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

Han Bao; Yue Zhang; Hui-min Tang; Ding-sheng Yu; Ri-wei Xu

doi:10.11777/j.issn1000-3304.2018.18166

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

Research Article | 更新时间：2021-01-26

- Study on the Structure and Properties of Bisphenol A-type Benzoxazine Resins Catalyzed by Organotin Oligomersesquioxanes
- Acta Polymerica Sinica Vol. 50, Issue 1, Pages: 55-61(2019)
- 作者机构：
  
  北京化工大学碳纤维及功能高分子教育部重点实验室　北京 100029
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2018.18166
  CLC：
- Published：2019-1，
  
  Published Online：8 September 2018，
  
  Received：17 July 2018，
  
  Revised：3 August 2018，
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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 50(1):55-61(2019)
DOI：

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 50(1):55-61(2019) DOI： 10.11777/j.issn1000-3304.2018.18166.

摘要

利用八异丁基二硅烷醇与二丁基二氯化锡封端反应合成了有机锡倍半硅氧烷(DOSn-Bu)，采用傅里叶红外光谱(FTIR)、核磁共振氢谱(

H-NMR)、X-射线单晶衍射等方法证实了化合物的分子结构. 随后利用溶液共混法制备了系列双酚A-苯胺型苯并噁嗪(BA-a-Bz)/DOSn-Bu杂化树脂. 从杂化树脂分段固化的FTIR图中可看出，噁嗪环在160 ~ 180 °C发生开环. DSC结果表明：DOSn-Bu的催化作用使BA-a-Bz的起始固化温度下降了约50 °C、峰值固化温度下降了约30 °C，动态力学热分析(DMTA)、热失重(TGA)测试结果也表明杂化材料的储能模量和残炭率有所提高. 从扫描电镜元素分布图(SEM mapping)看出，催化剂在体系中分散均一，与树脂基体相容性良好且断面SEM图像显示杂化后材料的粗糙度比纯噁嗪树脂的增加.

Abstract

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 Bu

SnCl

. 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 (

H-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 (

′) and glass transition temperature of the hybrid materials were improved. When 2 wt% of DOSn-Bu was added

the resins retained high storage modulus (

′ = 2.1 GPa at 50 °C) and high glass transtion temperature (

= 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.

关键词

有机锡倍半硅氧烷苯并噁嗪催化固化杂化材料

Keywords

DOSn-BuBenzoxazineCatalytic curingHybrid materials

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State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology

Department of Material Science and Engineering, Southwest Petroleum University

Institute of Chemistry, Chinese Academy of Sciences

University of Chinese Academy of Sciences

The key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology

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