【CAS名】Benzenemethanaminium, N-[4-[(2,4-disulfophenyl)[4-[ethyl(phenylmethyl)amino]phenyl]methylene]-2,5-cyclohexadien-1-ylidene]-N-ethyl-, inner salt, sodium salt.

【结构式】略

【分子式/分子量】C₃₇H₃₅N₂NaO₆S₂ = 690.81

【用途】织物染色和化妆品着色

资料I：BIOS 1433(=胶卷PB 81029), The manufacture of Triphenylmethane dyestuffs at Hoechst, Ludwigshafen and Leverkusen.

【Date of Investigation】September and October, 1946 (此书本人有收藏，所以抄录如下)

BIOS 1433, 22-25, Patent Blue A.F. (Hoechst) (其中CAS号为本人所加)

【Principle】1 mol Benzaldehyde 2,4-disulphonic acid [88-39-1] is condensed with two molecules ethylbenzylaniline [92-59-1], and the resulting leuco dyestuff [67828-29-9] oxidized with bichromate

【反应方程式】略。

【Plant】1. Leuco; 2. Dyestuff

【生产用设备】略

【Process 1】Leucodisulphonic acid (其CAS号[67828-29-9]) 3300 litres aldehyde disulpho [88-39-1] soln. containing 250kg aldehyde disulpho 100% M.W. 266 and about 2100kg monohydrate are charged in the condensation vessel. Sufficient caustic and soda is added to neutralize all but 1020kg of the H₂SO₄. To save time, a part of the soda ash necessary is replaced by the equivalent of 33 or 37% caustic soda soln. (e.g. 480kg soda ash and 453kg caustic 100%). The proportion of soda ash and caustic is determined by the percentage and volume of the aldehyde disulpho soln. and by the capacity of the vessel. The figure of 1020kg H₂SO₄ is quite empirical and has been found by experience to work satisfactorily. 425kg ethylbenzylaniline [92-59-1] (= theory + 7.15%) are run in via the measuring vessel, and after removing the blow out pipe the batch is agitated for 60 hrs. at a temP.of 100-103°C. The rather sticky condensation product formed at first, gradually hardens and eventually breaks up into a fine granular suspension with a pale blueish appearance. The dip pipe is inserted, and the contents of the vessel blown hot onto the nutsche. The nutsche is first flooded with cold water, to avoid too high a temperature on the washing under vacuum with about 1800 litres H₂SO₄ 5% soln. at 70°C followed by warm water till almost neutral. The leuco acid still contains excess ethylbenzyl aniline and is stirred with 2000 litres water in the dissolving vessel, and brought into solution by the addition of 110-120kg soda ash, at 60°C. The leuco acid is precipitated during 3-4hrs. with 420 litres 30% HCl. The precipitate is warmed to 80-85°C, agitated 2hrs., and whilst still under agitation, run to the second nutsche, filtered, washed first with 1800kg H₂SO₄ 5% at 70°C and then with almost boiling water to neutrality. The cake is sucked as dry as possible. The leuco acid is stirred with a second batch, processed similarly, into a rubber lined solution vessel and dissolved with 150kg soda ash and 20 litres ammonia 25%. The pHis adjusted to 6.9-7.1.

【Note】Almost boiling water must be used for washing to ensure satisfactory removal of the ethylbenzylaniline. A sample of the leuco acid is made alkaline in the lab. And the residual “green oil” estimated by extraction with ether. There should be less than 1% present. The solution of leuco disulpho sodium salt is blown to storage and from a sample the moisture content and sodium sulphate content estimated. (Sulphate about 0.5-1.0%). The dry weight of Na Salt (M.W. 714) is obtained, and the free acid content (M.W. 670) calculated.

【Yield】From 250kg aldehyde disulpho (M.W. 266) 570-575kg leuco disulpho (M.W. 670) (100/228-100/230)= 90.5-91.3% theory.

【Process 2】Dyestuff (其CAS号[3486-30-4])

Oxidations are in batches of 100kg leuco acid [67828-29-9] 100%. Test oxidations are made in the works lab. With variable quantities of bichromate and a fixed quantity of acid, the colour value and purity of product being nalysed in each case. The batch is then worked up on the best result obtained. About 550 litres leuco soln. containing 100kg leuco acid 100% are run into the oxidation vat via the measuring vessel, and diluted with water at 98°C to 2000 litres 25 litres bichromate soln. (= approx. 17kg 100%) (according to the best, test oxidation, in which 16.6, 18.0 and 19.4kg are used) are run in quickly from a measuring vessel. After 5 secs., under fast agitation and as quickly as possible, a solution of 24kg oxalic acid crystals in 150 litres water, 45kg acetic acid, 80% and 11kg H₂SO₄ 60°Be’ is added. The oxidation is stirred 1 hour at 95-100°C. To improve filtration 3kg kieselguhr are added, and the batch blown hot via a montejues through the sludge press to the conical vessel. Three such oxidations are heated to 80°C. and brought to 11°Be’ by the addition of 1200kg salt. Most of the colour separates at the bottom of the vessel in a glistening, bronzy form and is run direct on to the drying trays. The almost colourless mother liquor is removed by the copper siphon pipe and runs to waste via a separating tank. The colour which still remains in the vessel is steamed off and run to the drying trays. The dyestuff is dried in a vacuum oven at about 100°C.

【Yield】From 100kg leuco acid (100%) about 110kg Fw 38/100 = 290kg Type (97kg pure dye at 33.5/100). Services consumptions per ton product.

【公用工程单耗】略

资料II：PB 25626, Metods for production of dyestuffs, 1932-1939, 1107页, 【Price】Microfilm $6.00; Enlargement print $111.00.

PB 25626, 1282-1294, “Patentblau VF”, Jun 1932, 【Price】Microfilm $1.00; Photostat. $1.00.

Detailed and complete directions describe the processes and equipment for “Patentblau AF”and“Patentblau VF”. The former is made from benzaldehyde-2,4-disulfonic acid and ethylbenzylaniline; the latter uses diethylaniline. In German. (德文原件未抄录)

PB 25626, 1343, “Patentblau V” or “Xylenblau V” from benzaldehyde-disulfonic acid and ethylbenzylaniline. In German. (原件未抄录)

资料III：PB 74024, 902-904, Patentblau AF. (这是本人手工抄录的目录，原件未抄录)

资料IV：PB 74067, 142-144, Patentblau AF. (这也是手工抄录的目录，原件未抄录)

资料V：Colour Index Second Edition, 1956, Volume 3, Page 1351, C.I. 42080, C.I. Acid Blue 7 (Bright greenish blue)

【结构式】略

【制法】Condense 4-formyl-m-benzenedisulfonic acid with N-ethyl-N-phenylbenzylamine.

【发明者】Discoverer-Steiner, 1902.

【生产工艺参考文献】BIOS 1433, 22, 资料中未提到被美国人公开的PB报告！

资料VI：国内研究报告：

a.     天津染化二厂《酸性湖蓝A工艺改革》，[J] 染料工业, 1970, 2, 27-28。摘录：

1.     【缩合】一分子2,4-二磺酸苯甲醛与二分子乙基苄基苯胺，以硫酸为缩合剂，加入尿素作催化剂，使缩合时间由原72小时缩短到36小时

2.     【提纯】缩合后得到的粗无色基二磺酸，温水洗涤后碱熔，酸析，再以温水洗涤后成无色基二磺酸，砍掉了两次酸洗和一次水洗。

b.     天津染化二厂《酸性湖蓝A大型暂定操作规程》，[J] 染料工业, 1974, 3, 59.

将100% 2,4-二磺酸苯甲醛54公斤，溶于81公斤100% 硫酸中，加热至45-50°C时，加入100%乙基苄基苯胺91.8公斤，升温至100-103°C，保持72小时缩合反应，过滤。取滤饼用H₂SO₄和HCl提纯，将提纯后的物料用纯碱碱熔后，加入100% 重铬酸钾2.475-2.626公斤，硫酸1.29公斤，醋酸5.4公斤，草酸3.6公斤，于100°C氧化1小时，盐析，过滤，烘干得成品。

c.      潘国光《三芳甲烷系列酸性染料的合成》，[J] 染料工业, 1993, 4, 15-22。其中P.17，酸性湖蓝A。

1.     【缩合】将15% 硫酸升温至45°C，加入苯甲醛-2,4-二磺酸，搅拌至全部溶解，再于45-50°C下滴加乙基苄基苯胺，升温至至100-103°C，保温搅拌36小时至终点，然后过滤，水洗至pH5-6。若在反应体系中加入0.1-0.5%的尿素，能够加速缩合反应的完成。

2.     【提纯】将打成浆的无色基升温至60°C，用98%纯碱进行溶解，控制酸度，然后过滤，取滤液于60-85°C用盐酸进行酸析，然后过滤，水洗。取滤饼补水打浆后用98%纯碱中和，过滤，滤饼待氧化。

3.     【氧化盐析】取定量的提纯液，补水稀释，升温至100°C下加入计算量的重铬酸钾，硫酸，草酸与醋酸进行氧化。1小时后过滤，滤液于85°C下用精盐盐析，然后冷却至35-40°C，分出上层液，得盐析物。

资料VII：天津染料工业汇编，1980年，P.116-119，酸性湖蓝A生产工艺。

【产品结构式/反应式】略

【操作方法】如下：

1.     缩合：于缩合锅内配好15% 硫酸1620公斤，升温至45°C，加入2,4-二磺酸苯甲醛(100%)162公斤，搅至全溶，再于45-50°C，约2小时加入275公斤乙基苄基苯胺，搅拌10分钟后，加3.24公斤工业尿素，均速升温至100-103°C，保温搅拌36小时至终点，然后过滤水洗至pH=5-6。

1.     【提纯】用1000升水将无色基打成奖状，并升温60°C，用98% 75公斤纯碱进行溶解，控制pH=8，然后过滤，滤液放入酸析罐，补水至3900升，于60-85°C用111.09公斤100% 盐酸酸析，然后过滤水洗至pH=5-6，滤饼再次补水打浆，用98%纯碱58.5公斤中和至pH=7.3-7.5过滤，滤液补水到3000升分析含量，待氧化。

2.     【氧化盐析】取无色基液100% 27公斤，补水到600升，于100°C用99%重铬酸钾5.14公斤，92%硫酸2.8公斤，99%草酸7.2公斤，98%醋酸11公斤进行氧化。氧化保温100°C，1小时后过滤，滤液用72公斤精盐于85°C盐析，然后冷却到35-40°C，分出上面液层，并加热放出盐析物装入烤盘。

3.     【后处理】烤干盐析物于110-120°C左右，烤6-8小时后出箱经粉碎，混配，装桶入库。一锅缩合约得810公斤商品染料。

4.     【原料消耗定额】略

资料VIII：《日本化药染料便览》，1982年，P.314-315，Kayacyl Pure Blue FGA = C.I. Acid Blue 7。(资料为染色性能和各种织物上的染色牢度，不再抄录)

资料IX：Kosmetische Färbemittel / Colours for Cosmetics, 1984, C-WR Blau 11 = C.I. Acid Blue 7 = CAS [3486-30-4]. (共5页，其数据不再抄录)

资料IX：Coloring of Foods, Drugs and Cosmetics, 1999, P.204-205, C.I. Acid Blue 7, (C.I. 42080), 摘录：

【Chromatography】DC Kieselgel

【Carrer】Acetic acid ester 50ml + Ammonia 25% 10ml + Methanol 20ml

【Main applications】Cosmetics - Shampoo, shower gel; -Liquid soap.

资料X：国内不同年份“染料专业”出版物

(以前已引用过，再摘录编写，看来有点多余，所以不再重复了!)       

陈忠源 2022年1月26日，星期三