Polymerization of Vinyl Ethers

The tacticity of vinyl polymers has a profound effect on their physical properties. Despite the well-developed stereoselective methods for the polymerization of propylene and other nonpolar α-olefins, stereoselective polymerization of polar vinyl monomers has proven more challenging.

Science Figure

A The chiral ligand environment in coordination-insertion polymerizations enables stereoselective monomer enchainment by directing facial addition at the propagating polymer chain end. Polar monomers are typically not compatible with this mechanism because of catalyst poisoning. Me, methyl. B The achiral chain end in the cationic polymerizations of vinyl ethers provides no inherent mode for stereoinduction. Monomer addition occurs at either face of the oxocarbenium ion. C Our catalyst-controlled approach to stereoselective cationic polymerization relies on a chiral, BINOL-based counterion to bias the stereochemistry of monomer enchainment. The resultant isotactic PVEs are semicrystalline thermoplastics with intrinsic polarity.

Postdoctoral Research Associate Aaron J. Teator in the Frank Leibfarth group, published in Science, 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.

Aaron and Frank demonstrate that this method is general to vinyl ether substrates, providing access to a range of isotactic poly(vinyl ether)s with high degrees of isotacticity. The obtained materials display the tensile properties of commercial polyolefins but adhere more strongly to polar substrates by an order of magnitude, indicating their promise for next-generation engineering applications.