油酸甲酯烯烃复分解制备长链终端烯烃化学品探究  

Process optimization and mechanism of substrate on preparation high-carbon terminal-olefin compounds through cross-metathesis of methyl oleate

作　　者：舒恒毅 郑志锋 刘守庆 何宏舟 黄元波 SHU Hengyi;ZHENG Zhifeng;LIU Shouqing;HE Hongzhou;HUANG Yuanbo(School of Materials Science&Engineering,Southwest Forestry University,Kunming 650224,China;National Local Joint Engineering Research Center for Efficient Utilization of Forestry Biomass Resources,Key Laboratory for Highly-efficient Utilization of Forest Biomass Resources in the Southwest China,National Forestry and Grassland Administration,Southwest Forestry University,Kunming 650224,China;Xiamen Key Laboratory for High-valued Conversion Technology of Agricultural Biomass,Fujian Provincial Engineering and Research Center of Clean and High-valued Technologies for Biomass,College of Energy,Xiamen University,Xiamen 361102,China;School of Mechanical&Energy Engineering,Jimei University,Xiamen 361021,China)

机构地区：[1]西南林业大学材料科学与工程学院,昆明650224 [2]林业生物质资源高效利用技术国家地方联合工程研究中心,西南地区林业生物质资源高效利用国家林业和草原局重点实验室,昆明650224 [3]厦门市现代农业生物质高值化技术重点实验室,福建省生物质高值化技术工程研究中心,福建厦门361102 [4]集美大学机械与能源工程学院,福建厦门361021

出　　处：《林业工程学报》2021年第4期80-86,共7页Journal of Forestry Engineering

基　　金：国家自然科学基金(31860190,31670599);国家重点研发计划项目(2016YFD0600802);云南省研发经费投入补助项目(2017YB236);云南省重大科技专项计划项目(2018ZG003);云南省可再生能源发展专项基金项目(云财产业[2015]86号)。

摘　　要：以油酸甲酯为原料,通过烯烃交叉复分解反应制备长链终端烯烃化合物1-癸烯和9-癸烯酸甲酯,在4种典型的Grubbs催化剂中确定第二代Hoveyda-Grubbs催化剂能高效稳定地催化反应,考察了10种带有不同基团的短链液体烯烃底物,结合底物结构及实验结果,对底物影响反应机制进行分析,结论是可将底物分为4种类型,其中以丁香酚和苯乙烯为代表的带有大位阻和富电子基团的底物类型通过与催化剂络合形成关键螯合中间体,引导反应向目标产物方向进行,实现高选择性制备长链终端烯烃化合物。再以油酸甲酯转化率,1-癸烯和9-癸烯酸甲酯产率为评价指标,探究了反应温度、反应时间、催化剂用量和底物摩尔比对烯烃复分解反应制备1-癸烯的影响,最后通过正交实验设计优化得到最佳工艺条件。结果表明,对实验结果影响大小的因素是:催化剂用量>底物摩尔比>反应时间>反应温度,最佳工艺条件为反应温度40℃,反应时间40 min,催化剂用量0.5%(摩尔分数),底物摩尔比1∶10,在此条件下油酸甲酯转化率、1-癸烯和9-癸烯酸甲酯产率分别为97%,94%和91%。Cross-metathesis reaction is one of the most important organic reactions which can achieve the exchange of the chemical group through the ■ double bonds, for example, some chemical structures of medicine are synthesized by multiple steps, however, only one step is needed by the cross-metathesis reaction. The reaction has been applied in various areas with the development of robust catalysts like Grubbs and Hoveyda catalysts, it is ensured that the reaction proceeds smoothly in the environment where air and water exist. Therefore, this reaction was also used in fatty chemistry, for example, the terminal olefin chemicals were high-selectively produced from the ethenolysis of methyl oleate. However, there are still some difficulties that need to be solved for industrialization, such as the low conversion of raw material due to the liquid-solid reaction and the requirements of high purity of ethylene gas and high reaction pressure. Some researchers have sought liquid substrates to react with methyl oleate, but the main drawback is the low selectivity of terminal olefin products, which suggests that the structure of substrate influences the reaction greatly. Therefore, it is necessary to investigate the mechanism of substrate influence and then explore the most appropriate reaction conditions for preparation of aimed products. The high-carbon olefin compounds α-decene and methyl 9-decenoate were prepared through olefin metathesis reaction using methyl oleate in this study. It was confirmed that the second-generation Hoveyda-Grubbs catalyst can efficiently and stably catalyze the reaction among four types of Grubbs catalysts. The 10 low-chain olefin substrates which connect different chemical groups were categorized as four types according to the results, and the influence mechanism of four types of substrates was proposed. As the type Ⅳ substrate, the eugenol and styrene were the most beneficial ones to the preparation of terminal olefin products due to the large hindrance and the electron-rich group leads the re

关 键 词：油酸甲酯 烯烃交叉复分解 钌络合催化剂 Α-烯烃 长链终端烯烃化合物 

分 类 号：TQ35[化学工程] S216[农业科学—农业机械化工程]