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
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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。
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.
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。
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.
引文
[1] 梁足培，宫海波等．含溴阻燃剂十溴二苯醚的制备．精细石油化工．1998(1)：37～41．
[2] 许际清，李立军．塑料阻燃剂的现状与开发．沈阳化工．1996(1)：32～35．
[3] 陈玉琴，张志德等．含溴阻燃剂的现状及发展前景．化学工程师．1998(2)：33～35．
[4] 李巧玲，欧育湘．无卤阻燃剂的研究进展．化工进展．1998(5)：24～28．
[5] 李秀瑜．阻燃剂的最新进展．河北化工．1998(4)：30～32．
[6] 黄汉生．日本塑料阻燃剂发展动向．现代化工．1998(4)：38～41．
[7] 张约伯．溴系阻燃剂．山西化工．1986(1)：51～52．
[8] 高良．溴及溴系阻燃剂．海湖盐与化工．1999，28(5)：7～10．
[9] 欧育湘．有机阻燃剂最新进展．现代化工．1997(4)：9～12．
[10] 欧育湘．阻燃剂．北京：兵器工业出版社，1996．
[11] 郭如新．阻燃剂发展现状．海湖盐与化工．1998，28(1)：43～44．
[12] 欧育湘．新世纪前10年全球阻燃剂发展预测．化工进展．1996(6)：29～32．
[13] 李慧君，刘学富，王艳菊等．化工商品手册．北京：冶金工业出版社，1994．
[14] 任世荣．塑料助剂．天津：天津大学出版社，1996．
[15] 付丽荣，曲波，刘治钦．溴系阻燃剂十溴二苯醚的合成．山西化工．1996(4)：12～13．
[16] 路振华．阻燃作用机理与阻燃技术进展．海湖盐与化工．1996，25(3)：30～31，38．
[17] L.M.SHORR．溴在阻燃技术中的应用．阻燃材料与技术．1996(1)：7～11．
[18] 樊真．阻燃剂PBO的色泽改进研究．阻燃材料与技术．1996(6)：1～3．
[19] 张志德，陈玉琴．溴系阻燃剂的国内外新进展．精细石油化工．1999(5)：59～62．
[20] 吴哲浩，陈康生，缪维芳．我国十溴二苯醚生产状况及建议．海湖盐与化工．1997，26(2)：24～28．
[21] 吴哲浩，缪维芳，郭黎青等．国内外十溴二苯醚产品质量比较．浙江化工．1996，27(2)：37～41．
[22] 李述道．浅谈十溴二苯醚生产方法种种及国内生产技术现状．青岛化工．1993(2)：5～8
[23] Toyo Soda, et al. Decabromodiphenyl Ether. Jpn. Kokai Tokkyo Koho JP 58, 222, 043. 1982.
[24] Pedjac, et al. Bromination Process for Preparing Decabromodiphenyl Ether from Diphenyl Ether. EP 0,126,569 A_1. 1984.
[25] Decaudin, Robert, et al. Brominated Diphenyl Ether Derivatives. Ger. Often. DE 3,622,224. 1987.
[26] Stollar, et al. Process for the Preparation of Decabromodiphenyl Ether with Improved Thermal Stability. EP 0,265,150A_1. 1988.
[27] Stollar, et al. Method for the Preparation of Decabromodiphenyl Ether. EP 0,265,151A_1. 1988.
[28] Bonnie G., et al. Process for Making Decabromodiphenyl Oxide. US 4,778,933.1998.
[29] Kulawaki Jerzy, et al. Method for Manufacturing Aromatic Compounds. Pol, PL 154, 173. 1992.
[30] Kubo Masashige, et al. Apparatus And Method for Preparing Decabromodiphenyl Ether. Ger. Offen. DE 3,326,343. 1985.
[31] Jenkner Herbert, et al. Preparation of Highly Brominated Aromatic Compounds. Ger. Offen. DE 3,422,673.1985.
[32] Decaudin Robert, et al. Catalytic Decabromodiphenyl Ether Manufacture. Ger. Offen. DE 3,622,236. 1985.
[33] Toyo Soda, et al. Decabromodiphenyl Ether. Jpn. Kokai Tokkyo Koho JP 60,32,741. 1985.
[34] Wendell G., et al. Process for Producing Purified Brominated Aromatic Compounds. US. 4,659,021. 1987.
[35] Bulych, Valentina N, et al. Process for Preparing Decabromodiphenyl Ether. Russ. Ru 2,061,673. 1996.
[36] Akhrem, Irenas, et al. Decabromodiphenyl Ether Production Method. Russ. Ru 2,046,789. 1995.
[37] 属秀雄，香川巧．臭素化混合物、制造方法及配合难燃性树脂组成物．日本公开特许公报．特开平10-175893．1998．
[38] 属秀雄，香川巧．臭素化物制造方法．日本公开特许公报．特开平10-158202，1998．
[39] 张良．多溴二苯醚的制造方法．CN 86 1 03093A．1986．
[40] Jen-Tau Gu, Yuan-Ho. Purification of Halogenated Aromatic Compounds. US. 4,847,428. 1989.
[41] 周庆海．降低十溴二苯醚中游离溴含量的方法．精细石油化工．1993(2)：46～48．
[42] 周庆海．谈我国十溴联苯醚的生产．阻燃材料与技术．1992(1)：34～35．
[43] Wendell G., et al. Process for Producing Purified Prominated Aromatic Compounds. US 4,659,021.1987.
[44] Ayres, James T., Sands, John L., et al. Purified Brominated Aromatic Compounds. US 4,327,227.1983.
[45]牛宝琦．液溴精制方法．海湖盐与化工．1994，23(6)：7～11．
[46]张淑芬，王国强，蒋瑞春．氯化溴的新工艺研究．1999，28(6)：11～14．
[47]王伟，王汝志，高淑芹．制取氯化溴的室内试验．海湖盐与化工．1998，27(3)：39～40．
[48]卞光玉．固体有机溴化物中溴含量的测定方法．海湖盐与化工．1989，18(2)：56～57．
[49]王克信．十溴联苯醚的测定．广西化工．1998(1)：30～31，35．
[50]邢克兰．溴系阻燃剂中卤素分析方法的研究．海湖盐与化工．1989，18(2)：48～50．
[51]连云港市地方标准DB／3207 G20-88．
[52]分析化学手册(第二分册)．北京：化学工业出版社，1982．
[53]陈声宗．化工过程开发与放大(内部讲义)．
[2] 许际清，李立军．塑料阻燃剂的现状与开发．沈阳化工．1996(1)：32～35．
[3] 陈玉琴，张志德等．含溴阻燃剂的现状及发展前景．化学工程师．1998(2)：33～35．
[4] 李巧玲，欧育湘．无卤阻燃剂的研究进展．化工进展．1998(5)：24～28．
[5] 李秀瑜．阻燃剂的最新进展．河北化工．1998(4)：30～32．
[6] 黄汉生．日本塑料阻燃剂发展动向．现代化工．1998(4)：38～41．
[7] 张约伯．溴系阻燃剂．山西化工．1986(1)：51～52．
[8] 高良．溴及溴系阻燃剂．海湖盐与化工．1999，28(5)：7～10．
[9] 欧育湘．有机阻燃剂最新进展．现代化工．1997(4)：9～12．
[10] 欧育湘．阻燃剂．北京：兵器工业出版社，1996．
[11] 郭如新．阻燃剂发展现状．海湖盐与化工．1998，28(1)：43～44．
[12] 欧育湘．新世纪前10年全球阻燃剂发展预测．化工进展．1996(6)：29～32．
[13] 李慧君，刘学富，王艳菊等．化工商品手册．北京：冶金工业出版社，1994．
[14] 任世荣．塑料助剂．天津：天津大学出版社，1996．
[15] 付丽荣，曲波，刘治钦．溴系阻燃剂十溴二苯醚的合成．山西化工．1996(4)：12～13．
[16] 路振华．阻燃作用机理与阻燃技术进展．海湖盐与化工．1996，25(3)：30～31，38．
[17] L.M.SHORR．溴在阻燃技术中的应用．阻燃材料与技术．1996(1)：7～11．
[18] 樊真．阻燃剂PBO的色泽改进研究．阻燃材料与技术．1996(6)：1～3．
[19] 张志德，陈玉琴．溴系阻燃剂的国内外新进展．精细石油化工．1999(5)：59～62．
[20] 吴哲浩，陈康生，缪维芳．我国十溴二苯醚生产状况及建议．海湖盐与化工．1997，26(2)：24～28．
[21] 吴哲浩，缪维芳，郭黎青等．国内外十溴二苯醚产品质量比较．浙江化工．1996，27(2)：37～41．
[22] 李述道．浅谈十溴二苯醚生产方法种种及国内生产技术现状．青岛化工．1993(2)：5～8
[23] Toyo Soda, et al. Decabromodiphenyl Ether. Jpn. Kokai Tokkyo Koho JP 58, 222, 043. 1982.
[24] Pedjac, et al. Bromination Process for Preparing Decabromodiphenyl Ether from Diphenyl Ether. EP 0,126,569 A_1. 1984.
[25] Decaudin, Robert, et al. Brominated Diphenyl Ether Derivatives. Ger. Often. DE 3,622,224. 1987.
[26] Stollar, et al. Process for the Preparation of Decabromodiphenyl Ether with Improved Thermal Stability. EP 0,265,150A_1. 1988.
[27] Stollar, et al. Method for the Preparation of Decabromodiphenyl Ether. EP 0,265,151A_1. 1988.
[28] Bonnie G., et al. Process for Making Decabromodiphenyl Oxide. US 4,778,933.1998.
[29] Kulawaki Jerzy, et al. Method for Manufacturing Aromatic Compounds. Pol, PL 154, 173. 1992.
[30] Kubo Masashige, et al. Apparatus And Method for Preparing Decabromodiphenyl Ether. Ger. Offen. DE 3,326,343. 1985.
[31] Jenkner Herbert, et al. Preparation of Highly Brominated Aromatic Compounds. Ger. Offen. DE 3,422,673.1985.
[32] Decaudin Robert, et al. Catalytic Decabromodiphenyl Ether Manufacture. Ger. Offen. DE 3,622,236. 1985.
[33] Toyo Soda, et al. Decabromodiphenyl Ether. Jpn. Kokai Tokkyo Koho JP 60,32,741. 1985.
[34] Wendell G., et al. Process for Producing Purified Brominated Aromatic Compounds. US. 4,659,021. 1987.
[35] Bulych, Valentina N, et al. Process for Preparing Decabromodiphenyl Ether. Russ. Ru 2,061,673. 1996.
[36] Akhrem, Irenas, et al. Decabromodiphenyl Ether Production Method. Russ. Ru 2,046,789. 1995.
[37] 属秀雄，香川巧．臭素化混合物、制造方法及配合难燃性树脂组成物．日本公开特许公报．特开平10-175893．1998．
[38] 属秀雄，香川巧．臭素化物制造方法．日本公开特许公报．特开平10-158202，1998．
[39] 张良．多溴二苯醚的制造方法．CN 86 1 03093A．1986．
[40] Jen-Tau Gu, Yuan-Ho. Purification of Halogenated Aromatic Compounds. US. 4,847,428. 1989.
[41] 周庆海．降低十溴二苯醚中游离溴含量的方法．精细石油化工．1993(2)：46～48．
[42] 周庆海．谈我国十溴联苯醚的生产．阻燃材料与技术．1992(1)：34～35．
[43] Wendell G., et al. Process for Producing Purified Prominated Aromatic Compounds. US 4,659,021.1987.
[44] Ayres, James T., Sands, John L., et al. Purified Brominated Aromatic Compounds. US 4,327,227.1983.
[45]牛宝琦．液溴精制方法．海湖盐与化工．1994，23(6)：7～11．
[46]张淑芬，王国强，蒋瑞春．氯化溴的新工艺研究．1999，28(6)：11～14．
[47]王伟，王汝志，高淑芹．制取氯化溴的室内试验．海湖盐与化工．1998，27(3)：39～40．
[48]卞光玉．固体有机溴化物中溴含量的测定方法．海湖盐与化工．1989，18(2)：56～57．
[49]王克信．十溴联苯醚的测定．广西化工．1998(1)：30～31，35．
[50]邢克兰．溴系阻燃剂中卤素分析方法的研究．海湖盐与化工．1989，18(2)：48～50．
[51]连云港市地方标准DB／3207 G20-88．
[52]分析化学手册(第二分册)．北京：化学工业出版社，1982．
[53]陈声宗．化工过程开发与放大(内部讲义)．