环氧聚四氢苯酐二甘醇酯的合成及表征

摘要

Using tetrahydrophthalic anhydride(THPA), ethylene diglycol (DEG), 2-ethyl-hexanol and hydrogen peroxide as raw materials, tetra-n-butyl titanate and formic acid as catalysts, epoxided poly(diglycol tetrahydrophthalic anhydride) (EPTA-2) was prepared via esterification and epoxidation reaction. The influences of esterification and epoxidation reaction conditions, such as reaction temperature, reaction time, stuff ratio, amount of used chain-ending reagent, catalyst dosage and the amounts of H2O2 and formic acid, on the two reactions were investigated. The structure and thermostability of product were characterized by FT-IR, 1H-NMR, TGA, respectively. The results show that the optimized reaction conditions of esterification are as follows: the molar ratio of THPA, DEG and 2-ethyl-hexanol is 1.0:1.25:0.50, amount of catalyst 0.8%(based on the mass of THPA), reaction temperature 200 ℃and time 6 h. The optimized conditions of epoxidation are as follows:the mass ratio of PTA-2, formic acid and H2O2 is 1.0:0.50:0.90, reaction temperature 50℃ and time 1 h. The epoxy value of product is above 1.40% and residual iodine value is below 4.0 g⋅(100g)−1. The product is with higher flowability and thermostability. The addition of the prepared EPTA-2 to PVC improves the thermal stability of PVC effectively.%　　以四氢苯酐、二甘醇、2-乙基己醇、双氧水为原料,钛酸四正丁酯、甲酸为催化剂,分别经酯化和环氧化两步合成功能化环氧聚酯增塑剂环氧聚四氢苯酐二甘醇酯.考察了酯化反应温度、时间、醇酸摩尔比、封端剂用量、催化剂用量以及环氧化反应温度、时间、双氧水用量、甲酸用量对环氧聚四氢苯酐二甘醇酯合成的影响.采用红外光谱仪(FT-IR)、核磁共振仪(1H-NMR)、热重分析仪(TGA)对产品的结构和热稳定性等进行了表征.结果显示,最佳酯化反应条件为：四氢苯酐、二甘醇、2-乙基己醇的摩尔比为1.0：1.25：0.50,催化剂用量为酸酐质量的0.80%,反应温度200℃,反应时间6 h.最佳环氧化条件为：聚四氢苯酐二甘醇酯、甲酸、H2O2的质量比为1.0：0.50：0.90,反应温度50℃,反应时间1 h.产品环氧值>1.40%,碘值<4.0 g⋅(100g)−1,具有较好的流动性和热稳定性,加入PVC树脂中后,有效地提高了PVC的热稳定性.