CN106810905B - A kind of active red dye and its preparation and application - Google Patents
A kind of active red dye and its preparation and application Download PDFInfo
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- CN106810905B CN106810905B CN201611103380.7A CN201611103380A CN106810905B CN 106810905 B CN106810905 B CN 106810905B CN 201611103380 A CN201611103380 A CN 201611103380A CN 106810905 B CN106810905 B CN 106810905B
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- 239000001044 red dye Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229920000742 Cotton Polymers 0.000 claims abstract description 13
- 239000000835 fiber Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000009980 pad dyeing Methods 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 33
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 30
- 239000000975 dye Substances 0.000 claims description 23
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000012954 diazonium Substances 0.000 claims description 16
- 150000001989 diazonium salts Chemical class 0.000 claims description 16
- 238000009833 condensation Methods 0.000 claims description 15
- 230000005494 condensation Effects 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 235000010288 sodium nitrite Nutrition 0.000 claims description 15
- 230000008878 coupling Effects 0.000 claims description 13
- 238000010168 coupling process Methods 0.000 claims description 13
- 238000005859 coupling reaction Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 11
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 238000004537 pulping Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- 238000006149 azo coupling reaction Methods 0.000 claims description 5
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 5
- 238000007639 printing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 244000025254 Cannabis sativa Species 0.000 claims description 4
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 4
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 4
- 235000009120 camo Nutrition 0.000 claims description 4
- 235000005607 chanvre indien Nutrition 0.000 claims description 4
- 239000011487 hemp Substances 0.000 claims description 4
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 claims description 4
- 238000007641 inkjet printing Methods 0.000 claims description 3
- GSCPDZHWVNUUFI-UHFFFAOYSA-N 3-aminobenzamide Chemical compound NC(=O)C1=CC=CC(N)=C1 GSCPDZHWVNUUFI-UHFFFAOYSA-N 0.000 claims description 2
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 claims description 2
- 125000006125 ethylsulfonyl group Chemical group 0.000 claims description 2
- 229940100595 phenylacetaldehyde Drugs 0.000 claims description 2
- 239000004753 textile Substances 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 3
- 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 claims 1
- 229920000297 Rayon Polymers 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 238000010016 exhaust dyeing Methods 0.000 claims 1
- 239000002964 rayon Substances 0.000 claims 1
- 238000004043 dyeing Methods 0.000 abstract description 28
- 125000000217 alkyl group Chemical group 0.000 abstract description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 125000001624 naphthyl group Chemical group 0.000 abstract description 3
- 230000002829 reductive effect Effects 0.000 abstract description 3
- 229910052783 alkali metal Chemical group 0.000 abstract description 2
- 150000001340 alkali metals Chemical group 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 150000003335 secondary amines Chemical class 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- HJORILXJGREZJU-UHFFFAOYSA-L disodium 7-[(5-chloro-2,6-difluoropyrimidin-4-yl)amino]-4-hydroxy-3-[(4-methoxy-2-sulfonatophenyl)diazenyl]naphthalene-2-sulfonate Chemical compound ClC=1C(=NC(=NC1F)F)NC1=CC=C2C(=C(C(=CC2=C1)S(=O)(=O)[O-])N=NC1=C(C=C(C=C1)OC)S(=O)(=O)[O-])O.[Na+].[Na+] HJORILXJGREZJU-UHFFFAOYSA-L 0.000 description 8
- 238000000746 purification Methods 0.000 description 6
- 239000000985 reactive dye Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- -1 Phenyl Chemical group 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- VMKJWLXVLHBJNK-UHFFFAOYSA-N cyanuric fluoride Chemical compound FC1=NC(F)=NC(F)=N1 VMKJWLXVLHBJNK-UHFFFAOYSA-N 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000006268 reductive amination reaction Methods 0.000 description 4
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 0 *c1cc(N*)c2c(O)cc(*)cc2c1 Chemical compound *c1cc(N*)c2c(O)cc(*)cc2c1 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 229910004727 OSO3H Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material 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
- C09B62/51—Monoazo 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
- D06P1/384—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
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/66—Natural or regenerated cellulose using reactive dyes
- D06P3/666—Natural or regenerated cellulose using reactive dyes reactive group not directly attached to heterocyclic group
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Abstract
The invention discloses a kind of active red dye and its preparation and application, wherein active red dye has structure shown in formula (I), wherein X is F or Cl, and A is with SO2CHCH2Or CONHC2H4SO2CHCH2The monosubstituted or polysubstituted phenyl or naphthyl of group, D are with SO2CHCH2Or CONHC2H4SO2CHCH2The monosubstituted or polysubstituted phenyl of group, R C1~5The C of alkyl, phenyl or phenyl substitution1~3Alkyl；M is hydrogen or alkali metal.The active red dye structure novel of the present invention is had excellent performance, with good degree of fixation, color fastness, the consumption of resource can effectively be reduced, there is good stability after dyeing, bright in color light, it can be widely used in the dyeings such as the dip dyeings of the cotton Products such as polyester-cotton blend, fiber crops, synthetic cotton, pad dyeing, ink-jet printed, and production cost is low, it can be with large-scale promotion application.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, particularly relates to a reactive dye, and particularly relates to a reactive red dye, a preparation method thereof and application thereof in cotton fiber printing and dyeing.
Background
Reactive dyes (reaction dye) are also called reactive dyes. The molecule contains chemically active groups, and the dye can react with fibers such as cotton, wool and the like in aqueous solution to form a common bond. Although the double active groups can improve various performances of the dye, the double active groups have some defects, such as poor solubility of active red B-6BF, poor color tone, low fixation rate and poor washing fastness. The structure of B-6BF red is as follows:
the reactive dye with multiple reactive groups has better fixation rate than a single reactive group reactive dye, but blind stacking of the reactive groups has no practical significance to the dye, only can increase the cost of dye production, and the hydrolysis of the dye can also cause the waste of the reactive groups. Therefore, the synthesis and development of stable reactive dyes with multiple reactive groups are still the subject of research.
Disclosure of Invention
The invention aims to provide a reactive red dye which is novel in structure and excellent in performance on the basis of the prior art. The dye has good solubility, color fixing rate and color fastness, has good stability after dyeing, has bright color light, can be widely applied to dyeing processes such as dip dyeing, pad dyeing, ink-jet printing and the like of fiber products such as cotton, hemp, artificial cotton and the like, has low production cost, and can be popularized and applied on a large scale.
The invention also aims to provide a preparation method of the reactive red dye.
The third purpose of the invention is to provide the application of the reactive red dye in printing and dyeing of the fiber fabrics.
The object of the invention can be achieved by the following measures:
a reactive red dye with a structure shown in a formula (I),
wherein,
x is F or Cl;
a is a group having-SO2CHCH2or-CONHC2H4SO2CHCH2Mono-or polysubstituted by radicalsPhenyl or naphthyl, the substituents of which include C1～3Alkyl or-SO3M；
D is a group having-SO2CHCH2or-CONHC2H4SO2CHCH2Phenyl mono-or polysubstituted by radicals, the substituents of which include C1～3Alkyl or-SO3M；
R is C1～5Alkyl, phenyl or phenyl substituted C1～3An alkyl group;
m is hydrogen or an alkali metal.
In the present invention, the A group is a group having at least-SO2CHCH2or-CONHC2H4SO2CHCH2The phenyl or naphthyl group of the group, the A group may also contain other substituents in addition to the two preceding groups, including but not limited to C1～3Alkyl or-SO3M。
In a preferred embodiment, the a group is selected from one of the following groups:
in the present invention, the D group is a group bearing at least-SO2CHCH2or-CONHC2H4SO2CHCH2The phenyl, D group of the group may also contain other substituents in addition to the two preceding groups, including but not limited to C1～3Alkyl or-SO3M。
In a preferred embodiment, D is selected from the group consisting of:
in a preferred embodiment, R is selected from methyl, ethyl, n-propyl, isopropyl, phenyl, benzyl or phenethyl. In a preferred embodiment, M in the present invention is H, Na or K.
Among the reactive red dyes of the present invention, the following compounds are preferred:
the invention discloses a preparation method of the reactive red dye, which comprises the following steps:
(1) the diazo salt of the formula (II) and the compound of the formula (III) are coupled to obtain the compound of the formula (IV)
Wherein A is1To have-SO2CH2CH2OSO3H or-CONHC2H4SO2CH2CH2OSO3A group of H;
(2) carrying out condensation reaction on the compound of the formula (IV) and the compound of the formula (V) to obtain a compound of the formula (VI);
(3) the compound of the formula (VII) and the compound of the formula (VIII) are subjected to reductive amination reaction to obtain a compound of the formula (IX);
wherein D is1To have-SO2CH2CH2OSO3H or-CONHC2H4SO2CH2CH2OSO3A D group of H;
(4) the compound of formula (VI) and the compound of formula (IX) are subjected to condensation reaction to obtain the compound of formula (I').
(5) The compound of the formula (I') is hydrolyzed by alkali to obtain the compound of the formula (I)
In a preferable scheme, in the step (1), the diazonium salt shown in the formula (II) is added into the compound shown in the formula (III), the pH value is adjusted to 5-8, and the temperature is 0-10 ℃ for coupling, so that the compound shown in the formula (IV) is obtained.
In a preferable scheme, in the step (2), the compound of the formula (V) is subjected to ice-milling pulping, the compound of the formula (IV) is added for condensation reaction, the pH value is adjusted to 3-5, and the compound of the formula (VI) is obtained after full reaction.
In a preferred embodiment, in step (3), the compound of formula (VII) is catalytically reduced with the compound of formula (VIII) at a temperature of 40-80 ℃ to give the compound of formula (IX).
In a preferred embodiment, in step (4), the compound of formula (ix) is subjected to a condensation reaction with the compound of formula (vi) at a pH of 3-5 at 40-60 ℃ to give the compound of formula (i'); in step (5), the compound of formula (I') is heated at a pH of 9-10 to 40-70 ℃ to obtain the compound of formula (I).
Unless otherwise indicated, "alkyl" as used in the specification and claims denotes a saturated aliphatic group of 1 to 20 carbon atoms, including straight and branched chain groups (a range of numbers referred to in this application, e.g., "1 to 20", refers to the group, which in this case is alkyl, and may contain 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including 20 carbon atoms). Alkyl groups having 1 to 5 carbon atoms are referred to as lower alkyl groups. When a lower alkyl group has no substituent, it is referred to as unsubstituted lower alkyl. More preferably, the alkyl group is a medium size alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, pentyl, and the like. Preferably, the alkyl group is a lower alkyl group having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, or the like. Alkyl groups may be substituted or unsubstituted.
The invention discloses a dye composition, which takes the reactive red dye as a reactive component and is assisted by an auxiliary agent in the field of dyes.
The dye finished product prepared by the reactive red dye can exist in solid particles, powder or solution, and contains electrolyte salts, such as sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, and cosolvents and stabilizers commonly used in commercial dyes.
The reactive red dye can be applied to textile printing and dyeing, in particular to dip dyeing, pad dyeing or ink-jet printing of cotton, hemp or artificial cotton fibers.
The invention provides application of the reactive red dye in printing and dyeing of fiber fabrics. The fiber fabric can be cotton, hemp, artificial cotton and other materials. Compared with the prior art, the reactive red dye monomer compound has the advantages of novel structure, excellent performance, bright color, high solubility, high fixation rate, stable dye, good fastness to washing, rubbing and sunlight, good stability of combination with fiber, excellent brightness of finished products and suitability for large-scale popularization and application.
Detailed Description
The invention will now be further described with reference to specific examples, which include but are not limited to the scope of the invention.
Example 1: preparation of the Compound of formula (I-1)
(1) Diazo coupling reaction
Adding 20 parts (by mass) of ice, 24.3 parts of 30% hydrochloric acid and 28.1 parts of meta-ester into a 250ml beaker, pulping for 30min by using an ice mill, slowly adding 6.97 parts of sodium nitrite to generate diazonium salt, stirring for 1h after the sodium nitrite is completely added, and eliminating the slightly excessive sodium nitrite by using sulfamic acid; slowly and dropwise adding the diazonium salt into 31.9 parts of H acid, adjusting the pH value to 5.5-8.0 by using baking soda while dropwise adding, continuing to react for 2 hours after the addition is finished, completely eliminating the diazonium salt, and simultaneously keeping the temperature of the system to be 0-10 ℃.
(2) By primary condensation of coupling component with cyanuric fluoride
In a 1000ml flask, 50 parts (by mass) of ice is added to a coupling liquid, 13.5 parts (in percent) of cyanuric fluoride is added dropwise to the coupling liquid, the pH value is adjusted to 3.5-5.0 by sodium bicarbonate, the temperature is kept at 0-10 ℃, the reaction is carried out for 4-6h, the liquid is clear and transparent, the reaction endpoint is detected by an amino reagent, the temperature is kept stable, and secondary condensation is carried out.
(3) Reductive amination of aldehydes with amines
In a 1000ml flask, 7.2 parts of n-butyraldehyde and 28.1 parts of p-ester, 50 parts of ethanol, 1 part of nickel catalyst, 10MPaH2Reducing for 12h at the temperature of 60-80 ℃, filtering to remove the catalyst, and evaporating the solvent to dryness to obtain a secondary amine product.
(4) Secondary amine secondary condensation
Adding secondary amine into the first condensed component, heating the reaction liquid to 40-60 ℃, adjusting the pH value to 3.5-5.0 by using baking soda, keeping the temperature at 40-60 ℃, reacting for 4-6h, clarifying the feed liquid, and detecting the reaction end point by using an amino reagent.
(5) Hydrolysis of sulfuric acid ester
Adding sodium carbonate into the solution, adjusting pH to 9-10, heating to 40-70 deg.C, and reacting for 8-10 h. And carrying out standardized processing and spray drying to obtain a finished dye product. (after purification, its MS: [ M + H ] + ═ 845.07)
Example 2: preparation of the Compound of formula (I-2)
(1) Diazo coupling reaction
Adding 20 parts of ice, 24.3 parts of 30% hydrochloric acid and 28.1 parts of para-ester into a 250ml beaker, pulping for 30min by using an ice mill, slowly adding 6.97 parts of sodium nitrite into the beaker to generate diazonium salt, stirring for 1h after the sodium nitrite is completely added, and eliminating the slightly excessive sodium nitrite by using sulfamic acid; slowly and dropwise adding the diazonium salt into 31.9 parts of H acid, adjusting the pH value to 5.5-8.0 by using baking soda while dropwise adding, continuing to react for 2 hours after the addition is finished, completely eliminating the diazonium salt, and simultaneously keeping the temperature of the system to be 0-10 ℃.
(2) By primary condensation of coupling component with cyanuric fluoride
In a 1000ml flask, 50 parts (by mass) of ice is added to a coupling liquid, 13.5 parts (in percent) of cyanuric fluoride is added dropwise to the coupling liquid, the pH value is adjusted to 3.5-5.0 by sodium bicarbonate, the temperature is kept at 0-10 ℃, the reaction is carried out for 4-6h, the liquid is clear and transparent, the reaction endpoint is detected by an amino reagent, the temperature is kept stable, and secondary condensation is carried out.
(3) Reductive amination of aldehydes with amines
In a 1000ml flask, 10.6 parts of benzaldehyde and 28.1 parts of para-ester, 50 parts of ethanol, 1 part of nickel catalyst, 10MPaH2Reducing for 12h at the temperature of 60-80 ℃, filtering to remove the catalyst, and evaporating the solvent to dryness to obtain a secondary amine product.
(4) Secondary amine secondary condensation
Adding secondary amine into the first condensed component, heating the reaction liquid to 40-60 ℃, adjusting the pH value to 3.5-5.0 by using baking soda, keeping the temperature at 40-60 ℃, reacting for 4-6h, clarifying the feed liquid, and detecting the reaction end point by using an amino reagent.
(5) Hydrolysis of sulfuric acid ester
Adding sodium carbonate into the solution, adjusting pH to 9-10, heating to 40-70 deg.C, and reacting for 8-10 h. And carrying out standardized processing and spray drying to obtain a finished dye product. (after purification, its MS: [ M + H ] + ═ 925.04)
Example 3: preparation of Compound of formula (I-3)
(1) Diazo coupling reaction
Adding 20 parts of ice, 24.3 parts of 30% hydrochloric acid and 35.2 parts of 2- [2- (3-aminobenzamide) ethyl sulfonyl ] ethanol sulfate into a 250ml beaker, pulping for 30min by using an ice mill, slowly adding 6.97 parts of sodium nitrite into the beaker to generate diazonium salt, stirring for 1h after the sodium nitrite is completely added, and eliminating the slight excess of the sodium nitrite by using sulfamic acid; slowly and dropwise adding the diazonium salt into 31.9 parts of H acid, adjusting the pH value to 5.5-8.0 by using baking soda while dropwise adding, continuing to react for 2 hours after the addition is finished, completely eliminating the diazonium salt, and simultaneously keeping the temperature of the system to be 0-10 ℃.
(2) By primary condensation of coupling component with cyanuric chloride
Adding 50 parts (by mass) of ice into a 1000ml flask, adding into 18.5 parts (folded) of pulped cyanuric chloride, adjusting the pH value to 3.5-5.0 with sodium bicarbonate, keeping the temperature at 0-10 ℃, reacting for 4-6h, clarifying and detecting the reaction end point with an amino reagent, keeping the temperature stable, and waiting for secondary condensation.
(3) Reductive amines of aldehydes with amines
A1000 ml flask was charged with 12 parts phenylacetaldehyde and 28.1 parts para-ester, 50 parts ethanol, 1 part nickel catalyst, 10MPaH2Reducing for 12h at the temperature of 60-80 ℃, filtering to remove the catalyst, and evaporating the solvent to dryness to obtain a secondary amine product.
(4) Secondary amine secondary condensation
Adding secondary amine into the first condensed component, heating the reaction liquid to 40-60 ℃, adjusting the pH value to 3.5-5.0 by using baking soda, keeping the temperature at 40-60 ℃, reacting for 4-6h, clarifying the feed liquid, and detecting the reaction end point by using an amino reagent.
(5) Hydrolysis of sulfuric acid ester
Adding sodium carbonate into the solution, adjusting pH to 9-10, heating to 40-70 deg.C, and reacting for 8-10 h. And carrying out standardized processing and spray drying to obtain a finished dye product. (after purification, its MS: [ M + H ] + ═ 1026.06)
Example 4: preparation of the Compound of formula (I-4)
(1) Diazo coupling reaction
Adding 20 parts of ice, 24.3 parts of 30% hydrochloric acid and 41 parts of 6-hydroxyethyl sulfonyl sulfate-2-naphthylamine-1-sulfonic acid into a 250ml beaker, pulping for 30min by using an ice mill, slowly adding 6.97 parts of sodium nitrite into the beaker to generate diazonium salt, stirring for 1h after the sodium nitrite is completely added, and eliminating the slightly excessive sodium nitrite by using sulfamic acid; slowly and dropwise adding the diazonium salt into 31.9 parts of H acid, adjusting the pH value to 5.5-8.0 by using baking soda while dropwise adding, continuing to react for 2 hours after the addition is finished, completely eliminating the diazonium salt, and simultaneously keeping the temperature of the system to be 0-10 ℃.
(2) By primary condensation of coupling component with cyanuric chloride
Adding 50 parts (by mass) of ice water and 18.5 parts (per hundred) of cyanuric chloride into a 1000ml flask, pulping for 1h, adding the coupling solution into cyanuric chloride slurry, adjusting the pH to 3.5-5.0 by using sodium bicarbonate, keeping the temperature at 0-10 ℃, reacting for 4-6h, clarifying and transparent the feed liquid, detecting the reaction endpoint by using an amino reagent, keeping the temperature stable, and waiting for secondary condensation.
(3) Reductive amination of aldehydes with amines
In a 1000ml flask, 7.2 parts of n-butyraldehyde, 36.1 parts of sulfonated para-ester, 50 parts of ethanol, 1 part of nickel catalyst, 10MPaH2Reducing for 12h at the temperature of 60-80 ℃, filtering to remove the catalyst, and evaporating the solvent to dryness to obtain a secondary amine product.
(4) Secondary amine secondary condensation
Adding secondary amine into the first condensed component, heating the reaction liquid to 40-60 ℃, adjusting the pH value to 3.5-5.0 by using baking soda, keeping the temperature at 40-60 ℃, reacting for 4-6h, clarifying the feed liquid, and detecting the reaction end point by using an amino reagent.
(5) Hydrolysis of sulfuric acid ester
Adding sodium carbonate into the solution, adjusting pH to 9-10, heating to 40-70 deg.C, and reacting for 8-10 h. And carrying out standardized processing and spray drying to obtain a finished dye product. (after purification, its MS: [ M + H ] + ═ 1160.91)
Example 5:
the process as described in example 4 was followed except that step 3 was changed to acetaldehyde and meta-ester in ethanol as solvent, nickel as catalyst, 10MPaH2Reducing for 12h at the temperature of 60-80 ℃, filtering to remove the catalyst, evaporating the solvent to dryness to obtain a secondary amine product, keeping other procedures unchanged basically, and performing standardized processing and spray drying to obtain a dye finished product I-5. (after purification, its MS: [ M + H ]]+＝1030.94)。
Example 6:
according to the method described in the embodiment 4, except that the sulfonated para-ester in the step 3 is changed into meta-ester, other procedures and mixture ratio are basically unchanged, and the dye finished product I-6 is obtained through standardized processing and spray drying. (after purification, its MS: [ M + H ] + ═ 1058.98).
Dyeing example 1:
2g of the reactive red dye obtained according to examples 1 to 7 were mixed with anhydrous sodium sulphate to give 530ml of dye liquor. The cotton cloth is dip-dyed for a period of time at a constant temperature, then a certain amount of soda ash is added, the temperature is raised to 60 ℃ for fixation for a period of time, and then washing, soaping and drying are carried out. The rubbing color fastness, the light fastness and the washing fastness were tested according to the methods in GB/T3920-.
Table 2 dyeing example 1 comparison of properties
Note: the dyeing depth is 3%
From the dyeing results, the bath ratio of the reactive red dyes of the examples 1, 3, 5 and 6 provided by the invention is 1: 8 to B-6BF Red and Drimarene Red CL-5B dyeing bath ratio of 1: 20 percent less than 60 percent, and saves dyeing water by 60 percent; example 2 bath ratio of reactive red dye dyeing was 1: 10 to B-6BF Red and Drimarene Red CL-5B in a dyeing bath ratio of 1: 20 percent less than 50 percent, and saves dyeing water by 50 percent; example 4 bath ratio of reactive red dye dyeing was 1: 5 to B-6BF Red and Drimarene Red CL-5B dyeing bath ratio of 1: 20 percent to 75 percent, greatly saving dyeing water by 75 percent;
the dyeing intensity of the reactive red dye provided by the examples 1-6 reaches 115-140%, and the dye consumption used for dyeing the same depth can be saved by 15-40% compared with that of B-6BF red and Drimarene red CL-5B; the dyeing time is shortened by 20-30 minutes, and the energy consumption is saved by 20-30%;
after dyeing, the water consumption of washing and soaping is 800ml which is 20% less than that of B-6BF red and 1000ml of Drimarene red CL-5B, and the washing fastness is improved by 1-2 level;
the dyeings have excellent fastness properties, particularly the rubbing fastness (dry) is improved by 1 to 2 grades compared with B-6BF red and Drimarene red CL-5B, the rubbing fastness (wet) is improved by 1 to 2 grades compared with B-6BF red and Drimarene red CL-5B, and the light fastness is improved by 1 to 2 grades compared with B-6BF red and Drimarene red CL-5B.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A reactive red dye characterized by being selected from the following compounds:
2. a method of preparing the reactive red dye of claim 1, comprising the steps of:
(1) diazo coupling reaction: adding 20 parts of ice, 24.3 parts of 30% hydrochloric acid and 35.2 parts of 2- [2- (3-aminobenzamide) ethyl sulfonyl ] ethanol sulfate into a 250ml beaker, pulping for 30min by using an ice mill, slowly adding 6.97 parts of sodium nitrite into the beaker to generate diazonium salt, stirring for 1h after the sodium nitrite is completely added, and eliminating the slight excess of the sodium nitrite by using sulfamic acid; slowly and dropwise adding the diazonium salt into 31.9 parts of H acid, adjusting the pH value to 5.5-8.0 by using baking soda while dropwise adding, continuing to react for 2 hours after the addition is finished, completely eliminating the diazonium salt, and simultaneously keeping the temperature of the system to be 0-10 ℃;
(2) primary condensation of coupling component and cyanuric chloride: adding 50 parts of ice into coupling liquid in a 1000ml flask, then adding the coupling liquid into 18.5 parts of pulped cyanuric chloride, adjusting the pH value to 3.5-5.0 by using baking soda, keeping the temperature at 0-10 ℃, reacting for 4-6h, clarifying and transparent the liquid, detecting the reaction end point by using an amino reagent, keeping the temperature stable, and waiting for secondary condensation;
(3) reducing amine of aldehyde with amine: a1000 ml flask was charged with 12 parts phenylacetaldehyde and 28.1 parts para-ester, 50 parts ethanol, 1 part nickel catalyst, 10MPaH2Reducing for 12h at the temperature of 60-80 ℃, filtering to remove the catalyst, and evaporating the solvent to dryness to obtain a secondary amine product;
(4) secondary amine secondary condensation: adding secondary amine into the first condensed component, heating the reaction solution to 40-60 ℃, adjusting the pH value to 3.5-5.0 by using baking soda, keeping the temperature at 40-60 ℃, reacting for 4-6h, clarifying and transparent the feed liquid, and detecting the reaction end point by using an amino reagent;
(5) hydrolysis of sulfuric ester: adding sodium carbonate into the solution, adjusting the pH value to 9-10, heating to 40-70 ℃, and reacting for 8-10 h; carrying out standardized processing and spray drying to obtain a dye finished product;
3. a dye composition, which takes the reactive red dye as claimed in claim 1 as a reactive component and is supplemented with auxiliaries in the dye field.
4. Use of the reactive red dye according to claim 1 for textile printing.
5. Use of the reactive red dyes according to claim 1 for exhaust dyeing, pad dyeing or ink-jet printing of cotton, hemp or rayon fibers.
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| CN1503828A (en) * | 2001-04-20 | 2004-06-09 | 克莱里安特财务(Bvi)有限公司 | Fiber-reactive mono-Azo dyes |
| CN1568354A (en) * | 2001-10-17 | 2005-01-19 | 克莱里安特财务(Bvi)有限公司 | Trichromatic dyeing process and dye mixtures used therein |
| CN101255283A (en) * | 2008-04-08 | 2008-09-03 | 赵卫国 | Reactive red M-2B dye and preparation method thereof |
| WO2016180641A1 (en) * | 2015-05-12 | 2016-11-17 | Huntsman Advanced Materials (Switzerland) Gmbh | Mixtures of reactive dyes and their use for the dyeing or printing of textile fibre materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1503828A (en) * | 2001-04-20 | 2004-06-09 | 克莱里安特财务(Bvi)有限公司 | Fiber-reactive mono-Azo dyes |
| CN1568354A (en) * | 2001-10-17 | 2005-01-19 | 克莱里安特财务(Bvi)有限公司 | Trichromatic dyeing process and dye mixtures used therein |
| CN101255283A (en) * | 2008-04-08 | 2008-09-03 | 赵卫国 | Reactive red M-2B dye and preparation method thereof |
| WO2016180641A1 (en) * | 2015-05-12 | 2016-11-17 | Huntsman Advanced Materials (Switzerland) Gmbh | Mixtures of reactive dyes and their use for the dyeing or printing of textile fibre materials |
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