Citation: Han Bao, Yue Zhang, Hui-min Tang, Ding-sheng Yu, Ri-wei Xu. Study on the Structure and Properties of Bisphenol A-type Benzoxazine Resins Catalyzed by Organotin Oligomersesquioxanes[J]. Acta Polymerica Sinica, ;2019, 50(1): 55-61. doi: 10.11777/j.issn1000-3304.2018.18166 shu

Study on the Structure and Properties of Bisphenol A-type Benzoxazine Resins Catalyzed by Organotin Oligomersesquioxanes

Key Laboratory of Carbon Fiber and Functional Polymer, Ministry of Education, Beijing University of Chemical Technology, Beijing 100029

Corresponding author: Ri-wei Xu, xurw@mail.buct.edu.cn
Received Date: 17 July 2018
Revised Date: 3 August 2018
Available Online: 8 September 2018

Polybenzoxazines (PBz) is a new type of phenolic-like resins, which have excellent properties such as good mechanical and thermal properties, no volatile release upon cure, and molecular designing flexiblility. However, their major drawbacks are the high curing temperature and similar brittleness as phenolic resins. In this study, organotin silsesquioxanes (DOSn-Bu) are synthesized via capping reaction based on disilanol-POSS and Bu₂SnCl₂. Due to the cage-type hybrid structure, the metal-based oligomeric silsesquioxane (POMSS) possesses good thermal stability and mechanical properties. The mental centers are Lewis acid that catalyze ring-opening polymerization of benzoxazine monomers. The structure of DOSn-Bu was characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (¹H-NMR) and X-ray single crystal diffraction. A series of benzoxazine/DOSn-Bu hybrid resins were prepared by ultrasonic blending. FTIR results showed that the benzoxazine began to ring-open at 160 – 180 °C. The results of DSC showed that the initial curing temperature decreased by almost 50 °C and the peak curing temperature decreased by approximately 30 °C with the addition of DOSn-Bu. The thermal and mechanical properties of the hybrid material with different DOSn-Bu incorporation were measured by dynamic mechanical thermal analysis (DMTA) and thermal gravimetric analysis (TGA). DMTA result showed that the storage modulus ( E′) and glass transition temperature of the hybrid materials were improved. When 2 wt% of DOSn-Bu was added, the resins retained high storage modulus (E′ = 2.1 GPa at 50 °C) and high glass transtion temperature (T_g = 228 °C). TGA study showed that the hybrid materials possessed good thermal stability. From the scanning electron microscopy (SEM) mapping, it was found that the Si and Sn elements were greatly distributed in the system, thereby indicating that the catalysts were uniformly dispersed in the system with good compatibility with the resin matrix. The fracture surface morphologies of the cured resin were investigated by SEM. The roughness of the fracture surface of the hybrid material was increased compared with that of the pure benzoxazine resin and its texture became more complicated.
- DOSn-Bu,
- Benzoxazine,
- Catalytic curing,
- Hybrid materials
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