CN1051785C - Dry leuco sulphur dyes in particulate form - Google Patents
Dry leuco sulphur dyes in particulate form Download PDFInfo
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- CN1051785C CN1051785C CN93115065A CN93115065A CN1051785C CN 1051785 C CN1051785 C CN 1051785C CN 93115065 A CN93115065 A CN 93115065A CN 93115065 A CN93115065 A CN 93115065A CN 1051785 C CN1051785 C CN 1051785C
- Authority
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- China
- Prior art keywords
- drying
- dyeing
- temperature
- leuco sulphur
- reaction
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- 239000000975 dye Substances 0.000 title claims abstract description 41
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000005864 Sulphur Substances 0.000 title claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 37
- 238000004043 dyeing Methods 0.000 claims abstract description 19
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 6
- 239000012736 aqueous medium Substances 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 19
- 238000005507 spraying Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000003344 environmental pollutant Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 231100000719 pollutant Toxicity 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 238000006722 reduction reaction Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- -1 alkali metal sulfite Chemical class 0.000 claims description 3
- 229910052728 basic metal Inorganic materials 0.000 claims description 3
- 150000003818 basic metals Chemical class 0.000 claims description 3
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 claims description 3
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 208000007976 Ketosis Diseases 0.000 claims description 2
- 150000001323 aldoses Chemical class 0.000 claims description 2
- 150000002584 ketoses Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- ODFJOVXVLFUVNQ-UHFFFAOYSA-N acetarsol Chemical compound CC(=O)NC1=CC([As](O)(O)=O)=CC=C1O ODFJOVXVLFUVNQ-UHFFFAOYSA-N 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 150000001720 carbohydrates Chemical class 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 25
- 210000002268 wool Anatomy 0.000 abstract description 7
- 239000011541 reaction mixture Substances 0.000 abstract description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001694 spray drying Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract 2
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 229920001021 polysulfide Polymers 0.000 abstract 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 abstract 1
- 150000003568 thioethers Chemical class 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 description 12
- 235000019580 granularity Nutrition 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 239000004744 fabric Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 2
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- GZCGUPFRVQAUEE-UHFFFAOYSA-N 2,3,4,5,6-pentahydroxyhexanal Chemical compound OCC(O)C(O)C(O)C(O)C=O GZCGUPFRVQAUEE-UHFFFAOYSA-N 0.000 description 1
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001320 aldopentoses Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229940017705 formaldehyde sulfoxylate Drugs 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- SBGKURINHGJRFN-UHFFFAOYSA-N hydroxymethanesulfinic acid Chemical compound OCS(O)=O SBGKURINHGJRFN-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B49/00—Sulfur dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0077—Preparations with possibly reduced vat, sulfur or indigo dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/14—Wool
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Coloring (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
By reducing a sulphur dye (S) in aqueous medium with a reducing carbonyl compound in the presence of alkali metal hydroxide and optionally alkali metal (bi)sulphite at temperatures above 60 DEG C. and drying the reaction mixture, there are obtained very stable leuco sulphur dyes (L), which are practically free of sulphides and polysulphides, are readily and completely soluble in water and are usable for the dyeing of substrates dyeable with sulphur dyes, by which a disturbing development of H2S or a disturbing inorganic sulphide occurrance in the waste water can be efficiently avoided; by spray-drying in a drying time <4 minutes as described there are obtained sulphide-free, stable leuco sulphur dyes (L) readily soluble in water and particularly suitable for sulphide-free dyeing, in particular for the dyeing of polyamidic fibrous substrates, especially of wool.
Description
In No. 9210931. (open day: on November 25th, 1992 of UK Patent Application, numbering 2255981, GB-A-2255981 hereinafter referred to as, corresponding to Chinese patent application 92-103925.5 number, it is for referencial use that its content is merged in this paper) in the method for the water-soluble leuco thioxine dyes that following production does is disclosed: exist and can exist under the condition of alkali metal sulfite and/or basic metal hydrosulphite at alkali metal hydroxide, make thioxine dyes also dry in＞60 ℃ of reductibility carbonyl compound reactions with significant quantity in aqueous medium, wherein said reaction and drying can part be carried out at least simultaneously.
Have now found that, if this reaction mixture spraying drying is especially used hot gas, drying, preferably reaction and dry can be finished in the very short time, is less than 4 minutes, particularly can in seconds finish.
The present invention relates to described spray-drying process, relate to corresponding desciccate and the purposes aspect dyeing thereof.
Therefore the invention provides the production method of water-soluble dried leuco sulphur dye (L), wherein, with thioxine dyes (S) in aqueous medium and under＞60 ℃ temperature with the reductibility carbonyl compound (A) of significant quantity reaction and dry, be reflected under the condition that alkali metal hydroxide (B) exists and can exist alkali metal sulfite and/or basic metal hydrosulphite (C) and carry out; Wherein said drying is finished with spraying drying, time of drying＜4 minute.Composition (S), (A), (B) and (C) and accordingly amount and, if reaction and drying separately carry out, reaction conditions also as above-mentioned GB-A2255981 define.(S) can be any commercially available thioxine dyes, perhaps also can be oxidation or/and acidifying vulcanization reaction product, Shi form preferably, preferably washed filter cake.(A) specifically be ketose or the aldose or the pyruvic alcohol of monomeric or oligomer, preferably aldopentose monomer or aldohexose monomer.Operable (B) and (C) specifically be corresponding lithium, sodium or potassium compound wherein, preferentially selects sodium compound for use.(A) consumption in the scope of the 1-40% of (L) weight, is better with 5-15% preferably.(A)/(S) weight ratio is preferably in the scope of 5/100-40/100, is better with 10/100-20/100.(B)/(S) weight ratio is good with following situation, has excessive (B) in final product, is good with the 0.5-20% of (L) weight, is better with 3-10%.(C) consumption is comparatively favourable in the scope of the 1-40% of (L) weight, is good with 2-24%, and 5-10% is best.(C)/(S) weight ratio is good in the scope of 5/100-40/100, and is better in the scope of 10/100-20/100.(A)/(C) weight ratio is good in the scope of 1/5-5/1, is best with 2/1-1/2.Water content in the mixture to be dried, the total water content of the reaction mixture when promptly beginning drying is advisable with following situation at least: mixture is sprayed easily, and water is represented external phase; Water content≤95 weight % are comparatively favourable, described in above-mentioned GB-A2255981, are good with 10-90 weight %, and 20-80 weight % is best.
Drying can be finished by any known conventional spraying drying system own, for example with spraying-frost drying (if after drying has been finished in reaction) or the most handy hot gas (G).
Suitable gas (G) be under the spraying drying condition to (L) basic inert gasses, promptly in spraying drying, can not make product (L) produce the gas of substantial chemical modification.Admissible gas (G) has for example nitrogen, and superheated vapour is or/and air.With regard to the leuco sulphur dye (L) of producing easy-to-use warm air oxidation, gas is good with the rare gas element of anaerobic basically, preferably nitrogen or also can be the mixture of air and nitrogen.Leuco sulphur dye (L) for more anti-atmospheric oxidation, for example have higher initial stage warm air oxidation threshold and can be in spray-dryer by hot air treatment destructive leuco sulphur dye (L) in short-term the dyestuff (L) of Colour Index Leuco Sulphur Black 1 and 2 [for example corresponding to], warm air can be used as hot gas (G).The warm air that is suitable for generally is preferred for industrial reaction; It can be determined by several tentative experiments the suitability in given dyestuff (S) and each comfortable spraying drying of dyestuff (L).Most preferred (G) is nitrogen.
Carry out drying with hot gas (G) and have special benefit simultaneously with the reduction reaction part at least; Reduction reaction is preferably carried out simultaneously with drying, so that the water content that makes reaction mixture is consistent with the water content of mixture to be dried.
Dry can carrying out in the temperature range shown in the GB-A2255981, perhaps even can carry out under higher temperature, this depends on the dry system in the spray-dryer.The temperature in (i.e. (G) temperature when being admitted to spray-dryer) that enters the hot gas (G) of moisture eliminator can be within the scope of known routine operation temperature own, specifically be＞70 ℃, 〉=105 ℃ comparatively favourable,＞150 ℃ is best, the upper limit of temperature in (G) is mainly decided by the performance and the size of moisture eliminator, ≤ 300 ℃ comparatively favourable, ≤ 280 ℃ is best, enter the temperature in of spray-dryer for (G), preferred range is 150-300 ℃, especially 165-300 ℃, preferred temperature when (G) being admitted to moisture eliminator is that drying begins the temperature of carrying out, and promptly greater than the boiling temperature of water, specifically is in 105-300 ℃ scope, preferably in 150-280 ℃ scope, especially 〉=200 ℃.
Gas (G) suitable as 1.96 * 10
5～4.90 * 10
6Handkerchief (2-50kg/cm
2), best 2.45 * 10
5～2.45 * 10
6Handkerchief (2.5-25kg/cm
2), especially 2.94 * 10
5～1.18 * 10
6Handkerchief (3-12kg/cm
2) scope in superatmospheric pressure under be admitted to moisture eliminator.
Preferably mixture to be dried is sent in the spray-dryer at elevated temperatures, described temperature suits below the boiling temperature of mixture, is preferably in 50-100 ℃ the scope, and 70-98 ℃ comparatively favourable, being best in 85-98 ℃ scope.Drying in spray-dryer suits to carry out under such condition and parameter: the temperature out of gas (G) (promptly (G) leaves the temperature of spray-dryer), for warm air and/or nitrogen, comparatively favourable in 60-180 ℃ scope, preferably in 100-150 ℃ scope; Perhaps, comparatively favourable in 105-250 ℃ scope for superheated vapour, be good with 150-240 ℃.Moisture eliminator is suitable to be operated as follows: in the spraying granule dropping process in moisture eliminator, the temperature of reaction mixture raises greatly, and dried particles with than the high 10-60 of temperature ℃ of the mixture to be dried that is admitted to moisture eliminator, preferably high 15-40 ℃ temperature out is left moisture eliminator.
Spray-dryer can be the moisture eliminator that for example conventional spraying drying is used, and particularly can spray the exsiccant liquid composition by atomizing, specifically being the moisture eliminator that nozzle atomization, rotary-atomizing or sound atomisation become drying products with waiting.Hot gas (G) can feed with the mode that spraying granule is following current or adverse current.According to a preferred working method, spraying drying is finished with the injection atomizing.Another preferable methods is to use the rotary-atomizing method, especially vertical rotating atomization (for example also utilizing steam turbine).
Being used for that composition is sprayed into the nozzle of moisture eliminator or other feeding unit (for example cup, dish, steam turbine) should select by the principle that adapts with the composition that enters.Specifically, if composition to be painted is the dispersion that contains (S), then the selection of the kind of spraying plant, shape and size should be fit to dispersion to be sprayed.The preferable feature according to the present invention, waterborne compositions to be painted, be specifically do not use the composition of (A) reductive Containing Sulfur dyestuff (S) to be preferably in nothing (A) as yet and situation about (C) existing under be preheated to suitable temperature so that it easilier flows or become liquid.Described suitable temperature is≤100 ℃, and specifically be in 50-98 ℃ scope, be good with 60-95 ℃.Carry out comparatively favourable as follows: in this step, (S) to a great extent still unreacted become (L) but just use (B) solubilising.(A) and optional (C) should be admitted in the spray-dryer immediately after (S) and the aqueous mixture (B) [wherein (S) the most handy (B) solubilising] of preheating mix.
Specifically be that reaction and exsiccant time＜2 are minute comparatively favourable time of drying, is good in second at 1-60, is best in second with 2-30.To be dried, specifically be that the rate of feeding of question response and exsiccant composition should come surely according to other the parameter and the water content of composition, can be for example in 100-100001/ hour scope, preferably 200-50001/ hour, for example be approximately 4m
3/ hour, this also depends on the ability of moisture eliminator.
If in a preferred aspect, reaction in hot gas (G) and spraying drying to small part is carried out simultaneously, if still unreacted reactant admixture sprays into moisture eliminator and reduction reaction is carried out fully then better; In the drying process that spray droplet falls, exist and can exist (S) under the condition of (C) to carry out at (B) with being reflected in each spraying granule (A), within several seconds, just obtain the dried particles of water-soluble leuco thioxine dyes (L).Specifically, if in a preferred aspect, composition contains unreacted thioxine dyes (S), with hot gas (G) particle is carried out in the exsiccant process, thioxine dyes (S) is transformed into the improved reaction product of solubleness (L) gradually, and this reaction product (L) can be partially soluble in the water that is present in the particle at least; Yet water is evaporated in spray-drying process, therefore, when the outside of particulate during drying (L) during in enrichment, in particulate inside, still the water that exists promotes (S) that still exist further to react, when the dry end of particulate, the reaction that (S) in each particle generates (L) is actually completely.
This reaction is carried out fully surprisingly, and the product that is obtained is the water-soluble dried leuco sulphur dye (L) of graininess, is good with dumpable granularity.
As desciccate, specifically be desciccate (L), be meant as by as described in the drying means solid leuco sulphur dye that can get, particularly water content is a solid leuco sulphur dye as described below: by the weight of product, water content≤5% is good with≤2%, is best with≤0.5%.
According to system and the structure and the used operating parameters of spray-dryer, the dried particles that is obtained can be corresponding shape, size and consistence (consistency).For example form has: the rigidity porous particle or/and hollow particle or/and broken particle or/and particle or thin slice or other form of flattening.According to the structure and the working conditions of spray-dryer, desciccate is can multiple granularity obtained, and specifically, granularity is in the scope of 1 μ m-2mm.For example in preferred atomizer system, granularity is mainly in the scope of 1-20 μ m.Some dry particulate granularities are thin especially, the fine powder of granularity≤5 μ m and even 10 μ m particularly, then it has the advantage that can be accumulated into than the particle agglomerate of volume particle size, and the particle agglomerate is good in the 0.01-10mm scope, serving as better in 0.01-4mm, special 0.05-4mm scope; Help obtaining dustless basically product like this, for example thin slice or the particle form of granularity in the 0.2-2mm scope preferably.
If be necessary, the suitable system of gathering directly can be fixed or is connected on the outlet of moisture eliminator, so that fine powder is directly sent in the equipment of gathering.The described equipment that gathers can be the suitable system of any routine, and for example mixing tank, nodulizer, apparatus for making pearl ball or any other are suitable for providing the particulate system of required size.For fine powder being condensed into bigger particle, can use suitable, preferably non-water, water-soluble additive, the particularly known dust-proof additive that can be used for, for example glycerine, C usually
2-C
4Aklylene glycol class, oligomeric-(C
2-4-alkylidene group)-glycol ethers and C thereof
1-4Alkyl monoether class, preferred one or the dipropylene glycol monomethyl ether.The consumption of these anti-dust additives can be considerably less, and specifically, consumption heavily is good with 1-4 part in the heavy scope of per 100 parts of weights (L) 0.5-8 part.The selection of optimum amount can according to the size and the shape of powder particle and gather product needs granularity and consistence and also change according to used system.
With regard to subsequently the effect of gathering, particularly with anti-dust additive carry out gather with regard to, the dry powder of spray-dryer outlet preferably is cooled to＜100 ℃, for example in 50-100 ℃ and even lower scope, to be adapted to corresponding apparatus and additive especially.
The desciccate that is obtained (L) does not in fact contain inorganic sulphide and stable to atmospheric oxidation; They are also very soluble in water, and are for example also soluble in water in 5-25 ℃ temperature range even under≤40 ℃ temperature, so they are suitable for being directly used in dyeing very much, even are suitable for the low temperature dyeing method, and are suitable for preparing storing solution.
Be suitable for dyeing according to the leuco sulphur dye (L) that the present invention obtained, particularly the Mierocrystalline cellulose pollutant with the procrypsis form of thioxine dyes pollutant to any available sulfur dyeing; In addition, because therefore not sulfur compound and tool good solubility also be suitable for dying the polymeric amide pollutant, particularly fibrous pollutant, for example synthetic polymeric amide, wool and leather (for example also comprising band woolen skin), wherein wool is particularly preferred.The available own known ordinary method that dyes is finished, particularly with the dip composition that contains (L) flood [to the pollutant of dipping heat-treat (for example handling) with superheated vapour comparatively favourable] and finish by the painted conclusive oxidation in procrypsis stage to thioxine dyes stage, perhaps by dying (exhaustion) to the greatest extent by the aqueous solution that contains (L) (adding ionogen such as sodium sulfate are comparatively favourable) and finishing by the painted conclusive oxidation in procrypsis stage to thioxine dyes stage.This dyeing aqueous solution preferably also contains antioxidant addn, and for example reducing sugar, pyruvic alcohol, thiourea dioxide, sodium bisulfite are or/and formaldehydesulfoxylate.The dyeing of polymeric amide pollutant can be carried out in aqueous medium under the following conditions: slightly acidic is to weakly alkaline, and for example the pH value is good with 6.5-8.5 in the scope of 6-8.5, suitable temperature,＜100 ℃ comparatively favourable, and better in 40-90 ℃ scope, 70-85 ℃ is best; Washing also can be behind rinse, and the procrypsis form can be by with oxygenant, preferably use H
2O
2And on pollutant, be oxidized to the thioxine dyes form, described oxidation is carried out under the following conditions: slightly acidic (for example using acetate), temperature is preferably in 30-60 ℃ the scope, especially 35-50 ℃, in short-term, for example 10 seconds to 10 minutes, preferably 30 seconds to 4 minutes, decide according to corresponding pollutant and painted needs.Leuco sulphur dye (L) can anyly be suitable for the concentration of corresponding pollutant and required colour intensity to be used.The concentration of the aqueous solution of gained leuco sulphur dye (L) for example can reach 50-100g/l, and even higher.
Can obtain the dyeing of the following effect of tool: the color and luster of reinforcement and significant fastness, especially fastness to light and moisture-proof fastness.
Because desciccate (L) is substantially free of inorganic sulphide, so glitch-free in dyeing course, the appreciable H of organ
2S emits.Dying mother liquor (exhaustedmother liquors) to the greatest extent can be recycled and be used for further dyeing or/and at residual solution (for example by washing and rinse gained), the available known method of residual (L) own is for example removed solubilising and precipitated and separation with polyvalent metal ion or with mineral acid.
Liquid storage can be stablized several hours and can not form the interferential oxide film.Dying operation can carry out in dyeing machinery under the situation that essentially no any interferential oxidates exists.
The following example illustrates the present invention, and wherein, percentage ratio is weight percentage, and temperature is degree centigrade.
Embodiment 1
Make 200g2, the 4-dinitrochlorobenzene was reacted 2 hours with the 169g50% aqueous sodium hydroxide solution in 100 ℃.The product that obtains is added in the mixture of water (200g) solution of sodium sulphite (200g) and 127g sulphur, with this mixture heating up to 116-120 ℃ and under this temperature backflow 10-15 hour.Then with mixture with 200g water dilution and inflate air in this solution until making dye precipitated.Then the mixture that obtains is filtered and washes with water, get the black dyes filter cake, its water content is 40-60%.The filter cake that obtains is mixed with the 120g50% aqueous sodium hydroxide solution, with mixture heating up to 90 ℃ and to wherein adding 28g glucose and 28g sodium bisulfite.By the injection atomiser nozzle mixture that obtains is injected the warm air spray-dryer with 445 liters/hour speed immediately; Air is with 3.92 * 10
5～6.86 * 10
5Handkerchief (4-7Kg/cm
2) superatmospheric pressure and 165 ℃ temperature be imported into.Outlet air is 118 ℃, and 5-15 after drying in second is complete.Temperature at the exit desciccate is 105-110 ℃.The product that leaves moisture eliminator is that granularity is the fine powder of 5-10 μ m.
Embodiment 2
Under plant-scale operational condition, repeat embodiment 1 with hundred times of amounts (particularly composition and charge ratio), wherein the intake air temperature is 220 ℃, outlet air is 120 ℃.
Embodiment 3
Repeat embodiment 2, but hot gas (G) difference replaces warm air with nitrogen.
Embodiment 4
Repeat embodiment 3, but different is, the nitrogen inlet temperature is 280 ℃, and the nitrogen outlet temperature is 105 ℃.
Embodiment 5
Repeat embodiment 3, different is, the nitrogen inlet temperature is 300 ℃, and the nitrogen outlet temperature is 110 ℃.
Used reaction mixture is the non-dry mixture of the embodiment 8 of GB-A2255981 in above embodiment.
At each embodiment 1-7 of GB-A2255981, it is dry that other the undried mixture that is exemplified among the 9-14 and 8 (two)-11 (four) can use the method identical with the foregoing description 1-5.
Embodiment 6
The powder that obtains among the embodiment 1-5 is mixed with 2% dipropylene glycol monomethyl ether in mixing tank, get the particle aggregation thing, its granularity is in the scope of 0.2-2mm.
All products that obtained are all soluble in water and in fact do not contain inorganic sulphide.
Application Example A
5g is dissolved in the 90g water in 5 minutes according to the desciccate that embodiment 1 makes, and to wherein adding the 2.5g glucose and the 2g50% caustic soda aqueous solution.A cotton fabric contaminated to pick up with this solution reach 100%, then in 1 minute after scouring of 102 ℃ of logical steam.Again with this fabric in 40 ℃ with containing 5g/l H
2O
2(30%) and the aqueous solution of 5g/l acetate (80%) handle and to make its oxidation in 1 minute, washing and dry has obtained pitch black dyeing then.
Application Example B
The black desciccate of 0.7g embodiment 1 is dissolved in the water that 200g contains 4g sodium sulfate and 0.5g thiourea dioxide.The wool fabric of a heavy 10g was dyeed 1 hour in this solution in 75-80 ℃ and pH6.5-8.5 (regulating with acetate if desired).The wool fabric that to handle then washs also presses the similar approach oxidation described in the Application Example A, at last with painted wool fabric washing and dry, gets the black wool fabric of significant moisture-proof of tool and light fastness performance.
Similar with the desciccate of embodiment 1, above embodiment 2,3,4,5 or each desciccate of 6, or the corresponding product that is obtained after with embodiment 1-7, the 9-14 of GB-A2255981 and 8 (two)-11 (four) each cited undried mixture drying with the drying means of above embodiment 3 or 4 is used for above Application Example A and B, the dyeing of corresponding color and luster and fastness.
Claims (13)
1. the production method of water-soluble dried leuco sulphur dye (L), wherein, with thioxine dyes (S) in aqueous medium and under＞60 ℃ temperature with the reductibility carbonyl compound (A) of significant quantity reaction and dry, be reflected under the condition that alkali metal hydroxide (B) exists and can exist alkali metal sulfite and/or basic metal hydrosulphite (C) and carry out; Wherein said drying is finished with spraying drying, with reaction and time of drying＜4 minute, wherein said (A) is selected from the aliphatic cpd of 3 to 6 carbon atoms, the carbohydrate of 3 to 6 carbon atoms and their derivative, and wherein one or more existing hydroxyls replace by methyl-esterified or by amino or kharophen.
2. according to the process of claim 1 wherein that described carbonyl compound (A) is aldose, ketose or pyruvic alcohol.
3. according to the process of claim 1 wherein that described carbonyl compound (A) can be with following various the expression
Wherein, R
1And R
2In one represent hydrogen, another representative-OH ,-OCH
3Or-NH
2
R
3Representative-CH
3,-CH
2OH ,-CHO or-COOM,
M represent hydrogen or positively charged ion and
The integer of N representative from 1 to 5.
4. according to the process of claim 1 wherein that spraying drying finishes with hot gas (G), wherein hot gas (G) is selected from the nitrogen, superheated vapour of temperature＞70 ℃ and≤300 ℃ or/and air.
5. according to the method for arbitrary claim in the claim 1 to 4, wherein aqueous mixture is sprayed in the moisture eliminator through atomizing.
6. according to the method for claim 3, temperature in＞150 of gas (G) ℃ wherein.
7. according to the process of claim 1 wherein, dry and reduction reaction to small part is carried out simultaneously.
8. according to the process of claim 1 wherein, reduction reaction and drying were finished in＜2 minutes time.
9. according to the process of claim 1 wherein, the dried particles that is obtained is accumulated into the particle agglomerate of granularity in the 0.01-4mm scope.
10. use the leuco sulphur dye of doing (L) that method obtained according to arbitrary claim in the claim 1 to 9.
11. be used for the pollutant of available sulfur dyeing is carried out painted method, it comprises with the procrypsis form of thioxine dyes handles, and then the procrypsis form is oxidized to the thioxine dyes form; Wherein, the leuco sulphur dye (L) according to claim 10 is used as leuco sulphur dye.
12. according to the method for claim 11, it is used for the dyeing of tynex shape pollutant.
13. according to the method for claim 12, it is used for woolen dyeing.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9224368.2 | 1992-11-20 | ||
| GB929224368A GB9224368D0 (en) | 1992-11-20 | 1992-11-20 | Improvements in or relating to organic compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1088236A CN1088236A (en) | 1994-06-22 |
| CN1051785C true CN1051785C (en) | 2000-04-26 |
Family
ID=10725424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93115065A Expired - Fee Related CN1051785C (en) | 1992-11-20 | 1993-11-19 | Dry leuco sulphur dyes in particulate form |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JP3588135B2 (en) |
| KR (1) | KR100295722B1 (en) |
| CN (1) | CN1051785C (en) |
| BR (1) | BR9304762A (en) |
| CH (1) | CH686084A5 (en) |
| DE (1) | DE4338312A1 (en) |
| ES (1) | ES2073373B1 (en) |
| FR (1) | FR2698371B1 (en) |
| GB (2) | GB9224368D0 (en) |
| IT (1) | IT1262445B (en) |
| TR (1) | TR28694A (en) |
| TW (1) | TW349979B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19502968A1 (en) * | 1995-01-31 | 1996-08-01 | Basf Ag | Leuco vat dye preparations in granular form |
| GB9504870D0 (en) * | 1995-03-10 | 1995-04-26 | Sandoz Ltd | Improvements in or relating to organic compounds |
| US20030149288A1 (en) * | 2000-04-18 | 2003-08-07 | Natural Asa | Conjugated linoleic acid powder |
| CN100494288C (en) * | 2004-12-27 | 2009-06-03 | 阮加根 | Preparation process and products of sulfur black dye |
| CN102174272A (en) * | 2011-03-17 | 2011-09-07 | 浙江长征化工有限公司 | Preparation method and product of sulphur black dye |
| EP4654839A1 (en) * | 2023-01-27 | 2025-12-03 | Philip Morris Products S.A. | Pouch for oral use, method for producing a dry substrate, and use of a composition comprising glycerol for reducing dust formation of a dry substrate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2255981A (en) * | 1991-05-23 | 1992-11-25 | Sandoz Ltd | Dry leuco sulphur dyes |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4917706B2 (en) * | 1988-02-01 | 1996-02-20 | Sandoz Ltd | Liquid compositions of prereduced sulfur dyes and production thereof |
-
1992
- 1992-11-20 GB GB929224368A patent/GB9224368D0/en active Pending
-
1993
- 1993-11-10 DE DE4338312A patent/DE4338312A1/en not_active Withdrawn
- 1993-11-16 CH CH342093A patent/CH686084A5/en not_active IP Right Cessation
- 1993-11-16 IT ITRM930764A patent/IT1262445B/en active IP Right Grant
- 1993-11-17 FR FR9313816A patent/FR2698371B1/en not_active Expired - Fee Related
- 1993-11-18 BR BR9304762A patent/BR9304762A/en not_active IP Right Cessation
- 1993-11-18 GB GB9323809A patent/GB2273103B/en not_active Expired - Fee Related
- 1993-11-19 CN CN93115065A patent/CN1051785C/en not_active Expired - Fee Related
- 1993-11-19 KR KR1019930024771A patent/KR100295722B1/en not_active Expired - Fee Related
- 1993-11-19 JP JP29016893A patent/JP3588135B2/en not_active Expired - Fee Related
- 1993-11-19 ES ES09302423A patent/ES2073373B1/en not_active Expired - Fee Related
- 1993-11-19 TR TR01075/93A patent/TR28694A/en unknown
- 1993-11-25 TW TW081104058A01A patent/TW349979B/en active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2255981A (en) * | 1991-05-23 | 1992-11-25 | Sandoz Ltd | Dry leuco sulphur dyes |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9323809D0 (en) | 1994-01-05 |
| ITRM930764A1 (en) | 1995-05-16 |
| KR100295722B1 (en) | 2001-11-30 |
| KR940011585A (en) | 1994-06-21 |
| CN1088236A (en) | 1994-06-22 |
| FR2698371B1 (en) | 1995-08-18 |
| GB9224368D0 (en) | 1993-01-13 |
| ES2073373B1 (en) | 1996-02-16 |
| CH686084A5 (en) | 1995-12-29 |
| JPH06212084A (en) | 1994-08-02 |
| FR2698371A1 (en) | 1994-05-27 |
| TW349979B (en) | 1999-01-11 |
| TR28694A (en) | 1997-01-08 |
| ITRM930764A0 (en) | 1993-11-16 |
| IT1262445B (en) | 1996-06-19 |
| DE4338312A1 (en) | 1994-05-26 |
| ES2073373A1 (en) | 1995-08-01 |
| JP3588135B2 (en) | 2004-11-10 |
| GB2273103A (en) | 1994-06-08 |
| GB2273103B (en) | 1996-04-24 |
| BR9304762A (en) | 1994-05-24 |
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