耐水解钛系催化剂在生物可降解共聚酯PBAT中的应用  

Application of hydrolysis-resistant titanium catalysts in biodegradable copolyester PBAT

作　　者：况军 李应成 周文乐 熊金根 KUANG Jun;LI Yingcheng;ZHOU Wenle;XIONG Jingen(Sinopec Shanghai Research Institute of Petrochemical Technology Co.,Ltd.,Shanghai 201208,China)

机构地区：[1]中石化(上海)石油化工研究院有限公司,上海201208

出　　处：《工程塑料应用》2024年第11期26-34,44,共10页Engineering Plastics Application

摘　　要：通过与钛酸四丁酯(TBT)对比,详细考察了耐水解钛系催化剂(HRTiC)的耐水解性能、催化活性以及对所得聚对苯二甲酸-己二酸丁二酯(PBAT)性能的影响。水解试验表明HRTiC具有良好的耐水解性能,能够稳定分散在常温及高温水/丁二醇溶液中;聚合实验显示该催化剂酯化活性在催化剂用量为100μg/g及以上时与TBT相当或略高,缩聚活性在催化剂用量为80~120μg/g的范围内,均显著高于TBT催化剂;进一步配合磷酸酯稳定剂,所制得PBAT特性黏度高于且颜色优于TBT制备的PBAT样品,显示出HRTiC优异的催化性能。进一步通过气相色谱、核磁共振及差示扫描量热等考察了HRTiC对缩聚液组成、PBAT结构以及基础性能的影响。结果显示,HRTiC所得缩聚液组成与TBT所得缩聚液组成一致,但杂质含量更低,这将有利于1,4-丁二醇的回用;所得PBAT结构与TBT所得PBAT结构一致,均为无规共聚物,但己二酸含量略高、己二酸酯单元序列长度也略长;在性能方面,HRTiC所得PBAT结晶温度略低,熔点及热分解温度则相当;拉伸强度和断裂伸长率分别为21.3 MPa和993%,优于TBT所制PBAT,显示出该催化剂良好的应用性能。The hydrolysis resistance,catalytic activity,and impact on the performance of the obtained poly(butylene adipate terephthalate)(PBAT)were thoroughly examined by comparing the homemade hydrolysis resistant titanium catalyst(HRTiC)with tetrabutyl titanate(TBT).The hydrolysis test reveal that HRTiC exhibits excellent hydrolysis resistance and can be stably dispersed in water/butanediol solutions at room and high temperatures.The polymerization experiment reveal that the catalyst's esterification activity is equal to or slightly higher than that of TBT when the catalyst dosage is 100μg/g or higher.Additionally,the condensation activity is significantly greater than that of TBT catalyst within the catalyst dosage range of 80-120μg/g.By combining with phosphate stabilizers,PBAT samples with higher intrinsic viscosity and better color than those prepared by TBT can be obtained,demonstrating the excellent catalytic performance of HRTiC.Further investigation was conducted on the effects of HRTiC on the composition of the condensation solution,PBAT structure,and basic properties by using gas chromatography,nuclear magnetic resonance,differential scanning calorimetry,etc.The results indicate that the composition of the condensation solution obtained through HRTiC is similar to that obtained through TBT.However,the impurity content is lower,which would be beneficial for the reuse of 1,4-butanediol.The resulting PBAT structure is consistent with PBAT structure obtained from TBT,both of which are random copolymers.However,the content of adipic acid is slightly higher and the length of adipic acid ester unit sequence is also slightly longer.In terms of performance,the melt crystallization temperature of PBAT obtained from HRTiC is slightly lower,while the melting point and thermal decomposition temperature are comparable.The tensile strength and elongation at break are 21.3 MPa and 993%,respectively,which are better than the PBAT prepared by TBT,demonstrating the excellent application performance of the catalyst.

关 键 词：聚对苯二甲酸-己二酸丁二酯 催化剂 耐水解 聚合活性 聚酯性能 

分 类 号：TQ322.4[化学工程—合成树脂塑料工业]