烷基磷酸铝催化己内酯与环氧烷烃共聚合研究  

Alkyl aluminum phosphate-catalyzed copolymerization of caprolactone and epoxides

作　　者：陈首龙 李璠 郭方 Chen Shoulong;Li Fan;Guo Fang(School of Chemical Engineering,Dalian University of Technology,Dalian 116024,China)

机构地区：[1]大连理工大学化工学院,辽宁大连116024

出　　处：《合成树脂及塑料》2023年第5期1-6,共6页China Synthetic Resin and Plastics

摘　　要：研究了三异丁基铝(i-Bu_(3)Al)/H_(3)PO_(4)/1,8-二氮杂二环十一碳-7-烯(DBU)催化剂催化环氧烷烃[包括环氧乙烷(EO)、环氧氯丙烷(ECH)、环氧丙烷(PO)]与己内酯(CL)共聚合的性能,通过共聚合动力学、核磁共振波谱、凝胶渗透色谱和差示扫描量热法对所制共聚物的微观结构和热性能进行分析。结果表明:在室温甲苯溶剂中,i-Bu_(3)Al/H_(3)PO_(4)/DBU催化剂可以高效催化环氧烷烃与CL共聚合,制备的EO-CL共聚物、ECH-CL共聚物、PO-CL共聚物的收率均达99%以上。三种共聚物均为高相对分子质量、窄分布的聚合物,改变环氧烷烃和CL与i-Bu_(3)Al的比例可以调控共聚物的相对分子质量。不同组成的EO-CL共聚物的熔点在60℃左右;ECH-CL共聚物和PO-CL共聚物中,CL摩尔分数在30%以上,共聚物熔点在55℃左右。EO与CL共聚合时,EO的竞聚率为12.87±0.57,CL的竞聚率(r_(CL))为0.11±0.02;ECH与CL共聚合时,ECH的竞聚率为8.53±0.15,r_(CL)为0.13±0.01;PO与CL共聚合时,PO的竞聚率为2.08±0.20,r_(CL)为0.59±0.08。EO-CL共聚物为楔形共聚物,ECH-CL共聚物为梯度共聚物,PO-CL共聚物为无规共聚物。The copolymerization of epoxides[including ethylene oxide(EO),epichlorohydrin(ECH),propylene oxide(PO)]and caprolactone(CL)catalyzed by triisobutylaluminum(i-Bu_(3)Al)/H_(3)PO_(4)/1,8-diazabicyclo[5.4.0]undecane-7-ene(DBU)was investigated.The microstructures and thermal properties of the obtained copolymers were characterized by nuclear magnetic resonance spectrometry,gel permeation chromatography,differential scanning calorimetry and copolymerization kinetics.The results show that copolymerization of epoxides and CL has been successfully achieved at room temperature in toluene to obtain EO-CL,ECH-CL,PO-CL copolymers with controllable 99%of yields by i-Bu_(3)Al/H_(3)PO_(4)/DBU.The copolymers with high molecular mass and narrow distribution are obtained,and whose molecular mass can be adjusted by changing the molar ratio of epoxides,CL to i-Bu_(3)Al.The melting points of EO-CL copolymers with different compositions are about 60℃.The melting points of ECH-CL and PO-CL copolymers are 55℃when the molar fraction of CL in the copolymers is higher than 30%.Reactivity ratios of three copolymerization are as follows:rEO=12.87±0.57,r_(CL)=0.11±0.02;rECH=8.53±0.15,r_(CL)=0.13±0.01;rPO=2.08±0.20,r_(CL)=0.59±0.08,indicating that the obtained EO-CL,ECH-CL,PO-CL copolymers were copolymers with tapered,gradient and random structure.

关 键 词：己内酯 环氧烷烃 聚醚-聚酯 共聚合 熔点 竞聚率 

分 类 号：TQ326.5[化学工程—合成树脂塑料工业]