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离子液体催化合成碳酸二苯酯
王星星
Thesis Advisor成卫国
2017-01
Degree Grantor中国科学院研究生院
Degree Name硕士
Degree Discipline化学工程
Keyword碳酸二苯酯,酯交换,二氧化碳,离子液体
Abstract

碳酸二苯酯(DPC)是酯交换法合成聚碳酸酯的重要原料。传统的光气制备法由于使用剧毒的光气而将被淘汰,本文研究了更加绿色环保的酯交换法和二氧化碳制备法。合成了四甲基胍类离子液体,测定了碱性强度([TMG]Cl<[TMG][BA]<[TMG][Ac]<[TMG][Phe]<[TMG][Im]<[TMG][TFE]),并催化碳酸二甲酯(DMC)与苯酚(phenol)合成碳酸二苯酯的反应。在160–180 °C的温度范围内,反应8 h,苯酚的转化率小于4.0%,碳酸二苯酯收率不高于0.5%。将四甲基胍类离子液体应用到碳酸二甲酯与甘油(GL)酯交换的反应中,在80 °C、[TMG][TFE]用量为0.1 mol%、反应30 min的条件下,转化频率(TOF值)高达1754.0 h-1,苯酚的转化率、产物的选择性分别为91.8%、95.5%,并提出了该反应中阴离子活化甘油,阳离子活化碳酸二甲酯的协同催化机理。基于Beson基团贡献法估算了碳酸二苯酯的热力学参数,计算了在CCl4溶剂中二氧化碳与苯酚反应生成碳酸二苯酯的反应焓变,吉布斯自由能变和反应平衡常数。结果表明,在100–200 °C、4 MPa的条件下,该反应是个吸热反应且向正方向自发进行的趋势明显。以叔铵盐-氯化锌类离子液体为催化剂,研究了阳离子中碳链长度,离子液体组分比例对催化活性的影响,Pr3NHCl·2ZnCl2的催化性能最好。对反应条件进行了优化,在4 MPa、150 °C、8 h的条件下,以Pr3NHCl·2ZnCl2为催化剂,苯酚的转化率和碳酸二苯酯的收率分别为66.0%和18.5%。 ;Diphenyl carbonate is an important raw material for the production of polycarbonate, and its traditional synthetic route suffers from the high toxicity of phosgene which would be eliminated in the future. The greener and more environmental friendly routes, transesterification route and CO2 route, were investigated in this paper.The guanidine-based ionic liquids were synthesized, and the bascity strength tuned by adjusting the anion was determined ([TMG]Cl<[TMG][BA]<[TMG][Ac]<[TMG][Phe]<[TMG][Im]<[TMG][TFE]). The catalytic activities were tested for the transeterification between the dimethyl carbonate and phenol, the conversion of phenol was less than 4.0% and the yield of diphenyl carbonate was no more than 0.5% under the condition of 160–180 °C, 8 h and 1 mol% catalyst. The ionic liquids were also applied to the reaction between the dimethyl carbonate and glycerol. Under the optimized reaction conditions: 80 °C, catalyst amout of 0.1 mol%, reaction time of 30 min, the TOF could reach 1754.0 h-1 (91.8% of phenol conversion and 95.5% of glycerol carbonate) and the anion-cation synergistic catalytic mechanism was proposed.The thermodynamic data of DPC was calculated based on the Beson group contribution method and the thermodynamic analysis such as enthalpy change,Gibbs free energy change and equilibrium constant of the reaction between the CO2 and phenol in presence of CCl4 was carried out. It turned out that it was an endothermic reaction and spontaneous to occur under the condition of 100–200 °C,4 MPa. A series of ionic liquids, especially the tertiary amine based ionic liquid, were synthesized and screened as the catalysts. The effect of carbon chain length and the ratio between the tertiary amine salt and zinc chloride in the ionic liquids were investigated. The tripropylamine hydrochloride contained ionic liquid showed the best performance when the ratio between tripropylamine hydrochloride and zinc chloride was 1: 2. The reaction conditions such as pressure, temperature and reaction time were also optimized. At 4 MPa, 150 °C, 8 h, the phenol conversion and diphenyl carbonate yield were 66.0% and 28.0%, respectively. 

Language中文
Document Type学位论文
Identifierhttp://ir.ipe.ac.cn/handle/122111/26842
Collection中国科学院过程工程研究所
研究所(批量导入)
Recommended Citation
GB/T 7714
王星星. 离子液体催化合成碳酸二苯酯[D]. 中国科学院研究生院,2017.
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