Ti-Al双金属催化剂制备PEIT共聚酯及其热性能  

Preparation and thermal properties of poly (ethylene terephthalate-co-isosorbide terephthalate) with a novel Ti-Al catalyst

作　　者：谢尚栋 孙黎江 朱开阳 陈世昌[1] 陈文兴[1] XIE Shangdong;SUN Lijiang;ZHU Kaiyang;CHEN Shichang;CHEN Wenxing(National&Local United Engineering Laboratory on Textile Fiber Materials and Processing Technology,Zhejiang Sci-Tech University,Hangzhou 310018,China)

机构地区：[1]浙江理工大学纺织纤维材料与加工技术国家地方联合工程实验室,杭州310018

出　　处：《现代纺织技术》2022年第5期89-96,103,共9页Advanced Textile Technology

基　　金：浙江省重点研发计划项目(2021C01020)。

摘　　要：为了提高PET的玻璃化转变温度(T_(g)),拓宽PET的应用领域,以生物基异山梨醇(ISB)作为第三单体,使用自制Ti-Al双金属配位催化剂,通过直接酯化法制备了聚对苯二甲酸乙二醇-co-对苯二甲酸异山梨醇酯(PEIT)共聚酯。利用核磁共振仪、傅里叶红外光谱仪、差示扫描量热仪、热重分析仪等表征了共聚酯的结构和热性能。结果表明:自制催化剂对于ISB具有较好的催化活性,在加入15%以内ISB时其反应率可达90%,可快速得到特性黏度约为0.65 dL/g左右的共聚酯产物。共聚酯经液相增黏反应1.5 h后其特性黏度上升至约为1.20 dL/g,说明钛系催化剂制备的共聚酯在熔融缩聚时的链增长能力强。合成时提高ISB比例会使共聚酯的特性黏度降低,结晶温度(T_(c))上升,熔点(T_(m))下降。玻璃化转变温度(T_(g))与加入的ISB含量成正相关,当ISB加入量达到20%时,共聚酯的T_(g)达到94.7℃,并拟合得出T_(g)和ISB含量相关计算公式。而ISB加入量超过15%时聚合物开始转变为无定型聚合物,但对其热分解性能没有显著影响。In order to increase the glass transition temperature(T_(g))of polyethylene terephthalate(PET)and broaden the application field of PET,poly(ethylene terephthalate-co-isosorbide terephthalate)(PEIT)was prepared by direct esterification with bio-based isosorbide(ISB)as the third monomer and self-made Ti-Al bimetallic coordination compound as catalyst.The structure and thermal properties of the copolyester were characterized by nuclear magnetic resonance,Fourier transform infrared spectrometer,differential scanning calorimeter,and thermogravimetric analyzer.The results show that the self-made catalyst has good catalytic activity for ISB.When adding less than 15%of ISB,the reaction rate can reach 90%,and the copolyester product with an intrinsic viscosity of about 0.65 dL/g can be quickly obtained.The intrinsic viscosity of the copolyester increased to about 1.20 dL/g after 1.5 h of melting post polycondensation,which indicates that the copolyester prepared by the titanium-based catalyst has strong chain growth ability during melt polycondensation.Increasing the proportion of ISB in the synthesis will reduce the intrinsic viscosity of the copolyester,but the crystallization temperature(T_(c))of the copolyester will increase and the melting point(T_(m))will decrease.There is a positive correlation between glass transition temperature(T_(g))and the added ISB content.When the amount of ISB added reaches 20%,the T_(g) of the copolyester reaches 94.7℃,and the correlation calculation formula of T_(g) and ISB content is obtained by fitting.However,when the amount of ISB exceeds 15%,the polymer begins to transform into an amorphous polymer,but its thermal decomposition performance is not significantly affected.

关 键 词：共聚酯 异山梨醇 钛系催化剂 玻璃化转变温度 

分 类 号：TQ317[化学工程—高聚物工业]