Transition metal carbonyl catalysts for polymerizations of substituted acetylenes

Kaitian Xu, Han Peng, Jacky Wing Yip Lam, Tommy Wan Hong Poon, Yuping Dong, Hongyao Xu, Qunhui Sun, Kevin Ka Leung Cheuk, Fouad Salhi, Priscilla Pui Sze Lee, Ben Zhong Tang

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Abstract

Most of the existing metal carbonyl catalysts for acetylene polymerizations need to be preactivated by chlorine-containing additives or by UV irradiation in halogenated solvents. In this work, we developed a series of `simple' metal carbonyl catalysts of general structure M(CO)xLy (M = Mo, W), none of which require additives or pre-photoirradiation, most of which are air- and moisture-stable, and some of which work well in nonhalogenated solvents. The acetonitrile complexes M(CO)3(NCCH3)3 initiated polymerizations of a variety of mono- and disubstituted acetylenes at room temperature. The arene and diene complexes W(CO)3(mes) and Mo(CO)3(nbd) (mes = mesitylene, nbd = 2,5-norbornadiene) are tolerant of polar groups and effected polymerizations of functional acetylenes containing ester, ether, and cyano groups. The halogenated complexes MI2(CO)3(NCCH3)2 catalyzed polymerizations of phenylacetylene in toluene. The chlorine-containing acetylene monomers ClC triple bond CC6H5 and ClC triple bond CC6H13 were readily polymerized by the Mo complexes in nonhalogenated solvents such as toluene and dioxane, giving polymers with high molecular weights (Mw up to 883×103) in high yields (up to 100%).

Original languageEnglish (US)
Pages (from-to)6918-6924
Number of pages7
JournalMacromolecules
Volume33
Issue number19
DOIs
StatePublished - Sep 19 2000

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

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    Xu, K., Peng, H., Lam, J. W. Y., Poon, T. W. H., Dong, Y., Xu, H., Sun, Q., Cheuk, K. K. L., Salhi, F., Lee, P. P. S., & Tang, B. Z. (2000). Transition metal carbonyl catalysts for polymerizations of substituted acetylenes. Macromolecules, 33(19), 6918-6924. https://doi.org/10.1021/ma000843a