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第 36 卷第 1 期 精 细 化 工 Vol.36, No.1
201 9 年 1 月 FINE CHEMICALS Jan. 2019

催化与分离提纯技术
稀土金属有机骨架材料 Yb-BTC

催化合成聚碳酸酯二醇

王丽苹，赵粒成，张林艳

（曲靖师范学院 化学与环境科学学院，云南 曲靖 655011）

摘要：以 Yb(NO 3 ) 3 ·5H 2 O 和均苯三甲酸(H 3 BTC)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）、N 2 吸附-脱附技术和傅里叶变换红外光谱（FTIR）
2
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 m /g，孔径为 1.84 nm，颗
粒尺寸大小均一，粒径约为 2 μm。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。
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
中图分类号：TQ322.4+ 1 文献标识码：A 文章编号：1003-5214 (2019) 01-0088-07

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

WANG Li-ping, ZHAO Li-cheng, ZHANG Lin-yan
（College of Chemistry and Environmental Science, Qujing Normal University, Qujing 655011, Yunnan, China）

Abstract: A rare earth metal-organic framework Yb-BTC was prepared from Yb(NO 3) 3·5H 2O and
1,3,5-benzenetricarboxylic acid (H 3BTC) by the solvothermal method and characterized through X-ray
diffraction (XRD), scanning electron microscopy (SEM), N 2 absorption-desorption isotherm and Fourier
transform infrared spectroscopy (FTIR). The results showed that Yb-BTC was a typical microporous
2
material with a specific surface area of 560 m /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.
Key words: polycarbonate diol; rare earth metal-organic framework; Yb-BTC; catalysis technology
Foundation item: Applied Basic Research Project of Yunnan Province (2013FZ108)

收稿日期：2018-04-09; 定用日期：2018-08-21; DOI: 10.13550/j.jxhg.20180253
基金项目：云南省应用基础研究计划项目（2013FZ108）
作者简介：王丽苹（1982—），女，博士，副教授，E-mail：wanglp_csu@163.com。