Synthesis of Graft Copolymers

Graft copolymers are comb-shaped polymers consisting of a backbone and two or more branches which differ chemically from the backbone. Branches are usually distributed randomly along the backbone, although recent advances in synthetic methods have allowed for the preparation of better- 

The grafting from methodology was also utihzed for the synthesis of poly(4-methylphenoxyphosphazene-g-2-methyl-2-oxazoline) graft copolymers [187]. The synthetic approach involved the thermal polymerization of hexachlorophosphazene, in the presence of aluminum chloride, to give low molecular weight poly(dichlorophosphazene). The chloro groups were subsequently replaced by 4-methylphenoxy groups, followed by partial bromi- 

Polystyrene-g-poly(ethylene oxide) was synthesized by the copolymerization of styrene and styrenic PEO with CpTiCb/MAO catalyst [190]. In this case the macromonomer was prepared by first reacting the sodium salt of PEO-OH with NaH and then with a 5-fold amount of p-chloromethyl styrene. 

Thiol end-functionalized poly(2-hydroxyethyl methacrylate-g-ethylene glycol) graft copolymers were synthesized by ATRP copolymerization of 

An alternative route for the preparation of styrenic macromonomers is the reaction of living chains with 4-(chlorodimethylsilyl)styrene (CDMSS) [192]. The key parameter for the successful synthesis of the macromonomers is the faster reaction of the living anionic chain with the chlorosilane group rather than with the double bond of the CDMSS. Anionic in situ copolymerization of the above macromonomers (without isolation) with conventional monomers leads, under appropriate conditions, to well-defined comb-like chains with a variety of structures. 

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Corner, T. Free Radical Polymerization — The Synthesis of Graft Copolymers. Vol. 62, pp. 95— 142. 

Anionic polymerization techniques can also be applied to the synthesis of graft copolymers 6 7 87 1U). Kennedy s classification 134) is used here as shown in Scheme 5. 

Corner, T. Free Radical Polymerization — The Synthesis of Graft Copolymers. Vol. 62, pp. 95-142. Crescenzi, V. Some Recent Studies of Polyelectrolyte Solutions. Vol. 5, pp. 358-386. 

The enzymatic polymerization of lactones could be initiated at the hydroxy group of the polymer, which expanded to enzymatic synthesis of graft copolymers. The polymerization of c-CL using thermophilic lipase as catalyst in the presence of hydroxyethyl cellulose (HEC) film produced HEC-gra/f-poly( -CL) with degree of substitution from 0.10 to 0.32 [102]. 

Concerning the synthesis of graft copolymers, Jedlinski et al. have prepared poly(MMA-g-(3BL) copolymers via anionic grafting of 3BL from a modified PMMA backbone [85]. PMMA chains were partially saponified by potassium hydroxide and complexed by 18C6 crown ether so as to act as multifunctional mac-... 

The numerous ways for the synthesis of graft copolymers can be divided into three categories. 

The synthesis of graft copolymers can be achieved either by "grafting from or by grafting onto processes.— The former method seems more versatile, but it does not allow an adequate structure control, and it often yields rather polydisperse samples. On the contrary "grafting onto" methods allow a precise control of the size and of the nunber of grafts, but it is only applicable to a limited number of systems. 

Rogovin, Z. A., and U. Zhun-Zhui Structure and properties of cellulose and its esters. LXXXV. Synthesis of new derivatives of cellulose and other polysaccharides. IV. Synthesis of graft copolymers of carboxymethyl cellulose and caprolactam. Vysokomolekulyarnye Soedineniya 1, 1630 (1959). 

It is evident that the values of the transfer constants are dependent on the nature both of the attacking radicals and of the transfer agent itself, and that similar effects should be expected during the synthesis of graft copolymers by chain transfer methods. For example, with respect to toluene the chain transfer constant is a little greater for methyl methacrylate radicals than for styrene radicals on the contrary, with respect to halogenated solvents (CC14) the polystyrene radical is much more effective in the removal of a chlorine atom. Vinyl acetate chains are far more effective than either of the other two polymer radicals. 

The synthesis of graft copolymers by grafting from and grafting onto techniques are reported in Table 4. 

Amine functions readily react with oxonium sites. This reaction was used for the synthesis of graft copolymers involving reaction of living poly-THF with either poly(p-vinylpyridine) or poly(p-dimethylaminostyrene) S6K Attempts to synthesize macromonomers by a similar route were made57 but their characterization is difficult because they contain quaternary ammonium sites ... 

Another method is proposed by Hawker et al. [78], The principle is illustrated with the synthesis of grafted copolymer PS-g-PS ... 

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