Rybyan Artem A, Bilichenko Julia V, Kireev Vyacheslav V, Kolenchenko Alexander A, Chistyakov Evgeniy M
Faculty of Petrochemistry and Polymer Materials, Mendeleev University of Chemical Technology, 125047 Moscow, Russia.
Polymers (Basel). 2022 Dec 7;14(24):5334. doi: 10.3390/polym14245334.
As a result of this research, it was established that the chlorine atom replacement rates in hexa-chlorocyclotriphosphazene by o-, m-, and p-methylanilines' temperatures are crucial in determining which reaction is made. The speed of reaction practically does not affect the polarity of the synthesis solvent. For the formation of fully substituted o-, m-, and p-arilaminocyclotriphosphazenes, the reaction takes 5 h and is carried out in the diglyme at its boiling temperature. The structure of the synthesized AAP was confirmed by P and H NMR spectroscopy and MALDI-TOF mass spectrometry. By means of synchronous DSK and TGA, it is found that the synthesized AAP are crystalline and their thermal destruction has a stepped character. Thermal destruction is shown to be accompanied by the simultaneous removal of three aniline molecules from the AAP molecules. Conducted curing of epoxy resin DER-331 is carried out using the AAP as a curing agent. It has been established that due to steric difficulties, o- AAP does not interact with epoxy resin, unlike m- and p- AAP. The gel fraction in curing resin is measured, and the AAP relate to the stage processes of macromolecule formation. The result is that polymers based on DER-331 and m-, p-AAP have a gel fraction content up to 97 mass. %. These polymers have glass-transition temperatures 80 and 85 °C (m- and p-AAP-based, respectively) and demonstrate fire resistance to standard UL-94 of category V-0.
这项研究的结果表明,六氯环三磷腈中氯原子被邻、间、对甲基苯胺取代的速率以及温度对于确定发生哪种反应至关重要。反应速度实际上并不影响合成溶剂的极性。为了形成完全取代的邻、间、对芳氨基环三磷腈,反应需进行5小时,并在二甘醇二甲醚的沸点温度下进行。通过磷和氢核磁共振光谱以及基质辅助激光解吸电离飞行时间质谱对合成的芳氨基磷腈(AAP)的结构进行了确认。通过同步差示扫描量热法(DSC)和热重分析法(TGA)发现,合成的AAP是结晶性的,其热分解具有阶段性特征。热分解过程显示会同时从AAP分子中脱去三个苯胺分子。使用AAP作为固化剂对环氧树脂DER - 331进行固化。已经确定,由于空间位阻的原因,邻位AAP与环氧树脂不发生相互作用,而间位和对位AAP则不然。测量了固化树脂中的凝胶分数,AAP与大分子形成的阶段过程有关。结果是,基于DER - 331和间位、对位AAP的聚合物的凝胶分数含量高达97质量%。这些聚合物的玻璃化转变温度分别为80和85°C(分别基于间位和对位AAP),并显示出符合V - 0级标准UL - 94的阻燃性。