Abstract
The highly uniform and dense network structure of photopolymerized thiol−enes was chemically modified, and the enthalpy relaxation of the networks was measured. n-Alkyl acrylate and hydroxyl acrylate groups were incorporated into thiol−ene networks using a phosphine-catalyzed Michael addition reaction. The effect of flexible alkyl side chains and hydrogen bonding on sub-Tg relaxation was evaluated without sacrificing network uniformity. Overall both the rate and extent of enthalpy relaxation decreased as a function of the flexible n-alkyl chain length, while hydrogen bonding resulted in enhanced enthalpy relaxation. A trithiol−triene−triacrylate ternary system was investigated by correlating enthalpy relaxation and network uniformity. A multifunctional acrylate (TMPTA), being capable of homopolymerization as well as thiol−acrylate copolymerization, was incorporated into a thiol−ene network structure, thereby decreasing the network uniformity and significantly affecting the enthalpy relaxation behavior. In...
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