Polymerization of Cyclopropenes: Taming the Strain for the Synthesis of Controlled and Sequence-Regulated Polymers

Acc Chem Res. 2021 Jan 19;54(2):356-365. doi: 10.1021/acs.accounts.0c00638. Epub 2020 Dec 28.

Abstract

Cyclopropenes (CPEs) are highly strained cyclic olefins, yet there are surprisingly limited examples leveraging their high strain energy for polymerization. In the past, attempts had been made to polymerize CPEs via cationic and insertion polymerization, but side reactions often gave uncontrolled polymers with mixed backbone structures. Ring-opening metathesis polymerization (ROMP) represents an ideal strategy for polymerizing CPEs to access new types of polymers. The proximity of substituents to the olefin in the small framework of CPEs offers a modular handle to tune the kinetic barrier to propagation by the modulation of the substituents. While the first few studies focused on the homopolymerization of simple alkyl or phenyl disubstituted CPEs, we recently explored the metathesis of a wide range of CPEs with different substituents using Grubbs catalysts and discovered surprising and diverse reactivities that are contingent on the positions, sterics, and electronics of substituents. The observed reactivities ranged from living homopolymerization to catalyst deactivation to single addition to the catalyst without homopropagation. In particular, the exclusively single addition reactivity found in two families of CPEs, with either bis(methanol ester) or phenyl and methanol ester substituents at the allylic position, is unusual for any monomer and perhaps counterintuitive for highly strained cycles. These single-addition CPEs could, however, be copolymerized with low-strain cyclic olefins to generate perfectly alternating copolymers with controlled molecular weights and low dispersity and to introduce degradable backbone linkages. A single equivalent (relative to the active chain end) of such CPEs could also be added to the active chain end of living ROMP polymers to install functional terminal groups or during living ROMP to place single units of functional moieties or side chains at any desired chain locations in narrow-disperse homopolymers and block copolymers. This account summarizes the polymerization of CPEs with a focus on our journey to uncover the rich and unique metathesis reactivities of CPEs and their utility in synthesizing well-controlled and sequence-regulated polymers. It provides the first collective structure-metathesis reactivity relationships for CPEs in the context of polymer chemistry and an understanding of the interactions between the catalyst and the substituents of appended ring-opened CPEs. It may become clear from this Account that the exploration of strained cycles in polymer chemistry can be quite fruitful in discovering new chemistry and accessing new types of polymer materials.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.