Liu Zizhao, Gu Gaosheng, Chen Junwu, Duan Zhongyu, Liu Binyuan
Hebei Key Laboratory of Functional Polymer, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300401, China.
Polymers (Basel). 2022 Aug 31;14(17):3597. doi: 10.3390/polym14173597.
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 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.
随着环境保护意识的增强和石油资源的短缺，生物基聚氨酯因其生态友好、成本低和易于降解而受到越来越多的关注。本文以植物精油衍生的丁香酚（Eug）为原料制备了丁香基乙醇（Syol），并分别使Eug或Syol与六亚甲基二异氰酸酯（HDI）或4,4'-二苯基甲烷二异氰酸酯（MDI）反应得到三种单体。然后，通过烯烃复分解聚合反应合成了三种新型生物基聚氨酯P（Eug-HDI）、P（Syol-HDI）和P（Syol-MDI）。详细研究了催化剂类型、反应溶剂、反应温度、反应时间、催化剂用量与金属盐的摩尔比对Eug-HDI烯烃复分解聚合反应的影响。在最佳条件下，产率达到64.7%。值得注意的是，金属镍盐的加入能显著促进聚合反应，其中NiI可使产率提高到86.6%。此外，通过DSC和变温红外光谱对这些生物基聚氨酯的热分解行为进行了探究。测试结果表明，P（Eug-HDI）具有可逆热分解和一定的自修复性能。本文为生物基聚氨酯的制备提供了一种新方法。
