Thermal stability of polyurethane coating prepared by using diphenylolpropane

Thermal stability of polyurethane varnish coating prepared by using diphenylolpropane, polyetherpolyol and polyisocyanate with an equimolar ratio of isocyanate and hydroxyl groups was assessed in the air. The polyurethane weight loss thermogram shows three temperature regions: I – (217-275)°С, II – (275-380)°С, and III – above 380°С. For interpreting thermogram of the polyurethane under study the model substances simulating the urethane groups of a polymer were synthesized. The substance containing the urethane group formed by phenolic hydroxyl of diphenylolpropane was shown to demonstrate relatively low thermal stability and gets broken down into isocyanate and bisphenol. Decomposition of the substance containing the urethane group formed by alcoholic hydroxyl occurs at the higher temperature. The data obtained allow interpreting the occurrence of thermal decomposition step I in TGA curve by structural changes in the blocks formed by diphenylolpropane and polyisocyanate being the least stable when exposed to elevated temperatures. The next step can be attributed to decomposition of more thermostable urethane groups formed by functional groups of oligooxypropylenetriol and polyisocyanate. Transition to the step III accompanied by severe sample weight loss due to decomposition of urethane groups is explained by thermal oxidation of oligoether units of polymer. Based on the data obtained the conclusion was made that the presence of urethane groups formed by phenolic hydroxyl of diphenylolpropane in polymer structure results in the decreased thermooxidative decomposition onset temperature of polymer. At the same time, a deceleration of thermooxidative processes due to the stabilizing effect of diphenylolpropane released at the beginning of thermal decomposition of polyurethane is observed in a high-temperature region. The proposed polyurethane coating is inferior to commercial counterparts in thermal decomposition onset temperature but superior to them in the temperature corresponding to a 50% polymer weight loss.

Introduction of Reversible Urethane Bonds Based on Vanillyl Alcohol for Efficient Self-Healing of Polyurethane Elastomers

Urethane groups formed by reacting phenolic hydroxyl groups with isocyanates are known to be reversible at high temperatures. To investigate the intrinsic self-healing of polyurethane via a reversible urethane group, we synthesized vanillyl alcohol (VA)-based polyurethanes. The phenolic hydroxyl group of vanillyl alcohol allows the introduction of a reversible urethane group into the polyurethane backbone. Particularly, we investigated the effects of varying the concentration of reversible urethane groups on the self-healing of the polyurethane, and we proposed a method that improved the mobility of the molecules contributing to the self-healing process. The concentration of reversible urethane groups in the polyurethanes was controlled by varying the vanillyl alcohol content. Increasing the concentration of the reversible urethane group worsened the self-healing property by increasing hydrogen bonding and microphase separation, which consequently decreased the molecular mobility. On the other hand, after formulating a modified chain extender (m-CE), hydrogen bonding and microphase separation decreased, and the mobility (and hence the self-healing efficiency) of the molecules improved. In VA40-10 (40% VA; 10% m-CE) heated to 140 °C, the self-healing efficiency reached 96.5% after 30 min, a 139% improvement over the control polyurethane elastomer (PU). We conclude that the self-healing and mechanical properties of polyurethanes might be tailored for applications by adjusting the vanillyl alcohol content and modifying the chain extender.