writer：Lei Li, Shihui Li, and Dongmei Cui
keywords：Living polymerization; chemoselectivity; random copolymers; functional butadiene; thiol–ene reaction
source：期刊
specific source：http://pubs.acs.org/doi/pdf/10.1021/acs.macromol.5b02654
Issue time：2016年

Living polymerization of 3-methylenehepta-1,6-diene (MHD) catalyzed by bis(phosphino)carbazoleide-ligated yttrium alkyl complex afforded a new product bearing pendant terminal vinyl groups with high stereotacticity (cis-1,4-selectivity up to 98.5%), proved by the NMR (¹H, ¹³C, and 1D ROESY) spectroscopic analyses, which demonstrates overwhelmingly favorable chemoselectivity toward conjugated diene over α-olefin moieties. High cis-1,4 random copolymers of MHD and isoprene could also be obtained with pendant vinyl groups ranging from 10% to 90%. These vinyl groups in every chain unit can be cleanly and quantitatively converted into various functionalities via light-mediated thiol–ene reaction, resulting in homo- and copolymers of various functional butadiene derivatives, which display versatile thermal properties.