Synthesis of propylene carbonate from CO2 and propylene oxide: hydrogen bond activation strategy

doi:10.11949/0438-1157.20240083

Abstract

Abstract:

Under the background of “carbon peaking and carbon neutrality goals”, the comprehensive utilization of CO₂ meets 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. 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, this study quantitatively described the impact of the polar parameters of hydrogen bond donors (alcohols, phenols) on reaction performance by establishing a linear solvation energy relationship and a Kamlet-Taft expression. 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

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。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，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

CLC Number:

O 621.1

Guangyu ZHANG, Ranfei FU, Bing SUN, Juncong YUAN, Xiang FENG, Chaohe YANG, Wei XU. Synthesis of propylene carbonate from CO₂ and propylene oxide: hydrogen bond activation strategy[J]. CIESC Journal, 2024, 75(6): 2243-2251.

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, 2024, 75(6): 2243-2251.

Figures/Tables 8

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
	CH₃CH₂CH₂OH	53.89	100.00	0
	CH₃(CH₂)₃OH	57.46	100.00	0
	CH₃(CH₂)₅OH	97.10	98.32	1.68
	CH₃(CH₂)₉OH	94.12	98.83	1.17

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

Fig.1 Hydrogen bond donors polarity

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

氢键供体	$E_{T}^{(30)}$	$E_{T}^{N}$	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

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

氢键供体	$E_{T}^{(30)}$	$E_{T}^{N}$	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

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

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

$E_{T}^{(30)}$	$E_{T}^{N}$	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

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

$E_{T}^{(30)}$	$E_{T}^{N}$	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

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

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

References 34

1	Nemirowsky J. Ueber die einwirkung von chlorkohlenoxyd auf aethylenglycol; vorläufige mittheilung[J]. Journal Für Praktische Chemie, 1883, 28(1): 439-440.
2	Khokarale S G, Mikkola J P. Metal free synthesis of ethylene and propylene carbonate from alkylene halohydrin and CO₂ at room temperature[J]. RSC Advances, 2019, 9(58): 34023-34031.
3	Deng L L, Sun W Z, Shi Z J, et al. Highly synergistic effect of ionic liquids and Zn-based catalysts for synthesis of cyclic carbonates from urea and diols[J]. Journal of Molecular Liquids, 2020, 316: 113883.
4	Zhang Z F, Liu Z W, Lu J, et al. Synthesis of dimethyl carbonate from carbon dioxide and methanol over Ce _x Zr_1- _x O₂ and [EMIM]Br/Ce_0.5Zr_0.5O₂ [J]. Industrial & Engineering Chemistry Research, 2011, 50(4): 1981-1988.
5	Han F, Li H, Zhuang H F, et al. Direct synthesis of cyclic carbonates from olefins and CO₂: single- or multi-component catalytic systems via epoxide or halohydrin intermediate[J]. Journal of CO₂ Utilization, 2021, 53: 101742.
6	Fierro F, Lamparelli D H, Genga A, et al. I-LDH as a heterogeneous bifunctional catalyst for the conversion of CO₂ into cyclic organic carbonates[J]. Molecular Catalysis, 2023, 538: 112994.
7	Zhang F, Wang Y Y, Zhang X C, et al. Recent advances in the coupling of CO₂ and epoxides into cyclic carbonates under halogen-free condition[J]. Green Chemical Engineering, 2020, 1(2): 82-93.
8	Wang J L, Wang J Q, He L N, et al. A CO₂/H₂O₂-tunable reaction: direct conversion of styrene into styrene carbonate catalyzed by sodium phosphotungstate/n-Bu₄NBr[J]. Green Chemistry, 2008, 10(11): 1218-1223.
9	Li J X, Yue C G, Ji W H, et al. Recent advances in cycloaddition of CO₂ with epoxides: halogen-free catalysis and mechanistic insights[J]. Frontiers of Chemical Science and Engineering, 2023, 17(12): 1879-1894.
10	Chen Y L, Xu P, Arai M, et al. Cycloaddition of carbon dioxide to epoxides for the synthesis of cyclic carbonates with a mixed catalyst of layered double hydroxide and tetrabutylammonium bromide at ambient temperature[J]. Advanced Synthesis & Catalysis, 2019, 361(2): 335-344.
11	Isaeva V I, Timofeeva M N, Lukoyanov I A, et al. Novel MOF catalysts based on calix[4]arene for the synthesis of propylene carbonate from propylene oxide and CO₂ [J]. Journal of CO₂ Utilization, 2022, 66: 102262.
12	Alassmy Y A, Pescarmona P P. The role of water revisited and enhanced: a sustainable catalytic system for the conversion of CO₂ into cyclic carbonates under mild conditions[J]. ChemSusChem, 2019, 12(16): 3856-3863.
13	Roy S, Das K, Halder S. Development of suitable hydrogen bond donor (HBD) catalysts for the synthesis of cyclic carbonates and dithiocarbonates from epoxide[J]. Catalysis Letters, 2023, 154: 2243-2254.
14	Liu X J, Yan P, Han Y. H₂O-polyaluminium chloride-TBAB as synergistic catalysts for the synthesis of cyclic carbonate[J]. IOP Conference Series: Materials Science and Engineering, 2018, 292: 012118.
15	Yue S, Qu H L, Song X X, et al. Novel hydroxyl-functionalized ionic liquids as efficient catalysts for the conversion of CO₂ into cyclic carbonates under metal/halogen/cocatalyst/solvent-free conditions[J]. New Journal of Chemistry, 2022, 46(12): 5881-5888.
16	Wen Q, Yuan X X, Zhou Q Q, et al. Functionalized β-cyclodextrins catalyzed environment-friendly cycloaddition of carbon dioxide and epoxides[J]. Materials, 2022, 16(1): 53.
17	Liang S G, Liu H Z, Jiang T, et al. Highly efficient synthesis of cyclic carbonates from CO₂ and epoxides over cellulose/KI[J]. Chemical Communications, 2011, 47(7): 2131-2133.
18	Emenike B U, Sevimler A, Farshadmand A, et al. Rationalizing hydrogen bond solvation with Kamlet-Taft LSER and molecular torsion balances[J]. Physical Chemistry Chemical Physics: PCCP, 2023, 25(27): 17808-17814.
19	Kim Y, Oh H. Comparison between multiple regression analysis, polynomial regression analysis, and an artificial neural network for tensile strength prediction of BFRP and GFRP[J]. Materials, 2021, 14(17): 4861.
20	Wang X Y, Rinaldi R. Solvent effects on the hydrogenolysis of diphenyl ether with Raney nickel and their implications for the conversion of lignin[J]. ChemSusChem, 2012, 5(8): 1455-1466.
21	Soares B, Cunha F, Silva I, et al. Sodium hexanoate and dodecanoate salt-based eutectic solvents: density, viscosity, and Kamlet-Taft parameters[J]. Journal of Chemical & Engineering Data, 2021, 66(7): 2793-2802.
22	Taft R W, Kamlet M J. The solvatochromic comparison method(2): The α-scale of solvent hydrogen-bond donor (HBD) acidities[J]. Journal of the American Chemical Society, 1976, 98(10): 2886-2894.
23	Weiß N, Schmidt C H, Thielemann G, et al. The physical significance of the Kamlet-Taft π* parameter of ionic liquids[J]. Physical Chemistry Chemical Physics, 2021, 23(2): 1616-1626.
24	Duereh A, Guo H X, Honma T, et al. Solvent polarity of cyclic ketone (cyclopentanone, cyclohexanone): alcohol (methanol, ethanol) renewable mixed-solvent systems for applications in pharmaceutical and chemical processing[J]. Industrial & Engineering Chemistry Research, 2018, 57(22): 7331-7344.
25	Rosés M, Ortega J, Bosch E. Variation of E T 30 polarity and the Kamlet-Taft solvatochromic parameters with composition in alcohol-alcohol mixtures[J]. Journal of Solution Chemistry, 1995, 24(1): 51-63.
26	Kamlet M J, Taft R W. The solvatochromic comparison method(Ⅰ): The β-scale of solvent hydrogen-bond acceptor (HBA) basicities[J]. Journal of the American Chemical Society, 1976, 98(2): 377-383.
27	Marcus Y. The properties of organic liquids that are relevant to their use as solvating solvents[J]. Chemical Society Reviews, 1993, 22(6): 409-416.
28	邹建卫, 俞庆森, 商志才. 醇类溶剂溶剂化显色极性的理论分析[J]. 化学学报, 2000, 58(10): 1247-1253.
	Zou J W, Yu Q S, Shang Z C. Theoretical analysis of solvatochromic polarity scales on alcoholic solvents[J]. Acta Chimica Sinica, 2000, 58(10): 1247-1253.
29	刘汉文, 胡彩玲. 醇类溶剂的溶剂化显色参数 E T N 的相关分析[J]. 湘潭大学自然科学学报, 2005, 27(3): 67-70.
	Liu H W, Hu C L. Relevant analysis of solvatochromic parameter on alcoholic solvents[J]. Natural Science Journal of Xiangtan University, 2005, 27(3): 67-70.
30	Laurence C, Mansour S, Vuluga D, et al. Theoretical, semiempirical, and experimental solvatochromic comparison methods for the construction of the α1 scale of hydrogen-bond donation of solvents[J]. The Journal of Organic Chemistry, 2022, 87(9): 6273-6287.
31	冯流, 韩朔睽, 王连生, 等. 苯系物Lewis酸碱性定量及其应用[J]. 环境化学, 1995, 14(5): 417-424.
	Feng L, Han S K, Wang L S, et al. A new quantiative parameter of the Lewis acidity and basicity of benzene and its derivatives[J]. Environmental Chemistry, 1995, 14(5): 417-424.
32	Brehmer T, Duong B, Boeker P, et al. Simulation of gas chromatographic separations and estimation of distribution-centric retention parameters using linear solvation energy relationships[J]. Journal of Chromatography A, 2024, 1717: 464665.
33	韩长日. 溶剂极性的E_T 经验参数及其应用[J]. 化学通报, 1985, 48(7): 40-43.
	Han C R. E_T empirical parameter of solvent polarity and its application[J]. Chemistry, 1985, 48(7): 40-43.
34	Liu M S, Wang X, Jiang Y C, et al. Hydrogen bond activation strategy for cyclic carbonates synthesis from epoxides and CO₂: current state-of-the art of catalyst development and reaction analysis[J]. Catalysis Reviews, 2019, 61(2): 214-269.

[1]	Ziyang LI, Nan ZHENG, Jiabin FANG, Jinjia WEI. Performance analysis and multi-objective optimization of recompression S-CO₂ Brayton cycle [J]. CIESC Journal, 2024, 75(6): 2143-2156.
[2]	Chenggong CHANG, Haonan SONG, Feixia LEI, Zichen DI, Fangqin CHENG. Study on the carbon reduction potential of blast furnace injection process using reformed coke oven gas [J]. CIESC Journal, 2024, 75(6): 2344-2352.
[3]	Fangtao JIANG, Gang QIAN, Xinggui ZHOU, Xuezhi DUAN, Jing ZHANG. Efficient synthesis of fluoroethylene carbonate via phase transfer catalysis using [bmim][BF₄] [J]. CIESC Journal, 2024, 75(4): 1543-1551.
[4]	Ruirui WANG, Ying JIN, Yumei LIU, Mengyue LI, Shengwen ZHU, Ruiyi YAN, Ruixia LIU. Study on design of polymeric ionic liquids and the performance for selective oxidation of cyclohexane [J]. CIESC Journal, 2024, 75(4): 1552-1564.
[5]	Jiaqi WANG, Haoqi WEI, Ajing GOU, Jiaxing LIU, Xinlin ZHOU, Kun GE. Study on the formation mechanism of CO₂ hydrate under the action of nanoparticles [J]. CIESC Journal, 2024, 75(3): 956-966.
[6]	Yongjun XIAO, Zhaochong SHI, Ren WAN, Fan SONG, Changjun PENG, Honglai LIU. Prediction of self-diffusion coefficients of ionic liquids using back-propagation neural networks [J]. CIESC Journal, 2024, 75(2): 429-438.
[7]	Rui SUN, Hua TIAN, Zirui WU, Xiaocun SUN, Gequn SHU. Study on the critical properties calculation models of CO₂-based binary mixture working fluid [J]. CIESC Journal, 2024, 75(2): 439-449.
[8]	Zhi ZHU, Hengjie XU, Wei CHEN, Wenyuan MAO, Qiangguo DENG, Xuejian SUN. Study on critical chocked characteristics of supercritical carbon dioxide spiral groove dry gas seal under thermal-fluid coupling lubrication [J]. CIESC Journal, 2024, 75(2): 604-615.
[9]	Zexin ZHANG, Weizhong ZHENG, Yisheng XU, Dongdong HU, Xinyu ZHUO, Yuan ZONG, Weizhen SUN, Ling ZHAO. Research progress of wafer cleaning and selective etching in supercritical carbon dioxide media [J]. CIESC Journal, 2024, 75(1): 110-119.
[10]	Ruitao SONG, Pai WANG, Yunpeng WANG, Minxia LI, Chaobin DANG, Zhenguo CHEN, Huan TONG, Jiaqi ZHOU. Numerical simulation of flow boiling heat transfer in pipe arrays of carbon dioxide direct evaporation ice field [J]. CIESC Journal, 2023, 74(S1): 96-103.
[11]	Yifei ZHANG, Fangchen LIU, Shuangxing ZHANG, Wenjing DU. Performance analysis of printed circuit heat exchanger for supercritical carbon dioxide [J]. CIESC Journal, 2023, 74(S1): 183-190.
[12]	Qi WANG, Bin ZHANG, Xiaoxin ZHANG, Hujian WU, Haitao ZHAN, Tao WANG. Synthesis of isoxepac and 2-ethylanthraquinone catalyzed by chloroaluminate-triethylamine ionic liquid/P₂O₅ [J]. CIESC Journal, 2023, 74(S1): 245-249.
[13]	Ruimin CHE, Wenqiu ZHENG, Xiaoyu WANG, Xin LI, Feng XU. Research progress on homogeneous processing of cellulose in ionic liquids [J]. CIESC Journal, 2023, 74(9): 3615-3627.
[14]	Zehao MI, Er HUA. DFT and COSMO-RS theoretical analysis of SO₂ absorption by polyamines type ionic liquids [J]. CIESC Journal, 2023, 74(9): 3681-3696.
[15]	Meisi CHEN, Weida CHEN, Xinyao LI, Shangyu LI, Youting WU, Feng ZHANG, Zhibing ZHANG. Advances in silicon-based ionic liquid microparticle enhanced gas capture and conversion [J]. CIESC Journal, 2023, 74(9): 3628-3639.

Synthesis of propylene carbonate from CO₂ and propylene oxide: hydrogen bond activation strategy

CO₂-环氧丙烷合成碳酸丙烯酯：氢键供体效应研究

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 8

References 34

Related Articles 15

Recommended Articles

Metrics

Comments