H. Shinoda et K. Matyjaszewski, Structural control of poly(methyl methacrylate)-g-poly(lactic acid) graft copolymers by atom transfer radical polymerization (ATRP), MACROMOLEC, 34(18), 2001, pp. 6243-6248
Atom transfer radical copolymerization of methyl methacrylate (MMA) and (me
th)acrylate-terminated poly(lactic acid) (PLA) macromonomers was investigat
ed. The relative reactivity of methacrylate-terminated macromonomer (1/r(MM
A) = 1.75) and acrylate-terminated macromonomer (1/r(MMA) = 0.61) was close
to that of 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate, respec
tively. The difference in reactivity in ATRP and conventional radical polym
erization is discussed in terms of the diffusion control effect. A mixture
of methacrylate-terminated macromonomer and acrylate-terminated macromonome
r was copolymerized with MMA by ATRP to give a homogeneously branched PMMA-
g-PLA graft copolymer with low polydispersity (M-w/M-n = 1.15).