以莰烯、乙二醇、甲基丙烯酸甲酯为原料,经过醚化和酯交换反应合成了光固化涂料用活性稀释剂甲基丙烯酸异冰片基氧乙基酯(IBOEMA),采用GC-MS、IR等分析手段对合成产物的结构进行了分析测定。在莰烯与乙二醇的醚化过程中,以A-15作醚化催化剂,探讨了A-15用量、乙二醇与莰烯的物质量之比、反应温度、反应时间等对异冰片基羟乙基醚得率的影响。采用正交试验确定了异冰片基羟乙基醚的适宜合成条件:催化剂A-15的用量为6.0%,反应温度90 ℃,反应时间9 h,乙二醇与莰烯的物质量之比为3.5:1.0。在此条件下,莰烯转化率、反应选择性及产物得率分别达79%、93%和74%以上。在异冰片基羟乙基醚酯交换合成IBOEMA过程中,以环己烷为溶剂,反应在回流状态下进行,探讨了催化剂种类及用量、异冰片基羟乙基醚与甲基丙烯酸甲酯物质的量之比、反应时间、阻聚剂的种类和用量等对IBOEMA得率的影响。通过正交试验确定了异冰片基羟乙基醚与甲基丙烯酸甲酯酯交换反应的适宜工艺条件:以环己烷为溶剂进行回流反应,环己烷与异冰片基羟乙基醚物质的量之比为37:1,甲基丙烯酸甲酯与异冰片基羟乙基醚的物质量之比为1.25:1.00,催化剂KOH的用量为3%,反应时间8 h,吩噻嗪用量为1%。在此条件下,异冰片基羟乙基醚的转化率、反应选择性及产物得率分别达91%、93%和85%以上。
Abstract
Isobornyloxyethyl methacrylate(IBOEMA), a new type of active diluent for UV-curing coating, was synthesized from camphene as raw material by etherification and transesterification. In the etherification process of camphene and ethylene alcohol, A-15 was used as the catalyst, and theeffects of the amount of A-15, the molar ratios of ethylene glycol to camphene, reaction temperature and time on the yield of isobornyl hydroxyethyl ether were investigated, and the optimum synthesis conditions of isobornyl hydroxyethyl ether were determined based on orthogonal test results as follows: A-15 was used as the catalyst and its dosage was 6.0%(based on the total weight of camphene and ethylene glycol); ethylene glycol/camphene molar ratio was 3.5:1.0; reaction temperature and time were 90 ℃ and 9 h, respectively. The conversion ratio of camphene, reaction selectivity, and the yield of isobornyl hydroxyethyl ether reached 79%, 93%, and 74%, respectively, at aforesaid reaction conditions. In the transesterification process of isobornyl hydroxyethyl ether and methyl methacrylate, cyclohexane was used as the solvent, and the reaction was carried out at the condition of refluxing; the effects of the type and amount of catalyst, the molar ratio of isobornyl hydroxyethyl ether to methyl methacrylate, reaction time, the type and amount of inhibitor on the yield of IBOEMA were examined, and the optimum synthesis conditions of IBOEMA were determined based on the orthogonal test results as follows: methyl methacrylate/isobornyl hydroxyethyl ether molar ratio was 1.25:1.00; KOH was used as the catalyst for transesterification and it dosage was 3%(based on the total weight of methyl methacrylate and isobornyl hydroxyethyl ether); reaction time 8 h; phenothiazine was used as the inhibitor, and its dosage was 1%; cyclohexane was used as the solvent, and cyclohexane/isobornyl hydroxyethyl ether molar ratio was 37:1. The conversion ratio of isobornyl hydroxyethyl ether, reaction selectivity, and the yield of IBOEMA reached 91%, 93%, and 85%, respectively, at the aforesaid reaction conditions. The structures of isobornyl hydroxyethyl ether and IBOEMA were determined with GC-MS and FTIR spectra.
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基金
收稿日期:2012-08-10 修回日期:2012-10-23
基金项目:国家林业公益性行业科研专项项目(201104015)
第一作者:王士康,硕士生。*通信作者:王石发,教授。E-mail:usfyyq@njfu.com.cn。
引文格式:王士康,徐徐,徐晓维,等. 莰烯合成甲基丙烯酸异冰片基氧乙基酯的研究[J]. 南京林业大学学报:自然科学版,2013,37(4):127-132.
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