Zn-MOFs催化合成聚丁二酸乙二醇酯和碳酸二甲酯的研究  

Simultaneous Synthesis of Poly( ethylene succinate) and Dimethyl Carbonate Using Zn-MOFs as Catalysts

作　　者：唐文强[1,2] 刘绍英[1,3] 欧阳春[1,3] 姜伟[1,3] 王公应[1,3] 

机构地区：[1]中国科学院成都有机化学研究所 [2]中国科学院大学,北京100049 [3]中国科学院成都有机化学有限公司,成都610041

出　　处：《高分子学报》2016年第5期628-636,共9页Acta Polymerica Sinica

基　　金：十二五国家科技支撑计划课题(项目号2013BAC11B05);四川省青年科技创新团队项目(项目号2013TD0010);成都市创新创业团队项目(项目号成组通(2015)2号)资助

摘　　要：采用溶剂热法和直接混合法合成了3种金属有机骨架材料(Zn-MOFs),研究了其在碳酸乙烯酯(EC)与丁二酸二甲酯(DMSu)耦合反应制聚丁二酸乙二醇酯(PES)和碳酸二甲酯(DMC)反应中的催化性能,并对工艺条件进行了考察.采用X射线粉末衍射法(XRD),扫描电子显微镜(SEM),傅里叶转化红外光谱法(FTIR)和原子发射光谱法(ICP-AES)对Zn-MOFs进行了表征,对聚合物PES进行了FTIR和核磁共振(~1HNMR和^(13)C-NMR)测试.结果表明,既具有MOF-5结构,又含有较多Zn O的纳米Zn-MOF-L催化活性最好.在Zn-MOF-L催化下,最优反应条件如下:预缩聚反应温度215℃,预缩聚反应时间4 h,缩聚反应温度220℃,缩聚压力小于300 Pa,n(EC)/n(DMSu)=2,催化剂用量为1 wt%.最优反应条件下,DMC的收率可达到65.08%,PES的特性黏数[η]可达到0.572 d L/g,数均相对分子质量M_n为2.1×104,相对分子质量分布PDI为2.21.Three Zn-MOFs have been synthesized via solvothermal and direct mixing methods separately,and then the Zn-MOFs were used as catalysts for the synthesis of poly（ ethylene succinate）（ PES） and dimethyl carbonate（ DMC） by the coupling reaction of ethylene carbonate（ EC） and dimethyl succinate（ DMSu）. The Zn-MOFs were characterized using a variety of different techniques,including X-ray powder diffraction（ XRD）,scanning electron microscopy（ SEM）,Fourier transform infrared spectroscopy（ FTIR）,atomic emission spectrophotometry（ AES） and others,PES was characterized by FTIR and ~1H-NMR. The results showed that the Zn-MOF-L had the best catalytic activity. The MOF-5 and ZnO particles present in the MOF-L-300 contribute to the overall catalytic activity. The optimum conditions of the reaction were as follows： the reaction time,reaction temperature,n（ EC） / n（ DMSu） and the catalyst dosage were 4 h,215 ℃,2 and 1 wt%（ N2protection）,respectively,in the standard atmosphere pre-polymerization step. The reaction time,reaction pressure and reaction temperature were 2 h,300 Pa and 220 ℃,respectively,in the vacuum condensation step. Under these conditions,the yield of DMC was 65. 08%,the intrinsic viscosity [η] of PES was0. 572 d L / g,the Mnof PES was 21000 and the polydispersity index of PES was 2. 21.

关 键 词：金属有机骨架材料 碳酸乙烯酯 丁二酸二甲酯 碳酸二甲酯 聚丁二酸乙二醇酯 

分 类 号：O643.36[理学—物理化学] O631.5[理学—化学]