CIESC Journal ›› 2015, Vol. 66 ›› Issue (10): 4163-4169.DOI: 10.11949/j.issn.0438-1157.20150162

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

FU Lijuan1,2, LIU Yingying2, LU Houfang1,2, TANG Siyang1, LIANG Bin1,2   

  1. 1 College of Chemical Engineering, Sichuan University, Chengdu 610065, Sichuan, China;
    2 New Energy and Low-carbon Technology Research Institution, Sichuan University, Chengdu 610065, Sichuan, China
  • Received:2015-02-02 Revised:2015-05-26 Online:2015-10-05 Published:2015-10-05
  • Supported by:

    supported by the National Natural Science Foundation of China (21476150) and the Doctoral Fund of Ministry of Education of China (20130181130006).

醇羟基反应活性与DBU/C3-醇/CO2离子化合物稳定性

富丽娟1,2, 刘颖颖2, 鲁厚芳1,2, 唐思扬1, 梁斌1,2   

  1. 1 四川大学化工学院, 四川 成都 610065;
    2 四川大学新能源与低碳技术研究院, 四川 成都 610065
  • 通讯作者: 刘颖颖
  • 基金资助:

    国家自然科学基金面上项目(21476150);教育部博士点基金优先发展领域课题(20130181130006)。

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: