Copolymerization: Toward a Systematic Approach

Springer Science & Business Media
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Copolymerization is a very widely used industrial process, in fact the dominant process in macromolecular chemistry. With the advent of widespread computing power, this book will be very useful both to academic researchers in copolymerization and to researchers in industry concerned with the synthesis of polymers such as plastics, rubbers, chemical fibers, and paints. A disk with 15 computer programs accompanies the book.
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Additional Information

Publisher
Springer Science & Business Media
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Published on
Dec 6, 2012
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Pages
228
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ISBN
9781461541837
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Language
English
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Genres
Science / Chemistry / General
Science / Chemistry / Industrial & Technical
Science / Chemistry / Organic
Technology & Engineering / Textiles & Polymers
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Content Protection
This content is DRM protected.
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The development of polymers as an important class of material was inhibited at the first by the premature failure of these versatile compounds in many applications. The deterioration of important properties of both natural and synthetic polymers is the result of irreversible changes in composition and structure of polymers molecules. As a result of these reactions, mechanical, electrical and/or aesthetic properties are degraded beyond acceptable limits. It is now generally recognized that stabilization against degradation is necessary if the useful life of polymers is to be extended sufficiently to meet design requirements for long-term applications. Polymers degrade by a wide variety of mechanisms, several of which affect all polymers through to varying degree. This monograph will concentrate on those degradation mechanisms which result from reactions of polymers with oxygen in its various forms and which are accelerated by heat and/or radiation. Those stabilization mechanisms are discussed which are based on an understanding of degradation reaction mechanisms that are reasonably well established. The stabilization of polymers is still undergoing a transition from an art to a science as mechanisms of degradation become more fully developed. A scientific approach to stabilization can only be approached when there is an understanding of the reactions that lead to degradation. Stabilization against biodegradation and burning will not be discussed since there is not a clear understanding of how polymers degrade under these conditions.
The discoveries of organometallic catalysts for olefin polymerization by Karl Ziegler and that of stereoregular olefin polymers by Giulio Natta are probably the two most important achievements in the areas of catalysis and polymer chemistry in the second half of this century. They led to the development of a new branch of chemical industry, and to a large volume production of high-density and linear low-density polyethylene, isotactic polypropylene, ethylene-propylene rubbers, isotactic poly I-butene, and poly-4-methyl-l-pentene. These discoveries merited the Nobel prize, which was awarded to K. Ziegler and G. Natta in 1963. The initial works of Ziegler and Natta were followed by an "explosion" of scientific papers and patents covering all aspects of polymerization chemistry, catalyst synthesis, and polymerization kinetics as well as the structural, chemical, physical, and technological characteristics of stereo regular polyolefins, polydienes, and olefin copolymers. It is sufficient to say that in the twenty-five years after the first publications more than 15,000 papers and patents appeared on subjects related to the area. . The development brought about the establishment of several prominent groups of scientists occupied with the study of olefin polymerization. The most important of these were scientific schools in Italy, Germany, England, the United States, Japan, the Soviet Union, Czechoslovakia, and Venezuela. In addition, many major chemical and petrochemical corporations throughout the world established labora tories devoted to the development of the technology of catalyst synthesis and olefin polymerization.
In the ten years since the first edition appeared the renaissance in Free Radical Polymerization has continued to gain momentum. In this second revised edition, the authors critically evaluate the findings of the last decade, where necessary reinterpreting earlier work in the light of these ideas, and point to the areas where current and future research is being directed. The overall aim is to provide a framework for further extending our understanding of free radical polymerization and create a definable link between synthesis conditions and polymer structure and properties. The authors have updated all chapters, and added many new references and two new chapters to reflect the significant advances made in radical polymerization. One new chapter has been devoted to the area of living radical polymerization which is now responsible for a very substantial fraction of the papers in the field.

In addition to offering polymers with unique compositions and properties not achievable with other methodologies, living radical polymerization has also been combined with other processes and mechanisms to give structures and architectures that were not previously thought possible. The developments are seen to have great application particularly in the emerging areas of electronics, biotechnology and nanotechnology.

An excellent text suitable for graduates in polymer chemistry and a reference source for researchers and practitioners in radical polymerizationSeven chapters revised and updated with eight years of new researchA new chapter devoted to the growing field of living radical polymerization
During the past 30 years, the field of alkene polymerization over transition metal catalysts underwent several major changes:
1. The list of commercial heterogeneous Ziegler-Natta catalysts for the synthesis of polyethylene and stereoregular polyolefins was completely renewed affording an unprecedented degree of control over the polymer structure.
2. Research devoted to metallocene and other soluble transition-metal catalysis has vastly expanded and has shifted toward complexes of transition metals with multidentate ligands.
3. Recent developments in gel permeation chromatography, temperature-rising fractionation, and crystallization fractionation provided the first reliable information about differences between various active centers in transition-metal catalysts.
4. A rapid development of high-resolution 13C NMR spectroscopy resulted in greatly expanded understanding of the chemical and steric features of polyolefins and alkene copolymers.
These developments require a new review of all aspects of alkene polymerization reactions with transition-metal catalysts. The first chapter in the book is an introductory text for researchers who are entering the field. It describes the basic principles of polymerization reactions with transition-metal catalysts, the types of catalysts, and commercially manufactured polyolefins.
The next chapter addresses the principal issue of alkene polymerization catalysis: the existence of catalyst systems with single and multiple types of active centers. The subsequent chapters are devoted to chemistry and stereochemistry of elemental reaction steps, structures of catalyst precursors and reactions leading to the formation of active centers, kinetics of polymerization reactions, and their mechanisms.

The book describes the latest commercial polymerization catalysts for the synthesis of polyethylenes and polypropylene
The book provides a detailed description of the multi-center nature of commercial Ziegler-Natta catalysts.
The book devotes specialized chapters to the most important aspects of transition metal polymerization catalysts: the reactions leading to the formation of active centers, the chemistry and stereochemistry of elemental polymerization steps, reaction kinetics, and the polymerization mechanism.
The book contains an introductory chapter for researchers who are entering the field of polymerization catalysis. It describes the basic principles of polymerization reactions with transition-metal catalysts and the types of commercially manufactured polyolefins and copolymers
The book contains over 2000 references, the most recent up to end of 2006.
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