Hyperbranched Polymers: Synthesis, Properties, and Applications

Contributors xv

1. Promising Dendritic Materials: An Introduction to Hyperbranched Polymers 1

1.1 Importance of Branching 1

1.2 Polymer Architecture 1

1.3 Dendritic Polymers 3

1.4 Hyperbranched Polymers 5

1.5 Conclusions 21

1.6 References 22

2. Polycondensation of ABx Monomers 27

2.1 Introduction 27

2.2 Statistical Consideration 27

2.3 Polymerization of ABx -Type Monomers 30

2.4 References 74

3. Synthesis of Hyperbranched Polymers via Polymerization of Functionally Symmetric Monomer Pairs 79

3.1 Introduction 79

3.2 Theoretical Treatment of A2 + B3 Polymerization 81

3.3 Polymerization of Symmetrical Monomer Pairs 84

3.4 Conclusions 104

3.5 References 105

4. Synthesis of Hyperbranched Polymers via Polymerization of Asymmetric Monomer Pairs 107

4.1 Introduction 107

4.2 General Description of Polymerization of Asymmetric Monomer Pairs 108

4.3 Hyperbranched Polymers Prepared by Polymerization of Asymmetric Monomer Pairs 110

4.4 Conclusions 133

4.5 References 136

5. Self-Condensing Vinyl Polymerization 139

5.1 Introduction 139

5.2 Self-Condensing Vinyl Polymerization 140

5.3 Self-Condensing Vinyl Copolymerization (SCVCP) 150

5.4 Self-Condensing Processes in Presence of Initiators 162

5.5 SCVP of Macroinimers 167

5.6 Surface-Grafted Hyperbranched Polymers 169

5.7 References 172

6. Ring-Opening Multibranching Polymerization 175

6.1 Introduction 175

6.2 Classification of Ring-Opening Multibranching Polymerizations 178

6.3 Core-Containing Hyperbranched Polymers By Ring-Opening Multibranching Polymerization 195

6.4 Conclusion and Perspectives 198

6.5 References 200

7. Hyperbranched Copolymers Synthesized by Cocondensation and Radical Copolymerization 203

7.1 Introduction 203

7.2 Cocondensation of ABn and a Comonomer 204

7.3 Cocondensation of A2 + B2 + BB2 (or B B2) 214

7.4 SCVCP Via Charge-Transfer Complex Inimer 215

7.5 Free Radical Copolymerization of Multifunctional Vinyl Monomers 218

7.6 Conclusion 221

7.7 References 223

8. Convergent Synthesis of Hyperbranched Polymers and Related Approaches 227

8.1 Introduction 227

8.2 Convergent Control in Hyperbranched Synthesis 228

8.3 Results 231

8.4 Conclusions 247

8.5 References 247

9. Hyperbranched and Dendritic Polyolefins Prepared by Transition Metal Catalyzed Polymerization 251

9.1 Introduction 251

9.2 Results and Discussion 253

9.3 Summary and Perspective 266

9.4 References 269

10. Hyperbranched π-Conjugated Polymers 273

10.1 Introduction 273

10.2 Scope 274

10.3 Hyperbranched Poly(Arylene)s 274

10.4 Hyperbranched Poly(Arylenevinylenes) 282

10.5 Hyperbranched Poly(Aryleneethynylenes) 289

10.6 Conclusion 295

10.7 References 297

11. Degree of Branching (DB) 301

11.1 Definition of the Degree of Branching (DB) 301

11.2 Determination of DB 305

11.3 The Value Range of DB 308

A11.4 Appendix 311

11.5 References 314

12. Influence of Branching Architecture on Polymer Properties 317

12.1 Introduction 317

12.2 Influence of Branching Architecture on Polymer Properties 318

12.3 Conclusions 329

12.4 References 329

13. Kinetic Theory of Hyperbranched Polymerization 333

13.1 Introduction 333

13.2 AB2-Type Polycondensation 335

13.3 Copolycondensation of AB2- and AB-Type Monomers 351

13.4 Self-Condensing Vinyl Polymerization 354

13.5 References 366

14. Grafting and Surface Properties of Hyperbranched Polymers 369

14.1 Introduction 369

14.2 Surface Grafting 370

14.3 Surface Properties of Hyperbranched Polymers 380

14.4 Conclusions 382

14.5 References 383

15. Biological and Medical Applications of Hyperbranched Polymers 387

15.1 Introduction 387

15.2 Gene Delivery 388

15.3 Drug Delivery 397

15.4 Biomaterials 401

15.5 Biointeraction 407

15.6 Conclusions 410

15.7 References 411

16. Applications of Hyperbranched Polymers in Coatings, as Additives, and in Nanotechnology 415

16.1 Introduction 415

16.2 Hyperbranched Polymers in Coating and Resin Applications 416

16.3 Hyperbranched Polymers as Additives 423

16.4 Applications of Hyperbranched Polymers in Nanotechnology 426

16.5 Applications in Thin Films and Sensorics 431

16.6 References 434

17. Conclusions and Perspective: Toward Hyperbranched/Dendritic States 441

17.1 Achievements and Problems 441

17.2 Role of Hyperbranched Polymers in the Twenty-First Century 449

17.3 Hyperbranched/Dendritic State 451

17.4 References 452

Index 453