摘要
设计、合成了一种新型异核双金属配合物,用于催化环氧环己烷(CHO)和邻苯二甲酸酐(PA)的共聚反应,以制备聚(醚-酯)材料.分别通过核磁共振波谱和电喷雾质谱对聚合物及其水解后产物结构进行分析,证明所得共聚物为醚酯单元呈无规分布的聚(醚-酯).重点考察了配体结构、金属离子、反应温度和催化剂浓度对聚合反应的影响.最后,对所得聚(醚-酯)无规共聚物热性能进行研究,表明聚醚链段的引入可以调变其玻璃化转变温度,丰富了此类聚酯材料的应用场景.
The ring-opening copolymerization of epoxides and cyclic anhydrides constitutes a straightforward route for synthesizing polyesters.The resultant copolymers are mainly obtained with alternating structures,which might limit their application situations due to their low toughness caused by the high density of ester group.It has been demonstrated that the incorporation of ether segments into the mainchain of polyesters is an efficient strategy to tune the thermal and mechanical properties of polyesters,which is greatly limited by the lack of efficient catalyst.In response to these issues,this study proposed to achieve the random copolymerization of cyclohexene oxide(CHO)and phthalic anhydride(PA)to prepare poly(ether-ester)s via the hetero-bimetallic synergistic catalysis strategy.A series of heterodinuclear Al-K complex has been designed for catalyzing the copolymerization of CHO and PA.The structures of the resultant copolymers are confirmed as poly(ether-ester)s using nuclear magnetic resonance spectroscopy and electrospray ionization mass spectrometry.The exploration of the polymerization process further revealed the randomly structure of obtained poly(ether-ester)s,that is,ester and ether segments were randomly distributed in the polymer mainchain.Systemic studies on the effects of ligand structure,metal ions,reaction temperature and catalyst concentration on the copolymerization were explored,indicating that it is the synergistic cooperation between two metal centers that results in the formation of random copolymers.In addition,thermal property characterization of resultant copolymers indicates that the incorporation of polyether segments into polyester could effectively tune their glass transition temperatures,thus enriching the application of polyester materials.
作者
胥洋洋
乐天俊
赵金卓
任伟民
Yang-yang Xu;Tian-jun Yue;Jin-zhuo Zhao;Wei-min Ren(State Key Laboratory of Fine Chemicals,School of Chemical Engineering,Dalian University of Technology,Dalian 116024)
出处
《高分子学报》
SCIE
CAS
CSCD
北大核心
2024年第8期1001-1008,共8页
Acta Polymerica Sinica
基金
国家自然科学基金(基金号22171037,22101040)资助项目.
