CN102153884B - 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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- CN102153884B CN102153884B CN 201110038962 CN201110038962A CN102153884B CN 102153884 B CN102153884 B CN 102153884B CN 201110038962 CN201110038962 CN 201110038962 CN 201110038962 A CN201110038962 A CN 201110038962A CN 102153884 B CN102153884 B CN 102153884B
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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 is to contain the anils of sulfuryl as diazo component, and with beta naphthal-3, the 6-disulfonic acid as a kind of reactive dyestuffs that the coupling component obtains, is a kind of special copper complexing monoazo-dyes.The invention still further relates to preparation method and the purposes of above-mentioned ink-type dye.
Background technology
Reactive dyestuffs be a kind of in chemical structure the ink-type dye with active group, it in dyeing course with fiber on hydroxyl or the generation chemical reaction such as amino and form covalent linkage, therefore also claim chemically-reactive dyes.Reactive dyestuffs have the characteristics such as be widely used, excellent property, chromatogram are complete, bright in colour, moderate, 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 dyeing and the stamp of the fabrics such as cotton, hair, silk, fiber crops, polyamide fibre and viscose glue.
The reactive dyestuffs structure mainly is comprised of dye matrix, active group and abutment three parts.Can be divided into all large 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, and production technology is consummate, and research emphasis is crystal conversion; Triaryl first Zan compound is generally that hydrazone is produced in the condensation of hydrazine aldehyde, then makes first Zan compound with the diazonium salt reaction.Comparatively speaking, azo reactive dye copper complexing condition changes more, and the difference great disparity.
Complex compound claims again title complex, is to be contained molecule or the ion of lone-pair electron or π-electron 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 the general general character with complex compound, be called chelate effect.Metallized dye is actually a kind of of inner complex, because 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, known rosaniline dyes can not satisfy these requirements simultaneously at present, even some dye inks of producing have good light fastness, but colourity 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 for 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 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 in 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
4The substituting 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 usually contain be common in water-soluble, particularly fiber is with the electrolyte salt in dyestuff, as NaCl, KCl and Na
2SO
4, also can further contain the auxiliary agent that is common in commercial dyestuff, if with the pH value stabilization of the aqueous solution at 3 ~ 7 buffer substance, as Sodium Tetraborate, CH
3COONa, NaHCO
3, NaH
2PO
4, Na
2HPO
4, Trisodium Citrate, and a small amount of siccative; When they use as liquid or the aqueous solution, can comprise solubilizing agent such as ε-caprolactam; 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 Antifungi or the growth of bacterium, and guarantee that product is durable in use.
General formula of the present invention ink-type dye 1. is particularly useful as 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 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 swimmingly by the filter thin slice of printing head, successfully to spray from the fine spray orifice of printing head end in printer print procedure ink inside.In addition, printer paper is to be made of crisscross paper fiber, and what fill therebetween is the colloidality material.Due to the effect of the hydrophilic factor, be easy to after 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 ink-type dye structure of the present invention, than under rugged environment, molecule also is not easy to decompose and causes and fade, greatly improved acid and alkali-resistance and the resistance to light of ink, 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 the dyeing that is used for plastics film and textile fibres and stamp, film can be 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 is to provide 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 ammonium 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）
Then the amino benzenes compounds with general formula (d) carries out diazotization, and coupled reaction is carried out in the R acid (being beta naphthal-3, the 6-disulfonic acid) of its diazonium product and formula (e), namely obtains following formula diazonium compound dyestuff 2.:
②
The last copper agent with containing copper of formula diazonium compound dyestuff 2. carries out the copper complex reaction, namely 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, particularly preferably hydrogen or methyl.
In addition, R, R
1, R
2, R
3And m, n are identical with above-mentioned definition.
In the preparation method of above-described ink-type dye, preferred 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 the vitriol oil or oleum, sulphur trioxide, chlorsulfonic acid, sulfurous gas to add a kind of in chlorine, sulfurous gas oxygenation, S-WAT, 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 immediately sulfuric acid and hydrogenchloride.In sulfonation process, normally organism is slowly joined in chlorsulfonic acid, reinforced meeting produces more sulfone by product conversely, and chlorsulfonic acid must be excessive, otherwise will generate aromatic sulfonic acid.If alone chlorsulfonic acid can not make sulfonic group all transfer SULPHURYL CHLORIDE to, can add a small amount of thionyl chloride.
The temperature that the chlorosulphonation thing of general formula (b) carries out ammonium generally between 20 ~ 110 ℃, preferred 40 ~ 105 ℃.Amide can be selected ammoniacal liquor, Padil, β-alanine, N-methyl aminoacetic acid, thionamic acid, aminomethanesulfonic acid, taurine, aspartic acid etc.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 carry out with nitrite or mineral substance medium in acidic medium, but, also can carry out with other diazo reagent, 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, acetic acid, hydrochloric acid or mixture that these are sour, is preferably the mixture of hydrochloric acid, sulfuric acid and phosphoric acid and acetic acid.Diazotizing temperature is generally at-10 ~ 40 ℃, and preferred temperature range is 0 ~ 20 ℃.
The coupling of the diazonium compound 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 the environment of-10 ~ 40 ℃, preferred temperature range is 0 ~ 30 ℃.
The copper agent that carries out the copper complex reaction is generally the salt that contains positively charged ion copper, as copper sulfate, cupric chloride or neutralized verdigris.Also can select copper complex in some cases, copper-amine complex for example is as tetramino copper sulfate; Perhaps contain the copper that exists with form complexed in compound, for example aliphatics aminocarboxylic acid or hydroxycarboxylic acid are as the complex copper compound of Padil, lactic acid or tartaric an alkali metal salt, especially cupric tartrate sodium.
The copper complex reaction is generally to carry out in the aqueous solution or organic-aqueous solution.Reactor can be with the open container of reflux condensate device or the closed container of certain pressure is arranged.The temperature range of complex reaction is between 50 ~ 120 ℃.The pH value of complex reaction is decided by selected gold plating method, for example under the existence of alkali metal acetate (as sodium-acetate), carries out acid copper with copper sulfate and processes; Carrying out alkaline copper with tetramino copper sulfate processes.
General formula of the present invention ink-type dye 1. also can be used method well known in the prior art, and filamentary material, paper and aluminium foil etc. such as infiltration technique, roller printing or film stamp are printed and dyed and contained nitrogen and hydroxyl also are applicable to 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 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 1. is particularly useful as 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 during direct mixture with dyestuff or dyestuff and other additive is dissolved in a certain amount of water as ink-jet printing ink the time, then suction filtration, then requires to carry out nanofiltration or osmosis filtration according to particle diameter.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 simultaneously the aqueous ink dyestuff of good light fastness and high request beautiful in colour.Use the reactive dyestuffs of β-ethene sulfuryl sulfuric esters to compare with known some, 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 greatly improved the light fastness of ink.
Embodiment
For the purpose of further illustrating for convenience, will enumerate without limitation following examples 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 in 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; Also can be used as the ink of writing implement or ink-jet printer.
Embodiment 2.In the described ink-type dye of embodiment 1: R, R
4And R
5Be hydrogen, C
1~ C
4Alkyl, C
1~ C
4Alkoxyl group; Described halogen is fluorine or chlorine; R
1For-CH
3
Embodiment 3.In the described ink-type dye of embodiment 1: 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.The preparation method of a kind of general formula as described in any one in embodiment 1-3 ink-type dye 1., the step of the method is as follows: (1) carries out with the ethanamide benzene-like compounds of general formula (a) the chlorosulphonation thing that chlorosulphonation obtains general formula (b);
(2) chlorosulphonation thing (b) is carried out the sulfamide compound that ammonium 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 of its diazonium product and formula (e) acid, i.e. and beta naphthal-3, the 6-disulfonic acid carries out coupled reaction, namely 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, namely 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.In the described preparation method of embodiment 4: described R
6Be C
1~ C
4Alkyl.
Embodiment 6.In the described preparation method of embodiment 4 or 5:
In 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 thionyl chloride;
In step (2): the temperature that the chlorosulphonation thing of general formula (b) carries out ammonium is 20 ~ 110 ℃; Amide is selected from ammoniacal liquor, Padil, β-alanine, N-methyl aminoacetic acid, thionamic acid, aminomethanesulfonic acid, taurine or aspartic acid;
In 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, acetic acid, hydrochloric acid; Diazotizing temperature is-10 ~ 40 ℃;
In step (4): the coupling of the diazonium compound 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 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 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.In the described preparation method of embodiment 6:
In step (1): the sulfonation temperature the when compound of general formula (a) carries out sulfonation is 25～65 ℃;
In step (2): the temperature that the chlorosulphonation thing of general formula (b) carries out ammonium is 40 ~ 105 ℃; The ammonium process is regulated pH=7.0 ~ 8.0 with ammoniacal liquor or other alkali;
In step (3): described acidic medium is the mixture of phosphoric acid and acetic acid; Diazotizing temperature is 0 ~ 20 ℃;
In step (4): the coupling of the diazonium compound of general formula (d) and formula (e) is to carry out in the temperature environment of 0 ~ 30 ℃.
Embodiment 8.The preparation experiment one of ink-type dye.
(1) add the 180g chlorsulfonic acid in the reaction flask of drying, more slowly add 42.5g N-ethanoyl Ortho Anisidine, maintain the temperature at below 30 ℃.Then control temperature and stirred 10 hours between 35 ~ 40 ℃, add 100mL water and 100g ice, more on the rocks maintaining the temperature at below 15 ℃, suction filtration, the frozen water washing leaching cake is removed free acid as far as possible, and yield is 85% left and right.Reaction formula is as follows:
（a） （b）
(2) add 150g water, 17.5g Padil and 10.5g sodium carbonate in reaction flask, then (1) the step product (b) that adds half, add again subsequently 10.5g sodium carbonate, and add remaining product (b), at room temperature stirred 3 hours, and then be heated to 50 ~ 60 ℃ of stirring reactions until reach reaction end.Whole reaction process must keep alkalescence.After reaction finishes, products obtained therefrom carries out suction filtration, washing.Yield is 90 ~ 95%.Reaction formula is as follows:
（b） （c）
(3) add 200mL water, 70mL hydrochloric acid and 11g sulfuric acid monohydrate in reactor, be heated to boil, then add the product (c) in (2) step.Continue heating until all dissolvings add the 5g gac, reactant is fine boiling again, and then suction filtration obtains about 500mL liquid.Add 32g sodium carbonate in filtrate, until congo-red test paper is shown slightly acidic, then add the 5g sodium-acetate, stir rear standing.The product of filtering-depositing (d), cold water washing.Yield is in 90% left and right.
（d）
(4) add product (d) and the 100g frozen water in (3) step in reactor, fully stir, add the hydrochloric acid of 82g 30%, control temperature between 0 ~ 5 ℃, more slowly drip the inferior sodium solution of 25g 4N.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 control temperature between 5 ~ 10 ℃, regulate the pH=5.0 left and right 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 the wet cake in 400g left and right.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 reaction flask, then add 650g water, fully stir, at room temperature add 30g CuSO
45H
2O regulates pH=4.5 with sodium-acetate.Then be warming up between 90 ~ 95 ℃, add simultaneously sodium-acetate to regulate pH=3.9 ~ 4.5.In order to make reaction thoroughly, mixture is stirred for several hour with this understanding, reaches terminal point until thin-layer chromatography detects.Then be down to room temperature, and regulate pH=4.0 with sodium-acetate.Carry out again the nanofiltration desalination after the product suction filtration that obtains, 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) add the 90g chlorsulfonic acid in the reaction flask of drying, more slowly add 21.3g N-ethanoyl Ortho Anisidine, maintain the temperature at below 30 ℃.Then control temperature and stirred 10 hours between 35 ~ 40 ℃, add 50mL water and 50g ice, more on the rocks maintaining the temperature at below 15 ℃, suction filtration, the frozen water washing leaching cake is removed free acid as far as possible, and yield is 85% left and right.
(2) add 75g water, 16.1g taurine and 5.5g sodium carbonate in reaction flask; then (1) the step product (b) that adds half; add again subsequently 5.5g sodium carbonate; and add remaining product (b); at room temperature stirred 3 hours, and then be heated to 50 ~ 60 ℃ of stirring reactions until reach reaction end.Whole reaction process must keep alkalescence.After reaction finishes, products obtained therefrom carries out suction filtration, washing.Yield is 90 ~ 95%.Reaction formula is as follows:
（b） （c）
(3) add 100mL water, 35mL hydrochloric acid and 5.5g sulfuric acid monohydrate in reactor, be heated to boil, then add the product (c) in (2) step.Continue heating until all dissolvings add the 3g gac, reactant is fine boiling again, and then suction filtration obtains about 250mL liquid.Add 16g sodium carbonate in filtrate, until congo-red test paper is shown slightly acidic, then add the 2.5g sodium-acetate, stir rear standing.The product of filtering-depositing (d), cold water washing.Yield is in 90% left and right.
（d）
(4) add product (d) and the 50g frozen water in (3) step in reactor, fully stir, add the hydrochloric acid of 40g 30%, control temperature between 0 ~ 5 ℃, more slowly drip the inferior sodium solution of 12.5g 4N.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 control temperature between 5 ~ 10 ℃, regulate the pH=5.0 left and right 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 the wet cake in 210g left and right.The azoic dyestuff structural formula 2. that this step reaction obtains is as follows:
(5) 2. the 4th step product is put in reaction flask, then added 650g water, fully stir, at room temperature add 30g CuSO
45H
2O regulates pH=4.5 with sodium-acetate.Then be warming up between 90 ~ 95 ℃, add simultaneously sodium-acetate to regulate pH=3.9 ~ 4.5.In order to make reaction thoroughly, mixture is stirred for several hour with this understanding, reaches terminal point until thin-layer chromatography detects.Then be down to room temperature, and regulate pH=4.0 with sodium-acetate.Carry out again the nanofiltration desalination after the product suction filtration that obtains, 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 replaced with ammoniacal liquor, β-alanine, N-methyl aminoacetic acid, thionamic acid, aminomethanesulfonic acid, aspartic acid etc., can obtain the following general formula ink-type dye 1. that meets:
（03）
（04）
（05）
（06）
（07）
（08）
Claims (8)
1. ink-type dye with following general formula molecular structure 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 in 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 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 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. the preparation method of a general formula as described in any one in claim 1-3 ink-type dye 1., it is characterized in that, the step of the method is as follows: (1) carries out with the ethanamide benzene-like compounds of general formula (a) the chlorosulphonation thing that chlorosulphonation obtains general formula (b);
(2) chlorosulphonation thing (b) is carried out the sulfamide compound that ammonium obtains general formula (c);
(3) sulfamide compound of general formula (c) be hydrolyzed obtain the amino benzenes compounds of general formula (d):
(4) amino benzenes compounds with general formula (d) carries out diazotization, the R of its diazonium product and formula (e) acid, i.e. and beta naphthal-3, the 6-disulfonic acid carries out coupled reaction, namely obtains following general formula azo-compound dyestuff 2.;
(5) at last formula azo-compound dyestuff 2. and the copper agent that contains copper are carried out the copper complex reaction, namely 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 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 thionyl chloride;
In step (2): the temperature that the chlorosulphonation thing of general formula (b) carries out ammonium is 20 ~ 110 ℃; Amide is selected from ammoniacal liquor, Padil, β-alanine, N-methyl aminoacetic acid, thionamic acid, aminomethanesulfonic acid, taurine or aspartic acid;
In step (4): 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 acidic medium is selected from the mixture of one or more compositions in phosphoric acid, sulfuric acid, acetic acid, hydrochloric acid; Diazotizing temperature is-10 ~ 40 ℃;
In step (4): the coupling of the diazonium compound 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 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 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 step (1): the sulfonation temperature the when compound of general formula (a) carries out sulfonation is 25～65 ℃;
In step (2): the temperature that the chlorosulphonation thing of general formula (b) carries out ammonium is 40 ~ 105 ℃; The ammonium process is regulated pH=7.0 ~ 8.0 with ammoniacal liquor or other alkali;
In step (4): described acidic medium is the mixture of phosphoric acid and acetic acid; Diazotizing temperature is 0 ~ 20 ℃;
In step (4): the coupling of the diazonium compound of general formula (d) and formula (e) is to carry out in the temperature environment of 0 ~ 30 ℃.
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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| 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 |
| 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 |
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 |
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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 |
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