Assessing 1,9-Decadiene/Ethylene Copolymerization with Ziegler–Natta Catalyst to Access Long Chain-Branched Polyethylene

1,9-Decadiene/ethylene copolymerization is assessed as a way for Ziegler–Natta catalysts to access long chain-branched polyethylene (PE). A MgCl2/9,9-bis-(methoxymethyl)fluorine/TiCl4 catalyst with triethylaluminium as a cocatalyst is exemplified for the task. 1,9-Decadiene was found to induce a substantial comonomer effect on catalyst activity and continuing decreases of PE molecular weight. Both the double bonds of 1,9-decadiene were poorly reactive during polymerization, of which the polymer chain-attached was even much less reactive than the original one. As a consequence, at decreased feeds, 1,9-decadiene gave small amounts (<0.1 mol %) of pendant vinyl groups to PE without prompting the formation of long-chain branches. Long chain-branching was realized at increased 1,9-decadiene feeds, which was however accompanied by proportional gelation.