Hyperbranched Polymers: Synthesis, Properties, and Applications

Cover Page......Page 1
Title Page......Page 5
ISBN 9780471780144......Page 6
2. Polycondensation of ABx Monomers......Page 7
4. Synthesis of Hyperbranched Polymers via Polymerization of Asymmetric Monomer Pairs......Page 8
6. Ring-Opening Multibranching Polymerization......Page 9
8. Convergent Synthesis of Hyperbranched Polymers and Related Approaches......Page 10
10. Hyperbranched π-Conjugated Polymers......Page 11
13. Kinetic Theory of Hyperbranched Polymerization......Page 12
15. Biological and Medical Applications of Hyperbranched Polymers......Page 13
Index......Page 14
Preface......Page 15
Contributors......Page 17
1.2 POLYMER ARCHITECTURE......Page 20
1.3 DENDRITIC POLYMERS......Page 22
1.4.1 Concept and History......Page 24
1.4.2 Structure and Properties......Page 27
1.4.3 Synthesis Philosophy......Page 31
1.4.4 Applications......Page 34
1.5 CONCLUSIONS......Page 40
1.6 REFERENCES......Page 41
2.2.1 Polymerization Behavior......Page 46
2.2.2 Degree of Branching......Page 48
2.3.1 C–C Coupling Reactions......Page 49
2.3.2 C–O Coupling Reactions......Page 57
2.3.3 C–N Coupling Reactions......Page 74
2.3.4 Si–C or Si–O Coupling Reactions......Page 81
2.3.5 Other Coupling Reactions......Page 89
2.4 REFERENCES......Page 93
3.1 INTRODUCTION......Page 98
3.2 THEORETICAL TREATMENT OF A2+B3 POLYMERIZATION......Page 100
3.3.1 Polycondensation of A2 and B3 Monomers......Page 103
3.3.2 Proton-Transfer Polymerization of A2 and B3 Monomers......Page 118
3.3.3 The Michael Addition Polymerization of A2+B3 Monomers......Page 119
LIST OF ABBREVIATIONS......Page 123
3.5 REFERENCES......Page 124
4.1 INTRODUCTION......Page 126
4.2 GENERAL DESCRIPTION OF POLYMERIZATION OF ASYMMETRIC MONOMER PAIRS......Page 127
4.3.1 Poly(Sulfoneamine)......Page 129
4.3.2 Poly(Ester Amine)......Page 132
4.3.3 Poly(Amidoamine)......Page 134
4.3.4 Multihydroxy Hyperbranched Poly(Amine Ester)s......Page 137
4.3.5 Poly(Ester Amide)s......Page 139
4.3.6 Polyesters......Page 142
4.3.7 Poly(Urea-Urethane)s......Page 146
4.3.8 Other Polymers......Page 148
4.3.9 Highly Branched Copolymers......Page 150
LIST OF ABBREVIATIONS......Page 152
4.5 REFERENCES......Page 155
5.1 INTRODUCTION......Page 158
5.2.1 General Principles......Page 159
5.2.2 Various Mechanisms of SCVP......Page 163
5.2.3 Kinetics and MWD......Page 164
5.2.4 Degree of Branching......Page 167
5.3 SELF-CONDENSING VINYL COPOLYMERIZATION (SCVCP)......Page 169
5.3.1 Experimental Data......Page 170
5.3.2 Kinetics and MWD......Page 172
5.3.3 Degree of Branching......Page 178
5.3.4 Comparison with Experimental Data......Page 180
5.4.1 Kinetics and MWD......Page 181
5.4.2 Degree of Branching......Page 184
5.5 SCVP OF MACROINIMERS......Page 186
5.6 SURFACE-GRAFTED HYPERBRANCHED POLYMERS......Page 188
5.7 REFERENCES......Page 191
6.1 INTRODUCTION......Page 194
6.2.1 Cationic Ring-Opening Multibranching Polymerizations......Page 197
6.2.2 Anionic Ring-Opening Multibranching Polymerizations......Page 202
6.2.3 Catalytic Ring-Opening Multibranching Polymerizations......Page 208
6.3 CORE-CONTAINING HYPERBRANCHED POLYMERS BY RING-OPENING MULTIBRANCHING POLYMERIZATION......Page 214
6.4 CONCLUSION AND PERSPECTIVES......Page 217
6.5 REFERENCES......Page 219
7.1 INTRODUCTION......Page 222
7.2.1 ABn +AB Approach......Page 223
7.2.2 AB2 +AB2 Approach......Page 230
7.2.3 Combined ROP/AB2 Approach......Page 231
7.3 COCONDENSATION OF A2 +B2 +BB' (OR B'B2)......Page 233
7.4 SCVCP VIA CHARGE-TRANSFER COMPLEX INIMER......Page 234
7.5 FREE RADICAL COPOLYMERIZATION OF MULTIFUNCTIONAL VINYL MONOMERS......Page 237
LIST OF ABBREVIATIONS......Page 240
7.7 REFERENCES......Page 242
8.1 INTRODUCTION......Page 246
8.2 CONVERGENT CONTROL IN HYPERBRANCHED SYNTHESIS......Page 247
8.3.1 Hyperbranched Polymers by Convergent Living Anionic Polymerization......Page 250
8.3.2 Complex Branching by Convergent Hyperbranched Polymerization......Page 260
8.3.3 Related Procedures......Page 262
8.5 REFERENCES......Page 266
9.1 INTRODUCTION......Page 270
9.2.2 Branched Polyolefin Prepared by Tandem Action of Multiple Transition Metal Catalysts......Page 272
9.2.3 Hyperbranched and Dendritic Polyolefin Made by Late Transition Metal Catalysts......Page 275
9.3 SUMMARY AND PERSPECTIVE......Page 285
Acknowledgements......Page 287
9.4 REFERENCES......Page 288
10.1 INTRODUCTION......Page 292
10.3 HYPERBRANCHED POLY(ARYLENE)S......Page 293
10.4 HYPERBRANCHED POLY(ARYLENEVINYLENES)......Page 301
10.5 HYPERBRANCHED POLY(ARYLENEETHYNYLENES)......Page 308
10.6 CONCLUSION......Page 314
LIST OF ABBREVIATIONS AND SYMBOLS......Page 315
10.7 REFERENCES......Page 316
11.1 DEFINITION OF THE DEGREE OF BRANCHING (DB)......Page 320
11.1.1 Single Highly Branched Molecules......Page 321
11.1.2 A System of Hyperbranched Molecules......Page 323
11.2.1 Direct Determination......Page 324
11.2.2 Indirect Methods......Page 326
11.3 THE VALUE RANGE OF DB......Page 327
A11.4.1 Numbers of Isomers in Hyperbranched Polymers......Page 330
A11.4.2 Number of Units of Different Substitution Degree in Random Polymerization of ABf Monomer......Page 332
11.5 REFERENCES......Page 333
12.1 INTRODUCTION......Page 336
12.2.1 Rheological Property......Page 337
12.2.2 Crystallization and Melting Behaviors......Page 339
12.2.3 Glass Transition......Page 340
12.2.4 Thermal and Hydrolytic Degradations......Page 342
12.2.6 Optoelectronic Properties......Page 343
12.2.8 Self-Assembly Behavior......Page 344
12.2.9 Biomedical Applications......Page 346
12.4 REFERENCES......Page 348
13.1 INTRODUCTION......Page 352
13.2 AB2-TYPE POLYCONDENSATION......Page 354
13.2.1 Molecular Size Distribution Function......Page 355
13.2.2 Average Degree of Polymerization and Polydispersity......Page 358
13.2.3 Substitution Effect......Page 359
13.2.4 Degree of Branching......Page 362
13.2.5 Effect of Core Molecules......Page 365
13.3.1 Molecular Size Distribution Function......Page 370
13.3.2 Degree of Branching......Page 372
13.4 SELF-CONDENSING VINYL POLYMERIZATION......Page 373
13.4.1 Distribution Function and Molecular Parameters......Page 376
13.4.2 Degree of Branching......Page 378
13.4.3 Effect of Core Initiators......Page 381
13.5 REFERENCES......Page 385
14.1 INTRODUCTION......Page 388
14.2 SURFACE GRAFTING......Page 389
14.2.1 ‘‘Grafting from’’ Approach......Page 390
14.2.2 ‘‘Grafting to’’ Approach......Page 397
14.3 SURFACE PROPERTIES OF HYPERBRANCHED POLYMERS......Page 399
LIST OF ABBREVIATIONS......Page 401
14.5 REFERENCES......Page 402
15.1 INTRODUCTION......Page 406
15.2.1 Linear and Hyperbranched Poly(ethyleneimine) as Nonviral Gene Vectors......Page 407
15.2.2 Modificatio of Poly(ethyleneimine) and Use of Adjuvant Polyglycerol......Page 409
15.2.3 Hyperbranched Alternatives for Poly(ethyleneimine) as Gene Vectors......Page 412
15.3.1 Drug Encapsulation and Conjugation......Page 416
15.4 BIOMATERIALS......Page 420
15.4.1 Surface Modificatio......Page 421
15.4.2 Modificatio of Bulk Materials......Page 423
15.4.3 Modificatio of Dental Resins......Page 424
15.5.1 Hyperbranched Polymers as Supports for Ligand Presentation......Page 426
15.5.2 Other Applications......Page 428
15.6 CONCLUSIONS......Page 429
15.7 REFERENCES......Page 430
16.1 INTRODUCTION......Page 434
16.2 HYPERBRANCHED POLYMERS IN COATING AND RESIN APPLICATIONS......Page 435
16.2.1 Hyperbranched Polyesters in Reactive Formulation Application......Page 436
16.2.3 Hyperbranched Poly(urea-urethane)s......Page 440
16.3.1 Additives for Linear Thermoplastics......Page 442
16.3.3 Stabilizers......Page 444
16.4.1 Nanocomposites and Nanohybrids......Page 445
16.4.2 Nanoporous Materials......Page 449
16.5 APPLICATIONS IN THIN FILMS AND SENSORICS......Page 450
16.6 REFERENCES......Page 453
17.1.1 Ten Main Achievements......Page 460
17.1.2 Ten Noteworthy Problems and Topics......Page 467
17.2 ROLE OF HYPERBRANCHED POLYMERS IN THE TWENTY-FIRST CENTURY......Page 468
Acknowledgment......Page 470
17.4 REFERENCES......Page 471
A,B......Page 472
D......Page 473
E......Page 474
F,G,H......Page 475
M......Page 477
P......Page 478
S......Page 479
U,V,W......Page 480
Z......Page 481