Poly , chemical modifications

It may also be mentioned that a number of commercial polymers are produced by chemical modification of other polymers, either natural or synthetic. Examples are cellulose acetate from the naturally occurring polymer cellulose, poly(vinyl alcohol) from polyfvinyl acetate) and chlorosulphonated polyethylene (Hypalon) from polyethylene. 

As with poly(vinyl alcohol), poly(vinyl cinnamate) is prepared by chemical modification of another polymer rather than from monomer . One process is to treat poly(vinyl alcohol) with cinnamoyl chloride and pyridine but this is rather slow. Use of the Schotten Baumann reaction will, however, allow esterification to proceed at a reasonable rate. In one example poly(vinyl alcohol) of degree of polymerisation 1400 and degree of saponification of 95% was dissolved in water. To this was added a concentrated potassium hydroxide solution and then cinnamoyl chloride in methyl ethyl ketone. The product was, in effect a vinyl alcohol-vinyl cinnamate copolymer Figure 14.8)... 

Figure 2. Cyclic voltammograms of a poly(2,2 -bithiophene)-coated electrode in acetonitrile containing 0.1 M Bu4NC 04.34 (Reprinted from G. Zotti, C. Schiavon, and S. Zecchin, Irreversible processes in the electrochemical reduction of polythiophenes. Chemical modifications of the polymer and charge-trapping phenomena, Synth. Met. 72 (3) 275-281, 1995, with kind permission from Elsevier Sciences S.A.)...

Some tailor-made homopolymers can serve as starting points for chemical modifications to yield new species. Poly(hydroxyethyl methacrylate) and poly(glyceryl methacrylate) 16), already mentioned, are obtained upon hydrolysis of the OH-protecting groups that allow the anionic polymerization to proceed. Another example is the acid hydrolysis of poly(t-butyl methacrylate), a reaction which proceeds easily to completion, yielding poly(methacrylic acid) of known degree of polymerization and narrow molecular weight distribution 44 45). 

Unfortunately, the modification of the side chain is not a generally applicable approach. Among the major, naturally occurring amino acids, only L-lysine has a chemically reactive side chain that would be as readily available for chemical modification as the side chain of glutamic or aspartic acid. Since, however, poly (L-lysine) is known to be toxic (10), its derivatives cannot be candidates for generally applicable biomaterials. Thus, most of the poly(amino acids) that have so far been suggested as biomaterials are derivatives of gluteunic or aspartic acid or copolymers of such derivatives with leucine, methionine, or a limited number of additional amino acids (11). 

In their original form these cements came as a zinc oxide powder and a concentrated solution of poly(acrylic acid) (Wilson, 1975b). Since then they have been subject to a number of chemical modifications. 

SCHEME 1 Mechanism for chemical modification of poly(dimethysiloxane) (silicone rubber) membranes with ion-sensing active material. 

Chemical Modification of Poly(vinyl chloroformate) by Phenol Using Phase-Transfer Catalysis... 

From these results it is reasonable to conclude that no inversion in the order of the chemical shifts of the tertiary carbon atoms belonging to the different triads occurs from the starting PV0CC1 to the poly(vinyl phenyl carbonate). Moreover the chemical modification of PV0CC1 by phenol does not induce any degradation of the polymer. 

Chemical Modification of Poly(2,6-dimethyl-l,4-phenylene oxide) and Properties of the Resulting Polymers... 

The chemical modification of poly (2,6-dimethyl-l,4-phenylene oxide) (PPO) by several polymer analogous reactions is presented. The chemical modification was accomplished by the electrophilic substitution reactions such as bromination, sulfonylation and acylation. The permeability to gases of the PPO and of the resulting modified polymers is discussed. Very good permeation properties to gases, better than for PPO were obtained for the modified structures. The thermal behavior of the substituted polymers resembled more or less the properties of the parent polymer while their solution behavior exhibited considerable differences. 

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. 

Sherrington et al. were the first to attempt the synthesis of chiral polymeric metal complexes by the chemical modification route,78,177,178 whereby the [Mn(salen)Cl] units are attached in a pendant fashion, by only one of the aromatic rings, to poly(styrene) or poly(methacrylate) resin beads of various morphology. Epoxidation of 1-phenylcyclohexene gave enantioselectivity values between 61% and 91%. 

Functionalization of polysilanes by chemical modification (post-polymerization) was covered in COMC II (1995) (chapter Organopolysilanes, p 101), where the formation of precursor polysilanes with potentially functionalizable side groups such as chloride, type 34 (via HCI/AICI3 chlorodephenylation of PMPS), 6 triflate, type 35 (via triflate replacement of phenyl groups)135,137 or alkyl halide (via chloromethylation of phenyl groups,138,139 type 36, or addition of HC1 or HBr to double bonds140) was discussed. Four other precursor polysilanes, which utilize the reactivity of the Si-Cl or Si-H bond, have been successfully applied in functionalization since COMC (1995) perchloropolysilane, 17 (see Section 3.11.4.2.2.(i) for synthesis),103 poly[methyl(H)silylene-f >-methylphenylsilylene],... 

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. 

Note 2 Some polymers, are obtained by the chemical modification of other polymers such that the structure of the macromolecules that constitute the resulting polymer can be thought of as having been formed by the homopolymerization of a hypothetical monomer. These polymers can be regarded as homopolymers. A well-known example is poly(vinyl alcohol). 

Lenoir S, Riva R, Lou X, Detrembleur C, Jerome R, Lecomte P (2004) Ring-opening polymerization of a-chloro- -caprolactone and chemical modification of poly(a-chloro- -caprolactone) by atom transfer radical processes. Macromolecules 37 4055 061... 

The chemical modification of poly(arylene ether sulfone)s has already been described in numerous papers. They relate to sulfonation, fluorination, and halomethylation. These derivatives are particularly suitable for the preparation of hydrolysis- and temperature-resistant separation membranes. They are used already for sea water desalination, and also for the separation of gas mixtures. 

Liu L, Jiang M. Synthesis of novel triblock copolymers containing hydrogen-bond interaction groups via chemical modification of hydrogenated poly(styrene-h/ock-butadiene-h/ock-styrene). Macromolecules 1995 28 8702-8704. 

Tanase C, Wildeman J, Blom PWM, Mena Benito ME, de Leeuw DM, van Breemen AJJM, Herwig PT, Chlon CHT, Sweelssen J, Schoo HEM (2005) Optimization of the charge transport in poly(phenylene vinylene) derivatives by processing and chemical modification. J Appl Phys 97 123703... 

The second group already contains donor groups (usually oxygen or nitrogen) and, thus, requires no further chemical modification. These include polyacrylic acid (82, 83), polyvinyl alcohol (60), polymeric Schiff s bases (65), poly-L-methylethylenimine (52), poly-2-vinylpyridine (78, 79, 98), poly-4-vinylpyridine (24), and polyvinylamine (54, 59). 

Only syntheses which involve the formation of new glycosidic linkages will be considered in this article. This restriction excludes many interesting examples of copolymerization in which only one of the monomers is a carbohydrate (or carbohydrate derivative), the polymerization of carbohydrate derivatives which contain a polymerizable group4 (such as acrylate), and the polymerization of sugar lactones.1 Many of these topics have already been discussed in reviews.1-8 Also outside the scope of this article is the chemical modification of naturally occurring polysaccharides thus, we have excluded the industrially important process of dextrini-zation,10 except as it may pertain to acid condensation processes. The radiation-catalyzed polymerization and modification of carbohydrate poly-... 

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