2种脂肪酸甲酯烯烃交叉复分解制备长链终端烯烃化学品的对比研究

Comparation of Producing Long Chain Terminal Olefin Chemicals Through Cross-metathesis Among 2 Types of Fatty Acid Methyl Ester

为实现烯烃交叉复分解直接应用于植物油甲酯中获取长链终端烯烃化合物,本研究分别以油酸甲酯(MO)和亚油酸甲酯(ML)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(CM1)、1-庚烯(CM2)和9-癸烯酸甲酯(CM3)。对4种典型的Grubbs催化剂,10种短链液体烯烃底物以及不同的反应条件(反应温度、时间、催化剂用量和脂肪酸甲酯与烯烃底物物质的量之比)的影响规律进行对比分析,结果表明:4种催化剂中第二代Hoveyda-Grubbs催化剂(C3)适合于MO,第二代Grubbs催化剂(C2)适合ML,10种短链液体烯烃底物中丁香酚较有利于目标产物的生成。在反应温度0℃、反应时间20~60 min、催化剂用量0.5%~1%以及n(脂肪酸甲酯)∶n(丁香酚)为1∶10~1∶20范围内,两种原料均可获得较佳的结果,MO与ML的转化率最高均可达99%,CM1、CM2和CM3产率最高分别为80%、92%和73%。

In order to realize the direct application of olefin cross-metathesis on preparation of long-chain terminal olefin compounds from the crude fatty acid esters of vegetable oils,methyl oleate(MO)and methyl linoleate(ML)were used as raw materials to prepare long-chain terminal olefin compounds 1-decene(CM1),1-heptene(CM2)and methyl 9-decenoate(CM3)through olefin cross-metathesis reaction.4 typical Grubbs catalysts,10 short carbon chain fluid substrates were chosen and different reaction temperature,time,catalyst dosage and moles ratio of substrate as the reaction conditions were investigated and contrasted.The results showed that the second-generation Hovey-Grubbs catalyst(C3)and the second-generation Grubbs catalyst(C2)were suitable catalysts for raw materials MO and ML,respectively.Eugenol was the most appropriate partner among the 10 substrates for producing aim products.The influences of temperature,time,catalyst dosage and ratio of substrate were investigated,the suitable reaction conditions were reaction temperature 0℃,time 20-60 min,catalyst dosage 0.5%-1%and the mole ratio of fatty acid ester to substrates 1∶10-1∶20,the highest conversion of MO and ML were 99%,and the yields of CM1,CM2 and CM3 were 80%,92%and 73%,respectively.