Abstract
Chlorodiphenylphosphine (CDP) was used as a pre-initiator in the polymerization of methacrylates having methyl, benzyl, n-butyl, t-butyl, cyclohexyl, and n-hexyl substituents in the presence of catalytic amounts of epoxides. This polymerization system was influenced by solvents and epoxides structure, and polymer molecular weight and yield were dependent strongly on the alkyl group of ester of monomers. Under bulk conditions, the polymerization of methacrylates afforded easily high molecular weight polymers (Mn over five million) with relative narrow polydispersity (1.2–1.5). Based on several experimental results, it is discussed that the pre-initiator reacts with monomer forming phosphinoenolate from which the polymerization proceeds with the group transfer mechanism.
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The structure of 1:1 adduct from CDP and epoxide is not quite clear. At least, two isomers ClCH2CH(R)—OPPh2 and C̩H͟2-C͟H͟(R͟)-O͟-P̩+Ph2Cl− were speculated. The betaine analogous was not isolated because of unstableness in air atmosphere.
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Jin, RH., Hanazaki, Y. & Nishikubo, T. High Molecular Weight Polymers. Simple Polymerization of Methacrylic Monomers Using (Ph2PCl/Epoxide) as Pre-Initiator. Polym J 29, 113–118 (1997). https://doi.org/10.1295/polymj.29.113
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DOI: https://doi.org/10.1295/polymj.29.113