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Catalyzing Benzoxazine Polymerization with Titanium-Containing POSS to Reduce the Curing Temperature and Improve
Xiaoyi Sun1, Qixuan Fu1, Pei Dai2
1Key Laboratory of Carbon Fiber and Functional Polymers, Beijing University of Chemical Technology, Ministry of Education, Beijing 100029, China.
Abstract:
Trisilanolphenyl-polyhedral oligomeric silsesquioxane titanium (Ti-Ph-POSS) was synthesized through the corner-capping reaction, and Ti-Ph-POSS was dispersed in benzoxazine (BZ) to prepare Ti-Ph-POSS/PBZ composite materials. Ti-Ph-POSS could catalyze the ring-opening polymerization (ROP) of BZ and reduce the curing temperature of benzoxazine. In addition, Ti immobilized on the Ti-Ph-POSS cage could form covalent bonds with the N or O atoms on polybenzoxazine, improving the thermal stability of PBZ. The catalytic activity of the Ti-Ph-POSS/BZ mixtures was assessed and identified through 1H nuclear magnetic resonance (1H-NMR) and Fourier-transform infrared (FTIR) analyses, while thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA) were used to determine the thermal properties of the composite. It was found that PBZ exhibited a higher glass transition temperature (Tg) and better thermal stability when Ti-Ph-POSS was added. The curing behavior of the Ti-Ph-POSS/BZ mixtures showed that the initial (Ti) and peak (Tp) curing temperatures sharply decreased as the content of Ti-Ph-POSS and the heating rate increased. The curing kinetics of these Ti-Ph-POSS/BZ systems were analyzed using the Kissinger method, and the morphology of Ti-Ph-POSS/PBZ was determined via scanning electron microscopy (SEM). It was found that the Ti-Ph-POSS particles were well distributed in the composites. When the content exceeded 2 wt%, several Ti-Ph-POSS particles could not react with benzoxazine and were only dispersed within the PBZ matrix, resulting in aggregation of the Ti-Ph-POSS molecules.
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