摘要
1，2-环己二醇(CHD)是一种重要的有机合成原料，用于制备多种有机中间体，主要用于医药、农药、高档涂料、表面活性剂、橡胶助剂、液晶材料等诸多方面。本文针对国民经济发展的需要，结合我国化工行业的实际，对1，2-环己二醇的应用作了一些研究和探索，合成了聚己二酸1，2-环己二醇酯和1，2-环己二醇二缩水甘油醚。
本文借助正交实验设计和单因素寻优等有关实验方法对聚己二酸1，2-环己二醇酯的合成工艺进行了研究。首先确定了影响反应体系的关键因素：醇酸摩尔比、酯化时间、缩合时间和真空度。进而重点考察了反应温度、催化剂种类和催化剂用量对反应的影响，找到了较优的工艺条件：
(1)以钛酸四丁酯为催化剂时：醇酸摩尔比为1.5，催化剂用量为己二酸摩尔数的0.4％，酯化温度为180℃，酯化时间为4小时，采用逐步升高真空度的方法抽真空1小时，产品为淡黄色粘稠状物质，酸值＜5mgKOH／g；
(2)以对甲苯磺酸为催化剂时：醇酸摩尔比为1.5，催化剂用量为己二酸摩尔数的0.8％，酯化温度为180℃，酯化时间为2小时，采用逐步升高真空度的方法抽真空1小时，产品为淡黄色粘稠状物质，酸值＜10mgKOH／g。
以聚己二酸1，2-环己二醇酯为原料合成了一种硬度大、耐磨损、透明度高、耐热性能优良的聚氨酯材料。然后对合成聚己二酸1，2-环己二醇酯的反应动力学进行了探讨，得到的反应动力学方程为：
其次，本文用正交实验设计和单因素寻优等有关实验方法对1，2-环己二醇二缩水甘油醚的合成工艺进行了研究。重点考察了催化剂种类、催化剂用量、原料配比、醚化时间、醚化温度、闭环时间、闭环温度、反应介质对反应的影响，找到了最佳的工艺条件：各原料的摩尔比为环氧率丙烷(ECH)：NaOH：CHD)=2.3：2.1：1，催化剂三氟化硼-乙醚(或三氟化硼-四氢呋喃)用量为环己二醇摩尔数的0.4％，醚化温度为70℃，醚化时间为4小时，闭环温度为20℃，闭环时间为4小时。在此最佳工艺条件下的产品：收率为90％，环氧值达0.595eq／100g，无色透明液体，粘度为25mPa·S／25℃，有机氯含量为6×10~(-3)eq／100g。
最后对合成1，2一环己二醇二缩水甘油醚的反应过程进行了模拟，建立了适合
这类反应的数学模型，用此数学模型计算得到的结果与实验结果基本吻合。
1,2-cyclohexanediol(CHD) is an important raw material for organic synthesis. Many kinds of organic intermediate are prepared from it. 1,2-cyetohexanediol is used in medicine, pesticide, slap-up coating, surfactants, rubber assistants, liquid crystals etc. Aiming at the demand of national economy and linking the actual condition of domestic chemical industries, study and research on the application of 1,2-cyclohexanediol are performed in this paper. Poly(1,2-cyclohexanediol adipicate) and 1,2-cyclohexanediol diglycidyl ether have been synthesized.
With the orthogonal design method and siagle-factor-experiment, the technics of synthesizing poly(1,2-cyclohexanediol adipicate) has been studied in this paper. At first, the key factors affecting this complicate reaction are determined, such as the ratio of alcohol to acid, times of esterification, times of condensation and degree of vacuum. Furthuemore the influence of reaction temperature, differett categpries of catalysts and the quality of catalysts are refocused. An excellent technics to synthesize poly(1,2-cyclohexanediol adipicate) is obtained as follow:
(1) Tetrabutyl titanate is used as a catalyst in the amount of 0.4 mole percent based on adipic acid. The molar ratio of l,2-cyelohexanediol and adipic acid is 1.5. The esterification is performed for 4 hours on ISO.degfee.C. The condesation happens by rising vacuum progressively, with a residence time of 1 hour. A flaxen slabby transparent product is obtained, whose acid number of < 5 mg of KOH/g.
(2) P-tuluenesulfonic acid is used as a catalyst in the amount of 0.8 mole percent based on adipic acid. The molar ratio of l,2-cyclohexaaediol and adipic acid is 1.5. The esterification is performed for 2 hours on 180-degree.C. The condesation happens by rising vacuum progressively, with a residence tame of 1 hoar. A flaxen slabby transparent product is obtained, whose acid number of < 10 mg of KOH/g.
A polyurethane resin is synthesized by using this polyester. The polyurethane resin is high rigidity, wearable, high clarity and stabilization ia high temperature. Then the kinetics of synthesizing poly(l,2-cyclohexanfdiol adipicate) has studied and a kinetic equation is achieved as follow:
-d[COOH]/dt=ka [Cat][COOH][OH]+K [COOH]2[OH]
Moreover, With the orthogonal design method and single-factor-experiment, the technics of synthesizing 1,2-cyclohexanediol diglyeidyl ether has been studied in this paper. The influence of different categories of eatslyste, the quality of catalysts, proportions of the stuffs, reaction time of etherification, reaction temperature of etherification, reaction time of cyclization, reaction temperature of cyclization and reaction media are refocused. An excellent technics to synthesize 1,2-cyclohexanediol diglyeidyl ether is obtained. Boron trifluoride ethyl etherate (or boron trifluoride tetrahydron furan) is used as a catalyst in the amount of 0.4 mole percent based on 1,2-cyclohexanediol. The mole ratio of epichlorohydrin, sodium hydroxide and 1,2-cyclohexanediol is 2.3/2.1/1. The etherification temperature is 70.degree.C, with residence time of 4 hours. The cyclization temperature is 20. degree. C, with residence time of 4 hours. The product is an whiteness transparent liquid, whose viscosity is about 25cps, epoxide value is 0.595eq/100g and organic chloride is 6+100-3eq/100g.
At last, a simulation about the process of synthesizing 1,2-cyclohexanediol diglyeidyl ether is performed. The simulation can be used in this kinds of reactions .The simulative result is close to experimental resilt.
引文
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