十溴二苯醚催化合成及精制工艺和工艺条件优化研究乙嘧硫磷合成初步研究

【作者】 杨泽慧；

【导师】 陈声宗； 江多阶；

【作者基本信息】 湖南大学 ， 应用化学， 2002， 硕士

【摘要】 本文研究了采用新型金属型催化剂催化合成十溴二苯醚的溴素法和氯化溴法两种新工艺；利用均匀实验设计和单纯形优化试验技术对两种新工艺的工艺条件进行了优化研究，分别确定了两种工艺路线的最佳工艺条件；通过筛选，确定了一种十溴二苯醚的精制新工艺。 研究表明，新型金属型催化剂与传统的三氯化铝和三溴化铝相比，其活性更高，能使二苯醚溴化完全，并且克服了传统催化剂三氯化铝和三溴化铝极易潮解、吸水，不易运输储藏，使用不方便的缺陷。用氯化溴法催化合成十溴二苯醚，与传统的溴素法相比具有更高的反应活性和选择性的特点，副产物为氯化氢而不是溴化氢，提高了溴素的利用效率。 采用均匀实验设计考察了影响溴化反应的因素，通过单纯形优化试验得出最佳工艺条件如下： 氯化溴法催化合成十溴二苯醚新工艺的最佳工艺条件为：二苯醚与氯化溴的比(摩尔)为1:13，催化剂用量为二苯醚质量的10％，二苯醚滴加温度12℃，回流反应时间7.2h，在此优化工艺条件下，十溴二苯醚精品收率可达97.1％。 溴素法催化合成十溴二苯醚新工艺的最佳工艺条件为：二苯醚与溴素的比(摩尔)为1:30，催化剂用量为二苯醚质量的20％，二苯醚滴加温度30℃，二氯甲烷与二苯醚比(体积)为5:1，回流反应时间5.5h，在此优化工艺条件下，十溴二苯醚精品收率可达95.3％。 十溴二苯醚粗品经氯仿初洗后，以二甲苯作溶剂，用稀碱溶液除去粗品中的游离溴，母液负压脱溶得白色十溴二苯醚精品，其溴含量83.1％，溶点304～309℃。该精制工艺效果良好，操作简单，对设备要求低。更多还原

【Abstract】 This paper studied two new processes for catalytic synthesis of decabromodiphenyl ether which were carried out distinguishingly by brominating diphenyl oxide with bromine and bromine chloride in the presence of a novel metal catalyst. Uniform test design and simplex optimization were applied in the research, by which the optimum reaction conditions were obtained. And a new method of DBDPO purification was developed.The research demonstrated that the novel metal catalyst had an excellent catalytic performance, such as high catalytic activity, high catalytic selectivity compared to those of traditional ones such as aluminum trichloride and aluminum tribromide which were deliquescent, hygroscopic and unstoragible. Studies showed that the novel metal catalyst was more convenient to be used. As a brominating agent, bromine chloride had higher catalytic activity and selectivity than bromine. Furthermore, the utilization efficiency of bromine was improved by using bromine chloride because the by product was hydrochlgride not hydrobromide.The influential factors of brominating reaction were investigated by uniform test and the optimum process conditions were obtained by simplex optimization as follows:The optimum reaction conditions for catalytic synthesis of DBDPO by brominating diphenyl oxide with bromine chloride followed as: molar ratio of diphenyl ether to bromine chloride was 1:13, ratio of metal catalyst to diphenyl oxide was l:10(w/w), diphenyl ether feeding temperature 12 and reflux time 7.2 hours, the yield of purified DBDPO was up to 97.1%.The optimum reaction conditions of catalytic synthesis of DBDPO by brominating diphenyl oxide with bromine followed as: molar ratio of diphenyl ether to bromine was 1:30, ratio of metal catalyst to diphenyl oxide was l:5(w/w), diphenyl ether feeding temperature 30, ratio of dichloromethane to dipheny oxide was 5:l(v/v) and reflux time 5.5hours, the yield of purified DBDPO was up to 95.2%.A simple and convenient DBDPO purification method which applied xylene as solvent after DBDPO had been washed with chloroform was developed. Then the free bromine in the solution reacted with an alkali aqueous solution. The resulting solution was separated and the uper solution was distilled under a reduced pressure to remove its solvent. Thus the white purified DBDPO was obtained with the bromine content 83.1%, mp: 304-309.更多还原