【作者】 王淑娟； 井新利； 边城； 贾贝贝；

【Author】 Shujuan Wang;Xinli Jing;Cheng Bian;Beibei Jia;Department of Applied Chemistry, Xi’an Jiaotong University;

【机构】 西安交通大学理学院应用化学系；

【摘要】 含硼高分子具有优良的耐热性和阻燃性能,通过形成硼酸酯引入硼原子而构筑的超支化高分子具有更优越的性能和更广泛的应用。但是,关于PRB结构和热裂解机理认识上的不足,在很大程度限制了其应用。本研究以高成炭率的聚硼酸间苯二酚酯(PRB)为研究对象,通过分析PRB的结构,并跟踪其高温裂解过程中的结构演变,揭示了PRB具有优良耐热性能的原因。研究表明,PRB的分子骨架主要由芳香结构、硼酸酯结构和B-O-B结构构成,同时含有大量的硼羟基和酚羟基。在高温裂解过程中,PRB中大量的芳环碳转化为无定形炭,提高了成炭能力。PRB中的硼酸苯酚酯结构中的O-C键并不牢固,其在热裂解过程的早期(400℃)就发生破坏并形成氧化硼,有效地减少了小分子碳氧化合物的形成和挥发对碳原子造成的损失,提高了成炭率。本研究不仅为新型含硼高分子的结构设计和合成提供了新思路,还将有助于进一步改善拓展酚醛树脂和苯并噁嗪树脂等这类热固性树脂的耐热性能,拓宽其在耐烧蚀复合材料领域的应用。更多还原

【Abstract】 Boron-containing organic polymers have excellent thermal stability. Hyperbranched polymers in which boron atoms are introduced in the form of borates, exhibit superior performance. In the present study, the chemical structure of the poly(resorcinol borate)(PRB) and its structural evolution at high temperatures are investigated to clarify the reason for the high char yield of the PRB. The results indicated that the molecular skeleton of PRB mainly consisted of aromatic structures, borates, B–O–B structures, as well as a small number of boron hydroxyl groups and phenolic hydroxyl groups. A large amount of aromatic ring carbon was converted to the amorphous carbon during pyrolysis. Boron oxide was formed by the cleavage of O–C bonds from borates via pyrolysis, which effectively avoided the formation of volatile carbon dioxide, reducing the carbon loss. It is believed that the results are conductive to the solutions for designing and synthesizing novel boron-containing polymers.更多还原