稀土金属有机骨架材料Yb-BTC催化合成聚碳酸酯二醇  

Synthesis of Polycarbonate Diol Catalyzed by Rare Earth Metal-Organic Framework Yb-BTC

作　　者：王丽苹 赵粒成 张林艳 WANG Li-ping;ZHAO Li-cheng;ZHANG Lin-yan(College of Chemistry and Environmental Science,Qujing Normal University,Qujing 655011,Yunnan,China)

机构地区：[1]曲靖师范学院化学与环境科学学院,云南曲靖655011

出　　处：《精细化工》2019年第1期88-93,100,共7页Fine Chemicals

基　　金：云南省应用基础研究计划项目(2013FZ108)~~

摘　　要：以Yb(NO3)3·5H2O和均苯三甲酸(H3BTC)为原料,采用溶剂热法构筑了一种稀土金属有机骨架材料Yb-BTC。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、N2吸附-脱附技术和傅里叶变换红外光谱(FTIR)对其结构进行了表征。结果显示,Yb-BTC是一种典型的微孔材料,比表面积为560 m2/g,孔径为1.84 nm,颗粒尺寸大小均一,粒径约为2μm。考察了Yb-BTC在碳酸二苯酯(DPC)与1,5-戊二醇(PDO)酯交换制备聚碳酸酯二醇(PCDL)反应中的催化性能,并与三乙胺、醋酸锌、钛酸四丁酯和乙酰丙酮氧钛4种催化剂进行了比较。结果表明,Yb-BTC的催化活性与钛系催化剂活性相当。当PDO与DPC的物质的量比为1.2,Yb-BTC用量为0.05%(以DPC质量为基准,下同),180～185℃下常压酯交换反应2 h,160℃下减压缩聚4 h,获得数均相对分子质量为2300,羟值为49.3 mg KOH/g的PCDL。A rare earth metal-organic framework Yb-BTC was prepared from Yb(NO3)3·5 H2 O and 1,3,5-benzenetricarboxylic acid(H3 BTC) by the solvothermal method and characterized through X-ray diffraction(XRD),scanning electron microscopy(SEM),N2 absorption-desorption isotherm and Fourier transform infrared spectroscopy(FTIR).The results showed that Yb-BTC was a typical microporous material with a specific surface area of 560 m2/g and pore size of 1.84 nm,and Yb-BTC had uniform particle size,its size was about 2 μm.The catalytic activity of Yb-BTC for the preparation of polycarnonate diol(PCDL) via the transesterification between diphenyl carbonate(DPC) and 1,5-pentanediol(PDO) was investigated,and compared with that of catalysts reported such as triethylamine,zinc acetate,tetra-n-butyl titanate and titanium oxide bis(2,4-pentanedionate).The results exhibited that the catalytic activity of Yb-BTC was equivalent to that of titanium series catalysts.When the molar ratio of PDO to DPC was 1.2,the amount of Yb-BTC was 0.05%(the amount accounting for mass percent of DPC,as the below),the time of atmospheric transesterification at 180~185 ℃ was 2 h,the time of vacuum polycondensation at 160 ℃was 4 h,PCDL with a number-average relative molecular mass of 2300 and a hydroxyl value of 49.3 mg KOH/g was obtained.

关 键 词：聚碳酸酯二醇 稀土金属有机骨架材料 Yb-BTC 催化技术 

分 类 号：TQ322.41[化学工程—合成树脂塑料工业]