Physical-chemical modifications

The third possibility for synthesizing polymeric substances is the modification of existant natural or synthetic macromolecules (see Chap. 5). These processes can either be chemical or physical. Chemical modifications are reactions on macromolecules without degradation of the main chain (macromolecular substitution routes, polymer-analogous reactions ) like, for example, hydrolysis. 

Due to the nature of carbon materials, the presentation of representative methods for surface derivatization will follow an approach different from that described in the preceding section, which is based on the spatial target site where physical-chemical modification can take place (1) immobilization performed at edges and/or ends and defects of graphitic sheets, (2) immobilization onto the graphene sheets, and (3) exclusively for CNTs we present some examples of endohedral encapsulation of metal complexes. For the first two cases, covalent bonding and noncovalent interactions can occur directly between the transition metal complex and carbon supports or via spacers grafted to the carbon surface. 

Although chemical techniques can be used to modify the properties of biopolymers in order to expand their range of applications, this is not the unique way to improve biopolymer performance. There are different methods to transform biopolymers in sources of structural polymers that may supplant traditional commodity plastics, such as genetic manipulation of some plant species, polymerization of biological starting materials, or the creation of new gene sequences that can lead to novel protein polymers through the application of recombinant DNA methods. However, only biopolymer physical/chemical modifications will be discussed in this chapter. 

Topics of interest in relation to biopolymer surface modifications have already been addressed before. As these topics have continuously been reviewed during the last 30 years of polymer chemistry, the synthetic methods that were used most are covered here. This chapter emphasizes in particular the physical/chemical modifications necessary to improve the apphcation properties of biopolymers and hence their potential applications in drug dehvery systems, packaging, affinity chromatography, and biosensor fields. 

Table 5.28 gives the modifications in physical/chemical characteristics resulting from deeper and deeper hydrotreatment (Martin et al., 1992). The sulfur contents could thus be reduced to first as low as a few hundred ppm, then to a few ppm. The level of aromatics in the selected example drops from 39% to 7% while the cetane number increases from 49 to 60. Note here that such a treatment, possible through experimental means, does not correspond to current industrial practice because of its high cost and its very high hydrogen consumption. 

Chemical modification of the cotton fiber must be achieved within the physical framework of this rather compHcated architecture. Uniformity of reaction and distribution of reaction products are iaevitably iafiuenced by rates of diffusion, swelling and shrinking of the whole fiber, and by distension or contraction of the fiber s iadividual stmctural elements duting finishing processes. 

Cellulose Derivatives. Chemical modification markedly alters the physical properties of ceUulose. Common derivatives iaclude methylceUulose ethylceUulose [9004-57-3] ptopylceUulose /7(9(93 -/ -7/, hydroxyethjlceUulose /7(9(94- 52-(97, hydtoxyptopylceUulose [9004-64-2],... 

Modifications of the wood surface can be performed by various physical, mechanical and chemical treatments. Chemical treatments especially are performed in order to enhance the dimensional stability, but also for amelioration of physical and mechanical properties or a higher resistance against physical, chemical and biological degradation. 

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. 

When the physical modification method is used, PS is modified by mechanical stirring with various synthetic rubbers such as polybutadiene, polybutadiene styrene, polyisopropene, polychloropropene, polybutadiene styrene-acrylonitrile copolymers. In the chemical modification, PS is modified with polyfunctional modificators in the presence of cationic catalysis. 

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. 

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. 

Although, the heat resistance of NBR is directly related to the increase in acrylonitrile content (ACN) of the elastomer, the presence of double bond in the polymer backbone makes it susceptible to heat, ozone, and light. Therefore, several strategies have been adopted to modify the nitrile rubber by physical and chemical methods in order to improve its properties and degradation behavior. The physical modification involves the mechanical blending of NBR with other polymers or chemical ingredients to achieve the desired set of properties. The chemical modifications, on the other hand, include chemical reactions, which impart structural changes in the polymer chain. 

Our interest in the synthesis of poly (amino acids) with modified backbones is based on the hypothesis that the replacement of conventional peptide bonds by nonamide linkages within the poIy(amino acid) backbone can significantly alter the physical, chemical, and biological properties of the resulting polymer. Preliminary results (see below) point to the possibility that the backbone modification of poly(amino acids) circumvents many of the limitations of conventional poly(amino acids) as biomaterials. It seems that backbone-modified poly (amino acids) tend to retain the nontoxicity and good biocompatibility often associated with conventional poly (amino acids)... 

Unnecessary derivatization (use of blocking groups, protection/de-protection, and temporary modification of physical/chemical processes) should be minimized or avoided if possible, because such steps require additional reagents and can generate waste. 

Owing to multi-functionahty, physical properties such as solubihty and the glass transition temperature and chemical functionahty the hyperbranched (meth) acrylates can be controlled by the chemical modification of the functional groups. The modifications of the chain architecture and chemical structure by SCV(C)P of inimers and functional monomers, which may lead to a facile, one-pot synthesis of novel functionahzed hyperbranched polymers, is another attractive feature of the process. The procedure can be regarded as a convenient approach toward the preparation of the chemically sensitive interfaces. 

The in situ bulk polymerization of vinyl monomers in PET and the graft polymerization of vinyl monomers to PET are potential useful tools for the chemical modification of this polymer. The distinction between in situ polymerization and graft polymerization is a relatively minor one, and from a practical point of view may be of no significance. In graft polymerization, the newly formed polymer is covalently bonded to a site on the host polymer (PET), while the in situ bulk polymerization of a vinyl monomer results in a polymer that is physically entraped in the PET. The vinyl polymerization in the PET is usually carried out in the presence of the swelling solvent, thereby maintaining the swollen PET structure during polymerization. The swollen structure allows the monomer to diffuse in sufficient quantities to react at the active centers that have been produced by chemical initiation (with AIBM) before termination takes place. 

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