Green Polymerization Methods E-Book

• Herausgeber: Wiley-VCH
• Kategorie: Fachliteratur
• Sprache: Englisch

Seitenzahl: 580

Veröffentlichungsjahr: 2011

Beschreibung

Designing polymers and developing polymerization processes that are safe, prevent pollution, and are more efficient in the use of materials and engergy is an important topic in modern chemistry. Today, green polymer research can be seen increasingly in academia nd industry. It tackles all aspects of polymers and polymerization - everything from chemical feedstocks, synthetic pathways, and reaction media to the nature of the final polymer as related to its inherent nontoxicity or degradability. This book summarizes and evaluates the latest developments in green polymerization methods. Specifically, new catalytic methods and processes which incorporate renewable resources will be discussed by leading experts in the field of polymer chemistry. This book is a must-have for Polymer Chemists, Chemists Working with/on Organometallics, Biochemists, Physical Chemists, Chemical Engineers, Biotechnologists, Materials Scientists, and Catalytic Chemists.

Leseprobe

Table of Contents

Related Titles

Title Page

Copyright

List of Contributors

Part I: Introduction

Chapter 1: Why are Green Polymerization Methods Relevant to Society, Industry, and Academics?

1.1 Status and Outlook for Environmentally Benign Processes

1.2 Importance of Catalysis

1.3 Brief Summaries of Contributions

Part II: Integration of Renewable Starting Materials

Chapter 2: Plant Oils as Renewable Feedstock for Polymer Science

2.1 Introduction

2.2 Cross-Linked Materials

2.3 Non-Cross-Linked Polymers

2.4 Conclusion

Chapter 3: Furans as Offsprings of Sugars and Polysaccharides and Progenitors of an Emblematic Family of Polymer Siblings

3.1 Introduction

3.2 First Generation Furans and their Conversion into Monomers

3.3 Polymers from Furfuryl Alcohol

3.4 Conjugated Polymers and Oligomers

3.5 Polyesters

3.6 Polyamides

3.7 Polyurethanes

3.8 Furyl Oxirane

3.9 Application of the Diels–Alder Reaction to Furan Polymers

3.10 Conclusions

Chapter 4: Selective Conversion of Glycerol into Functional Monomers via Catalytic Processes

4.1 Introduction

4.2 Conversion of Glycerol into Glycerol Carbonate

4.3 Conversion of Glycerol into Acrolein/Acrylic Acid

4.4 Conversion of Glycerol into Glycidol

4.5 Oxidation of Glycerol to Functional Carboxylic Acid

4.6 Conversion of Glycerol into Acrylonitrile

4.7 Selective Conversion of Glycerol into Propylene Glycol

4.8 Selective Coupling of Glycerol with Functional Monomers

4.9 Conclusion

Part III: Sustainable Reaction Conditions

Chapter 5: Monoterpenes as Polymerization Solvents and Monomers in Polymer Chemistry

5.1 Introduction

5.2 Monoterpenes as Monomers

5.3 Monoterpenes as Solvents and Chain Transfer Agents

5.4 Conclusion

Acknowledgments

Chapter 6: Controlled and Living Polymerization in Water: Modern Methods and Application to Bio-Synthetic Hybrid Materials

6.1 Introduction

6.2 Ring-Opening Metathesis Polymerization (ROMP)

6.3 Living Free Radical Methods for Bio-Synthetic Hybrid Materials

Acknowledgments

Chapter 7: Towards Sustainable Solution Polymerization: Biodiesel as a Polymerization Solvent

7.1 Introduction

7.2 Solution Polymerization and Green Solvents

7.3 Biodiesel as a Polymerization Solvent

7.4 Experimental Section

7.5 Effect of FAME Solvent on Polymerization Kinetics

7.6 Effect of Biodiesel Feedstock

7.7 Conclusion

Part IV: Catalytic Processes

Chapter 8: Ring-Opening Polymerization of Renewable Six-Membered Cyclic Carbonates. Monomer Synthesis and Catalysis

8.1 Introduction

8.2 Preparation of 1,3-Propanediol from Renewable Resources

8.3 Preparation of Dimethylcarbonate from Renewable Resources

8.4 Synthesis of Trimethylene Carbonate

8.5 Six-Membered Cyclic Carbonates: Thermodynamic Properties of Ring-Opening Polymerization

8.6 Catalytic Processes Using Green Catalysts Methods

8.7 Thermoplastic Elastomers and their Biodegradation Processes

8.8 Concluding Remarks

Acknowledgments

Chapter 9: Poly(lactide)s as Robust Renewable Materials

9.1 Introduction

9.2 Ring-Opening Polymerization of Lactide

9.3 Poly(lactide) Properties

9.4 Thermoplastic Elastomers

9.5 Future Developments/Outlook

Chapter 10: Synthesis of Saccharide-Derived Functional Polymers

10.1 Introduction

10.2 Polyethers

10.3 Polyamides

10.4 Polyurethanes and Polyureas

10.5 Glycosilicones

Chapter 11: Degradable and Biodegradable Polymers by Controlled/Living Radical Polymerization: From Synthesis to Application

11.1 Introduction

11.2 (Bio)degradable Polymers by CRP

11.3 Conclusions

Abbreviations

Part V: Biomimetic Methods and Biocatalysis

Chapter 12: High-Performance Polymers from Phenolic Biomonomers

12.1 Introduction

12.2 Coumarates as Phytomonomers

12.3 LC Properties of Homopolymers

12.4 LC Copolymers for Biomaterials

12.5 LC Copolymers for Photofunctional Polymers

12.6 LC Copolymers for High Heat-Resistant Polymers

12.7 Conclusion

Acknowledgments

Chapter 13: Enzymatic Polymer Synthesis in Green Chemistry

13.1 Introduction

13.2 Polymers

13.3 Green Media for Enzymatic Polymerization

13.4 Conclusions and Outlook

Chapter 14: Green Cationic Polymerizations and Polymer Functionalization for Biotechnology

14.1 Introduction

14.2 Enzyme Catalysis

14.3 “Green” Cationic Polymerizations and Polymer Functionalization Using Lipases

14.4 Natural Rubber Biosynthesis – the Ultimate Green Cationic Polymerization

14.5 Green Synthetic Cationic Polymerization and Copolymerization of Isoprene

Acknowledgments

Index

Related Titles

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The Editors

Prof. Dr. Robert T. Mathers

Pennsylvania State University

Department of Chemistry

3550 Seventh Street Rd.

New Kensington, PA 15068

USA

Prof. Dr. Michael A. R. Meier

Karlsruhe Institute of Technology (KIT)

Institute of Organic Chemistry

Fritz-Haber-Weg 6, Building 30 . 42

76131 Karlsruhe

Germany

All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.

Library of Congress Card No.: applied for

British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library.

Bibliographic information published by the Deutsche Nationalbibliothek The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at <http://dnb.d-nb.de>.

© 2011 WILEY-VCH Verlag & Co. KGaA, Boschstr. 12, 69469 Weinheim, Germany

All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.

ISBN: 978-3-527-32625-9

ePDF: 978-3-527-63618-1

ePub: 978-3-527-63617-4

Mobi: 978-3-527-63619-8

List of Contributors

Joël Barrault

Université de Poitiers

CNRS

Laboratoire de Catalyse en Chimie Organique

86022 Poitiers

France

Jan M. Becker

University of Warwick

Department of Chemistry

Coventry CV4 7AL

UK

Chengching K. Chiang

The University of Akron

Department of Polymer Science

170 University Avenue

Akron, OH 44325

USA

Donald J. Darensbourg

Texas A&M University

Department of Chemistry

College Station, TX 77843

USA

Andrew P. Dove

University of Warwick

Department of Chemistry

Coventry CV4 7AL

UK

Marc A. Dubé

University of Ottawa

Department of Chemical and Biological Engineering

161 Louis Pasteur Pvt.

Ottawa, Ontario K1N 6 N5

Canada

Todd Emrick

University of Massachusetts

Conte Center for Polymer Research

Polymer Science & Engineering Department

120 Governors Drive

Amherst, MA 01003

USA

Alessandro Gandini

University of Aveiro

CICECO and Chemistry Department

3810-193 Aveiro

Portugal

Andreas Heise

Dublin City University

School of Chemical Sciences

Glasnevin

Dublin 9

Ireland

and

Eindhoven University of Technology

Laboratory of Polymer Chemistry

Den Dolech 2, P.O. Box 513

5600 MB Eindhoven

The Netherlands

François Jérôme

Université de Poitiers

CNRS

Laboratoire de Catalyse en Chimie Organique

86022 Poitiers

France

Tatsuo Kaneko

Japan Advanced Institute of Science and Technology

School of Materials Science

1-1 Asahidai

Nomi 923-1292

Japan

Katrina Kratz

University of Massachusetts

Conte Center for Polymer Research

Polymer Science & Engineering Department

120 Governors Drive

Amherst, MA 01003

USA

Stewart P. Lewis

Innovative Science, Inc.

3154 State Street

STE 2300

Blacksburg, VA 24060

USA

Robert T. Mathers

Pennsylvania State University

Department of Chemistry

3550 Seventh Street Road

New Kensington, PA 15068

USA

Michael A. R. Meier

Karlsruhe Institute of

Technology (KIT)

Institute of Organic Chemistry

Fritz-Haber-Weg 6

Building 30 . 42

76131 Karlsruhe

Germany

Inge van der Meulen

Eindhoven University of Technology

Laboratory of Polymer Chemistry

Den Dolech 2, P.O. Box 513

5600 MB Eindhoven

The Netherlands

Adriana I. Moncada

Texas A&M University

Department of Chemistry

College Station, TX 77843

USA

Judit E. Puskas

The University of Akron

Department of Polymer Science

170 University Avenue

Akron, OH 44325

USA

Somaieh Salehpour

University of Ottawa

Department of Chemical and Biological Engineering

161 Louis Pasteur Pvt.

Ottawa, Ontario K1N 6 N5

Canada

Debasis Samanta

University of Massachusetts

Conte Center for Polymer Research

Polymer Science & Engineering Department

120 Governors Drive

Amherst, MA 01003

USA

Mustafa Y. Sen

The University of Akron

Department of Polymer Science

170 University Avenue

Akron, OH 44325

USA

Joachim Thiem

University of Hamburg

Faculty of Science

Department of Chemistry

Martin-Luther-King-Platz 6

20146 Hamburg

Germany

Julian Thimm

University of Hamburg

Faculty of Science

Department of Chemistry

Martin-Luther-King-Platz 6

20146 Hamburg

Germany

Nicolay V. Tsarevsky

Southern Methodist University

Department of Chemistry

3215 Daniel Avenue

Dallas, TX 75275

USA

Stephanie J. Wilson

Texas A&M University

Department of Chemistry

College Station, TX 77843

USA

Part I

Introduction

1

Why are Green Polymerization Methods Relevant to Society, Industry, and Academics?

Robert T. Mathers and Michael A. R. Meier

1.1 Status and Outlook for Environmentally Benign Processes

In June 1992, the “Rio Declaration on Environment and Development” (Rio declaration) of the United Nations Conference on Environment and Development (UNCED) announced in Principle 1 [1] that human beings are at the center of concerns for sustainable development and that they are entitled to a healthy and productive life in harmony with nature. Since the Rio declaration, the necessity for sustainable development has become obvious [2]. Most frequently, sustainable development is defined as development that meets the needs of the present without compromising the ability of future generations to meet their own needs [3]. Much has happened since then and the principles of green chemistry [4] are now known and applied by chemists worldwide. Recently, Paul T. Anastas stated in his keynote speech at the 2010 ACS (American Chemical Society) national meeting in San Francisco: “Building a sustainable world is the most taxing intellectual exercise we have ever engaged in. It is also the most important for the future of our world” [5]. Thus, great challenges remain and in the field of green chemistry there are plenty of possibilities in the future for innovation and environmentally friendlier consumer products.

As the use of polymers is becoming increasingly more common for many applications in modern society, polymer science is able to make diverse contributions to the rapidly growing field of green chemistry. In particular, polymer science offers manifold possibilities for the sustainable use of renewable raw materials. Even though utilizing renewable resources to meet current needs without creating adverse health or environmental impacts can be challenging, renewable resources offer potentially less toxic products as these resources can be expected to be biodegradable and, more importantly, biocompatible. However, we are fully aware that this is a generalization and a careful case by case evaluation is absolutely necessary! Moreover, nature offers a great synthetic potential to the polymer chemist, and it is up to us to develop new methods to incorporate renewable resources into polymeric materials. This development has to begin now in order to be ready to apply these methods industrially in a few decades, as fossil reserves continue to deplete and become more expensive. Equally important, we need more sustainable routes toward known polymeric products in order to avoid waste, contamination, high energy consumption, and many other environmental concerns. In the United States, the National Research Council, in its report entitled “Sustainability in the Chemical Industry: Grand Challenges and Research Needs,” has advocated that all areas of the chemical industry focus on long-term strategies to minimize toxicity and environmental impact while creating sustainable processes [6].

Therefore, we are certain that this edited volume will assist in training a future generation of scientists and engineers to consider green chemistry and sustainability within the field of polymer science as the most beneficial long-term strategy. Because these peer-reviewed chapters come from departments of polymer science, chemical engineering, chemistry, and materials science, we anticipate that this volume will build upon previous polymer science [7, 8] and green chemistry [9] books to provide a state-of-the-art resource for industry and academia. Moreover, this variety clearly reflects the need for collaboration between these (and other) disciplines to reach our final goal of sustainability. Specifically, new catalytic and biomimetic methods, alternative reaction media, and the utilization of renewable resources are described in this edited volume. Additionally, these discussions cover emerging areas in condensation, controlled free radical, anionic, cationic, and metathesis polymerizations. Based on the excellent contributions in this volume, which originate from a number of science and engineering venues, we can only assume that the idea of a green polymerization method will continue to be an important part of polymer science for many years.

1.2 Importance of Catalysis

In 1836, Berzelius described his newly coined concept of “catalysis” and “catalytic power” in an article for The Edinburgh New Philosophical Journal entitled “Considerations respecting a New Power which acts in the Formation of Organic Bodies”. He described these new idioms as “a power, which is capable of effecting chemical reactions in unorganized substances, as well as organized bodies” [10]. Years later, Karl Zeigler and Giudio Natta received the 1963 Nobel Prize for catalysis research related to polyolefins. More recently, Nobel prizes have been awarded for asymmetric catalysis (2001) and olefin metathesis catalysts (2005).

At the present time, refined ideas regarding catalysis have become very common in science and engineering disciplines, as evidenced by the large number of journal articles devoted to this subject each year. From an industrial standpoint, catalysts have played an integral role in the manufacture of chemical raw materials [11], polyolefins [12], and many other polymeric materials. To gain a perspective on the importance of catalysis in green polymer chemistry, it is helpful to mention that during the formulation of the principles of green chemistry [4], catalysis was described as a foundational pillar [13]. Since that time, major advances in organocatalysis and biocatalysis have continued to emerge as complementary methods to traditional metal-based catalysts [14]. As a result, this edited volume contains an emphasis on catalytic processes that includes metal-based catalysts, organocatalysts, and biocatalysts.

Considering the expense of developing or licensing particular catalysts, why are catalysts such an integral part of green chemistry? Certainly, the ability to avoid stoichiometric amounts of reagents or recycle catalysts on heterogeneous supports promotes atom economy and reduces waste [15]. The efficiency is normally measured by turnover numbers (TONs), the number of catalytic cycles or catalyst activity (kg polymer/mol catalyst·h). To accurately understand the amount of waste produced in relation to the amounts of the starting materials, it is helpful to consider the well-known E-factor [16] value for reactions. The E-factor concept quantifies the amount of waste produced (in kilograms) during a reaction compared with kilograms of the desired product. The ideal E-factor would be zero, but many reactions do not result in 100% conversion, show side reactions, necessitate protecting groups, or require (toxic) solvents. Several contributions in this volume contain discussions of alternative reaction media. Another compelling reason to incorporate catalytic processes is the ability to utilize renewable resources in ways that would not otherwise be possible. For instance, catalytic methods to convert glycerol into acrylic acid or to make cyclic carbonates with CO2 represent some of the numerous examples of non-petroleum based monomer synthesis in this volume.

1.3 Brief Summaries of Contributions

Creating sustainable polymers presents a significant multidisciplinary challenge and this volume represents a diverse effort to utilize a broad range of renewable resources such as lignin, triglycerides, polysaccharides, monoterpenes, furans, lactides, and natural rubber. The methods represented are also diverse. In the first section of the book, some authors report on utilizing renewable resources directly. For example, Michael Meier describes new advances in the use of renewable feedstocks based on plant oils, showing that plant oils are a perfectly suitable renewable resource for the polymer industry. In Chapter 3, Alessandro Gandini summarizes the versatility of furans as monomers in the synthesis of resins, conjugated polymers, and reversible cross-links. Francois Jerome and Joel Barrault examine processes for converting glycerol into functional monomers. Their chapter discusses the integration of biomass with heterogeneous catalysis.

In the second section, the focus involves sustainable reaction conditions that reduce waste or eliminate petroleum solvents. In this regard, methods for integrating petroleum-based polymerizations with renewable starting materials are mentioned by Stewart Lewis and Robert Mathers, who provide a current review of monoterpenes in cationic and ring-opening polymerizations. Debasis Samanta, Katrina Kratz, and Todd Emrick discuss controlled and living polymerizations in water as an important method for synthesizing bio-synthetic hybrid materials. Their chapter highlights possibilities for decreasing volatile organic solvents. Marc Dube and Somaieh Salehpour show that biodiesel is a very useful polymerization solvent for free-radical polymerizations. Fatty acid methyl esters are definitely an alternative to conventional petroleum based solvents.

The third section focuses on catalytic processes to synthesize monomers and polymers. Donald Darensbourg, Adriana Moncada, and Stephanie Wilson nicely summarize the ring-opening polymerization of renewable carbonates made from 1,3-propanediol. These six-membered cyclic carbonates, for instance, are suitable monomers for thermoplastic elastomers and biomaterials. Jan Becker and Andrew Dove detail the synthesis and polymerization of lactides using organocatalysts. Julian Thimm and Joachim Thiem assess polysaccharides as a major component of biomass. In Chapter 11, Nicolay Tsarevsky reviews the synthesis of macromolecules with biodegradable linkages using controlled radical polymerization.

In the fourth section, biomimetic methods and biocatalysis are discussed. Tatsuo Kaneko discusses the use of phenolic biomonomers in developing high-performance liquid crystalline polymers. Andreas Heise and Inge van der Meulen focus on recent advances in enzymatic polymer synthesis related to polyesters, polyphenols, polyanilines, and green media for enzymes. Judit Puskas, Chengching Chiang, and Mustafa Sen summarize green cationic polymerizations using biotechnology. Specifically, they describe the biosynthesis of natural rubber.

We hope that this book will be of value to its readers and promote the concepts of green chemistry and sustainability within polymer science. Last but not least, we would like to express our sincere thanks to all authors for their excellent contributions to this edited volume.

References

1. United Nations Conference on Environment and Development (1992) Report of the United Nations Conference on Environment and Development, Rio de Janeiro. http://www.un.org/esa/sustdev. (accessed on 29 December 2010).

2. Eissen, M., Metzger, J.O., Schmidt, E., and Schneidewind, U. (2002) Angew. Chem. Int. Ed. Engl., 41, 414–436.

3. Brundtland, G. (1987) Our Common Future, Oxford University Press, Oxford.

4. Anastas, P.T. and Warner, J.C. (1998) Green Chemistry: Theory and Practice, Oxford University Press, Oxford.

5. Baum, R. (2010) Chem. Eng. News88(Mar 29), 8.

6. National Research Council Board on Chemical Sciences and Technology (2005) Sustainability in the Chemical Industry: Grand Challenges and Research Needs – A Workshop Report. www.nap.edu. (accessed on 2005)

7. Anastas, P. Bickart, P.H., and Kirchhoff, M.M. (2000) Designing Safer Polymers, John Wiley & Sons, Inc., New York.

8. Belgacem, M.N. and Gandini, A. (eds) (2008) Monomers, Polymers and Composites from Renewable Resources, Elsevier Ltd., Oxford.

9. Sheldon, R.A., Arends, I., and Hanefeld, U. (2007) Green Chemistry and Catalysis, Wiley-VCH Verlag GmbH, Weinheim.

10. Berzelius, M. (1836) Edinburgh New Philos. J., XXI, 223–228.

11. Cavani, F., Centi, G., Perathoner, S., and Trifiro, F. (2009) Sustainable Industrial Chemistry, Wiley-VCH Verlag GmbH, Weinheim.

12. Hoff, R. and Mathers, R.T. (eds) (2010) Handbook of Transition Metal Polymerizations Catalysts, John Wiley & Sons, Inc., Hoboken.

13. Anastas, P.T. and Kirchhoff, M.M. (2002) Acc. Chem. Res.35, 686–694.

14. List, B. (2007) Chem. Rev.107, 5413–5415.

15. Trost, B.M. (2002) Acc. Chem. Res.35, 695–705.

16. Sheldon, R.A. (1992) Chem. Ind. (London), 903–906.

Part II

Integration of Renewable Starting Materials