Chemical modification polymer materials

Polymer thermodynamics is a supporting science that proved to be very successful due to it s intensive interactions with neighbouring disciplines (such as process optimization, polymer chemistry and chemical modification, polymer characterization, morphology and interface sciences, but also with areas as polymer processing and material science). The future of polymer thermodynamics thus will strongly depend on developments made in these neighbouring research area s. I thus will present a kind of outlook for polymer thermodynamics and the possibilities of compressed or supercritical media, based on some pioneering research results in polymer chemistry and the reported molecular architectures obtained. 

Kurita, K., Ishii, S., Tomita, K., Nishimura, S., and Shimoda, K. (1993) Reactivity Charactestics of Squid Beta-Chitin as Compared with Those of Shrimp Chitin-High Potentials of Squid Chitin as a Starting Material for Facile Chemical Modifications/. Polym. Sci., Part A Polym. Chem. 32, 1027-1032. 

Whereas celluloid was the first plastics material obtained by chemical modification of a polymer to be exploited, the phenolics were the first commercially successful fully synthetic resins. It is interesting to note that in 1963, by a merger of two subsidiary companies of the Union Carbide and the Distillers organisations, there was formed the Bakelite Xylonite Company, an intriguing marriage of two of the earliest names in the plastics industry. 

The synthesis of new polymeric materials having complex properties has recently become of great practical importance to polymer chemistry and technology. The synthesis of new materials can be prepared by either their monomers or modification of used polymers in industry. Today, polystyrene (PS), which is widely used in industrial applications as polyolefins and polyvinylchlorides, is also used for the production of plastic materials, which are used instead of metals in technology. For this reason, it is important to synthesize different PS plastic materials. Among the modification of PS, two methods can be considered, viz. physical and chemical modifications. These methods are extensively used to increase physico-mechanical properties, such as resistance to strike, air, or temperature for the synthesizing of new PS plastic materials. 

New elastic polymeric materials (resistance to higher stroke or air) can be obtained by using physical modification methods, but using this method, two phases (PS and rubber) in the mixture were formed. Small rubber particles spread as a PS layer and, after awhile, the relationship between the layers decreases and rubber particles gather in the upper layer of the materials. This can be the cause of the loss of resistance of the materials. These material disadvantages have stimulated the polymer synthesis to increase the PS resistance to higher physico-mechanical properties, such as higher temperature and stroke for the chemical modification of PS with various functional modifiers. 

PS has apolar characteristics and, thus, it is difficult to form a bond with metzils or polar materials. The adhesion capability of saturated polyhydrocarbons are dependent on the basis of polar properties of polymers [25]. Mitsu-aki and Masyasu [26] investigated the chemical modification of PS for anchoring of the carboxyl group to PS macromolecules with maleic anhydride (MA) in the presence of radiczil catalysis at 90-150°C. These authors... 

These observations demonstrate that the different functional groups can be attached to the aromatic ring of PS with various chemical modification conditions, and it is possible to obtain different technical properties for polymer materials. 

Grafting reactions alter the physical and mechanical properties of the polymer used as a substrate. Grafting differs from normal chemical modification (e.g., functionalization of polymers) in the possibility of tailoring material properties to a specific end use. For example, cellulose derivatization improves various properties of the original cellulose, but these derivatives cannot compete with many of the petrochemically derived synthetic polymers. Thus, in order to provide a better market position for cellulose derivatives, there is little doubt that further chemical modification is required. Accordingly, grafting of vinyl monomers onto cellulose or cellulose derivatives may improve the intrinsic properties of these polymers. 

Radiation-induced modification or processing of a polymer is a relatively sophisticated method than conventional thermal and chemical processes. The radiation-induced changes in polymer materials such as plastics or elastomers provide some desirable combinations of physical and chemical properties in the end product. Radiation can be applied to various industrial processes involving polymerization, cross-linking, graft copolymerization, curing of paints and coatings, etc. 

A good example of a reactive modifier which has been used (14) to enhance properties of polyolefins is maleic anhydride (MA). The formation of maleic adduct in polypropylene (PP), for example, can be used to effect several modifications e.g. to improving hydrophilicity, adhesion and dyeabflity. Moreover, the polymer-maleic adduct has an availabla additional functionality to effect other chemical modifications for achieving the desired material design objectives. Reactions of MA with polymers in solution are described in the patent literature (15). 

Unsaturated groups are very interesting for application development because this specific functionality opens up a broad range of possibilities for further (chemical) modification of the polymer structure, and therefore its physical and material properties. The direct microbial incorporation of other functional substituents to the polymer side chains, e.g. epoxy-, hydroxy-, aromatic-, and halogen functional groups, influences the physical and material properties of poly(HAMCL) even further [28,33,35,39-41]. This features many possibilities to produce tailor-made polymers, depending on the essential material properties that are needed for the development of a specific application. 

A kinetic model based on the Flory principle is referred to as the ideal model. Up to now this model by virtue of its simplicity, has been widely used to treat experimental data and to carry out engineering calculations when designing advanced polymer materials. However, strong experimental evidence for the violation of the Flory principle is currently available from the study of a number of processes of the synthesis and chemical modification of polymers. Possible reasons for such a violation may be connected with either chemical or physical factors. The first has been scrutinized both theoretically and experimentally, but this is not the case for the second among which are thermodynamic and diffusion factors. In this review we by no means pretend to cover all theoretical works in which these factors have been taken into account at the stage of formulating physicochemical models of the process... 

Widespread chlorine-containing polymers would include, 1) stable molding material for practical use such as polyvinyl chloride (PVC), polyvinylidene chloride and poly(epichlorohydrin)(PECH) and, 2) reactive polymers capable to introduce additional functional groups via their active chlorines such as chloromethyl polystyrene, poly (3-chloroethyl vinyl-ether) and poly (vinyl chloroacetate). While the latter, especially the chloromethyl polystyrene, has been widely used recently for the synthesis of variety of functional polymers, we should like to talk in this article about the chemical modification of the former, mainly of PVC and PECH, which was developed in our laboratory. 

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