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SmI 2 /SmI 3 as a Convenient Bisinitiator for the Living Polymerization of Methacrylates
Author(s) -
Gosho Akiko,
Nomura Ryoji,
Tomita Ikuyoshi,
Endo Takeshi
Publication year - 2001
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/1521-3935(20010601)202:9<1614::aid-macp1614>3.0.co;2-w
Subject(s) - polymer chemistry , polymerization , monomer , living polymerization , dispersity , polymer , methyl methacrylate , living anionic polymerization , chemistry , molar mass distribution , chain transfer , methacrylate , end group , anionic addition polymerization , radical polymerization , organic chemistry
A combined initiator comprising SmI 2 and SmI 3 has proven to serve as an excellent and convenient bisinitiator for the living polymerization of methyl (MMA) and tert ‐butyl methacrylates (TBMA). The polymerization of MMA or TBMA with SmI 2 in the presence of catalytic amounts of SmI 3 led to the quantitative formation of polymers with low polydispersity ( M̄ w / M̄ n = 1.08–1.11). A linear relationship between the feed ratio of the monomers to SmI 2 and the M̄ n of the polymers was recognized, which implies the absence of chain transfer reactions. The absence of termination was confirmed by the post‐polymerization technique in which – after the complete consumption of the initially charged monomer – the second feed of MMA resulted in an increase in M̄ n of the polymer maintaining its narrow molecular weight distribution. The initiation efficiency of the living polymerization of MMA was as high as 98%. Functionalization of the end group of living poly(MMA) was also accomplished with various electrophiles to give telechelic polymers.