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十二碳二元酸酯类增塑剂的绿色合成研究
陈勇
学位类型硕士
导师赵文军 ; 高林
2009-06-04
学位授予单位中国科学院研究生院
学位授予地点北京
学位专业有机化学
关键词十二碳二元酸酯 增塑剂 酯化反应 绿色催化
摘要液体酸催化酯化反应时,存在副产物难分离、催化剂难回收、设备腐蚀严重及废酸排放等问题。因而,酯化反应的绿色催化合成研究存在潜在的应用前景。增塑剂是现代塑料工业最大的助剂品种。本工作利用自制杂多阴离子离子液体为催化剂,以环己酮为原料合成的十二碳二元酸与异丁醇酯化合成长链二元酸酯类耐寒增塑剂。该催化剂的使用克服了传统浓硫酸催化工艺活性不高、副反应多、后处理复杂、设备腐蚀以及三废污染等缺点。本文主要内容包括以下几方面工作:(1)以环己酮为原料,双氧水氧化制备十二碳二元酸。讨论了由环己酮氧化制备十二碳二元酸的制备过程及其机理。包括反应温度对产物组成的影响以及反应时间对产品收率的影响。(2)利用合成的九种杂多阴离子离子液体、3种Brønsted酸性离子液体以及杂多酸等酸催化剂,分别考察了十二碳二元酸与异丁醇的酯化反应。结果表明,在以[MIMPS]3PMo12O40为催化剂情况下,以酯化率为指征时,合成十二碳二异丁酯的最佳工艺条件是酯化反应时间3 h,反应温度120 ℃,n(异丁醇):n(十二碳二元酸)=4:1,催化剂用量占0.5%。(3)研究了十二碳二异丁酯化反应动力学。包括酯化反应的级数、反应速率常数、速率方程、反应速率常数的影响因素等。还考察了十二碳二元酸与其它醇的酯化反应,且有相同的反应现象。脂肪族二元酸酯类增塑剂是一类优良的耐寒增塑剂,本文所考察的醇均为低碳数醇,能否用含碳数更高的醇或者混合醇来合成不对称的十二碳二元酸酯,以期得到性能更加优良的耐寒增塑剂,有待进一步研究。
其他摘要Liquid acids are usually selected as the catalysts of esterification. However,they are difficult to separation recycle from the product,and they also unfavorably affects eormsion prevention of synthesis equipment. Green catalysis technology may make up for these deficiencies. The plasticizer is one of the most important plasticizer assistants. In this paper, Long-chain fatty acid ester chillnes resistant plasticizer was prepared by esterification of dodecanedioic acid with isobutanol, in which heteropolyanion-based ionic liquids were used as catalysts. The use of the catalyst has overcome the traditional activity of concentrated sulfuric acid catalyzed process is not high, side effects and more complex post-processing, equipment corrosion, as well as the shortcomings of waste pollution. The main contents of this article include the following aspects: (1) To cyclohexanone as the raw material, hydrogen peroxide as oxidation agent, produce dodecanedioic acid. We discussed preparation process of dodecanedioic acid and its formation mechanism. Including the effect of reaction temperature on product composition and reaction time on product yield. (2) We investigated the esterification of dodecanedioic acid with isobutanol, by using nine kinds of heteropolyanion-based ionic liquids、three kinds of Brønsted acid ionic liquids and HPA as catalysts. Take [MIMPS]3PMo12O40 as example, the results show that: the optimum reaction condition of dodecanedioic acid with isobutanol is (4:1) of mol ratio of alcohol and acid, 0.5% of catalyst amount, 3 h reaction time and 120 ℃ reaction temperature. (3) We also studied reaction kinetics of esterification of dodecanedioic acid with isobutanol. Including esterification of the series, the reaction rate constant, rate equation and the effect of reaction rate constant. Also inspected esterification of dodecanedioic acid with other alchols, with the same reaction phenomenon. Long-chain fatty acid ester is a class of excellent cold-resistant plasticizer. In this paper, the alcohols we used are low carbon number alcohols. It give us some advices if we could use some higher number alcohols and mixed alcohols to synthesize some no-symmetrical esters of dodecanedioic acid, in purpose to produce excellent performance cold-resistant plasticizer, pending on further study.
文献类型学位论文
条目标识符http://ir.xjipc.cas.cn/handle/365002/3558
专题资源化学研究室
作者单位中国科学院新疆理化技术研究所
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陈勇. 十二碳二元酸酯类增塑剂的绿色合成研究[D]. 北京. 中国科学院研究生院,2009.
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