Table Of ContentStudies in Polymer Science 7
Studies in Polymer Science
Other titles in the series
1. Elastomers and Rubber Compounding Materials edited by I. Franta
2. Molecular Conformation and Dynamics of Macromolecules in Condensed
Systems edited by M. Nagasawa
3. Design of Plastic Moulds and Dies by L. Sors and I. Balazs
4. Polymer Thermodynamics by Gas Chromatography by R. VTIcu and M. Leca
5. Optical Techniques to Characterize Polymer Systems edited by H. Bassler
6. Plastics: Their Behaviour in Fires by G. Pal and H. Macskasy
Studies in Polymer Science 7
by
Ser van der Ven
Billiton Research, P.O. Box 40, 6800 A A Arnhem, The Netherlands
ELSEVIER
Amsterdam — Oxford — New York — Tokyo 1990
ELSEVIER SCIENCE PUBLISHERS B.V.
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Distributors for the United States and Canada:
ELSEVIER SCIENCE PUBLISHING COMPANY INC.
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Library of Congress Cataloging-in-Publication Data
Ven, Ser van der.
Polypropylene and other polyolefins : polymerization and
characterization / by Ser van der Ven.
p. cm. — (Studies in polymer science ; 7)
Includes bibliographical references.
ISBN 0-444-88690-7 (U.S.)
1. Polypropylene. I. Title. II. Series.
TP1180.P68V46 1990
868. 4'234—dc20 90-33336
CIP
ISBN 0-444-88690-7
© Elsevier Science Publishers B.V., 1990
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Printed in The Netherlands
C O N T E N TS
PREFACE xin
INTRODUCTION xv
CHAPTER 1 POLYPROPYLENE; CATALYSTS AND POLYMERIZATION ASPECTS
(by Brian L.Goodall)
1.1 Introduction 1
1.2 Historical background 1
1.3 The architecture of a catalyst particle; catalyst morphology 4
1.4 Composition and structure of the catalysts 11
1.4.1 First generation TiCl„ catalysts 11
1.4.2 Second generation TiCl catalysts 19
1.4.3 Third generation (supported) catalysts 26
1.4.4 Homogeneous catalysts 37
1.5 Co-catalyst chemistry 50
1.5.1 TiCl catalysts 52
1.5.2 Supported catalysts 59
1.6 The effect of catalyst and process variables on the molecular
weight and its distribution ("chain transfer") 71
1.6.1 The effect of catalyst modification (TiCl catalyst) 72
1.6.2 The effect of process conditions 74
1.6.3 On the mechanism of chain transfer 82
1.7 Mechanism and kinetics of propylene polymerization 84
1.7.1 On the mechanism of the Ziegler-Natta catalyzed
polymerization of propylene 84
(i) TiCl catalysts and general aspects 86
(ii) Supported catalysts 98
1.7.2 Kinetic aspects 104
1.8 Process aspects 118
1.8.1 Types of commercial processes 119
(i) The slurry process 120
(ii) The liquid propylene process 122
(iii) The gas-phase process 123
(iv) The solution process 125
References 125
CHAPTER 2 CHARACTERIZATION OF POLYPROPYLENE HOMOPOLYMER
2.1 Introduction 134
2.2 Characterization of the volatile fraction of polypropylene 138
2.3 Characterization of reactor solubles 143
2.4 Characterization of the solubles 149
2.4.1 Tacticity 149
2.4.2 Molecular weight and molecular weight distribution 153
2.4.3 Solubility 153
2.4.4 Crystallinity 154
2.4.5 Fractionation of solubles 156
2.4.6 Stereoblock polymer 161
2.5 Characterization of the isotactic fraction 166
2.6 Characterization of total polymers, effects of catalyst,
co-catalyst and polymerization conditions 168
2.6.1 The effect of catalyst type on the polymers produced 169
2.6.2 The effect of the co-catalyst on the polymer produced 177
2.6.3 The effect of polymerization conditions on the composition
of the polymer 184
(i) solvent/diluent 184
(ii) catalyst concentration 185
(iii)monomer pressure 185
(iv) chain transfer agent 187
(v) polymerization temperature 191
(vi) polymerization time 196
2.7 Crystalline properties 196
2.8 Characterization of syndiotactic polypropylene 200
2.9 Conclusion (mainly for TiCl -catalysts) 205
References 208
CHAPTER 3 COPOLYMERS OF PROPYLENE AND OTHER OLEFINS ("RANDOM" COPOLYMERS
AND RUBBERS). POLYMERIZATION ASPECTS
3.1 Introduction 213
3.2 Copolymerization aspects 214
3.3 Vanadium catalysts 216
3.4 Titanium trichloride and other isospecific catalysts 220
3.5 Homogeneous and other catalysts 225
3.6 Copolymerization processes 228
References 229
CHAPTER 4 CHARACTERIZATION OF "RANDOM" COPOLYMERS AND RUBBERS
4.1 Introduction 232
4.2 Composition, kinetic parameters 232
4.3 Fractionation, comonomer distribution 242
4.4 Melting behaviour, (co)crystallization 247
4.5 Glass transition 254
4.6 Yield stress 257
4.7 Formation of dispersed systems 259
4.8 Concluding remarks on characterization 260
4.9 Relation of copolymer composition and copolymerization kinetics
with catalyst properties 261
References 264
CHAPTER 5 IN-SITU PREPARED TOUGHENED POLYPROPYLENE ("BLOCK" COPOLYMERS),
POLYMERIZATION ASPECTS
5.1 Introduction 268
5.2 Polymerization aspects of in-situ prepared toughened
polypropylene 269
5.2.1 Kinetics 270
5.2.2 Morphology of ex-reactor products 273
5.2.3 Block-copolymerization 275
5.2.4 Sequential polymerization of ethylene and propylene 283
5.3 Toughened polypropylene processes 285
References 286
CHAPTER 6 CHARACTERIZATION OF IN-SITU MADE TOUGHENED POLYPROPYLENES
6.1 Introduction 289
6.2 Characterization of in-situ prepared toughened polypropylenes 290
6.2.1 Composition 290
6.2.2 Morphology 293
6.2.3 Crystallization 310
6.2.4 Dynamic mechanical analysis, glass transition 317
6.2.5 Rheology 321
6.2.6 Mechanical properties 323
6.2.7 Discussion 326
(i) Theory of energy absorption 326
(ii) Effect of E 328
c
(iii)Effect of molecular weight, effect of particle size 329
(iv) Blends versus in-situ prepared toughened polypropylenes 331
(v) Rubber-matrix compatibility 331
(vi) Approach to impact grade development 334
References 335
CHAPTER 7 CONTINUOUS VERSUS BATCH PREPARED TOUGHENED POLYPROPYLENES
7.1 Introduction 337
7.2 Some characterization data on inhomogeneities 338
7.3 Explanation of the effects of continuous polymerization, the
effect of process variables 341
7.4 Described ways of overcoming the problem 344
7.5 Concluding remarks 345
References 345
CHAPTER 8 PREPARATION AND CHARACTERIZATION OF HIGH-IMPACT POLYPROPYLENE
BLENDS
8.1 Introduction 347
8.2 Preparation of blends 347
8.3 Characterization of blends 349
8.3.1 Morphology in blends 349
8.3.2 Crystalline properties of blends 351
8.3.3 Mechanical properties of blends 357
8.4 Characterization of surmised block copolymers and their effects
in blends 357
References 360
CHAPTER 9 POLYETHYLENE, CATALYSTS AND (CO-)POLYMERIZATION
9.1 Introduction 363
9.2 Radical and anionic polymerization 366
9.3 Coordination catalysts for ethylene polymerization 367
9.3.1 First generation TiCl 369
9.3.2 Supported catalysts 369
(i) chromium-containing catalysts 369
(ii) titanium supported on magnesium chloride 380
(iii)supported organometallic compounds 382
9.3.3 Homogeneous catalysts 384
9.3.4 Overview of activities 388
9.4 Polymerization behaviour, kinetics and molecular weight 390
9.4.1 First generation TiCl 390
9.4.2 Supported catalysts 393
(i) chromium-containing catalysts 393
(ii) titanium supported on magnesium chloride 403
(iii)supported organometallic compounds 406
9.4.3 Homogeneous catalysts 409
9.4.4 Molecular weight distribution control 413
9.5 Copolymerization 413
9.5.1 First generation TiCl 414
9.5.2 Supported catalysts 417
(i) chromium-containing catalysts 417
(ii) titanium supported on magnesium chloride 421
(iii)supported organometallic compounds 427
9.5.3 Homogeneous catalysts 427
9.5.4 Block copolymerization 431
9.5.5 Peculiarities in copolymerization 433
9.6 Polyethylene processes 434
References 438
CHAPTER 10 CHARACTERIZATION OF POLYETHYLENES
10.1 Introduction 447
10.2 Composition, its measurement and the relation with the
preparation process 447
10.2.1 Composition via infrared 447
10.2.2 Radiolysis 450
10.2.3 Pyrolysis studies 451
13
10.2.4 Composition via C-NMR spectroscopy 453
(i) HDPE 453
(ii) linear copolymers 454
(iii)LDPE 458
10.2.5 Fractionation 463
10.3 Crystallinity related properties, structure of crystals 467
10.3.1 Melting temperature, melting enthalpies and density 470
10.3.2 Crystal structure, fate of alien groups 482
10.4 Dynamic mechanical analysis 486
10.5 Mechanical properties 487
References 489
CHAPTER 11 POLY(l-BUTENE), ITS PREPARATION AND CHARACTERIZATION
11.1 Introduction 494
11.2 Catalysts 495
11.2.1 TiCl catalysts 495
3
11.2.2 Supported catalysts 498
11.2.3 Homogeneous catalysts 499
11.2.4 Catalyst comparison w.r.t. isotacticity 500
11.3 Polymerization aspects 501
11.4 Copolymerization 506
11.5 Polymerization process 507
11.6 Characterization 508
11.6.1 Composition 510
11.6.2 Crystallinity related characterization 513
11.7 Dynamic mechanical analysis 519
11.8 Syndiotactic poly(l-butene) 519
