Developments in the Theory of Cationoid Polymerisations

Cover Page......Page 1
Title Page......Page 2
ISBN 1859572707......Page 3
Contents (with page links)......Page 4
Foreword......Page 8
1 General Introduction......Page 14
2 Developments in the Cationic Polymerisation of Alkenes......Page 18
1 Introduction......Page 19
2.1 The start......Page 20
2.2 The discovery of co-catalysis......Page 21
3.1 Popper said.........Page 23
3.2.1 The isomerisation of cis-stilbene......Page 24
3.2.2 The alleged isomerisation-polymerisation of alkylstyrenes......Page 25
3.2.3 Direct initiation......Page 26
3.2.5 Radical-cations and NVC......Page 28
4.2 The start at Keele, Cationic Symposium 2 and the numbering of Cationic Polymerisation Symposia......Page 29
4.3 Complexes I......Page 30
4.4 The origins of the BIE studies......Page 31
4.5 Complexes II......Page 32
4.6 Polymerisation kinetics......Page 34
4.7 Pseudo-cationic polymerisation......Page 35
5.2 New views on the cationic polymerisations induced by ionising radiations......Page 36
6 Conclusion......Page 37
3 Reviews......Page 44
1 Introduction......Page 46
2 The peculiarity of isobutene......Page 47
3 The structure of polyisobutene......Page 49
4 Catalytic systems......Page 52
5 Kinetic investigations......Page 57
3.2 Cationic Polymerisation from‘Progress in High Polymers’ (1968)......Page 108
2.1 The origin and status of the carbonium ion theory......Page 110
2.2 Polymerization without carbonium ions......Page 114
3 The mechanism of catalysis......Page 116
3.1 The function of the co-catalyst......Page 117
3.2 Co-catalysis in the polymerization of oxygen compounds......Page 128
3.3 The mechanism of pseudo-cationic polymerization......Page 130
4.1 Aliphatic mono-olefins......Page 131
4.3 Comparison between aliphatic and aromatic mono-olefins......Page 133
4.4 Oxygen compounds......Page 134
4.5 Nitrogen compounds......Page 137
5.1 Introduction......Page 138
5.2 Algebraic treatment......Page 140
5.3 Kinetic evidence concerning termination......Page 143
5.4 Chemistry of chain-breaking reactions......Page 145
5.5 Factors influencing the chain-breaking reactions......Page 148
6.1 Multiplicity of chain-carriers......Page 149
6.2 Free ions and ion-pairs......Page 151
6.3 Complexed and uncomplexed chain-carriers......Page 158
7 Conclusion......Page 162
3.3 Some Considerations Concerning Energetics (1955)......Page 172
3.4 Theoretical Attempts at Improving Initiators for Cationic Polymerisation of Alkenes (1982)......Page 188
1 Stability and reactivity......Page 189
2 The kinetic requirements......Page 190
3 Solubility......Page 191
4 The equilibria associated with carbocation salts......Page 193
5 The initiation reaction......Page 202
3.5 Thermochemical Aspects of the Initiation of Cationic Polymerisations by Organic Cations. Conflation of Two Unpublished Conference Contributions (1999)......Page 208
3.6 The Relation Between Reduction Potential and Solvation Energy for some Aryl Methylium Ions (1989)......Page 216
4 Theorising about Reaction Mechanisms......Page 228
4.1 Suggestions Concerning the IonicPolymerisation of Vinyl Ethers (1950)......Page 230
4.2 Developments in the Theory of Cationic Polymerization, Part I (1951)......Page 236
4.3 Developments in the Theory of Cationic Polymerization. Part II (1954)......Page 246
4.4 The Mechanism of Cationic Polymerisations Catalysed by Metal Halides (1959)......Page 256
4.5 A New Theory of Initiation by Aluminium Halides (1972)......Page 262
4.6 Approaches Towards a Comprehensive Theory of the Cationic Polymerisation of Olefins (1974)......Page 282
4.7 The Initiation of Polymerisations by Aluminium Halides (1980)......Page 294
4.8 Some Effects of the Complex Formation Between Cations and Monomers......Page 328
4.9 New Views on Cationic Polymerizations Induced by Ionizing Radiations (1993)......Page 338
4.10A General Theory Explaining Discontinuous Variations of the Degree of Polymerisation with the Concentration of the Reagents (1964)......Page 392
5 About Propagating Species and Propagation Rate-Constants in Cationic Polymerisations......Page 412
5.1 The Propagation Rate-Constants in Cationic Polymerisations (1971)......Page 414
2 Why are we so ignorant about kp-s in cationic polymerisations?......Page 415
3 Electrochemical considerations......Page 417
4.1 The study of polymerising solutions......Page 420
4.2 The short-stop method......Page 423
5 Pseudo-cationic polymerisations......Page 424
6.2 Comparison of some kp values......Page 428
6.3 The effect of temperature and solvent polarity on kp......Page 430
7 Conclusion......Page 431
5.2 Nature of the Propagating Species in Cationic Polymerisationsa (1973)......Page 434
2 Outline of the historical development......Page 435
3 Unpaired and paired cationsa......Page 437
4.1 The carbenium ions......Page 441
4.2 Hetero-cations......Page 442
5.1 Olefin polymerisations......Page 444
7 Acknowledgements......Page 445
1 Introduction......Page 450
2 Choice of reaction conditions......Page 453
3 The determination of kp+......Page 454
4 Some kp+ values and the factors affecting them......Page 456
5 Where do we go from here?......Page 460
5.4 An Account of the Propagating Species in Cationic Polymerisations(1989)......Page 464
5.5 The Propagation Rate Constants of the Cationic Polymerisation of Alkenes - Part III. Indene, Two Vinyl Ethers and General Discussion* (1990)......Page 468
5.6 The Propagation Rate-Constants of the Cationic Polymerisation of Some Alkenes in Nitrobenzene - IV. Not the Real kp+ *† (1993)......Page 492
1 Introduction......Page 493
3 The nature of the propagators......Page 495
4 What next?......Page 499
5.7 The Propagation Rate-Constants of the Cationic Polymerisation of Alkenes (1993)......Page 502
1.1 Preamble......Page 503
1.2 Glossary and list of symbols......Page 507
2.1 The fundamental equations and definitions......Page 508
2.2 The solvation of Pn+ by monomer......Page 509
2.3 The solvation of Pn+ by polymers......Page 511
2.4 Electrochemical considerations......Page 512
2.5.2 Unimolecular propagation......Page 516
2.5.3 Bimolecular propagation......Page 518
2.5.5 Conclusion......Page 519
3.1 Measurement of the polymerisation rate......Page 520
3.1.2 Adiabatic calorimetry......Page 521
3.1.3 The stopped-flow technique......Page 522
3.2.1 Outline......Page 523
3.2.2 Initial group determinations......Page 524
3.2.3 The short-stop (end-group) method......Page 525
3.2.4 Spectroscopic determination of growing ends......Page 526
3.3.3 Sequestration of the initiator......Page 527
3.3.4 The initiator and/or the growing end is involved in a BIE......Page 528
4.1.1 Introduction......Page 529
4.1.2 Theory of bulk polymerisations......Page 531
4.1.3 The hydrocarbon monomers and 4-methoxystyrene in bulk......Page 535
4.1.4 Alkyl vinyl ethers in bulk......Page 536
4.1.6 Theory of polymerisations in solution......Page 537
4.1.8 Other monomers in solution......Page 540
4.2.1 The Bawn - Ledwith - Sherrington group......Page 541
4.2.2 P. Sigwalt’s group......Page 548
4.2.3 P. H. Plesch’s group......Page 554
4.2.4 V. T. Stannett’s group......Page 559
4.2.5 J. M. Rooney......Page 560
4.2.7 M. Marek and M. Chmelir......Page 562
4.2.8 M. Rodriguez and L. M. Leon......Page 563
4.3.1 D. C. Pepper’s group......Page 566
4.3.2 A digression on initiation......Page 567
4.3.3 T. Kunitake and K. Takarabe......Page 569
4.3.4 T. Higashimura’s group......Page 573
4.3.5 J-P. Vairon’s group......Page 575
5.2 Second-order rate-constants......Page 576
5.8 Rate Constants of Cationic Polymerisations and Mayr’s Rate Constants, Reconciled † (2001)......Page 590
1.1 Preamble......Page 591
1.2 Summary of Mayr’s findings......Page 592
2.1 Origin of the discrepancy......Page 593
2.2 Cation-monomer complex......Page 594
2.3 Propagation......Page 595
3 Some consequences and suggestions......Page 597
4 Related phenomena......Page 599
6 Pseudocationic Polymerisation, Renamed ca.1998 ‘Cationoid Insertion Polymerisation’......Page 602
6.1 The Interaction Between Perchloric Acid and Styrene in Methylene Dichloride (1964)......Page 604
6.2 Pseudocationic and True Cationic Polymerisation of Styrene with Various Catalysts (1965)......Page 612
6.3 Cationic and Pseudocationic Polymerisation of Aromatic Olefins Part I. Kinetics and Mechanism of the Pseudocationic Polymerisation of Styrene by Perchloric Acid (1965)......Page 616
6.4 New Views on Cationic Polymerisation(1966)......Page 626
6.5 Reaction Mechanism in Cationic and Pseudocationic Polymerisations (1966)......Page 636
6.6 Cationic and Pseudocationic Polymerisation of Aromatic Olefins-II. The Reactions Following Polymerisation of Styrene by Perchloric Acid (1968)......Page 648
6.7 Cationic and Pseudocationic Polymerisation of Aromatic Olefins - III [la, b]. A Re-investigation of the Polymerisation of Styrene by Perchloric Acid in Methylene Dichloride (1976)......Page 674
1 Introduction......Page 684
2 Some facts and explanations relating to the theory of pseudocationic polymerisation......Page 686
3 Conclusions......Page 692
6.9 Kinetics of Living Polymerisations(1988)......Page 698
6.10 Cationoid Living Polymerisations 1(1992)......Page 702
7 The Polymerisation of 1,3-Dioxacycloalkanes......Page 726
7.1 The Mechanism of the Polymerisation of Cyclic Formals (1971)......Page 728
7.2 The Propagating Species in the Polymerisation of 1,3-Dioxacycloalkanes by Perchloric Acid (1975)......Page 738
7.3 Some Aspects of the Polymerisation of 1,3-Dioxacycloalkanes (1976)......Page 754
8 The Chemical Publications of P. H. Plesch in Chronological Order, 1946 - 2001......Page 770
Abbreviations and Acronyms......Page 784
Back Page......Page 788