# Thiyl radical reversible-deactivation polymerization via degenerative transfer with vinyl sulfides

## TL;DR

The paper introduces a new method to control thiyl radical polymerizations using vinyl sulfides, enabling precise synthesis of sulfur-containing polymers with tunable properties.

## Contribution

A novel thiyl radical reversible-deactivation polymerization strategy using vinyl sulfides as degenerative transfer agents is introduced.

## Key findings

- The polymerization method enables precise control with tunable molecular weights and low dispersities.
- Density functional theory calculations confirmed the reversible-deactivation mechanism of vinyl sulfides.
- The method is versatile and compatible with various thiyl radical polymerizations and copolymer synthesis.

## Abstract

Precise control over thiyl radical polymerizations remains a significant challenge in polymer chemistry, particularly within the framework of traditional reversible-deactivation radical polymerization (RDRP) techniques. In this work, we introduce a novel thiyl radical reversible-deactivation polymerization (SRDP) strategy that employs vinyl sulfides as degenerative transfer agents to reversibly deactivate the propagating thiyl radicals, thus enabling direct and efficient control over the thiyl radical polymerizations to afford polymers with tunable molecular weights and low dispersities. The controlled nature of this polymerization was further confirmed by first-order kinetics, a linear relationship between molecular weight and conversion, and efficient chain extension. In addition, density functional theory calculations offered valuable insights into the reversible-deactivation ability of vinyl sulfides. The versatility of the SRDP method was demonstrated through its compatibility with a wide range of thiyl radical polymerizations and its successful application in synthesizing structurally diverse copolymers. This study represents a new reversible-deactivation pattern for thiyl radical polymerizations and would lead to a powerful platform for the precise synthesis of complex functional materials.

This study presents a novel vinyl sulfide-based radical dynamic chemistry that effectively controls various thiyl radical polymerizations, resulting in sulfur-containing polymers with well-defined architectures.