磷钨酸季铵盐催化制备环氧化桐油甲酯及其性能研究

doi:10.3969/j.issn.0253-2417.2017.03.008

林产化学与工业 ›› 2017, Vol. 37 ›› Issue (3): 61-66.doi: 10.3969/j.issn.0253-2417.2017.03.008

磷钨酸季铵盐催化制备环氧化桐油甲酯及其性能研究

郑敏睿¹, 张猛^1,2, 胡立红^1,2, 薄采颖¹, 周永红^1,2

1. 中国林业科学研究院林产化学工业研究所;生物质化学利用国家工程实验室;国家林业局林产化学工程重点开放性实验室;江苏省生物质能源与材料重点实验室, 江苏南京 210042;
2. 中国林业科学研究院林业新技术研究所, 北京 100091

收稿日期:2016-10-14 出版日期:2017-06-25 发布日期:2017-07-03
通讯作者: 周永红,研究员,博士,博士生导师,主要从事生物资源利用与开发研究;E-mail:zyh@icifp.cn E-mail:zyh@icifp.cn
作者简介:郑敏睿(1990-),男,安徽安庆人,硕士生,主要从事生物基聚氨酯泡沫及其阻燃改性研究
基金资助:
国家自然科学基金资助项目（31670577）；中国林科院中央级公益性科研院所基本科研业务费专项资金（CAFYBB2014QB021）

Synthesis and Properties of Epoxidized Tung Oil Methyl Ester from Tung Oil Methyl Ester with Quaternary Ammonium Phosphotungstate as Catalyst

ZHENG Minrui¹, ZHANG Meng^1,2, HU Lihong^1,2, BO Caiying¹, ZHOU Yonghong^1,2

1. Institute of Chemical Industry of Forest Products, CAF;National Engineering Lab. for Biomass Chemical Utilization;Key and Open Lab. of Forest Chemical Engineering, SFA;Key Lab. of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China;
2. Research Institute of Forestry New Technology, CAF, Beijing 100091, China

Received:2016-10-14 Online:2017-06-25 Published:2017-07-03

摘要/Abstract

摘要： 以磷钨酸、 30% H₂O₂和十二烷基氯化吡啶为原料制备了磷钨酸季铵盐相转移催化剂（C₁₂H₂₅C₆H₅N）₃[PW₄O₁₆]，并将该催化剂用于催化桐油甲酯（TOME）合成环氧桐油甲酯（ETOME），考察了不同反应条件对TOME环氧化反应的影响。研究发现：该相转移催化剂与H₂O₂和TOME相互作用的体系可以视为均相反应，且反应速率快，当n（C=C）：n（H₂O）为1：1.6，TOME和催化剂的质量比1：0.03，反应温度为 50 ℃，反应时间为3 h时，制得的ETOME的环氧值达到4.9%；热重（TG）分析表明桐油（TO）、TOME和ETOME的热稳定性顺序为ETOME > TO > TOME。

关键词: 磷钨酸季铵盐, 桐油甲酯, 环氧化, 相转移

Abstract: A quaternary ammonium phosphotungstates phase transfer catalyst (C₁₂H₂₅C₆H₅N)₃[PW₄O₁₆] was synthesized by using phosphotungstic, hydrogen peroxide(30%) and dodecylpyridinium chloride as feedstock. This phase transfer catalyst was used for the epoxidation of tung oil methyl ester(TOME) and manufacture the epoxidized tung oil methyl ester(ETOME). It was found that the system consist of phase transfer catalyst, TOME and hydrogen peroxide can be regarded as a homogeneous system and the reaction rate was accelerated. Effect of different conditions on the epoxidation reaction of methyl tung oil was investigated. Results showed that the optimum conditions were 50℃ reaction temperature, 3 h reaction time, 1.6:1 molar ratio of hydrogen peroxide to double bond and catalyst dosage was 3.0%. The epoxy value of ETOME can reach 4.9% under these optimum condition. Thermogravimetric analysis showed that the descending order of thermal stability of the products was ETOME > TO > TOME.

Key words: quaternary ammonium phosphotungstates, tung oil methyl ester, epoxidation, phase transfer

中图分类号:

TQ35

郑敏睿, 张猛, 胡立红, 薄采颖, 周永红. 磷钨酸季铵盐催化制备环氧化桐油甲酯及其性能研究[J]. 林产化学与工业, 2017, 37(3): 61-66.

ZHENG Minrui, ZHANG Meng, HU Lihong, BO Caiying, ZHOU Yonghong. Synthesis and Properties of Epoxidized Tung Oil Methyl Ester from Tung Oil Methyl Ester with Quaternary Ammonium Phosphotungstate as Catalyst[J]. Chemistry and Industry of Forest Products, 2017, 37(3): 61-66.

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磷钨酸季铵盐催化制备环氧化桐油甲酯及其性能研究

Synthesis and Properties of Epoxidized Tung Oil Methyl Ester from Tung Oil Methyl Ester with Quaternary Ammonium Phosphotungstate as Catalyst

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