Ru(Cp*)Cl(PPh 3 ) 2 (Cp* = pentamethylcyclopentadienyl; PPh 3 = triphenylphosphine) has been found to be a versatile catalyst that is applicable to living radical polymerization of methyl methacrylate (MMA), methyl acrylate (MA), and styrene (St) with Al(O i -Pr) 3 as an additive. The number-average molecular weights ( M n ) of the obtained polymers increased in proportion to monomer conversion, and the molecular weight distributions were very narrow ( M w / M n < 1.1). Effective initiators were all alkyl halides (R−X), where X = Cl for MMA; Cl and Br for St; and Cl, Br, and I for MA. Ru(Cp*)Cl(PCy 3 ) (Cy = cyclohexyl) also proved an effective catalyst for living radical polymerization of MMA, faster than that with Ru(Cp*)Cl(PPh 3 ) 2, to produce polymers with narrow molecular weight distributions ( M w / M n < 1.2).
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Watanabe et al. (2001) studied this question.
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