苄基磺酸官能化介孔分子筛催化合成邻苯二甲酸二乙二醇双甲基丙烯酸酯

Catalytic synthesis of phthalic diglycol dimethacrylate on mesoporous MCM-41 functionalized with benzylsulfonic acid groups

以苄基磺酸官能化的介孔分子筛(MCM-41-B-S)为催化剂,以邻苯二甲酸酐(PA)、一缩二乙二醇(DEG)、甲基丙烯酸(MA)为原料,经两步酯化法合成了邻苯二甲酸一缩二乙二醇双甲基丙烯酸酯(PA-DEG-DMA)。结果表明,合成PA-DEG-DMA的反应温度在85～90℃,催化剂用量为DEG质量的4.5%,MA与邻苯二甲酸一缩二乙二醇酯(DEGP)的物质的量比为1.1∶1,带水剂甲苯用量为反应总质量的40%,阻聚剂4-甲氧基酚的用量为DEG质量的1.0%和回流时间为6h的优化条件下,获得了最佳反应结果,产品总收率可达83.4%,纯度大于98%。且产品外观质量好,反应后处理方便。并用X-射线衍射(XRD)、红外光谱(IR)、差示扫描量热(DSC)和Hammett指示剂对催化剂的结构和酸强度进行了表征和测定。

The phthalic diglycol dimethacrylate（PA-DEG-DMA）was synthesized with phthalic anhydride（PA）,diethylene glycol（DEG）and methacrylic acid（MA）as raw materials.It was found that benzylsulfonic acid functionalized MCM-41 molecular sieve（MCM-41-S-B）as catalyst was superior to sulphuric acid and other protonic acids in the esterification of MA with DEGP.The results showed that under the optimum conditions of molar ratio of 1.1∶1 of MA to DEGP,mass ratio of 4.5% of catalyst to DEG,total mass ratio of 1.0% of polymerization inhibitor 4-methoxyphenol to DEG,total mass ratio of 40% of water-entrainer toluene to reactant,reaction time 6h,and reaction temperature 85~90 ℃,the yield of PA-DEG-DMA reached to 83.4%.The structure and acid strength of MCM-41-S-B catalyst were characterized by XRD,IR spectroscopy,DSC and indicator of Hammett.