CH303288A

CH303288A - Process for the manufacture of sulfur dyes.

Info

Publication number: CH303288A
Authority: CH
Inventors: Corporation Southern Dyestuff
Original assignee: Southern Dyestuff Corp
Priority date: 1952-02-29
Filing date: 1952-04-24
Publication date: 1954-11-30

Description

Procede de fahrication de colorants au soufre. La. presente Invention se rapporte au pro- (-6d6 connu de fabrication de colorarits au sou- fre par thionation d'un compose renfermant uii atome d'azote rel.ie, dune Part, ä un noyau aroinatique et, d'autre Part, ä un noyau benzenique substitue en para par un atome d'oxvgene ou un groupe hydroxyle. L'inven- tion a pour btit de perfeetionner ce procede, en. v ue de realiser un certain nombre d'avan- tages industriell tres importants. Jusqu'ä present, dans la fabrication de ces eolorants au soufre, la thionation etait suivie dune operation de preeipitation et de filtra- t.ion, en vue d'obtenir ui gäteau de filtre presse. La fil.tration a pour but d'enlever du colorant l.'exces de polysulfures ou de leurs produits d'oxvdation tels que 1'hyposulfite de so < lium et, d'obtenir un gäteau de colorant rau- sonnablement eoneentre, exempt de diluants et de polysulfures. 0n saut qu'il se produit toujours des pertes dann .des operations telles que aeration, filtration et manipulation du Aateau de filtre-presse, qu'il s'agisse de pro < luits liquides, en päte ou en poudre. L'op6ra- tion finale d'aeration est söuvent la cause prineipale de ees pertes. La filtration et les operations annexes sont lon@ues et coüteuses et. exigent beaucoup de ma.3n-d'oeuvre. Process for the production of sulfur dyes. The present invention relates to the known process for the production of sulfur colors by thionation of a compound containing a nitrogen atom linked, on the one hand, to an aromatic nucleus and, on the other hand. , has a benzene nucleus substituted in para by an oxygen atom or a hydroxyl group The purpose of the invention is to improve this process, with a view to realizing a certain number of very important industrial advantages. Until now, in the manufacture of these sulfur dyes, thionation has been followed by a precipitation and filtration operation, in order to obtain a filter press cake. to remove excess polysulphides or their oxidation products such as sodium hyposulphite from the dye and, to obtain a reasonably balanced dye cake, free of diluents and polysulphides. Losses always occur in operations such as aeration, filtration and handling of the filter press vessel, whether liquid, paste or powder products are involved. The final aeration operation is often the main cause of these losses. Filtration and related operations are long and expensive and. are labor intensive.

L?n. autre inconvenient, des procedes con- nus est la quantitA de solvant organique qu'ilrs exigent et qui eonstitue une depense impor- ta.nte. Le procede selon 1'invention est earacte- ris6 en ce que, en vue d'obtenir 1e colorant soss forme de solution eoneentree, an effectue la thionation en presenee dun sulfonate aro- matique. Ce compose seit d'agent solubilisaut. There. Another disadvantage of the known processes is the amount of organic solvent which they require and which constitutes a significant expense. The process according to the invention is characterized in that, in order to obtain the soss dye in the form of a one-input solution, an thionation is carried out in the presence of an aromatic sulfonate. This compound is a solubilizing agent.

0n evit.e ainsi 1'a necessite de s6parer un gä- teau de filtre-presse; il devient egalement pos- sible de reduire la quantite de solvant n6ces- saire dann une Proportion atteignant 9011/o, e'est-ä-dire d'utiliser seulement un dixieme en- viron de la quantite de solvant neeessaire jus- qit'ä present; ce procede perfectionne permet, en oatre, d'augmenter 1e rendement en colo- rant jusqu'ä 75 % ou plus,; il permet enfin une amelioration appreciable de fa eoneentra- tion de la solution du eolorant, qui, dann les procedes anterieurs ne depassait pas 5 ä 7 0/0 environ, alors quelle pest atteindre dann 1e present procede environ 10 ä, 15 0/0, soit sen- siblement 1e double. This avoids the need to separate a filter press cake; it also becomes possible to reduce the amount of solvent required by as much as 90%, i.e. to use only about one tenth of the amount of solvent required down to here; this improved process also makes it possible to increase the coloring yield up to 75% or more; finally, it allows an appreciable improvement in the way in which the dye solution enters, which, in the previous processes did not exceed approximately 5 to 7%, whereas what can be achieved in the present process is approximately 10 to 15% , or substantially double.

Comme sulTonates aromatiques, an pest utiliser les sulfonates sodiques du toluene, du xylene, du cymene, RTI ID="0001.0268"WI="4" HE="4" LX="1373" LY="1839"> .de la dimithylaniline et du tetrahydronaphtalene ou d'autres compo- ses semblables qui possedent la propriete d'augmenter la solubilhte du colorant dann la solution finale. Le compose quiS'est avere 1e plus avantageuy, est 1e xylene-sulfonate de so- dium. De preferenee, an utilise 1e sulfonate aromdtique ä une concentration de 3 ä 15 0/0, calculee sur fe poids total de la masse soumise ä 1a. thionation, ou bien de 3 ä 7 /o, ealculee sur 1e poids de la solution du colorant sulfure. .La masse obtenue par thionation peut ehre utilisee directement pour la, preparation dune solution liqlllde du eolorant prete pour la teinture, sans necessiter de filtration, paree que 1e sulfonate aromatique present dans la solution ameliore notablement la concentra- tion du eolorant restant en solution, et evite la precipitation habituelle de eolorant solide. As aromatic sulTonates, one can use the sodium sulphonates of toluene, xylene, cymene, RTI ID="0001.0268"WI="4" HE="4" LX="1373" LY="1839">.dimithylaniline and tetrahydronaphthalene or other similar compounds which have the property of increasing the solubility of the dye in the final solution. The compound which has proven most advantageous is sodium xylene sulfonate. Preferably, the aromatic sulphonate is used at a concentration of 3 to 15%, calculated on the total weight of the mass subjected to the a. thionation, or 3 to 7%, calculated on the weight of the solution of the sulphide dye. .The mass obtained by thionation can be used directly for the preparation of a liquid solution of the dye ready for dyeing, without the need for filtration, because the aromatic sulphonate present in the solution notably improves the concentration of the dye remaining in solution, and avoids the usual precipitation of solid eolorant.

Le procede est done particulierement avan- tageux en c6 qui concerne les colorants diffi- eilement solubles. Il Uait jusqu'ici indispen- sable de filtrer Ges colorants, ce qui entrai- nait las difficultes exposees ei-dessus. The process is therefore particularly advantageous with regard to poorly soluble dyes. It has hitherto been essential to filter the dyes, which gave rise to the difficulties described above.

Exemple 1: 0n ajoute 240 Parties de p-hydroxyphe- riyl-ss-naphtylamine ä un melange de 150 Par ties d'eau, 100 Parties de xylene-sulfonate de sodium, 100 Parties d'ether monoethylique du diethylene-glycol, 120 Parties de sulfure de sodium en paillettes et 212 pärties de soufre broye. 0n Fait bouillir au reflux Pendant 24 ä 36 heisres. La. masse Fondue est alors preie ä eire diluee ä, la concentration et ajustee ä 1'alcalinite v oulues. Example 1: 240 parts of p-hydroxypheriyl-ss-naphthylamine are added to a mixture of 150 parts water, 100 parts sodium xylene sulfonate, 100 parts monoethyl ether. diethylene glycol, 120 parts flake sodium sulfide and 212 parts ground sulfur. 0n Boil under reflux for 24 to 36 hours. The molten mass is then prepared to be diluted to the desired concentration and adjusted to the alkalinity.

Dans la formule ei-dessus, la quantite de solvant utilisee est inferieure ä 10 % de la quantite normalement necessaire. 0n notera egalement que la quantite de soufre est tres inferieure ä la quantite usuelle. 0n constate en effet que la majeure Partie .du soufre est consommee dann la thionation, de sorte qu'il Wen reste que peu en exces, contrairement aux procedes anterieiirs. In the above formula, the amount of solvent used is less than 10% of the amount normally required. It will also be noted that the quantity of sulfur is much lower than the usual quantity. 0n finds indeed that the major part of .du sulfur is consumed dann thionation, so that Wen remains only slightly in excess, unlike the previous processes.

Pour 1a. preparation dune solution du co- lorant prete pour la teinture, an peut operer comme seit : 1.50 Parties de la masse fondue ei-dessus sont additionnees de 178 Parties Beau, 12 pariies .de sulfure de sodium en paillettes et 80 Parties d'hydrosulfite de so- dium ä 40 010. Une teinture ä 20 % de ce co- lorant sur du coton .donne des nuances plei- nes sann addition d'autres produits ehimiques quelconques, sauf 1e sel normalement util!ise pour epuiser les bains de colorants au soufre. Exemple 2: La charge comprend 240 pa.rties de carba,- zol-p-quinone-imine sous forme de päte hu- mide, 350parties d'ether mono-ethyliqiiedudi- ethylene-glycol, 350 Parties de m6ta-xylene- sulfonate de sodium, 260 Parties de sulfure de sodium en paillettes et 400 Parties de sou- fre. 0n chauffe lentement Bette masse jusqu'ä 1'ebullition et an la Fait bouillir (101-106 C ) Pendant. 24 'a 36 heisres. 0n obtient une masse fondue d'un colorant bleu (Color Index N 969) qii'on peut utiliser directement pour la preparation dune solution. du eolorant prete pour 1a. teinture, en operant de la ma- niere decrite Jans 1'exemple 1 ei-dessiLs. Ce eolorant Leint aussi bien dann un bain de soude caustique et d'hy drosulfite de sodium que RTI ID="0002.0270" WI="7" HE="4" LX="1223" LY="839"> dans un bain forme directement par la sohtion ainsi preparee. La: nuance est nota- blement plus werte et plus viv e que Gelle obte- nue par 1e procede normal de fabrication. Exemple 3: 0n me1ange 567 kg de p-phenyliamino-p'- hydroxy-diphen-#rl-amine (ou de 1'indophenol correspondant.) avec .100 kg de 1'ether mono et.hylique du diethylene-glucol, 400 kg de xylene-sulfonate de sodium, 300 kg de sulfure de sodium solide, 500 kg de soufre broye et environ 1600 kg d'eau. 0n chauffe cette masse en 1'agitant jusqu'ä, l06 C, puis an 1,a soii- met au reflux Pendant 40 ä 48 heisres. La masse fondue est alors preie ä. ehre solubilisee, ce qui peut ehre effectiie par addition de 3300 kg d'eau, 450 kg de xylene-sulfonate de sodium, 550 kg de soude caustique ä. 50 % et 2360 kg dune solution d'hy drosulfite de so- dium ä 42 0/0. 0n obtient une solution aqueiise, prete ä. 1'emploi dun coloran.t. bleu (Color In dex N 961), dune nuance tres vive, verdä- treetdonnant des teintures plus regulieresque 1e eolorant pr'epare de la. maniere ordinaire. La production de ce eolorant West pas accom- pagn4e des ennuis habituels tels que la For mation .de goudrons au cours de la thiona- tion. Exemple 4: Si Fon remplace, dans la fabrication de- crite ä 1'exemple 2, la parbazol-p-quinone- imine par une quantite equivalente de N-ethyl- carbazol-p-quinone-imine, an obtient un autre eolorant bleu (Color Index N 971). Exemple 5: 0n dissout 150 Parties de p-liydroxy-di- phenylamine dans 200 Parties d'eaLi conte- nant 75 Parties de 1'ether monoethyliqLie du diethy lene-gly col, 75 Parties de xylene-smlfo- nate de soditim et 100 Parties de sulfure de sodium ä 60 0/0. 0n ajoLite ensuite 175 Parties de soufre broy4 et an agite la masse fondtie a 90 C Pendant 2 heures. 0n elev e ensuite la temperature jusqLi'ä 110-1l5 C et an ehauffe au reflLix jusqu'ä. obtention dela teinte brun rosige desiree, dRerminee par des essais de teinture. La masse fondLie est une solu- tion coneentree et homogene, eompletement exempte de matieres gotidronneLises et conve- iiant tres bien ä l@a preparation Tune solution du colorant pret.e ä 1'usage. Le colorant brun rosige a-insi prepare permet d'obtenir des tein- tures presentant une tres Bonne solidit4 aii lavage, au chlore et ä la himPre. For 1a. preparation of a solution of the dye ready for dyeing, one can operate as follows: 1.50 Parts of the melted mass above are added with 178 Parts Beau, 12 parts of sodium sulphide in flakes and 80 Parts of sodium hydrosulphite. 40,010 sodium. A 20% dyeing of this dye on cotton gives full shades without the addition of any other chemicals except the salt normally used to exhaust dye baths with sulfur. Example 2: The feed comprises 240 parts of carba,-zol-p-quinone-imine in the form of a wet paste, 350 parts of mono-ethyl ether, edudi-ethylene-glycol, 350 parts of of sodium meta-xylene sulphonate, 260 parts of flake sodium sulphide and 400 parts of sulphur. Bette mass is slowly heated to boiling and boiled (101-106 C ) for. 24' to 36 hours. A melt of a blue dye (Color Index N 969) is obtained which can be used directly for the preparation of a solution. eolorant ready for 1a. dyeing, operating in the manner described in Example 1 above. This Leint stain both in a bath of caustic soda and sodium hydrosulphite and RTI ID="0002.0270" WI="7" HE="4" LX="1223" LY="839"> in a bath forms directly by the solution thus prepared. The shade is noticeably richer and more vivid than gel obtained by the normal manufacturing process. Example 3: 567 kg of p-phenyliamino-p'-hydroxy-diphen-#rl-amine (or the corresponding indophenol) are mixed with 100 kg of the mono ether. hylic acid of diethylene glucol, 400 kg of sodium xylene sulphonate, 300 kg of solid sodium sulphide, 500 kg of ground sulfur and approximately 1600 kg of water. This mass is heated with stirring up to 106° C., then for 1 hour under reflux for 40 to 48 hours. The melt is then prepared. ehre solubilized, which can ehre effectiie by adding 3300 kg of water, 450 kg of sodium xylene sulfonate, 550 kg of caustic soda. 50% and 2360 kg of a 42% sodium hydrosulphite solution. 0n obtains an aqueous solution, ready to use. 1'emploi dun coloran.t. blue (Color In dex N 961), of a very lively shade, greenish and giving more regular dyeings than the eolorant prepared from there. ordinary way. The production of this eolorant is not accompanied by the usual troubles such as the formation of tars during thionation. Example 4: If Fon replaces, in the manufacture described in Example 2, the parbazol-p-quinone-imine by an equivalent quantity of N-ethyl-carbazol-p-quinone-imine , an obtains another blue eolorant (Color Index N 971). Example 5: 0n dissolves 150 Parts of p-liydroxy-di-phenylamine in 200 Parts of water containing 75 Parts of diethyl ether monoethyl ether, 75 Parts of sodium xylene sulfonate and 100 Parts of 60% sodium sulfide. 0n then added 175 parts of ground sulfur and stirred the melted mass at 90° C. for 2 hours. 0n then raises the temperature to 110-115 C and warms up to reflux. Obtaining the desired pinkish-brown shade, determined by dyeing trials. The melted mass is a concentrated and homogeneous solution, completely free of gotidronized materials and very suitable for the preparation of a solution of the dye ready for use. The pinkish-brown dye prepared in this way makes it possible to obtain dyes with very good fastness to washing, to chlorine and to water.

ha, p-hydroxy-diphenylamine peut etre reinplacee par des composes semblables, tels que la p-mgthyl@p'-hy droxy-diph6nylamine, wie p-aleoxy-p'-hydroxy-diphenylamine, ete., avec lesqLiels an obtient des colorants bruii rosige de solidite analogie. ha, p-hydroxy-diphenylamine can be replaced by similar compounds, such as p-methyl@p'-hydroxy-diphenylamine, wie p-aleoxy-p'-hydroxy-diphenylamine, ete., with which bruii rosige dyes of analogy fastness.

Claims

CLAIM Process for the manufacture of sulfur dyes by thionation of a compound containing a nitrogen atom linked, on the one hand, to. an aromatic nucleus and, on the other hand, a benzene nucleus substituted in para by an oxygen atom or a hydroxyl group, characterized in that, in order to obtain the dye in the form of a concentrated solution, an effectiae 1a. thionation in the presence of an aromatic sulfonate. 1. Process according to claim, characterized in that the aromatic sulphonate is a sodium xylene sulphonate.

2. Process according to claim, characterized in that the aromatic sulphonate is a sodium toluene sulphonate.

3. Process according to claim, characterized in that the aromatic sulphonate is a sodium eymene sulphonate.

4. Process according to claim, characterized in that the first aromatic sulphonate is a sodium sulphonate of dimethylaniline.

5. Process according to claim, characterized in that the aromatic sulphonate is a sodium tetrahydronaphthalene sulphonate.

6. Process according to claim, characterized in that from 3 to 15% of aromatic sulfonate is used, calculated on the total weight of the mass subjected to thionation.

7. Process according to claim, characterized in that 3 to 7% of aromatic sulphonate, calculated on the weight of the sulphide dye solution, is used.