CN113214675A - Reactive dye compound and preparation method and application thereof - Google Patents
Reactive dye compound and preparation method and application thereof Download PDFInfo
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- CN113214675A CN113214675A CN202110379823.XA CN202110379823A CN113214675A CN 113214675 A CN113214675 A CN 113214675A CN 202110379823 A CN202110379823 A CN 202110379823A CN 113214675 A CN113214675 A CN 113214675A
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- reactive dye
- dye compound
- diazonium salt
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 95
- 239000000985 reactive dye Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004744 fabric Substances 0.000 claims abstract description 24
- -1 alkali metal salt Chemical class 0.000 claims abstract description 16
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 239000004952 Polyamide Substances 0.000 claims abstract description 6
- 229920002647 polyamide Polymers 0.000 claims abstract description 6
- 239000012954 diazonium Substances 0.000 claims description 36
- 150000001989 diazonium salts Chemical class 0.000 claims description 36
- 238000005859 coupling reaction Methods 0.000 claims description 30
- UYEMGAFJOZZIFP-UHFFFAOYSA-N 3,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-UHFFFAOYSA-N 0.000 claims description 24
- 238000006193 diazotization reaction Methods 0.000 claims description 24
- 239000000975 dye Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 18
- 230000008878 coupling Effects 0.000 claims description 17
- 238000010168 coupling process Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 238000004537 pulping Methods 0.000 claims description 6
- 229910004727 OSO3H Inorganic materials 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 5
- 150000004982 aromatic amines Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims 1
- 238000004043 dyeing Methods 0.000 abstract description 26
- 239000000835 fiber Substances 0.000 abstract description 11
- 238000005406 washing Methods 0.000 abstract description 10
- 229920000742 Cotton Polymers 0.000 abstract description 7
- 210000002268 wool Anatomy 0.000 abstract description 3
- 229920000297 Rayon Polymers 0.000 abstract 1
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 50
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 43
- 239000000243 solution Substances 0.000 description 39
- 239000007788 liquid Substances 0.000 description 32
- 235000010288 sodium nitrite Nutrition 0.000 description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000003513 alkali Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 9
- 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 9
- 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 8
- 239000012085 test solution Substances 0.000 description 8
- 239000012752 auxiliary agent Substances 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 238000009980 pad dyeing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ZNXSFVXZQBETRJ-UHFFFAOYSA-N (3-aminophenyl)urea Chemical compound NC(=O)NC1=CC=CC(N)=C1 ZNXSFVXZQBETRJ-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- NTOLGSSKLPLTDW-UHFFFAOYSA-N hydrogen sulfate;phenylazanium Chemical compound OS(O)(=O)=O.NC1=CC=CC=C1 NTOLGSSKLPLTDW-UHFFFAOYSA-N 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- LUYAMNYBNTVQJG-UHFFFAOYSA-N 1-chloro-2-(2-chloroethylsulfonyl)ethane Chemical compound ClCCS(=O)(=O)CCCl LUYAMNYBNTVQJG-UHFFFAOYSA-N 0.000 description 1
- SRDOTWUOTQTGAK-UHFFFAOYSA-N C=O.C1(=CC=CC2=CC=CC=C12)S(=O)(=O)OCC1=CC=CC=C1 Chemical compound C=O.C1(=CC=CC2=CC=CC=C12)S(=O)(=O)OCC1=CC=CC=C1 SRDOTWUOTQTGAK-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- QQNXPCCFPQRLMK-UHFFFAOYSA-N S(O)(O)(=O)=O.OCCS(=O)(=O)CCO Chemical compound S(O)(O)(=O)=O.OCCS(=O)(=O)CCO QQNXPCCFPQRLMK-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 125000005236 alkanoylamino group Chemical group 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001049 brown dye Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- WQHQCQSAAOGHQP-UHFFFAOYSA-N formaldehyde;2-methylnaphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=CC2=C(S(O)(=O)=O)C(C)=CC=C21 WQHQCQSAAOGHQP-UHFFFAOYSA-N 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Images
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
-
- 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
- D06P3/24—Polyamides; Polyurethanes
- D06P3/248—Polyamides; Polyurethanes 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
- 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 reactive dye compound and a preparation method and application thereof. The reactive dye compound is a compound with a structure shown as the following formula (I) or an alkali metal salt thereof, wherein in the formula (I), D is1、D2Each independently is a group of the formula (a), formula (b), formula (c) or formula (D), and D1、D2Not simultaneously represented by the following formula (a), formula (b), formula (c) or formula (d). The invention also provides a reactive dye product containing the reactive dye compound, and provides application of the reactive dye product in printing and dyeing of cellulose fibers, polyamide fibers or fabrics thereof, and the reactive dye product has excellent color fastness, especially excellent washing fastness and rubbing fastness, and can be used with fibersThe fiber has good binding stability and can meet the requirements of conventional dyeing and printing of cotton, artificial cotton, silk, viscose, wool and blended fabrics thereof.
Description
(I) technical field
The invention relates to a reactive dye compound, a preparation method thereof and application thereof in printing and dyeing of cellulose fibers, polyamide fibers and fabrics thereof.
(II) background of the invention
The improvement of the lifting power and the washing fastness of the fabric dyed by the reactive dye is always the key and difficult point in the printing and dyeing production. The covalent bond between part of the reactive dye and the cotton fiber is affected by external conditions, and the bond breakage and hydrolysis are easy to occur, so that the color fastness of the dyed fabric is deteriorated, and particularly the color fastness to washing and staining cannot well meet the production requirement. In order to solve the problems, the inventor develops a novel reactive dye structure, adopts 3, 5-dihydroxy benzoic acid as a coupling component, and carries out intensive research on the compound to obtain orange to red brown dyes with excellent properties such as fastness, lifting power and the like on the basis of a large number of experiments.
Disclosure of the invention
The invention aims to provide a reactive dye compound with novel structure and excellent performance, a preparation method thereof and application thereof in printing and dyeing of cellulose fibers, polyamide fibers and fabrics thereof.
The technical solution adopted by the present invention is specifically explained below.
In a first aspect, the present invention provides a reactive dye compound which is a compound having a structure represented by the following formula (i):
in formula (I):
D1、D2each independently is a group of the formula (a), formula (b), formula (c) or formula (D), and D1、D2Not both being a group of the formula (a), formula (b), formula (c) or formula (d):
in the above formulas (a) to (d):
R1、R2、R3、R5、R6、R8、R9are independent of each other H, C1～C4Straight or branched alkyl, C1～C4Alkoxy or sulfonic acid groups;
m is 0 to 3, each R4Each independently selected from amino, sulfonic acid, ureido, C1～C4Alkyl of (C)1～C4Alkanoylamino or C1～C4An alkoxy group;
n is 0 to 3, each R7Each independently selected from hydroxyl, amino or sulfonic acid;
X1、X2、X3、X4are independent of each other H, C1～C4Straight or branched alkyl, C1～C4Alkoxy, -SO2Y1、-NHCO(CH2)pSO2Y2or-CONH (CH)2)qSO2Y3And D is1、D2At least one of which contains fibre-reactive groups, i.e. -SO2Y1、-NHCO(CH2)pSO2Y2or-CONH (CH)2)qSO2Y3Wherein Y is1～Y3Each independently is-CH ═ CH2、-C2H4OSO3H or-CH2CH2Cl，p＝1-3，q＝1-3。
In the present invention, said C1～C4The straight or branched alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.; said C1～C4The alkoxy group may be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, etc.; said C1～C4The alkanoylamino group of (a) may be formylamino, acetylamino, n-propionylamino, isopropionylamino, n-butyrylamino, isobutyrylamino, t-butyrylamino and the like.
Further, in the formulae (a) to (d):
R1、R2、R3、R5、R6、R8、R9independently of one another, H, methyl, methoxy or sulfonic acid;
m is 1 or 2, each R4Each independently preferably being a methyl group, a sulfonic acid group, a ureido group or an acetamido group;
n is 0 or 1, each R7Each independently selected from hydroxyl or sulfonic acid group;
X1、X2、X3、X4independently of one another are-SO2Y1、-NHCO(CH2)pSO2Y2or-CONH (CH)2)qSO2Y3Wherein Y is1～Y3Each independently is-CH ═ CH2、-CH2CH2Cl or-C2H4OSO3H，p＝1-3，q＝1-3。
Further, D1Preferably a group of formula (a) or (b), said D2Preferred are groups of formula (c) or (d).
Further, the reactive dye compound has a structure represented by the following formula (Ia) or formula (Ib):
the substituents in the formula (Ia) and the formula (Ib) are as defined in the formula (I).
Further, in the reactive dye compound, the formula (a) is preferably selected from one of the following groups:
further, in the reactive dye compound, the formula (b) is preferably selected from one of the following groups:
further, in the reactive dye compound, the formula (c) is preferably selected from one of the following groups:
further, in the reactive dye compound, the formula (d) is preferably selected from one of the following groups:
the invention specifically recommends that the reactive dye compound is selected from one of the compounds shown in the following formulas (I-1) to (I-112) and alkali metal salts thereof:
further, in the present invention, it is preferable that the reactive dye compound is one selected from the group consisting of compounds represented by formulae (I-1) to (I-52), formulae (I-59) to (I-68), formulae (I-74) to (I-83), and alkali metal salts thereof.
Further, in the present invention, it is preferable that the reactive dye compound is one selected from the group consisting of compounds represented by formulae (I-1) to (I-16), formulae (I-27) to (I-48), and alkali metal salts thereof.
It is to be emphasized that the reactive dye compounds (I) according to the invention, the dyes coupled in the ortho position to the phenolic hydroxyl group, often exist in the form of quinone hydrazone compounds, i.e. the dyes of the general formula (I) contain quinone hydrazone structures represented by the following formulae (ie) and/or (if) and/or (ig) and/or (ih), and that the writing of azo compounds is still used in the summary and the examples section of the present invention, taking into account the writing habits of the skilled person, without affecting the essence of the present invention:
the substituents in the formulae (ie) to (ih) are as defined for formula (I).
In a second aspect, the present invention provides a process for the preparation of a compound of formula (i) comprising:
(1) diazotization is carried out according to the following steps A and B and/or C:
A. diazotizing the arylamine compounds shown in the formula (IIa), the formula (IIb), the formula (IIc) and/or the formula (IId) respectively to obtain respective diazonium salts;
B. coupling the diazonium salt shown in the formula (IIc) with arylamine shown in the formula (IIIa) to obtain a compound shown in the formula (IVa), and diazotizing the compound shown in the formula (IVa) to obtain the diazonium salt for later use;
C. coupling the diazonium salt shown in the formula (IId) with arylamine shown in the formula (IIIb) to obtain a compound shown in the formula (IVb), and diazotizing the compound shown in the formula (IVb) to obtain the diazonium salt for later use;
(2) coupling reaction: adding water into 3, 5-dihydroxy benzoic acid, pulping, performing primary coupling on the pulped solution and one of the diazonium salt of the formula (IIa), the diazonium salt of the formula (IIb), the diazonium salt of the formula (IVa) and the diazonium salt of the formula (IVb) in the step (1), and performing secondary coupling on the solution and one of the diazonium salt of the formula (IIa), the diazonium salt of the formula (IIb), the diazonium salt of the formula (IVa) and the diazonium salt of the formula (IVb), wherein the diazonium salts adopted in the primary coupling and the secondary coupling can not be the diazonium salt of the formula (IIa), the diazonium salt of the formula (IIb), the diazonium salt of the formula (IVa) or the diazonium salt of the formula (IVb), so as to obtain the active dye compound (I);
the substituents in the above formulae (IIa) to (IId), formulae (IIIa), (IIIb), formulae (IVa) and formulae (IVb) are as defined for formula (I).
Further, the compound (i) is preferably synthesized by the following steps:
(1) diazotization:
A. according to the requirement, the compounds shown in the formula (IIa), the formula (IIb), the formula (IIc) and/or the formula (IId) are respectively pulped with water and ice for 1-2h, a certain amount of hydrochloric acid is added after pulping is finished, then a sodium nitrite solution is added within 20-30min, diazotization is carried out under the conditions that the pH is controlled to be 0.5-3.0 (preferably 0.5-2.0) and the temperature T is controlled to be 0-30 ℃ (preferably 0-20 ℃), and the end point is detected by an ethanol solution of 4-dimethylaminobenzaldehyde (namely, the compound does not change color within 5 s); after the diazotization end point is reached, sulfamic acid is used for eliminating excessive sodium nitrite to respectively obtain diazo liquid of the formula (IIa), the formula (IIb), the formula (IIc) or the formula (IId) for storage and standby; wherein, the molar ratio of the compound of formula (IIa), formula (IIb), formula (IIc) or formula (IId) to the hydrochloric acid and the sodium nitrite is 1 (1-3) to (1-1.1), preferably 1 (1-1.8) to (1-1.02);
B. adding the compound of the formula (IIIa) into the diazotized solution of the formula (IIc) prepared above, controlling the pH value to be 4.0-6.0 by using liquid alkali and controlling the temperature to be 0-30 ℃ (preferably 0-20 ℃), carrying out coupling reaction, testing diazo by using H acid test solution, and obtaining the compound of the formula (IVa) when the diazo is colorless at the seepage ring, namely the diazo has completely reacted to the end point, wherein the molar ratio of the compound of the formula (IIIa) to the compound of the formula (IIc) is 1 (0.95-1.2), preferably 1 (0.98-1.08);
adding a certain amount of hydrochloric acid into the compound of the formula (IVa), adding a sodium nitrite solution within 20-30min, controlling the pH to be 0.5-3.0 (preferably 0.5-2.0) and the temperature T to be 0-30 ℃ (preferably 0-20 ℃) to carry out diazotization reaction, detecting an end point (namely no discoloration within 5 s) by using an ethanol solution of 4-dimethylaminobenzaldehyde, and eliminating excessive sodium nitrite by using sulfamic acid after the diazotization end point is reached to obtain a diazo solution of the formula (IVa) for storage and standby;
C. adding the compound of the formula (IIIb) into the diazotized solution of the formula (IId) prepared above, controlling the pH value to be 4.0-6.0 by using liquid alkali and controlling the temperature to be 0-30 ℃ (preferably 0-20 ℃), carrying out coupling reaction, testing diazo by using H acid test solution, and obtaining the compound of the formula (IVb) when the diazo is colorless at the seepage ring, namely the diazo has completely reacted to the end point, wherein the molar ratio of the compound of the formula (IIIb) to the compound of the formula (IId) is 1 (0.95-1.2), preferably 1 (0.98-1.08);
adding a certain amount of hydrochloric acid into the compound of the formula (IVb), adding a sodium nitrite solution within 20-30min, controlling the pH to be 0.5-3.0 (preferably 0.5-2.0) and the temperature T to be 0-30 ℃ (preferably 0-20 ℃) to carry out diazotization reaction, detecting an end point (namely no discoloration within 5 s) by using an ethanol solution of 4-dimethylaminobenzaldehyde, and eliminating excessive sodium nitrite by using sulfamic acid after the diazotization end point is reached to obtain a diazo solution of the compound of the formula (IVb) for storage and standby;
(2) coupling reaction: adding water into 3, 5-dihydroxy benzoic acid, pulping and dispersing, and controlling the temperature to be 15-25 ℃. Adding the dispersed 3, 5-dihydroxybenzoic acid into the diazo liquid of the formula (IIa), the diazo liquid of the formula (IIb), the diazo liquid of the compound of the formula (IVa) or the diazo liquid of the compound of the formula (IVb) prepared in the step (1), controlling the pH value to be 2.0-5.0 and the temperature to be 0-30 ℃ (preferably 0-20 ℃) by using liquid alkali or sodium bicarbonate to carry out coupling reaction, testing diazo by using an H acid test solution, and obtaining a coupling product 1 when the ring seepage is colorless, namely the diazo has completely reacted to the end;
adding the diazo liquid of the formula (IIa), the diazo liquid of the formula (IIb), the diazo liquid of the compound of the formula (IVa) or the diazo liquid of the compound of the formula (IVb) obtained in the step (1) into a coupling product 1, controlling the pH to be 5.0-8.0 and the temperature to be 0-30 ℃ (preferably 0-20 ℃) by using liquid alkali or baking soda to carry out coupling reaction, testing diazo by using an H acid test solution, and obtaining the reactive dye compound of the formula (I) of the invention when the diazo is colorless at a ring penetration position, namely the diazo has completely reacted to the end point;
the diazo liquid used in the two coupling reactions can not be the diazo liquid of the formula (IIa), the diazo liquid of the formula (IIb), the diazo liquid of the compound of the formula (IVa) or the diazo liquid of the compound of the formula (IVb); wherein the molar ratio of the formula (IIa), the formula (IIb), the formula (IVa) or the formula (IVb) to the 3, 5-dihydroxybenzoic acid is (0.95-1.2): 1, preferably (0.98-1.08): 1.
it is known in the art that in the reactive dye compounds of the formula (I) according to the invention, when Y is1～Y3is-C2H4OSO3H or-CH2CH2Cl, (-SO) beta-hydroxyethyl sulfone sulfate in typical reactive dye dyeing applications2C2H4OSO3H) Or beta-chloroethylsulfone (-SO)2C2H4Cl) in alkaline medium to generate vinylsulfonyl (-SO) through elimination reaction2CH＝CH2) And then carrying out nucleophilic addition reaction with the cellulose fiber to form a covalent bond.
The reactive dye compounds (I) according to the invention, during their preparation, also allow the presence of by-products in amounts not exceeding 30%, which can be used without isolation, directly in the processing of commercial dyes, including, without limitation, compounds or mixtures of the following structure:
in the above by-products, the substituents are as defined in the above formula (I).
The reactive dye compounds according to the invention, formula (I) being embodied in the form of the free acid, are generally prepared and isolated in the actual synthesis process in the form of their alkali metal salts (preferably sodium or potassium salts, most preferably sodium salts) and are also used for dyeing in the form of their salts, as is also known to the person skilled in the art, i.e. the carboxyl groups, sulfonic acid groups in formula (I) can be present in the form of sodium carboxylates, sodium sulfonates.
The reactive dye compounds according to the invention may be present in the form of powders, granules, aqueous solutions or synthesis solutions, and the isolation of the dye compounds according to the invention from the synthesis solutions may be carried out by generally known methods, for example by salting out the dye from the reaction medium with an electrolyte, such as sodium chloride or potassium chloride, or by evaporating and spray-drying the solution, and the dye compounds therefore generally comprise the electrolyte salts customary for reactive dyes, such as sodium chloride, sodium sulfate, etc.
In the third aspect, when the reactive dye compound of the present invention is sold as a commercial product, no auxiliary agent may be added, or conventional auxiliary agents in commercial dyes, such as a cosolvent, a dispersant, an alkali-resistant auxiliary agent, a dust-proofing agent, a surfactant, a buffer, an accelerating agent, etc., may be added. Therefore, the invention also provides a reactive dye product which contains the reactive dye compound. Preferably, the reactive dye product contains the reactive dye compound and an auxiliary agent, wherein the weight of the auxiliary agent is not more than 45% of the weight of the reactive dye compound, and preferably not more than 40%. The auxiliary agent is preferably one or the combination of any several of the following components: naphthalenesulfonic acid formaldehyde condensate (NNO), methylnaphthalenesulfonic acid formaldehyde condensate (dispersant MF), dispersant CNF (benzylnaphthalenesulfonate formaldehyde condensate), sodium sulfate (industrial sodium sulfate), lignosulfonate, sodium acetate, sodium hydrogen carbonate, sodium citrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, thickener, and the like. The auxiliary agents are all conventional types sold in the market.
In a fourth aspect, the invention provides the use of the reactive dye product in printing and dyeing of cellulose fibers, polyamide fibers or fabrics thereof. The cellulose fiber is preferably cotton fiber or regenerated fiber, but may also include other plant fiber, such as hemp fiber or fabric; the polyamide fiber is preferably an animal fiber material including a sheath, a wool or a silk, and a synthetic fiber material such as nylon 6 and nylon 66. When the fiber material is printed and dyed by using the reactive dye compound or the reactive dye product, the dyeing can be carried out according to a known reactive dye dyeing method, such as a common reactive dye dip dyeing method and a pad dyeing method, wherein the dip dyeing method is a method of dipping the fabric into a dye solution to gradually dye the fabric, and the procedures of dyeing, fixing color, washing, soaping, washing, dewatering, drying and the like are usually required.
The pad dyeing is a dyeing method that a fabric is soaked in a dye solution, then the fabric passes through a roller, the dye solution is uniformly rolled into the fabric, and then the fabric is steamed or hot-melted and the like, and generally the procedures of pad dyeing, drying- (pad fixing solution), steaming or baking, washing, soaping, washing, drying and the like are needed.
Generally, the dye usage amount is different due to different dyeing requirements on fabrics, when a dip dyeing method is used for dyeing, the dyeing depth (owf) is generally 0.1-10% (the dye accounts for the weight percent of the fabrics), the bath ratio is 1: 2-1: 60 (the weight ratio of the fabrics to the dye liquor is preferably 1: 10-1: 30), the initial dyeing temperature is controlled to be 30-60 ℃, the dyeing time is 10-30 minutes, the soaping temperature is 85-95 ℃, the soaping time is 10-15 minutes, the color fixing temperature is 60-100 ℃, the color fixing time is 10-50 minutes, and the color fixing pH value is 9-11. When the pad dyeing method is used for dyeing, the pad retention rate of the cellulose fiber is generally 60-80%, the steaming temperature is 100-103 ℃, and the steaming time is 1-3 minutes. In the pad dyeing method, a cold pad-batch dyeing method is frequently used at present, and a dye and an alkaline substance are introduced into a pad dyeing machine, coiled and stacked at room temperature for 2-30 hours for color fixation, and then thoroughly rinsed.
The invention has the beneficial effects that: the reactive dye compound has a novel structure, excellent washing fastness and rubbing fastness, and good combination stability with fibers, and is suitable for dyeing and printing fibers such as cotton, artificial cotton, silk, wool and the like.
(IV) description of the drawings
FIG. 1 is a UV-Vis spectrum of a reactive dye compound prepared in example 3;
FIG. 2 is a mass spectrum of the reactive dye compound prepared in example 3, wherein m/Z-553.82 is a target molecule double charge ionization peak.
(V) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
the dye compound prepared in the embodiment of the invention is sodium salt and is applied in the form of sodium salt, but for the convenience of writing, all structural formulas in the embodiment are embodied in the form of free acid, and the substantial dyeing performance of the free acid and the sodium salt is known to be equivalent by persons skilled in the art.
Example 1
(1) Diazotization:
41.1g (0.1mol) of 2-amino-6-hydroxyethyl sulfone sulfate ester-1-naphthalenesulfonic acid was put into 100g of water and 100g of ice and slurried for about 1 hour, 20g of 31% hydrochloric acid (containing 0.17mol) was added thereto, 24g of 30% sodium nitrite solution (containing 0.104mol of sodium nitrite) was added thereto within 20 to 30 minutes, diazotization was carried out at a pH of 0.5 to 2.0 and a temperature T of 0 to 20 ℃ for 1 to 2 hours, and the end point was detected by an ethanol solution of 4-dimethylaminobenzaldehyde (i.e., no discoloration was observed within 5 seconds). After the diazotization end point is reached, using sulfamic acid to eliminate excessive sodium nitrite, and storing the obtained 2-amino-6-hydroxyethyl sulfone sulfate ester-1-naphthalenesulfonic acid diazotization solution for later use.
36.1g (0.1mol) of sulfonated para-ester (2-sulfonic acid-4-beta-hydroxyethyl sulfone sulfate aniline) is put into 100g of water and 100g of ice and pulped for about 1 hour, 20g of 31% hydrochloric acid (containing 0.17mol of HCl) is added, 24g of 30% sodium nitrite solution (containing 0.104mol of sodium nitrite) is added within 20-30min, diazotization is carried out for 1-2 hours at the pH value of 0.5-2.0 and the temperature T of 0-20 ℃, and the end point is detected by using an ethanol solution of 4-dimethylaminobenzaldehyde (namely, the end point is not discolored within 5 s). And (4) after the diazotization end point is reached, using sulfamic acid to eliminate excessive sodium nitrite, and storing the obtained sulfonated para-ester diazotization liquid for later use.
Adding 0.1mol of the sulfonated para-ester diazo solution into 15.1g (0.1mol) of m-urea (m-ureidoaniline), controlling the pH to be 4.0-6.0 by using 30% liquid alkali, controlling the temperature T to be 0-20 ℃, carrying out coupling reaction for 0.5-2H, testing diazo by using an H acid test solution, testing diazo until the color of a permeable ring is colorless, namely the diazo has completely reacted to the end point (if not, continuously reacting to the end point), obtaining a chromophore 1, adding 20g of 31% hydrochloric acid (containing 0.17mol) into the chromophore 1, adding 24g of 30% sodium nitrite solution (containing 0.104mol of sodium nitrite) into 20-30min, controlling the pH to be 0.5-2.0 and the temperature T to be 0-20 ℃ to carry out diazotization reaction for 1-2H, detecting the end point (namely, not discoloring within 5 s) by using an ethanol solution of 4-dimethylaminobenzaldehyde, eliminating the excessive sodium nitrite by using sulfamic acid after the end point is reached, the diazo liquid of the obtained chromophore 1 is stored for later use.
(2) Coupling:
firstly, 154g (0.1mol) of 3, 5-dihydroxybenzoic acid is added into 200g of water for pulping, the temperature is controlled at 20-25 ℃, the pulped 3, 5-dihydroxybenzoic acid solution is added into the diazo liquid of 2-amino-6-hydroxyethyl sulfone sulfate-based-1-naphthalenesulfonic acid obtained in the step (1), the pH is controlled at 2.0-4.0 by 30% liquid alkali, the temperature is controlled at 0-20 ℃, the reaction is carried out for 15-20h, and the free 3, 5-dihydroxybenzoic acid is controlled below 3% by HPLC to obtain the end point, thus obtaining the chromophore 2 shown in the following formula (A).
And (2) adding the diazo solution of the chromophore 1 prepared in the step (1) into the chromophore 2, controlling the pH to be 5.0-8.0 by using 30% liquid alkali, controlling the temperature T to be 0-20 ℃, further performing coupling reaction for 5-10H, testing diazo by using an H acid test solution, and obtaining an orange reactive dye compound (I-1) when the diazo reaction is completely finished after the color at the ring seepage position is colorless, wherein the lambda max in an aqueous solution is 505 nm.
Example 2
(1) Diazotization:
40.0g (0.1mol) of 4-acetyl (4' -beta-hydroxyethyl sulfuryl sulfate aniline) aniline is put into 100g of water and 100g of ice and pulped for about 1 hour, 20g of 31% hydrochloric acid (containing 0.17mol of HCl) is added, 24g of 30% sodium nitrite solution (containing 0.104mol of sodium nitrite) is added within 20-30min, diazotization is carried out for 1-2 hours at a pH of 0.5-2.0 and a temperature T of 0-20 ℃, and the end point is detected by using an ethanol solution of 4-dimethylaminobenzaldehyde (namely, no discoloration occurs within 5 s). After the diazotization end point is reached, the excessive sodium nitrite is eliminated by sulfamic acid, and the obtained 4-acetyl (4' -beta-hydroxyethyl sulfuryl sulfate aniline) aniline diazo liquid is stored for later use.
36.1g (0.1mol) of sulfonated para-ester (2-sulfonic acid-4-beta-hydroxyethyl sulfone sulfate aniline) is put into 100g of water and 100g of ice and pulped for about 1 hour, 20g of 31% hydrochloric acid (containing 0.17mol of HCl) is added, 24g of 30% sodium nitrite solution (containing 0.104mol of sodium nitrite) is added within 20-30min, diazotization is carried out for 1-2 hours at the pH value of 0.5-2.0 and the temperature T of 0-20 ℃, and the end point is detected by using an ethanol solution of 4-dimethylaminobenzaldehyde (namely, the end point is not discolored within 5 s). And (4) after the diazotization end point is reached, using sulfamic acid to eliminate excessive sodium nitrite, and storing the obtained sulfonated para-ester diazotization liquid for later use.
Adding 0.1mol of the sulfonated para-ester diazo solution into 15.1g (0.1mol) of m-urea (m-ureidoaniline), controlling the pH to be 4.0-6.0 by using 30% liquid alkali, controlling the temperature T to be 0-20 ℃, carrying out coupling reaction for 0.5-2H, testing diazo by using an H acid test solution, testing diazo until the color of a permeable ring is colorless, namely the diazo has completely reacted to the end point (if not, continuously reacting to the end point), obtaining a chromophore 3, adding 20g of 31% hydrochloric acid (containing 0.17mol) into the chromophore 3, adding 24g of 30% sodium nitrite solution (containing 0.104mol of sodium nitrite) within 20-30min, controlling the pH to be 0.5-2.0 and the temperature T to be 0-20 ℃ to carry out diazo reaction for 1-2H, detecting the end point (namely, not discoloring within 5 s) by using an ethanol solution of 4-dimethylaminobenzaldehyde, eliminating the excessive sodium nitrite by using sulfamic acid after the end point is reached, the diazo liquid of the obtained chromophore 3 is stored for later use.
(2) Coupling:
firstly, 154g (0.1mol) of 3, 5-dihydroxybenzoic acid is added into 200g of water for pulping, the temperature is controlled at 20-25 ℃, the pulped 3, 5-dihydroxybenzoic acid solution is added into the 4-acetyl (4' -beta-hydroxyethyl sulfuryl sulfate aniline) aniline diazo liquid obtained in the step (1), the pH is controlled at 2.0-4.0 by 30 percent liquid alkali, the temperature is controlled at 0-20 ℃, the reaction is carried out for 15-20h, and the free 3, 5-dihydroxybenzoic acid is controlled below 3 percent by HPLC to obtain the end point, thus obtaining the chromophore 4 shown in the following formula (B).
And (2) adding the diazo solution of the chromophore 3 prepared in the step (1) into the chromophore 4, controlling the pH to be 5.0-8.0 by using 30% liquid alkali, controlling the temperature T to be 0-20 ℃, further performing coupling reaction for 5-10H, testing diazo by using an H acid test solution, and obtaining the red light orange reactive dye compound (I-27) when the diazo reaction is completely finished, wherein the lambda max in an aqueous solution is 495 nm.
Examples 3 to 112:
dye compounds having the structures shown in Table 1 below were prepared by stepwise diazotization and coupling reactions using intermediate raw materials well known in the art according to the azo dye preparation methods described in example 1 or example 2, respectively.
TABLE 1
Application example 1
The reactive dyes prepared in the embodiments 1-112 of the invention are respectively dissolved in water, and 50g/L of anhydrous sodium sulphate is added to prepare dye liquor. The dyeing concentration is 4 percent (dye to cloth weight), the bath ratio is 1:20 (cloth weight grams to volume milliliters of dyeing liquid), the fabric is placed into cotton cloth for adsorption for 30 minutes at the temperature of 60 ℃, and alkali (20 g/L of sodium carbonate) is added for fixation for 45 minutes. And washing, soaping and drying the dyed fabric to obtain orange to reddish brown dyed fabric. The wash fastness and rubbing fastness tests were carried out according to the methods in ISO 105C10-2006, ISO 105X12, and the results are shown in Table 2:
TABLE 2
As can be seen from Table 2, the reactive dye compound of the present invention is excellent in washing fastness and rubbing fastness.
Claims (12)
1. A reactive dye compound which is a compound having a structure represented by the following formula (I) or an alkali metal salt thereof (preferably sodium salt or potassium salt):
in formula (I):
D1、D2each independently is a group of the formula (a), formula (b), formula (c) or formula (D), and D1、D2Not both being a group of the formula (a), formula (b), formula (c) or formula (d):
in the above formulas (a) to (d):
R1、R2、R3、R5、R6、R8、R9are independent of each other H, C1～C4Straight or branched alkyl, C1～C4Alkoxy or sulfonic acid groups;
m is 0 to 3, each R4Each independently selected from amino, sulfonic acid, ureido, C1～C4Alkyl of (C)1～C4Alkanoylamino or C1～C4An alkoxy group;
n is 0 to 3, each R7Each independently selected from hydroxyl, amino or sulfonic acid;
X1、X2、X3、X4are independent of each other H, C1～C4Straight or branched alkyl, C1～C4Alkoxy, -SO2Y1、-NHCO(CH2)pSO2Y2or-CONH (CH)2)qSO2Y3And D is1、D2At least one of which contains fibre-reactive groups, i.e. -SO2Y1、-NHCO(CH2)pSO2Y2or-CONH (CH)2)qSO2Y3Wherein Y is1～Y3Each independently is-CH ═ CH2、-C2H4OSO3H or-CH2CH2Cl，p＝1-3，q＝1-3。
2. The method of claim 1A dye compound characterized by: d1Is a group of formula (a) or (b), said D2Is a group represented by the formula (c) or (d).
3. A reactive dye compound according to claim 1, wherein: the reactive dye compound has a structure shown in a formula (Ia) or a formula (Ib):
the substituents in the formula (Ia) and the formula (Ib) are as defined in the formula (I).
4. A reactive dye compound according to any one of claims 1 to 3, characterized in that: the formula (a) is selected from one of the following groups:
5. a reactive dye compound according to any one of claims 1 to 3, characterized in that: in the reactive dye compound, the formula (b) is selected from one of the following groups:
6. a reactive dye compound according to any one of claims 1 to 3, characterized in that: in the reactive dye compound, the formula (c) is selected from one of the following groups:
7. a reactive dye compound according to claim 1 or 2, characterized in that: in the reactive dye compound, the formula (d) is selected from one of the following groups:
8. a reactive dye compound according to claim 1, wherein: the reactive dye compound is selected from one of compounds shown in the following formulas (I-1) to (I-112) and alkali metal salts thereof:
9. dye compound according to one of claims 1 to 3, characterized in that: the compound shown in the formula (I) contains a quinone hydrazone structure shown in the following formula (ie) and/or (if) and/or (Ig) and/or (ih),
the substituents in the formulae (ie) to (ih) are as defined for formula (I).
10. A process for the preparation of a reactive dye compound of formula (i) as claimed in claim 1, which comprises:
(1) diazotization is carried out according to the following steps A and B and/or C:
A. diazotizing the arylamine compounds shown in the formula (IIa), the formula (IIb), the formula (IIc) and/or the formula (IId) respectively to obtain respective diazonium salts;
B. coupling the diazonium salt shown in the formula (IIc) with arylamine shown in the formula (IIIa) to obtain a compound shown in the formula (IVa), and diazotizing the compound shown in the formula (IVa) to obtain the diazonium salt for later use;
C. coupling the diazonium salt shown in the formula (IId) with arylamine shown in the formula (IIIb) to obtain a compound shown in the formula (IVb), and diazotizing the compound shown in the formula (IVb) to obtain the diazonium salt for later use;
(2) coupling reaction: adding water into 3, 5-dihydroxy benzoic acid, pulping, performing primary coupling on the pulped solution and one of the diazonium salt of the formula (IIa), the diazonium salt of the formula (IIb), the diazonium salt of the formula (IVa) and the diazonium salt of the formula (IVb) in the step (1), and performing secondary coupling on the solution and one of the diazonium salt of the formula (IIa), the diazonium salt of the formula (IIb), the diazonium salt of the formula (IVa) and the diazonium salt of the formula (IVb), wherein the diazonium salts adopted in the primary coupling and the secondary coupling can not be the diazonium salt of the formula (IIa), the diazonium salt of the formula (IIb), the diazonium salt of the formula (IVa) or the diazonium salt of the formula (IVb), so as to obtain the active dye compound (I);
the substituents in the above formulae (IIa) to (IId), formulae (IIIa), (IIIb), formulae (IVa) and formulae (IVb) are as defined for formula (I).
11. A reactive dye preparation comprising the reactive dye compound of claim 1.
12. Use of a reactive dye preparation according to claim 11 in the printing of cellulose fibres, polyamide fibres or fabrics thereof.
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| CN107501997A (en) * | 2017-07-28 | 2017-12-22 | 浙江科永化工有限公司 | A kind of reactive navy blue is to black dye composition and dye preparations |
| CN112457686A (en) * | 2019-09-06 | 2021-03-09 | 浙江科永化工有限公司 | Yellow reactive dye compound and preparation method and application thereof |
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| CN107501997A (en) * | 2017-07-28 | 2017-12-22 | 浙江科永化工有限公司 | A kind of reactive navy blue is to black dye composition and dye preparations |
| CN109233333A (en) * | 2017-07-28 | 2019-01-18 | 浙江科永化工有限公司 | A kind of orange active dye compound and its preparation method and application |
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