Synthesis and properties of a novel autocatalytic phthalonitrile monomer and its copolymerization with multi‐functional fluorene‐based benzoxazine monomers

作者：Ting Wang, Zilong Wang, Abdul Qadeer Dayo, Chengyu Shi, Hui‐bo Liu, Zhongcheng Pan, Athar Ali Khan Gorar, Jun Wang, Heng Zhou, Wenbin Liu · 发表于：Journal of Applied Polymer Science · 年份：2022 · DOI：10.1002/app.52193 · 被引用次数：17 · 研究领域：Epoxy Resin Curing Processes、Synthesis and properties of polymers、Injection Molding Process and Properties

Abstract A novel autocatalytic phthalonitrile monomer [4,4′‐(((((oxy‐bis [4,1‐phenylene]) bis (azanediyl)) bis (methylene)) bis (2‐methoxy‐4,1‐phenylene)) bis (oxy)) diphthalonitrile, OPD] is obtained by nucleophilic substitution of 4‐nitro‐phthalonitrile and bisphenol compound [4,4′‐(((oxy bis [4,1‐phenylene]) bis (azanylylidene)) bis (methanylylidene)) bis (2‐methoxyphenol)]. Bisphenol compound is a reductant with secondary amine groups of Schiff base derived from the reaction of vanillin and 4,4′‐diaminodiphenylether. The OPD monomer has a self‐catalytic polymerizing reaction. OPD monomer has good processability, and the processing window was 130°C. Moreover, OPD polymer [poly(OPD)] shows higher glass‐transition temperature (345°C). The 5% and 10% thermal decomposition temperatures of poly(OPD) and char yield at 800°C are 407, 451°C, and 69%, respectively. To further improve the properties of poly(OPD), the OPD monomer was modified by multi‐functional fluorene‐based benzoxazine monomers (MFFB) due to their excellent reaction activities. The results showed that OPD/MFFB systems had high reaction activities. The similar thermal stabilities between OPD and MFFB can give stable and excellent thermal stability to the poly(OPD/MFFB). Compared with poly(OPD), the T g values of poly(OPD/MFFB) were significantly increased, and their stiffness values were reduced. The tensile, flexural, and impact properties for poly(OPD/MFFB) were improved significantly.