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Über dieses Buch

Emphasis is on a broad description of the general methods and processes for the synthesis, modification and characterization of macromolecules. These more fundamental chapters will be supplemented by selected and detailed experiments. In addition to the preparative aspects the book also gives the reader an impression on the relation of chemical constitution and morphology of Polymers to their properties, as well as on their application areas. Thus, an additional textbook will not be needed in order to understand the experiments.

The 5th edition contains numerous changes: In recent years, so-called functional polymers which have special electrical, electronic, optical and biological properties, have gained more and more in interest. This textbook was therefore supplemented by recipes which describe the synthesis of these materials in a new chapter "Functional polymers". Together with new experiments in chapter 3,4 and 5 the book now contains more than 120 recipes that describe a wide range of macromolecules.

From the reviews of recent editions:

"This is an excellent book for all polymer chemists engaged in synthesis research studies and education. It is educationally sound and has excellent laboratory synthetic examples. The fundamentals are well done for the teaching of students and references are resonably up-to-date. As in previous issues, there are sections dealing with an introduction; structure and nomenclature; methods and techniques for synthesis, characterization, processing and modification of polymers.

....The authors have noted the following changes from previous editions- a new section on correlations of structure, morphology and properties; revision and enlargement of other property and characterization procedures; additional new experiments such as controlled radical polymerization; enzymatic polymerizations; microelmulsions; and electrical conducting polymers.

This is a high quality textbook at a reasonable price and should be considered as a suitable reference for all engaged in synthetic areas of polymer research." (Eli M. Pearce, Polytechnic University, Brooklyn, NY, USA)



1. Introduction

The origin of polymer science as a part of organic chemistry goes back to the end of the nineteenth century when chemists detected that the properties of many substances with colloidal properties are connected with their molecular size. As a result of these and preferably of his own studies Hermann Staudinger (1881–1965) concluded in the early 1920s that substances like natural rubber, cellulose, and proteins but also many synthetic resins obtained by so-called polyreactions consist of large molecules, for which Staudinger proposed the term “macromolecules”. Nowadays, macromolecules and polymers are synonyms for substances with especially high molecular masses. However a sharp boundary cannot be drawn between low-molecular-weight and macromolecular substances; rather there is a gradual transition between them. One can say that macromolecules consist of a minimum of several hundred atoms. Accordingly, the lower limit for their molecular mass can be taken as around 103 g mol−1.
Dietrich Braun, Harald Cherdron, Matthias Rehahn, Helmut Ritter, Brigitte Voit

2. Methods and Techniques for Synthesis, Characterization, Processing, and Modification of Polymers

In this chapter, the fundamentals and the most common methods and techniques for the synthesis, processing, characterization, and modification of macromolecular materials are described briefly, as an introduction to the special Chaps. 3, 4, and 5. The main emphasis is on the description of methods and techniques used in laboratories, but some examples from industrial practice are also mentioned.
Dietrich Braun, Harald Cherdron, Matthias Rehahn, Helmut Ritter, Brigitte Voit

3. Synthesis of Macromolecules by Chain Growth Polymerization

Polymerization reactions can proceed by various mechanisms, as mentioned earlier, and can be catalyzed by initiators of different kinds. For chain growth (addition) polymerization of single compounds, initiation of chains may occur via radical, cationic, anionic, or so-called coordinative-acting initiators, but some monomers will not polymerize by more than one mechanism. Both thermodynamic and kinetic factors can be important, depending on the structure of the monomer and its electronic and steric situation. The initial step generates active centers that generally cause the reaction to propagate very rapidly via macroradicals or macroions; chain termination yields inactive macromolecules. It is important to note that in classical uncontrolled chain growth mechanism the molar mass of the formed polymers increases fast in the first reaction period but reaches a plateau value even at relatively low monomer conversion which leads to the fact that monomer as well as terminated final polymer chains are present in the reaction system. The most important initiators are summarized in Table 3.1.
Dietrich Braun, Harald Cherdron, Matthias Rehahn, Helmut Ritter, Brigitte Voit

4. Synthesis of Macromolecules by Step Growth Polymerization

Condensation polymerizations (polycondensations) are stepwise reactions between bifunctional or polyfunctional components, with elimination of small molecules such as water, alcohol, or hydrogen and the formation of macromolecular substances. For the preparation of linear condensation polymers from bifunctional compounds (the same considerations apply to polyfunctional compounds which then lead to branched, hyperbranched, or crosslinked condensation polymers) there are basically two possibilities. One either starts from a monomer which has two unlike groups suitable for polycondensation (AB type), or one starts from two different monomers, each possessing a pair of identical reactive groups that can react with each other (AABB type). An example of the AB type is the polycondensation of hydroxycarboxylic acids:
Dietrich Braun, Harald Cherdron, Matthias Rehahn, Helmut Ritter, Brigitte Voit

5. Modification of Macromolecular Substances

The term “modification of macromolecular substances” is used for chemical and physical processes that are carried out after the actual synthesis, i.e., on the finished macromolecule. Chemical modifications are, for example, the conversion of ester side groups to hydroxy groups, chemical degradation, and crosslinking reactions. Physical modifications are also of great importance in industrial practice. The utilization of additives to improve the processability (processing agents) or to increase the resistance to oxygen and light (oxidation inhibitors, photostabilizers) are among such modifications. Finally, there are some methods applied in order to modify the mechanical properties of polymers. These include the admixing of inorganic fillers (“filled polymers”), the introduction of inorganic or organic fibers (“reinforced polymers”), the admixing of other polymers (“polymer blends”), as well as stretching and foaming.
Dietrich Braun, Harald Cherdron, Matthias Rehahn, Helmut Ritter, Brigitte Voit

6. Functional Polymers

The overwhelming number of known polymers can be basically sub-divided into those for structural applications and those, which come over with specific functions. The former ones as well as the later ones, called Functional Polymers, play important roles since the early days of polymer science and technology. The latter ones, however, usually are not so much characterized by their thermo-mechanical properties, but rather by their inherent functionalities instead, which they develop due to special constitutional features. For example, some of their atoms or groups of atoms may undergo specific interactions with solvents, ions, cells, surfaces, fillers or other polymers. Alternatively, specific optical or electronic properties may result from the molecular and supramolecular architecture of these macromolecules. Polyelectrolytes like poly(acrylic acid) or poly(diallyldimethylammonium chloride), and polymeric stabilizers like polyvinylalcohol or polyethyleneglycol [poly(ethylene oxide), PEO], all of them characteristic examples of functional polymers, are large-scale technical products nowadays. They have found widespread application in e.g. hygiene and cosmetics products. Moreover, polymeric additives and compatibilizers simplify polymer processing and morphology design, and allow the preparation of transparent nanocomposites with improved or even novel property profiles. Photoresins and photoresists are key compounds of photolithography. As such, they are revolutionizing the printing technology, and paved the way for semiconductor and microelectronics industry. In the year 2000, moreover, the Nobel prize was awarded to A. J. Heeger, A. G. MacDiaramid and H. Shirakawa for the development of electrically (semi)conducting polymers, which are key players in our today’s organic (opto)electronic.
Dietrich Braun, Harald Cherdron, Matthias Rehahn, Helmut Ritter, Brigitte Voit


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