Thiyl radical induced cis / trans isomerism in double bond containing elastomers.

This report presents an evaluation of thiyl radical-induced cis / trans isomerism in double bond-containing elastomers, such as natural, polychloroprene, and polybutadiene rubbers. The study aims to extensively investigate structural changes in polymers after functionalisation using thiol-ene chemistry, a useful click reaction for modifying polymers and developing materials with new functionalities. The paper reports on the use of different thiols, and cis / trans isomerism was detected through 1 H NMR analysis, even at very low alkene/thiol mole ratios. The study finds that the configurational arrangements between non-functionalised elastomer units and thiolated units followed a trans -functionalised- cis units arrangement up to an alkene/thiol mole feed ratio of 0.3, while from 0.4 onward, a combination of trans -functionalised- cis and cis -functionalised- trans configurations are found. Additionally, it is observed that by increasing the level of functionalisation, the glass transition temperature of the resulting modified elastomer also increases. Overall, this study provides valuable insights into the effects of thiol-ene chemistry on the structure and properties of elastomers and could have important implications for the development of new materials with enhanced functionality.