Tandem coordinative chain transfer polymerization for long chain branched Polyethylene: The role of chain displacement

Abstract

The controlled introduction of long chain branches (LCBs) in the commonly linear structure of polyolefins has been frequently pursued by researchers to improve their melt processability. To account for that, we introduce a new tandem dual catalytic system for the formation of LCB in ethylene polymerization. Coordinative chain transfer polymerization in the first step produces Al-alkyls via frequent transfer of growing polymer chains from the single-site α-diimine nickel polymerization catalyst to AlEt2Cl chain transfer agent (CTA). Next, the displacement catalyst, Ni(acac)2, converts the dormant alkyl chains into macromers through a β-hydride elimination and retrieves the Al-based CTA. Due to the high comonomer affinity of the polymerization catalyst, the released macromers are incorporated in growing polymer chains. By repeating this reaction cycles, a branch-on-branch structure is formed. Interestingly, a separate cocatalyst is not required, as AlEt2Cl serves as both the cocatalyst and the CTA for the CCTP system. This reaction scheme employs the “nickel-effect” mechanism for the formation of LCB in coordinative polymerization for the first time. The efficiency of the proposed mechanism in the formation of LCBs is confirmed by comprehensive rheological studies and NMR spectroscopy. Moreover, density functional theory (DFT) simulations rationalize the formation of LCBs through the proposed Ni-based displacement reaction.