摘要
1,2-环己二醇是一种重要的有机合成原料,主要用于制造聚酯、医药、农药等精细化工产品。随着石油化工技术的发展,其生产成本越来越低,产量大大增加,因此其衍生物的合成和应用越来越受到人们的关注。本文主要对1,2-环己二醇的衍生物之一聚己二酸-1,2-环己二醇酯的合成进行了研究。
首先对聚己二酸-1,2-环己二醇酯的合成进行了预实验,实验中考察了影响合成反应的各种因素,筛选出了适于本合成体系的较佳催化剂。
实验采用水洗-沉淀法对产物进行分离,并对分离过程中溶剂乙醇和沉淀剂水的比例和用量及水洗时沉淀剂水的温度进行了考察,实验发现,产物用乙醇溶解后加水沉淀时,所加水的温度低于30℃时,溶解液呈现白色乳状液,此种情况下,产物被乳化,无法进行提纯,随着水温升高上述现象会得到缓解。经过多次实验发现水温在50℃左右,溶剂乙醇和沉淀剂水的比例为1∶1.5,水洗四次后效果较好。
酸值和羟值是目的产品的两个特征值,实验采用酸碱滴定法来确定两个特值。实验发现,碱液的配置对酸值和羟值的测定影响较大,用水作溶剂配置氢氧化钾碱液,发现滴定时会出现白色混浊,滴定终点难以判定。改用乙醇作溶剂配制碱液时滴定终点明显清晰、无混浊现象出现。实验中还对溶解产物的溶剂进行了筛选,常用的溶剂有甲苯-甲醇、苯-乙醇、甲苯-乙醇。实验中发现产物在三种溶剂中的溶解性能大致相同,对滴定结果影响甚小。从溶剂的毒性、劳动保护、成本等方面考虑最终选用甲苯-乙醇作为本实验的溶剂。同时在羟值的分析过程中对酰化时间和水解时间也进行了考察。得出了较佳的酰化和水解时间。
在预实验的基础上,利用单因素实验的方法对反应过程中的重要影响因素如:酸醇物料配比、反应温度、反应升温方式、反应时间、抽空方式、催化剂和稳定剂的用量进行了逐一优化,得到了较佳的反应工艺条件,并在此基础上进行了三次重复实验,实验的再现性良好。
实验还利用红外光谱对合成出的最终产品—聚己二酸1,2-环己二醇酯的结
1, 2-cyclohexanediol is a kind of important organic synthesis raw materials, mainly used for making such fine chemical products as the polyester, medicine, agriculture chemical ,etc. With the development of technology of petrochemical industry, its production cost is lower and lower, the output increases greatly, so the synthesis and application of its derivative are paid close attention to people. In this text ,we mainly research the synthesis of poly(1, 2-cyclohexanedioladipicate) which is one of the derivatives of 1, 2-cyclohexanediol.At first, the synthesis of poly(1, 2-cyclohexanediol adipicate) was test in advance ,and investigate various kinds of factors that reflects the synthesis in the experiment and screen better catalyst that is suitable for the synthetic system.We adopt the method of water-washed-precipitate to separate the produce, and investigate the temperature of water of the precipitator, the proportion and dosage of the solvent of ethanol and water of precipitator while washing in the separation process.In the experiment, while adding water and precipitating after the produce is dissolved with the ethanol , we find the dissolved liquid appears white milk form when water temperature lower than 30℃, under this kind of situation, the produce was emulsifiated and can not sublimate, with the temperature rising ,the above-mentioned phenomena can be alleviated. Through many experiments ,find when the proportion of the solvent of ethanol and precipitator of water is 1:1. 5 and the temperature of water is about 50 ℃, the result is better after water-washing four times.Acid value and hydroxyl value are two pieces of characteristic value of the purpose products and the experiment adopts the titrimetric law of acid and alkali to confirm them. In the experiment, we find the disposition of the lye exerts a great influence on survey of acid value and hydroxyl value.When dispose the potassium hydroxide lye with water, find the solution will present the white muddily when dripping and the titrimetric terminal point is difficult to judge,while use the ethanol instead the titrimetric terminal point is obviously clear and no muddy phenomenon is
appeared.We also screen the solvent which dissolved the produce in the experiment. The commonly used solvent is toluene- methyl alcohol,benzene- ethanol and toluene-ethanol. Find the performance of dissolving of the produce in three kinds of solvents is roughly the same,and has little power to the titrimetric result in the experiment. Considering the toxicity, labour protection and cost of the solvent ,etc. Finally.we select the toluene- ethanol as the solvent of the experiment. In the course of analysis of hydroxyl value at the same time, we also investigate the hydrolysised and acyl time and draw better conclusionOn the basis of testing in advance,utilize the method of the single factor to optimize the important influence factor reacting in the course one by one, for instance: the matching of acid and diol, react temperature ,the way of temperature rising, react time , the dosage of catalyst and stabilizer, and receive the better process conditions .We also has carried on the repeated experiment three times on this basis, and the reproducing of the experiment is good.We still use infrared spectrum to identify the synthesized produce and compare it with the standard infrared spectrum and find they accord well. Finally,we synthesize the poly(1, 2-cyclohexanediol adipicate)which is a yellowish,translucent and viscid liquid.Tts acid value <9.3mg/g. hydroxyl value between 50-70mg/g and molecular weight between 1000-2000
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