Polymer tacticity is directly linked to the physical properties exhibited by synthetic materials. It has been widely shown that introducing even limited degrees of stereoregularity to otherwise atactic materials can have pronounced effects on their thermal, mechanical, and optical properties. In comparison to coordination polymerizations (<i>e.g.</i>, ethylene, propylene, etc.), cationic polymerization methods typically display relatively low degrees of stereoinduction and result in materials with undesirable mechanical properties. We have designed chiral counterions that systematically bias the reactivity and chain-end stereochemical environment during cationic polymerization. This approach overrides conventional chain-end stereochemical bias to achieve catalyst-controlled stereoselective polymerization. The method is general to vinyl ether substrates and provides access to a range of poly(vinyl ether)s with high degrees of isotacticity. The obtained materials represent a new class of thermoplastics with a unique combination of mechanical and surface properties. This presentation will discuss the application of this methodology to a variety of vinyl monomers, as well as the impact of isotacticity and monomer design on the properties of the obtained materials.

Catalyst-controlled stereoselective polymerization of vinyl ethers to access new polar thermoplastics

2019 Fall National Meeting

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.