Ultraviolet curable polyureas and polyurethanes enjoy a wide range of applications in the coatings industry. They demand less energy for curing compared to thermal processes that offer relatively low viscosities before photocuring, and provide mechanical property improvements due to hydrogen bonding physical crosslinks. Mechanical properties of the coatings are dependent on a variety of factors, including chemical composition, molecular weight, and molecular weight distribution. Formulations are designed for a wide variety of end use applications, ranging from soft, elastomeric coatings to harder, nonflexible sealants. This report demonstrates that the thermomechanical behavior of photocured coatings is a function of molecular weight distribution. Step-growth polymerization and endcapping afforded a variety of acrylate-terminated, urea-/urethane-containing photocurable oligomers from amine-terminated poly(propylene glycol), dicyclohexylmethane-4,4′-diisocyanate (HMDI), and 2-hydroxyethyl acrylate (HEA) at various stoichiometric ratios. The state-of-the-art supercritical fluid chromatography coupled with evaporative light-scattering detection (SFC-ELSD) enabled the elucidation of oligomeric molecular weight distributions as a function of reaction stoichiometry. SFC-ELSD demonstrated the efficient separation of oligomeric species with single repeat unit resolution (i.e., n = 2 vs. n = 3). Dynamic mechanical analysis probed thermomechanical response of photocured films as a function of molecular weight distribution and demonstrated that the presence of a hydrogen-bonding, small molecule photoactive reaction byproduct, i.e., HEA doubly-endcapped HMDI, had a much more profound effect on thermomechanical response as compared to changes in oligomer molecular weight in the molecular weight range investigated. This combination of chromatographic technique and thermomechanical analysis afforded an in-depth investigation of the structure–property relationships of urea-/urethane-containing photocurable oligomers.
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