Copolymerization, anionic grafting

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. ... 

Recently it has been shown that anionic functionalization techniques can be applied to the synthesis of macromonomers — macromolecular monomers — i.e. linear polymers fitted at chain end with a polymerizable unsaturation, most commonly styrene or methacrylic ester 69 71). These species in turn provide easy access to graft copolymers upon radical copolymerization with vinylic or acrylic monomers. 

A radical initiator based on the oxidation adduct of an alkyl-9-BBN (47) has been utilized to produce poly(methylmethacrylate) (48) (Fig. 31) from methylmethacrylate monomer by a living anionic polymerization route that does not require the mediation of a metal catalyst. The relatively broad molecular weight distribution (PDI = (MJM ) 2.5) compared with those in living anionic polymerization cases was attributed to the slow initiation of the polymerization.69 A similar radical polymerization route aided by 47 was utilized in the synthesis of functionalized syndiotactic polystyrene (PS) polymers by the copolymerization of styrene.70 The borane groups in the functionalized syndiotactic polystyrenes were transformed into free-radical initiators for the in situ free-radical graft polymerization to prepare s-PS-g-PMMA graft copolymers. 

The living anionic ends can be functionalized by adding such agents as ethylene oxide, carbon dioxide, and methacryloyl chloride [33]. The resulting new polymer is capable of being copolymerized with additional monomers. This process can lead to the formation of various graft copolymers [29-32]. 

Another way for increasing filler-elastomer interactions could be the grafting of a polymer on the solid surface. A number of methods exist to secure the attachment of macromolecules to the surface of carbon black particles e.g., a polymeric chain may be grown on an initiation site on the surface, small molecules previously attached to the surface may be copolymerized with a monomer, a polymeric chain, either radical, cationic, or anionic in nature, may be terminated on an active site of the solid surface, etc. 55 63). 

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... 

A macromonomer is a macromolecule with a reactive end group that can be homopolymerized or copolymerized with a small monomer by cationic, anionic, free-radical, or coordination polymerization (macromonomers for step-growth polymerization will not be considered here). The resulting species may be a star-like polymer (homopolymerization of the macromonomer), a comblike polymer (copolymerization with the same monomer), or a graft polymer (copolymerization with a different monomer) in which the branches are the macromonomer chains. 

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. 

Recently, Muller et al. studied block and graft copolymers poly(n-butyl acrylate)-Wocfc/gra/f-poly(acrylic acid), PnBA-h/g-PAA [136]. The non-polar block/backbone has a low glass transition temperature, thus dynamic micelles were expected the ionic block/side-chains are weak anionic polyelectrolytes, thus a strong dependence of micellization on pH could be expected. The graft copolymers were synthesized by ATRP copolymerization of poly(-ferf-butyl acrylate) macromonomers with n-butyl acrylate, followed by hydrolysis of the terf-butyl acrylate side-chains to PAA [137]. The length of the PAA side chains was varied from 20 to 85 monomer units and their number from 1.5 to 10, whereas the length of the backbone was kept at ca. 130 units. 

---