Classification polymer synthesis

As disciissed in Chapter 1, under a scheme proposed by Carothers, polymers are classified as addition or condensation polymers depending on the type of polymerization reaction involved in their synthesis. This classification scheme, however, does not permit a complete difierentiation between the two classes of polymers. A more complete but still oversimplified scheme that is still based on the dilTerent polymerization processes places polymers into three classes condensation, addition, and ring-opening polymers. This scheme reflects the stractures of the starting monomers. Probably the most general classification scheme is based on the polymerization mechanism involved in polymer synthesis. Under this scheme, polymerization processes are classified as step-reaction (condensation) or chain-reaction (addition) polymerization. In this chapter, we will discuss the different types of polymers based on the different polymerization mechanisms. 

The use of light olefins, diolefins, and aromatic-based monomers for producing commercial polymers is dealt with in the last two chapters. Chapter 11 reviews the chemistry involved in the synthesis of polymers, their classification, and their general properties. This book does not discuss the kinetics of polymer reactions. More specialized polymer chemistry texts may be consulted for this purpose. 

Table 1. Classification of different types of monomers for synthesis of hyperbranched polymers...

The chemical and physical properties of the polymers obtained by these alternate methods are identical, except insofar as they are affected by differences in molecular weight. In order to avoid the confusion which would result if classification of the products were to be based on the method of synthesis actually employed in each case, it has been proposed that the substance be referred to as a condensation polymer in such instances, irrespective of whether a condensation or an addition polymerization process was used in its preparation. The cyclic compound is after all a condensation product of one or more bifunctional compounds, and in this sense the linear polymer obtained from the cyclic intermediate can be regarded as the polymeric derivative of the bifunctional monomer(s). Furthermore, each of the polymers listed in Table III may be degraded to bifunctional monomers differing in composition from the structural unit, although such degradation of polyethylene oxide and the polythioether may be difficult. Apart from the demands of any particular definition, it is clearly desirable to include all of these substances among the condensation... 

The A-B type iniferters are more useful than the B-B type for the more efficient synthesis of polymers with controlled structure The functionality of the iniferters can be controlled by changing the number of the A-B bond introduced into an iniferter molecule, for example, B-A-B as the bifunctional iniferter. Detailed classification and application of the iniferters having DC groups are summarized in Table 1. In Eqs. (9)—(11), 6 and 7 serve as the monofunctional iniferters, 9 and 10 as the monofunctional polymeric iniferters, and 8 and 11 as the bifunctional iniferters. Tetrafunctional and polyfunctional iniferters and gel-iniferters are used for the synthesis of star polymers, graft copolymers, and multiblock copolymers, respectively (see Sect. 5). When a polymer implying DC moieties in the main chain is used, a multifunctional polymeric iniferter can be prepared (Eqs. 15 and 16), which is further applied to the synthesis of multiblock copolymers. 

Polyamides, polyethers is based on the common chemical linkages found in these polymers. Classification Based on the Mode of Synthesis of Polymers... 

Basie definitions of terms relating to polymerization reactions [1,2] and stereochemical definitions and notations relating to polymers [3] have been published, but no reference was made explieitly to reaetions involving the asymmetric synthesis of polymers. It is the aim of the present doeument to recommend classification and definitions relating to asymmetrie polymerizations that may produce optically active polymers. 

In this section, enzymes in the EC 2.4. class are presented that catalyze valuable and interesting reactions in the field of polymer chemistry. The Enzyme Commission (EC) classification scheme organizes enzymes according to their biochemical function in living systems. Enzymes can, however, also catalyze the reverse reaction, which is very often used in biocatalytic synthesis. Therefore, newer classification systems were developed based on the three-dimensional structure and function of the enzyme, the property of the enzyme, the biotransformation the enzyme catalyzes etc. [88-93]. The Carbohydrate-Active enZYmes Database (CAZy), which is currently the best database/classification system for carbohydrate-active enzymes uses an amino-acid-sequence-based classification and would classify some of the enzymes presented in the following as hydrolases rather than transferases (e.g. branching enzyme, sucrases, and amylomaltase) [91]. Nevertheless, we present these enzymes here because they are transferases according to the EC classification. 

Proanthocyanidins and Procyanidins - In a classical study Bate-Smith ( ) used the patterns of distribution of the three principal classes of phenolic metabolites, which are found in the leaves of plants, as a basis for classification. The biosynthesis of these phenols - (i) proanthocyanidins (ii) glycosylated flavonols and (iii) hydroxycinnamoyl esters - is believed to be associated with the development in plants of the capacity to synthesise the structural polymer lignin by the diversion from protein synthesis of the amino-acids L-phenylalanine and L-tyro-sine. Vascular plants thus employ one or more of the p-hydroxy-cinnarayl alcohols (2,3, and 4), which are derived by enzymic reduction (NADH) of the coenzyme A esters of the corresponding hydroxycinnamic acids, as precursors to lignin. The same coenzyme A esters also form the points of biosynthetic departure for the three groups of phenolic metabolites (i, ii, iii), Figure 1. 

Classification by End Use Chemical reactors are typically used for the synthesis of chemical intermediates for a variety of specialty (e.g., agricultural, pharmaceutical) or commodity (e.g., raw materials for polymers) applications. Polymerization reactors convert raw materials to polymers having a specific molecular weight and functionality. The difference between polymerization and chemical reactors is artificially based on the size of the molecule produced. Bioreactors utilize (often genetically manipulated) organisms to catalyze biotransformations either aerobically (in the presence of air) or anaerobically (without air present). Electrochemical reactors use electricity to drive desired reactions. Examples include synthesis of Na metal from NaCl and Al from bauxite ore. A variety of reactor types are employed for specialty materials synthesis applications (e.g., electronic, defense, and other). 

Major advances and problems in the field of synthesis, properties, structure and applications of polymers containing metallochelate units are discussed. Included are terminology, classification and nomenclature of these compounds as well as major approaches to calculating the equilibrium constants of chelation with polymeric ligands and chelate effect in metallopolymeric systems. Special attention is paid to the production and structural features of polymers containing metallochelate units. The most important applications of such polymers are classified... 

Let s start by developing an overview of the major types of polymers. We can categorize polymers in a number of ways. We will develop chemical as well as structural classifications later in the text when we learn about their synthesis and properties. However to begin, we will divide them on the basis of origin and function. We have already alluded to two different types natural and synthetic. Table 1-1 lists several types of natural polymers and provides examples of each. As their name implies, natural polymers occur in nature. 

Hybrid framework compounds, including both metal-organic coordination polymers and systems that contain extended inorganic connectivity (extended inorganic hybrids), have recently developed into an important new class of solid-state materials. We examine the diversity of this complex class of materials, propose a simple but systematic classification, and explore the chemical and geometrical factors that influence their formation. We also discuss the growing evidence that many hybrid frameworks tend to form under thermodynamic rather than kinetic control when the synthesis is carried out under hydrothermal conditions. Finally, we explore the potential applications of hybrid frameworks in areas such as gas separations and storage,... 

TABLE 1 Classification of Natural and Synthetic Polymers and Their Methods of Purification or Synthesis... 

The most fundamental classification of polymers is whether they are naturally occurring or synthetic. Common natural polymers (often referred to as biopolymers) include macromolecules such as polysaccharides e.g., starches, sugars, cellulose, gums, etc.), proteins e.g., enzymes), fibers e.g., wool, silk, cotton), polyisoprenes e.g., natural rubber), and nucleic acids e.g., RNA, DNA). The synthesis of biodegradable polymers from natural biopolymer sources is an area of increasing interest, due to dwindling world petroleum supplies and disposal concerns. 

Polymers can be usefully classified in many ways, such as by source of raw materials, method of synthesis, end use, and fabrication processes. Some classifications have already been considered in this chapter. Polymers are grouped by end use in this section, which brings out an important difference between macromolecules and other common materials of construction. This is that the chemical structure and size of a polymeric species may not completely determine the properties of an article made from such a material. The process whereby the article is made may also exert an important influence. 

In order to ensue a clear presentation of the results the authors decided to segregate both synthetic principles All synthetic strategies developed from the multifunctional condensations of Stille and Marvel were assigned to this general type of reaction. At the same time the first multistep sequences (polymer-analogous cyclization of poly(methyl vinyl ketone) and polyacrylonitrile) are used as point of reference for the classification of the other type of synthesis (stepwise procedures). 

In this entry, the classification, preparation, properties, fabrication, safety considerations, and economics of fluoropolymers are discussed. Monomer synthesis and properties have also been discussed. Increasing the fluorine content of a polymer increases chemical and solvent resistance, flame resistance, and photostability, improves electrical properties, such as dielectric constant, lowers coefficient of friction, raises melting point, increases thermal stability, and weakens mechanical properties. 

Latex is a dispersion of polymer particles in a liquid medium, where the particles will remain suspended indefinitely. This property means that latices are colloidal dispersions. By nature of its origin, latex is classified into natural latex for dispersions obtained from plants, and synthetic latex for dispersions that are man made, typically by a process called emulsion polymerization. Blackley discusses a number of further classifications including artificial latex for dispersions in which the polymer is dispersed after synthesis, and modified latex where a chemical modification of existing latex is made. 

Over the past two decades, liquid crystal polymers (LCP s) have received a considerable amount of attention in both academic and industrial laboratories. Often termed mesomorphic (meaning having "middle form"), liquid crystalline phases have a degree of order between that of the zero ordered liquid and that of the three dimensional crystal lattice. Recent reviews of liquid crystal polymers have provided a fundamental understanding of the synthesis, classification, morphology, and rheology of this unique class of materials (52-541. 

Classification by Decomposition Behavior. The decomposition mechanism is a reasonable way to classify polymers. They can either depolymerize upon irradiation, for example, poly(methylmethacrylate), or decompose into fragments such as poly-imides or polycarbonates. This method of classification is closely related to the synthesis of polymers. Polymers that are produced by radical polymerization from monomers, which contain double bonds, are likely to depolymerize into monomers, while polymers that have been formed by reactions like polycondensation will not depolymerize into monomers upon irradiation, but will be decomposed into different fragments. The second group cannot be used to produce films with the same structure or molecular weight as the original material with methods such as PLD. 

Initiation. The most recent classification of initiators for cationic ring-opening polymerization was presented and discussed by Penczek et al. (IJ. Only a few classes of initiators that are very useful both for mechanistic studies as well as for synthesis of well-defined polymers will be presented here. 

Polymers can be classified in many ways, such as by source, method of synthesis, structural shape, thermal processing behavior, and end use of polymers. Some of these classifications have already been considered in earlier sections. Thus, polymers have been classified as natural and synthetic according to source, as condensation and addition (or step and chain) according to the method of synthesis or polymerization mechanism, and as linear, branched, and network according to the structural shape of polymer molecules. According to the thermal processing behavior, polymers are classified as thermoplastics and thermosets, while according to the end use it is convenient to classify polymers as plastics, fibers, and elastomers (Rudin, 1982). 

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