Graft copolymerization anionic

Anionic Graft Copolymerization onto Polystyrene. We have been able to initiate graft copolymerization onto polystyrene by the use of anionic initiators but even here the reaction does not proceed as one may expect. Once again one would likely think that the benzylic hydrogen is the most acidic and should be the one removed by a lithium reagent... 

An anionic technique by indirect grafting was proposed for N-metallation of Nylon by Yamaguchi (153-155), in which alcali metals dissolved in liquid ammonia displace the amidic hydrogen atoms. Nylon derivatives and graft copolymers can be synthetized from the N-metallated Nylon (153). For ethylene oxide as grafting monomer, the metallated fibers were soaked in a tetrahydro-furan solution of the monomer, at 60° C (154). Methyl methacrylate is grafted on Nylon with a conversion over 90% by this technique (155). Other procedures involve the use of sodium methoxide in methanol solution and subsequent anionic graft copolymerization of acrylonitrile in a tetrahydrofuran solution (156). 

Zilkha, A., B. A. Feit, and A. Bar-Nun Anionic graft copolymerization of vinyl monomers on natural polyhydroxy compounds, their derivatives, and on synthetic polyhydroxy polymers. Israeli Pat. 15 962, Oct. 1962 C. A. 58, 5803 (1963). 

Bamford, Eastmond and coworkers have employed metal complexpolymeric halide redox systems to initiate block and graft copolymerization. The polymeric halides can be synthesized by a variety of techniques, including radical polymerization,281 anionic polymerization (Scheme 7.28),"so... 

Anionic polymerization of pivalolactone with the polystyrene anion produced only homopolymer mixtures, but the polystyrene carboxylate anion was able to give a block copolymer336. The block efficiency depends on catalyst ratio and conversion because the initiation step is slow compared with propagation337. Tough and elastic films were obtained by graft copolymerization or block copolymerization of pivalolactone onto elastomers containing tetrabutylammonium carboxylate groups338,339. ... 

In this paper graft copolymerization onto both polystyrene and styrene-butadiene block copolymer will be discussed. It will be shown that radical processes do not permit the addition of monomers onto polystyrene and that one must use anionic initiation in order... 

Muller et al. [53] prepared similar PMMA-g-PMMA by radical copolymerization of MMA with methacrylate-terminated PMMA macromonomer, 29, and characterized the samples by SEC-multiangle laser fight scattering (MALLS). The power law exponent, a, in the equation, 1/2°cMa, was found to be 0.36. In remarkable contrast to the result of Ward et al. [51], the shrinking factor decreased with increase of MW. This may imply that the difference in graft copolymerization method, anionic or radical, results in the graft copolymers with very different branch distribution. 

Grafting from is based on the use of a macromolecular initiator, that is, a polymer backbone containing dioxolenium salts as precursors of carbenium and oxocarbeniura ions (i.e., labile halides or acylhalides). The last two functional groups can be transformed into a carbenium ion by reaction with a silver salt containing a stable anion. When the monomer used is a strong nucleophile (such a cyclic imino ethers) the labile halide itself can initiate graft copolymerization. 

Kostov, G.K. and Turmanova, S.C. 1997. Radiation-initiated graft copolymerization of 4-vinylpyridine onto polyethylene and polytetrafluoroethylene films and anion-exchange membranes therefrom. J Appl Polym Sci. 64 1469-1475. 

Another example of ionic graft copolymerization is a reaction carried out on pendant olefinic groups using Ziegler-Natta catalysts in a coordinated anionic-type polymerization. The procedure consists of two steps. In the first, diethylaluminum hydride is added across the double bonds. In the second the product is treated with a transition metal halide. This yields an active catalyst for polymerizations of a-olefms. By this method polyethylene and polypropylene can be grafted to butadiene styrene copolymers. Propylene monomer polymerization results in formations of isotactic polymeric branches ... 

Redox polymerizations are among the most popular techniques for grafting reactions, and of the possible initiator systems, ferrous ion oxidation and those based on ceric ion reduction are widely used. In a redox polymerization, a hydroperoxide or similar group is reduced to a free radical plus an anion, while the metal ion is oxidized to a higher valency state, and at the same time a monomer is added. When the reducible group is attached to a polymeric chain, the free radical grafting sites thus formed on the macro-molecular backbone act as initiators for graft copolymerization... 

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