Hyperbranched Polymers E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Fachliteratur
• Serie: Wiley Series on Plastics Engineering and Technology
• Sprache: Englisch

Seitenzahl: 729

Veröffentlichungsjahr: 2011

Beschreibung

A much-needed overview of the state of the art of hyperbranched polymers

The last two decades have seen a surge of interest in hyperbranched polymers due to their ease of synthesis on a large scale and their promising applications in diverse fields, from medicine to nanotechnology.

Written by leading scientists in academia and industry, this book provides for the first time a comprehensive overview of the topic, bringing together in one complete volume a wealth of information previously available only in articles scattered across the literature. Drawing on their work at the cutting edge of this dynamic area of research, the authors cover everything readers need to know about hyperbranched polymers when designing highly functional materials. Clear, thorough discussions include:

• How irregular branching affects polymer properties and their potential applications

• Important theoretical basics, plus a useful summary of characterization techniques

• How hyperbranched polymers compare with dendrimers as well as linear polymers

• Future trends in the synthesis and application of hyperbranched polymers

Geared to novices and experts alike, Hyperbranched Polymers is a must-have resource for anyone working in polymer architectures, polymer engineering, and functional materials. It is also useful for scientists in related fields who need a primer on the synthesis, theory, and applications of hyperbranched polymers.

Leseprobe

Table of Contents

Title Page

Copyright

Preface

Contributors

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

1.1 Importance of Branching

1.2 Polymer Architecture

1.3 Dendritic Polymers

1.4 Hyperbranched Polymers

1.5 Conclusions

References

Chapter 2: Polycondensation of ABx Monomers

2.1 Introduction

2.2 Statistical Consideration

2.3 Polymerization of ABx-Type Monomers

References

Chapter 3: Synthesis of Hyperbranched Polymers via Polymerization of Functionally Symmetric Monomer Pairs

3.1 Introduction

3.2 Theoretical Treatment of A2 + B3 Polymerization

3.3 Polymerization of Symmetrical Monomer Pairs

3.4 Conclusions

List of Abbreviations

References

Chapter 4: Synthesis of Hyperbranched Polymers via Polymerization of Asymmetric Monomer Pairs

4.1 Introduction

4.2 General Description of Polymerization of Asymmetric Monomer Pairs

4.3 Hyperbranched Polymers Prepared by Polymerization of Asymmetric Monomer Pairs

4.4 Conclusions

List Of Abbreviations

References

Chapter 5: Self-Condensing Vinyl Polymerization

5.1 Introduction

5.2 Self-Condensing Vinyl Polymerization

5.3 Self-Condensing Vinyl Copolymerization (SCVCP)

5.4 Self-Condensing Processes in Presence of Initiators

5.5 SCVP of Macroinimers

5.6 Surface-Grafted Hyperbranched Polymers

References

Chapter 6: Ring-Opening Multibranching Polymerization

6.1 Introduction

6.2 Classification of Ring-Opening Multibranching Polymerizations

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

6.4 Conclusion and Perspectives

References

Chapter 7: Hyperbranched Copolymers Synthesized by Cocondensation and Radical Copolymerization

7.1 Introduction

7.2 Cocondensation of ABn and a Comonomer

7.3 Cocondensation of A2 + B2 + BB′ (or B′B2)

7.4 SCVCP Via Charge-Transfer Complex Inimer

7.5 Free Radical Copolymerization of Multifunctional Vinyl Monomers

7.6 Conclusion

List of Abbreviations

References

Chapter 8: Convergent Synthesis of Hyperbranched Polymers and Related Approaches

8.1 Introduction

8.2 Convergent Control in Hyperbranched Synthesis

8.3 Results

8.4 Conclusions

References

Chapter 9: Hyperbranched and Dendritic Polyolefins Prepared by Transition Metal Catalyzed Polymerization

9.1 Introduction

9.2 Results and Discussion

9.3 Summary and Perspective

List of Abbreviations

References

Chapter 10: Hyperbranched π-Conjugated Polymers

10.1 Introduction

10.2 Scope

10.3 Hyperbranched Poly(Arylene)s

10.4 Hyperbranched Poly(Arylenevinylenes)

10.5 Hyperbranched Poly(Aryleneethynylenes)

10.6 Conclusion

List of Abbreviations and Symbols

References

Chapter 11: Degree of Branching (DB)

11.1 Definition of the Degree of Branching (DB)

11.2 Determination of DB

11.3 The Value Range of DB

11.4 Appendix

List of Abbreviations

References

Chapter 12: Influence of Branching Architecture on Polymer Properties

12.1 Introduction

12.2 Influence of Branching Architecture on Polymer Properties

12.3 Conclusions

References

Chapter 13: Kinetic Theory of Hyperbranched Polymerization

13.1 Introduction

13.2 AB2-Type Polycondensation

13.3 Copolycondensation of AB2- and AB-Type Monomers

13.4 Self-Condensing Vinyl Polymerization

References

Chapter 14: Grafting and Surface Properties of Hyperbranched Polymers

14.1 Introduction

14.2 Surface Grafting

14.3 Surface Properties of Hyperbranched Polymers

14.4 Conclusions

List of Abbreviations

References

Chapter 15: Biological and Medical Applications of Hyperbranched Polymers

15.1 Introduction

15.2 Gene Delivery

15.3 Drug Delivery

15.4 Biomaterials

15.5 Biointeraction

15.6 Conclusions

References

Chapter 16: Applications of Hyperbranched Polymers in Coatings, as Additives, and in Nanotechnology

16.1 Introduction

16.2 Hyperbranched Polymers in Coating and Resin Applications

16.3 Hyperbranched Polymers as Additives

16.4 Applications of Hyperbranched Polymers in Nanotechnology

16.5 Applications in Thin Films and Sensorics

References

Chapter 17: Conclusions and Perspective: Toward Hyperbranched/ Dendritic States

17.1 Achievements and Problems

17.2 Role of Hyperbranched Polymers in the Twenty-First Century

17.3 Hyperbranched/Dendritic State

References

Index

Copyright © 2010 by John Wiley & Sons, Inc. All rights reserved.

Published by John Wiley & Sons, Inc., Hoboken, New Jersey.

Published simultaneously in Canada.

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Library of Congress Cataloging-in-Publication Data:

Hyperbranched polymers : synthesis, properties, and applications / edited

by Deyue Yan, Chao Gao, Holger Frey.

p. cm.– (Wiley series on polymer engineering and technology)

Includes index.

ISBN 978-0-471-78014-4 (cloth)

1. Dendrimers. 2. Polymers. I. Yan, Deyue. II. Gao, Chao. III. Frey, Holger.

TP1180.D45H97 2011

668.9–dc22

2010028351

Preface

Since the first works on the fundamental principles of polymerization reactions by Hermann Staudinger in the early 1920s, numerous types of linear polymers have been synthesized and commercialized. This area has now become a mature field, as is demonstrated by the vast applications of such materials in our everyday life.

A novel kind of dendritic polymer architecture emerged in the 1980s. The so-called “dendritic polymers,” which mainly comprise the “hyperbranched polymers” and the perfectly branched “dendrimers,” are macromolecules with highly branched, three-dimensional globular topology. Normally, dendrimers have to be prepared in demanding multistep syntheses in a classic organic approach. In pronounced contrast, the randomly cascade-branched hyperbranched polymers are obtained in a typical polymer approach at the expense of polydispersity with regard to both molecular weight and branching structure.

Because of to their unusual structures, specific properties, and potential applications, hyperbranched polymers have attracted the increasing attention of both scientists and engineers over the last two decades and the field has become a cutting-edge area in polymer research. Hyperbranched polymers resemble dendrimers in many physical and chemical properties, such as low viscosity, excellent solubility, and large number of functional groups. Yet, they can be readily prepared by one-step polymerizations on a large scale. The first monograph on dendritic macromolecules was published by Wiley-VCH in 1997. Since then, several books on dendrimers and dendrons have been published; however, until now a comprehensive book on hyperbranched polymers does not exist.

Owing to the many facets of synthesis methodologies, characterization of the relevant parameters such as degree of branching (DB) and molar mass, and kinetic theories for various hyperbranched polymerization systems, as well as the increasing number of publications, it has been quite difficult to organize the first monograph on hyperbranched polymers. Invited by Dr. Edmund H. Immergut, a consulting editor for Wiley and Wiley-VCH publishers, we started to conceive and organize the edition of this book since May, 2005. In 2005 and 2006, Chao and Holger met at Mainz, Bayreuth, and Freiburg, Germany several times to discuss the details of this project face-to-face. In July, 2009 when the project was drawing to an end, Deyue and Holger met at Ludwigshafen for further improving the manuscripts. During the Chinese New Year holiday of 2010, Chao, Deyue, and Holger made the final revisions.

This book is targeted to become a comprehensive and useful volume for anybody working in the area of polymer science and polymer engineering, as well as in functional materials. For “newcomers” it will be a valuable source of information on the synthesis, theory, and application of hyperbranched polymers. The book is potentially useful also for readers who work in the fields of organic chemistry, physical chemistry, surface chemistry, theoretical chemistry, supramolecular chemistry, combinational chemistry, pharmaceutical chemistry, medicinal chemistry, environmental chemistry, biochemistry, and bioengineering. There is also a strong link to nanoscience and nanotechnology.

Leading scientists, invited from both academic and industrial fields, contributed chapters covering basic concepts, synthesis, properties, characterizations, theories, modifications, and applications of hyperbranched polymers. So, this book is appropriate as a textbook for courses including polymer chemistry, polymer physics, nanopolymers, biopolymers, functional materials, biomaterials, nanomaterials, and nanochemistry. It is also an interdisciplinary frontier reference book for undergraduates, graduates, teachers, researchers, and engineers.

Even though we have tried our best to bring together the state of the art of hyperbranched polymers, many important articles were not included in this book, partly because the reports on hyperbranched polymers are related to too many other topics and subjects, and partly because this field is still rapidly developing. Also, this book might contain some errors and overlapping content in definitions, classifications, descriptions, and comments. We hope that the readers will give us their valuable comments and advice, so that the book can be further modified in the next edition.

We would like to thank all the authors who have contributed to this book, for their valuable work, patience, and understanding. It is their contributions that have laid the foundation of this book. We also wish to express our sincere gratitude to the editors, Edmund H. Immergut, Jonathan T. Rose, and Amy R. Byers, for their great support, constructive suggestions, and long-term effort. It was their continuing encouragement that helped us to finish this five-year project.

The twentieth century has witnessed the birth, development, and resplendence of conventional linear polymers. It is expected that the twenty-first century will witness the thrive and prosperity of dendritic polymers. As the saying goes, a single flower does not make a spring. We hope that the publication of this primary book will attract more researchers, engineers, students, teachers and enterprisers to grow, irrigate, and cultivate molecular “trees” and make them further bloom and flourish in the near future.

Deyue Yan, Chao Gao, and Holger Frey

March, 2010

Contributors

Bernd Bruchmann

Polymer Research,

BASF SE,

Carl-Bosch-Strasse 38,

Ludwigshafen D-67056, Germany

Holger Frey

Institute of Organic Chemistry,

Organic and Macromolecular Chemistry,

Duesbergweg 10–14

Johannes-Gutenberg University Mainz,

Mainz D-55099, Germany

Henryk Galina

Wydział Chemiczny

Politechnika Rzeszowska,

35–959 Rzeszów,

Al. Powstanców, W-wy 6 Poland

Chao Gao

MOE Key Laboratory of Macromolecular Synthesis and Functionalization,

Department of Polymer Science and Engineering,

Zhejiang University,

38 Zheda Road,

Hangzhou 310027, P. R. China

Zhibin Guan

Department of Chemistry,

516 Rowland Hall,

University of California, Irvine,

Irvine CA 92697-2025, USA

Matthias Häuβler

Department of Chemistry,

The Hong Kong University of Science & Technology,

Clear Water Bay, Kowloon,

Hong Kong, P. R. China

Mitsutoshi Jikei

Department of Engineering in Applied Chemistry,

Akita University, Akita, Japan

Masa-aki Kakimoto

Department of Organic and Polymeric Materials,

Tokyo Institute of Technology,

S8-26, Meguro-ku,

Tokyo 152–8552, Japan

Daniel M. Knauss

Chemistry Department,

Colorado School of Mines,

Golden CO 80401, USA

Timothy E. Long

Department of Chemistry,

Macromolecules and Interfaces Institute,

Virginia Polytechnic Institute and State University,

Blacksburg VA 24061, USA

Hideharu Mori

Department of Polymer Science and Engineering,

Graduate School of Science and Engineering,

Yamagata University,

4-3-16, Jonan,

Yonezawa 992–8510, Japan

Axel H. E. Müller

Macromolecular Chemistry II,

University of Bayreuth,

Bayreuth D-95440, Germany

Jörg Nieberle

Institute of Organic Chemistry,

Organic and Macromolecular Chemistry,

Duesbergweg 10–14,

Johannes-Gutenberg University Mainz,

Mainz D-55099, Germany

Gozde I. Ozturk

Department of Chemistry,

Macromolecules and Interfaces Institute,

Virginia Polytechnic Institute and State University,

Blacksburg VA 24061, USA

Sergiy Peleshanko

School of Materials Science and Engineering & School of Polymer, Textile, and Fiber Engineering

Georgia Institute of Technology,

Atlanta GA 30332, USA

Peter F. W. Simon

Institute of Polymer Research,

GKSS Research Centre Geesthacht GmbH,

Geesthacht D-21502, Germany;

Present address:

Department of Life Sciences,

Rhine-Waal University of Applied Sciences, Kleve D-47533, Germany

Mario Smet

Department of Chemistry,

University of Leuven,

Celestijnenlaan 200F,

Leuven B-3001, Belgium

Hongyun Tai

School of Chemistry,

Bangor University,

Deiniol Road, Bangor,

LL57 2UW, UK

Ben Zhong Tang

Department of Chemistry,

The Hong Kong University of Science & Technology,

Clear Water Bay, Kowloon, Hong Kong,

P. R. China and Department of Polymer Science and Engineering,

Zhejiang University,

Hangzhou 310027, P. R. China

VladimirV. Tsukruk

School of Materials Science and Engineering,

& School of Polymer, Textile, and Fiber Engineering,

Georgia Institute of Technology,

Atlanta GA 30332, USA

Serkan Unal

Department of Chemistry,

Macromolecules and Interfaces Institute,

Virginia Polytechnic Institute and State University,

Blacksburg VA 24061, USA

Brigitte Voit

Leibniz-Institut für Polymerforschung Dresden e.V.,

Hohe Strasse 6,

Dresden D-01069, Germany

Wenxin Wang

Network of Excellence for Functional Biomaterials,

National University of Ireland,

Galway, Republic of Ireland

Daniel Wilms

Institute of Organic Chemistry,

Organic and Macromolecular Chemistry,

Duesbergweg 10–14,

Johannes-Gutenberg University Mainz,

Mainz D-55099, Germany

Deyue Yan

College of Chemistry and Chemical Engineering,

Shanghai Jiao Tong University,

800 Dongchuan Road,

Shanghai 200240, P. R. China

Yu Zheng

School of Chemistry,

University of Nottingham,

University Park,

Nottingham NG7 2RD, UK

Yongfeng Zhou

College of Chemistry and Chemical Engineering,

Shanghai Jiao Tong University,

800 Dongchuan Road,

Shanghai 200240, P. R. China

Zhiping Zhou

School of Materials Science and Engineering,

Jiangsu University,

301 Xuefu Road,

Zhenjiang 212013, P. R. China

Xinyuan Zhu

College of Chemistry and Chemical Engineering,

Shanghai Jiao Tong University,

800 Dongchuan Road,

Shanghai 200240, P. R. China

Chapter 1

Promising Dendritic Materials: An Introduction to Hyperbranched Polymers

Chao Gao,1 Deyue Yan,2 and Holger Frey3

1MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou P. R. China

2College of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, P. R. China

3Institute of Organic Chemistry, Johannes-Gutenberg University Mainz, Mainz, Germany

1.1 Importance of Branching

In nature and universe from living to nonliving things, branching occurs anywhere and anytime, such as the Crab Nebula, forked lightning, river basins, trees, nerves, veins, snow crystals, nervures, and proteoglycan ranging from light-years to kilometers, and to microscale and nanoscales (see Figure 1.1 for selected branching patterns). Hence, branching is a general and important phenomenon that could result in faster and more efficient transfer, dissipation, and distribution of energy and/or matter.

Figure 1.1 Selected branching patterns observed in universe and nature (from left to right: Crab Nebula, forked lightning, tree, vascular network, snow crystal). The images were obtained from the Internet.

1.2 Polymer Architecture

The past century has witnessed pioneering work and blossoming of polymer science and industry, for which various star scientists like Staudinger, Flory, Ziegler, Natta, de Gennes, Shirakawa, Heeger, MacDiarmid, Noyori, Sharpless, Grubbs, and others have made great contributions. Notably, their focus has mainly concentrated on linear chains. Since the first beacon publication of “Über Polymerisation” (on Polymerization) in 1920, (1) and the definition of “macromolecules” as primary valence chain systems in 1922 by Staudinger, (2) numerous types of macromolecules with various architectures have been synthesized successfully. Figure 1.2 shows besides linear polymers that seem to approach a period of fatigue nowadays, (3) new paradigms including chain-branched, cross-linked, cyclic, starlike, ladderlike, dendritic, linear brush-like (or comblike), cyclic brushlike, sheetlike, tubal, and supramolecular interlocked architectures keep coming to the fore, promising an unlimited future for and sustainable development of polymer science and technology. Except the linear, cyclic, and interlocked polymers, all other architectures possess branched structures, also indicating the significance of branching in the molecular construction.

Figure 1.2 Architectures of synthesized macmolecules: (a) linear, (b) chain-branched, (c) cross-linked, (d) cyclic, (e) starlike, (f) ladderlike, (g) dendritic, (h) linear brush-like, (i) cyclic brush-like, (j) sheetlike, (k) tubelike, and (l) interlocked.

1.3 Dendritic Polymers

In the 1980s, a kind of highly branched three-dimensional macromolecules, also named dendritic polymers, was born, and gradually became one of the most interesting areas of polymer science and engineering. Despite the 12 architectures shown in Figure 1.2, dendritic architecture is recognized as the main fourth class of polymer architecture after traditional types of linear, cross-linked, and chain-branched polymers that have been widely studied and industrially used. (4) Up to now, eight subclasses of dendritic polymers have been developed: (i) dendrons and dendrimers, (ii) linear-dendritic hybrids, (iii) dendronized polymers, (iv) dendrigrafts or dendrimer-like star macromolecules (DendriMacro), (v) hyperbranched polymers (HPs), (vi) hyperbranched polymer brushes (HPBs), (vii) hyperbranched polymer-grafted linear macromolecules, and (viii) hypergrafts or hyperbranched polymer-like star macromolecules (HyperMacro) (Figure 1.3), of which the first four subclasses have the perfect and ideally branched structures with the degree of branching (DB) of 1.0, and the latter four exhibit a random and irregular branched configuration with lesser DB (normally, 0.4–0.6). (5) Dendrimers and HPs have been extensively studied as the representative regular and irregular dendritic polymers, respectively.

Figure 1.3 Dendritic polymers with different structures. (a) Dendrimer, (b) linear-dendritic hybrid, (c) dendronized polymer, (d) DendriMacro, (e) hyperbranched polymer, (f) multiarm star polymer or hyperbranched polymer brush, (g) HP-grafted polymer, (h) HyperMacro, (i) 3D model of HP with initial unit, (j) 3D model of dendron, (k) 3D model of HP with a core, and (l) 3D model of dendrimer.

Dendrons and dendrimers can be synthesized by divergent and convergent methodologies (Figure 1.4). (4, 6) Generally, step-by-step synthesis, purification, protection, and deprotection are needed for accessing dendrimers with controlled molecular structure, shape, size, and functions and functional groups. Nevertheless, the employment of “click” chemistry, especially the Cu (I)-catalyzed Huisgen 1,3-dipolar cycloaddition between azides and acetylene derivatives (also called ) (7) and thiol-ene click chemistry possessing the merits of specificity, fast reaction, tolerance to common functional groups and water, greatly furthers the progress of dendrimer synthesis because the tedious protection/deprotection and chromatography-based purification steps are not required any more. (8) There is no doubt that the facile availability of dendrimers would boost their real applications. However, the accessible varieties and structures through click chemistry are still limited at present.