高档颜料中间体丁二酰丁二酸二甲酯（DMSS）的改进研究
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摘要
丁二酰丁二酸二甲酯(简称:DMSS)是合成喹吖啶酮类颜料、1, 4-环己二酮和光敏聚合物的重要中间体。本论文利用石油的低级产物——丁二酸为原料,通过大分子树脂催化酯化反应、狄克曼缩合反应、酸碱中和反应及一系列的物理分离等方法,获得了一条对环境友好、生产成本低的工艺路线;得到与欧洲大公司(如荷兰DSM公司等)相媲美的高质量的丁二酰丁二酸二甲酯,为我公司获得了又一新的自主知识产权。
首先,将丁二酸与过量的甲醇在大分子树脂催化剂的催化下发生酯化反应,经精馏获得纯度99.8 %以上的中间产物丁二酸二甲酯(简称:DMS),一次反应收率达92 %,循环反应收率达98 %以上;而且大分子树脂催化剂可以无限次的循环使用;过量的甲醇及精馏的残余物丁二酸甲酯(简称:单酯)循环到下一批酯化反应中。没有废渣等产生,对环境无污染。
接着,采用过量的DMS与甲醇钠发生狄克曼反应,得到丁二酰丁二酸二甲酯钠盐(简称:DMSS钠盐)与DMS的混合物,采用高压力的膜压滤分离装置将二者分离,DMS循环回用,DMSS钠盐再用稀硫酸中和、分离即得到目标产物DMSS;纯度达99.5 %以上(注:是液相色谱含量),外观奶黄～白色;DMSS产品的主原料丁二酸消耗为1.8 t/t(理论消耗为1.034 t/t,一般的文献提供的消耗在2.4 t/t以上);不使用二甲苯、二甲亚砜等对环境有害的溶剂,整个工艺是绿色环保的。
Dimethyl 1,4-cyclohexanedione-2,5-dicarboxylate (DMSS) is an important intermediate for Quinairdone pigment, 1,4-cyclohexdianone and photosensitive polymer. In the present dissertation, a series of high-quality DMSS have been synthesized using succinic acid from the low level outcome of petroleum as an initial material and macromolecule resin as catalyst. The processes included esterification, Dieckmann reaction, neutralization and physical separating methods. The obtained products exhibit the same quality lever as European top manufacturer (e.g. DSM Corporation in Holland).
The esterification reaction was performed with succinic acid and excess methanol in the present of macromolecule resin, yielded dimethyl succinate (DMS) with a purity over 99.8 %. Significantlly, the macromolecule resin catalyzer could be recycle endlessly. The excess methanol and the remaining methyl succinate ( Monoester ) could be circulated in next esterifying reaction. There are not waste residue in this route. It won’t cause pollution.
Dieckmann reaction was carried out between excess DMS and sodium methylate. A mixture of dimethyl 1,4-cyclohexanedione-2,5-dicarboxylate sodium salt (sodium salt of DMSS) and DMS were obtained. Subsequently, a high-pressure thin-film separator was used to separate above mixture. DMS could be circulated in the process. The salt of DMSS was neutralized by sulfuric acid, separated by centrifugal machine, and then a purified DMSS solid was obtained with purity over 99.5%. The appearance of DMSS shows milk-yellow to white color. The consume amount of main material was 1.8 tons of succinic acid per ton of DMSS. The theoretic consume is 1.034 t/t, and normal literature reported was over 2.4 t/t. In this modified process, harmful organic solvents such as xylene, dimethyl sulfoxide were not employed, indicated that the novel route is of friendly-environment.
首先,将丁二酸与过量的甲醇在大分子树脂催化剂的催化下发生酯化反应,经精馏获得纯度99.8 %以上的中间产物丁二酸二甲酯(简称:DMS),一次反应收率达92 %,循环反应收率达98 %以上;而且大分子树脂催化剂可以无限次的循环使用;过量的甲醇及精馏的残余物丁二酸甲酯(简称:单酯)循环到下一批酯化反应中。没有废渣等产生,对环境无污染。
接着,采用过量的DMS与甲醇钠发生狄克曼反应,得到丁二酰丁二酸二甲酯钠盐(简称:DMSS钠盐)与DMS的混合物,采用高压力的膜压滤分离装置将二者分离,DMS循环回用,DMSS钠盐再用稀硫酸中和、分离即得到目标产物DMSS;纯度达99.5 %以上(注:是液相色谱含量),外观奶黄～白色;DMSS产品的主原料丁二酸消耗为1.8 t/t(理论消耗为1.034 t/t,一般的文献提供的消耗在2.4 t/t以上);不使用二甲苯、二甲亚砜等对环境有害的溶剂,整个工艺是绿色环保的。
Dimethyl 1,4-cyclohexanedione-2,5-dicarboxylate (DMSS) is an important intermediate for Quinairdone pigment, 1,4-cyclohexdianone and photosensitive polymer. In the present dissertation, a series of high-quality DMSS have been synthesized using succinic acid from the low level outcome of petroleum as an initial material and macromolecule resin as catalyst. The processes included esterification, Dieckmann reaction, neutralization and physical separating methods. The obtained products exhibit the same quality lever as European top manufacturer (e.g. DSM Corporation in Holland).
The esterification reaction was performed with succinic acid and excess methanol in the present of macromolecule resin, yielded dimethyl succinate (DMS) with a purity over 99.8 %. Significantlly, the macromolecule resin catalyzer could be recycle endlessly. The excess methanol and the remaining methyl succinate ( Monoester ) could be circulated in next esterifying reaction. There are not waste residue in this route. It won’t cause pollution.
Dieckmann reaction was carried out between excess DMS and sodium methylate. A mixture of dimethyl 1,4-cyclohexanedione-2,5-dicarboxylate sodium salt (sodium salt of DMSS) and DMS were obtained. Subsequently, a high-pressure thin-film separator was used to separate above mixture. DMS could be circulated in the process. The salt of DMSS was neutralized by sulfuric acid, separated by centrifugal machine, and then a purified DMSS solid was obtained with purity over 99.5%. The appearance of DMSS shows milk-yellow to white color. The consume amount of main material was 1.8 tons of succinic acid per ton of DMSS. The theoretic consume is 1.034 t/t, and normal literature reported was over 2.4 t/t. In this modified process, harmful organic solvents such as xylene, dimethyl sulfoxide were not employed, indicated that the novel route is of friendly-environment.
引文
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2. 李建生,孙洋洲. 丁二酰丁二酸二乙烷基酯.精细与专用化学品,1998,21
3. 郭玉良,陈声宗,张竞,李文生,叶姣. 丁二酰丁二酸二甲酯合成工艺研究.天然气化工.2001,26:17-18.
4. 林进,王兰芝,王红.磷钨酸催化合成丁二酸二乙酯的研究.广东化工,1999,1: 4-5.
5. 肖刚,孙朝晖.杂环有机颜料的最新技术进展.染料化工,2002,39(1):3-6
6. 张永坚.γ-型喹吖啶酮颜料的制备.涂料工业,1998,1:8-10.
7. 王庆河,张水生等.喹吖啶酮有机颜料制备工艺.CN 1229107A.1999,9,22.
8. 张利华. 喹吖啶酮颜料.中国涂料,1995,2:40-41.
9. 张水生. 喹吖啶酮有机颜料及其制备方法. 湖南化工,1995,25(1):21-25.
10. 王庆河,欧阳兰萍.二卤代苯胺对苯二甲酸的生产方法. CN 1244522A.2000,2,16.
11. 周瑜,李玉林,郑成潮,王碧玉.酸性树脂用作丁二酸二甲酯合成催化剂的研究.福建化工,2001,4:22-23.
12. 李顺芬,贾朝霞等. 甲醇钠和甲酸钠的化学分析.天然气化工,1999,第 24 卷.
13. 张越主编.精细化工中间体生产流程图解.化学工业出版社.1999.
14. 工业甲醇钠甲醇溶液 HG/T2561-94
15. 赵镶主编.催化剂.中国物资出版社
16. 周春隆等编著.有机颜料—结构,特性及应用.化学工业出版社.
17. 张思规主编.精细有机化学品技术手册(上下册).北京科学出版社.1992.
18. 凌关庭,王亦芸,唐述潮等编著.食品添加剂手册(上册).北京化学工业出版 社.1989.
19. 毛春晖,林原斌,朱美香等编著.2,5-二氧-1,4-环己二酸二甲酯的合成新方法[J].化学试剂,1998,20(4).
20. 毕向东,周春隆编著.高档有机颜料--喹吖啶酮颜料化学及进展[J].化工进展,1992,(6).
21. 周春隆,穆振义编著.有机颜料化学及工艺学[M].北京中国石化出版社.1997.164
22. Campbell, Colin D, Jaffe, Edward E, Process for the synthesis of dialkyl
succinylsuccinate esters and their conversion to dialkyl 2, 5-bis(arylamino)-3, 6-dihydroterephthalate esters [P]. EP:536083, 1993-04-07.
23. Meinhard Rolf, Leverkusen, Deffef-Ingo Schutze,Rutger Neeff,Process for the preparation of dimethyl succinylosuccinate, the disodium salt thereof, dianilinodihydroterephthalic acids, the dimethyl esters and salts thereof, and dianilinoterephthalic acids, and the dimethyl esters and salts thereof[P]. US: 4 435 586,1982-01-21.
24. Campbell, Colin D, Cole,Damien Thurber,Taylor,Harold Raymond,Process for the preparation of dialkyl succinylsuccinates[P]. EP:764 630,1996-07-24.
25. Schneider, Rudolf, Kahofer, Leo, Dialkyl succinylosuccinates [P]. DE: 3423 548,1986-01-02.
26. 森田光,ヅㄋルキルサヶシニルヶシネートの制造法[P]. 公開特许公 (A),平: 7-10809, 1995-01-13.
27. 狄原尊男,衣裴万将, 藤田信一. サクシニルいヶ酸ヅヱラルの制造法[P]. 公開特许公 (A), 平:8-268960,1996-10-15.
28. 陈新,孙连云,张继才编著. 辽宁化工,1995, (3): 32.
29. 陈新,孙连云,张继才编著. 化学世界,1995, (3): 126.
30. 吴庆银,林静雯编著. 辽宁化工,1994, (1): 28.
31. 王箴主编.化工辞典(第三版).化学工业出版社.21.
32. 周国泰主编.危险化学品安全技术全书.化学工业出版社.329.
33. 郭玉良等主编. 2,5-二氧-1,4-环己烷二甲酸二甲酯合成工艺研究. 精细化工,2000,(17):12.
34. 韩瑞生等主编.对甲苯磺酸催化合成丁二酸二甲酯的研究.化学工程师,2000.12.
35. 後藤勝彦.サクシニルいヶ酸ヅヱラルの制造法[P].日本國,公開特许公 (A),昭 52-59135,1977-05-16
36. 罗代暄主编.化学试剂与精细化学品合成基础(有机分册)[M],北京:高等教育出版社,1991.377.
37. 圜田武三,下山文舆. サクシニルいヶ酸ヅヱラルの制造法[P]. 公開特许公報(A),昭 62-106062,1987-05-16.
38. 任建南,孙福生等.英汉精细化学品辞典,北京理工大学出版社.
39. Olah G A,Keumi T,Meiclar D,Synethesis,9,29 (1978).
40. 张毓瑞等.精细石油化工, (1),24 (1986).
41. 李述文,范如霖编译.实用有机化学手册,上海:上海科学技术出版社.1981.
42. Clinton.R.O. and Larkowerk.J.Am.Chem.Scc,1948,70 (3):3135.
43. 俞眷信,唐艳倩,梁哲辉.精细石油化工,1996. (2):31-32.
44. 张向宇等编.实用化学手册,国防工业出版社,1988.
45. 刘宝殿,张爱黎,朱东升,潘华德等.钯(O)/离子交换树脂对有机锡试剂和有机卤化物偶联反应的催化性能和结构表征.催化学报,Vol 14,No 2,1994.
46. 宋丽娟,杜桐林.分子筛醚化催化剂的发展动态.石油炼制与化工, Vol 25,No 4,1994.
47. 姚蒙正,程侣柏,王家儒编.精细化工产品合成原理,中国石化出版社.1992
48. L. T. Harrison and S.Harrison,Compendium of Organic Synthetic Methods, Vol. 1(1971). Vol.2(1974), Vol.3,New York,Wiley,1977.
49. 日公開特许,昭 51-414742.,(1976).
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