Controlled “living” anionic polymerization of glycidyl methacrylate

Abstract

SynopsisThe living anionic polymerization of glycidyl methacrylate (GMA) in THF at low temperature initiated with diphenyl hexyl lithium, 9-anthracenyl methyl lithium, and a-methylstyryl lithium leads to well characterized homo-and block copolymers, with predictable and narrow molecular weight distributions and with all the oxirane groups intact. Broadening of the molecular weight distributions above a certain and very critical supported the idea that the living polymerization at low temperature might proceed in micelle-like structures. Diffusional restriction of the monomer access towards the living centers, due to lesser solvation and increasing compactness of the polymer coils is thought to give rise to broadening of the molecular weight distribution of PGMA homoand block copolymers.

Poly[glycidyl methacrylate(GMA)/methylmethacrylate(MMA)-b-butadiene(B)-b-GMA/MMA] reactive thermoplastic elastomers: Synthesis and characterization

“…It is worth noting that Leemans et al have reported on the broadening of the molecular weight distribution of PGMA when the chain length is increased, which has been accounted for by the decreasing solubility of longer PGMA chains in THF at low temperature. 14 In this work, the inconvenience of PGMA insolubility is alleviated by attachment of the PGMA blocks to long PBD chains perfectly soluble in THF at low temperature.…”

Grafting byin situ coupling of epoxy groups of a living copolymer with an anionic living polymer

“…7,8 In the present paper, the THF solution of living poly(MMA-co-GMA) was prepared in a similar way (see Experimental). The initial monomer concentrations were fixed at Table I, M n ϭ 2990, M w /M n ϭ 1.07) and the molecular weight distributions are narrow in all cases (M w /M n ϭ 1.07-1.13; see Table I).…”

“…As shown in Scheme 1, the THF solution of the living random copolymer of MMA and glycidyl methacrylate (GMA) was prepared by the anionic copolymerization of the two monomers according to a reported method. 7,8 Because the epoxy groups of the GMA units in the copolymer (1 in Scheme 1) remained unreacted, an in situ coupling reaction was carried out by introducing a benzene solution of the anionic living poly(St) or polyisoprene (poly(Is)) into the above living copolymer solution. In this manner, a pure graft copolymer (2 in Scheme 1) consisting of a poly(MMA-co-GMA) backbone and poly(St) or poly(Is) side chains was obtained.…”

Precise synthesis of dendron-like hyperbranched polymers and block copolymers by an iterative approach involving living anionic polymerization, coupling reaction, and transformation reaction

“…Since many living anionic polymers of substituted methacrylate monomers with functional groups have been synthesized at the present time, [23][24][25][26][27][28][29][30][31][32][33][34][35] various functional segments can be intentionally incorporated into dendron-like hyperbranched polymers. In this section, we have synthesized a series of dendronlike hyperbranched block copolymers consisting of PMMA and PRfMA segments in order to design and synthesize effective surface-functionalized materials.…”