 crystallizatian temperature, effect of 122 injktion moldings 167 " isotacticlatactic blends 23 1 isothermal thickening 128 , melting point, relation to 124 mesomorphic form 143 optical classifications (a-form), effect of 122 syndiotactic PP I66 a-form 120 fl-f~m135 . 7-form 139 Landfill 278 Lawn (outdoor) furniture 359 Lewis bases 1 3 , 2 2 4 4 stereoregulating effect of 65-69 Life cycle analys~s,for recycling 278 Llppshac process 294 Liquid monomer process 291 Loop reactors 294 Low temperature impact strength 239 Luggage 359 Magnesium alkoxides 23, 43, 64 Magnesium alkyls 23 Magnesium hydroxide 188 MA0 J4,46,4R, 50,403 Material safety data sheets 308, 382 Mcdical applications 364 regulations 394 Medical waste containers 364 Melt blown fabric 311,314

4l5

hlclt fluw r ~ t c237 hlclt forming 335 Mclt stabiliiy 200 Mclt unifomiry 304 blclting factors influencing 124 equilibrium melting 124 lamellar thickness 124 Hohann-Weeks extrapolation I25 mesomorphic form I43 multiple endothems 226 polymorphism, effect of 127, f 36,140, 143 syndiotactic PP 147 tarticity 124 z-fom 124 P-form 136 7-form 140 Mesomorphic form 122-124 Metal deactivator 198 Merallocene catalysts 14, 446, 69,403 activation 48 aspecific 52, 70 propylene concentration effects 50 isospecifir: 49, 70 structure 46, 49, 69 supported 54 symmetry 46, 52, 69 syndiospeci fic 52,73 Mechylaluminoxane, see M A 0 Methyl-p-totuate, see M R MgBr;, as support 22 MgCI, 13,26 activation 22-23 crystal surfaces 68 structure 23 MgC12-supported catalysts 12, 14 composition 26 interaction w ~ t hcocabtalysts 33-36 polymerization with 3 6 4 5 preparation 22 structure 26, 2'1 Ti oxidation sralc in 36 Mica-reinforced PP 214, 227 Mill~ngof catalyst 16, 22 Miscibility 131 Mitsui Pclr~chcmi~al 2514 MnCIz as support 22 Modulus 237 Moisture barrier 250, 346 Mold rclcasc agcnu 195

416

Index

Molding cycle 340 Molecular wight 242 from heterogeneous catalysts 3 7,39, 42 from homogeneous catalysts 49, S I Molecular weight distribution, see M W D Monofilaments 322 Monomer insertion mechanism, see Inscnian Monomer

regime analysis 129 syndiotactic PP I47 a-form 131 p-f~m137 7-form I42

Oleamide 201 Olefin polymers regulation for food contact 387 Opaque BOPP film 328,374 Optical properties 244, 253 Onentation I J6, 242, 249, 269, 309 in injection moldings 165, 167-149 measurement 3 I3 process 3 10 properties 31 I r-mesomorphic transition 143 zl-zltransition 120 fl-3 tsans~tion 136 7-x m s i t i e n 140 Outdoor furniture 359 Oxygen barrier 250,307,

demand 264 quality 263,298 self sufliciency 262 sources 262 Montecatini 7, 275 Montedrson 9, 275 Mantell 9, 271, 274, 407

Morphology of polper 86 of EPR blends 92,148,218 of thermoplastic vulcanizates 223 MPT (Methyl-p-toluate) 13, 32, 38 Multiple melting 126, 136, 140, 143 syndiotactic PP 148 fi-form I36 MWD 42, 69,96,192,242,252,317,318,320,

-

-

343,405

Nana, GirrIio 7, 8, 274 Nening 32?, 3-74 Nicolais-Narkis equation 21 9 Nimoxyl species 186 NMR of catalyst 67, 69 of PP 41.56, 60, 90, 252 Nondorncstic Substances List WDSL), Cmada 355 Nonolcfinlc alloy copolymers 4117 Nonwoven fabncs 31 4. 353 Noticc o f Cornn~cr~ccmcnt (NOC) of conimcrcializat~on354 Novolcn process 292 Nuclcar trr:lgnrtic resonance. scc N M R NucIcatirl~agcnls I YO Nuclcarion 114, 242, ?4+3 is013ctic ,aractic hlcnds 13 1 suriicc. 129 /)-!hm? 13 7

I;-rtcoli\.cnion

1.26 7 - r comcrslon 110 Nliclcil~Et~r~ rl~ctlry

Packa_@g 325-336, 365 food regulations 386 potable water 394 Patent 9, 274 PCL, Lrd. 7 Peroxide decomposers 186 Peroxide-assisted degradation 192, 245, 261, 299,315 Peroxy radicals 1 78, 204 PES 32. 36 P-ethox!.-ethylbenzoate (PEEB) 29 Ph3Cf [i3(ChFs)4]- 4h' Phenyl coumar~n l97 Phcnylmcrhexysilanc, scc FES Phillips Petrolcum Co. 274. 29 I Phosphitcs 178 Phosphonitcs 178 PhthnI~~t..'i~lkoxysilan~ donor syslcm 38 Phthalic nctd csrurs as dor~ors3 Fipc

.i.?.7

Po1~dispcmityiridcx (PI) 243,252 PoZyct h!-Icnc 7 PoIyncr c;~gc 178 Pulyl~lcrqunlrty atr qucnct~cdhlowu fit111 .:32

BOPP fitm 328 bulkcd conlin~~t~us filaments 320 chill mi1 cast film 330 contiriuous fit:lmt.nts 3 1R injection molding 34.2 mclt blown hbric 314 rnonotilarncnts 322 shcct 333 slit tapc 324 spunbondcd hbric 3 17 staple fibcrs 322 strapping 321 thin wall injcclion molding 3-13 water quenched blown film 331 Polymerization nte 74 determining step 81 catalyst concenmtion effect 75 cocatalyst concentdon effect 73-76 hydrogen cencenmtjon effect 7 6 7 7 monomer concentration efFect 76 polymerization medium effect 80 pofymerizat~ontime effect 78-40 polymerization temperature effect 78 ' PaIymorphisrn 134 injection molding 167 melting, effecton 127, 136, 140, 142 syndiotactic PP 145 a ,-a2 bansition I20 8-a transition ,136 ?-a transition I40 PolypropyIene atactic 4, 12, 52, 287 elastomeric 53 morphology of 86 syndiotactic 52 Porosity and surface area of catalyst, see Catalyst, surface area Post-consumer recycling 276 Potable water 394 Prcrnanufacrure Notice (PMN) 384 Production, growth rate 257 Profiles, extruded 337 Profit margin 264 Propagation rate constant 74, 80 Propane dehydrogenation 263

Quenching the cxtrudate 3(Ci Quinonc structure IN4

,' Radical scavcngcss 18J Random copolyrncrs 5, Wl. 244 Rarc dctcrmining stcp in polynlcrir~~tion 8/33 Reactivity mtios in copotytncrs YO, Yci Rcactor granulc 249, 271 Recycling 27r5, 3366, 3711 Rcgiorcgularity 4, 56, 4113 Reinforced PP 227 Replication of catalyst cYb distribution af active ccntcE 89 difFi~sionlimitations 87 expanding universe model 87 muitigrain model 87 Rexa II, Rexene process 29 1 Rope 322,356 Rubber modification 149 blend thermodynamics 132, f 49 blush resistance 158 capillary number JW crush resistance 156 crystallization I31 film 162 impact 149,151, 158 interfacial tension 149 morphology f 32,15&165 paintability 158 processing effect 154 viscosity ratio I51 Taylor dispersion 154 Weber number IS4 Rubber phase composition 218, 247 dispersion, particle site 246

Secondary crystaIIization 318

Secondary monomer insertion 57 Sel f-cenification 381 SHAC 13 Sheet process 332 Shell 9 Silica as support 194 Sinn, H. 46 SilyI-ethcrs 13, 32, 42 Skin-core morphology 113, f 115 rubbcr modification 150, 156 homopolymcr 165 praccss parameters, effect on 151, 154, 165, IciH Slip agents 193, 201

418

Index

Slit tape 323,351 Slurry process 259, 287 Smectic form, see Mesomorphic form Solid phase pressure forming (SPPF) 335 Solid waste 276 Solution pTQCeSS 288 Solvay catalyst f 2, 20, 259 Source reductien, for recycling 2 78 Sphenpol process 10,260, 267,293 Sphemlite 114 birefringence (3-fom) 122 birefringence (J-form) 136 crystallktion tempmtm, effect of 122, 136 injection moldings 167 isotacticlatactic blends 131 optrcal classifications (2-form) I22 optical classifications (B-form) 135 non-linear growth 132 radial growth rate I29 ' syndiotacitc PP 147 a-form I20 /?-form 134, 243 y-form 139 Spunbonded fabric 3 11 , 3 15 Stadium seating 360 Stain resistance 239 Standard Oil of Indiana 274 Staple fibers 321 Stat~oneryfilm products 375 Stereochemical control mechanism 5$-6 1 chain end conrrol 59-61 enannomorphic slte conuol 59-61 Stereospecifici~of catalysts 4, 12 elecwon donor effects 37. 65 monomer concentration effects 50. 72, 73 potymerizar~onmedium effects 73 polymcrimrion tempcram c f f e c ~49, ~ 50. 32 Stcrilizarion 20: Strapptng -324. .i 76 Strcss whstct~lt~g 215 Suucrunl ftxirn molding 34-f Slruc~urc~propcrry rclatto~lrl~ips1 16 blush rcsist;~ncc IJS, lJ8 crush rr.zist;~ncs 1.FS till11 !43. l h 2 , 2.50. .?[I6 ficxural tncldulus /ha\', 240 3 1 c u d~s~isninn In,\'. 2411 inip;bct, ruhhcr n~odi ticu ion 14 Y- 1b0, 2J.i ~ I I I ~ I : II. C I~onloprlymcr165. 240 ~ ~ ~ c c ~ ~i :i [~~ ~n si ic>it r~t ~l 1%. p y I t>,Y. JJ2

paintability 156 shrinkage 168,310 tensile properties 168, 240 toughness 156 Super-active third genesation catalysts 13 Super high activity catalysts, see SHAC Supponed catalysts J2,22,54 Syndiospecific catalysts 52 Spdiotactic PP 4, 52, 115, 144 crystallization kinetics 148 crystallographic symmetry 145 equilibrium melting point 147 . fold surface energy 149 lamellar morphology 146 metallocene-baed 406 spherulite morphology 147 melting behavior 147 work for chain folding I48 Synergism in stabilization 186 Synthetic turf 353 Syringes 202, 364

Tacncjty 114 atactic I31 blends J 31 crystallinity 11 4, 126 crystallization kinetics 131 injection moldings 168 inm-chain d~stributionI16 inter-chain distribution 116 isotactic 115, 134 melting 124-128, 147 srereoblock I 15 surface free energy 130 syndioractic 115, I43 U'AXS pattcms 11.5 1.-fomt I41 Taste m d odor trrlnsfcr ,706 T,\lc-tiilcd PP IY4, 226 Ti!.lor dispcrsion 1.54 TE.4. scc AlEt3 Tu~.;ilcsrrcngth -737 Tcnttwd I30PF film 326 7.2.6.t~-T~.tr,irnc~4~ylpip~ri11ti~c (TMP) 29, 42 Tl~crn~oll~mtng .533 Thcniioplrsi~colcfins ('rFOs) 371 lhcnrlolil;~stlc vr~lciinix:itcs(TPVs) 222 Thin \\;ill uc~nvait~crs .3(1(1 l't1111\1';111 I I ~ C C ( ~ Omolditig !I 34.3

Tllr io cornpolinds IIYfi Third party ccrti2ic:ltion 3,Y I Ti(all~1)~ 45 Ti(bcnzyll, JS TIBA, scc Ali-Bk~,, Tic!, I I , 12, 14-22.174, 33, 36. S6,57, 61-63, 76. 78. ,DCJ, 82, 84, cY6, 911

brown

(8) 16

crystal surfaces 61 violct (3. /i. arrd B ) IS TiCI, 1 I- l4. 11. 211-23. 26-29, 34-45, 56.i;. 64. 65, 75-70, 90 complcs with Lewis Base 67 milling 16 reduction 16. 10 TilCth dirner 65. M

Ti oxidation state 36 TMP 29,,12 Toughening mechmism Z / S Toughness 141 Toxic Substances Control Act (TSCA) 383 Transition metal-olefin R-complex 83 Transportation applications 368 Triethylaluminum, see AIEt Triiso-burylalum!num, see Ali-Bu, Tubular BOPP film 325

UL74hA short term properties 398 UL746B long term properties 398 UL94 flammability 396 Underwriters Laboratories (UL)395 Union Carbide Co. 294 UnipoI process 294 Unit cell 114 epitaxy En cross-hatching I20 epitaxy in r,;-forms 139 growth direction (r-form) 120 growth direction (fi-fom) 13s polymorphism 1 17, 13.4, 138, 142, 144 melting, effect on 126, 136. 140, 143 mesomorphic form 142 regime transitions, retation to 131 syndiotactic PP 144 thermal expansion 146 ?-form PI8 11-form (34 ?-form 138 United Statcs Depanment of Agriculture (USDAj 384

Vanadium-bascd catalysts 35 VCI, 4.5 Vcrband Dcutschct Elrktmtcclmikcr (VDE), Gcmany 39.7 Viscosity ntio 147, 150. .?I7 VOClf 45 VO(OEt),CI 4S Water carryover 323 Water quenche'd blown film WQBF) 330 Whitening agents 197 Wire and cable coating 337,376 Workplace Hazardous Materials Information System (WHMIS) 352 Xantrix concentrates 299

Ziegler, Karl 7, 274 Zrjallyl), 45 Z r ( b t ~ 1 )45~ z-Agostic interactions 63, 72 % - f o m I J 8-1 3 1

birefringence 122 density 126 equilibrium melting point f 24 equilibrium heat of fusion 123 fold surface energy 131 growth directi~n 120 multipie melting 126 work for chain folding 131 z -z2 transitions 1 18

Ijl-form 1 3 4 1 3 7

shear, effcct of 137, I67 /]-methyl elimination 85 1-sclssion 181 7-form 138-141 rolc in cross-hatching 121