草酸/聚乙二醇低温共熔体催化α-蒎烯水合反应

袁冰; 张东强; 解从霞; 于凤丽; 于世涛

doi:10.1016/S1872-5813(21)60017-8

草酸/聚乙二醇低温共熔体催化α-蒎烯水合反应

doi: 10.1016/S1872-5813(21)60017-8

袁冰^1, ,,
张东强¹,
解从霞^1, ,,
于凤丽¹,
于世涛²

1.
生态化工国家重点实验室培育基地，青岛科技大学化学与分子工程学院，山东青岛 266042
2.
青岛科技大学化工学院，山东青岛 266042

基金项目: 国家自然科学基金（31870554，31470595），山东省重点研发计划（公益类专项）（2017GGX40105）和山东省泰山学者项目（ts201511033）资助

详细信息

通讯作者:
Tel：13255573327，E-mail：yuanbing@qust.edu.cn

xiecongxia@126.com

中图分类号: O643.32
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出版历程
- 收稿日期: 2020-07-07
- 修回日期: 2020-09-13
- 网络出版日期: 2021-03-19
- 刊出日期: 2021-03-19

Hydration of α-pinene catalyzed by oxalic acid/polyethylene glycol deep eutectic solvents

1.
State Key Laboratory Base of Eco-chemical Engineering, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
2.
College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China

Funds: The project was supported by the National Natural Science Foundation of China (31870554, 31470595), the Shandong Key R & D Plan (Public Welfare Special Project) (2017GGX40105) and the Taishan Scholars Projects of Shandong (ts201511033)

摘要

摘要: 以天然有机二元羧酸草酸（OA）作为氢键供体，各种聚合度的聚乙二醇（PEG）作为氢键受体，构建出羧酸功能化低温共熔体（DES），将其用于催化α-蒎烯水合制备α-松油醇的反应中。傅里叶变换红外光谱（FT-IR）、核磁共振氢谱（¹H NMR）、热重分析（TGA）等表征证实了OA与PEG之间氢键的形成。DES中PEG组分的存在对其酸强度影响较小，但随PEG分子量和用量的增加，DES总酸量减小，从而降低其催化活性。研究表明，分子量最小的PEG200与OA制备的OA/0.6PEG200 DES具有较佳的催化 α-蒎烯水合反应性能，在DES催化剂用量0.03 mol（以OA计），α-蒎烯用量0.06 mol，水用量0.3 mol，反应温度75 ℃，反应时间8 h的优化条件下，获得81.5%的α-蒎烯转化率及51.2%的α-松油醇选择性。催化剂相反应结束后静置冷藏过夜即可分层分离，且循环使用性能良好。该OA/0.6PEG200 低温共熔体制备简单，原子经济性高，为一步法催化α-松油醇的清洁制备开辟了新路线。
- α-蒎烯 /
- α-松油醇 /
- 水合反应 /
- 低温共熔体
Abstract: A series of carboxylic acid-functionalized deep eutectic solvents (DES) were constructed by a natural organic dicarboxylic acid, oxalic acid (OA), as the hydrogen bond donor and the polyethylene glycol (PEG) with different polymerization degrees as the hydrogen bond acceptors, which are used in the hydration of α-pinene to produce α-terpineol. Fourier transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance spectroscopy (¹H NMR), and thermogravimetric analysis (TGA) were used to prove the hydrogen bonding between OA and PEG. It is found that the presence of PEG has a less impact on the acid strength of DES. However, an increase in both molecular weight and dosage of PEG results in a decrease in total acidity and catalytic activity. Among them, OA/0.6PEG200, a DES catalyst prepared by PEG with the smallest molecular weight, exhibits a favorable catalytic performance. Under an optimal reaction condition with 0.03 mol of DES (based on OA), 0.06 mol of α-pinene, 0.3 mol of water, at 75 °C for 8 h, an α-pinene conversion of 81.5% and an α-terpineol selectivity of 51.2% are obtained. The catalyst phase can be separated by refrigerating overnight after reaction and reused directly with relatively stable catalytic performance. Thus, OA/0.6PEG200, as a DES catalyst prepared by a simple and highly atom economical process, will offer a clean catalytic route for the one-step production of α-terpineol.
- α-pinene /
- α-terpineol /
- hydration /
- deep eutectic solvents

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图 1 OA、PEG200及OA/0.6PEG200 DES的FT-IR谱图

Figure 1 FT-IR spectra of OA, PEG200 and OA/0.6PEG200 DES

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图 2 OA、PEG200及OA/0.6PEG200 DES的 ¹H NMR谱图

Figure 2 ¹H NMR spectra of OA, PEG200 and OA/0.6PEG200 DES

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图 3 OA、PEG200及OA/0.6PEG200 DES的TG曲线

Figure 3 TG curves of OA, PEG200 and OA/0.6PEG200 DES

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图 4 DES催化剂的UV-vis谱图

Figure 4 UV-vis curves of DES catalysts

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图 5 OA与PEG200比例对催化性能的影响

Figure 5 Effect of ratios of OA to PEG200 on catalytic performance

reaction conditions: 0. 06 mol of α-pinene, 0.3 mol of water, 0.03 mol (based on OA) of OA/xPEG200, 75 ℃, 8 h)

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图 6 不同比例DES在75 ℃时的黏度变化

Figure 6 Viscosity change of DES with different ratios at 75 ℃

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图 7 OA/0.6PEG200黏度随温度的变化

Figure 7 Viscosity change of OA/0.6PEG200 with temperature

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图 8 反应温度对催化性能的影响

Figure 8 Effect of reaction temperature on catalytic performance

reaction conditions: 0.06 mol α-pinene, 0. 3 mol water, 0.03 mol (based on OA) OA/0.6PEG200, 8 h

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图 9 催化剂用量对催化性能的影响

Figure 9 Effect of catalyst dosage on catalytic performance

reaction conditions: 0.06 mol of α-pinene, 0.3 mol of water, OA:PEG200 = 1:0.6, 75 ℃, 8 h

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图 10 水量对催化性能的影响

Figure 10 Effect of water dosage on catalytic performance

reaction conditions: 0.06 mol α-pinene, 0.03 mol (based on OA) OA/xPEG200, 75 ℃, 8 h

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图 11 OA/0.6PEG200与不同量水混合物的FT-IR谱图

Figure 11 FT-IR spectra of the mixture of OA/0.6PEG200 with different dosages of water

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图 12 OA/0.6PEG200与不同量水混合物的 ¹H NMR谱图

Figure 12 ¹H NMR spectra of the mixture of OA/0.6PEG200 with different dosages of water

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图 13 反应时间对催化性能的影响

Figure 13 Effect of reaction time on catalytic performance

reaction conditions: 0.06 mol of α-pinene, 0.03 mol (based on OA) of OA/xPEG200, 75 ℃

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图 14 OA/0.6PEG200的循环使用性能

Figure 14 Recycling performance of OA/0.6PEG200

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图 15 OA/0.6PEG200的循环使用性能(补充草酸)

Figure 15 Recycling performance of OA/0.6PEG200 (with added OA)

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表 1 聚乙二醇聚合度对DES催化性能的影响

Table 1 The effect of the degree of polymerization of polyethylene glycol on the catalysis of DES

HBD	HBA	Conversion of α-pinene/ %	Selectivity of α-terpineol/%	Distribution of reaction products/ %
				isomerization products				e	f
				a	b	c	d	e	f
OA	−	51.5	26.7	4.5	11.6	24.2	26.5	30.4	2.8
OA	PEG200	91.7	45.0	4.6	16.4	18.8	6.4	51.0	2.8
OA	PEG400	58.6	50.8	7.5	15.1	15.8	5.4	52.3	3.9
OA	PEG600	61.4	49.1	7.4	16.1	16.2	4.1	51.1	5.1
OA	PEG2000	53.0	50.0	7.8	15.1	16.1	4.2	53.2	3.6
reaction conditions: 0.06 mol of α-pinene, 0.3 mol of water, 0.03 mol (based on OA) of catalyst, 80 ℃, 8 h; products: a (camphene), b (limonene), c (terpinolene), d (other terpenes), e (total hydration products), f (other by-products)

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表 2 DES催化剂的酸量

Table 2 Acidity of DES catalyst

Catalyst	Acidity/ (mmol H⁺·g⁻¹)
OA	24.07
OA/ 0.6PEG200	6.62
OA/ 0.6PEG400	4.49
OA/ 0.6PEG600	3.71
OA/ 0.6PEG2000	1.09
OA/ 0.8PEG200	5.22
OA/ 1.0PEG200	4.32
OA/ 1.2PEG200	3.67
OA/ 2.0PEG200	1.83

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表 3 DES催化剂的密度

Table 3 Density of DES catalysts

DES	ρ/(g·cm⁻³)
OA/ 0.6PEG200	1.303
OA/ 0.8PEG200	1.256
OA/ 1.0PEG200	1.213
OA/ 1.2PEG200	1.190
OA/ 2.0PEG200	1.148

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表 4 柠檬烯、异松油烯、α-松油醇的相互转化

Table 4 Mutual conversion of limonene, terpinolene, and α-terpineol

Reactants	Components of the reaction mixture/ %
	isomers ofterpene				e	f	g
	a	b	c	d	e	f	g
Limonene	−	87.7	1.3	4.0	5.4	0.5	1.1
Terpinolene	−	4.0	76.0	18.0	0.9	0.4	0.7
α-terpineol	−	11.0	11.0	9.0	56.5	11.9	0.6
reaction conditions: 0.06 mol of reactants, 0.3 mol of water, 0.03 mol(based on OA) of OA/0.6PEG200, 75 ℃, 8 h; products: a (camphene), b (limonene), c (terpinolene), d (other terpenes), e (α-terpineol), f (other hydration products), g (by-products)

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