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CAS号[83-83-0]生产工艺-联邻甲苯胺-3,3’-二磺酸

【CAS名】[1,1’-Biphenyl]-2,2’-disulfonic acid, 4,4’-diamino-5,5’-dimethyl-

【用途】染料中间体：酸性黄44；酸性红89, 145用。

BIOS 1153 (=胶卷PB 85687), The manufacture of miscellaneous Dyestuff intermediates (Excluding Naphthalene derivatives).

 

BIOS 1153, 283-5, O-Tolidine-6,6’-disulphonic acid. (Leverkusen), 书价1.12英磅。

【反应式】略

【产品】C14H16N2O6S2 = 372.42

【CAS号】[83-83-0] (抄录文中CAS号为本人所加)

【Plant】4 1000L capacity C.I. pans (reducers), 1 Filter press (for zinc residue), 1 Receiver, 1 Conversion vat. Iron, rubber and tile-lined. Lead cooling coil (brine) and lead agitator, 1 Nutsche(抽滤槽). Acid resisting vat (for acidification of pure product).

【Materials】2-Nitrotoluene-4-sulphonic acid [97-06-3], 4 X 188kg. 100% (sodium salt)  (≈ 60 kg. NaNO2) Soda ash [497-19-8] 2 X 100kg + 4 X 2kg Caustic liquor 50%, 4 X 14L. Hydrochloric acid 190Be’ 1800L (for conversion). Hydrochloric acid 190Be’ as required (for purification).

【Process】Reduction: 4 Reduction vats, each of 1000L capacity, are each charged with 180L of water and 2kg of soda. To each is then charged 188kg of 100% 2-nitrotoluene-4-sulphonic acid (sodium salt) and the mixture well agitated. 7L of 50% caustic liquor is charged (to each) and the temperature adjusted to 30°C, 65kg of zinc dust (90%) are added in small portion (21/2kg) over 8–10 hours at 30–35°C.  After stirring for a further 10 hours at this temperature, a further 7L of caustic liquor are added followed by another 65kg of zinc during 8–10 hours. After stirring for 6 hours, the temperature is raised during 4 hours to 80–85°C, and held 6 hours. If the batch becomes very thick more water can be added at this stage. At this stage, reduction has reached the azo-compound. A further 130L of water are added followed by 35–40kg zinc dust at 85–90°C during 4–5 hours. Reduction to the hydrazo-compound is complete when a sample spotted on filter paper gives a colourless outspread. When satisfactory, the reducer is filled up with water and the temperature adjusted to 50°C. The batch is blown through the screening press and the other three reducers similarly screened. The combined residue is washed with 500L of warm water, and then charged back into 2 of the reducers and re-extracted. The slurry is re-filtered. The total volume of screened liquor is approx. 6000L.

【Conversion】The conversion vat is charged with 500L of 190Be’ hydrochloric acid and 1000L of water. It is cooled to 0°C with brine and the Hydrazo solution run in simultaneously with a further 1300L of 190Be’ hydrochloric acid. The temperature is held at 0–5°C. After stirring a further 2 hours, 5–6kg of zinc are added.

The precipitated tolidine disulphonic acid is filtered on a nutsche. 1500L of the mother liquor is charged back for the next conversion and the remainder runs to drain.

【Purification】The paste is charged into two of the reducers (1/2 to each) containing 500L of 20% soda solution. The mixture is heated to Dissolve, screened through a press and the clarified solution acidified with hydrochloric acid (strong acid to Congo). The precipitated tolidine disulphonic acid is cooled to 15°C and dropped to the nutsche. The mother liquor goes to drain.

【Yield】75 – 76% theory. It can be dried on enamel trays and then ground.

 

PB 25624. Manufacturing of Dyes and Intermediates. 共696页。

PB 25624, 992 – 993, Tolidine disulfonic acid. 德文生产工艺。

 

张澍声编译《精细化工中间体工业生产技术–BIOS FIAT PB Reporter》,《染料工业》编辑部出版，1996年，P. 177。

联邻甲苯胺-6,6’-二磺酸，译自BIOS 1153, 283

【结构式】略

【书价】￥ 258.00.

【还原】共4个还原锅，每隔1000L，每个加入180L水和2kg Na2CO3，然后加入188 kg 100% 2-硝基甲苯-4-磺酸钠，混合物很好搅拌。 每锅加入7L 50% NaOH溶液，温度调节到30°C。在30–35°C于8–10 hr内以每批2.5kg加入65kg 90%锌粉，再在此温度搅拌10hr后，再加入7L 50% NaOH溶液，于8–10 hr内加入另外65kg锌粉。搅拌6hr后，于4hr内升温至80–85°C，并保持6hr。在此阶段如果反应物变得很粘稠，可以加入更多的水。在此阶段还原到偶氮化合物。

于4–5hr内在85–90°C再加入130L水，随后加入35–40kg锌粉。当取样滴在滤纸上得到无色渗圈，即完成了还原到氢化偶氮化合物。如果满足这些条件，还原锅用水充满，温度调节到50°C，滤清，其他3个还原锅也相似进行。合并的滤饼用500L温水洗涤，然后返回到两个还原锅中，并再萃取，然后过滤。过滤得滤液总体积接近6000L。

【重排】重排锅中加入500L 30% 盐酸和1000L水，用冰盐水冷却到0°C，将上述氢化偶氮化合物溶液和1300L 30% 盐酸同时流入，温度保持在0–5°C，再搅拌2hr，加入5–6kg锌粉。沉淀的联邻甲苯胺二磺酸抽滤，1500L滤液用于下次重排加料，其余的排放。

【精制】滤饼加到两个还原锅中(各占一半)，锅内预先加有500L 20% 碳酸钠溶液。混合物加入溶解，滤清，澄清溶液用盐酸酸化至对刚果红呈强酸性。沉淀的联邻甲苯胺二磺酸冷却到15°C，抽滤，母液排放，滤饼可在搪瓷盘中干燥，研磨。

【收率】75%–76%。 该产品不在致癌氨基物之列。

 

张澍声编译《精细化工中间体及产品生产工艺》，沈阳院出版，2006年，P. 423。联邻甲苯胺-6,6’-二磺酸，译自BIOS 1153, 283，译文完全相同，不再抄录。书价：￥ 480.

 

Colour Index Second Edition, 1956, Volume 3, Page 3695. 2,2’-Biphenyldisulfonic acid, 4,4’-diamino-5,5’-dimethyl-. C14H16N2O6S2, Mol. Wt. 372. 用于C.I.23900, 23905, 23910.

 

何岩彬主编《染料品种大全》，沈阳出版社出版，2018年，P. 1995，中文名称：5,5’-二甲基联苯胺-2,2’-二磺酸。可合成的染料：C.I.酸性黄44；C.I.酸性红89；C.I.酸性红145。书价：￥ 1,700.

 

陈忠源 2021年9月6日，星期一

 



文章作者：陈忠源