摘要
以环三磷腈碱(CTPB)为催化剂,以苄醇(BnOH)为引发剂,实现了ω-十五内酯(PDL)的高效可控开环聚合.通过优化实验条件,得到了高分子量的聚ω-十五内酯(PPDL).示差扫描量热法(DSC)表征证明了PPDL聚酯材料较好的结晶性.高分子量的PPDL不仅有与聚乙烯相似的力学性质、结晶性和高熔点(T_(m)=95.5℃),而且还具有聚酯类材料的降解性.合成了PDL与ε-己内酯(ε-CL)的无规共聚物,证明可以通过改变ε-CL的含量实现共聚物的熔点、力学性质和降解性可控调节.进一步通过双官能团引发剂合成中低分子量的双羟基端PPDL,证明可以通过与二异氰酸酯进行扩链反应制备高分子量PPDL(PPDL-E),力学性能能够得到有效提升.最后在碱性条件下实现了PPDL共聚酯的水解,验证了PPDL及其与ε-CL共聚物的水解性能.
This study reported that an efficient and controllable ring-opening polymerization of ω‑pentadecalactone(PDL)by using cyclic trimeric phosphazene base(CTPB)as a catalyst and benzyl alcohol(BnOH)as an initiator.High molecular weight PPDL was obtained after optimizing the experimental conditions.The PPDL film with high molecular weight not only showed similar mechanical properties,crystallinity and high melting point(T_(m)=95.5℃)as polyethylene,but also exhibited the degradability of aliphatic polyesters.Differential scanning calorimetry(DSC)tests proved that PPDL had good crystallinity.Wide-angle X-ray scattering(WAXS)showed that PPDL had a unit cell structure similar to that of commercial high-density polyethylene(HDPE).Moreover,bishydroxylend-capped PPDL(PPDL-diol)can be easily prepared via ring opening polymerization(ROP)of PDL with 1,4-benzenedimethanol(BDM)as initiator.Then the PPDLs with high molecular weights were obtained by chain extension reactions with diisocyanates and showed enhanced mechanical properties.In addition,we synthesized a variety of random copolymers with different ratios of PDL toε-caprolactone(ε-CL).The melting points and hydrolysis of the copolymers could be adjusted by changing the ratio ofε-CL.The melting points of the obtained random copolymers could be adjusted in the range of 53.0-95.5℃ by changing the ratio ofε-CL.Finally,the hydrolysis of PPDL copolyester was achieved under alkaline conditions.Compared with PPDL homopolymer,the hydrolysis of random copolymers showed faster hydrolysis rate and adjustability.
作者
黄炳政
韩瑞
李峥
李志波
Bing-zheng Huang;Rui Han;Zheng Li;Zhi-bo Li(College of Chemical Engineering,Qingdao University of Science and Technology,Qingdao 266042;College of Polymer Science and Engineering,Qingdao University of Science and Technology,Qingdao 266042)
出处
《高分子学报》
SCIE
CAS
CSCD
北大核心
2024年第8期976-985,共10页
Acta Polymerica Sinica
基金
国家自然科学基金(基金号22031005)资助项目.
关键词
开环聚合
有机碱
类聚乙烯高分子
可降解聚酯
Ring-opening polymerization
Organobase
Polyethylene-like polymers
Degradable polyester
