Highly Cis-1,4-Selective Living Polymerization of 3-Methylenehepta-1,6-diene and Its Subsequent Thiol–Ene Reaction: An Efficient Approach to Functionalized Diene-Based Elastomer
作者：Lei Li, Shihui Li, and Dongmei Cui
关键字：Living polymerization; chemoselectivity; random copolymers; functional butadiene; thiol–ene reaction
论文来源：期刊
具体来源：http://pubs.acs.org/doi/pdf/10.1021/acs.macromol.5b02654
发表时间：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.
