The Effect of Hydrogen Bonding on Polymerization Behavior of Monofunctional Vinyl Cyclopropane-Amides with Different Side Chains

The synthesis of four different monofunctional vinyl cyclopropane (VCP) amides and their photopolymerization behavior are presented. All VCPs can form hydrogen bonds, with one being the amide linkage of the VCP unit and the other one being the side chain. The number of additional hydrogen bonds is regulated by the different side chains being, carbonate, urethane, urea, and amide. Hydrogen bonds should lead to a preorganization of the monomers, leading to a fast polymerization. Kinetic studies of the photopolymerization, analysis of hydrogen bond strength via solid-state nuclear magnetic resonance (NMR) experiments, and theoretical calculations are used to correlate the degree of conversion and the amount of preorganization. A fast polymerization could be observed due to hydrogen bonding near the active site, while hydrogen bonds in the side chain make a minor difference.

Automated summary

This study presents the synthesis of four different monofunctional vinyl cyclopropane amides and investigates their photopolymerization behavior. It is found that all the amides can form hydrogen bonds, with one being the amide linkage and the other being the side chain. The number of additional hydrogen bonds is regulated by different side chains. The study demonstrates that hydrogen bonds can preorganize the monomers and lead to fast polymerization.