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

doi:10.3969/j.issn.1673-5854.2022.02.001

Abstract

Abstract:

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.

Key words: methyl oleate, methyl linoleate, olefin cross-metathesis, α-olefin, high-carbon terminal olefin chemical

CLC Number:

TQ35
S216

Yuanbo HUANG, Hengyi SHU, Zhifeng ZHENG, Shouqing LIU, Hailong MA, Hao LI. Comparation of Producing Long Chain Terminal Olefin Chemicals Through Cross-metathesis Among 2 Types of Fatty Acid Methyl Ester[J]. Biomass Chemical Engineering, 2022, 56(2): 1-8.

Figures/Tables 6

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Table 2

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References 20

1	魏静, 阎杰, 冯晓萌, 等. 无溶剂体系中废弃油脂的环氧化改性[J]. 粮食与油脂, 2019, 32 (1): 69- 72. doi: 10.3969/j.issn.1008-9578.2019.01.019
2	张飞, 胡云, 刘承果, 等. 羟基化木本油脂的合成及其结构表征[J]. 林产化学与工业, 2018, 38 (6): 27- 32. doi: 10.3969/j.issn.0253-2417.2018.06.004
3	谷婷婷, 宋焕玲, 丑凌军. 油脂加氢催化剂研究进展[J]. 分子催化, 2020, 34 (3): 242- 251.
4	KEITZ B K , ENDO K , PATEL P R , et al. Improved ruthenium catalysts for Z-selective olefin metathesis[J]. Journal of the American Chemical Society, 2012, 134 (1): 693- 699. doi: 10.1021/ja210225e
5	GESSLER S , RANDL S , BLECHERT S . Synthesis and metathesis reactions of a phosphine-free dihydroimidazole carbene ruthenium complex[J]. Tetrahedron Letters, 2000, 41 (51): 9973- 9976. doi: 10.1016/S0040-4039(00)01808-6
6	KUHN K M , CHAMPAGNE T M , HONG S H , et al. Low catalyst loadings in olefin metathesis: Synthesis of nitrogen heterocycles by ring-closing metathesis[J]. Organic Letters, 2010, 12 (5): 984- 987. doi: 10.1021/ol9029808
7	SCHWAB P , FRANCE M B , ZILLER J W , et al. A series of well-defined metathesis catalysts-synthesis of[RuCl₂(=CHR)(PR₃)₂] and its reactions[J]. Angewandte Chemie International Edition, 1995, 34 (18): 2039- 2041. doi: 10.1002/anie.199520391
8	THOMAS R M , KEITZ B K , CHAMPAGNE T M , et al. Highly selective ruthenium metathesis catalysts for ethenolysis[J]. Journal of the American Chemical Society, 2011, 133 (19): 7490- 7496. doi: 10.1021/ja200246e
9	PARK C P , VAN WINGERDEN M M , HAN S , et al. Low pressure ethenolysis of renewable methyl oleate in a microchemical system[J]. Organic Letters, 2011, 13 (9): 2398- 2401. doi: 10.1021/ol200634y
10	RYBAK A , MEIER M A R . Cross-metathesis of fatty acid derivatives with methyl acrylate: Renewable raw materials for the chemical industry[J]. Green Chemistry, 2007, 9 (12): 1356- 1361. doi: 10.1039/b712293d
11	JACOBS T , RYBAK A , MEIER M A R . Cross-metathesis reactions of allyl chloride with fatty acid methyl esters: Efficient synthesis of α, ω-difunctional chemical intermediates from renewable raw materials[J]. Applied Catalysis A: General, 2009, 353 (1): 32- 35. doi: 10.1016/j.apcata.2008.10.026
12	舒恒毅, 郑志锋, 刘守庆, 等. 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.
13	NASCIMENTO D L , FOGG D E . Origin of the breakthrough productivity of ruthenium-cyclic alkyl amino carbene catalysts in olefin metathesis[J]. Journal of the American Chemical Society, 2019, 141 (49): 19236- 19240. doi: 10.1021/jacs.9b10750
14	HONG S H , DAY M W , GRUBBS R H . Decomposition of a key intermediate in ruthenium-catalyzed olefin metathesis reactions[J]. Journal of the American Chemical Society, 2004, 126 (24): 7414- 7415. doi: 10.1021/ja0488380
15	CHATTERJEE A K , CHOI T L , SANDERS D P , et al. A general model for selectivity in olefin cross metathesis[J]. Journal of the American Chemical Society, 2003, 125 (37): 11360- 11370. doi: 10.1021/ja0214882
16	DESHMUKH P H , BLECHERT S . Alkene metathesis: The search for better catalysts[J]. Dalton Transactions, 2007, (24): 2479- 2491. doi: 10.1039/b703164p
17	JAWICZUK M , MODZIKOWSKA K , TRZASKOWSKI B . Impact of the olefin structure on the catalytic cycle and decomposition rates of Hoveyda-Grubbs metathesis catalyst[J]. Physical Chemistry Chemical Physics, 2020, 22 (23): 13062- 13069. doi: 10.1039/D0CP01798A
18	JAWICZUK M , MARCZYK A , TRZASKOWSKI B . Decomposition of ruthenium olefin metathesis catalyst[J]. Catalysts, 2020, 10 (8): 887- 942. doi: 10.3390/catal10080887
19	DUY L , CHANATIP S , KEN T , et al. Efficient conversion of renewable unsaturated fatty acid methyl esters by cross-metathesis with eugenol[J]. ACS Omega, 2018, 3 (9): 11041- 11049. doi: 10.1021/acsomega.8b01695
20	OGBA O M , WARNER N C , O'LEARY D J , et al. Recent advances in ruthenium-based olefin metathesis[J]. Chemical Society Reviews, 2018, 47 (12): 4510- 4544. doi: 10.1039/C8CS00027A

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

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底物 substrate	MO			ML
底物 substrate	转化率/% conversion	CM1产率/% CM1 yield	CM3产率/% CM3 yield	转化率/% conversion	CM2产率/% CM2 yield	CM3产率/% CM3 yield
2-甲氧基丙烯2-methoxypropylene	43	0	0	62	0	0
氯丙烯allyl chloride	58	14	14	49	4	6
丙烯酸甲酯methyl acrylate	79	2	1	95	3	2
乙酸烯丙酯allyl acetate	48	12	12	96	10	13
烯丙基缩水甘油醚allyl glycidyl ether	28	2	2	51	2	2
丙烯醇allyl alcohol	24	1	2	36	1	2
苯乙烯styrene	59	40	37	72	19	23
丁香酚eugenol	96	78	76	99	49	72
烯丙基三甲基硅烷allyltrimethylsilane	89	34	34	93	19	28
丙烯腈acrylonitrile	44	3	2	45	1	1

反应条件 reaction condition		MO			ML
反应条件 reaction condition		转化率/% conversion	CM1产率/% CM1 yield	CM3产率/% CM3 yield	转化率/% conversion	CM2产率/% CM2 yield	CM3产率/% CM3 yield
反应温度 reaction temperature	0 ℃	97	58	60	99	80	55
	20 ℃	97	58	58	90	83	41
	30 ℃	97	34	33	87	78	40
	40 ℃	98	16	12	74	65	39
	50 ℃	98	7	11	73	55	51
反应时间 reaction time	10 min	84	63	47	97	61	42
	20 min	90	80	44	95	92	58
	30 min	94	68	59	97	64	45
	60 min	97	58	67	99	71	40
	120 min	97	59	71	99	66	44
催化剂用量 catalyst dosage	0.1%	25	24	20	44	14	19
	0.3%	53	41	44	58	20	28
	0.5%	76	58	73	92	46	47
	1%	94	76	54	97	64	45
	3%	94	75	69	99	52	39
n(脂肪酸甲酯)∶ n(丁香酚) n (fatty acid ester)∶ n (eugenol)	1∶1	90	15	15	97	32	11
	1∶3	98	33	53	99	47	31
	1∶5	99	27	60	99	46	43
	1∶10	97	70	73	97	64	45
	1∶20	96	59	62	95	57	61