Living Radical Polymerization via Reversible Homolytic Activation of Carbon-Halogen Bonds with Metal Complexes
Living radical polymerizations of methyl methacrylate and related acrylic monomers have been achieved with ternary initiating systems that consist of an alkyl chloride (R—Cl), ruthenium(II) chloride tris(triphenylphosphine) complex [RuCl2(PPh3)3], and a Lewis acid (MX n ), where R—Cl = CCl4, CCl3CO2CH3, CCl3COCH3, CCl3COC6H5, etc.; MX n = A1CH3(2,6-di-t-butylphenoxy)2, Al(OiPr)3, Ti(OiPr)4, etc. The produced polymers had controlled molecular weights, nearly proportional to conversion, and narrow molecular weight distributions; in particular, the CCl3COCH3/RuCl2(PPh3)3/Al(OiPr)3 system led to polymers with very narrow MWDs (Mw/Mn ≤ 1.1). Sequential polymerizations of methacrylic and acrylic monomers also gave AB- and ABA-type block copolymers.
KeywordsToluene Adduct Ketone Alkene Vinyl
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