生物基聚酯单体合成及聚合机理研究

本项目围绕生物基聚酯单体1，3-丙二醇（1,3-PDO），对二甲苯（PX）和聚酯聚对苯二甲酸丙二醇酯（PTT）合成中存在的构建生物合成新途径、反应机理和催化剂构效关系等关键科学问题开展系列研究。通过构建以廉价的葡萄糖为原料高效生产1,3-PDO的新途径，实现微生物利用葡萄糖高效生产1,3-PDO的新路线。深入探索生物质合成PX的三条路线：2，5-二甲基呋喃（DMF）与烯烃加成、乙醇为原料经己烯选择脱氢、生物质热解聚产物催化转化，确定生物基PX高效合成新工艺。研究PTT合成的有机钛类催化剂及相关构效关系，通过改变有机配体分子结构调控钛中心化学活性，构建有机复合钛催化PTT合成的聚合机理和催化体系，实现兼具高特性黏度和色泽好的聚酯PTT合成。本项目通过对单体1,3-PDO和PX到聚酯PTT各环节的合成路线和方法的创新为我国建立自主知识产权的生物基聚酯提供技术和方法基础。

This project focuses on some scientific keypoints, which are constructing a new biosynthetic pathway of 1,3-propanediol (1,3-PDO), reaction mechanism and structure-activity relationship of the catalysts in the synthesis of para-xylene (PX) and polytrimethylene terephthalate (PTT). One new metabolic pathway via cheap glucose as stock was constructed to realize highly efficient generation of 1,3-PDO. Exploring the three routes of PX synthesis from biomass: addition reaction between 2,5-dimethyl furfural (DMF) and olefins, selective dehydrogenation of hexane based on ethanol stocks, catalytic conversion of biomass pyrolysis vapor, and studied the efficient synthesis process of bio-based PX. Study on the structure-activity relationship of organic titanium catalyst which participated into PTT polycondensation. By ligand structure change adjusting the catalyst activity of titanium center, the plausible mechanism of PTT polymerization was deduced, which would guide to obtain the satisfied polyester PTT with high viscosity and good color through design the organic complex titanium catalyst. This project provides the technology and method foundation for our country to establish the independent intellectual property rights of the bio-based polyester through innovation of 1,3-PDO, PX and PTT synthesis routes.