CN102153884A - Ink-type dye, and preparation method and application thereof - Google Patents
Ink-type dye, and preparation method and application thereof Download PDFInfo
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- CN102153884A CN102153884A CN2011100389622A CN201110038962A CN102153884A CN 102153884 A CN102153884 A CN 102153884A CN 2011100389622 A CN2011100389622 A CN 2011100389622A CN 201110038962 A CN201110038962 A CN 201110038962A CN 102153884 A CN102153884 A CN 102153884A
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Abstract
The invention discloses an ink-type dye of which the general formula is disclosed as (1). The invention also discloses a preparation method of the ink-type dye. The ink-type dye can be in a powdery solid state or a water-soluble liquid state, and can comprise some common assistants. The ink-type dye is especially suitable to be used as a raw material of an ink for writing tools, such as ball pens, fountain pens or ink-jet printers. The ink-type dye has the advantages of high color brightness and favorable fastness to light. The ink-type dye can be used for dyeing and printing on paper, wood, textile fiber materials, plastic film, aluminum foils or the like, and can also be used for dyeing and printing on silk products, wool products, synthetic polyamide fibers, polyurethane and cellulose fiber materials.
Description
Technical field
The present invention relates to a kind of ink type dye, this dyestuff be with the anils that contains sulfuryl as diazo component, with beta naphthal-3, the 6-disulfonic acid is a kind of special copper complexing monoazo-dyes as a kind of reactive dyestuffs that the coupling component obtains.The invention still further relates to the preparation method and the purposes of above-mentioned ink type dye.
Background technology
Reactive dyestuffs are a kind of ink type dyes that have active group in chemical structure, it in dyeing course with fiber on hydroxyl or generation chemical reaction such as amino and form covalent linkage, so also claim chemically-reactive dyes.Reactive dyestuffs have be widely used, characteristics such as excellent property, chromatogram are complete, bright in colour, moderate cost, in the competition of all multiclass dyestuffs, be in the leading position of first developing, become the most important dyestuff of cellulose dyeing and stamp, be the dyestuff that a class has development potentiality, be widely used in coloration of textile materials and stamps such as cotton, hair, silk, fiber crops, polyamide fibre and viscose glue.
The reactive dyestuffs structure mainly is made up of dye matrix, active group and abutment three parts.Can be divided into all big classes such as azo, anthraquinone, first Zan, phthalocyanine, triphendioxazine by the parent chemical structure.The copper phthalocyanine synthetic method is different from the common metal complex compound, the production technology consummation, and research emphasis is crystal conversion; Triaryl first Zan compound generally is that hydrazone is produced in the condensation of hydrazine aldehyde, makes first Zan compound with the diazonium salt reaction again.Comparatively speaking, azo-type reactive dyestuffs copper complexing condition changes more, and the difference great disparity.
Complex compound claims title complex again, is to be contained the molecule or the ion of lone-pair electron or πDian Zi and had the stable structure unit that the central ion or atom of empty valence orbit is combined into by two or more.Inner complex is the abbreviation of chela type complex compound, also claims inner complex.Inner complex also because of its characteristics with ring structure, has special stability except that the general general character with complex compound, be called chelate effect.Metallized dye is actually a kind of of inner complex, because of it has color, can be used as dyestuff, is therefore studied as a type of dyestuff.And reactive dyestuffs are kinds in this type dyestuff.Usually the metal complex kind of reactive dyestuffs contains copper, cobalt, three kinds of metallic elements of chromium.
The dyestuff of using as ink will satisfy good light fastness and high request beautiful in colour simultaneously, present known rosaniline dyes can not satisfy these requirements simultaneously, even some dye inks of producing have good light fastness, but colourity is generally darker and gorgeous degree is also lower, as reactive red 23; In addition, other known dye ink has high gorgeous degree but light fastness can not be met the need of market.
Summary of the invention
One of technical problem to be solved by this invention is at the deficiencies in the prior art, provide a kind of new chemical stability good, have good light fastness and an a kind of ink type dye of color and luster.
The thinking that the present invention addresses the above problem is to change the molecular structure of existing magenta dye, and then obtains a kind of ink type dye with following general formula molecular structure 1.:
①
Wherein:
R is: hydrogen, C
1~ C
8Alkyl (as-CH
3,-CH
2CH
3,-CH
2CH
2CH
3Deng), C
1~ C
8Alkoxyl group (as CH
3O-, CH
3CH
2O-, CH
3CH
2CH
2O-etc.), C
1~ C
8Alkylthio, halogen, amino, amide group, urea groups, hydroxyl, sulfonic group ,-Y-COOH or
, wherein Y is C
1~ C
8Alkyl, C
1~ C
8Alkoxyl group, C
1~ C
8Alkylthio, amino, amide group, urea groups, carbonyl, R
4And R
5Can select for use independently or identical hydrogen, halogen, C
1~ C
8Alkyl, C
1~ C
8Alkoxyl group, C
1~ C
8Carboxyl, amino, amide group, urea groups, hydroxyl.R, R
4And R
5Preferred hydrogen, C
1~ C
4Alkyl, C
1~ C
4Alkoxyl group, the preferred fluorine or chlorine of halogen.
R
1For :-H, C
1~ C
4Alkyl, Ph-,-CH
2CH
2OH ,-[CH
2CH(CH
3) O]
pH ,-(CH
2CH
2O)
pA kind of among the H, described p are naphthylamine base that substituting group or unsubstituted are arranged on the natural number, aromatic ring of 1-8, morpholine, piperidyl, piperidines amido, piperazinyl etc.Aryl is phenyl particularly, and it can be by one or more such as C
1~ C
4Alkyl, C
1~ C
4Alkoxyl group, fluorine, chlorine and-SO
3H replaces.R
1Preferably-H ,-CH
3, Ph-.
R
2:-H ,-(CH
2)
q-in a kind of, wherein q is the natural number of 1-8, the natural number of the preferred 1-4 of q;-(CH
2)
q-in H can be by C
1~ C
4Substituting group such as alkyl, carboxyl replace.
R
3:-SO
3H ,-COOH or-H, R
3Preferably-SO
3H or-COOH.
The integer of m:0 ~ 2.
The integer of n:1 ~ 2.
General formula of the present invention dyestuff 1. exists as the liquid or solid form usually.Their solid form contain usually be common in water-soluble, particularly fiber is with the electrolyte salt in the dyestuff, as NaCl, KCl and Na
2SO
4, also can further contain the auxiliary agent that is common in the commercial dyestuff, as pH value of aqueous solution being stabilized in 3 ~ 7 buffer substance, as Sodium Tetraborate, CH
3COONa, NaHCO
3, NaH
2PO
4, Na
2HPO
4, Trisodium Citrate, and small quantity of drying; When they use as liquid or the aqueous solution, can comprise solubilizing agent such as ε-Ji Neixianan; Also can comprise thickening material such as alginate (as sodiun alginate), starch ethers etc., synthetic thickening agent such as vinylformic acid or acrylamide; Also can comprise other additive such as tensio-active agent or wetting agent, suitable tensio-active agent comprises anionic or nonionic surface active agent, and wetting agent can be the mixture of urea, Sodium.alpha.-hydroxypropionate and glycerine or polyoxyethylene glycol.Dyestuff of the present invention also can comprise some conventional additives, as mould inhibitor, can suppress the growth of fungi or bacterium, guarantees that product is durable in use.
General formula of the present invention ink type dye particularly suitable is 1. made the ink that writing implement such as ballpoint pen, fountain pen or ink-jet printer are used, and very high degree beautiful in colour is not only arranged, and good light fastness is arranged.Also be applicable to the dyeing and the stamp of paper, timber, textile fiber material, plastics film or aluminium foil etc., also can be used for silk goods, wool product, synthetic polyamide fiber and polyurethane and cellulosic fibre material, because ink type dye of the present invention contains a plurality of hydrophilic factor-SO
3H, the solvability in water is fabulous, and viscosity is very little, can not stop up the shower nozzle of ink-jet printer, thereby has guaranteed can successfully to spray from the fine spray orifice of printing head end swimmingly by the filter thin slice of printing head in printer prints process ink inside.In addition, printer paper is to be made of crisscross paper fiber, and what fill therebetween is the colloidality material.Because the effect of the hydrophilic factor is easy to after the air brushing by absorbed, color representation power is good.And, replaced such as the easy group of alkali cancellation such as β-ethene sulfuryl sulfuric ester with the sulfonamides structure in the ink type dye structure of the present invention, than under the rugged environment, molecule also is not easy to decompose and causes and fade, improved the acid and alkali-resistance and the resistance to light of ink greatly, thereby the stability of ink is strengthened.
General formula of the present invention ink type dye 1. is as marking ink the time, almost can be widely used in all Alhue papers, developing out paper, satin paper and plastic coat paper, as Epson Alhue paper, Epson printing paper, Epson satin paper, the HP Alhue paper, Encad printing paper and satin paper, Ilford printing paper etc., preferred Epson satin paper.When dyeing that is used for plastics film and textile fibres and stamp, film can be an oyster white, transparent or opaque, the preferably transparent film.Textile fiber material especially contains the filamentary material of nitrogen and hydroxyl, as cellulosic fibre, silk, wool or synthesizing polyamides.
Two of subject matter to be solved by this invention provides a kind of preparation method of general formula ink type dye 1., and its key step is as follows.
At first, the ethanamide benzene-like compounds of general formula (a) is carried out the chlorosulphonation thing that chlorosulphonation obtains general formula (b), again chlorosulphonation thing (b) is carried out the sulfamide compound that ammoniumization obtains general formula (c), then the sulfamide compound of general formula (c) being hydrolyzed obtains the amino benzenes compounds of general formula (d):
（a） （b）
（c）
（d） （e）
Amino benzenes compounds with general formula (d) carries out diazotization then, and coupled reaction is carried out in the R acid of its diazonium product and formula (e) (being beta naphthal-3, the 6-disulfonic acid), promptly obtains following formula diazonium compound dyestuff 2.:
②
Formula diazonium compound dyestuff 2. is last to carry out the copper complex reaction with the copper agent that contains copper, promptly obtains general formula of the present invention ink type dye 1.:
Wherein, R
6Can be hydrogen, C
1~ C
8Alkyl, C
1~ C
8Alkoxyl group, preferred hydrogen, C
1~ C
4Alkyl, preferred especially hydrogen or methyl.
In addition, R, R
1, R
2, R
3And m, n are identical with above-mentioned definition.
Among the preparation method of above-described ink type dye, optimized technical scheme is:
When the compound of general formula (a) carried out sulfonation, sulfonation temperature was 20 ~ 130 ℃, and best sulfonation temperature is 25～65 ℃.Sulphonating agent can select for use the vitriol oil or oleum, sulphur trioxide, chlorsulfonic acid, sulfurous gas to add a kind of in chlorine, sulfurous gas oxygenation, S-WAT, the thionyl chloride, preferred chlorsulfonic acid or thionyl chloride, more preferably chlorsulfonic acid.The sulfonation of chlorsulfonic acid is very capable, meets water and is hydrolyzed to sulfuric acid and hydrogenchloride immediately.In sulfonation process, normally organism is slowly joined in the chlorsulfonic acid, reinforced conversely meeting produces more sulfone by product, and chlorsulfonic acid must be excessive, otherwise will generate aromatic sulfonic acid.If list can not make sulfonic group all transfer SULPHURYL CHLORIDE to chlorsulfonic acid, can add a small amount of thionyl chloride.
The temperature that the chlorosulphonation thing of general formula (b) carries out ammoniumization generally between 20 ~ 110 ℃, preferred 40 ~ 105 ℃.Amide can be selected ammoniacal liquor, Padil, β-An Jibingsuan, N-methyl aminoacetic acid, thionamic acid, aminomethanesulfonic acid, taurine, aspartic acid etc. for use.The ammonium process can be regulated pH=7.0 ~ 8.0 with ammoniacal liquor or other alkali (as organic bases Monoethanolamine MEA BASF, trolamine, pyridine etc.), also can not control the pH value.
The diazotization of the amino benzenes compounds of general formula (d) can be undertaken by method well known in the prior art.Normally in acidic medium, carry out, but, also can carry out with other diazo reagent with nitrite or mineral substance medium, but the most cheap with nitrite.Described nitrite is preferably alkali metal nitrites salts, more preferably Sodium Nitrite.Described acidic medium is selected a kind of in phosphoric acid, sulfuric acid, acetate, the hydrochloric acid or mixture that these are sour for use, is preferably the mixture of hydrochloric acid, sulfuric acid and phosphoric acid and acetate.Diazotizing temperature is generally at-10 ~ 40 ℃, and preferred temperature range is 0 ~ 20 ℃.
The coupling of the diazotization thing of general formula (d) and formula (e) can be to be undertaken by method well known in the prior art.Normally acid, neutral to weakly alkaline, i.e. pH=0 ~ 8, temperature range is carried out in-10 ~ 40 ℃ environment, preferred temperature range is 0 ~ 30 ℃.
The copper agent that carries out the copper complex reaction generally is the salt that contains positively charged ion copper, as copper sulfate, cupric chloride or neutralized verdigris.Also can select copper complex for use in some cases, copper-amine complex for example is as tetramino copper sulfate; Perhaps contain the copper that exists with form complexed in the compound, for example aliphatics aminocarboxylic acid or hydroxycarboxylic acid are as the complex copper compound of Padil, lactic acid or alkali metal salts of tartaric acid, especially cupric tartrate sodium.
The copper complex reaction generally is to carry out in the aqueous solution or organic-aqueous solution.Reactor can be the closed container that has the open container of reflux condensate device or certain pressure is arranged.The temperature range of complex reaction is between 50 ~ 120 ℃.The pH value of complex reaction is then decided by selected gold plating method, for example in the presence of alkali metal acetate (as sodium-acetate), carries out acid copper with copper sulfate and handles; Carrying out alkaline copper with tetramino copper sulfate handles.
General formula of the present invention ink type dye 1. also can be used method well known in the prior art, for example soaks into filamentary material, paper and aluminium foil etc. that technology, roller printing or film stamp are printed and dyed and contained nitrogen and hydroxyl, also is applicable to the stamp and the mordant dyeing of timber.Filamentary material comprises silk, wool, synthetic polyamide fiber and polyurethane and various cellulosic fibre material, as cotton, flax and hemp products, and Mierocrystalline cellulose and regenerated cellulose.The filamentary material of hydroxyl generally is present in the BLENDED FABRIC, as the blending thing of cotton and trevira or tynex.All these fibers can be various form processings, as fiber, yarn, woven fabrics or knitted fabrics.
General formula of the present invention ink type dye particularly suitable is 1. made ink, is particularly useful for register system such as ink-jet printer.Ink general requirement saltiness is lower, and therefore, the dyestuff of supersalinity must carry out desalting treatment when being used as ink, can pass through the membrane sepn step, carries out desalination as ultrafiltration, reverse osmosis or dialysis.General formula of the present invention ink type dye 1. is that direct mixture with dyestuff or dyestuff and other additive is dissolved in a certain amount of water as ink-jet printing ink the time, and suction filtration requires to carry out nanofiltration or osmosis filtration according to particle diameter then again.The present invention just is being based on these problems, has carried out some special adaptations on the basis of original dyestuff, provides some can satisfy the aqueous ink dyestuff of good light fastness and high request beautiful in colour simultaneously.Compare with the reactive dyestuffs of more known use β-ethene sulfuryl sulfuric esters, ink dye of the present invention has not only reduced raw materials cost, the more important thing is and has introduced the not sulfonamides structure of facile hydrolysis, has improved the light fastness of ink greatly.
Embodiment
For the purpose of conveniently further specifying, will enumerate following examples without limitation as more detailed description.Wherein, except as otherwise noted, all materials all by weight.
Embodiment 1.A kind of ink type dye with following general formula molecular structure 1.:
①
Wherein:
R is: hydrogen, C
1~ C
8Alkyl, C
1~ C
8Alkoxyl group, C
1~ C
8Alkylthio, halogen, amino, amide group, urea groups, hydroxyl, sulfonic group ,-Y-COOH or
Y is C
1~ C
8Alkyl, C
1~ C
8Alkoxyl group, C
1~ C
8Alkylthio, amino, amide group, urea groups, carbonyl;
R
4And R
5For independently or identical hydrogen, halogen, C
1~ C
8Alkyl, C
1~ C
8Alkoxyl group, C
1~ C
8Carboxyl, amino, amide group, urea groups or hydroxyl.
R
1For :-H, C
1~ C
4Alkyl, Ph-,-CH
2CH
2OH ,-[CH
2CH(CH
3) O]
pH ,-(CH
2CH
2O)
pA kind of among the H; Wherein: p is naphthylamine base, morpholine, piperidyl, piperidines amido or the piperazinyl that substituting group or unsubstituted are arranged on the natural number, aromatic ring of 1-8; Wherein: aryl is phenyl particularly, can be by one or more C
1~ C
4Alkyl, C
1~ C
4Alkoxyl group, fluorine, chlorine or-SO
3H replaces;
R
2For :-H ,-(CH
2)
q-in a kind of; Wherein: q is the natural number of 1-8;-(CH
2)
q-in H can be by C
1~ C
4Alkyl, carboxyl replace;
R
3For :-SO
3H ,-COOH or-H; M is: 0 ~ 2 integer; N is: 1 ~ 2 integer;
General formula ink type dye 1. can be used as the dyeing of paper, timber, textile fiber material, plastics film, aluminium foil, silk goods, wool product, synthetic polyamide fiber, polyurethane or cellulosic fibre material or the dyestuff of stamp; The ink that also can be used as writing implement or ink-jet printer.
Embodiment 2.In the embodiment 1 described ink type dye: R, R
4And R
5Be hydrogen, C
1~ C
4Alkyl, C
1~ C
4Alkoxyl group; Described halogen is a fluorine or chlorine; R
1For-CH
3
Embodiment 3.In the embodiment 1 described ink type dye: described C
1~ C
8Alkyl be-CH
3,-CH
2CH
3Or-CH
2CH
2CH
3C
1~ C
8Alkoxyl group be CH
3O-, CH
3CH
2O-or CH
3CH
2CH
2O-.
Embodiment 4.A kind of preparation method as any one described general formula ink type dye 1. among the embodiment 1-3, the step of this method is as follows: (1) carries out the chlorosulphonation thing that chlorosulphonation obtains general formula (b) with the ethanamide benzene-like compounds of general formula (a);
(2) chlorosulphonation thing (b) is carried out the sulfamide compound that ammoniumization obtains general formula (c);
（a） （b）
（c）
(3) sulfamide compound of general formula (c) be hydrolyzed obtain the amino benzenes compounds of general formula (d):
（d） （e）
(4) amino benzenes compounds with general formula (d) carries out diazotization, the R acid of its diazonium product and formula (e), i.e. and beta naphthal-3, the 6-disulfonic acid carries out coupled reaction, promptly obtains following general formula azo-compound dyestuff 2.;
②
(5) at last formula azo-compound dyestuff 2. and the copper agent that contains copper are carried out the copper complex reaction, promptly obtain general formula ink type dye 1.;
Wherein: described R, R
1, R
2, R
3, the definition of m, n and claim 1,2 or 3 described identical; R
6Be selected from hydrogen, C
1~ C
8Alkyl, C
1~ C
8Alkoxyl group.
Embodiment 5.Among the embodiment 4 described preparation methods: described R
6Be C
1~ C
4Alkyl.
Embodiment 6.Among embodiment 4 or the 5 described preparation methods:
In the step (1): when the compound of general formula (a) carried out sulfonation, sulfonation temperature was 20 ~ 130 ℃; Sulphonating agent is selected from the vitriol oil, oleum, sulphur trioxide, chlorsulfonic acid, sulfurous gas and adds a kind of in chlorine, sulfurous gas oxygenation, S-WAT or the thionyl chloride;
In the step (2): the temperature that the chlorosulphonation thing of general formula (b) carries out ammoniumization is 20 ~ 110 ℃; Amide is selected from ammoniacal liquor, Padil, β-An Jibingsuan, N-methyl aminoacetic acid, thionamic acid, aminomethanesulfonic acid, taurine or aspartic acid;
In the step (3): the diazotization of the amino benzenes compounds of general formula (d) is to carry out with nitrite or mineral substance medium in acidic medium; Described nitrite is preferably alkali metal nitrites salts; Described acidic medium is selected from the mixture of one or more compositions in phosphoric acid, sulfuric acid, acetate, the hydrochloric acid; Diazotizing temperature is-10 ~ 40 ℃;
In the step (4): the coupling of the diazotization thing of general formula (d) and formula (e) be acid, neutral to weakly alkaline, i.e. carry out in the environment of temperature-10 ~ 40 ℃ pH=0 ~ 8;
In the step (5): the copper agent that carries out the copper complex reaction is to contain in the salt of positively charged ion copper or copper complex or the compound to contain the copper that exists with form complexed; Copper complex reaction one is carried out in the aqueous solution or organic-aqueous solution, and the temperature of complex reaction is 50 ~ 120 ℃.
Embodiment 7.Among the embodiment 6 described preparation methods:
In the step (1): the sulfonation temperature the when compound of general formula (a) carries out sulfonation is 25～65 ℃;
In the step (2): the temperature that the chlorosulphonation thing of general formula (b) carries out ammoniumization is 40 ~ 105 ℃; The ammonium process is regulated pH=7.0 ~ 8.0 with ammoniacal liquor or other alkali;
In the step (3): described acidic medium is the mixture of phosphoric acid and acetate; Diazotizing temperature is 0 ~ 20 ℃;
In the step (4): the coupling of the diazotization thing of general formula (d) and formula (e) is to carry out in 0 ~ 30 ℃ temperature environment.
Embodiment 8.The preparation experiment one of ink type dye.
(1) in the exsiccant reaction flask, adds the 180g chlorsulfonic acid, slowly add 42.5g N-ethanoyl Ortho Anisidine again, maintain the temperature at below 30 ℃.Controlled temperature stirred 10 hours between 35 ~ 40 ℃ then, added 100mL water and 100g ice, on the rocks again maintaining the temperature at below 15 ℃, and suction filtration, the frozen water washing leaching cake is removed free acid as far as possible, and yield is about 85%.Reaction formula is as follows:
（a） （b）
(2) in reaction flask, add 150g water, 17.5g Padil and 10.5g yellow soda ash, (1) the step product (b) that adds half then, add 10.5g yellow soda ash subsequently again, and the remaining product (b) of adding, at room temperature stirred 3 hours, and be heated to 50 ~ 60 ℃ of stirring reactions then until reaching reaction end.Entire reaction course must keep alkalescence.Reaction finishes the back products obtained therefrom and carries out suction filtration, washing.Yield is 90 ~ 95%.Reaction formula is as follows:
（b） （c）
(3) in reactor, add 200mL water, 70mL hydrochloric acid and 11g sulfuric acid monohydrate, be heated to and boil, add the product (c) in (2) step again.Continue heating until whole dissolvings, add the 5g gac, reactant is fine again to be boiled, and suction filtration obtains about 500mL liquid then.In filtrate, add 32g yellow soda ash,, add the 5g sodium-acetate again, leave standstill after stirring until congo-red test paper is shown slightly acidic.The product of filtering-depositing (d), cold water washing.Yield is about 90%.
（d）
(4) add (3) product (d) and the 100g frozen water that goes on foot in reactor, fully stir, add the hydrochloric acid of 82g 30%, controlled temperature slowly drips the inferior sodium solution of 25g 4N again between 0 ~ 5 ℃.Diazotization is removed excessive inferior sodium with urea or thionamic acid after finishing.
Above-mentioned acid diazonium compound slurries are joined in advance in the coupling solution (be 60g beta naphthal-3, the 6-disulfonic acid is dissolved in 400g water) of preparation, during controlled temperature between 5 ~ 10 ℃, regulate about pH=5.0 with sodium acetate soln.In order to make reaction thoroughly, mixture is at room temperature stirred spend the night.Product is saltoutd with 300g NaCl, suction filtration then, and the salt water washing with 25% obtains wet cake about 400g.The azoic dyestuff structural formula 2. that this step reaction obtains is as follows:
(5) get the 4th step product 2. half amount put in the reaction flask, add 650g water again, fully stir, at room temperature add 30g CuSO
45H
2O regulates pH=4.5 with sodium-acetate.Be warming up to then between 90 ~ 95 ℃, add sodium-acetate simultaneously and regulate pH=3.9 ~ 4.5.In order to make reaction thoroughly, mixture is stirred for several hour with this understanding, detects until thin-layer chromatography to reach terminal point.Reduce to room temperature then, and regulate pH=4.0 with sodium-acetate.Carry out the nanofiltration desalination behind the product suction filtration that obtains again, be general formula of the present invention ink type dye 1., about nearly 85g.Structural formula is as follows:
（01）
Embodiment 9.The preparation experiment two of ink type dye.
(1) in the exsiccant reaction flask, adds the 90g chlorsulfonic acid, slowly add 21.3g N-ethanoyl Ortho Anisidine again, maintain the temperature at below 30 ℃.Controlled temperature stirred 10 hours between 35 ~ 40 ℃ then, added 50mL water and 50g ice, on the rocks again maintaining the temperature at below 15 ℃, and suction filtration, the frozen water washing leaching cake is removed free acid as far as possible, and yield is about 85%.
(2) in reaction flask, add 75g water, 16.1g taurine and 5.5g yellow soda ash; (1) the step product (b) that adds half then; add 5.5g yellow soda ash subsequently again; and the remaining product (b) of adding; at room temperature stirred 3 hours, and be heated to 50 ~ 60 ℃ of stirring reactions then until reaching reaction end.Entire reaction course must keep alkalescence.Reaction finishes the back products obtained therefrom and carries out suction filtration, washing.Yield is 90 ~ 95%.Reaction formula is as follows:
（b） （c）
(3) in reactor, add 100mL water, 35mL hydrochloric acid and 5.5g sulfuric acid monohydrate, be heated to and boil, add the product (c) in (2) step again.Continue heating until whole dissolvings, add the 3g gac, reactant is fine again to be boiled, and suction filtration obtains about 250mL liquid then.In filtrate, add 16g yellow soda ash,, add the 2.5g sodium-acetate again, leave standstill after stirring until congo-red test paper is shown slightly acidic.The product of filtering-depositing (d), cold water washing.Yield is about 90%.
（d）
(4) add (3) product (d) and the 50g frozen water that goes on foot in reactor, fully stir, add the hydrochloric acid of 40g 30%, controlled temperature slowly drips the inferior sodium solution of 12.5g 4N again between 0 ~ 5 ℃.Diazotization is removed excessive inferior sodium with urea or thionamic acid after finishing.
Above-mentioned acid diazonium compound slurries are joined in advance in the coupling solution (be 30g beta naphthal-3, the 6-disulfonic acid is dissolved in 200g water) of preparation, during controlled temperature between 5 ~ 10 ℃, regulate about pH=5.0 with sodium acetate soln.In order to make reaction thoroughly, mixture is at room temperature stirred spend the night.Product is saltoutd with 150g NaCl, suction filtration then, and the salt water washing with 25% obtains wet cake about 210g.The azoic dyestuff structural formula 2. that this step reaction obtains is as follows:
(5) 2. the 4th step product is put in the reaction flask, added 650g water again, fully stir, at room temperature add 30g CuSO
45H
2O regulates pH=4.5 with sodium-acetate.Be warming up to then between 90 ~ 95 ℃, add sodium-acetate simultaneously and regulate pH=3.9 ~ 4.5.In order to make reaction thoroughly, mixture is stirred for several hour with this understanding, detects until thin-layer chromatography to reach terminal point.Reduce to room temperature then, and regulate pH=4.0 with sodium-acetate.Carry out the nanofiltration desalination behind the product suction filtration that obtains again, be general formula of the present invention ink type dye 1., about nearly 90g.Structural formula is as follows:
（02）
Embodiment 10.The preparation experiment three of ink type dye.
Step is with embodiment 8 and 9; only amide Padil and taurine in (2) step are waited and replace with ammoniacal liquor, β-An Jibingsuan, N-methyl aminoacetic acid, thionamic acid, aminomethanesulfonic acid, aspartic acid, then can obtain following general molecular formula ink type dye 1.:
（03）
（04）
（05）
（06）
（07）
（08）
Claims (8)
1. ink type dye with following general formula molecular structure 1.:
①
Wherein:
R is: hydrogen, C
1~ C
8Alkyl, C
1~ C
8Alkoxyl group, C
1~ C
8Alkylthio, halogen, amino, amide group, urea groups, hydroxyl, sulfonic group ,-Y-COOH or
Y is C
1~ C
8Alkyl, C
1~ C
8Alkoxyl group, C
1~ C
8Alkylthio, amino, amide group, urea groups, carbonyl;
R
4And R
5For independently or identical hydrogen, halogen, C
1~ C
8Alkyl, C
1~ C
8Alkoxyl group, C
1~ C
8Carboxyl, amino, amide group, urea groups or hydroxyl;
R
1For :-H, C
1~ C
4Alkyl, Ph-,-CH
2CH
2OH ,-[CH
2CH(CH
3) O]
pH ,-(CH
2CH
2O)
pA kind of among the H; Wherein: p is naphthylamine base, morpholine, piperidyl, piperidines amido or the piperazinyl that substituting group or unsubstituted are arranged on the natural number, aromatic ring of 1-8; Wherein: aryl is phenyl particularly, can be by one or more C
1~ C
4Alkyl, C
1~ C
4Alkoxyl group, fluorine, chlorine or-SO
3H replaces;
R
2For :-H ,-(CH
2)
q-in a kind of; Wherein: q is the natural number of 1-8;-(CH
2)
q-in H can be by C
1~ C
4Alkyl, carboxyl replace;
R
3For :-SO
3H ,-COOH or-H; M is: 0 ~ 2 integer; N is: 1 ~ 2 integer.
2. ink type dye according to claim 1 is characterized in that: R, R
4And R
5Be hydrogen, C
1~ C
4Alkyl, C
1~ C
4Alkoxyl group; Described halogen is a fluorine or chlorine; R
1For-CH
3
3. ink type dye according to claim 1 is characterized in that: described C
1~ C
8Alkyl be-CH
3,-CH
2CH
3Or-CH
2CH
2CH
3C
1~ C
8Alkoxyl group be CH
3O-, CH
3CH
2O-or CH
3CH
2CH
2O-.
4. preparation method as any one described general formula ink type dye 1. among the claim 1-3, it is characterized in that the step of this method is as follows: (1) carries out the chlorosulphonation thing that chlorosulphonation obtains general formula (b) with the ethanamide benzene-like compounds of general formula (a);
(2) chlorosulphonation thing (b) is carried out the sulfamide compound that ammoniumization obtains general formula (c);
（a） （b）
（c）
(3) sulfamide compound of general formula (c) be hydrolyzed obtain the amino benzenes compounds of general formula (d):
（d） （e）
(4) amino benzenes compounds with general formula (d) carries out diazotization, the R acid of its diazonium product and formula (e), i.e. and beta naphthal-3, the 6-disulfonic acid carries out coupled reaction, promptly obtains following general formula azo-compound dyestuff 2.;
②
(5) at last formula azo-compound dyestuff 2. and the copper agent that contains copper are carried out the copper complex reaction, promptly obtain general formula ink type dye 1.;
Wherein: described R, R
1, R
2, R
3, the definition of m, n and claim 1,2 or 3 described identical; R
6Be selected from hydrogen, C
1~ C
8Alkyl, C
1~ C
8Alkoxyl group.
5. preparation method according to claim 4 is characterized in that: described R
6Be C
1~ C
4Alkyl.
6. preparation method according to claim 4 is characterized in that:
In the step (1): when the compound of general formula (a) carried out sulfonation, sulfonation temperature was 20 ~ 130 ℃; Sulphonating agent is selected from the vitriol oil, oleum, sulphur trioxide, chlorsulfonic acid, sulfurous gas and adds a kind of in chlorine, sulfurous gas oxygenation, S-WAT or the thionyl chloride;
In the step (2): the temperature that the chlorosulphonation thing of general formula (b) carries out ammoniumization is 20 ~ 110 ℃; Amide is selected from ammoniacal liquor, Padil, β-An Jibingsuan, N-methyl aminoacetic acid, thionamic acid, aminomethanesulfonic acid, taurine or aspartic acid;
In the step (3): the diazotization of the amino benzenes compounds of general formula (d) is to carry out with nitrite or mineral substance medium in acidic medium; Described nitrite is preferably alkali metal nitrites salts; Described acidic medium is selected from the mixture of one or more compositions in phosphoric acid, sulfuric acid, acetate, the hydrochloric acid; Diazotizing temperature is-10 ~ 40 ℃;
In the step (4): the coupling of the diazotization thing of general formula (d) and formula (e) be acid, neutral to weakly alkaline, i.e. carry out in the environment of temperature-10 ~ 40 ℃ pH=0 ~ 8;
In the step (5): the copper agent that carries out the copper complex reaction is to contain in the salt of positively charged ion copper or copper complex or the compound to contain the copper that exists with form complexed; The copper complex reaction is generally carried out in the aqueous solution or organic-aqueous solution, and the temperature of complex reaction is 50 ~ 120 ℃.
7. preparation method according to claim 6 is characterized in that:
In the step (1): the sulfonation temperature the when compound of general formula (a) carries out sulfonation is 25～65 ℃;
In the step (2): the temperature that the chlorosulphonation thing of general formula (b) carries out ammoniumization is 40 ~ 105 ℃; The ammonium process is regulated pH=7.0 ~ 8.0 with ammoniacal liquor or other alkali;
In the step (3): described acidic medium is the mixture of phosphoric acid and acetate; Diazotizing temperature is 0 ~ 20 ℃;
In the step (4): the coupling of the diazotization thing of general formula (d) and formula (e) is to carry out in 0 ~ 30 ℃ temperature environment.
8. the purposes of a general formula as claimed in claim 1 ink type dye 1., described purposes are as paper, timber, textile fiber material, plastics film, aluminium foil, silk goods, wool product, synthetic polyamide fiber, polyurethane or the dyeing of cellulosic fibre material or the dyestuff of stamp with general formula ink type dye 1.; Perhaps be used as the ink of writing implement or ink-jet printer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618082A (en) * | 2012-03-16 | 2012-08-01 | 金华双宏化工有限公司 | Method for preparing water-soluble ink jet dye |
| CN103304451A (en) * | 2013-05-13 | 2013-09-18 | 台州市前进化工有限公司 | Preparation method of aromatic hydrocarbon sulfonyl chloride derivative |
| CN103588660A (en) * | 2013-11-18 | 2014-02-19 | 中国医学科学院生物医学工程研究所 | Novel acyl aniline compound and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007020652A1 (en) * | 2005-08-12 | 2007-02-22 | Suven Life Sciences Limited | Aminoaryl sulphonamide derivatives as functional 5-ht6 ligands. |
| WO2008121592A2 (en) * | 2007-03-30 | 2008-10-09 | Takeda Pharmaceutical Company Limited | Acetyl coenzyme a carboxylase inhibitors |
| WO2009053997A1 (en) * | 2007-10-26 | 2009-04-30 | Suven Life Sciences Limited | Amino arylsulfonamide compounds and their use as 5-ht6 ligands |
-
2011
- 2011-02-16 CN CN 201110038962 patent/CN102153884B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007020652A1 (en) * | 2005-08-12 | 2007-02-22 | Suven Life Sciences Limited | Aminoaryl sulphonamide derivatives as functional 5-ht6 ligands. |
| WO2008121592A2 (en) * | 2007-03-30 | 2008-10-09 | Takeda Pharmaceutical Company Limited | Acetyl coenzyme a carboxylase inhibitors |
| WO2009053997A1 (en) * | 2007-10-26 | 2009-04-30 | Suven Life Sciences Limited | Amino arylsulfonamide compounds and their use as 5-ht6 ligands |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618082A (en) * | 2012-03-16 | 2012-08-01 | 金华双宏化工有限公司 | Method for preparing water-soluble ink jet dye |
| CN102618082B (en) * | 2012-03-16 | 2014-03-12 | 金华双宏化工有限公司 | Method for preparing water-soluble ink jet dye |
| CN103304451A (en) * | 2013-05-13 | 2013-09-18 | 台州市前进化工有限公司 | Preparation method of aromatic hydrocarbon sulfonyl chloride derivative |
| CN103304451B (en) * | 2013-05-13 | 2015-07-22 | 台州市前进化工有限公司 | Preparation method of aromatic hydrocarbon sulfonyl chloride derivative |
| CN103588660A (en) * | 2013-11-18 | 2014-02-19 | 中国医学科学院生物医学工程研究所 | Novel acyl aniline compound and application thereof |
| CN103588660B (en) * | 2013-11-18 | 2016-06-01 | 中国医学科学院生物医学工程研究所 | A kind of novel acyl group aniline compound and purposes |
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|---|---|
| CN102153884B (en) | 2013-06-19 |
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