CN114213869A - Multi-active-group monoazo yellow reactive dye and preparation method thereof - Google Patents
Multi-active-group monoazo yellow reactive dye and preparation method thereof Download PDFInfo
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- CN114213869A CN114213869A CN202111320388.XA CN202111320388A CN114213869A CN 114213869 A CN114213869 A CN 114213869A CN 202111320388 A CN202111320388 A CN 202111320388A CN 114213869 A CN114213869 A CN 114213869A
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- 239000000985 reactive dye Substances 0.000 title claims abstract description 83
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000000975 dye Substances 0.000 claims abstract description 34
- -1 polyazo Polymers 0.000 claims abstract description 33
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 238000004043 dyeing Methods 0.000 claims abstract description 14
- 239000012954 diazonium Substances 0.000 claims abstract description 11
- 150000001989 diazonium salts Chemical class 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 3
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 130
- 230000007246 mechanism Effects 0.000 claims description 50
- 238000003825 pressing Methods 0.000 claims description 40
- 238000000227 grinding Methods 0.000 claims description 37
- 238000007789 sealing Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 23
- 239000000835 fiber Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 13
- 229920000742 Cotton Polymers 0.000 claims description 12
- 229920003043 Cellulose fiber Polymers 0.000 claims description 10
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- VMKJWLXVLHBJNK-UHFFFAOYSA-N cyanuric fluoride Chemical compound FC1=NC(F)=NC(F)=N1 VMKJWLXVLHBJNK-UHFFFAOYSA-N 0.000 claims description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000004809 thin layer chromatography Methods 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 5
- YFRQBLYSYSHFLU-UHFFFAOYSA-N n-ethyl-n-[2-(hydroxyamino)ethyl]hydroxylamine Chemical compound CCN(O)CCNO YFRQBLYSYSHFLU-UHFFFAOYSA-N 0.000 claims description 5
- 235000010288 sodium nitrite Nutrition 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 238000006193 diazotization reaction Methods 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- WQHQCQSAAOGHQP-UHFFFAOYSA-N formaldehyde;2-methylnaphthalene-1-sulfonic acid Chemical group O=C.C1=CC=CC2=C(S(O)(=O)=O)C(C)=CC=C21 WQHQCQSAAOGHQP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004537 pulping Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 230000008595 infiltration Effects 0.000 claims description 3
- 238000001764 infiltration Methods 0.000 claims description 3
- 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 3
- 238000005192 partition Methods 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 2
- 229920000297 Rayon Polymers 0.000 claims description 2
- 235000009120 camo Nutrition 0.000 claims description 2
- 235000005607 chanvre indien Nutrition 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 239000011487 hemp Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004811 liquid chromatography Methods 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims 6
- 235000017491 Bambusa tulda Nutrition 0.000 claims 6
- 241001330002 Bambuseae Species 0.000 claims 6
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims 6
- 239000011425 bamboo Substances 0.000 claims 6
- 238000009826 distribution Methods 0.000 claims 1
- 238000010030 laminating Methods 0.000 claims 1
- 239000004202 carbamide Substances 0.000 abstract description 23
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 18
- 230000009471 action Effects 0.000 abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 abstract description 6
- 229920000768 polyamine Polymers 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- ORLGPUVJERIKLW-UHFFFAOYSA-N 5-chlorotriazine Chemical compound ClC1=CN=NN=C1 ORLGPUVJERIKLW-UHFFFAOYSA-N 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 241000276425 Xiphophorus maculatus Species 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910021653 sulphate ion Inorganic materials 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 241001504664 Crossocheilus latius Species 0.000 description 2
- 241000338702 Cupido minimus Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical class [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001044 red dye Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZNXSFVXZQBETRJ-UHFFFAOYSA-N (3-aminophenyl)urea Chemical compound NC(=O)NC1=CC=CC(N)=C1 ZNXSFVXZQBETRJ-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- JVMSQRAXNZPDHF-UHFFFAOYSA-N 2,4-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C(N)=C1 JVMSQRAXNZPDHF-UHFFFAOYSA-N 0.000 description 1
- QURYKNGBCPCUKG-UHFFFAOYSA-N 2-aminobenzenesulfonic acid;sulfuric acid Chemical compound OS(O)(=O)=O.NC1=CC=CC=C1S(O)(=O)=O QURYKNGBCPCUKG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000009980 pad dyeing Methods 0.000 description 1
- GCFAQSYBSUQUPL-UHFFFAOYSA-I pentasodium 5-[[4-chloro-6-[3-(2-sulfonatooxyethylsulfonyl)anilino]-1,3,5-triazin-2-yl]amino]-3-[(1,5-disulfonatonaphthalen-2-yl)diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].Oc1c(N=Nc2ccc3c(cccc3c2S([O-])(=O)=O)S([O-])(=O)=O)c(cc2cc(cc(Nc3nc(Cl)nc(Nc4cccc(c4)S(=O)(=O)CCOS([O-])(=O)=O)n3)c12)S([O-])(=O)=O)S([O-])(=O)=O GCFAQSYBSUQUPL-UHFFFAOYSA-I 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- UIEBGVDTKLYGTN-UHFFFAOYSA-J tetrasodium;7-[[2-(carbamoylamino)-4-[[4-chloro-6-[3-(2-sulfonatooxyethylsulfonyl)anilino]-1,3,5-triazin-2-yl]amino]phenyl]diazenyl]naphthalene-1,3,6-trisulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].C=1C=C(N=NC=2C(=CC3=CC(=CC(=C3C=2)S([O-])(=O)=O)S([O-])(=O)=O)S([O-])(=O)=O)C(NC(=O)N)=CC=1NC(N=1)=NC(Cl)=NC=1NC1=CC=CC(S(=O)(=O)CCOS([O-])(=O)=O)=C1 UIEBGVDTKLYGTN-UHFFFAOYSA-J 0.000 description 1
- 238000004065 wastewater treatment 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
- C09B62/4401—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 with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
- C09B62/4403—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 with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
- C09B62/4411—Azo dyes
- C09B62/4415—Disazo or polyazo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
- C09B62/507—Azo dyes
- C09B62/513—Disazo or polyazo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0072—Preparations with anionic dyes or reactive dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0079—Azoic dyestuff preparations
Abstract
The invention discloses a multi-active-group monoazo yellow reactive dye, which comprises a compound shown in a structural general formula I, wherein R1 in the structural general formula I is-NHCONH 2, -NH2 or-NHCH 2CH2 COOM; r2 is-H or-SO 3M; r4 and R5 are-H, -CH3, -OCH3 or-SO 3M; r6 is-CONHCH 2CH2SO2CH2CH2OSO3M or-SO 2CH2CH2OSO3M, M is H or alkali metal, and the preparation method comprises the following steps: (1) preparing a diazonium salt solution of 4-beta-ethyl sulfuryl sulfate aniline-2-sulfonic acid; (2) preparing the meta-urea orange-yellow monoazo reactive dye; (3) preparing a reaction solution of a polycondensation product of cyanuric chloride; (4) preparing solid powder of polyazo yellow reactive dye I-1 with multiple reactive groups. The flexible aliphatic chain polyamine in the yellow reactive dye contains two hydroxyl groups, has hygroscopicity and hydrotropy, and can replace the action of urea during printing, so that the use amount of the urea during printing of the dye can be effectively reduced, and the problem that the content of ammonia nitrogen in printing and dyeing wastewater exceeds the standard due to the large use amount of the urea during printing of the conventional yellow reactive dye is solved.
Description
Technical Field
The invention relates to the technical field of reactive dyes, in particular to a multi-reactive-group monoazo yellow reactive dye and a preparation method thereof.
Background
The reactive dye has rich varieties and bright colors, and the molecular structure of the reactive dye contains reactive groups which can chemically react with hydroxyl groups on cellulose fibers, amino groups on protein fibers and other groups and are combined with the fibers through covalent bonds, so that various fastness properties of the dyed fibers are excellent.
According to the content and category of active groups in the structure of the reactive dye, the reactive dye can be generally divided into a K type (containing monochlorotriazine active group), a KN type (containing beta-vinylsulfone active group), an M type (two different active groups, monochlorotriazine type + beta-vinylsulfone active group) and the like, because the reactive dye is applied in an aqueous medium, the reactive group in the molecular structure of the dye reacts with hydroxyl, amino and the like on the fiber and also has a hydrolysis side reaction of the reactive group and water molecules, when the reactive dye is applied to the coloring of the cellulose fiber, the color fixing rate is usually between 60 and 70 percent, and a large amount of hydrolyzed dye not only reduces the effective utilization rate of the dye, and the hydrolytic dye exists in the printing and dyeing wastewater, so that colored organic pollutants in the printing and dyeing wastewater are increased, the problem of environmental pollution is caused, and the cost of wastewater treatment is further increased.
The fixation rate of the reactive dye on the fiber has a close relationship with the type and the number of the active groups, and the increase of the number of the active groups in the molecular structure of the reactive dye can improve the probability of the reaction of the reactive dye molecules and the fiber, thereby improving the fixation rate of the dye on the fiber.
When the reactive dye is innovatively developed, the number of the active groups is increased, so that the cost of the dye is improved, the utilization rate of the active groups is greatly reduced, for example, the M-type reactive dyes such as C.I reactive yellow 145, C.I reactive red 195, C.I reactive violet 45, and the like which are commercially available at present contain two reactive groups in the molecular structure, but only one chromogen, continuing to increase the number of reactive groups on the basis of having one chromophore increases the molar mass of the dye and results in a decrease in the molar extinction coefficient of the final dye, and therefore, in practical applications, more dye is required to achieve the corresponding color intensity, which in fact makes the use of the reactive groups less efficient, and thus it can be seen that, when the reactive dye is innovatively developed, in order to increase the fixation rate of the dye, the number of the chromogens is increased while the number of the reactive groups is increased, therefore, the reactive dye developed by innovation not only has high fixation rate but also has high molar extinction coefficient.
A large amount of urea is required to be added during reactive dye printing, the urea mainly plays a role in dissolving and absorbing moisture in the reactive printing, the urea does not participate in chemical reaction of the dye and fibers, and is finally washed away by water and enters a sewage system of a dye factory, the urea is decomposed under a high-temperature condition to generate ammonia nitrogen compounds polluting the water body, and eutrophication of the water quality is caused, so that how to innovatively develop a dye structure, the using amount of the urea during printing is reduced, and the content of the ammonia nitrogen compounds in the printing and dyeing wastewater is further reduced is always a technical problem to be solved by the dye and printing and dyeing industry.
Disclosure of Invention
The invention aims to provide a multi-active-group monoazo yellow reactive dye and a preparation method thereof, wherein the yellow reactive dye comprises four active groups and two monoazo yellow chromogens which are separated by flexible aliphatic chain polyamine, so that the molecular directness is reduced, the problem of low color fixing rate caused by insufficient number of active groups of the existing yellow reactive dye molecules is solved, the utilization rate of the active groups is greatly improved, the flexible aliphatic chain polyamine in the yellow reactive dye comprises two hydroxyl groups, has hygroscopicity and hydrotropy, and can replace the action of urea during printing, thereby effectively reducing the usage amount of the urea during printing of the dye, and overcoming the problem that the content of ammonia nitrogen in printing and dyeing wastewater exceeds the standard due to the use of a large amount of urea during printing of the existing yellow reactive dye The lifting power and the use amount of urea are low, and the light fastness performance is excellent, so that the application prospect is wide.
In order to achieve the purpose, the invention provides the following technical scheme: a multi-active-group monoazo yellow reactive dye, wherein the yellow reactive dye is a compound shown in a structural general formula I;
the X is F or Cl;
in the general structural formula I, R1 is-NHCONH 2, -NH2 or-NHCH 2CH2 COOM; the R2 is-H or-SO 3M; the R3 is:
wherein R4 and R5 are-H, -CH3, -OCH3 or-SO 3M; r6 is-CONHCH 2CH2SO2CH2CH2OSO3M or-SO 2CH2CH2OSO3M, and M is H or alkali metal.
Preferably, X in the structural general formula I is Cl; the R1 is-NHCONH 2, -NH2 or-NHCH 2CH2 COOM; the R2 is-H or-SO 3M; the R3 is:
wherein R4 is-H; the R5 is-SO 3M; r6 is-CONHCH 2CH2SO2CH2CH2OSO3M or-SO 2CH2CH2OSO3M, and M is Na.
Preferably, in the structural general formula I, X is Cl; the R1 is-NHCONH 2 or-NH 2; the R2 is-H or-SO 3M; the R3 is:
wherein R4 is-H; the R5 is-SO 3M; r6 is-SO 2CH2CH2OSO3M, and M is Na.
Preferably, in the structural general formula I, X is Cl; when R1 is-NHCONH 2, R2 is-H; when the R1 is-NH 2, the R2 is-SO 3M; the R3 is:
wherein R4 is-H; the R5 is-SO 3M; r6 is-SO 2CH2CH2OSO3M, and M is Na.
Preferably, in the structural general formula I, X is Cl; when R1 is-NHCONH 2, R2 is-H; when the R1 is-NH 2, the R2 is-SO 3M; the R3 is:
wherein R4 is-H; the R5 is-SO 3M; r6 is-SO 2CH2CH2OSO3M, and M is Na.
Preferably, the mass percentage of the raw materials and various raw materials contained in the commercial dye is 75-85% of yellow reactive dye, 5-15% of dispersing agent, 0.1-0.5% of dust-proof agent and 5-15% of anhydrous sodium sulphate, wherein the dispersing agent is a methyl naphthalene sulfonic acid formaldehyde condensation compound; the dust-proof agent is a water-soluble high molecular compound, and the commercial dye is used for dyeing and printing cellulose fibers; the cellulose fiber is hydroxyl and/or nitrogen-containing cellulose fiber, and the cellulose fiber is cotton, viscose, hemp or various blended fiber fabrics thereof.
Preferably, the preparation method of the compound shown in the structural general formula I is carried out according to the following scheme:
the preparation method of the compound with the general structural formula I comprises the following specific steps:
(1) diazotization reaction
Adding a sulfuryl arylamine compound (a1 or a2) containing ethyl sulfate, crushed ice and a small amount of water into a beaker, ice-milling for 2 hours, adding HCl solution, continuously stirring and reacting for 1 hour, slowly dropwise adding sodium nitrite solution, continuously reacting for 30-60 minutes after dropwise adding is finished, detecting the reaction end point by an Ehrlich reagent, removing excessive nitrous acid by sulfamic acid to prepare a diazonium salt (b1 or b2) containing the sulfuryl arylamine compound containing ethyl sulfate,
the molar ratio of the ethyl sulfate-containing sulfonyl arylamine compound to the sodium nitrite is 1: 1.01-1.03; the molar ratio of the ethyl sulfate-containing sulfuryl arylamine compound to the hydrochloric acid is 1: 1-1: 1.05;
(2) coupling reaction
Adding aniline compound c into the diazonium salt solution containing the ethyl sulfate sulfuryl arylamine compound prepared in the step (1), controlling the pH value of the reaction to be 6-6.5, keeping the temperature to be 0-5 ℃, keeping the reaction for 2-5 hours under the condition, detecting the reaction endpoint by a ring infiltration method, and after the reaction is finished, preparing orange-yellow monoazo reactive dye (d1 or d2),
the molar ratio of the diazonium salt containing the ethyl sulfate sulfonyl arylamine compound to the aniline compound c is 0.98: 1-1.02: 1;
(3) mono-condensation reaction of cyanuric chloride
Pulping cyanuric chloride or cyanuric fluoride for half an hour, slowly dropwise adding the orange monoazo reactive dye (d1 or d2) solution prepared in the step (2) into cyanuric chloride or cyanuric fluoride pulping liquid, controlling the reaction pH value to be between 3 and 4, keeping the temperature to be between 0 and 5 ℃, keeping the reaction for 1 to 2 hours under the condition, and detecting the reaction end point through thin-layer chromatography to prepare a reaction liquid containing a polycondensation product of cyanuric chloride; the molar ratio of the cyanuric chloride or the cyanuric fluoride to the orange monoazo reactive dye (d1 or d2) is 1: 1-1.03: 1;
(4) dimeric reaction of cyanuric chloride
Dissolving N, N' -dihydroxyethyl ethylenediamine in water, slowly dropwise adding into the reaction liquid of the cyanuric chloride or cyanuric fluoride polycondensate obtained in the step (3), controlling the reaction temperature to be between 35 and 45 ℃, controlling the pH value to be between 6.0 and 7.0, keeping the reaction for 4 to 6 hours under the condition, detecting the reaction end point through thin-layer chromatography and liquid chromatography, drying at 75 ℃ after the reaction is finished, and grinding to obtain the active dye solid powder shown in the final compound (I); the molar ratio of the N, N' -dihydroxyethyl ethylenediamine to the cyanuric chloride or cyanuric fluoride polycondensate is 0.49: 1-0.52: 1.
Preferably, the processing device comprises a processing box and a box cover, wherein the processing box is internally divided into a processing cavity and an electrical cavity from top to bottom, a refrigerating piece used for keeping the interior of the processing cavity of the processing box at a constant low temperature is arranged in a partition plate between the processing cavity of the processing box and the electrical cavity of the processing box, a variable frequency motor is arranged in the electrical cavity of the processing box, a rotating shaft is arranged at the output end of the variable frequency motor, the other end of the rotating shaft extends to the axis of the processing cavity of the processing box, a material grinding mechanism, a material shoveling mechanism, a material pressing mechanism and a material crushing mechanism are arranged in the processing cavity of the processing box, and the material grinding mechanism comprises a material grinding support, a support cylinder, a support rod, a support plate and a small amount of water, Supporting spring and stone roller, grind the material support mounting in the rotation axis is located one side of processing case process chamber inside, a supporting cylinder install in grind on the material support, the one end of bracing piece is located inside the supporting cylinder, the other end of bracing piece extends to supporting cylinder bottom, the backup pad install in the bracing piece is located on the inside port of supporting cylinder, supporting spring set up in the backup pad with between the supporting cylinder inner wall, grind the material stone roller install in the bracing piece extends to on the port of supporting cylinder bottom, shovel material mechanism includes shovel material support and shovel material blade, shovel material support mounting in the rotation axis is located the inside opposite side of processing case process chamber, the shovel material blade be linear array set up in on the shovel material support.
Preferably, the material pressing mechanism comprises a connecting piece, a reset rod, a reset plate, a reset spring, a top plate, a roller, a limiting slide way, a material pressing support and a material pressing blade, the connecting piece is symmetrically arranged at the top of the material shoveling support, one end of the reset rod is arranged at the top of the connecting piece, the other end of the reset rod penetrates through a reset cavity formed in the connecting piece and extends to the bottom of the connecting piece, the reset plate is arranged on the outer wall of the reset rod positioned in the reset cavity of the connecting piece, the reset spring is arranged between the reset plate and the inner wall of the reset cavity of the connecting piece, the top plate is arranged on the port of the two reset rods positioned at the top of the connecting piece, the roller is arranged at the center of the top plate, the limiting slide way is arranged on the inner side of the box cover and is of a wave-shaped structure, and the limiting slide way is assembled to be attached to the top of the roller, the material pressing support is arranged on the two ports at the bottom of the connecting piece, the material pressing blades are arranged on the material pressing support in a linear array mode, extend to the position, in the same vertical plane, of the material shoveling blades and are distributed in a staggered mode.
Preferably, the crushing mechanism comprises a crushing support, a crushing main shaft, a sealing pipe, a sealing shaft collar, a main bevel gear, a ring-shaped bevel gear, a main chain wheel, a crushing roller, a secondary chain wheel and a chain belt, the crushing support is mounted on one side, adjacent to the material shoveling support, of the rotating shaft in the processing chamber of the processing box, and is connected to the connecting piece, one end of the crushing main shaft is located in a gear chamber formed in the crushing support, the sealing pipe is mounted on the inner side of the processing box, the sealing shaft collar is connected to the inner side of the sealing pipe, the other end of the crushing main shaft penetrates through the sealing shaft collar and extends to the inner side of the sealing pipe, the main bevel gear is mounted on a port of the crushing main shaft extending to the inner side of the sealing pipe, and the ring-shaped bevel gear is mounted in the sealing pipe and is meshed with the main bevel gear, the main sprocket install in the crushed aggregates main shaft is located on the port of crushed aggregates support gear intracavity portion, the crushed aggregates roller be linear array set up in on the crushed aggregates support, and with the shovel material blade keeps the parallel state, the one end coupling of crushed aggregates roller in on the crushed aggregates support, the other end of crushed aggregates roller extends to crushed aggregates support gear intracavity portion, from the sprocket install in the crushed aggregates roller extends to on the port of crushed aggregates support gear intracavity portion, the chain belt connect in main bevel gear with from between the sprocket.
In the technical scheme, the invention has the beneficial effects that:
(1) the yellow reactive dye provided by the invention has four active groups and two monoazo yellow color bodies, wherein the four active groups are two monochlorotriazine active groups and two beta-vinylsulfonyl active groups, and the yellow reactive dye is suitable for printing, pad dyeing and medium and high temperature dip dyeing processes. The monochlorotriazine group has higher stability, the beta-vinylsulfonyl active group has higher reaction capability, so that the beta-vinylsulfonyl active group can be used for preferentially reacting with the fiber when the yellow reactive dye is actually applied, even if partial beta-vinylsulfonyl active group and water molecules generate side reaction, the monochlorotriazine group can also be used for reacting with the fiber, the four active groups not only improve the reaction probability of the yellow reactive dye and the fiber, but also improve the reaction efficiency of the yellow reactive dye and the fiber, and finally the yellow reactive dye has high color fixing rate.
(2) The yellow reactive dye provided by the invention has the advantages that two of four active groups are beta-vinylsulfonyl active groups, and the two beta-vinylsulfonyl active groups are not only taken as reactive groups but also exist independently. Because the two beta-vinyl sulfone active groups belong to ethyl sulfate sulfone arylamine compounds which are diazo components in the color body and are components of the color body, the final yellow active dye contains two color bodies and four active groups, and the two beta-vinyl sulfone active groups exist as a part of the color body, so that the utilization efficiency of the active groups is greatly improved.
(3) The two color bodies of the yellow reactive dye are isolated by the flexible aliphatic chain polyamine, the flexible aliphatic chain can rotate freely in a three-dimensional space and exists in a para-crossing space conformation with the lowest energy, and the aliphatic amine group in the molecular structure of the dye exists in a tertiary amine form, so that the steric hindrance is larger, the interaction among dye molecules is reduced, the molecule substantivity is reduced, the association between molecules can be effectively reduced in an aqueous solution, and the dye molecules are enabled to take on action in a single molecular form.
(4) The flexible aliphatic chain polyamine in the yellow reactive dye contains two hydroxyethyl groups, and when the yellow reactive dye is printed, pad-dyed or dip-dyed under an alkaline condition, hydroxyl groups can be dissociated to form hydroxyl anions which have higher water solubility and can further improve the solubility of the dye in water.
(5) The invention adds the compound (a1 or a2) containing the sulphate ethyl sulfuryl arylamine, crushed ice and a small amount of water into a processing cavity of a processing box, then covers the box cover, and keeps a limit slideway at the inner side of the box cover in fit connection with a roller, at this time, a refrigerating sheet and a variable frequency motor can be started, and a material grinding mechanism, a material shoveling mechanism, a material pressing mechanism and a crushed material mechanism on a rotating shaft are driven by the variable frequency motor to keep axial rotation, at this time, a support plate arranged in a support cylinder on a material grinding support can keep the material grinding roller arranged on the support rod in fit with the inner wall of the processing cavity of the processing box under the elastic action of a support spring, and the sulphate ethyl sulfuryl arylamine compound (a1 or a2), the crushed ice and the small amount of water are ground into small pieces of crushed ice, in the process, the contact area between the crushed ice and the sulphate ethyl sulfuryl arylamine compound (a1 or a2) can be effectively increased, so as to increase the grinding effect, and at the same time, the material shoveling bracket can also drive the material shoveling blade to shovel small platy crushed ice after being rolled by the material roller, and the roller can also drive the reset rod on the top plate to move towards the direction of the material pressing blade under the supporting force of the convex part of the limiting slideway with the wave-shaped structure in a reciprocating manner, at the same time, the reset rod can drive the reset plate in the reset cavity of the connecting piece to exert the acting force on the reset spring to deform the reset spring and drive the material pressing blade arranged on the material pressing bracket to impact the material shoveling blade, so as to extrude the small crushed ice shoveled by the material shoveling blade into a crushed block again, when the roller moves to the concave part of the limiting slideway, the reset plate can drive the reset rod to move towards the direction of the top plate under the acting force of the reset spring restoring deformation, so as to ensure that the roller on the top plate is kept attached to the limiting slideway and the material pressing blade is separated from the material shoveling blade, the small crushed ice can be further crushed into small particles by the reciprocating impact of the material pressing blade on the material shoveling blade, the grinding effect is further improved, meanwhile, when a crushing main shaft arranged on the crushing support rotates along with the rotating shaft, the sealing shaft collar can be driven to keep axial motion on the sealing pipe, at the moment, the main bevel gear can drive the crushing main shaft to keep axial rotation under the action of the annular bevel gear, and a chain belt on a main chain wheel in a gear cavity of the crushing support drives a crushing roller connected with a driven chain wheel to keep axial rotation, so that the crushing roller further crushes the small crushed particle crushed ice crushed by the reciprocating impact of the material pressing blade on the material shoveling blade, the crushed ice is further crushed, the contact area between the crushed ice and the ethyl sulfate sulfone aromatic amine compound (a1 or a2) is improved, and the grinding effect is improved.
Drawings
In order to more clearly illustrate the embodiments of the present application or technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings can be obtained by those skilled in the art according to the drawings.
FIG. 1 is a reaction scheme of the present invention;
FIG. 2 is a front cross-sectional structural view of the present invention;
FIG. 3 is an enlarged view of point A of FIG. 2 according to the present invention;
FIG. 4 is an enlarged view of point B of FIG. 2 according to the present invention;
FIG. 5 is a schematic view of a partial cross-sectional structure of the material grinding mechanism of the present invention;
FIG. 6 is a schematic front perspective view of the shoveling mechanism, the pressing mechanism and the crushing mechanism of the present invention;
FIG. 7 is a rear perspective view of the shoveling mechanism, the pressing mechanism and the crushing mechanism according to the present invention;
FIG. 8 is a side view cross-sectional structural schematic view of the shoveling mechanism, the pressing mechanism and the crushing mechanism of the present invention;
fig. 9 is a rear sectional structural schematic view of the shoveling mechanism, the pressing mechanism and the crushing mechanism according to the invention.
In the figure: 1. a processing box; 101. a box cover; 2. a refrigeration plate; 3. a variable frequency motor; 4. a material grinding mechanism; 5. A material shoveling mechanism; 6. a material pressing mechanism; 7. a crushing mechanism; 8. a rotating shaft; 9. grinding a material bracket; 10. a support cylinder; 11. a support bar; 12. a support plate; 13. a support spring; 14. grinding the material; 15. a material shoveling bracket; 16. a shoveling blade; 17. a connecting member; 18. a reset lever; 19. a reset plate; 20. a return spring; 21. a top plate; 22. a roller; 23. a limiting slide way; 24. a material pressing bracket; 25. a swaging blade; 26. A crushed material support; 27. a crushed material main shaft; 28. a sealing tube; 29. a seal collar; 30. a main bevel gear; 31. A ring-shaped bevel gear; 32. a main sprocket; 33. a crushing roller; 34. a slave sprocket; 35. a chain belt.
Detailed Description
In order to make the technical solutions of the present invention better understood, those skilled in the art will now describe the present invention in further detail with reference to the accompanying drawings.
Example one
The invention provides a technical scheme that: a multi-active-group monoazo yellow reactive dye, wherein the yellow reactive dye is a compound shown in a structural general formula I;
the preparation method of the yellow reactive dye I-1 comprises the following steps:
(1) 36.1g of 4-. beta. -ethylsulfonyl sulfate aniline-2-sulfonic acid (P acid) reduced to 100%, 200g of ice and 20mL of water were added to a 1000mL beaker, and ice-milled for 2 hours. 12.2g of technical hydrochloric acid (30%) are added and the reaction is continued with stirring for 1 hour. After dissolving 7.1g of sodium nitrite solid with the concentration of 100% in 30mL of water, slowly dripping the solid into the system, and keeping the reaction solution in a little blue on Congo red test paper and a little blue on KI test paper in the dripping process. After the dropwise addition is finished, keeping the temperature of the reaction system at 0-5 ℃, continuously reacting for 1 hour, detecting the reaction end point by using an Ehrlich reagent, and after the reaction is finished, removing excessive nitrous acid by using sulfamic acid to prepare a diazonium salt solution of 4-beta-ethylsulfuryl sulfate aniline-2-sulfonic acid;
(2) adding 100% m-ureido aniline (m-urea) 15.1g into the diazonium salt solution, controlling the pH value of the reaction to be between 6.0 and 6.5, keeping the temperature to be between 0 and 5 ℃, keeping the reaction for 3 hours under the condition, detecting the reaction endpoint by a ring infiltration method, and preparing the m-urea orange-yellow monoazo reactive dye after the reaction is finished;
(3) 19.2g of cyanuric chloride 100%, 200g of ice and 20mL of water were added to a 1000mL beaker and slurried for 45 minutes with stirring. Slowly adding the meta-urea orange-yellow monoazo reactive dye prepared in the step (2) into the serosity of the cyanuric chloride, adding baking soda under stirring, controlling the pH value of the reaction to be between 3 and 4, keeping the temperature to be between 0 and 5 ℃, keeping the reaction for 2 hours under the condition, and detecting the reaction end point by thin-layer chromatography to prepare a reaction solution of a first condensation product of the cyanuric chloride;
(4) and (3) dropwise adding 7.4g of N, N' -dihydroxyethyl ethylenediamine with the volume percent of 100% into the reaction solution of the monoacid product of the cyanuric chloride prepared in the step (3), heating to 35-40 ℃, regulating and controlling the pH value of the reaction system to be 6.0-7.0, keeping the reaction condition for continuously reacting for 4 hours, and detecting the reaction end point by thin layer chromatography or liquid phase chromatography. And after the reaction is finished, drying at 75 ℃, and grinding to obtain final solid powder of the multi-active-group monoazo yellow reactive dye I-1.
Preparation of commercial dye
The commercial yellow reactive dye is prepared by mixing the yellow reactive dye I-1 with a diffusant (a methyl naphthalene sulfonic acid formaldehyde condensate with the condensation degree of 4 and the sulfonation degree of 2), an aqueous high-molecular dustproof agent and anhydrous sodium sulphate according to the mass percentage of 85%, 5%, 0.1% and 9.9%.
As shown in figures 2-9, the high-temperature-resistant active red dye for chlorine-resistant cotton and the preparation method thereof are characterized in that a processing device which is adopted in a diazotization reaction and is used for adding a sulfuryl arylamine compound (a1 or a2) containing ethyl sulfate, crushed ice and a small amount of water into a beaker for ice grinding comprises a processing box 1 and a box cover 101, the inside of the processing box 1 is divided into a processing cavity and an electric cavity from top to bottom, a refrigerating sheet 2 used for keeping the inside of the processing cavity of the processing box 1 at constant low temperature is arranged in a partition plate between the processing cavity of the processing box 1 and the electric cavity of the processing box 1, a variable frequency motor 3 is arranged in the electric cavity of the processing box 1, a rotating shaft 8 is arranged at the output end of the variable frequency motor 3, the other end of the rotating shaft 8 extends to the axis inside the processing cavity of the processing box 1, a material grinding mechanism 4, a material shoveling mechanism 5, a material pressing mechanism 6 and a material crushing mechanism 7 are arranged in the processing cavity of the processing box 1, the material grinding mechanism 4 comprises a material grinding support 9, a support cylinder 10, a support rod 11, a support plate 12, a support spring 13 and a material grinding lump 14, the material grinding support 9 is installed on one side of a rotating shaft 8, which is located inside a processing cavity of the processing box 1, the support cylinder 10 is installed on the material grinding support 9, one end of the support rod 11 is located inside the support cylinder 10, the other end of the support rod 11 extends to the bottom of the support cylinder 10, the support plate 12 is installed on a port of the support rod 11, which is located inside the support cylinder 10, the support spring 13 is arranged between the support plate 12 and the inner wall of the support cylinder 10, the material grinding lump 14 is installed on a port of the support rod 11, which extends to the bottom of the support cylinder 10, the material shoveling mechanism 5 comprises a material shoveling support 15 and a material shoveling blade 16, the material shoveling support 15 is installed on the other side of the rotating shaft 8, which is located inside the processing cavity of the processing box 1, the material shoveling blade 16 is arranged on the material shoveling support 15 in a linear array, the material pressing mechanism 6 comprises a connecting piece 17, The material pressing device comprises a reset rod 18, a reset plate 19, a reset spring 20, a top plate 21, rollers 22, a limiting slide way 23, a material pressing bracket 24 and a material pressing blade 25, wherein the connecting pieces 17 are symmetrically arranged at the tops of the shoveling brackets 15, one end of the reset rod 18 is positioned at the tops of the connecting pieces 17, the other end of the reset rod 18 penetrates through a reset cavity formed in the connecting pieces 17 and extends to the bottoms of the connecting pieces 17, the reset plate 19 is arranged on the outer wall of the reset rod 18 positioned in the reset cavity of the connecting pieces 17, the reset spring 20 is arranged between the reset plate 19 and the inner wall of the reset cavity of the connecting pieces 17, the top plate 21 is arranged on the ports of the two reset rods 18 positioned at the tops of the connecting pieces 17, the rollers 22 are arranged at the center of the top plate 21, the limiting slide way 23 is arranged on the inner side of the box cover 101 and is of a wave-shaped structure, the limiting slide way 23 is assembled to be attached to the tops of the rollers 22, the material pressing bracket 24 is arranged on the ports of the two reset rods 18 positioned at the bottoms of the connecting pieces 17, the material pressing blades 25 are arranged on the material pressing support 24 in a linear array, extend to a position which is located in the same vertical plane with the material shoveling blades 16 and are distributed in a staggered manner, the material crushing mechanism 7 comprises a material crushing support 26, a material crushing main shaft 27, a sealing pipe 28, a sealing shaft collar 29, a main bevel gear 30, a ring-shaped bevel gear 31, a main chain wheel 32, a material crushing roller 33, a secondary chain wheel 34 and a chain belt 35, the material crushing support 26 is arranged on one side, adjacent to the material shoveling support 15, of a rotating shaft 8 in a processing cavity of the processing box 1 and connected to the connecting piece 17, one end of the material crushing main shaft 27 is located in a gear cavity formed in the material crushing support 26, the sealing pipe 28 is arranged on the inner side of the processing box 1, the sealing shaft collar 29 is connected to the inner side of the sealing pipe 28, the other end of the material crushing main shaft 27 penetrates through the sealing shaft collar 29 and extends to the inner side of the sealing pipe 28, the main bevel gear 30 is arranged on a port, of the material crushing main shaft 27 extending to the inner side of the sealing pipe 28, annular bevel gear 31 installs in the inside of sealing tube 28, and mesh mutually with main bevel gear 30, main sprocket 32 is installed on crushed aggregates main shaft 27 is located the port of crushed aggregates support 26 gear intracavity portion, crushed aggregates roller 33 is linear array and sets up on crushed aggregates support 26, and keep parallel state with shovel material blade 16, the one end coupling of crushed aggregates roller 33 is on crushed aggregates support 26, the other end of crushed aggregates roller 33 extends to crushed aggregates support 26 gear intracavity portion, install on the port that crushed aggregates roller 33 extends to crushed aggregates support 26 gear intracavity portion from sprocket 34, chain belt 35 is connected between main bevel gear 30 and from sprocket 34.
Example 2
The commercial yellow reactive dye is prepared by mixing the yellow reactive dye I-2 with a diffusant (a methyl naphthalene sulfonic acid formaldehyde condensate with the condensation degree of 4 and the sulfonation degree of 2), an aqueous high-molecular dustproof agent and anhydrous sodium sulphate according to the mass percentage of 85%, 5%, 0.1% and 9.9%.
In this example, the preparation method of the reactive dye I-2 is the same as that in example 1, except that 2, 4-diaminobenzenesulfonic acid (m-bis) and 4- β -ethylsulfonyl sulfate aniline-2-sulfonic acid diazonium salt are subjected to coupling reaction to obtain an orange-yellow chromophore, instead of the yellow chromophore obtained by the reaction of m-urea and 4- β -ethylsulfonyl sulfate aniline-2-sulfonic acid diazonium salt in the preparation step (2) of I-1, to prepare the corresponding yellow reactive dye.
The commercial yellow reactive dye prepared in the embodiment 1-2 is applied to the coloring application of cotton fibers by adopting a printing and dip-dyeing process.
Dip dyeing:
3 parts of commercial yellow reactive dye prepared in the embodiments 1-2 are respectively taken, 6 parts of anhydrous sodium sulphate, 1 part of soda ash and water are added to prepare a dyeing bath with a bath ratio of 1:15, the cotton fabric is dyed for 60min at the temperature of 60 ℃ according to a conventional operation method, then the cotton fabric is neutralized and washed, finally the cotton fabric is soaped, washed with hot water, washed with cold water and dried, and the yellow cotton fabric is obtained, and the product performance test result is shown in table 1.
Printing:
the printing process flow comprises the following steps: semi-finished product → reactive paste printing → drying → steaming (102 ℃ X7 min, relative humidity 75%) → water washing → soaping → water washing → ironing.
The printing paste formula comprises: 5g of dye, x g g of urea, 2.5g of baking soda, 60g of sodium alginate paste, 1g of dye-resistant salt and the balance of water, and the total amount is 100 g.
The product performance test results are shown in Table 2.
TABLE 1 Dip dyeing Performance test results of yellow reactive dyes prepared in examples 1-2
The data in table 1 show that the color fixing rate of the yellow reactive dye on cotton fibers is over 87% when the yellow reactive dye is subjected to a dip dyeing process, the color staining fastness and the light fastness of cotton are good and reach 4-5 levels, and the yellow reactive dye has good lifting performance after the molecular structure of the reactive dye is innovatively designed, the Integ value of the dyed fibers reaches more than 12 when 1% of the dye is used, and the strength is improved by about 2 times when 5% of the dye is used.
TABLE 2 printing performance test results of the yellow reactive dyes prepared in examples 1-2
Determination of the relative color depth of the printed fabrics, based on the Integ value without addition of urea
As can be seen from the data in Table 2, the fixation rate of the yellow reactive dye on cotton fibers is over 92% when the yellow reactive dye is subjected to a printing process, and when the dosage of urea is over 2%, the urea has no obvious influence on the relative color depth of printed fabrics. Therefore, when a printing process is adopted, the using amount of the yellow reactive dye urea provided by the invention can be reduced to below 2%, and is reduced by more than 2 times compared with the existing commercial dye using urea with the content of more than 5%.
The specific action principle of the processing device adopted by the method for adding the sulfuryl arylamine compound (a1 or a2) containing the ethyl sulfate, the crushed ice and a small amount of water into the beaker for ice grinding in the diazotization reaction of the active red dye for the high-temperature chlorine-resistant cotton is as follows: firstly, adding a sulfuryl ethyl sulfate arylamine compound (a1 or a2), crushed ice and a small amount of water into a processing cavity of a processing box 1, then covering a box cover 101, and keeping a limiting slide 23 at the inner side of the box cover 101 in a joint connection with a roller 22, at this time, starting a refrigerating sheet 2 and a variable frequency motor 3, driving a grinding mechanism 4, a shoveling mechanism 5, a pressing mechanism 6 and a crushing mechanism 7 on a rotating shaft 8 to keep axial rotation through the variable frequency motor 3, at this time, a support plate 12 in a support cylinder 10 arranged on a grinding support 9 can make a grinding roller 14 arranged on a support rod 11 keep in a joint with the inner wall of the processing cavity of the processing box 1 under the elastic action of a support spring 13, and repeatedly grinding the sulfuryl ethyl sulfate arylamine compound (a1 or a2), the crushed ice and the small amount of water, and in the process, grinding large crushed ice into small pieces, so that the contact area between the crushed ice and the sulfuryl ethyl sulfate arylamine compound (a1 or a2) can be effectively increased, so as to increase the grinding effect, the material shoveling bracket 15 can also drive the material shoveling blade 16 to shovel small platy crushed ice after being rolled by the material rolling stone 14, and the roller 22 can also drive the reset rod 18 on the top plate 21 to move towards the direction of the material pressing blade 25 under the supporting force of the convex part of the limiting slide way 23 with the wave-shaped structure, at this time, the reset rod 18 can drive the reset plate 19 in the reset cavity of the connecting piece 17 to apply acting force to the reset spring 20 to deform the reset plate, and drive the material pressing blade 25 arranged on the material pressing bracket 24 to impact the material shoveling blade 16, so as to extrude the small platy crushed ice shoveled by the material shoveling blade 16 into a crushed block again, when the roller 22 moves to the concave part of the limiting slide way 23, the reset plate 19 can drive the reset rod 18 to move towards the direction of the top plate 21 under the acting force of the reset spring 20 restoring deformation, so as to ensure that the roller 22 on the top plate 21 is kept attached to the limiting slide way 23, meanwhile, the material pressing blade 25 is separated from the material shoveling blade 16, the material shoveling blade 16 is impacted by the material pressing blade 25 in a reciprocating manner, small crushed ice can be further crushed into small particles, the grinding effect is further improved, the material crushing main shaft 27 arranged on the material crushing support 26 can drive the sealing collar 29 to keep axial movement on the sealing pipe 28 when rotating along with the rotating shaft 8, at the same time, the main bevel gear 30 can drive the material crushing main shaft 27 to keep axial rotation under the action of the annular bevel gear 31, the material crushing roller 33 connected with the driven sprocket 34 is driven by the chain belt 35 on the main sprocket 32 in the gear cavity of the material crushing support 26 to keep axial rotation, so that the material crushing roller 33 can further crush the small crushed ice crushed by the material shoveling blade 16 in a reciprocating manner of the material pressing blade 25, the crushed ice is further crushed, the contact area between the crushed ice and the ethyl sulfate sulfone arylamine compound (a1 or a2) is improved, the grinding effect is increased.
The spring constants of the support spring 13 and the return spring 20 mentioned above meet the technical requirements of the solution of the present invention.
The electrical components presented in the document are all electrically connected with an external master controller and 220V mains, and the master controller can be a conventional known device controlled by a computer or the like.
While certain exemplary embodiments of the present invention have been described above by way of illustration only, it will be apparent to those of ordinary skill in the art that the described embodiments may be modified in various different ways without departing from the spirit and scope of the invention. Accordingly, the drawings and description are illustrative in nature and should not be construed as limiting the scope of the invention.
Claims (10)
1. A multi-active-group monoazo yellow reactive dye is characterized in that: the yellow reactive dye is a compound shown in a structural general formula I;
the X is F or Cl;
in the general structural formula I, R1 is-NHCONH 2, -NH2 or-NHCH 2CH2 COOM; the R2 is-H or-SO 3M; the R3 is:
wherein R4 and R5 are-H, -CH3, -OCH3 or-SO 3M; r6 is-CONHCH 2CH2SO2CH2CH2OSO3M or-SO 2CH2CH2OSO3M, and M is H or alkali metal.
2. The multi-reactive monoazo yellow reactive dye according to claim 1, wherein: in the general structural formula I, X is Cl; the R1 is-NHCONH 2, -NH2 or-NHCH 2CH2 COOM; the R2 is-H or-SO 3M; the R3 is:
wherein R4 is-H; the R5 is-SO 3M; r6 is-CONHCH 2CH2SO2CH2CH2OSO3M or-SO 2CH2CH2OSO3M, and M is Na.
3. The multi-reactive monoazo yellow reactive dye according to claim 2, wherein: in the general structural formula I, X is Cl; the R1 is-NHCONH 2 or-NH 2; the R2 is-H or-SO 3M; the R3 is:
wherein R4 is-H; the R5 is-SO 3M; r6 is-SO 2CH2CH2OSO3M, and M is Na.
4. The multi-reactive monoazo yellow reactive dye according to claim 3, wherein: in the general structural formula I, X is Cl; when R1 is-NHCONH 2, R2 is-H; when the R1 is-NH 2, the R2 is-SO 3M; the R3 is:
wherein R4 is-H; the R5 is-SO 3M; r6 is-SO 2CH2CH2OSO3M, and M is Na.
5. The multi-reactive monoazo yellow reactive dye according to claim 4, wherein: in the general structural formula I, X is Cl; when R1 is-NHCONH 2, R2 is-H; when the R1 is-NH 2, the R2 is-SO 3M; the R3 is:
wherein R4 is-H; the R5 is-SO 3M; r6 is-SO 2CH2CH2OSO3M, and M is Na.
6. The commercial dye prepared from the multi-reactive-group monoazo yellow reactive dye according to claims 1 to 5, wherein the reactive dye is prepared from: the mass percentage of the raw materials and various raw materials contained in the commercial dye is 75-85% of yellow reactive dye, 5-15% of dispersing agent, 0.1-0.5% of dust-proof agent and 5-15% of anhydrous sodium sulphate, wherein the dispersing agent is a methyl naphthalene sulfonic acid formaldehyde condensation compound; the dust-proof agent is a water-soluble high molecular compound, and the commercial dye is used for dyeing and printing cellulose fibers; the cellulose fiber is hydroxyl and/or nitrogen-containing cellulose fiber, and the cellulose fiber is cotton, viscose, hemp or various blended fiber fabrics thereof.
7. The method for preparing the multi-reactive-group monoazo yellow reactive dye according to any one of claims 1 to 5, wherein the method comprises the following steps: the preparation method of the compound shown in the general formula I is carried out according to the following process:
the preparation method of the compound with the general structural formula I comprises the following specific steps:
(1) diazotization reaction
Adding a sulfuryl arylamine compound (a1 or a2) containing ethyl sulfate, crushed ice and a small amount of water into a beaker, ice-milling for 2 hours, adding HCl solution, continuously stirring and reacting for 1 hour, slowly dropwise adding sodium nitrite solution, continuously reacting for 30-60 minutes after dropwise adding is finished, detecting the reaction end point by an Ehrlich reagent, removing excessive nitrous acid by sulfamic acid to prepare a diazonium salt (b1 or b2) containing the sulfuryl arylamine compound containing ethyl sulfate,
the molar ratio of the ethyl sulfate-containing sulfonyl arylamine compound to the sodium nitrite is 1: 1.01-1.03; the molar ratio of the ethyl sulfate-containing sulfuryl arylamine compound to the hydrochloric acid is 1: 1-1: 1.05;
(2) coupling reaction
Adding aniline compound c into the diazonium salt solution containing the ethyl sulfate sulfuryl arylamine compound prepared in the step (1), controlling the pH value of the reaction to be 6-6.5, keeping the temperature to be 0-5 ℃, keeping the reaction for 2-5 hours under the condition, detecting the reaction endpoint by a ring infiltration method, and after the reaction is finished, preparing orange-yellow monoazo reactive dye (d1 or d2),
the molar ratio of the diazonium salt containing the ethyl sulfate sulfonyl arylamine compound to the aniline compound c is 0.98: 1-1.02: 1;
(3) mono-condensation reaction of cyanuric chloride
Pulping cyanuric chloride or cyanuric fluoride for half an hour, slowly dropwise adding the orange monoazo reactive dye (d1 or d2) solution prepared in the step (2) into cyanuric chloride or cyanuric fluoride pulping liquid, controlling the reaction pH value to be between 3 and 4, keeping the temperature to be between 0 and 5 ℃, keeping the reaction for 1 to 2 hours under the condition, and detecting the reaction end point through thin-layer chromatography to prepare a reaction liquid containing a polycondensation product of cyanuric chloride; the molar ratio of the cyanuric chloride or the cyanuric fluoride to the orange monoazo reactive dye (d1 or d2) is 1: 1-1.03: 1;
(4) dimeric reaction of cyanuric chloride
Dissolving N, N' -dihydroxyethyl ethylenediamine in water, slowly dropwise adding into the reaction liquid of the cyanuric chloride or cyanuric fluoride polycondensate obtained in the step (3), controlling the reaction temperature to be between 35 and 45 ℃, controlling the pH value to be between 6.0 and 7.0, keeping the reaction for 4 to 6 hours under the condition, detecting the reaction end point through thin-layer chromatography and liquid chromatography, drying at 75 ℃ after the reaction is finished, and grinding to obtain the active dye solid powder shown in the final compound (I); the molar ratio of the N, N' -dihydroxyethyl ethylenediamine to the cyanuric chloride or cyanuric fluoride polycondensate is 0.49: 1-0.52: 1.
8. The method for preparing a multi-reactive-group monoazo yellow reactive dye according to claim 7, wherein: the processing device comprises a processing box (1) and a box cover (101), wherein the processing box (1) is internally divided into a processing cavity and an electric cavity, a refrigerating sheet (2) used for keeping the interior of the processing cavity of the processing box (1) at a constant low temperature is arranged in a partition plate between the processing cavity of the processing box (1) and the electric cavity of the processing box (1), a variable frequency motor (3) is arranged in the electric cavity of the processing box (1), a rotating shaft (8) is installed at the output end of the variable frequency motor (3), the other end of the rotating shaft (8) extends to the axis of the interior of the processing cavity of the processing box (1), and a material grinding mechanism (4) and a material grinding mechanism are arranged in the interior of the processing cavity of the processing box (1), Shovel mechanism (5), swager mechanism (6) and crushed aggregates mechanism (7), grind material mechanism (4) including grinding material support (9), a support section of thick bamboo (10), bracing piece (11), backup pad (12), supporting spring (13) and grind material mound (14), grind material support (9) install in rotation axis (8) are located one side of processing case (1) process chamber inside, install in support section of thick bamboo (10) grind on material support (9), the one end of bracing piece (11) is located inside support section of thick bamboo (10), the other end of bracing piece (11) extends to support section of thick bamboo (10) bottom, backup pad (12) install in bracing piece (11) are located on the port of support section of thick bamboo (10) inside, supporting spring (13) set up in backup pad (12) with between support section of thick bamboo (10) inner wall, the material grinding block (14) is installed on a port of the bottom of the supporting cylinder (10) extended to the supporting rod (11), the material shoveling mechanism (5) comprises a material shoveling support (15) and a material shoveling blade (16), the material shoveling support (15) is installed on the other side of the inner portion of the processing cavity of the processing box (1) located on the rotating shaft (8), and the material shoveling blade (16) is arranged on the material shoveling support (15) in a linear array mode.
9. The method for preparing a multi-reactive monoazo yellow reactive dye according to claim 8, wherein: the pressing mechanism (6) comprises a connecting piece (17), a reset rod (18), a reset plate (19), a reset spring (20), a top plate (21), rollers (22), a limiting slide way (23), a pressing support (24) and a pressing blade (25), the connecting piece (17) is symmetrically arranged at the top of the shoveling support (15), one end of the reset rod (18) is positioned at the top of the connecting piece (17), the other end of the reset rod (18) penetrates through a reset cavity formed in the connecting piece (17) and extends to the bottom of the connecting piece (17), the reset plate (19) is arranged on the outer wall of the reset rod (18) positioned in the reset cavity of the connecting piece (17), the reset spring (20) is arranged between the reset plate (19) and the inner wall of the reset cavity of the connecting piece (17), the top plate (21) is arranged on the port of the two reset rods (18) positioned at the top of the connecting piece (17), the utility model discloses a material pressing device, including box lid (17), gyro wheel (22), spacing slide (23), pressure material support (24), reset rod (18), material pressing blade (25) are linear array set up in press material support (24) on, and extend to with it is located same vertical plane to shovel material blade (16), and be crisscross the distribution, gyro wheel (22) set up in roof (21) central point puts, spacing slide (23) set up in case lid (101) inboard, and be the wave mode structure, spacing slide (23) be assembled for the laminating connect in gyro wheel (22) top, press material support (24) to install in two reset rod (18) are located on the port of connecting piece (17) bottom.
10. The method for preparing a multi-reactive-group monoazo yellow reactive dye according to claim 9, wherein: the crushing mechanism (7) comprises a crushing support (26), a crushing main shaft (27), a sealing pipe (28), a sealing shaft collar (29), a main bevel gear (30), an annular bevel gear (31), a main chain wheel (32), a crushing roller (33), a driven chain wheel (34) and a chain belt (35), the crushing support (26) is arranged in a gear cavity formed in the crushing support (26) and provided with a rotating shaft (8) positioned inside a processing cavity of the processing box (1) and adjacent to one side of the shoveling support (15) and connected to the connecting piece (17), one end of the crushing main shaft (27) is positioned in the gear cavity formed inside the crushing support (26), the sealing pipe (28) is arranged inside the processing box (1), the sealing shaft collar (29) is connected to the inner side of the sealing pipe (28), the other end of the crushing main shaft (27) penetrates through the sealing shaft collar (29) and extends to the inner side of the sealing pipe (28), the main bevel gear (30) is arranged on a port of the crushing main shaft (27) extending to the inside of the sealing pipe (28), the annular bevel gear (31) is arranged inside the sealing pipe (28) and meshed with the main bevel gear (30), the main chain wheel (32) is arranged on the port of the crushing main shaft (27) located inside a gear cavity of the crushing support (26), the crushing roller (33) is arranged on the crushing support (26) in a linear array and keeps a parallel state with the shoveling blade (16), one end of the crushing roller (33) is connected to the crushing support (26) in a shaft mode, the other end of the crushing roller (33) extends to the inside of the gear cavity of the crushing support (26), the auxiliary chain wheel (34) is arranged on the port of the crushing roller (33) extending to the inside of the gear cavity of the crushing support (26), the chain belt (35) is connected between the main bevel gear (30) and the slave sprocket (34).
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