以碳酸二乙酯(DEC)、1,6-己二胺(HDA)为原料、无水醋酸锰为催化剂,合成了1,6-六亚甲基二氨基甲酸乙酯(HDEC)。通过红外光谱、核磁共振氢谱、气相色谱确定HDEC标样的结构和纯度,并建立了定量分析方法。进一步采用气质联用对反应的主副产物进行定性分析,推测反应路径。同时,对合成工艺进行反应参数优化,并推测反应机理。结果表明,该反应通过两步实现,首先HDA与DEC反应生成单取代的1-(6-氨基)-六亚甲基单氨基甲酸乙酯(HMEC)中间体,HMEC进一步与DEC羰化反应生成HDEC目标产物,同时反应过程中DEC与HDA以及HMEC反应生成脲类副产物。在最佳反应条件原料DEC与HDA摩尔比为3.5:1、反应温度120℃、无水醋酸锰催化剂用量为HAD初始用量的15%、反应时间5 h、转速400 r/min下,HDA转化率为100%,HDEC收率达89.6%。本研究为非光气法合成六亚甲基二异氰酸酯(HDI)重要中间体HDEC提供理论借鉴。
Hexamethylene dicarbamate (HDI) is an important aliphatic isocyanate are often used in aerospace, aviation, and polymer materials. Compared with aromatic isocyanates, HDI does not contain a benzene ring and has a symmetrical carbon chain skeleton, which makes it light stable and highly decorated. Studies have shown that the non-phosgene method can be used to prepare HDI through the thermal decomposition of the key intermediate hexamethylene dicarbamate. In this work, 1,6-hexanediamine (HDA) and diethyl carbonate (DEC) are used to synthesis hexamethylene dicarbamate ethyl ester (HDEC) under the catalysis of manganese acetate anhydrous. The structure and purity of the self-made HDEC standard sample are determined by FT-IR, 1H-NMR and TG, and a quantitative analysis method is established. Furthermore, qualitative analysis of the main and side products of the reaction is carried out by GC-MS, and the reaction pathway is inferred. At the same time, the reaction parameters are optimized and the reaction mechanism is speculated. The results show that the reaction is achieved in two steps. First, HDA reacts with DEC to form a monosubstituted 1-(6-amino)-hexamethylene monocarbamate (HMEC) intermediate, the process is that manganese acetate attacks -NH2 at one end of HDA to form reactive intermediate I [H2N(CH2)6NHCOCH3], and reactive intermediate I reacts with DEC to form HMEC. Second, HMEC further reacts with DEC to form HDEC target product, the process is that manganese acetate attacks -NH2 at the end of HMEC to form reactive intermediate II [CH3CH2COONH(CH2)6NHCOCH3], and reactive intermediate (II) reacts with DEC to form HDEC. The CH3COOCH2CH3 reacts with Mn(OH)2 to form manganese acetate catalyst in the reaction process. In addition, DEC reacts with HDA and HMEC to form urea by-products during the reaction. Under the optimum reaction conditions, the molar ratio of DEC to HDA is 3.5:1, the reaction temperature is 120℃, the amount of anhydrous manganese acetate catalyst is 15% of HAD initial amount, the reaction time is 5 h and the rotating speed is 400 r/min, the conversion of HDA is 100% and the yield of HDEC is 89.6%.