The only comprehensive reference covering the properties, synthesis and applications of hyperbranched polymers. * Helps the reader gain a better understanding of irregular branching and its relationship to a polymer's properties and potential applications, aiding in the design of highly functional materials. * Covers the important theoretical aspects of the topic, as well as summarizing available techniques for characterizing these polymers. * Compares hyperbranched polymers with conventional linear polymeric materials as well as perfectly branched dendrimers. * Includes perspectives on future challenges in the synthesis and use of hyperbranched polymers in functional materials.

Deyue Yan, PhD, is a professor at the School of Chemistry and Chemical Engineering of Shanghai Jiao Tong University, P.R. China, and a member of the Chinese Academy of Sciences. Dr. Yan has served on the editorial board of Macromolecular Theory and Simulations and is currently on the editorial board of the Chinese Journal of Polymer Science. Chao Gao, PhD, is Professor in the Department of Polymer Science and Engineering at Zhejiang University, P.R. China. Dr. Gao also serves on the editorial advisory boards of the Open Macromolecules Journal and the Open Process Chemistry Journal. Holger Frey, PhD, is Full Professor of Organic and Macromolecular Chemistry at the Institute of Organic Chemistry at Johnannes Gutenberg University Mainz, Germany. Dr. Frey has served on the editorial advisory boards of several polymer journals.

Preface xiii 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 À-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