Coordinative chain transfer polymerization (CCTP) catalysts are known to produce extremely high Mw polymers in the absence of chain transfer agents, largely due to the lack of typical chain termination pathways including chain transfer to monomer and beta-hydride elimination. Polymer Mw can be controlled by use of chain transfer agents such as hydrogen, aluminum alkyls, or zinc alkyls, all of which lead to saturated polymer end-groups. The polymers produced lack the typical end-group unsaturation common in metallocene produced polymers, and are therefore strictly linear polymers. Because CCTP catalysts readily chain transfer to most aluminum alkyls, we hypothesized that the same should be true for aluminum alkenyls. This paper will describe synthetic pathways to aluminum alkenyls, and their use with CCTP catalysts to produce “vinyl-terminated” polymers with -(CH2)nCH=CH2 chain-ends capable of reinserting and forming long chain branched polymers. Polymerization studies using CCTP and aluminum alkenyl chain transfer agents will be presented.

Coordinative chain transfer polymerization catalysts with aluminum alkenyl chain transfer agents for producing long chain branched polymers

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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