以大孔强酸性阳离子交换树脂为催化剂,莰烯与2-甲基-1,3-丙二醇反应主要生成异冰片基羟异丁基醚.在小试搅拌反应釜内分别考察了不同阳离子交换树脂、搅拌速度、催化剂用量、反应物配比、溶剂和反应温度等对该烷氧基化反应的影响.结果表明,较佳的工艺条件为:催化剂为无水Lewatit2620,用量为总的液体物料质量的20%,莰烯与2-甲基-1,3-丙二醇的初始质量比为1.5∶1,反应温度为353K,反应时间为4h,此时莰烯的转化率为78.80%,异冰片基羟异丁基醚的选择性为93.5%.Lewatit2620重复使用8次后仍具有良好的反应活性.为校正溶液的非理想性,采用UNIFAC基团贡献法估算活度系数,并得到不同温度下的反应平衡常数.此外,基于同样的反应条件,在放大20倍的搅拌反应釜器中,莰烯的转化率与小试的结果基本一致.
The alkoxylation of camphene with 2-methyl-1,3-propanediol was carried out in the presence of anhydrous macroporous and strong acid cation exchange resins.The effects of various parameters,such as agitation speed,catalyst type,solvent,initial mass ratio of reactants,reaction temperature and reusability of catalysts,were investigated in a 250 mL glass stirred tank reactor in order to optimize the reaction conditions.The conditions for the alkoxylation of camphene with 2-methyl-1,3-propanediol under the catalytic action of anhydrous Lewatit2620 were optimized as follows:agitation speed was 400r·min-1;initial mass ratio of camphene to 2-methyl-1,3-propanediol was 1.5∶1;catalyst loading based on the total mass of reactants was 20%;reaction temperature was 353 Kand reaction time was four hours.Under these optimum conditions,the conversion of camphene was 78.80% and the selectivity of isobornyl hydroxyl isobutyl ether was 93.5%.Besides,the catalyst showed good catalytic activity after reusing by eight times.Through lengthening the reaction time,thermodynamic equilibrium constants at 333~370Kwere derived.The UNIFAC group contribution method was used to calculate activity coefficients of reactants and to correct the nonideality of reactants.The equilibrium constants decreased with increasing temperature,which demonstrated the alkoxylation of camphene with 2-methyl-1,3-propanediol was exothermic.The equilibrium constants based on concentrationwere significantly different from that based on activity,which indicated that it was necessary to take the nonideality of the mixture into account in calculation.Besides,the optimized reaction conditions were also verified in a 5Ldouble layer glass reaction kettle.From the perspective of conversion of camphene and selectivity of isobornyl hydroxyl isobutyl ether,result of the experiment in a 5Llayer glass reaction kettle is almost the same as that of the smallscale experiment,which providing evidence for industrial application by using industrial-grade camphene as the material.