Construction of Bio-Based Polyurethanes via Olefin Metathesis and Their Thermal Reversible Behavior

With the increase in awareness of environmental protection and the shortage of oil resources, bio-based polyurethane has attracted increasing attention due to its ecological friendliness, low cost and easy degradation. In this paper, using Eugenol (Eug) derived from plant essential oils as the raw resource, syringyl ethanol (Syol) was prepared, and three monomers were obtained by the reaction of the Eug or Syol with Hexamethylene diisocyanate (HDI)or 4,4′-methylene di (phenyl isocyanate) (MDI), respectively. Then, three novel bio-based polyurethanes, P(Eug-HDI), P(Syol-HDI) and P(Syol-MDI), were synthesized by olefin metathesis polymerization. The effects of the catalyst type, reaction solvent, reaction temperature, reaction time, molar ratio of catalyst dosage and metal salts on the Eug-HDI olefin metathesis polymerization were investigated in detail. Under the optimal conditions, the yield reached 64.7%. It is worth noting that the addition of metal Ni salts could significantly promote the polymerization, in which NiI(2) could increase the yield to 86.6%. Furthermore, the thermal decomposition behaviors of these bio-based polyurethanes were explored by DSC and variable temperature infrared spectroscopy. The test results showed that P(Eug-HDI) had a reversible thermal decomposition and a certain self-healing performance. This paper provided a new method for the preparation of bio-based polyurethane.