Controlling molar mass and dispersity in polymers through deuteration: the case of poly(phenyl D3-vinyl sulfide)

Polymer properties can be defned by functionalizing the monomer and tuned by modifying key properties, such as, molar mass and dispersity. Typically, these modification approaches require significant alterations to the synthesis process, or even re-optimization of the whole process. In this study, we demonstrate that deuteration, a mainly overlooked method, can significantly influence the properties without altering the chemical structure of the monomer or the synthesis procedure. For the poly(phenyl vinyl sulfide), we introduce a technique for integrating deuterium into a monomer, providing a novel way to adjust the properties of the resulting polymer without changing its chemical nature. This method is both accessible and cost-effective, adhering to the principles of green chemistry. Quantum chemical analysis revealed that this control over properties is due to a reduction in the rate of the polymerization deactivation, which proceeds through the chain transfer mechanism. The opportunity hgighlighted in the present study may be well-applicable for a number of ohter polyemrs, leading to a new approach to pracical tuning of polymer properties and developing materials with enhanced properties.