四苯基双酚A二磷酸酯及复配体系阻燃环氧树脂的热动力学分析

Thermo-dynamic study on pyrolysis of bisphenol A diphosphate and the compounding system of flame-retarded epoxy resins

采用热分析仪对四苯基双酚A二磷酸酯(BDP)及复配APP体系阻燃环氧树脂(EP)进行TG分析,研究BDP及其复配体系阻燃EP降解的过程,并在动力学理论模型基础上计算阻燃EP的活化能。结果表明,与未阻燃EP相比,阻燃EP在600℃时残炭率增加,15%BDP阻燃EP的残炭率由未阻燃的20.41%增加到28.06%,15%BDP+9%APP阻燃EP的残炭率增加到34.78%;BDP及其复配体系阻燃EP的活化能显著提高,15%BDP阻燃EP的活化能由未阻燃的80.39 kJ/mol提高到141.06 kJ/mol,15%BDP+9%APP阻燃EP的活化能提高到199.68 kJ/mol。研究表明,阻燃EP体系耐热性能好,阻燃效果明显,且复配体系阻燃效果进一步提高。

This paper aims to introduce our study on the properties and flame-retarded mechanism of bisphenol A diphosphate （BDP） and BDP/APP in EP, and their preparation methods through TGA. As is known, BDP is a new kind of nonhalogenate diphosphate, whose properties and flame-retarded mechanism in EP have so far not yet been reported. In this paper, we have done some of thermal analyses over the curves of flame-retarded performances of the epoxy resins of BDP, BDP and APP （ammonium polyphosphate） by using a thermal analytical apparatus and studied their pyrolysis course. On the basis of our thermodynamic analysis model, we have gained their thermodynamic parameter-the activation energy of flame-retarded epoxy resins from the thermal analytical data concerned. The results of our research have shown that, in comparison with the non-resistant EP, char formation rate of flame-retarding epoxy resins increases at 600 ℃ . The char formation rate of 15% BDP flame-retarded epoxy resin would from 20.41% to 28.06%, and the char formation rate of 15% BDP＋ 9% APP flame-retarded epoxy resin would increase by 34.78% . The active energy of 15 % BDP flame-retarded epoxy resin also turns to increase significantly, from 80.39 kJ/mol to 141.06 kJ/mol, and the active energy of 15% BDP ＋ 9% APP flame-retarded epoxy resin is added to 199.68 kJ/mol. As a result, both its thermal stability and heat-resistance prove to have greatly improved. What is more, it can also be concluded form the TGA analysis that BDP plays an important role. In addition, our study indicates that the flame retardant and inflame retardant materials also play the retardant role in the condensing the flames during and after the combustion going on.