CN112745247A - Novel dye intermediate, novel dye and preparation method thereof - Google Patents
Novel dye intermediate, novel dye and preparation method thereof Download PDFInfo
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- CN112745247A CN112745247A CN202011630828.7A CN202011630828A CN112745247A CN 112745247 A CN112745247 A CN 112745247A CN 202011630828 A CN202011630828 A CN 202011630828A CN 112745247 A CN112745247 A CN 112745247A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000975 dye Substances 0.000 claims abstract description 112
- 230000009467 reduction Effects 0.000 claims abstract description 15
- 238000005886 esterification reaction Methods 0.000 claims abstract description 13
- 230000032050 esterification Effects 0.000 claims abstract description 9
- 238000009833 condensation Methods 0.000 claims abstract description 6
- 230000005494 condensation Effects 0.000 claims abstract description 6
- 238000010790 dilution Methods 0.000 claims abstract description 6
- 239000012895 dilution Substances 0.000 claims abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 66
- 239000000243 solution Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 17
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 238000004537 pulping Methods 0.000 claims description 15
- 238000006722 reduction reaction Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 230000008878 coupling Effects 0.000 claims description 12
- 238000010168 coupling process Methods 0.000 claims description 12
- 238000005859 coupling reaction Methods 0.000 claims description 12
- 238000006482 condensation reaction Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000005185 salting out Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- GSTCLLCEBJUOLB-UHFFFAOYSA-N 3,5-dinitrobenzenesulfonyl chloride Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=CC(S(Cl)(=O)=O)=C1 GSTCLLCEBJUOLB-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007859 condensation product Substances 0.000 claims description 6
- 238000006193 diazotization reaction Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 5
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- VMKJWLXVLHBJNK-UHFFFAOYSA-N cyanuric fluoride Chemical compound FC1=NC(F)=NC(F)=N1 VMKJWLXVLHBJNK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 4
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 4
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 4
- QZZSAWGVHXXMID-UHFFFAOYSA-N 1-amino-4-bromo-9,10-dioxoanthracene-2-sulfonic acid Chemical compound C1=CC=C2C(=O)C3=C(Br)C=C(S(O)(=O)=O)C(N)=C3C(=O)C2=C1 QZZSAWGVHXXMID-UHFFFAOYSA-N 0.000 claims description 3
- GGZZISOUXJHYOY-UHFFFAOYSA-N 8-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C(N)=CC=CC2=C1O GGZZISOUXJHYOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 229940045803 cuprous chloride Drugs 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000985 reactive dye Substances 0.000 abstract description 2
- 239000004744 fabric Substances 0.000 description 18
- 229920000742 Cotton Polymers 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000003912 environmental pollution Methods 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- GRDXCFKBQWDAJH-UHFFFAOYSA-N 4-acetamidobenzenesulfonyl chloride Chemical compound CC(=O)NC1=CC=C(S(Cl)(=O)=O)C=C1 GRDXCFKBQWDAJH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- DFRAKQKBZGHDES-UHFFFAOYSA-N S(=O)(=O)(O)O.C(=C)S(=O)(=O)C=C Chemical compound S(=O)(=O)(O)O.C(=C)S(=O)(=O)C=C DFRAKQKBZGHDES-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000000434 metal complex dye Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- 239000000979 synthetic dye Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- PKKGGWLTUCMSSD-UHFFFAOYSA-N 3,5-diamino-2,4,6-trimethylbenzenesulfonic acid Chemical compound CC1=C(N)C(C)=C(S(O)(=O)=O)C(C)=C1N PKKGGWLTUCMSSD-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000983 mordant dye Substances 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- -1 sulfuryl alcohol Chemical compound 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
- C07C317/36—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atoms of the amino groups bound to hydrogen atoms or to carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/08—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with halogenosulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C313/02—Sulfinic acids; Derivatives thereof
- C07C313/04—Sulfinic acids; Esters thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- 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
- C09B62/505—Anthracene 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coloring (AREA)
Abstract
The application relates to the field of reactive dyes, and particularly discloses a novel dye intermediate, a novel dye and a preparation method thereof. The preparation method of the novel dye intermediate comprises the following steps: a. chlorosulfonation; b. reduction; c. condensation; d. hydrogenation reduction; e. and (4) esterification and dilution. The novel dye has the advantages of higher dyeing rate, higher fixation rate, better color fastness and more environment-friendly production process.
Description
Technical Field
The present application relates to the field of reactive dyes, more specifically it relates to a novel dye intermediate, a novel dye and a process for its preparation.
Background
At present, the main dyes on the market mainly comprise acid dyes, mordant dyes and metal complex dyes, the dyes of the types have poor fastness of dyed materials, insufficient bright color, low fixation rate and large environmental pollution, and particularly, free heavy metals possibly appearing in the metal complex dyes are harmful to human bodies and the environment.
In recent years, due to the environmental ecological restriction, the requirements of the dye industry on dye uptake, fixation and dyeing wastewater treatment are increasing, so the inventor considers that a new dye intermediate capable of improving the performance of the dye and a high-performance dye are required to be developed.
Disclosure of Invention
In order to solve the problems of low fixation rate, low fixation rate and large environmental hazard of the conventional dye, the application provides a novel dye intermediate, a novel dye and a preparation method thereof.
In a first aspect, the present application provides a novel dye intermediate, which adopts the following technical scheme:
a novel dye intermediate has a general structural formula shown in formula (I):
Through adopting above-mentioned technical scheme, the novel dyestuff midbody prepared by this application is used for preparing novel dyestuff, and required raw materials is with low costs, and the product solubility is high, and the color and luster is bright-colored, and the application performance is excellent, and the suitability is strong, and the preparation process can reduce environmental pollution and have higher rate of dyeing, fixation rate and better colour fastness, and produced accessory substance can be retrieved and recycled in the production process, and is more environmental protection, can effectively reduce environmental pollution and waste water treatment cost.
In a second aspect, the present application provides a method for preparing a novel dye intermediate, which adopts the following technical scheme:
a preparation method of a novel dye intermediate comprises the following steps:
a. chlorosulfonation: adding mixed solution of chlorosulfonic acid and thionyl chloride into a mixture of m-dinitrobenzene and phosphorus pentoxide to react, separating and filtering other byproducts, and hydrolyzing redundant raw materials to obtain 3, 5-dinitrobenzenesulfonyl chloride with a structure shown as a formula (I) -1;
b. reduction: b, pulping the 3, 5-dinitrobenzene sulfonyl chloride obtained in the step a by using water, and then adding sodium metabisulfite to react to obtain a reduction product with a structural formula of (I) -2;
c. condensation: adding ethylene oxide into the reduction product obtained in the step b for condensation reaction, dehydrating the reaction liquid after the reaction is finished, and drying the solid product to obtain a condensation product with a structural formula of (I) -3;
d. hydrogenation reduction: adding a catalyst into the condensation product obtained in the step c, introducing hydrogen for reaction, and cooling, salting out and drying after the reaction is finished to obtain 3, 5-diaminosulfonyl alcohol with the structural formula of (I) -4;
e. esterification and dilution: adding the 3, 5-diaminosulfonyl alcohol obtained in the step d into concentrated sulfuric acid for esterification, then diluting the reaction solution and salting out to obtain a novel dye intermediate
By adopting the technical scheme, the dye intermediate in the application is chlorosulfonated by using chlorosulfonic acid and thionyl chloride, and then is esterified by using concentrated sulfuric acid, so that sulfonyl chloride is achieved, and then is esterified by using concentrated sulfuric acid after ethylene oxide condensation, thereby achieving the purpose of introducing vinyl sulfone sulfate, and enabling the solution degree and the reaction activity of the dye intermediate to be stronger.
Optionally, in the step a, the dropping speed of the mixed solution of chlorosulfonic acid and thionyl chloride is 0.08-0.12ml/s, and the reaction temperature is controlled at 13-17 ℃.
By adopting the technical scheme, the mixed solution of chlorosulfonic acid and thionyl chloride is dripped at the speed of 0.05-0.12ml/s, so that the reaction is more sufficient, and the reaction time is shorter and the conversion rate is higher by matching with the reaction temperature of 13-17 ℃.
Optionally, in the step b, sodium pyrosulfate is added and stirred until the sodium pyrosulfate is dissolved, and then the reaction is carried out by adjusting the pH value to 7.0-7.5 and controlling the temperature to 27-33 ℃.
By adopting the technical scheme, the reaction is quicker and more sufficient under the reaction condition, and the conversion rate is higher.
Optionally, in the step c, the pH is always adjusted to 7.5 to 8.0 during the condensation reaction, and the reaction temperature is controlled to 38 to 42 ℃.
By adopting the technical scheme, the reaction is quicker and more sufficient under the reaction condition, and the conversion rate is higher.
Optionally, in the step d, the hydrogenation reduction reaction is performed in a nitrogen-filled environment, the reaction temperature is 95-105 ℃, and the pressure of introduced hydrogen is 1.2 MPa.
By adopting the technical scheme, the reaction is quicker and more sufficient under the reaction condition, and the conversion rate is higher.
Optionally, in the step e, the temperature is controlled to be 10-15 ℃ when the 3, 5-diaminosulfonyl alcohol is added, then the esterification reaction is carried out at the temperature of 25-30 ℃, ice is added after the reaction is finished, and the temperature is controlled not to exceed 15 ℃ to dilute the reaction solution.
By adopting the technical scheme, the temperature of the 3, 5-diaminosulfonyl alcohol is controlled to be more stable in concentrated sulfuric acid, and the esterification and dilution temperatures are controlled to achieve the purposes of shortening the reaction time and improving the material conversion rate.
In a third aspect, the present application provides a novel dye, which adopts the following technical scheme:
a novel dye prepared from the novel dye intermediate has a structural formula shown as a formula (II) or a formula (III):
by adopting the technical scheme, the synthetic dye of the formula (II) is an active dye containing F and has more active activity compared with the active dye, so that the dyeing temperature is lower, the color fixing rate is higher, and the color fixing rate can reach more than 90 percent; the dye in the formula (III) contains a large amount of vinylsulfone sulfate groups, and has the advantages of high solubility, high color fixing rate and high fastness.
In a fourth aspect, the present application provides a method for preparing the novel dye of formula (ii), which adopts the following technical scheme:
a preparation method of a novel dye comprises the following steps:
s1, preparing a chromophore: heating and dissolving bromamine acid, adding baking soda, M acid and cuprous chloride for reaction, sequentially adding diatomite and active carbon, stirring to remove insoluble substances, salting out, filtering to obtain a chromophore filter cake, and pulping to obtain a chromophore slurry;
s2, first condensation reaction: adding the cyanuric fluoride into the chromophore slurry obtained in the step S1, and reacting to obtain a condensate;
s3, secondary condensation reaction: has a structural formula of
Adding water into the novel dye intermediate, pulping, adding the novel dye intermediate into the condensate obtained in the step S2, and reacting to obtain the novel dye of the formula (II);
in a fifth aspect, the present application provides a method for preparing the novel dye of formula (iii), which adopts the following technical scheme:
a preparation method of a novel dye comprises the following steps:
(1) para-ester diazotization: adding para-ester dry powder into water, pulping, adding NaNO2Reacting at low temperature for 2h to obtain diazo liquid a;
(2) acid coupling: adding the diazo liquid obtained in the step (1) into a diazo liquid with a structural formula
The novel dye intermediate is adjusted to have acidic pH and reacts to obtain acid coupling liquid b;
(3) diazotization of sulfonated para-ester: adding sulfonated para-ester into water, pulping, adding hydrochloric acid, and adding NaNO2Reacting the solution to obtain diazo liquid c;
(4) basic coupling: adding the diazo liquid c obtained in the step (3) into the acid coupling liquid b obtained in the step (2), and reacting to obtain a product solution d;
(5) refining: adding kieselguhr into the product solution d obtained in the step (4), filtering insoluble substances, removing by-products and inorganic salts, and spray-drying to obtain the novel dye of the formula (III);
by adopting the technical scheme, the novel dyes of the (II) and (III) formulas adopt the novel dye intermediate of the (I) formula, the intermediate structure has two amino groups, and the activity of the two amino groups is high, so that the intermediate structure can be used as a connecting group, the synthetic reaction is rapidly obtained by introducing the double fluorine-containing active groups, the synthetic dye has high dyeing fixation rate, bright color and other effects.
In summary, the present application has the following beneficial effects:
1. the novel dye intermediate prepared by the application is used for preparing novel dyes, the cost of required raw materials is low, the product solubility is high, the color is bright, the application performance is excellent, the applicability is strong, the preparation process can reduce environmental pollution, and the novel dye intermediate has higher color rendering index, color fixing index and better color fastness, and the generated by-products in the production process can be recycled, so that the novel dye intermediate is more environment-friendly, and the environmental pollution and the waste water treatment cost can be effectively reduced. 2. The double fluorine-containing active groups are introduced, and due to the high activity of the cyanuric fluoride, the effects of short process time, complete reaction and high conversion rate during synthesis are obtained.
3. According to the method, reaction parameters are reasonably controlled in each reaction stage, so that the reaction is quicker and more sufficient, and the conversion rate is higher. .
Detailed Description
The present application is further described in detail with reference to the following examples, which are intended to illustrate: the following examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer, and all the starting materials in the following examples were obtained from the ordinary commercial sources except for the specific conditions.
Examples
Example 1
A novel dye intermediate having the formula (I) -a:
this example also provides a method for preparing the novel dye intermediate, comprising the steps of:
a. chlorosulfonation: mixing 1.0mol of m-dinitrobenzene and 0.5mol of phosphorus pentoxide, mixing 1.5mol of chlorosulfonic acid and 1.2mol of thionyl chloride, and then dropwise adding the mixed solution of chlorosulfonic acid and thionyl chloride into the mixture of m-dinitrobenzene and phosphorus pentoxide at the speed of 0.1ml/s, wherein the reaction temperature is controlled to be 13-17 ℃; standing for 0.5h after the dropwise addition is finished; the reaction formula of the process is as follows:
hydrogen chloride and sulfur dioxide gas generated in the reaction process are absorbed and treated by two-stage liquid caustic soda; after the reaction is finished, cooling the reaction liquid to separate out 4-acetamido benzene sulfonyl chloride, then filtering and separating out 4-acetamido benzene sulfonyl chloride, and then filteringIntroducing fresh water into the solution to hydrolyze excessive chlorosulfonic acid and thionyl chloride, filtering the filtrate and drying the solid product to obtain the product with the structural formula
The yield of the white solid powder of 3, 5-dinitrobenzenesulfonyl chloride is 87.6 percent; the hydrogen chloride gas generated in the process is absorbed by adopting fifth-grade water to prepare hydrochloric acid as a byproduct for sale;
b. reduction: taking 1mol of the 3, 5-dinitrobenzene sulfonyl chloride obtained in the step a, adding 5mol of water for pulping, adding 2.7mol of sodium metabisulfite after uniform dispersion, uniformly stirring, adjusting the pH to 7.0-7.5 by using white liquor after the sodium metabisulfite is completely dissolved, always keeping the pH, controlling the reaction temperature to be 30 ℃, reacting for 4 hours, and obtaining the compound with the structural formula of
The reduction product of (a); the reaction formula of the process is as follows:
c. condensation: adding 1.5mol of ethylene oxide into the reduction product obtained in the step b for condensation reaction, continuously adjusting the pH value to 7.5-8.0 in the reaction process, keeping the reaction temperature at 40 ℃, keeping the reaction time at 2h, cooling the reaction solution to 5-10 ℃ after the reaction is finished, centrifugally dewatering and drying to obtain the product with the structural formula of
The yield from reduction to condensation of the solid condensation product of (3) was 98.4%; the reaction formula of the process is as follows:
d. hydrogenation reduction: putting the condensation product obtained in the step c into an autoclave, adding 100g of methanol and 10g of Raney nickel, introducing nitrogen into the sealed autoclave to replace the interiorIntroducing hydrogen into the reaction solution, heating the reaction solution to 100 ℃ for reaction, keeping the pressure of the introduced hydrogen to be 1.2MPa all the time in the reaction process, keeping the reaction time to be 3 hours, cooling the reaction solution to 35-40 ℃ after the reaction is finished, adding refined salt accounting for 15% of the volume of the reaction solution, separating the materials, filtering and drying to obtain the product with the structural formula of
3, 5-diaminosulfonylalcohol; the reaction formula of the process is as follows:
e. esterification and dilution: slowly adding 1mol of 3, 5-diaminosulfonyl alcohol prepared in the step d into 5mol of concentrated sulfuric acid with the mass concentration of 99%, and controlling the temperature to be 10-15 ℃ all the time in the process; after the addition, uniformly stirring, carrying out esterification reaction at 25-30 ℃, and detecting that no sulfuryl alcohol is taken as an esterification reaction end point to obtain an esterification product solution with the yield of 99.7%;
the reaction formula of the process is as follows:
adding 28mol of ice water into the esterification product solution, controlling the temperature to be not more than 15 ℃, adding 5% of refined salt into the diluted material after the dilution, separating the material and filtering to obtain the product with the structural formula
A novel dye intermediate of (1).
The final product, namely the novel dye intermediate of the formula (I) -a, is subjected to chromatographic analysis, the chromatographic purity reaches more than 97 percent, the product content is calculated by adopting a chemical titration amino value, and the calculated yield reaches 70 to 75 percent.
Example 2
A novel dye intermediate having the formula (I) -b:
this example also provides a process for preparing the novel dye intermediate, which comprises the steps of preparing (I) -a in example 1, adding 1mol of the novel dye to 5mol of water, dispersing uniformly, adjusting pH to 7.0-7.5 with sodium bicarbonate, soda ash or sodium hydroxide, adding 15 vol% industrial salt, salting out, and filtering to obtain a white solid powder having a structural formula of
A novel dye intermediate of (1).
The reaction equation for this process is as follows:
the novel dye with the structural formula of (I) -b as a final product is subjected to chromatographic analysis, the chromatographic purity reaches more than 97 percent, the product content is calculated by adopting a chemical titration amino value, and the calculated yield reaches 60 to 65 percent.
Example 3
A novel dye intermediate having the formula (I) -c:
this example also provides a process for preparing the novel dye intermediate, which comprises the steps of preparing (I) -a in example 1, adding 1mol of the novel dye to 5mol of water, dispersing uniformly, adjusting pH to 7.0-7.5 with potassium bicarbonate, potassium carbonate or potassium hydroxide, adding 15% by volume of industrial salt, salting out, and filtering to obtain a white solid powder having a structural formula of
A novel dye intermediate of (1).
The reaction equation for this process is as follows:
example 4
A novel dye has a structural formula shown as a formula (II):
the embodiment also provides a preparation method of the novel dye, which comprises the following steps:
s1, preparing a chromophore: heating and dissolving 1mol of bromamine acid, sequentially adding 2.5mol of baking soda, 1mol of M acid (3, 5-diamino-2, 4, 6-trimethylbenzene sulfonic acid) and 1mol of cuprous chloride, keeping the temperature at 80-90 ℃, reacting for 4-5h, then cooling to below 40 ℃, adding a proper amount of diatomite, continuously stirring for 1h, and filtering to remove insoluble substances; then regulating the pH value of the filtrate to be 7.0-7.5 by using hydrochloric acid, heating to 50-60 ℃, adding a proper amount of activated carbon, stirring for 1h, filtering out insoluble substances, heating the secondary filtrate to 70-75 ℃, adding 0.1mol of hydrochloric acid, stirring for 2h, adding refined salt for salting out, stirring, filtering to obtain a color base filter cake, then pulping under an acidic condition to ensure that the solid content of the color base slurry is 35-40%, and stirring for 6h to obtain the color base slurry;
s2, first condensation reaction: taking 1mol of the chromophore slurry obtained in the step S1, adding ice to cool the chromophore to 0 ℃, adding 200ml of water until the chromophore is completely dissolved, adjusting the pH value to 5.5-6.0 by using hydrochloric acid, controlling the temperature to be 0-5 ℃, adding 1.1mol of cyanuric fluoride within 10min (the pH value is maintained to 5.5 by using liquid caustic soda all the time in the feeding process), and reacting for 5min after the feeding is finished to obtain a polycondensate;
s3, secondary condensation reaction: taking 0.47mol of the novel dye intermediate prepared in the example 2, adding 100ml of water, pulping, uniformly dispersing, adjusting the pH value to 5.0-5.5 by using baking soda, then quickly adding the mixture into the polycondensate obtained in the step S2, adjusting the pH value to 7.0 by using liquid alkali, maintaining the pH value, controlling the temperature to be 20-25 ℃, reacting for 1.5h, and obtaining a novel dye solution shown in the formula (II);
adding a proper amount of diatomite into the novel dye solution, filtering to remove insoluble substances, and then removing by-products and inorganic salts in the novel dye solution to obtain the finished novel dye.
Dyeing and sample preparation: 4g of the novel dye are taken, dissolved with water and then brought to a volume of 500 ml. Sucking 10ml of dye liquor to mix with 50ml of water, adding 4g of cotton cloth and 1g of sodium sulfate, raising the temperature to 60 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 30 minutes, adding 0.5g of sodium carbonate, keeping the temperature for 60 ℃ to dye for 30 minutes, taking out the dyed cotton cloth, boiling and soaping the dyed cotton cloth for 15 minutes by using a non-ionic detergent, cleaning the dyed cotton cloth by using water at 60 ℃, and drying the dyed cotton cloth at about 70 ℃ to obtain an orange fabric with bright color and good leveling property.
The dyed samples in the example were tested for dyeing properties according to GB/T2391, ISO205C04, ISO105B02, ISO105E04, ISO102-X12 detection standards, respectively.
The dye properties of the novel dyes of this example are given in the table below.
Example 5
A novel dye has a structural formula shown as a formula (II):
this example also provides a process for the preparation of the novel dye, which differs from example 4 in that the novel dye intermediate prepared from example 1 in step S3 is used
Equivalent amounts of materials were substituted for the novel dye intermediate prepared in example 2
Dyeing and sample preparation: 4g of the novel dye are taken, dissolved with water and then brought to a volume of 500 ml. Sucking 10ml of dye liquor to mix with 50ml of water, adding 4g of cotton cloth and 1g of sodium sulfate, raising the temperature to 60 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 30 minutes, adding 0.5g of sodium carbonate, keeping the temperature for 60 ℃ to dye for 30 minutes, taking out the dyed cotton cloth, boiling and soaping the dyed cotton cloth for 15 minutes by using a non-ionic detergent, cleaning the dyed cotton cloth by using water at 60 ℃, and drying the dyed cotton cloth at about 70 ℃ to obtain an orange fabric with bright color and good leveling property.
The dyed samples in the example were tested for dyeing properties according to GB/T2391, ISO205C04, ISO105B02, ISO105E04, ISO102-X12 detection standards, respectively.
The dye properties of the novel dyes of this example are given in the table below.
Example 6
A novel dye has a structural formula shown as a formula (II):
this example also provides a process for the preparation of the novel dye, which differs from example 4 in that the novel dye intermediate prepared from example 1 in step S3 is used
Equivalent amounts of materials were substituted for the novel dye intermediate prepared in example 3
Dyeing and sample preparation: 4g of the novel dye are taken, dissolved with water and then brought to a volume of 500 ml. Sucking 10ml of dye liquor to mix with 50ml of water, adding 4g of cotton cloth and 1g of sodium sulfate, raising the temperature to 60 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 30 minutes, adding 0.5g of sodium carbonate, keeping the temperature for 60 ℃ to dye for 30 minutes, taking out the dyed cotton cloth, boiling and soaping the dyed cotton cloth for 15 minutes by using a non-ionic detergent, cleaning the dyed cotton cloth by using water at 60 ℃, and drying the dyed cotton cloth at about 70 ℃ to obtain an orange fabric with bright color and good leveling property.
The dyed samples in the example were tested for dyeing properties according to GB/T2391, ISO205C04, ISO105B02, ISO105E04, ISO102-X12 detection standards, respectively.
The dye properties of the novel dyes of this example are given in the table below.
Example 7
A novel dye having the formula (III):
the embodiment also provides a preparation method of the novel dye, which comprises the following steps:
(1) para-ester diazotization: adding 1mol of para-ester dry powder into 0.5ml of water, pulping, stirring for 0.5h, adding 1mol of hydrochloric acid with the mass fraction of 30%, cooling to 0 ℃ by using an ice water bath, and then rapidly adding 1.1mol of NaNO2(NaNO2Preparing into 30% water solution), stirring, reacting at low temperature for 2 hr, and removing excessive NaNO in the system with sulfamic acid2Obtaining diazo liquid a;
(2) acid coupling: adding 0.5mol of the diazo solution obtained in the step (1) into the diazo solution prepared in the step (1), wherein the structural formula of the diazo solution is shown in the specification
Controlling the temperature to be 10-15 ℃, continuously stirring for 4h, adjusting the pH value to be 5.0-5.5 by using baking soda, and reacting for 3h to obtain acid coupling solution b;
(3) diazotization of sulfonated para-ester: adding 0.5mol of sulfonated para-ester into 0.5ml of water, pulping, stirring for 0.5h, adding 1mol of hydrochloric acid with the mass fraction of 30%, controlling the temperature in an ice-water bath at 20 ℃, and then dropwise adding 1.1mol of NaNO at a constant speed within 30min2(NaNO2Preparing into 30% water solution), stirring, reacting at room temperature for 2 hr, and removing excessive NaNO with sulfamic acid2Obtaining diazo liquid c;
(4) basic coupling: dropwise adding the diazo liquid c obtained in the step (3) into the acid coupling liquid b obtained in the step (2), and adding Na2CO3Adjusting pH to 7-7.5, controlling temperature at 15-20 deg.C, maintaining for 3-4h, detecting reaction end point with plate layer or chromatogram, and reacting to obtain product solution d;
(5) refining: adding a proper amount of diatomite into the product solution d obtained in the step (4), filtering insoluble substances, removing by-products and inorganic salts, and spray-drying to obtain a novel dye shown in a formula (III);
the novel dyes of the formula (III) according to the present example have the following dye properties.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A novel dye intermediate is characterized by having a general structural formula shown as a formula (I):
2. A method for preparing a novel dye intermediate as claimed in claim 1, comprising the steps of:
a. chlorosulfonation: adding mixed solution of chlorosulfonic acid and thionyl chloride into a mixture of m-dinitrobenzene and phosphorus pentoxide to react, separating and filtering other byproducts, and hydrolyzing redundant raw materials to obtain 3, 5-dinitrobenzenesulfonyl chloride with a structure shown as a formula (I) -1;
b. reduction: b, pulping the 3, 5-dinitrobenzene sulfonyl chloride obtained in the step a by using water, and then adding sodium metabisulfite to react to obtain a reduction product with a structural formula of (I) -2;
c. condensation: adding ethylene oxide into the reduction product obtained in the step b for condensation reaction, dehydrating the reaction liquid after the reaction is finished, and drying the solid product to obtain a condensation product with a structural formula of (I) -3;
d. hydrogenation reduction: adding a catalyst into the condensation product obtained in the step c, introducing hydrogen for reaction, and cooling, salting out and drying after the reaction is finished to obtain 3, 5-diaminosulfonyl alcohol with the structural formula of (I) -4;
e. esterification and dilution: adding the 3, 5-diaminosulfonyl alcohol obtained in the step d into concentrated sulfuric acid for esterification, then diluting the reaction solution and salting out to obtain a novel dye intermediate
Wherein R is-H, -Na or-K.
3. The method for preparing a novel dye intermediate as claimed in claim 2, wherein the dropping speed of the mixed solution of chlorosulfonic acid and thionyl chloride in the step a is 0.08-0.12ml/s, and the reaction temperature is controlled at 13-17 ℃.
4. The method of claim 3, wherein in the step b, sodium pyrosulfate is added and stirred until it is dissolved, and the reaction is carried out while adjusting the pH to 7.0 to 7.5 and controlling the temperature to 27 to 33 ℃.
5. The method for preparing a novel dye intermediate according to claim 4, wherein in the step c, the pH is adjusted to 7.5 to 8.0 throughout the condensation reaction, and the reaction temperature is controlled to 38 to 42 ℃.
6. The method for preparing a novel dye intermediate according to claim 5, wherein in the step d, the hydrogenation reduction reaction is carried out in a nitrogen-filled environment, the reaction temperature is 95-105 ℃, and the pressure of introduced hydrogen is 1.2 MPa.
7. The method for preparing a novel dye intermediate according to claim 6, wherein in the step e, the temperature of the 3, 5-diaminosulfonyl alcohol is controlled to 10-15 ℃ when it is added, the esterification reaction is carried out at 25-30 ℃, ice is added after the reaction is finished, and the temperature is controlled not to exceed 15 ℃ to dilute the reaction solution.
8. A novel dye prepared from the novel dye intermediate of claim 1, having a formula as shown in formula (ii) or formula (iii):
9. a process for the preparation of the novel dyes of formula (ii) according to claim 8, comprising the following steps:
s1, preparing a chromophore: heating and dissolving bromamine acid, adding baking soda, M acid and cuprous chloride for reaction, sequentially adding diatomite and active carbon, stirring to remove insoluble substances, salting out, filtering to obtain a chromophore filter cake, and pulping to obtain a chromophore slurry;
s2, first condensation reaction: adding the cyanuric fluoride into the chromophore slurry obtained in the step S1, and reacting to obtain a condensate;
s3, secondary condensation reaction: has a structural formula of
Adding water into the novel dye intermediate, pulping, adding the novel dye intermediate into the condensate obtained in the step S2, and reacting to obtain the novel dye of the formula (II);
10. a process for the preparation of the novel dyes of formula (iii) according to claim 8, comprising the following steps:
(1) para-ester diazotization: adding para-ester dry powder into water, pulping, adding NaNO2Reacting at low temperature for 2h to obtain diazo liquid a;
(2) acid coupling: adding the diazo liquid obtained in the step (1) into a diazo liquid with a structural formula
The novel dye intermediate is adjusted to have acidic pH and reacts to obtain acid coupling liquid b;
(3) diazotization of sulfonated para-ester: adding sulfonated para-ester into water, pulping, adding hydrochloric acid, and adding NaNO2Reacting the solution to obtain diazo liquid c;
(4) basic coupling: adding the diazo liquid c obtained in the step (3) into the acid coupling liquid b obtained in the step (2), and reacting to obtain a product solution d;
(5) refining: adding kieselguhr into the product solution d obtained in the step (4), filtering insoluble substances, removing by-products and inorganic salts, and spray-drying to obtain the novel dye of the formula (III);
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