C.I. 酸性蓝1 =C.I. 食品蓝3（C.I. 42045）生产工艺。   CAS号 [129-17-9]

CAS名：Ethanaminium, N-[4-[[4-(diethylamino)phenyl](2,4-disulfophenyl)methylene]-2,5-cyclohexadien-1-ylidene]-N-ethyl-, inner salt, sodium salt.   Beil. 14. E2, 511; E3, 2298; E4, 2878.

【原版】Second Edition - Colour Index: Discoverer（发明者）- Steiner 1902.  摘录并翻译如下内容，同时抄录英文译文如下：

生产工艺参考文献：BIOS 1433, 25, 28; FIAT 1313, 2, 352; FIAT 764 – Patentblau VF and neu.

制法：Condense 4-formyl-m-benzenedisulfonic acid with N,N-diethylaniline, oxidize and convert the product into the sodium salt.

      Patent Blue VF Special is the free acid.

制法：4-甲醛基-间苯二磺酸与N,N-二乙基苯胺缩合，缩合物经氧化，然后转化成钠盐，专利蓝VF特制品为游离酸。

物性：Very soluble in cold and hot water (Blue); Soluble in ethanol (blue); H2SO4 conc. – mustard yellow; on dilution – golden yellow;

      Aqueous solution + NaoH – blue; violet on boiling.

物性：易溶于冷水和热水（呈蓝色）；溶于乙醇（呈蓝色）；溶于浓硫酸为芥黄色；用水稀释呈金黄色；染料水溶液加碱呈蓝

色，加热沸腾后为紫色。

BIOS 1433, 25.（=胶卷PB81029）。Patent Blue V new.  英国人译自德文，无资料来源说明。反应式本人有加注，如下。

Principle: 生产原理：

1 mol. benzaldehyde disulpho is condensed with 2 mols. Diethylaniline and the leuco disulpho oxidized with bichromate.

Plant: 设备： 1. Leuco acid. 1. 隐色酸用。（抄注：以下抄录不再分项！）。

 2 X 5500 litre condensation montejues, lead and tile lined, with lead covered agitators, hard lead heating coils and copper blow out pipes.

1 X 750 litre iron measuring vessel for diethylaniline。   1 X 4900 litre round nutsche, lead and tile lined with agitator capble of being raised or lowered, usual filtrate outlet and second one close to the filtering surface。   1 X 9500 litre lead and tiled storage and soln. vessel, with lead covered with phenytal。

2 X 12,000 litre storage vessels for leuco acid soln., with air agitation, bottom outlet, float gauge.

2.  Dyestuff.  2. 染料用。

1 X 6700 litre wooden vat, with wooden agitator, copper boiling pipe and wooden fume dust。   1 X 1400 litre iron measuring vessel for leuco soln.。

1 X 70 litre measuring vessel for chrome liquor。   1 X 4600 litre lead lined monteju, with wooden stirrer。   1 sludge press, 16 chambers, 800 / 800。

2 X 11,000 litre salting out vats, with hard lead boiling pipes, lead cooling coils, wooden agitators。   Centrifugal pump。   1 X 37 chamber“Monstre”press 1200 / 1200。  Vacuum drying oven, water heated, with pump, water heater, condense receiver。   1 X 20 tray rack with emptying device and dust extractor。

Process: 操作步骤。 1.  Leuco acid.  1. 隐色酸。

3000 litres aldehyde disulpho soln., containing 230 kg. aldehyde disulpho 100% M.W. 266 and about 1900 kg. monohydrate are charged in the condensation montejus and sufficient soda ash and caustic added to neutralize all but 280 kg. acid.  The proportion of soda ash caustic is variable for the reasons stated in the process Patent Blue AF – e. g. 528 kg. caustic 100% = 1170 litres 33% and 920 kg. Soda.  290 kg. diethylaniline (theory + 12.4%), is run from a measuring vessel into this solution, and the melt agitated 120 hours at 100 – 103℃.  The condensation, when complete, is blown hot on to the agitated nutsche after flooding the latter with cold water.  The agitator is not in operation during this initial filtration.  The cake is washed with 1800 litres H2SO4 5% and then with hot water to neutrality.  The cake is flooded with warm water, the vacuum shut off and bottom outlet closed, slurried by the agitator through the top outlet of the soln. montejus, followed by 200 litres rinse water.  The suspension is dissolved by adding about 80 kg. soda and 20 litres ammonia 25% and the pH adjusted to 7.9 – 8.1.  The solution is blown to storage, the moisture content and sulphate estimated, and the dry content of leuco acid sodium salt calculated.

Yield. From 230 kg. aldehyde disulpho, 437 – 448 kg. leuco acid M. W. 546 (100/190 – 100/195) = 92.5 – 95% theory.

2.  Dyestuff.  2.  染料。

From the soln. of three or four batches three test oxidations are made on the plant, each with 100 kg. leuco acid 100% using a constant of bichromate and oxalic acid and a variable quantity of H2SO4 600Be’ (56 – 60 – 64 kg.).  The batch is worked up on thebest oxidation result in 200 kg. portions as follows: -

About 1000 litres leuco soln. (200 kg. 100%) are run into the oxidation vat, and diluted with water at 30℃. to 3500 litres.  40 kg. Na bichromate 100% (as a 70% soln.) are run in, followed by 44 kg. oxalic acid in about 200 litres water, and 120 kg. H2SO4 600Be’ diluted with 100 kg. ice and water, added simultaneously.  The temp. rises to about 37℃. and is maintained at 37 – 38℃. for 0.5 hr.  The soln. is made faintly alkaline to B.Y. with 100 kg. soda ash, 3 kg.kieselguhr added, and the soln. filtered via. A montejus through the sludge press to the salting out vat, where it is brought to 310Be’ by addition of 2200 kg. sulphate, at 45℃.  The soln. is at this stage acid.  The dyestuff is isolated in a crystalline form, and is pressed, and dried.

Yield. From 200 kg. leuco acid M. W. 546, about 230 kg. FW. 52/100 Type V. = about 440 kg. Type V = about 174 kg. Pure Dye (39.5/100).

BIOS 1433, 28-9.（=胶卷PB81029）。  Patent Blue VF and VF special.  英国人译自德文。

Both brands are made from V New.  VF is the sodium salt with red outward appearance.  VF special is the free acid with green outward appearance.

Plant: 设备：

1 X 3500 litre soln. montejus (lead and tile lined) with wooden agitator, heating coil and lead blow out pipe。  1 X 3500 litre crystallizing montejus, as above。

1 X 330 litre rubber lined HCl measuring vessel。  1 X 20 chamber sludge press 800/800。  1 X 37 chamber“Monstre”press 1200/1200。  1 X 11,000 litre salting out vessel for mother liquors. With wooden agitator, lead coils and boiling pipe。  Separting tank for filtrate。  Vacuum drying chamber, tile lined, with 120 trays.

Process:  操作步骤：1.  Patent Blue VF.  1. 专利蓝VF。

The wet press cake from Patent Blue V New (from 500 kg. leuco acid 100%) is dissolved in 1000 litres water at 85℃. The Be’ of the soln. is reduced to 110 by adding about 50 litres of water and then raised to 16.5 - 170 by stirring in 200 kg. salt at 85℃.  The soln. is heated to 95℃. and blown through the sludge press to the crystallization montejus and stirred to cool to 20℃.  The dyestuff is pressed off, the filtrate running to the salting out vessel.  The crystalline dyestuff is dried in a vacuum oven at 80 – 90℃.  The filtrate from several batches is warmed to 40℃., the Be’ adjusted to 270 by the addition of sulphate, and the soln. just neutralized to Congo Red with soda ash.  The tar obtained is separated from the liquor after settling and dried.

Yield: From Patent Blue V new equivalent to 500 kg. leuco acid.  a.  415 kg. 45/100 Type V = 920 kg. Type VF.

b.  172 kg. dyestuff from the liquor 80/100 Type V and a much duller red appearance.

2.  Patent Blue VF Special.   2.  专利蓝VF 特制品。

The wet press cake from Patent Blue V new (500 kg. leuco acid 100%) is dissolved in 1000 litres water at 85 – 90℃.  The soln. is clarified hot, cooled to 40 – 50℃. and 115 litres HCl run in at this temp. from a measuring vessel.  The batch is cooled to atmospheric temp., and, after a 12 hr. stand without agitation, pressed.  The colour is dried in a vacuum chamber at 80 – 90℃.  The filtrate is pumped to the salting out vat, and worked up as VF.

Yield: From 500 kg. leuco acid 100%.  1.  415 kg. FW. About 42/100 Type V = about 990 kg. Type VF. = about 391 kg. Pure Dye (39.5/100).

2.  about 115 kg. from the liquor at a strength of 90/100 and much duller v. Type V.

The manufacture of VF Special has advantages in yield over that of VF.  The yield of pure dye is about 86% of the V new charge, wheres that of VF isonly 80%, and the yield of impure colour from the liquor is only 10%, as against 15%.

细田豊 《理论制造染料化学》。技報當 出版。1957年。P. 781.   パテント  ブル- V ニユ(IG). 译自BIOS 1433.

（1）“リウコ酸”

5.5 m3 の缩合机にベンザルデヒド-2,4-ジスルホン酸230 kgとH2SO4 1.9 tを含む溶液3 m3 をNaOH 33% 1170 lとNa2CO3 920 kgで中和してH2SO4 280 kgを残し，ジエチルアニリン290 kg（理论 + 12.4%）を加え，100 - 1030 に120 h搅拌する。热いままヌツュで滤過し，5% 硫酸液1.8 m3 で洗い，湯洗し，湯とかきまぜて9.5 m3 槽に移し水200 lで洗い落し，Na2CO3 80 kgとNH3 25% 20 lで溶しpHを7.9 – 8.1に调节する。リウコ酸437 – 448 kg,收率92.5 – 95%。

（2）Patent Blue V new（酸化）。

    数回分リウコ酸溶液を混合しその中からリウコ酸100 kgずつとり，重クロム酸盐と修酸の量，を一定にし，600Be’硫酸の量だけを56 – 60 – 64 kgと变化して3回试验作业をなし，その中，最良の结果によつて次のように作业する。

    リウコ酸200 kgを含む溶液1 m3 を水でうすめて3.5 m3，300 とし，重クロム酸ソ- ダ40 kgを70% 液として加え，修酸44 kg + 水200 lを加え。约370 に上り37 - 380 に0.5 h保温後Na2CO3 100 kgて弱アルカリ性にし，硅藻土3 kgを加え滤過し，滤液に450 でNa2SO4 2.2 tを加えて310Be’ とし析出した染料を滤過，亁燥する。230 kg (pure 174 kg) = 440 标准。

BIOS 1433, 25-27，本人摘译如下：

    1.  隐色酸的制备：缩合锅内，加入230公斤100% 2,4-二磺酸苯甲醛湿品和约1900公斤100% 硫酸，其总量为3000升，,1170升33% 液碱和920公斤碳酸钠中和到残酸量为280公斤，通过计量槽加入290公斤二乙基苯胺（过量12.4%），于100 – 103℃反应120小时，趁热用有搅拌的抽滤罐过滤，滤饼用1800升5% 稀硫酸洗涤，再用热水洗到中性，再用水浸泡，关真空，在搅拌下打入杨液器，设备用水冲洗，悬浮液用80公斤碳酸钠和20升氨水调pH到7.9 – 8.1，打入12立方米隐色酸贮槽。

得量；投入230公斤二磺化苯甲醛，得437 – 448公斤隐色酸，收率：92.5 – 95%。

2.  氧化合成染料：通过隐色酸计量槽，将1000升隐色酸液（合200公斤100% 隐色酸）加到氧化锅内，用30℃温水稀释到3500升，加入100% 重铬酸钠40公斤（配成70% 溶液），44公斤草酸（加200升水），同时加入用100公斤冰水稀释的600波美硫酸120公斤，加热升温到37℃，在37 – 38℃保温半小时，氧化液用100公斤碳酸钠中和到弱碱性，再加入3公斤硅藻土，然后用残渣压滤机过滤，滤液经盐盐析锅，在45℃加入2200公斤硫酸钠到310波美，进行盐析，此时溶液仍有酸性，用染料压滤机过滤，湿滤饼装盘烘干。

得量：投入200公斤隐色酸，得440公斤染料标准品。

FIAT 1313,II, 352.（=胶卷PB85172）。 Patent Blue VF. (Hoechst).  美国人译自德文，无资料来源说明。

To about 3300 l. disulfo benzaldehyde solution containing 330 kg. 100% aldehyde (M. W. 266) and about 2300 kg. 100% sulfuric acid add about 1975 kg. sodium carbonate to neutralize all acid in excess of 325 kg.  Add 406 kg. diethylaniline.  Heat 12 hours at 100℃., then 48 hours at 110℃, in closed vessel.  Drown in 3000 l. water and dilute to 9000 l. Filter.  Wash leuco cake with 1800 l. 5% sulfuric acid.  Wash cake acid free.  Dissolve cake at 90℃. by adding sodium carbonate (about 110 kg.) until weakly alkaline.  Analyze by evaporating sample to dryness and correcting for sodium sulfate content.  Yield was 635 kg. Mol. Wt. 546 or 93.5% of theoretical.

For oxidation, dilute solution equivalent to 100 kg. leuco as sodium salt to 1000 l. at 30℃.  Add 17 kg. sodium bichromate, followed by a solution of 30 kg. 95% sulfuric acid and 22 kg. oxalic acid crystals in 250 l. water at 90℃.  Agitate 10 minutes.  Neutralize free acid with 33 kg. limestone.  Filter.  Combine filtrates from 3 charges and salt to 230Be’ with 1530 kg.  Filter in presss and wash with 10% brine to displace mother liquor.  Dry in vacuo.  The yield per oxidation is 94 kg. dry weight, equivalent to 163 kg.  Patent Blue L or 187 kg. Patent Blue V.

PB 25626, 1282-1294. “Patentblau VF”.  Jun 1932年。12 pp. 1 美元，美国人介绍如下。

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 (see also PB 67416 = Method for producing“benaldehyde-2,4-disulfonic acid”); the latter uses diethylaniline.  In German.  这是德文专利蓝VF生产工艺，原件未抄录。

PB 74024, 911-3.  Patent Blue VF and new.  德文生产工艺，未抄录。

PB 74067, 145-7.  Patent Blue V. 德文生产工艺，未抄录。

PB 74067, 148-150.  Patent Blue V new.  德文生产工艺，未抄录。

PB 74067, 151-3.  Patent Blue VF.  德文生产工艺，未抄录。（以上均是本人手工抄录的目录，未表明年份！）。

天津染料工业汇编。1980年。P. 119-121.  酸性湖蓝“V” 操作方法。

1.  无色酸的制备：

在缩合锅内配15% 硫酸1620公斤，然后于常温到 -45℃，0.5小时加入100% 2,4-二磺酸苯甲醛162公斤，搅拌至全溶后，再于45 – 50℃，1小时加入二乙基苯胺199.2公斤，待成乳浊液后，可调节温度至100℃，加入元明粉648公斤（工业品），再升温106 – 109℃，回流保温48小时至终点，然后过滤，水洗，待酸洗。

2.  提纯：

用5% 硫酸600公斤，浸泡酸洗无色基饼，并用温水洗至pH = 6，然后用1000升水打浆，于60℃用纯碱液280公斤进行碱溶，调整体积为2500升，控制最终pH = 8.5，碱溶后，补水至3000升，取样分析含量，待氧化。

3.  氧化：

取无色酸液（折100% 50公斤）补水到600升，于30 – 40℃，用100% 重铬酸钠9.9公斤，100% 硫酸14.7公斤硫酸，工业草酸11.5公斤，工业碳酸钙20公斤，进行氧化，氧化后过滤，用300公斤精盐于60℃盐析，降温到30℃过滤。

4.  后处理：

滤饼吸干装盘于60 – 70℃，烤干，然后粉碎混配，装桶入库。每锅缩合约得600公斤商品染料。

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. P. 17. 酸性湖蓝V。

    1.  无色酸制备：于常温 -45℃，将苯甲醛-2,4-二磺酸加入到15% 硫酸中，搅拌至全溶。再于45 – 50℃下滴加二乙基苯胺，待成乳浊液后，调整温度至100℃，加入无水硫酸钠，再升温至106 – 109℃，回流保温反应48小时至终点，然后过滤，水洗，待酸洗

2.  提纯：将无色酸滤饼用5% 硫酸浸泡后酸洗，然后用温水洗至pH = 6，滤饼稀释打浆后于60℃用30% 碳酸钠液进行碱溶，调整体积，最终pH 控制在8.5，稀释后取样分析含量，待氧化。酸洗务必干净，以除尽未反应的二乙基苯胺，否则影响染料质量。

3.  氧化：提纯液经稀释后于30 – 40℃用重铬酸钠，硫酸，草酸与硫酸钙进行氧化，氧化完成后过滤，滤液于60℃加精盐盐析，降温至30℃后过滤。

关于染料用于化妆品的资料：

DFG 《Kosmetische Färbemittel / Colours for Cosmetics》. Second Revised Edition. 1984.  C-ext. Blau 13. 共6页。

Dünnschicht / Thin layer:  两个斑点，

Axel Mixa 《Coloring of Foods, Drugs and Cosmetics》. 1999. P.200-201.  C.I. 42045.  Patentblau VF.

Chromatography: DC（蒲板层析法）。 Kieselgel   Carrier（展开剂）。Acetic acid ester 11 ml + Pyridine 5 ml + Water 4 ml

Main applications:  Cosmetics:  -Shampoo, foam batch, shower gel;  -liquid soap.

C.I. 酸性蓝1，国内出版物的回顾：

1995年。 中国化工信息中心 出版，《染料品种指南》。 P. 87.  C.I. 酸性蓝1（C.I. 42045）。

2000年。沈阳院 出版。 《世界染料品种 – 2000年》。 P. 241.  C.I. 酸性蓝1（C.I. Acid Blue 1  C.I. 42-45）。

2005年。全国染料工业信息中心 出版。《世界染料品种 – 2005年》。 P. 113.  C.I. 酸性蓝1 （C.I. Acid Blue 1, C.I. 42045, CAS 129-17-9）。

何岩彬 主编 《染料品种大全》沈阳出版社 出版。2018年。 P. 202-3. C.I. 酸性蓝1 （C.I. 42045, CAS:129-17-9; EC 204-934-1）

陈忠源 2020年11月29日星期日。