Abstract:

Using 3,3′,5,5′⁃tetramethylbiphenol (TMBP), 2⁃(chloromethyl)⁃1,2⁃epoxypropane (MECH), and sodium hydroxide as raw materials, a biphenyl⁃type epoxy resin (3,3′,5,5′⁃tetramethylbiphenyl bisphenol dimethyl glycidyl ether) was synthesized by a two⁃step method. The biphenyl⁃type epoxy resin with relatively low chlorine mass fraction was obtained by removing residual inorganic chlorine in the product using an anion exchange resin. The structure and properties of the samples were characterized using FTIR, 1H NMR, DSC, HPLC, and a rotational rheometer. The influence of different raw material ratios, reaction temperatures, and reaction times on the product yield was investigated through orthogonal experiments. The results show that when the raw material ratio is n(TMBP)/n(MECH)=1.0∶10.0, the reaction temperature in the first stage is 90 ℃, the reaction temperature in the second stage is 80 °C, n(NaOH)/n(TMBP)=2.1∶1.0, and the reaction time in both stages is 4 h, within the selected experimental range, this process condition is relatively optimized. The effective substance mass fraction of the obtained sample is above 85%, the measured epoxy value is 0.5 eq/(100 g), which is relatively close to the theoretical value. The resin exhibits a low melt viscosity of 0.12 Pa·s at 150 ℃, making it suitable for applications such as epoxy encapsulation.

Key words: Epoxy resin, Chloromethyl epoxy propane, 3,3′,5,5′?Tetramethylbiphenyl bisphenol dimethyl glycidyl ether, Low chlorine mass fraction

摘要：

以3，3′，5，5′⁃四甲基联苯二酚（TMBP）、2⁃(氯甲基)⁃1，2⁃环氧丙烷（MECH）、氢氧化钠为原料，采用两步法合成联苯型环氧树脂（3，3′，5，5′⁃四甲基联苯双酚二甲基缩水甘油醚）；通过阴离子交换树脂对产物中残余的无机氯进行后处理，得到氯质量分数相对较低的联苯型环氧树脂；采用FTIR、1H NMR、DSC、HPLC及旋转流变仪，对样品的结构与性能进行了表征与测试，并通过正交实验考察了原料配比、反应温度、反应时间等因素对产物收率的影响。结果表明，在筛选的实验范围内，较优的工艺条件为：原料配比为n(TMBP)/n(MECH）=1.0∶10.0，第一阶段反应温度为90 ℃，第二阶段反应温度为80 ℃，n(NaOH)/n(TMBP)=2.1∶1.0，两个阶段的反应时间均为4 h；在较优的工艺条件下，所得样品中有效物质量分数达85%以上，实测环氧值为0.5 eq/(100 g)，与理论值较为接近；纯化后的联苯型环氧树脂在150 ℃温度下的熔融黏度仅为0.12 Pa·s，有望在环氧封装等应用领域得到实际应用。

关键词: 环氧树脂, 氯甲基环氧丙烷, 3, 3′, 5, 5′?四甲基联苯双酚二甲基缩水甘油醚, 低氯质量分数