CAJ | 학술논문

以1，4-丁二酸和1，4-丁二醇为原料，分别以SnCl2，异辛酸亚锡[Sn(Oct)2]，ZnCl2，乙酸锌[Zn(OAc)2]， Sb2O3和SO42-/ZrO2固体超强酸为催化剂，采用直接熔融缩聚法合成了聚丁二酸丁二酯(PBS)。通过测试酯化反应阶段的出液量、PBS的收率及其特性黏度、数均分子量和熔融温度等性质，比较了6种催化剂在PBS聚合反应中的催化效果。以SnCl2为例，利用傅立叶变换红外光谱和热重分析研究了由其催化合成的PBS的结构和热稳定性能。结果表明，实验合成的产物为羟基封端PBS；6种催化剂都能促进1，4-丁二酸和1，4-丁二醇分子间的脱水酯化反应，除Sn(Oct)2外，其它几种催化剂均能有效减少四氢呋喃副产物的生成；锡类化合物的催化效果总体上最好，其中SnCl2作催化剂时所合成的PBS的收率、特性黏度、数均分子量和熔融起始温度最高，其热分解温度为280℃。以PBS分子量为指标，6种催化剂的催化效果高低顺序为：SnCl2＞Sn(Oct)2＞Sb2O3＞SO42-/ZrO2＞ZnCl2＞Zn(OAc)2。
이1，4-정이산화1，4-정이순위원료，분별이SnCl2，이신산아석[Sn(Oct)2]，ZnCl2，을산자[Zn(OAc)2]， Sb2O3화SO42-/ZrO2고체초강산위최화제，채용직접용융축취법합성료취정이산정이지(PBS)。통과측시지화반응계단적출액량、PBS적수솔급기특성점도、수균분자량화용융온도등성질，비교료6충최화제재PBS취합반응중적최화효과。이SnCl2위례，이용부립협변환홍외광보화열중분석연구료유기최화합성적PBS적결구화열은정성능。결과표명，실험합성적산물위간기봉단PBS；6충최화제도능촉진1，4-정이산화1，4-정이순분자간적탈수지화반응，제Sn(Oct)2외，기타궤충최화제균능유효감소사경부남부산물적생성；석류화합물적최화효과총체상최호，기중SnCl2작최화제시소합성적PBS적수솔、특성점도、수균분자량화용융기시온도최고，기열분해온도위280℃。이PBS분자량위지표，6충최화제적최화효과고저순서위：SnCl2＞Sn(Oct)2＞Sb2O3＞SO42-/ZrO2＞ZnCl2＞Zn(OAc)2。
Poly(butylene succinate) (PBS) was synthesized respectively from 1,4-succinic acid and 1,4-butanediol using SnCl2,Sn(Oct)2,ZnCl2,Zn(OAc)2,Sb2O3 or SO42-/ZrO2 as catalyst by direct melt polycondensation method. The catalytic effects of the 6 kinds of catalysts in the polymerization reaction of PBS were compared by measuring liquid yield in the esterification reaction stage,yield and properties of PBS,such as intrinsic viscosity,molecular weight and melting temperature. Taking SnCl2 as example, the structure and thermal stability of PBS synthesized by SnCl2 were studied with FTIR and TG. The results show that the synthesized product is hydroxyl-capped PBS. The 6 kinds of catalysts all can promote dehydration esterification reaction of 1,4-succinic acid and 1,4-butanedio. Except for Sn(Oct)2,several other catalysts can effectively reduce the formation of tetrahydrofuran by-product. Overall,the catalytic effects of stannum compound are best among these catalyst and when SnCl2 is used as catalyst,the yield, intrinsic viscosity,number average molecular weight and original melting temperature of the synthesized PBS are best and it’s decomposition temperature is 280℃. Taking molecular weight of PBS as index,the order of the catalytic effects of the 6 catalysts is SnCl2>Sn(Oct)2>Sb2O3>SO42-/ZrO2>ZnCl2>Zn(OAc)2.