油酸甲酯烯烃交叉复分解制备烯烃化学品中底物影响机制探究

doi:10.3969/j.issn.0253-2417.2021.03.002

林产化学与工业 ›› 2021, Vol. 41 ›› Issue (3): 11-18.doi: 10.3969/j.issn.0253-2417.2021.03.002

油酸甲酯烯烃交叉复分解制备烯烃化学品中底物影响机制探究

舒恒毅¹^,³, 郑志锋³^,⁴, 刘守庆¹^,³, 何宏舟², 黄元波²^,³^,*()

1. 西南林业大学材料科学与工程学院, 云南昆明 650224
2. 集美大学机械与能源工程学院, 福建厦门 361021
3. 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, 西南林业大学, 云南昆明 650224
4. 厦门市现代农业生物质高值化技术重点实验室(厦门大学); 福建省生物质高值化技术工程研究中心(厦门大学); 厦门大学能源学院, 福建厦门 361102

收稿日期:2020-10-27 出版日期:2021-06-28 发布日期:2021-07-01
通讯作者: 黄元波 E-mail:youthshow@163.com
作者简介:黄元波, 副教授, 硕士生导师, 主要从事生物质能源与材料研究教学工作; E-mail: youthshow@163.com
舒恒毅(1994-), 男, 云南曲靖人, 硕士生, 主要从事生物质能源与化学转化研究
基金资助:
国家自然科学基金资助项目(31860190);国家自然科学基金资助项目(31670599);国家重点研发计划资助项目(2016YFD0600802)

Effect Mechanism of Substrates on Cross-metathesis Reaction for Preparation of Long-chain Terminal Olefin Chemicals from Methyl Oleate

Hengyi SHU¹^,³, Zhifeng ZHENG³^,⁴, Shouqing LIU¹^,³, Hongzhou HE², Yuanbo HUANG²^,³^,*()

1. School of Materials Science & Engineering, Southwest Forestry University, Kunming 650224, China
2. School of Mechanical & Energy Engineering, Jimei University, Xiamen 361021, China
3. 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
4. Xiamen Key Laboratory for High-valued Conversion Technology of Agricultural Biomass(Xiamen University); Fujian Provincial Engineering and Research Center of Clean and High-valued Technologies for Biomass; College of Energy, Xiamen University, Xiamen 361102, China

Received:2020-10-27 Online:2021-06-28 Published:2021-07-01
Contact: Yuanbo HUANG E-mail:youthshow@163.com

摘要/Abstract

摘要：

利用油酸甲酯（MO）与液态短链烯烃底物通过烯烃交叉复分解反应制备长链终端烯烃化学品1-癸烯（CM1）和9-癸烯酸甲酯（CM2）。首先，通过油酸甲酯的自复分解反应评估4种典型催化剂，确定最佳催化剂为第二代Hoveyda-Grubbs催化剂。然后，选取4种不同结构的底物探讨其对目标产物选择性的影响机理，并利用另外6种底物验证上述机理的合理性，实验表明，具有大位阻富电子基团的苯乙烯、丁香酚及烯丙基三甲基硅烷有利于目标产物生成，特别是具有π键的苯环与催化剂活性体进行螯合组成环式关键中间体将引导反应向目标产物方向进行，提高目标产物选择性。

关键词: 油酸甲酯, 烯烃交叉复分解, 钌络合催化剂, α-烯烃, 9-癸烯酸甲酯

Abstract:

The long-chain terminal olefin compounds 1-decene(CM1) and methyl 9-decenoate(CM2) were prepared through olefin cross-metathesis of methyl oleate(MO) with low olefin substrate. The second-generation Hoveyda-Grubbs catalyst was screened out from 4 typical ruthenium-catalyst through the self-metathesis of methyl oleate. The catalytic mechanism was discussed with 4 substrates, then the proposed mechanism was verified by 6 substrates. The results suggested that the short-chain substrates containing electron-rich and bulk-large group like styrene, eugenol and allyl trimethylsilane were beneficial for the preparation of terminal olefin products, since the property of aromatic group, which could chelate with central metal and formed the key ring intermediate, so that it changed the route of reaction and prepared the highly-selectivity of the aim product yield.

Key words: methyl oleate, olefin cross-metathesis, ruthenium-complex catalyst, α-olefin, methyl 9-decenoate

中图分类号:

TQ35
S216

舒恒毅, 郑志锋, 刘守庆, 何宏舟, 黄元波. 油酸甲酯烯烃交叉复分解制备烯烃化学品中底物影响机制探究[J]. 林产化学与工业, 2021, 41(3): 11-18.

Hengyi SHU, Zhifeng ZHENG, Shouqing LIU, Hongzhou HE, Yuanbo HUANG. Effect Mechanism of Substrates on Cross-metathesis Reaction for Preparation of Long-chain Terminal Olefin Chemicals from Methyl Oleate[J]. Chemistry and Industry of Forest Products, 2021, 41(3): 11-18.

图/表 9

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催化剂 catalyst	不同反应时间下MO转化率/% MO conversion of diverse reaction time
催化剂 catalyst	10 min	20 min	40 min
C1	0	0	0
C2	63	56	53
C3	63	68	62
C4	0	0	0

烯烃底物 olefin substrate	MO转化率MO conversion/%			CM1产率CM1 yield/%			CM2产率CM2 yiled/%
烯烃底物 olefin substrate	0 ℃	30 ℃	50 ℃	0 ℃	30 ℃	50 ℃	0 ℃	30 ℃	50 ℃
烯丙基缩水甘油醚 allyl glycidyl ether	30	27	29	3	2	2	2	2	2
2-甲氧基丙烯 2-methoxypropylene	51	59	50	0	0	0	0	0	0
苯乙烯styrene	59	54	54	37	29	26	35	28	24
氯丙烯allyl chloride	67	57	82	17	17	4	18	18	6

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油酸甲酯烯烃交叉复分解制备烯烃化学品中底物影响机制探究

Effect Mechanism of Substrates on Cross-metathesis Reaction for Preparation of Long-chain Terminal Olefin Chemicals from Methyl Oleate

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