Ring-Opening Polymerization. Kinetics, Mechanisms, and Synthesis

Title Page......Page 1
Half Title Page......Page 3
Copyright......Page 4
ACS Symposium Series......Page 5
FOREWORD......Page 6
PdftkEmptyString......Page 0
PREFACE......Page 7
1 Ring-Opening Polymerization: Introduction......Page 8
Thermodynamic Considerations......Page 11
Kinetic and Mechanistic Overview......Page 13
References......Page 27
2 Anionic Polymerization of Cyclosiloxanes with Cryptates as Counterions......Page 30
Anionic Polymerization of D3......Page 31
Anionic Polymerization of D4......Page 36
Molecular Weight Distributions of PDMS......Page 40
Literature Cited......Page 41
3 Anionic Polymerization of Ethylene Oxide with Lithium Catalysts Solution Properties of Styrene-Ethylene Oxide Block Polymers......Page 43
Experimental......Page 44
Results and Discussion......Page 45
Literature Cited......Page 50
4 Free Radical Ring-Opening Polymerization......Page 52
Free Radical Ring-Opening of Cyclic Ketene Acetals......Page 54
Nitrogen and Sulfur Analogs of Cyclic Ketene Acetals......Page 57
Ring-Opening Polymerization of Cyclic Vinyl Ethers......Page 58
Double Ring-Opening in Free Radical Polymerization......Page 62
Copolymerization with Cyclic Ketene Acetals......Page 64
Synthesis of Biodegradable Addition Polymers......Page 65
Ketene Acetals as New Chain Transfer Agents......Page 66
Acknowledgments......Page 67
Literature Cited......Page 68
5 Mechanism of N-Carboxy Anhydride Polymerization......Page 71
Background and Critique......Page 72
Acid-base Considerations......Page 77
Kinetic Considerations......Page 78
Concerning the Analogy Between the "a.m." Mechanism for NCA Polymerization and The Mechanism for The Anionic Polymerization of Lactams.......Page 80
Role of Self-Condensation Reactions......Page 81
The Carbamate Ion Mechanism as a Viable Alternative......Page 86
Literature Cited......Page 87
6 Ring-Opening Polymerization in the Synthesis of Block Copolymers......Page 90
Transformation Reactions......Page 91
Anion to Cation......Page 92
Cation to Anion......Page 93
Cation to Free Radical......Page 94
Reactions of Living Anionic Polymers With Living Poly THF......Page 95
Block Copolymers With Ionic Linking Groups......Page 96
Literature Cited......Page 97
7 Metal-Alcoholate Initiators Sources of Questions and Answers in Ring-Opening Polymerization of Heterocyclic Monomers......Page 99
Synthesis and properties of active μ-oxo-bimetallic alkoxides......Page 100
Polymerization of oxiranes......Page 101
Polymerization of other monomers......Page 104
Literature Cited......Page 105
8 Solvent and Substituent Effects in the Anionic Polymerization of α,α-Disubstituted β-Propiolactones......Page 107
Results and Discussion......Page 109
Experimental......Page 117
Literature Cited......Page 118
9 Structure-Reactivity Relationships in Ring-Opening Polymerization......Page 119
Determination of the chemical structures of the growing species......Page 120
Isomerism of the ionic active centers......Page 123
Covalent growing species......Page 124
Macroion-pairs and macroions......Page 126
Macroions and macroion-pairs in propagation......Page 129
Solvation phenomena......Page 130
Correlation of the structures and reactivities......Page 132
Literature Cited......Page 135
10 Control of Ring-Opening Polymerization with Metalloporphyrin Catalysts Mechanistic Aspects......Page 138
Structure and Reactivity of Growing Species in the Polymerization of Epoxide......Page 139
Copolymerization of Epoxide with CO2, and Epoxide with Cyclic Acid Anhydride......Page 141
Catalytic Reaction on Both Sides of a Metalloporphyrin Plane......Page 143
Literature Cited......Page 147
11 Anionic Ring-Opening Polymerization of Octamethylcyclotetrasiloxane in the Presence of 1,3-Bis(aminopropyl)-1,1,3,3-tetramethyldisiloxane......Page 148
A. Catalyst Preparation......Page 153
D. Capillary Gas Chromatography......Page 154
Results and Discussion......Page 155
Conclusions......Page 158
Literature Cited......Page 161
12 An Improved Process for є-Caprolactone-Containing Block Polymers......Page 162
Results and Discussion......Page 164
Conclusions......Page 171
Literature Cited......Page 174
13 Organolithium Polymerization of є-Caprolactone......Page 175
Results and Discussion......Page 176
Effect of Terminating Agent......Page 178
Literature Cited......Page 182
14 Cationic Heterocyclic Polymerization......Page 183
Mechanism and Kinetics......Page 184
Results and Discussion......Page 185
Cyclic Acetal Polymerization......Page 189
Grafting onto Experiments......Page 191
Literature Cited......Page 193
15 Thermally or Photochemically Induced Cationic Polymerization......Page 195
Photoinitiated Cationic Polymerization......Page 196
Thermally Initiated Cationic Polymerization......Page 197
Literature Cited......Page 203
Polymerization of Styrene Oxide......Page 205
Anionic Polymerization by Sodium Methoxide Catalyst......Page 207
Polymerization by Aluminum Alkoxides Catalyst......Page 209
Polymerization by ZnEt2/H2O Catalyst......Page 211
Controlled Polymerization of Oxiranes......Page 212
Polymerization of Epoxy Aldehydes and Derived Oxacyclic Monomers......Page 213
Literature Cited......Page 217
Results and Discussion......Page 218
Literature Cited......Page 228
18 Block Copolymer of Poly(ethylene glycol) and Poly(N-isovalerylethylenimine) Kinetics of Initiation......Page 229
Experimental......Page 230
Results......Page 231
Literature Cited......Page 240
19 Synthesis and Applications of Polysiloxane Macromers......Page 242
Preparation and Characterization of Polysiloxane Graft Copolymers......Page 243
Preparation and Characterization of Polysiloxane Macromers and Oligosiloxane Monomers......Page 246
Literature Cited......Page 257
20 Homopolymerization of Epoxides in the Presence of Fluorinated Carbon Acids Catalyst Transformations......Page 259
Results and Discussion......Page 260
Conclusions......Page 268
Literature Cited......Page 270
21 Mechanism of Ring-Opening Polymerization of Bicycloalkenes by Metathesis Catalysts......Page 271
Mechanistic Framework......Page 272
Cis Content......Page 273
Cis/Trans Distribution; Blockiness......Page 276
Head-tail Bias in Polymers of Asymmetric Monomers......Page 280
Tacticity......Page 283
Literature Cited......Page 287
22 Electrophilic Ring-Opening Polymerization of New Cyclic Trivalent Phosphorus Compounds A Novel Mechanism of Ionic Polymerization......Page 289
2-Phenyl-1,2-oxaphospholane (1)......Page 291
1-Phenyl-3H-2,1-benzoxaphosphole (2)......Page 296
Ionic Polymerization......Page 303
2-Phenyl-1,2-thiaphospholane(4) and 2-Phenyl-1,2-thiaphosphorinane(5)......Page 304
2-Phenyl-1,3,2-dioxaphosphepane(6)......Page 306
Literature Cited......Page 307
23 Synthesis and Polymerization of Atom-Bridged Bicyclic Acetals and Ortho Esters A Dioxacarbenium Ion Mechanism for Ortho Ester Polymerization......Page 309
Bicyclic Acetals: Synthesis......Page 310
Acid Hydrolysis of Bicyclic Acetals......Page 311
Polymerization of Bicyclic Acetals......Page 312
Bicyclic Orthoesters: Synthesis......Page 314
Polymerization of Bicyclic Orthoesters......Page 317
Conclusion......Page 324
Experimental of Bicyclic Orthoesters Mechanism Studies......Page 325
Literature Cited......Page 328
24 Radiation-Induced Cationic Polymerization of Limonene Oxide, α-Pinene Oxide, and β-Pinene Oxide......Page 330
Experimental......Page 331
Kinetic Characteristics of Polymerization......Page 332
1H-NMR Studies......Page 336
13C-NMR Studies......Page 343
Discussion......Page 347
Literature Cited......Page 352
25 Cationic Ring-Opening Polymerization of Epichlorohydrin in the Presence of Ethylene Glycol......Page 355
Results and Discussion......Page 356
Polymerization Mechanism......Page 360
Polyepichlorohydrin Polyols......Page 363
Experimental......Page 364
Literature Cited......Page 366
26 Lactone Polymerization Pivalolactone and Related Lactones......Page 367
Polymerization Mechanism......Page 369
Pivalolactone Polymers......Page 372
Block Copolymers......Page 373
Literature Cited......Page 378
Author Index......Page 380
A......Page 381
B......Page 382
C......Page 383
D......Page 384
E......Page 385
M......Page 386
P......Page 387
T......Page 389
X......Page 390