木质素衍生物定向转化酚酯的界面协同催化与产物调控机制研究

Phenolic ester is an important intermediate monomer for synthesis of common chemicals or medicine, which has broad application prospects. The synthesis of phenolic ester from phenolic compounds formed from lignin degradation and waste fatty acids can reduce environmental pollution and alleviate the dependence of phenolic ester on the petrochemical industry. This project focuses on the synthesis of biomass-based phenolic ester effectively, the mechanism of enhancing product regulation and interface synergistic catalysis. The research focuses on three aspect: one is the preparation and regulation of mesoporous silicon catalyst with acidic functionalized group and hydrophobic interface; the second is the esterification reaction property and process; the last one is the enhanced regulatory mechanism of phenolic ester from fatty acid and phenols. The morphology structure of catalysts, optimization and the assembly mechanism of acidic functional components and hydrophobic groups will be revealed. The catalytic esterification reaction characteristics and process of the model compounds will be studied. The function model for thermodynamics and kinetics will be established. The influence of functionalized mesoporous silica on the heat and mass transfer during the conversion will be studied, inducing the strengthening regulation mechanism of yield and conversion by catalyst orientation design. The transformation process of key intermediate, the selective adsorption and activation of phenolic hydroxyl and COOH- from phenolic derivatives and fatty acid will be studied, which will dedicate the mechanism of enhancing product regulation and interface synergistic catalysis. The interaction mechanism between the real phenolic derivatives from lignin degradation will be studied. This program will establish foundation for producing phenolic ester effectively.

酚酯是合成常见化工品或西药的重要中间单体，具有广阔应用潜力。利用木质素降解酚类衍生物与废弃脂肪酸转化生成生物质基酚酯能减少环境污染，缓解酚酯对石化行业的依赖。本项目重点创制具有疏水界面的功能化介孔硅催化剂，实现木质素衍生物定向转化酚酯，探讨酚酯高效酯化制备中界面协同催化与产物强化调控机理。从催化剂的制备与调控、催化酯化反应特性和历程、产物强化调控机制三方面开展逐层递进研究。揭示催化剂形貌结构、酸功能组分和疏水基团的优化匹配与组装机制及酸性精准调控规律；探究模型化合物催化酯化反应特性和历程；研究功能化介孔硅对转化过程的传质传热影响，掌握催化剂定向设计对产物选择性、转化率的强化调控机理；研究酚类衍生物的酚羟基和脂肪酸的羧基选择性吸附活化及关键中间产物迁移转化历程，揭示产物强化调控与界面协同催化机制。为生物质基酚酯的高效制备奠定基础。

本项目通过原位一步合成和合成后嫁接的方式，合成了SiO2-phenyl-SO3H和 SBA-15-Ph-TMS-SO3H系列催化剂，研究了其催化木质素降解酚类衍生物与废弃油酸酯化反应活性。并利用XRD、TG、Mass，固体核磁等技术对催化剂进行了表征分析。关联催化剂的制备工艺对功能化介孔硅材料形貌结构，孔径大小，孔结构有序度，酸活性组分分布的影响；探讨制备工艺对酸功能组分SO3H、有机疏水基团合成TMS、Ph、耦合组装及成键方式等因素的影响。探究了反应温度，反应物摩尔比，催化剂担在量，反应时间等因素对反应效果的影响。分析酸功能组分对酚OH-、COOH-选择性活化吸附机制及疏水官能团对酸性位点密度、疏水、相邻酸位点横向作用力的影响机制；以研究催化剂的制备工艺与结构特性之间的调控规律。进一步地，关联催化剂的结构特性与酯化反应速率及产物分布的内在联系，建立催化剂结构形貌与酯化反应活性的构效机制。该研究为木质素高值化利用制备长链酯类物质提供了科学依据和数据支撑。