A disubstituted-norbornene-based comonomer strategy to address polar monomer problem

The transition-metal-catalyzed copolymerization of olefins with polar comonomers is a direct strategy to access polar-functionalized polyolefins in an economical manner. Due to the intrinsic poisoning effect of polar groups towards Lewis acidic metal centers and the drastic reactivity differences of polar comonomers versus non-polar olefins, it is challenging to develop catalysts that provide the desired polymer molecular weight, comonomer incorporation, and activity. In this contribution, we tackle this issue from a comonomer perspective using 5,6-disubstituted norbornenes, which are highly versatile, easily accessible, inexpensive, and capable of introducing two functional groups in a single insertion. More importantly, they are only mildly poisoning due to the presence of long spacers between double bonds and polar groups, and are not prone to b-hydride elimination due to their cyclic structures. As strong Itdonors, they can competitively bind to metal centers versus olefins. Indeed, phosphine-sulfonate palladium catalysts can catalyze the copolymerization of ethylene with 5,6-disubstituted norbornenes and simultaneously achieve a high polymerization activity, copolymer molecular weight, and comonomer incorporation. The practicality of this system was demonstrated by studying the properties of the resulting polymers, copolymerization in hydrocarbon solvents or in bulk, recovery/utilization of unreacted comonomer, molecular weight modulation, and large-scale synthesis. (c) 2021 Science China Press. Published by Elsevier B.V. and Science China Press. All rights reserved.

Automated summary

The article explores a method utilizing 5,6-disubstituted norbornenes as comonomers to address challenges in the copolymerization of olefins with polar comonomers using catalysts. The use of phosphine-sulfonate palladium catalysts enables high polymerization activity, copolymer molecular weight, and comonomer incorporation, resulting in polar-functionalized polyolefins.