Reactivity of hydroxyls and stability of DBU/C3-alcohol/CO2 ionic compounds

doi:10.11949/j.issn.0438-1157.20150162

Abstract

Abstract:

The DBU/C₃-alcohol/CO₂ ionic compounds were synthesized by reacting the C₃-alcohols, namely 1-propanol, 2-propanol, 1,2-propanediol, 1,3-propanediol and glycerol with CO₂ and 1,8-diazabicycloundec-7-ene (DBU), respectively. The composition and structure of them were characterized by FT-IR, NMR and TG. The reactivity of the hydroxyls at different position in C₃-alcohol and the steric effect in polyols were studied. The results showed that the reactivity of the primary hydroxyl of 1-propanol was higher than the secondary hydroxyl of 2-propanol in the reaction of DBU+C₃-alcohol+CO₂. For the diols, the steric hindrance and the electronic effect significantly lowered the activity of the second hydroxyl, and such interaction in 1,2-diols was stronger than that of 1,3-diols. For the DBU+glycerol+CO₂ system, the main ionic compound was formed by reacting with only one of the primary hydroxyl in glycerol. The second most abundant product was formed by reacting both of the primary hydroxyls in glycerol. However, the complete conversion of all three hydroxyls seemed not possible due to the high steric hindrance effect.

Key words: ionic compounds, DBU, alcohol, CO₂, reactivity, stability

摘要：

利用红外光谱、核磁共振和热重分析表征了1,8-二氮杂环[5,4,0]十一烯-7(DBU)和CO₂分别与C₃-醇,即正丙醇、异丙醇、1,2-丙二醇、1,3-丙二醇和甘油,反应生成的离子化合物的组成和结构,研究了伯羟基和仲羟基与DBU和CO₂反应的活性,以及空间位阻对羟基反应活性和生成的离子化合物的热稳定性的影响。结果表明,DBU+C₃-醇+CO₂体系中伯羟基比仲羟基具有更高的反应活性,反应产物更稳定。由于空间位阻和电子效应等影响,二元醇中第2个羟基的反应活性远低于第1个羟基。在DBU+甘油+CO₂体系中由于空间位阻和电子效应的影响,当DBU和甘油的摩尔比为3:1时,其中1位羟基的转化率可达100%,3位羟基的转化率约为34%,而2位的仲羟基反应很少。

关键词: 离子化合物, DBU, 醇, CO₂, 活性, 稳定性

CLC Number:

TQ031.2

FU Lijuan, LIU Yingying, LU Houfang, TANG Siyang, LIANG Bin. Reactivity of hydroxyls and stability of DBU/C₃-alcohol/CO₂ ionic compounds[J]. CIESC Journal, 2015, 66(10): 4163-4169.

富丽娟, 刘颖颖, 鲁厚芳, 唐思扬, 梁斌. 醇羟基反应活性与DBU/C₃-醇/CO₂离子化合物稳定性[J]. 化工学报, 2015, 66(10): 4163-4169.

References 22

[1]	Jessop P G, Heldebrant D J, Wang X L, Eckert C A, Liotta C L. Green chemistry: reversible nonpolar-to-polar solvent [J]. Nature, 2005, 436 (7054): 1102.
[2]	Heldebrant D J, Jessop P G, Thomas C, Eckert C A, Liotta C L. The reaction of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) with carbon dioxide [J]. The Journal of Organic Chemistry, 2005, 70 (13): 5335-5338.
[3]	Boyd A R, Jessop P G, Dust J M, Buncel E. Switchable polarity solvent (SPS) systems: probing solvatoswitching with a spiropyran (SP)-merocyanine (MC) photoswitch [J]. Organic & Biomolecular Chemistry, 2013, 11: 6047-6055.
[4]	Phan L, Brown H, White J, Hodgson A, Jessop P G. Soybean oil extraction and separation using switchable or expanded solvents [J]. Green Chemistry, 2009, 11 (1):53-59.
[5]	Xue D L, Mu Y, Mao Y, Yang T K, Xiu Z L. Kinetics of DBU-catalyzed transesterification for biodiesel in the DBU-ethanol switchable-polarity solvent [J]. Green Chemistry, 2014, 16 (6): 3218.
[6]	Nowicki J, Muszyński M, Gryglewicz S. Novel basic ionic liquids from cyclic guanidines and amidines—new catalysts for transesterification of oleochemicals [J]. Journal of Chemical Technology and Biotechnology, 2014, 89 (1): 48-55.
[7]	Cao X F, Xie H B, Wu Z L, Shen H W, Jing B. Phase-switching homogeneous catalysis for clean production of biodiesel and glycerol from soybean and microbial lipids [J]. ChemCatChem., 2012, 4 (9): 1272-1278.
[8]	Munshi K M, Biradar S P, Gade M S, Rane H V, Kelkar A A. Efficient synthesis of glycerol carbonateglycidol using 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) based ionic liquids as catalyst [J]. RSC Advances, 2014, 4 (33): 17124-17128.
[9]	Feng Xiaoqing (冯筱晴), Shen Li (沈力), Wang Ruirui (王瑞瑞), Wang Yanchen (王彦臣), Song Guoqiang (宋国强). Synthesis and application of DBU [J]. Chemical Industry and Engineering Progress (化工进展), 2013, 32 (1): 174-179.
[10]	Jessop P G, Mercer S M, Heldebrant D J. CO2-triggered switchable solvents, surfactants, and other materials [J]. Energy & Environmental Science, 2012, 5 (6): 7240-7253.
[11]	Heldebrant D J, Yonker C R, Jessop P G, Phan L. Organic liquid CO2 capture agents with high gravimetric CO2 capacity [J]. Energy & Environmental Science, 2008, 1 (2): 487-493.
[12]	Taylor J E, Bull S D, Williams J M J. Amidines, isothioureas, and guanidines as nucleophilic catalysts [J]. Chemical Society Reviews, 2012, 41 (6): 2109-2121.
[13]	AtadashiI M, Aroua M K, Abdul Aziz A R, Sulaiman N M N. Refining technologies for the purification of crude biodiesel [J]. Applied Energy, 2011, 88 (12): 4239-4251.
[14]	Isahak W N R W, Ramli Z A C, Ismail M, Jahim J M, Yarmo M A. Recovery and purification of crude glycerol from vegetable oil transesterification [J]. Separation and Purification Reviews, 2014, 44 (3): 250-267.
[15]	Guo Yan (郭燕), Chen Fuming (陈福明), Jin Yong (金涌). Water washing technique in the alkaline-catalyzed production process of biodiesel [J]. China Oils and Fats, 2011, 36 (8): 66-69.
[16]	Phan L, Chiu D, Heldebrant D J, Huttenhower H, John E, Li X, Pollet P, Wang R, Eckert C A, Liotta C L, Jessop P G. Switchable solvents consisting of amidine/alcohol or guanidine/alcohol mixtures [J].Industrial & Engineering Chemistry Research, 2008, 47: 539-545.
[17]	Anugwom I, Mäki-Arvela P, Virtanen P, Willför S, Damlin P, Hedenström M, Mikkola J P. Treating birch wood with a switchable1,8-diazabicyclo-[5.4.0]-undec-7-ene-glycerol carbonate ionic liquid [J]. Holzforschung, 2012, 66 (7): 809 -815.
[18]	Anugwom I, Mäki-Arvela P, Virtanen P, Damlin P, Sjöholm R, Mikkola J P. Switchable ionic liquids (SILs) based on glycerol and acid gases [J]. RSC Advances, 2011, 1 (3): 452.
[19]	Vaidya P D, Kenig E Y. CO2-alkanolamine reaction kinetics: a review of recent studies [J]. Chemical Engineering & Technology, 2007, 30 (11): 1467-1474.
[20]	Mathias P M, Afshar K, Zheng F, Bearden M D, Freeman C J, Andrea T, Koech P K, Kutnyakov I, Zwoster A, Smith A R, Jessop P G, Nik O G, Heldebrant D J. Improving the regeneration of CO2-binding organic liquids with a polarity change [J]. Energy & Enrironmental Science, 2013, 6 (7): 2233-2242.
[21]	Ostonen A, Sapei E, Uusi-Kyyny P, Klemelä A, Alopaeus V. Measurements and modeling of CO2 solubility in 1,8-diazabicyclo-[5.4.0]-undec-7-ene—glycerol solutions [J]. Fluid Phase Equilibria, 2014, 374: 25-36.
[22]	Liu Yuxin (刘玉鑫), Wang Feng (王峰), Li Guilan (李桂兰), Yang Lixian (杨丽贤). Spectrum Analysis (波谱分析) [M]. Chengdu: Sichuan University Press, 2004: 210-213.

Reactivity of hydroxyls and stability of DBU/C₃-alcohol/CO₂ ionic compounds

醇羟基反应活性与DBU/C₃-醇/CO₂离子化合物稳定性

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