CN109233334A - A kind of dark blue reactive dye - Google Patents
A kind of dark blue reactive dye Download PDFInfo
- Publication number
- CN109233334A CN109233334A CN201811261227.6A CN201811261227A CN109233334A CN 109233334 A CN109233334 A CN 109233334A CN 201811261227 A CN201811261227 A CN 201811261227A CN 109233334 A CN109233334 A CN 109233334A
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- 239000000985 reactive dye Substances 0.000 title abstract description 12
- 239000001045 blue dye Substances 0.000 claims description 27
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 53
- 238000002360 preparation method Methods 0.000 abstract description 12
- 239000007921 spray Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 description 81
- 239000000243 solution Substances 0.000 description 71
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 64
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 44
- 239000007788 liquid Substances 0.000 description 39
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 238000001514 detection method Methods 0.000 description 32
- 235000010288 sodium nitrite Nutrition 0.000 description 32
- 239000007787 solid Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- 238000003756 stirring Methods 0.000 description 24
- 229910000029 sodium carbonate Inorganic materials 0.000 description 22
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 20
- 239000005711 Benzoic acid Substances 0.000 description 19
- 238000005859 coupling reaction Methods 0.000 description 18
- 230000008569 process Effects 0.000 description 17
- 230000000694 effects Effects 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 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 13
- 229920002472 Starch Polymers 0.000 description 13
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 229910052708 sodium Inorganic materials 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- 239000008107 starch Substances 0.000 description 13
- 235000019698 starch Nutrition 0.000 description 13
- 230000002378 acidificating effect Effects 0.000 description 12
- 238000009833 condensation Methods 0.000 description 12
- 230000005494 condensation Effects 0.000 description 12
- 230000008878 coupling Effects 0.000 description 12
- 238000010168 coupling process Methods 0.000 description 12
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 12
- 238000009413 insulation Methods 0.000 description 12
- 238000012805 post-processing Methods 0.000 description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 11
- 229910052748 manganese Inorganic materials 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- 239000010813 municipal solid waste Substances 0.000 description 11
- 230000001105 regulatory effect Effects 0.000 description 11
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 10
- 238000005070 sampling Methods 0.000 description 10
- 229950000244 sulfanilic acid Drugs 0.000 description 9
- 238000005360 mashing Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 8
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000010612 desalination reaction Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000011435 rock Substances 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 6
- 239000012192 staining solution Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000003801 milling Methods 0.000 description 5
- 238000012797 qualification Methods 0.000 description 5
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 4
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PSDYQSWHANEKRV-UHFFFAOYSA-N [S]N Chemical compound [S]N PSDYQSWHANEKRV-UHFFFAOYSA-N 0.000 description 2
- 229960004050 aminobenzoic acid Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- ZAOCWQZQPKGTRN-UHFFFAOYSA-N nitrous acid;sodium Chemical compound [Na].ON=O ZAOCWQZQPKGTRN-UHFFFAOYSA-N 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- -1 2- carboxyanilino Chemical group 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 241000208202 Linaceae Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical class OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 210000002268 wool Anatomy 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
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
- C09B62/507—Azo dyes
- C09B62/513—Disazo or polyazo 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
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
- C09B62/08—Azo dyes
- C09B62/09—Disazo or polyazo 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
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
- D06P1/382—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group directly attached to heterocyclic group
-
- 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
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
- D06P1/384—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group not directly attached to heterocyclic group
-
- 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
- D06P3/148—Wool using reactive 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
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/30—Ink jet printing
Abstract
The present invention relates to a kind of dark blue reactive dye, and The present invention gives the structural formula of the dark blue reactive dye and preparation method, dye fixing rate prepared by the present invention is high, and solubility is high, and frost resistance is good, is not easy to plug spray head, are suitable for digital ink-jet printed.It can also be used as conventional dyes use.
Description
Technical field
The present invention relates to a kind of reactive dye, especially one kind to be applicable in digital ink-jet printed active dark blue dye and its preparation
Method, the active dark blue dye of this method preparation are also the dyestuff of a function admirable on traditional dyeing and stamp.
Background technique
Digital ink-jet printed technology is a kind of completely new stamp mode, it eliminates Conventional decal mode and needs to make a plate this
Complicated link, can direct spray printing on the fabric, improve the precision of stamp, be truly realized high-quality stamp.It shortens print
Flower process process solves the problems, such as Conventional decal contaminated wastewater, has the advantages that several: 1. total digitalization processing, without making a plate,
Modulate mill base；2. high-quality produces, precision is high, and colour image expressive force is strong；3. clean manufacturing, environmentally friendly.Reactive dye
Ink is most popular a kind of ink in current digital ink-jet printed application field, it is suitable for the fibers such as cotton, fiber crops, flax
Cellulose fiber can be also used on the protein fibres such as wool, silk.Reactive dye be through covalent bond in conjunction with fiber, it
With excellent water-fastness, the performances such as fastness to rubbing.Currently, the digital ink-jet printed reactive dye sold on the market exist
Some applied defects or deficiency, such as: 1. degree of fixation is low, and ink-jet ink must have the characteristic of high colour-fast rate, and fixation is low to be made
At the waste of ink, also can cause environmental pollution；2. insoluble matter is high, the thing of blocking spray head is easy to appear in ink jet process
Therefore spray head can also be damaged；3. compatibility is poor, keep the color of image to gush out uneven, ideal coloured light cannot be reached；
4. frost resistance is poor, because the change of environment temperature is so that ink performance changes, standard of normal use etc. cannot be reached and lacked
It falls into.Thus reactive dye prepared by the present invention improve the deficiency in terms of these, it has degree of fixation high, and solubility is high, freeze proof
The features such as property is good, is not easy to plug spray head, suitable for digital ink-jet printed reactive dye.
Summary of the invention
Active dark blue dye and preparation method thereof is prepared the present invention provides a kind of.The dyestuff has degree of fixation high, dissolves
The features such as degree is high, and frost resistance is good, is not easy to plug spray head, suitable for digital ink-jet printed reactive dye.
The technical solution adopted by the present invention are as follows:
A kind of active dark blue dye, molecular structural formula general formula is such as shown in (I):
Note: Cyanuric Chloride molecular structural formula are as follows:
It is reduced in molecular structural formula according to the present invention
R1, R2 substituent group are following several selection modes:
When R1 is-CH2COONa、R2 is
When R1 isR2 is
When R1 isR2 is
When R1 isR2 is
Specifically, the present invention also provides a kind of active dark blue dye, the structural formulas of the active dark blue dye are as follows:
Specifically, the present invention also provides a kind of active dark blue dye, the structural formulas of the active dark blue dye are as follows:
Specifically, the present invention also provides a kind of active dark blue dye, the structural formulas of the active dark blue dye are as follows:
Specifically, the present invention also provides a kind of active dark blue dye, the structural formulas of the active dark blue dye are as follows:
Specifically, the present invention also provides a kind of active dark blue dye, the structural formulas of the active dark blue dye are as follows:
Part dye structure selection (sulfate group ethylene the sulfuryl)-benzoic acid Intermediate of 2- amino -5 synthesis in the present invention,
It is that comparison is harsh as making all technical required by digital ink-jet printed ink, is synthesized in reactive dye ink
When, the high activity of ink cannot be pursued simply, and excessively high active group can increase hydrolysis during long-time is stored
The danger that by-product generates.The activity that the intermediate feed increases dyestuff is introduced, it is prior to dye prepared by para-ester
Expect activity performance, also can be used sulfonation para-ester intermediate feed, but due to the sulfonic group-SO3 in sulfonation para-ester it
Activity is again too strong, so having selected (sulfate group ethylene the sulfuryl)-benzoic acid of 2- amino -5 is intermediate feed, can increase
The activity of dyestuff, and can increase the solubility of dyestuff.Since molecular structure of dye formula joined carboxyl-COOH structure, also
Enhance the shelf stability and frost resistance of ink.
Specifically, the preparation method of the active dark blue dye, includes the following steps:
Step 1, condensation reaction
(1), dissolve
A), 2.4- diamino benzene sulfonic acid sodium is dissolved with water, temperature is controlled at 30~35 DEG C, with concentration 15%~20%
Sodium carbonate liquor controls medium 6.0~7.0, so that whole materials are completely dissolved, obtains 2.4- diamino benzene sulfonic acid sodium solution, standby
With.
It b), is NH by structural formula2The compound of-R1 is dissolved with water, is adjusted with the sodium carbonate liquor of concentration 15%~20%
Between pH=4.0~7.0, so that material all dissolves, NH is obtained2- R1 solution, it is spare.
(2), primary condensation
Bottom water, trash ice, Cyanuric Chloride are added in another reaction kettle, 2.4- diamino benzene sulfonic acid sodium is then at the uniform velocity added
Solution, temperature is kept for 0~10 DEG C during dropwise addition, uses manganese hydrogen sodium regulating solution pH=2.5~3.5 at any time, and medium is kept to stir
It mixes 1.5 hours, sample detection reaction end is 2.4- diamino benzene sulfonic acid sodium without until；Obtain a contracting object；
(3), secondary condensation
One contracts after reaction, cooling on the rocks, the NH that will have been dissolved2- R1 solution, which is at the uniform velocity added in a contracting object, carries out two contractings
Reaction keeps 5~10 DEG C of temperature after finishing, stir 3~3.5 hours, and sampling is without an extra contracting object with liquid chromatographic detection
It is qualified；Obtain two contracting things；
Step 2, diazo-reaction
It a), is NH by structural formula2Hydrochloric acid is added after mashing 1 hour in the compound of-R2, is kept for 0~15 DEG C of temperature with ice,
Rapidly join sodium nitrite solution, keep the aobvious blue of starch potassium iodide paper, in 0~15 DEG C insulation reaction 2~2.5 hours, use
Sulfamic acid removes extra sodium nitrite, obtains NH2- R2 diazo liquid；
B), hydrochloric acid is added in two contracting things, is kept for 0~15 DEG C of temperature with ice, rapidly join sodium nitrite solution, keeps starch
The aobvious blue of potassium iodide starch paper, in 0~15 DEG C insulation reaction 3.5~4 hours, extra sodium nitrite is removed with sulfamic acid, is obtained
Two contracting things diazo liquid.
Step 3, coupling reaction
H acid solution or H acid solid powder are added directly into NH2In-R2 diazo liquid, with 15%~20% carbonic acid of concentration
Sodium solution controls between pH=2.5~3.0, and temperature is adjusted to 15~20 DEG C, is stirred to react 1.5 hours, then being dissolved with sodium carbonate will
Medium is adjusted to 3.5~4.0, stirs 2.5 hours, obtains acidic coupling object；Finally two contracting things diazo liquid is added in acidic coupling object, uses sodium carbonate
Solution controls pH=6.5~7.0, and temperature is controlled at 15~20 DEG C, is stirred to react 2 hours, after reaction sample detection.Detection
Finished product is filtered to obtain after qualification.
The above method further includes following steps:
Step 4.
Finished product is directly spray-dried, solid powder packaging is obtained, is sold as conventional dyes；Or post-processing
Afterwards, as digital ink-jet printed dyestuff, the post-processing are as follows: stock staining solution after detection is qualified with nanometer film carry out desalination,
The processes such as purification after all technical is qualified, adjust dye content 20%~35%, as the digital ink-jet printed dyestuff of liquid
Sale；Or it is dry with spray drying process, solid powder is obtained, can also be used as the digital ink-jet printed dyestuff sale of solid.
Possessed by of the invention the utility model has the advantages that
Dye fixing rate prepared by the present invention is high, and solubility is high, and frost resistance is good, is not easy to plug spray head, is suitable for digital spray
It is ink-printed.
Specific embodiment
To illustrate technical solution of the present invention, the specific embodiment technical side that the present invention will be described in detail is set forth below
Case, the embodiment do not form any limitation of the invention.
Embodiment 1
A kind of digital ink-jet dye activity is dark blue, and molecular structural formula is shown in formula (II):
The dark blue preparation method of the digital ink-jet dye activity, includes the following steps:
Step 1, condensation reaction
(1), dissolve
A), bottom water 1800L is added in 5000L reaction kettle, 30~35 DEG C are warming up to, by the 2.4- diamino of 538.5Kg
Benzene sulfonic acid sodium salt is dissolved with water, controls medium 6.5~7.0 with the sodium carbonate liquor of concentration 15%~20%, so that whole materials are complete
Fully dissolved obtains 2.4- diamino benzene sulfonic acid sodium solution, spare.
B), (sulfate group ethylene the sulfuryl)-benzoic acid of 2- amino -5 is dissolved according to mass concentration 20%, it is anti-in 5000L
Addition bottom water 2500L in kettle is answered, 2- amino -5 (sulfate group ethylene sulfuryl)-benzoic acid 692.7Kg of 100% amount is added, is used
The sodium carbonate liquor of concentration 15%~20% is adjusted between pH=4.0~4.5, so that material all dissolves, obtains 2- amino-
5 (sulfate group ethylene sulfuryl)-benzoic acid solutions；It is spare.
(2), primary condensation
A), bottom water 800L, 2500Kg trash ice, Cyanuric Chloride 400Kg are added in 20000L reaction kettle, ice milling aid is added
5Kg, ice time consuming are 15 minutes, and then 2.4- diamino benzene sulfonic acid sodium solution was at the uniform velocity added in 30 minutes used times, during dropwise addition
Temperature is kept for 0~5 DEG C, uses pH=2.5~3.0 of manganese hydrogen sodium regulating solution at any time, and medium is kept to stir 1.5 hours, sampling
Detect reaction end be without extra 2.4- diamino benzene sulfonic acid sodium until, stay a contracting object sample after qualified.
Or addition bottom water 800L, 2500Kg trash ice, Cyanuric Chloride 400Kg, addition ice mill help b), in 20000L reaction kettle
Agent 5Kg, ice time consuming are 15 minutes, and then 2- amino -5 (sulfate group ethylene sulfuryl)-benzene first was at the uniform velocity added in 30 minutes used times
Acid solution, temperature is kept for 0~5 DEG C during dropwise addition, uses pH=2.5~3.0 of manganese hydrogen sodium regulating solution at any time, keeps medium
Stirring 1.5 hours, sample detection reaction end be without extra 2- amino -5 (sulfate group ethylene sulfuryl)-benzoic acid until, close
A contracting object sample is stayed after lattice.
(3), secondary condensation
One contracts after reaction, cooling on the rocks, by the 2.4- diamino benzene sulfonic acid sodium solution dissolved or 2- amino -5
(sulfate group ethylene sulfuryl)-benzoic acid solution, (when 2- amino -5 (sulfate group ethylene sulfuryl)-benzene first is added in previous step
When acid solution, 2.4- diamino benzene sulfonic acid sodium solution is added in this step, when previous step addition 2.4- diamino benzene sulfonic acid sodium is molten
When liquid, this step be added 2- amino -5 (sulfate group ethylene sulfuryl)-benzoic acid solution) at the uniform velocity be added a contracting object in carry out two
Contracting reaction, keeps 5~10 DEG C of temperature after finishing, stir 3~3.5 hours, sampling liquid chromatographic detection is without an extra contracting object
For qualification；Obtain two contracting things.
Step 2, diazo-reaction
A), bottom water 1500L is added in 35000L reaction kettle, p-aminobenzene sulfonic acid 375Kg is added and adds after mashing 1 hour
Enter 510Kg hydrochloric acid, is kept for 8~14 DEG C of temperature with ice, rapidly join sodium nitrite solution and (dissolved sodium nitrite 150Kg in advance
It is spare), keep the aobvious blue of starch potassium iodide paper, control pH ﹤ 2, in 8~14 DEG C insulation reaction 2~2.5 hours, with amino sulphur
Acid removes extra sodium nitrite, obtains p-aminobenzene sulfonic acid diazo liquid.
B), 510Kg hydrochloric acid is added in two contracting things, is kept for 0~8 DEG C of temperature with ice, rapidly joins sodium nitrite solution and (mention
Before to have dissolved sodium nitrite 150Kg spare), keep the aobvious blue of starch potassium iodide paper, pH ﹤ 2 controlled, in 0~8 DEG C of insulation reaction
3.5~4 hours, extra sodium nitrite is removed with sulfamic acid, obtains two contracting things diazo liquid.
Step 3, coupling reaction
The H acid solid powder of 394Kg is added directly into p-aminobenzene sulfonic acid diazo liquid, with 15%~20% carbon of concentration
Acid sodium solution controls between pH=2.5~3.0, and temperature rises to 15~20 DEG C, and medium is kept to be stirred to react 1.5 hours, then will be situated between
Matter is adjusted to 3.5~4.0, stirs 2.5 hours.Acid is even after reaction, obtains acidic coupling object, then acidic coupling object is added in two contracting things diazo liquid
In, pH=6.5~7.0 are controlled with sodium carbonate liquor, are kept for 15~20 DEG C of temperature, are kept between medium 6.5~7.0, stirring is anti-
Answer 2 hours, after reaction sample detection.
Filter to obtain finished product after detection is qualified, can be directly spray-dried, obtain solid powder packaging, as conventional dyes into
Marketing is sold.If as digital ink-jet printed dyestuff, to postprocessing working procedures.
Step 4, post-processing
Stock staining solution after detection is qualified carries out the processes such as desalination, purification with nanometer film, after all technical is qualified, adjusts
Whole dye content 20%~35% can be used as the digital ink-jet printed dyestuff sale of liquid；It is dry with spray drying process, obtain solid powder
End also can be used as the digital ink-jet printed dyestuff sale of solid.
Embodiment 2
A kind of digital ink-jet dye activity is dark blue, and molecular structural formula is shown in formula (III):
The dark blue preparation method of the digital ink-jet dye activity, includes the following steps:
Step 1, condensation reaction
(1), dissolve
A), bottom water 1800L is added in 5000L reaction kettle, 30~35 DEG C are warming up to, by the 2.4- diamino of 538.5Kg
Benzene sulfonic acid sodium salt is dissolved with water, controls medium 6.5~7.0 with the sodium carbonate liquor of concentration 15%~20%, so that whole materials are complete
Fully dissolved obtains 2.4- diamino benzene sulfonic acid sodium solution, spare.
B), para-ester is dissolved according to mass concentration 20%, bottom water 2500L is added in 5000L reaction kettle, contraposition is added
Ester 628Kg is adjusted between pH=4.0~4.5 with the sodium carbonate liquor of concentration 15%~20%, so that all dissolution is material
Can, contraposition ester solution is obtained, it is spare.(2), primary condensation
A), bottom water 800L, 2500Kg trash ice, Cyanuric Chloride 400Kg are added in 20000L reaction kettle, ice milling aid is added
5Kg, ice time consuming are 15 minutes, and then 2.4- diamino benzene sulfonic acid sodium solution was at the uniform velocity added in 30 minutes used times, during dropwise addition
Temperature is kept for 0~5 DEG C, uses pH=2.5~3.0 of manganese hydrogen sodium regulating solution at any time, and medium is kept to stir 1.5 hours, sampling
Detect reaction end be without extra 2.4- diamino benzene sulfonic acid sodium until, stay a contracting object sample after qualified.
Or addition bottom water 800L, 2500Kg trash ice, Cyanuric Chloride 400Kg, addition ice mill help b), in 20000L reaction kettle
Agent 5Kg, ice time consuming be 15 minutes, then 30 minutes used times is at the uniform velocity added contraposition ester solution, during dropwise addition temperature holding 0~
5 DEG C, pH=2.5~3.0 of manganese hydrogen sodium regulating solution are used at any time, keep medium to stir 1.5 hours, sample detection reaction end
Until without extra para-ester, a contracting object sample is stayed after qualified.
(3), secondary condensation
After reaction, cooling on the rocks is molten by the 2.4- diamino benzene sulfonic acid sodium solution or para-ester that have dissolved for one contracting
Liquid at the uniform velocity carries out two contracting reactions, 5~10 DEG C of temperature is kept after finishing, is stirred 3~3.5 hours, liquid is used in sampling in one contracting object of addition
The detection of phase chromatography is qualification without an extra contracting object, obtains two contracting things.
Step 2, diazo-reaction
A), bottom water 3000L is added in 35000L reaction kettle, p-aminobenzoic acid 294Kg is added and adds after mashing 1 hour
Enter 510Kg hydrochloric acid, is kept for 8~14 DEG C of temperature with ice, rapidly join sodium nitrite solution and (dissolved sodium nitrite 150Kg in advance
It is spare), keep the aobvious blue of starch potassium iodide paper, control pH ﹤ 2, in 8~14 DEG C insulation reaction 2~2.5 hours, with amino sulphur
Acid removes extra sodium nitrite, obtains p-aminobenzoic acid diazo liquid.
B), 510Kg hydrochloric acid is added in two contracting things, is kept for 0~8 DEG C of temperature with ice, rapidly joins sodium nitrite solution and (mention
Before to have dissolved sodium nitrite 150Kg spare), keep the aobvious blue of starch potassium iodide paper, pH ﹤ 2 controlled, in 0~8 DEG C of insulation reaction
3.5~4 hours, extra sodium nitrite is removed with sulfamic acid, obtains two contracting things diazo liquid.
Step 3, coupling reaction
Dissolution: being added bottom water 1200L in 2000L reaction kettle, and the H acid of 394Kg is added, and mashing dissolution 1 hour obtains H acid
Solution, it is spare.
H acid solution is added directly into p-aminobenzene sulfonic acid diazo liquid, with 15%~20% sodium carbonate liquor control of concentration
Between pH=2.5~3.0 processed, temperature rises to 15~20 DEG C, and medium is kept to be stirred to react 1.5 hours, then medium is adjusted to 3.5~
4.0, it stirs 2.5 hours.Acid is even after reaction, obtains acidic coupling object；Two contracting things diazo liquid is added in acidic coupling object again, uses sodium carbonate
Solution controls pH=6.5~7.0, is kept for 15~20 DEG C of temperature, keeps being stirred to react 2 hours between medium 6.5~7.0, react
After sample detection.
Filter to obtain finished product after detection is qualified, can be directly spray-dried, obtain solid powder packaging, as conventional dyes into
Marketing is sold.If as digital ink-jet printed dyestuff, to postprocessing working procedures.
Step 4, post-processing
Stock staining solution after detection is qualified carries out the processes such as desalination, purification with nanometer film, after all technical is qualified, adjusts
Whole dye content 20%~35% can be used as the digital ink-jet printed dyestuff sale of liquid；It is dry with spray drying process, obtain solid powder
End also can be used as the digital ink-jet printed dyestuff sale of solid.
Embodiment 3
A kind of digital ink-jet dye activity is dark blue, and molecular structural formula is shown in formula (IV):
The dark blue preparation method of the digital ink-jet dye activity, includes the following steps:
Step 1, condensation reaction
(1), dissolve
A), bottom water 1800L is added in 5000L reaction kettle, 30~35 DEG C are warming up to, by the 2.4- diamino of 538.5Kg
Benzene sulfonic acid sodium salt is dissolved with water, controls medium 6.5~7.0 with the sodium carbonate liquor of concentration 15%~20%, so that whole materials are complete
Fully dissolved obtains 2.4- diamino benzene sulfonic acid sodium solution, spare.
B), p-aminobenzene sulfonic acid is dissolved according to mass concentration 20%, bottom water 1500L is added in 5000L reaction kettle, risen
P-aminobenzene sulfonic acid 375Kg is added to 35~40 DEG C in temperature, with the sodium carbonate liquor of concentration 15%~20% adjust pH=6.5~
Between 7.0, so that material all dissolves, p-aminobenzene sulfonic acid solution is obtained, it is spare.
(2), primary condensation
A), bottom water 800L, 2500Kg trash ice, Cyanuric Chloride 400Kg are added in 20000L reaction kettle, ice milling aid is added
5Kg, ice time consuming are 15 minutes, and then 2.4- diamino benzene sulfonic acid sodium solution was at the uniform velocity added in 30 minutes used times, during dropwise addition
Temperature is kept for 0~5 DEG C, uses pH=2.5~3.0 of manganese hydrogen sodium regulating solution at any time, and medium is kept to stir 1.5 hours, sampling
Detect reaction end be without extra 2.4- diamino benzene sulfonic acid sodium until, stay a contracting object sample after qualified.
Or addition bottom water 800L, 2500Kg trash ice, Cyanuric Chloride 400Kg, addition ice mill help b), in 20000L reaction kettle
Agent 5Kg, ice time consuming are 15 minutes, and then p-aminobenzene sulfonic acid solution, temperature during dropwise addition was at the uniform velocity added in 30 minutes used times
It is kept for 0~5 DEG C, uses pH=2.5~3.0 of manganese hydrogen sodium regulating solution at any time, keep medium to stir 1.5 hours, sample detection
Reaction end be without extra p-aminobenzene sulfonic acid until, stay a contracting object sample after qualified.
(3), secondary condensation
One contracts after reaction, cooling on the rocks, the 2.4- diamino benzene sulfonic acid sodium solution or p-aminophenyl that will have been dissolved
Sulfonic acid solutions at the uniform velocity carry out two contracting reactions, 5~10 DEG C of temperature are kept after finishing, stirs 3~3.5 hours, takes in one contracting object of addition
Sample is qualification without an extra contracting object with liquid chromatographic detection, obtains two contracting things.
Step 2, diazo-reaction
A), bottom water 3000L is added in 35000L reaction kettle, (the sulfate group vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) of 2- amino -5 of 100% amount is added
Base)-benzoic acid 692.7Kg, after mashing 1 hour, addition 510Kg hydrochloric acid is kept for 0~8 DEG C of temperature with ice, rapidly joins nitrous acid
Sodium solution (it is spare to have dissolved sodium nitrite 150Kg) in advance, keeps the aobvious blue of starch potassium iodide paper, pH ﹤ 2 is controlled, in 0~8
DEG C insulation reaction 2~2.5 hours, extra sodium nitrite was removed with sulfamic acid, obtains (the sulfate group vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) of 2- amino -5
Base)-benzoic acid diazo liquid.
B), 510Kg hydrochloric acid is added in two contracting things, is kept for 0~8 DEG C of temperature with ice, rapidly joins sodium nitrite solution and (mention
Before to have dissolved sodium nitrite 150Kg spare), keep the aobvious blue of starch potassium iodide paper, pH ﹤ 2 controlled, in 0~8 DEG C of insulation reaction
3.5~4 hours, extra sodium nitrite is removed with sulfamic acid, obtains two contracting things diazo liquid.
Step 3, coupling reaction
The H acid powder of 394Kg is added directly into 2- amino -5 (sulfate group ethylene sulfuryl)-benzoic acid diazo liquid,
With between 15%~20% sodium carbonate liquor of concentration control pH=2.5~3.0, temperature rises to 15~20 DEG C, keeps medium stirring
Reaction 1.5 hours, then medium is adjusted to 3.5~4.0, it stirs 2.5 hours.Acid is even after reaction, obtains acidic coupling object, then two are contracted
Object diazo liquid is added in acidic coupling object, controls pH=6.5~7.0 with sodium carbonate liquor, is kept for 15~20 DEG C of temperature, keeps medium
Between 6.5~7.0, it is stirred to react 2 hours, after reaction sample detection.
Filter to obtain finished product after detection is qualified, can be directly spray-dried, obtain solid powder packaging, as conventional dyes into
Marketing is sold.If as digital ink-jet printed dyestuff, to postprocessing working procedures.
Step 4, post-processing
Stock staining solution after detection is qualified carries out the processes such as desalination, purification with nanometer film, after all technical is qualified, adjusts
Whole dye content 20%~35% can be used as the digital ink-jet printed dyestuff sale of liquid；It is dry with spray drying process, obtain solid powder
End also can be used as the digital ink-jet printed dyestuff sale of solid.
Embodiment 4,
A kind of digital ink-jet dye activity is dark blue, and molecular structural formula is shown in formula (V):
The dark blue preparation method of the digital ink-jet dye activity, includes the following steps:
Step 1, condensation reaction
(1), dissolve
A), bottom water 1800L is added in 5000L reaction kettle, 30~35 DEG C are warming up to, by the 2.4- diamino of 538.5Kg
Benzene sulfonic acid sodium salt is dissolved with water, controls medium 6.5~7.0 with the sodium carbonate liquor of concentration 15%~20%, so that whole materials are complete
Fully dissolved obtains 2.4- diamino benzene sulfonic acid sodium solution；It is spare.
B), (sulfate group ethylene the sulfuryl)-benzoic acid of 2- amino -5 is dissolved according to mass concentration 20%, it is anti-in 5000L
Addition bottom water 2500L in kettle is answered, 2- amino -5 (sulfate group ethylene sulfuryl)-benzoic acid 692.7Kg of 100% amount is added, is used
The sodium carbonate liquor of concentration 15%~20% is adjusted between pH=4.0~4.5, so that material all dissolves, obtains 2- amino-
5 (sulfate group ethylene sulfuryl)-benzoic acid solutions, it is spare.
(2), primary condensation
A), bottom water 800L, 2500Kg trash ice, Cyanuric Chloride 400Kg are added in 20000L reaction kettle, ice milling aid is added
5Kg, ice time consuming are 15 minutes, and then 2.4- diamino benzene sulfonic acid sodium solution was at the uniform velocity added in 30 minutes used times, during dropwise addition
Temperature is kept for 0~5 DEG C, uses pH=2.5~3.0 of manganese hydrogen sodium regulating solution at any time, and medium is kept to stir 1.5 hours, sampling
Detect reaction end be without extra 2.4- diamino benzene sulfonic acid sodium until, stay a contracting object sample after qualified.
Or addition bottom water 800L, 2500Kg trash ice, Cyanuric Chloride 400Kg, addition ice mill help b), in 20000L reaction kettle
Agent 5Kg, ice time consuming are 15 minutes, and then 2- amino -5 (sulfate group ethylene sulfuryl)-benzene first was at the uniform velocity added in 30 minutes used times
Acid solution, temperature is kept for 0~5 DEG C during dropwise addition, uses pH=2.5~3.0 of manganese hydrogen sodium regulating solution at any time, keeps medium
Stirring 1.5 hours, sample detection reaction end be without extra 2- amino -5 (sulfate group ethylene sulfuryl)-benzoic acid until, close
A contracting object sample is stayed after lattice.
(3), secondary condensation
One contracts after reaction, cooling on the rocks, by the 2.4- diamino benzene sulfonic acid sodium solution dissolved or 2- amino -5
(sulfate group ethylene sulfuryl)-benzoic acid solution, at the uniform velocity addition one contracting object in carry out two contracting reaction, after finishing holding temperature 5~
It 10 DEG C, stirs 3~3.5 hours, sampling is qualified without an extra contracting object with liquid chromatographic detection.
Step 2, diazo-reaction
A), bottom water 1500L is added in 35000L reaction kettle, meta position ester 628Kg is added and is added after mashing 1 hour
510Kg hydrochloric acid is kept for 0~10 DEG C of temperature with ice, rapidly joins sodium nitrite solution and (it is standby to have dissolved sodium nitrite 150Kg in advance
With), keep the aobvious blue of starch potassium iodide paper, control pH ﹤ 2, in 0~10 DEG C insulation reaction 2~2.5 hours, use sulfamic acid
Extra sodium nitrite is removed, meta position ester diazo liquid is obtained.
B), 510Kg hydrochloric acid is added in two contracting things, is kept for 0~8 DEG C of temperature with ice, rapidly joins sodium nitrite solution and (mention
Before to have dissolved sodium nitrite 150Kg spare), keep the aobvious blue of starch potassium iodide paper, pH ﹤ 2 controlled, in 0~8 DEG C of insulation reaction
3.5~4 hours, extra sodium nitrite is removed with sulfamic acid, obtains two contracting things diazo liquid.
Step 4, coupling reaction
The H acid solid powder of 394Kg is added directly into meta position ester diazo liquid, it is molten with 15%~20% sodium carbonate of concentration
Between hydraulic control pH=2.5~3.0, temperature rises to 15~20 DEG C, keeps medium to be stirred to react 1.5 hours, then medium is adjusted to
3.5~4.0, it stirs 2.5 hours.Acid is even after reaction, obtains acidic coupling object；The diazo liquid of two contracting things is added in acidic coupling object again,
PH=6.5~7.0 are controlled with sodium carbonate liquor, are kept for 15~20 DEG C of temperature, keep being stirred to react 2 between medium 6.5~7.0
Hour, sample detection after reaction.
Filter to obtain finished product after detection is qualified, can be directly spray-dried, obtain solid powder packaging, as conventional dyes into
Marketing is sold.If as digital ink-jet printed dyestuff, to postprocessing working procedures.
Step 4, post-processing
Stock staining solution after detection is qualified carries out the processes such as desalination, purification with nanometer film, after all technical is qualified, adjusts
Whole dye content 20%~35% can be used as the digital ink-jet printed dyestuff sale of liquid；It is dry with spray drying process, obtain solid powder
End also can be used as the digital ink-jet printed dyestuff sale of solid.
Embodiment 5
A kind of digital ink-jet dye activity is dark blue, and molecular structural formula is shown in formula (VI):
The dark blue preparation method of the digital ink-jet dye activity, includes the following steps:
Step 1, condensation reaction
(1), dissolve
A), bottom water 1800L is added in 5000L reaction kettle, 30~35 DEG C are warming up to, by the 2.4- diamino of 538.5Kg
Benzene sulfonic acid sodium salt is dissolved with water, controls medium 6.5~7.0 with the sodium carbonate liquor of concentration 15%~20%, so that whole materials are complete
Fully dissolved obtains 2.4- diamino benzene sulfonic acid sodium solution, spare.
B), bottom water 600L is added in 2000L reaction kettle, amion acetic acid 161Kg is added, so that all dissolution is material
Can, obtain amion acetic acid solution；It is spare.
(2), primary condensation
A), bottom water 800L, 2500Kg trash ice, Cyanuric Chloride 400Kg are added in 20000L reaction kettle, ice milling aid is added
5Kg, ice time consuming are 15 minutes, and then 2.4- diamino benzene sulfonic acid sodium solution was at the uniform velocity added in 30 minutes used times, during dropwise addition
Temperature is kept for 0~5 DEG C, uses pH=2.5~3.0 of manganese hydrogen sodium regulating solution at any time, and medium is kept to stir 1.5 hours, sampling
Detect reaction end be without extra 2.4- diamino benzene sulfonic acid sodium until, stay a contracting object sample after qualified.
Or addition bottom water 800L, 2500Kg trash ice, Cyanuric Chloride 400Kg, addition ice mill help b), in 20000L reaction kettle
Agent 5Kg, ice time consuming are 15 minutes, and then amion acetic acid solution was at the uniform velocity added in 30 minutes used times, and temperature keeps 0 during dropwise addition
~5 DEG C, pH=2.5~3.0 of manganese hydrogen sodium regulating solution are used at any time, medium is kept to stir 1.5 hours, and sample detection reaction is eventually
Point is stays a contracting object sample after qualified until without extra amion acetic acid.
(3), secondary condensation
One contracts after reaction, cooling on the rocks, the 2.4- diamino benzene sulfonic acid sodium solution or amion acetic acid that will have been dissolved
Solution at the uniform velocity carries out two contracting reactions, 5~10 DEG C of temperature is kept after finishing, is stirred 3~3.5 hours, sampling is used in one contracting object of addition
Liquid chromatographic detection is qualification without an extra contracting object.
Step 2, diazo-reaction
A), bottom water 3000L is added in 35000L reaction kettle, (the sulfate group vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) of 2- amino -5 of 100% amount is added
Base)-benzoic acid 692.7Kg, after mashing 1 hour, addition 510Kg hydrochloric acid is kept for 0~8 DEG C of temperature with ice, rapidly joins nitrous acid
Sodium solution (it is spare to have dissolved sodium nitrite 150Kg) in advance, keeps the aobvious blue of starch potassium iodide paper, pH ﹤ 2 is controlled, in 0~8
DEG C insulation reaction 2~2.5 hours, extra sodium nitrite was removed with sulfamic acid, obtains (the sulfate group vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) of 2- amino -5
Base)-benzoic acid diazo liquid.
B), 510Kg hydrochloric acid is added in two contracting things, is kept for 0~8 DEG C of temperature with ice, rapidly joins sodium nitrite solution and (mention
Before to have dissolved sodium nitrite 150Kg spare), keep the aobvious blue of starch potassium iodide paper, pH ﹤ 2 controlled, in 0~8 DEG C of insulation reaction
3.5~4 hours, extra sodium nitrite is removed with sulfamic acid, obtains two contracting things diazo liquid.
Step 3, coupling reaction
Dissolution: being added bottom water 1200L in 2000L reaction kettle, and the H acid of 394Kg is added, and mashing dissolution 1 hour is spare.
H acid solution is added directly into 2- amino -5 (sulfate group ethylene sulfuryl)-benzoic acid diazo liquid, concentration is used
15%~20% sodium carbonate liquor controls between pH=2.5~3.0, and temperature rises to 15~20 DEG C, and medium is kept to be stirred to react 1.5
Hour, then medium is adjusted to 3.5~4.0, it stirs 2.5 hours.It is sour even to obtain acidic coupling object after reaction, then by the weight of two contracting things
Nitrogen liquid be added acidic coupling object in, with sodium carbonate liquor control pH=6.5~7.0, keep 15~20 DEG C of temperature, keep medium 6.5~
Between 7.0, it is stirred to react 2 hours, after reaction sample detection.
Filter to obtain finished product after detection is qualified, can be directly spray-dried, obtain solid powder packaging, as conventional dyes into
Marketing is sold.If as digital ink-jet printed dyestuff, to postprocessing working procedures.
Step 4, post-processing
Stock staining solution after detection is qualified carries out the processes such as desalination, purification with nanometer film, after all technical is qualified, adjusts
Whole dye content 20%~35% can be used as the digital ink-jet printed dyestuff sale of liquid；It is dry with spray drying process, obtain solid powder
End also can be used as the digital ink-jet printed dyestuff sale of solid.
Application performance detection:
Currently, the digital ink-jet reactive navy blue largely used on selling market, molecular structural formula is shown in (VII):
It detects and compares with its embodiment of the present invention 1-5 application performance:
Detection data report
It is drawn a conclusion by application performance comparison, reactive navy blue prepared by the present invention is better than the activity of other structures type
Dark blue dye.
Embodiment 6
The preparation method of intermediate, includes the following steps:
The wherein structure of intermediate are as follows:
1), chlorosulfonation: 1 part of dry 2- carboxyanilino is slowly added into 6 parts of chlorosulfonic acids, and temperature is controlled during charging
Degree is at 50 DEG C or less；After charging, stir evenly；It is to slowly warm up to 100 DEG C, is kept for 100-130 DEG C after reaction 6-8 hours,
It is down to room temperature.Material is precipitated in ice, obtains pale solid A.
2) it, restores: 1 part of pale solid A is slowly added into the solution dissolved with 1.3 parts of sodium sulfites, feed process
Middle to control pH=7.5-8 with liquid alkaline, temperature is kept for 10-50 DEG C.After reaction 2 hours, white solid B is obtained by filtration.
3), hydroxyethylation: white solid B is dissolved into water and is placed in closed pressure resistant container, epoxy is passed through into solution
Ethane gas, temperature are maintained at 50-80 DEG C, use H2SO4(20%) it adjusts pH=6.8-7.2. to react 10-12 hours, be obtained by filtration
White solid C.
4) it, is esterified: dry white solid C is slowly added into 4 parts of concentrated sulfuric acids, be sufficiently stirred during charging and warm
Degree control is at 40 DEG C or less.Then it is warming up to 40-45 DEG C, is kept for 4 hours.End of reaction, ice analyse discharging of saltouing and obtain white admittedly
Body product to obtain the final product.
Dyestuff and dyestuff preparation method of the invention is described by specific embodiment.Those skilled in the art
Member can use for reference the links such as the appropriate feed change of the contents of the present invention, process conditions to realize corresponding other purposes, correlation
Change all without departing from the contents of the present invention, all similar substitutions and modifications are aobvious and easy to those skilled in the art
See, is considered as being included within the scope of the present invention.
Claims (6)
1. a kind of active dark blue dye, it is characterised in that: its general formula of molecular structure is such as shown in (I):
R1, R2 substituent group are following several selection modes:
When R1 is-CH2COONa、R2 is
When R1 isR2 is
When R1 isR2 is
When R1 isR2 is
2. a kind of active dark blue dye according to claim 1, it is characterised in that: the structural formula of the active dark blue dye
Are as follows:
3. a kind of active dark blue dye according to claim 1, it is characterised in that: the structural formula of the active dark blue dye
Are as follows:
4. a kind of active dark blue dye according to claim 1, it is characterised in that: the structural formula of the active dark blue dye
Are as follows:
5. a kind of active dark blue dye according to claim 1, it is characterised in that: the structural formula of the active dark blue dye
Are as follows:
6. a kind of active dark blue dye according to claim 1, it is characterised in that: the structural formula of the active dark blue dye
Are as follows:
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| WO2020246342A1 (en) * | 2019-06-06 | 2020-12-10 | 日本化薬株式会社 | Ink composition and ink-jet recording method including using same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481540A (en) * | 2008-12-12 | 2009-07-15 | 天津市德凯化工有限公司 | Preparation of reactive blue 2G dye |
| CN102433026A (en) * | 2011-09-29 | 2012-05-02 | 天津德凯化工股份有限公司 | Black active dye for pure cotton or cotton and wool blended textile dyeing and preparation method thereof |
| CN102504581A (en) * | 2011-09-29 | 2012-06-20 | 天津德凯化工股份有限公司 | Extra-dark black active dye and preparation method thereof |
| CN103627206A (en) * | 2013-11-21 | 2014-03-12 | 天津德凯化工股份有限公司 | Novel active navy blue dye |
| CN108102420A (en) * | 2017-12-19 | 2018-06-01 | 天津德凯化工股份有限公司 | A kind of dark blue reactive dye and preparation method thereof |
-
2018
- 2018-10-26 CN CN201811261227.6A patent/CN109233334A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481540A (en) * | 2008-12-12 | 2009-07-15 | 天津市德凯化工有限公司 | Preparation of reactive blue 2G dye |
| CN102433026A (en) * | 2011-09-29 | 2012-05-02 | 天津德凯化工股份有限公司 | Black active dye for pure cotton or cotton and wool blended textile dyeing and preparation method thereof |
| CN102504581A (en) * | 2011-09-29 | 2012-06-20 | 天津德凯化工股份有限公司 | Extra-dark black active dye and preparation method thereof |
| CN103627206A (en) * | 2013-11-21 | 2014-03-12 | 天津德凯化工股份有限公司 | Novel active navy blue dye |
| CN108102420A (en) * | 2017-12-19 | 2018-06-01 | 天津德凯化工股份有限公司 | A kind of dark blue reactive dye and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020246342A1 (en) * | 2019-06-06 | 2020-12-10 | 日本化薬株式会社 | Ink composition and ink-jet recording method including using same |
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Application publication date: 20190118 |