二甲基硅烷芴基环氧树脂的合成、表征及非等温固化动力学分析

摘要

以双酚芴、二甲基二氯硅烷、环氧氯丙烷为原料，合成了二甲基硅烷芴基环氧树脂（BMEBF），并利用FT IR、1 H NMR确认了产物结构，盐酸-丙酮法测定其环氧值为0.22。热重分析表明，BMEBF的初始分解温度达347.66℃，较环氧树脂E-51高89℃；在600℃时的残余质量分数也高出21个百分点。对二氨基二苯甲烷（DDM）-BMEBF固化体系的非等温固化动力学研究发现，根据Kissinger法及Ozawa法得到的该固化反应活化能分别为53.616 kJ/mol和57.980 kJ/mol，反应级数都接近1；BMEBF-DDM体系的固化温度为140～150℃，后固化温度为180～190℃。%Silicone epoxy resin containing fluorene (BMEBF)was synthesized by bisphenol fluorene, dimethyl dichlorosilane and epoxy chloropropane,and the chemical structure of BMEBF was characterized by FT IR and 1 H NMR. Epoxy value of BMEBF was 0. 22 by epoxy equivalent weight titration. TG analysis dis-played that preliminary thermal decomposition temperature of BMEBF was 347 . 66℃,89℃ higher than epoxy resin E-51 and the residual mass fraction at 600℃was 21% higher. Curing kinetic parameters of BMEBF-diaminodiphenyl methane(DDM)curing system was systematically studied by DSC non-isothermal curing kinetics. Activation energy calculated by Kissinger method and Ozawa method was 53. 616 kJ/mol and 57. 980 kJ/mol, respectively. Reaction order of curing reaction obtained from the above methods was close to 1. Optimal curing condition of BMEBF-DDM system was decided by the dynamic DSC and results showed that the curing temper-ature would be 140~150℃ and post-curing temperature 180~190℃.