液态聚碳酸酯二醇的合成及工艺  

Synthesis and Processes of Liquid Polycarbonate Diol

作　　者：黄华莹 徐启奎 傅利才 罗彦凤[2] 蒋弟勇 李浩 潘永柯 王光辉 HUANG Huaying;XU Qikui;FU Licai;LUO Yanfeng;JIANG Diyong;LI Hao;PAN Yongke;WANG Guanghui(Sichuan Lutianhua Innovation Research Institute Co.,Ltd.,Luzhou 646300,China;Bioengineering College,Chongqing University,Chongqing 400000,China)

机构地区：[1]四川泸天化创新研究院有限公司,四川泸州646300 [2]重庆大学生物工程学院,重庆400000

出　　处：《塑料工业》2024年第12期23-29,共7页China Plastics Industry

基　　金：泸州市科技计划项目(2022-JYJ-102)。

摘　　要：为了获得一种聚碳酸酯二醇(PCDL)高效合成工艺,本文以1,4-丁二醇(BDO)、1,6-己二醇(HDO)和碳酸二甲酯(DMC)为原料,钛酸四丁酯(TBOT)为催化剂,采用酯交换法制备了共聚型聚碳酸酯二醇(PCDL-BH)。研究了催化剂用量、反应温度、反应时间对PCDL-BH合成的影响,对产物进行了羟值、核磁共振氢谱(^(1)H NMR)、傅里叶变换红外光谱(FTIR)、凝胶渗透色谱(GPC)、差示扫描量热仪(DSC)和黏度检测。研究结果表明,催化剂用量为二醇质量的0.04%~0.08%时,随着催化剂用量的增加,PCDL-BH羟值测试下的数均分子量(M_(n,羟值))增大,当催化剂用量超过二醇质量的0.08%后,继续增加催化剂用量对PCDL-BH的M_(M_(n,羟值))影响不大。随着常压反应温度(120~150℃)和减压反应温度(170~200℃)的提高,PCDL-BH的M_(n,羟值)逐渐增加。随着减压反应时间由1 h增加到3 h,PCDL-BH的M_(n,羟值)显著增加。在催化剂用量为二醇质量的0.08%,常压反应温度150℃,减压反应温度200℃,减压反应时间2 h的工艺条件下,高效地制备出了M_(n,羟值)约2000的羟基封端的液态PCDL-BH。PCDL-BH的玻璃化转变温度(T g)为-71.5℃,可用于制备柔性聚氨酯或聚氨酯弹性体。To obtain an efficient synthesis process for polycarbonate diol(PCDL),this study used 1,4-butanediol(BDO),1,6-hexanediol(HDO)and dimethyl carbonate(DMC)as raw materials and tetrabutyl titanate(TBOT)as a catalyst to prepare a copolycarbonate diol(PCDL-BH)by a transesterification method.The effects of the catalyst dosages,reaction temperatures,and reaction time on the synthesis of PCDL-BH were studied.The products were characterized by proton nuclear magnetic spectroscopy(^(1)H NMR),Fourier infrared spectroscopy(FTIR),gel permeation chromatography(GPC),differential scanning calorimetry(DSC)and determination of hydroxyl value and viscosity.The experiment results show that when the catalyst dosage is between 0.04%and 0.08%of the diol mass,the number-average molecular weight(M_(n,hydroxyl value))calculated from hydroxyl value tests of PCDL-BH increases with the increase content of catalyst dosage.When the catalyst content exceeds 0.08%of the diol mass,increasing the catalyst dosage has little effect on n,hydroxyl value of PCDL-BH.As the atmospheric reaction temperature(120~150℃)and decompression reaction temperature(170~200℃)increase,the M_(n,hydroxyl value)value of PCDL-BH gradually increases.With the decompression reaction time increases from 1 h to 3 h,the M_(n,hydroxyl value)value of PCDL-BH significantly increases.Under the conditions of TBOT content accounting for 0.08%of the diol mass,atmospheric reaction temperature at 150℃,decompression reaction temperature at 200℃,and decompression reaction time for 2 h,the hydroxy-terminated liquid PCDL-BH with a M_(n,hydroxyl value)value of about 2000 is efficiently prepared.The glass transition temperature(T g)of PCDL-BH is-71.5℃,which could be used to prepare flexible polyurethane and polyurethane elastomers.

关 键 词：1 4-丁二醇 1 6-己二醇 聚碳酸酯二醇 酯交换反应 

分 类 号：TQ320.61[化学工程—合成树脂塑料工业]