Handbook of Engineering and Specialty Thermoplastics, Volume 2 E-Book

Johannes Karl Fink

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 521

Veröffentlichungsjahr: 2011

Beschreibung

This book focuses on common types of polymers belonging to the class of water soluble polymers. It covers a wide range of applications: food, cosmetic, medical, lithography and ink jet printing, agricultural, wastewater cleaning, and oilfield. The text is arranged according to the chemical constitution of polymers and reviews the developments that have taken place in the last decade. Each chapter follows the same template. A brief introduction to the polymer type is given and previous monographs and reviews dealing with the topic are listed for quick reference. The text continues with monomers, polymerization, fabrication techniques, properties, applications, as well as safety issues. Providing a rather encyclopedic approach to water soluble polymers, the Handbook of Engineering and Specialty Thermoplastics: * Presents a listing of suppliers and commercial grades * Reviews current patent literature, essential for the engineer developing new products * Contains an extensive tradenames index with information that is fairly unique * Concludes with an index of acronyms and a general index The Handbook of Engineering and Specialty Thermoplastics: Water Soluble Polymers provides a comprehensive reference for chemical engineers and offers advanced students a textbook for use in courses on chemically biased plastics technology and polymer science.

Leseprobe

Contents

Cover

Half Title page

Title page

Copyright page

Preface

Acknowledgements

Chapter 1: Poly(ethylene oxide)

1.1 Monomers

1.2 Polymerization and Fabrication

1.3 Properties

1.4 Special Additives

1.5 Applications

1.6 Suppliers and Commercial Grades

1.7 Environmental Impact and Recycling

References

Chapter 2: Poly(vinyl alcohol)

2.1 Monomers

2.2 Polymerization and Fabrication

2.3 Properties

2.4 Applications

2.5 Suppliers and Commercial Grades

2.6 Safety

2.7 Environmental Impact and Recycling

References

Chapter 3: Polysaccharides

3.1 Polymers

3.2 Starch

3.3 Chitosan

3.4 Carboxymethyl cellulose

3.5 Guar

3.6 Carrageenan

3.7 Suppliers and Commercial Grades

References

Chapter 4: Poly((meth)acrylic acid)

4.1 Monomers

4.2 Polymerization and Fabrication

4.3 Properties

4.4 Applications

4.5 Suppliers and Commercial Grades

References

Chapter 5: Poly(acrylamide)

5.1 Monomers

5.2 Polymerization and Fabrication

5.3 Properties

5.4 Special Additives

5.5 Applications

5.6 Suppliers and Commercial Grades

5.7 Safety

5.8 Environmental Impact and Recycling

References

Chapter 6: Poly(vinylamine)

6.1 Monomers

6.2 Polymerization and Fabrication

6.3 Applications

6.4 Suppliers and Commercial Grades

6.5 Safety

References

Chapter 7: Poly(vinylpyridine)

7.1 Monomers

7.2 Polymerization and Fabrication

7.3 Properties

7.4 Applications

7.5 Suppliers and Commercial Grades

7.6 Safety

7.7 Environmental Impact and Recycling

References

Chapter 8: Poly(vinylimidazole)

8.1 Monomers

8.2 Polymerization and Fabrication

8.3 Properties

8.4 Applications

8.5 Suppliers and Commercial Grades

8.6 Safety

References

Chapter 9: Poly(vinylpyrrolidone)

9.1 Monomers

9.2 Polymerization and Fabrication

9.3 Properties

9.4 Special Additives

9.5 Applications

9.6 Suppliers and Commercial Grades

9.7 Safety

9.8 Environmental Impact and Recycling

References

Chapter 10: Other Cationic Polymers

10.1 Manufacture

10.2 Applications

References

Chapter 11: Other Anionic Polymers

11.1 2-Acrylamido-2-methyl-1-propane sulfonic acid

11.2 Poly(sulfonic acid)s

11.3 Sulfonated Asphalt

11.4 Lignosulfonate

References

Index

Tradenames

Acronyms

Chemicals

General Index

Handbook of Engineering and Speciality Thermoplastics

Scrivener Publishing3 Winter Street, Suite 3Salem, MA 01970

Scrivener Publishing Collections Editors

James E. R. CouperRichard ErdlacRafiq IslamPradip KhaladkarNorman LiebermanPeter MartinW. Kent MuhlbauerAndrew Y. C. NeeS. A. SherifJames G. Speight

Publishers at ScrivenerMartin Scrivener ([email protected])Phillip Carmical ([email protected])

Copyright © 2011 by Scrivener Publishing LLC. All rights reserved.

Co-published by John Wiley & Sons, Inc. Hoboken, New Jersey, and Scrivener Publishing LCC, Salem, Massachusetts.

Published simultaneously in Canada.

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Cover designed by Russell Richardson.

Library of Congress Cataloging-in-Publication Data:

ISBN 978-1-118-06275-3

Preface

This book focuses on water soluble polymers. The text is arranged according to the chemical constitution of polymers and reviews the developments that have taken place in the last decade.

Most chapters follow the same template. A brief introduction to the polymer type is given and previous monographs and reviews dealing with the topic are listed for quick reference. The text continues with monomers, polymerization and fabrication techniques, and discusses aspects of application as well. Following this, suppliers and commercial grades are presented.

How to Use this Book

Utmost care has been taken to present reliable data. Because of the vast variety of material presented here, however, the text cannot be complete in all relevant aspects, and it is recommended to the reader to study the original literature for complete information.

The reader should be aware that in case of patent literature mostly US patents have been cited if available, but not the corresponding equivalent patents in other countries. For this reason, the author cannot assume responsibility for the completeness and validity of, nor for the consequences of, the use of the material presented here. Every attempt has been made to identify trademarks; however, there were some that the author was unable to locate.

Index

There are four indices: an index of trademarks, an index of acronyms, an index of chemicals, and a general index.

In the index of chemicals, compounds that occur extensively, e.g., “acetone”, are not included at every occurrence, but rather when they appear in an important context.

Acknowledgements

I am indebted to our university librarians, Dr. Christian Hasenhüttl, Dr. Johann Delanoy, Franz Jurek, Margit Keshmiri, Dolores Knabl, Friedrich Scheer, Christian Slamenik, and Renate Tschabuschnig for support in literature acquisition. I also want to express my gratitude to all the scientists who have carefully published their results concerning the topics dealt with here. This book could not have been otherwise compiled.

Last, but not least, I want to thank the publisher, Martin Scrivener, for his abiding interest and help in the preparation of the text.

Johannes Fink

20th January 2011

Chapter 1

Poly(ethylene oxide)

Poly(ethylene oxide) (PEO) is sometimes addressed as poly(ethylene glycol) (PEG). This came about because it can be considered as being derived from the etherification of ethylene glycol (EG) into the polymer. On the other hand, the industrial synthesis, as explained below, starts with ethylene oxide (EO). We will use both names simultaneously, in the same way, as given in the references.

PEG was first studied by Lourenço in 1861 (1). He reported the synthesis of oligomeric PEGs up to hexaethylene glycol. It seems to be the first example of a condensation polymerization reaction at all (2). The first patents appeared around 1930 (3,4). Soon afterwards PEGs were used as components for poly(urethane)s (5).

1.1 Monomers

The basic monomers for PEO are shown in Table 1.1. The structures are shown in Figure 1.1.

Table 1.1 Monomers for Poly(ethylene oxide) Types

MonomerRemarksEthylene oxideBasic MonomerPropylene oxideLess water solubleButylene oxideLess water solubleGlycidolBranched structures (6)Ethoxy ethyl glycidyl etherBranched structures (6)

Figure 1.1 Monomers used for Poly(ethylene oxide)

The basic monomer is EO. According to the nomenclature of heterocycles, EO is also addressed as oxiran. EO is synthesized by the addition of oxygen to ethene. Propylene oxide or trimethylene oxide may also be used as comonomer together with EO. However, these comonomers should be used only in those small amounts as not to render the resulting copolymer water insoluble. Glycidol is a suitable comonomer for branched structures.

1.2 Polymerization and Fabrication

Water-soluble PEO is prepared by the ring opening polymerization of EO, usually in the presence of a small amount of an initiator such as low molecular weight glycol or triol alcoholate (7). Examples of such initiators include alcoholates of EG, diethylene glycol and other oligomers. Branched types are synthesized with multifunctional alcoholates, such as the potassium salts of glycerol, pentaerythritol, dipentaerythritol, or sorbitol (8). The basic mechanism is shown in Figure 1.2, top.

Figure 1.2 Basic Mechanism of Polymerization

In Figure 1.2, bottom, the reaction of glycidol is shown. After addition, the negative charge may change its position, which causes the growth from both ends. In the course of the reaction a pendant hydroxyl group may again be activated as it turns into an alcoholate. This leads again to a growth reaction. In this way, branched strictures are formed.

EO or various epoxides, and other cyclic ethers can be polymerized with anionic, cationic, and coordination catalysts. For the commercial production of polymer of such type, the most effective catalysts found are (CH3)3N and SnCl4, CaCO3, FeCl3. Other compounds with catalytic activity are NaNH2, ZnO, SrO, and CaO (8).

The living polymerization techniques are preferred in comparison to other methods because molecular weight and polydispersity can be better controlled. The polymerization of EO can be carried out in polar solvents such as tetrahydrofuran (THF), N,N-dimethyl-formamide, dimethyl sulfoxide, etc.

1.2.1 Functionalization

The endgroups can be functionalized (9). The functionalization of the endgroups in the course of a living polymerization can be achieved by two different strategies (8):

1. By deactivation of the living species with a suitable electrophile or chain transfer reagent, or

2. By initiation of the living process with an organic anionic species that bears the protected functionalized group.

A disadvantage in the first strategy is that any polymer chain which has been terminated during the propagation for some reason will not react with the electrophile.

In general, functionalized polymeric chains can be obtained by a chemical modification of functional groups, either endgroups or side groups of the polymeric backbone (8).

The effective functionalization can result in end-reactive polymers. This is becoming more important due to the high versatility of the introduced endgroups. One of the most important utilizations of PEG is the construction of polymer brushes, a densely packed layer of tethered polymers anchored on the surface utilizing the end functionality of the polymer chain. Such a PEG brush significantly changes the surface properties. For example, in such a treated surface, the PEG chains are densely packed on a surface and attached by the end of the polymer chain, showing an effective rejection of protein adsorption resulting in a good blood compatibility (8).

Commercially available methoxy-ended PEGs with a methoxy group at one end and a hydroxy group at the other end are used as starting materials for the preparation of monochelic PEG. When PEG is chemically bound to a water-insoluble compound, the resulting conjugate becomes water soluble as well as soluble in many organic solvents.

When PEG is attached to a drug, its activity is commonly retained. Moreover, the bounded drug may display altered pharmacokinetics, which can be favorable. Proteins coupled to PEG exhibit an enhanced blood circulation life time because of reduced kidney clearance and reduced immunogenicity. The lack of toxicity of the polymer and its rapid clearance from the body are advantageous for pharmaceutical applications (8).

In order to couple a PEG chain to a protein or a small drug molecule, it is necessary to activate the hydroxyl end group. For example, the hydroxyl group can be converted into an aldehyde group.