CO2-环氧丙烷合成碳酸丙烯酯：氢键供体效应研究

doi:10.11949/0438-1157.20240083

摘要/Abstract

摘要：

“双碳”背景下，CO₂的综合利用迎来了挑战与机遇，将CO₂转化为高附加值化学品对于节能减排和碳循环利用具有重要意义。其中，将CO₂与环氧化合物经过环加成反应转化为环状碳酸酯是碳资源循环利用的重要方式之一。本文研究了环氧丙烷（PO）在以四丁基溴化铵（TBABr）为催化剂的均相体系中氢键供体效应对环加成反应的影响，探究了不同碳数醇类以及酚类极性对反应的影响。研究发现，在温和条件（100 ℃，2 h，1.5 MPa）下，以邻苯二酚为氢键供体时，PO的转化率可以达到99.8%，碳酸丙烯酯（PC）选择性可以达到99.51%，性能远远高于无氢键供体体系。此外，本研究通过建立线性溶剂化能关系式以及Kamlet-Taft表达式，定量描述了氢键供体（醇类、酚类）极性参数对反应性能的影响，阐明了氢键供体对提高CO₂-PO环加成反应效率的影响。

关键词: 环氧丙烷, 二氧化碳, 离子液体, Kamlet-Taft表达式, 氢键供体, 活化

Abstract:

Under the background of "carbon peaking and carbon neutrality goals", the comprehensive utilization of CO₂meets great challenges and opportunities. Furthermore, the conversion of CO₂ into high value-added chemicals is of great significance for energy conservation, emission reduction and carbon recycling. Among this, the conversion of CO₂ and epoxides into cyclic carbonates through cycloaddition reaction is one of the important ways of carbon resource recycling. The effects of hydrogen bond donor on cycloaddition reaction of propylene oxide (PO) in homogeneous system with tetrabutylammonium bromide (TBABr) as catalyst were explored in detail. In addition, the polarity of linear alcohols and phenols were investigated for enhancing the catalytic performance, respectively. It was found that the conversion of PO shows significantly increased propylene epoxide conversion from 49.8%to 99.8% while maintaining high propylene carbonate selectivity (99.51%) under the mild conditions (100 ℃, 2 h, 1.5 MPa), which is much higher than that of non-hydrogen bond donor system. In addition, the polarity parameters of hydrogen bond donors (alcohols and phenols) was quantitatively describes by linear solvation energy equation and Kamlet-Taft equation. Meanwhile, the reaction mechanism of the hydrogen bond donor was elucidated.

Key words: propylene oxide, carbon dioxide, ionic liquids, Kamlet-Taft equation, hydrogen bond donor, activation

中图分类号:

O 621.1

张广宇, 付然飞, 孙冰, 袁俊聪, 冯翔, 杨朝合, 徐伟. CO₂-环氧丙烷合成碳酸丙烯酯：氢键供体效应研究[J]. 化工学报, DOI: 10.11949/0438-1157.20240083.

Guangyu ZHANG, Ranfei FU, Bing SUN, Juncong YUAN, Xiang FENG, Chaohe YANG, Wei XU. Synthesis of propylene carbonate from CO₂ and propylene oxide:[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240083.

图/表 8

表1 不同氢键供体对环氧丙烷环加成反应的影响

Table 1 Effect of different hydrogen bond donors on propylene oxide

催化剂名称	氢键供体类型	环氧丙烷转化率（%）	选择性（%）
催化剂名称	氢键供体类型	环氧丙烷转化率（%）	碳酸丙烯酯	1,2-丙二醇
TBABr	/	49.82	98.68	1.32
	CH₃CH₂OH	53.63	100.00	0.00
	CH₃CH₂CH₂OH	53.89	100.00	0.00
	CH₃(CH₂)₃OH	57.46	100.00	0.00
	CH₃(CH₂)₅OH	97.10	98.32	1.68
	CH₃(CH₂)₉OH	94.12	98.83	1.17

表2 不同氢键供体对环氧丙烷环加成反应的影响

Table 2 Effect of different hydrogen bond donors on propylene oxide

催化剂名称	氢键供体类型	环氧丙烷转化率（%）	选择性（%）
催化剂名称	氢键供体类型	环氧丙烷转化率（%）	碳酸丙烯酯	1,2-丙二醇
TBABr		99.30	97.93	2.07
		99.80	99.51	0.49
		96.68	99.52	0.48
		98.19	97.00	3.00
		95.86	97.72	2.28

图1 氢键供体极性对应图

Fig. 1 Hydrogen bond donors polarity

图2 醇类Kamlet-Taft参数与转化率关系以及理论计算与实验测定的转化率的对比图

Fig. 2 The relationship between Kamlet-Taft parameters and conversion of PC and the comparison between theoretical calculation and experimental conversion

表3 醇类Kamlet-Taft参数［28-30］

Table 3 Kamlet-Taft parameters of alcohol［28-30］

氢键供体	E_T(30)	$E N T$	α	β	Π*	环氧丙烷转化率（%）
CH₃CH₂OH	51.90	0.66	0.86	0.75	0.54	53.63
CH₃CH₂CH₂OH	50.70	0.62	0.84	0.90	0.52	53.89
CH₃(CH₂)₃OH	50.20	0.60	0.84	0.84	0.47	57.46
CH₃(CH₂)₅OH	48.80	0.56	0.80	0.84	0.40	97.10
CH₃(CH₂)₉OH	47.60	0.53	0.70	0.82	0.45	94.12

表3 醇类Kamlet-Taft参数［28-30］

Table 3 Kamlet-Taft parameters of alcohol［28-30］

氢键供体	E_T(30)	$E N T$	α	β	Π*	环氧丙烷转化率（%）
CH₃CH₂OH	51.90	0.66	0.86	0.75	0.54	53.63
CH₃CH₂CH₂OH	50.70	0.62	0.84	0.90	0.52	53.89
CH₃(CH₂)₃OH	50.20	0.60	0.84	0.84	0.47	57.46
CH₃(CH₂)₅OH	48.80	0.56	0.80	0.84	0.40	97.10
CH₃(CH₂)₉OH	47.60	0.53	0.70	0.82	0.45	94.12

表4 酚类Kamlet-Taft参数与转化率［31-33］

Table 4 Kamlet-Taft parameters and conversion of phenol［31-33］

E_T⁽³⁰⁾	$E N T$	α	β	Π^*	环氧丙烷转化率（%）
53.40	0.70	1.10	0.30	0.67	99.30
52.10	0.66	0.85	0.58	1.07	99.80
53.60	0.71	0.61	0.60	1.00	96.68
54.40	0.73	1.16	0.52	1.00	98.19
51.90	0.66	0.52	0.34	0.69	95.86

表4 酚类Kamlet-Taft参数与转化率［31-33］

Table 4 Kamlet-Taft parameters and conversion of phenol［31-33］

E_T⁽³⁰⁾	$E N T$	α	β	Π^*	环氧丙烷转化率（%）
53.40	0.70	1.10	0.30	0.67	99.30
52.10	0.66	0.85	0.58	1.07	99.80
53.60	0.71	0.61	0.60	1.00	96.68
54.40	0.73	1.16	0.52	1.00	98.19
51.90	0.66	0.52	0.34	0.69	95.86

图3 酚类Kamlet-Taft参数与转化率关系以及理论计算与实验测定的转化率对比图

Fig. 3 The relationship between Kamlet-Taft parameters and conversion of PC and the comparison between theoretical calculation and experimental conversion

图4 氢键供体存在下TBABr催化PO环加成反应机理

Fig. 4 Plausible reaction mechanism of the cycloaddition reaction for the synthesis of propylene carbonate over the TBABr in the presence of HBD

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CO₂-环氧丙烷合成碳酸丙烯酯：氢键供体效应研究

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