摘要
环氧化物和环酸酐的开环共聚(ROCOP)是合成具有创新结构和功能聚酯的一种有效的方法。在二元催化体系双三苯基膦氯化铵(PPNCl)/氨酚铁配合物(APFe)介导下,通过调控两者的比例,实现了邻苯二甲酸酐(PA)、5-降冰片烯-exo-2,3-二甲酸酐(exo-NA)和环氧环己烷(CHO)的开环共聚,利用核磁氢谱(1H NMR)和凝胶渗透色谱(GPC)对反应进行追踪,发现反应机理会从阳离子聚合过渡到配位阴离子聚合,反应活性呈现先降低后增强的“V”字型变化,由于不同酸酐与金属配合物配位能力以及插入增长链能力存在差距,因此反应拐点会产生差异。利用不同亲核性的助催化剂四丁基氯化铵(TBACl)和APFe组成的二元体系催化9,10-二氢蒽-9,10-α,β-丁二酸酐(HASA)和CHO开环共聚,同样观察到反应活性转变的特性,利用紫外-可见(UV-Vis)光谱对配合物结构进行表征,证实了助催化剂的亲核性会对反应机理的转变产生影响。
Ring-opening copolymerization (ROCOP) of epoxides and cyclic anhydrides is a powerful approach to synthesize polyesters with innovative structures and properties. In this work, the ROCOP of phthalic anhydride (PA), exo -norbornene anhydride ( exo -NA) and cyclohexene oxide (CHO) has been achieved by modulating the ratio of the two under the mediation of the binary catalytic system bis(triphenylphosphine)iminium chloride (PPNCl)/iron aminotriphenolate complexes (APFe). The reaction was followed by nuclear magnetic resonance spectroscopy ( 1H NMR) and gel permeation chromatography (GPC), it was found that the reaction mechanism would change from cationic polymerization to coordination anionic polymerization, and the reaction activity would show a “V” pattern of decreasing and then increasing. The inflection point of the reaction would vary due to the different ability of the different anhydrides to coordinate with the metal complexes and insert into the growing chain. The ring-opening copolymerization of 9, 10-dihydroanthracene-9, 10-α, β-succinic anhydride (HASA) and CHO was catalyzed using a binary system composed of different types of cocatalyst tetrabutylammonium chloride (TBACl) and APFe. A shift in the reactivity was also observed. Structural characterization of the complexes using ultraviolet-visible (UV-Vis) spectroscopy confirms that the nucleophilicity of the cocatalyst affects the shift in the reaction mechanism.
作者
杨安冉
段文升
武宪民
丁慧宁
温叶倩
刘国栋
刘宾元
YANG Anran;DUAN Wensheng;WU Xianmin;DING Huining;WEN Yeqian;LIU Guodong;LIU Binyuan(School of Chemical Engineering and Technology,Hebei University of Technology,Tianjin 300401,China;College of Chemical Engineering,Shijiazhuang University,Shijiazhuang 050035,China)
出处
《材料导报》
北大核心
2025年第12期237-241,共5页
Materials Reports
基金
河北省自然科学基金(E2022202015)。
关键词
聚酯
开环共聚反应
氨酚铁配合物
环氧化合物
环酸酐
polyester
ring-opening copolymerization
iron aminotriphenolate complexes
epoxide
cyclic anhydride
