摘要
二元醇类作为医药、涂料工业的重要中间体应用非常广泛,传统的二元醇有1,4-丁二醇(1,4BDO)、二甘醇、新戊二醇(NPG)、1,3-丙二醇(1,3PDO)、己二醇(HDO)等。2-甲基-1,3-丙二醇(MPO)是一种新型二元醇,由于其独特的分子结构使其在很多方面正逐渐取代传统二元醇,有很大的市场前景,但国内尚无完整地生产工艺。
本文提出了一种新的合成MPO的工艺路线,即采用以异丁烯为原料经氯化、水解、加氢等过程合成得到该产品。该工艺过程具有设备简单、工艺先进、便于操作、投入较少、易于实现等特点,同时又为异丁烯的应用开辟了一条新路,弥补了国内合成空白。
本文在氯化反应过程中,自行设计制作出了氯化管式反应器,在该反应器中异丁烯和氯气迅速混合反应生成二氯异丁烯,根据该氯化反应特征利用正交试验和单因素试验考察了有关因素的影响并优化得到了最佳工艺条件,二氯异丁烯的总收率达65%以上,选择性达80%;接着,对二氯异丁烯进行水解反应制得了2-甲烯-1,3-丙二醇,讨论了相关因素对水解反应的影响,并通过正交试验和单因素试验得到了较佳工艺条件,二氯异丁烯的转化率达100%;同时还对制备的2-甲烯-1,3-丙二醇在常压下采用三氧化二铝负载钯催化剂催化加氢得目的产物MPO,并对产品进行了鉴定,从而打通了整个工艺路线。
本文根据工程设计以及应用方面的需要还对MPO及其水溶液的表面性质进行了研究,为此新型二元醇的应用提供了一定量的基础数据。
As important industrial chemicals, dihydroxy alcohols are applied for many fields, classical dihydroxy alcohols include l,4BD0, diglycol, NPG, 1,3PDO, HDO and so on. MPO is a kind of new dihydroxy alcohols. Because of its unique molecular structure, 2-methyl-1,3-propanediol(MPO) is instead of classical dihydroxy alcohols gradually. So MPO has huge market foreground. But MPO has not been had a integrated production technology in China.
A new synthesis route: the preparation of MPO, which 2-methyl-1-propene reacted with chlorine, alkali and hydrogen was discussed. This process have a lot of excellences, such as simple equipments, advanced process, being convenient of manipulation, less devotion, being prone to come true and so on, at the same time, the route inaugurated another application for 2-methyl-1-propene, making up synthesis blank in China and abroad.
First, a chlorinator was self-designed in this paper, and dichloride of 2-methyl-1-propene was synthesized by 2-methyl-1-propene reacted with chlorine fast in this reactor. By means of the Orthogonal Experiments design and single factor experiments, the influence of several reaction variables on the yield were examined and the optimum reaction conditions under the intervallic operation were obtained, the yield and selectivity of dichloride of 2-methyl-1-prop-ene were more than 65% and 80% respectively. Second, the preparation of 2-methylene-1, 3-propanediol, which dichloride of 2-methyl-1-propene reacted with alkali was investigated. By means of the Orthogonal Experiments design and single factor experiments, the influence of several reaction variables on the yield were examined and the optimum reaction conditions under the intervallic operation were obtained, the conversion of dichloride of 2-methyl-1-propene was 100%. Moreover the preparation of MPO, which 2-methylene-1, 3-propanediol reacted with hydrogen, in presence of Al_2O_3-Pd catalyst, was gotten, and the product was appraised. So the route was opened up.
In addition, in order to cater for engineering design and application, interfacial forces of pure product and MPO+H_2O were studied in this paper. A mass of base data were provided for application of this new dihydroxy alcohols.
引文
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