CN113583468A - Dispersed brown and preparation method thereof - Google Patents
Dispersed brown and preparation method thereof Download PDFInfo
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- CN113583468A CN113583468A CN202111032512.2A CN202111032512A CN113583468A CN 113583468 A CN113583468 A CN 113583468A CN 202111032512 A CN202111032512 A CN 202111032512A CN 113583468 A CN113583468 A CN 113583468A
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- compound
- nitroaniline
- reaction
- hydrogen
- brown
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000004043 dyeing Methods 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000000835 fiber Substances 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 22
- -1 halogenated p-nitroaniline compound Chemical class 0.000 claims description 82
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 29
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 26
- 150000002431 hydrogen Chemical class 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 21
- 230000035484 reaction time Effects 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 20
- 238000006193 diazotization reaction Methods 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000005859 coupling reaction Methods 0.000 claims description 17
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 238000005886 esterification reaction Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- KRNUKKZDGDAWBF-UHFFFAOYSA-N 2-(n-ethyl-n-m-toluidino)ethanol Chemical compound OCCN(CC)C1=CC=CC(C)=C1 KRNUKKZDGDAWBF-UHFFFAOYSA-N 0.000 claims description 5
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- YMZIFDLWYUSZCC-UHFFFAOYSA-N 2,6-dibromo-4-nitroaniline Chemical compound NC1=C(Br)C=C([N+]([O-])=O)C=C1Br YMZIFDLWYUSZCC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 4
- XDQFCGOZDVZOMI-UHFFFAOYSA-N 2-(n-ethyl-3-methylanilino)ethyl benzoate Chemical compound C=1C=CC(C)=CC=1N(CC)CCOC(=O)C1=CC=CC=C1 XDQFCGOZDVZOMI-UHFFFAOYSA-N 0.000 claims description 3
- GLUCALKKMFBJEB-UHFFFAOYSA-N 2-bromo-6-chloro-4-nitroaniline Chemical compound NC1=C(Cl)C=C([N+]([O-])=O)C=C1Br GLUCALKKMFBJEB-UHFFFAOYSA-N 0.000 claims description 3
- LOCWBQIWHWIRGN-UHFFFAOYSA-N 2-chloro-4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1Cl LOCWBQIWHWIRGN-UHFFFAOYSA-N 0.000 claims description 3
- BIXZHMJUSMUDOQ-UHFFFAOYSA-N dichloran Chemical compound NC1=C(Cl)C=C([N+]([O-])=O)C=C1Cl BIXZHMJUSMUDOQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 30
- 239000000986 disperse dye Substances 0.000 abstract description 22
- 239000003513 alkali Substances 0.000 abstract description 20
- 239000004744 fabric Substances 0.000 abstract description 13
- 229920000728 polyester Polymers 0.000 abstract description 11
- 238000007639 printing Methods 0.000 abstract description 10
- 238000009991 scouring Methods 0.000 abstract description 6
- 238000004061 bleaching Methods 0.000 abstract description 4
- 239000003086 colorant Substances 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 125000004185 ester group Chemical group 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical class NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000004344 phenylpropyl group Chemical group 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- 229920004933 Terylene® Polymers 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ROPYWXVRNREIQD-UHFFFAOYSA-N 2-[n-(2-cyanoethyl)-4-[(2,6-dichloro-4-nitrophenyl)diazenyl]anilino]ethyl acetate Chemical compound C1=CC(N(CCC#N)CCOC(=O)C)=CC=C1N=NC1=C(Cl)C=C([N+]([O-])=O)C=C1Cl ROPYWXVRNREIQD-UHFFFAOYSA-N 0.000 description 2
- 238000010669 acid-base reaction Methods 0.000 description 2
- 229910052789 astatine Inorganic materials 0.000 description 2
- RYXHOMYVWAEKHL-UHFFFAOYSA-N astatine atom Chemical compound [At] RYXHOMYVWAEKHL-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 238000009874 alkali refining Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
- C09B29/0833—Amino benzenes characterised by the substituent on the benzene ring excepted the substituents: CH3, C2H5, O-alkyl, NHCO-alkyl, NHCOO-alkyl, NHCO- C6H5, NHCOO-C6H5
- C09B29/0844—Amino benzenes characterised by the substituent on the benzene ring excepted the substituents: CH3, C2H5, O-alkyl, NHCO-alkyl, NHCOO-alkyl, NHCO- C6H5, NHCOO-C6H5 substituted by alkyl, e.g. CF3
-
- 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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
- D06P3/54—Polyesters using dispersed dyestuffs
Abstract
The invention provides disperse brown and a preparation method and application thereof, and relates to the technical field of dye chemical industry. The disperse brown dyed polyester fiber and the blended fabric thereof present special reddish brown colors, can be used for single color and can be combined with alkali-resistant disperse dyes of other colors; the disperse brown has the characteristics of excellent alkali resistance, excellent oxidation resistance and the like due to the unique molecular structure, solves the technical problems that the disperse dye is difficult to be applied to general alkaline printing and dyeing processing, a scouring dyeing one-bath process, a bleaching dyeing one-bath process and a disperse active same-size printing process, and achieves the technical effects of good fastness performance and dyeing performance.
Description
Technical Field
The invention relates to the technical field of dye chemical industry, in particular to a disperse brown and a preparation method thereof.
Background
At present, polyester fibers and blended fabrics thereof have very important application in high-grade fabrics, and the applicable dye is disperse dye. When polyester fiber products are dyed by disperse dyes, an acid dye bath is generally used, however, under an acid condition, fabric is easy to cause defects such as stain, color point and dyeing due to staining of oligomers.
The alkaline dyeing process of the disperse dye can effectively remove oligomers generated in the dyeing process, and has the characteristics of short production process flow, energy conservation, consumption reduction, high efficiency and the like. In recent years, the pressure of energy conservation, emission reduction and cost promotes printing and dyeing enterprises and dye assistant manufacturers to make a joint effort to develop various alkali-resistant disperse dyes and matched dyeing assistants thereof, and an alkali scouring and dyeing one-bath process is newly developed on the basis of an alkali dyeing process.
At present, most of brown disperse dyes on the market are obtained by matching a plurality of dyes, the single brown is not much, most of colored lights are yellow brown, and the fastness and the dyeing performance of the disperse dyes are greatly different, for example, the disperse brown 19 with the structure as shown in the following formula:
the structure of the dye contains carboxylic acid methyl ester, the carboxylic acid methyl ester belongs to simple ester, the carboxylic acid methyl ester can be decomposed into carboxylic acid and methanol under the alkaline condition, and the carboxylic acid can further generate acid-base reaction to generate carboxylate, so that the hydrolysis reaction is promoted to be balanced and carried out forward, the dye C.I. disperse brown 19 is extremely weak against alkali and cannot be used for alkaline bath dyeing, the colored light of the dyed fiber is yellow brown, and the fastness performance is general; and c.i. dispersed orange 30 having the structure:
the dye is orange after dyeing fibers, most of disperse brown products on the market are formed by matching the dye with other dyes, ester groups contained in the structure of the dye are different from ester groups in C.I. disperse brown 19 and belong to bulky esters, and generally, alkali does not attack ester groups easily due to steric influence, so that the reaction is generally slow and difficult to hydrolyze, so that C.I. disperse orange 30 has certain alkali resistance, but the dye has certain alkali resistance and is only suitable for a dye bath with the pH value of less than 9, and cannot be used for an alkali refining dyeing one-bath process.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
One of the purposes of the invention is to provide a disperse brown which has a unique molecular structure, can be applied to general alkaline printing and dyeing processing, a scouring and dyeing one-bath process, a bleaching and dyeing one-bath process and a disperse active same-size printing process, and has the technical advantages of good fastness performance and dyeing performance.
The second purpose of the invention is to provide a method for preparing dispersed brown, which is to obtain the dispersed brown by diazotization-coupling reaction of halogenated p-nitroaniline compound and alkyl aniline compound, and has simple process, convenient operation and high yield.
The invention also aims to provide the application of the dispersed palm in the dyeing of fiber products.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, the invention provides a dispersed brown having a structure represented by formula (1):
wherein m is an integer from 1 to 6;
X1、X2、X3、X4independently is halo or hydrogen, and X1、X2、X3、X4Not hydrogen at the same time;
R1、R2、R3、R4、R5、R6independently is hydrogen, C1～C6Alkyl of (C)6～C10Substituted or unsubstituted aryl of (a), and R1、R2、R3、R4Not hydrogen at the same time.
Further, the dispersed brown has a structure shown in a formula (2):
wherein m is an integer from 1 to 3;
X3、X4independently fluorine, chlorine, bromine or iodine;
R2、R5、R6independently is C1～C3Alkyl of (C)6～C8Substituted or unsubstituted aryl of (a).
Further, the dispersed brown has a structure shown in a formula (3):
wherein, X3、X4Independently is chlorine or bromine;
R2、R5independently methyl or ethyl;
R6is ethyl, propyl or phenyl.
Further, the disperse brown is any one of the following compounds:
in a second aspect, the invention provides a preparation method of the above dispersed brown, which comprises the following steps:
carrying out diazotization-coupling reaction on a halogenated p-nitroaniline compound and an alkyl aniline compound to obtain the disperse brown;
wherein the halogenated p-nitroaniline compound has a structure shown in a formula (4):
X5、X6、X7、X8independently is halo or hydrogen, and X5、X6、X7、X8Not hydrogen at the same time;
the alkylaniline compound has a structure represented by formula (5):
n is an integer from 1 to 6;
R7、R8、R9、R10、R11、R12independently is hydrogen, C1～C6Alkyl of (C)6～C10Substituted or unsubstituted aryl of (a), and R7、R8、R9、R10Not hydrogen at the same time.
Further, the preparation method comprises the following steps:
A. carrying out diazotization reaction on halogenated p-nitroaniline compound and diazotization agent in acid liquor to obtain diazotized solution;
wherein the temperature of the diazotization reaction is 0-50 ℃, and the reaction time is 1-6 h;
the diazotizing agent comprises nitrosyl sulfuric acid;
the molar ratio of the diazotization agent to the halogenated p-nitroaniline compound is 1-1.5: 1;
the acid solution comprises a solution of sulfuric acid;
preferably, the molar ratio of the sulfuric acid to the halogenated p-nitroaniline compound is 1-8: 1;
B. carrying out coupling reaction on the diazo liquid obtained in the step A and an alkyl aniline compound in an acid solution to obtain the dispersed brown;
wherein the temperature of the coupling reaction is 0-25 ℃, and the reaction time is 1-5 h;
the acid solution comprises an aqueous solution of concentrated sulfuric acid;
preferably, the volume ratio of the concentrated sulfuric acid to the water is 1: 50 to 100.
Further, the molar ratio of the alkylaniline compound to the halogenated p-nitroaniline compound is 1-1.2: 1, preferably 1.01-1.1: 1;
preferably, the alkylaniline compound comprises at least one of N-ethyl-N-benzoyloxyethyl-m-toluidine, N-methyl-N-propionyloxyethyl-m-toluidine, and N-ethyl-N-propionyloxyethyl-m-toluidine;
preferably, the halogenated p-nitroaniline compound comprises at least one of 2, 6-dibromo-p-nitroaniline, 2, 6-dichloro-p-nitroaniline, o-chloro-p-nitroaniline and 2-bromo-6-chloro-4-nitroaniline;
preferably, the temperature of the diazotization reaction is 10-30 ℃, and the reaction time is 2-5 h;
preferably, the molar ratio of the diazotizing agent to the halogenated p-nitroaniline compound is 1.01-1.1: 1;
preferably, the molar ratio of the sulfuric acid to the halogenated p-nitroaniline compound is 1.01-5: 1;
preferably, the temperature of the coupling reaction is 0-10 ℃, and the reaction time is 1-3 h;
preferably, the volume ratio of the concentrated sulfuric acid to the water is 1: 55-85.
Further, the preparation method of the alkylaniline compound comprises the following steps:
carrying out esterification reaction on a hydroxyalkyl aniline compound and an acyl halide compound in a solvent to obtain the alkyl aniline compound;
wherein the hydroxyalkyl aniline compound has a structure represented by formula (6):
t is selected from an integer of 1 to 6;
R13、R14、R15、R16、R17independently is hydrogen, C1～C6Alkyl of (C)6～C10Substituted or unsubstituted aryl of (a), and R13、R14、R15、R16Not hydrogen at the same time;
the acid halide compound has a structure represented by formula (7):
x is a halogen group;
R18is hydrogen, C1～C6Alkyl of (C)6～C10Substituted or unsubstituted aryl of (a);
preferably, the molar ratio of the hydroxyalkyl aniline compound to the acyl halide compound is 1-1.3: 1;
preferably, the molar ratio of the hydroxyalkyl aniline compound to the acyl halide compound is 1-1.1: 1;
preferably, the temperature of the esterification reaction is 50-100 ℃, and the reaction time is 1-4 h;
preferably, the temperature of the esterification reaction is 60-90 ℃, and the reaction time is 2-3 h;
preferably, the solvent comprises at least one of methanol, acetone, acetic acid and water.
Further, the hydroxyalkyl aniline compound includes at least one of N-ethyl-N-hydroxyethyl m-toluidine and N-methyl-N-hydroxyethyl m-toluidine;
the acid halide compound includes at least one of benzoyl chloride and propionyl chloride.
In a third aspect, the invention provides a use of the above dispersed brown in dyeing fiber products.
Compared with the prior art, the dispersed palm and the preparation method and application thereof provided by the invention have at least the following beneficial effects:
the disperse brown dyed polyester fiber and the blended fabric thereof have special reddish brown color, can be used for single color and can be combined with alkali-resistant disperse dyes of other colors; the disperse brown has the characteristics of excellent alkali resistance, oxidation resistance and the like due to the unique molecular structure, can be applied to the common alkaline printing and dyeing processing of polyester fiber materials, can also be applied to a scouring dyeing one-bath process or a bleaching dyeing one-bath process and a disperse active same size printing process, and has the advantages of good fastness and dyeing property.
The preparation method of the dispersed brown provided by the invention has the technical advantages of simple reaction process, convenience in operation, high yield and the like.
The application of the disperse brown in the fiber product dyeing has the characteristics of high fastness and good dyeing performance.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to a first aspect of the invention, there is provided a dispersed brown having a structure represented by formula (1):
wherein m is an integer from 1 to 6, m is 1, 2, 3, 4, 5 or 6;
X1、X2、X3、X4independently is halo or hydrogen, X1、X2、X3、X4May be the same or different, and X1、X2、X3、X4Not simultaneously hydrogen, and the halogen group is a halogen element including, but not limited to, fluorine, chlorine, bromine, iodine, and astatine;
R1、R2、R3、R4、R5、R6independently is hydrogen, C1～C6Alkyl of (C)6～C10Substituted or unsubstituted aryl of, R1、R2、R3、R4、R5、R6May be the same or different, and R1、R2、R3、R4When not simultaneously hydrogen, the alkyl group may be straight or branched, including but not limited to methyl (CH)3-, ethyl (C)2H5-) n-propyl (-CH)2CH2CH3) Isopropyl (-CH (CH)3)2) N-butyl (-CH)2CH2CH2CH3) Isobutyl (-CH)2CH(CH3)CH3) Sec-butyl (-CH (CH)3)CH2CH3) And tert-butyl (-C (CH)3)2CH3) Substituted or unsubstituted aryl groups include, but are not limited to, phenyl, benzyl, phenethyl, and phenylpropyl.
The disperse brown provided by the invention has the advantages of high alkali resistance, good fastness and good dyeing performance due to the unique molecular structure (the disperse brown belongs to ester with large volume, and alkali is not easy to attack ester group due to steric influence, so that the disperse brown is difficult to hydrolyze). The disperse brown dye-uptake polyester fiber and the blended fabric thereof of the invention present special reddish brown color, can be used for single color, can also be used in combination with alkali-resistant disperse dyes of other colors, can be applied to the common alkaline dyeing and printing processing of polyester fiber materials, can also be applied to a scouring dyeing one-bath process or a bleaching dyeing one-bath process, and a disperse active one-slurry printing process, can fill the market blank, and has considerable market prospect.
In a preferred embodiment, the dispersed brown of the present invention has a structure represented by formula (2):
wherein m is an integer from 1 to 3, m is 1, 2 or 3;
X3、X4independently of one another are fluorine, chlorine, bromine or iodine, X3、X4May be the same or different;
R2、R5、R6independently is C1～C3Alkyl of (C)6～C8Substituted or unsubstituted aryl of, R2、R5、R6Which may be the same or different, alkyl groups may be straight or branched chain and include, but are not limited to, methyl (CH)3-, ethyl (C)2H5-) n-propyl (-CH)2CH2CH3) And isopropyl (-CH (CH)3)2) Substituted or unsubstituted aryl groups include, but are not limited to, phenyl, benzyl, and phenethyl.
In a preferred embodiment, the dispersed brown of the present invention has a structure represented by formula (3):
wherein, X3、X4Independently of one another are chlorine or bromine, X3And X4Simultaneously being chlorine, X3And X4While being bromine, X3When it is bromine X4Is chlorine, X4When it is bromine X3Is chlorine;
R2、R5independently is methyl or ethyl, R2And R5Simultaneously being methyl, R2And R5While being ethyl, R2R being methyl5Is ethyl, R2R in the case of ethyl5Is methyl;
R6is ethyl, propyl or phenyl.
The typical structure of the dispersed brown of the invention is any one of the following structures:
according to a second aspect of the invention, there is provided a method for preparing dispersed brown, comprising the steps of:
carrying out diazotization-coupling reaction on a halogenated p-nitroaniline compound and an alkyl aniline compound to obtain the disperse brown;
wherein, the halogenated p-nitroaniline compound of the invention has a structure shown in a formula (4):
X5、X6、X7、X8independently is halo or hydrogen, X5、X6、X7、X8May be the same or different, and X5、X6、X7、X8Not simultaneously hydrogen, and the halogen group is a halogen element including, but not limited to, fluorine, chlorine, bromine, iodine, and astatine;
the alkylaniline compound of the present invention has the structure represented by formula (5):
n is an integer from 1 to 6, n is 1, 2, 3, 4, 5 or 6;
R7、R8、R9、R10、R11、R12independently is hydrogen, C1～C6Alkyl of (C)6～C10Substituted or unsubstituted aryl of, R7、R8、R9、R10、R11、R12May be the same or different, and R7、R8、R9、R10When not simultaneously hydrogen, the alkyl group may be straight or branched, including but not limited to methyl (CH)3-, ethyl (C)2H5-) n-propyl (-CH)2CH2CH3) Isopropyl (-CH (CH)3)2) N-butyl (-CH)2CH2CH2CH3) Isobutyl (-CH)2CH(CH3)CH3) Sec-butyl (-CH (CH)3)CH2CH3) And tert-butyl (-C (CH)3)2CH3) Substituted or unsubstituted aryl groups include, but are not limited to, phenyl, benzyl, phenethyl, and phenylpropyl.
The preparation method of the dispersed brown provided by the invention has the technical advantages of simple reaction process, convenience in operation, high yield and the like.
In a preferred embodiment, the method for preparing dispersed brown according to the invention comprises the following steps:
A. carrying out diazotization reaction on halogenated p-nitroaniline compound and diazotization agent in acid liquor to obtain diazotized solution;
wherein, the temperature of the diazotization reaction is 0-50 ℃, the typical but non-limiting reaction temperature is, for example, 10 ℃, 20 ℃, 30 ℃, 40 ℃ and 50 ℃, the reaction time is 1-6 h, and the typical but non-limiting reaction time is, for example, 1h, 2h, 3h, 4h, 5h and 6h (the process of the diazotization reaction of the invention can be monitored by a conventional test method (such as TLC) in the field, and the disappearance of the p-nitroaniline compound is taken as a reaction end point);
diazotizing agents of the present invention include, but are not limited to, nitrosylsulfuric acid;
the molar ratio of the diazotizing agent to the halogenated p-nitroaniline compound in the step A of the invention is 1-1.5: 1, and the typical but non-limiting molar ratio is 1: 1. 1.1: 1. 1.2: 1. 1.3: 1. 1.4: 1. 1.5: 1;
the acid solution in the step A of the invention includes but is not limited to a solution of sulfuric acid, and the molar ratio of the sulfuric acid to the halogenated p-nitroaniline compound is 1-8: 1, in a typical but non-limiting molar ratio, for example 1: 1.2: 1. 3: 1. 4: 1.5: 1. 6: 1. 7: 1. 8: 1;
B. carrying out coupling reaction on the diazo liquid obtained in the step A and an alkyl aniline compound in an acid solution to obtain the dispersed brown;
wherein, the temperature of the coupling reaction is 0-25 ℃, the typical but non-limiting reaction temperature is, for example, 10 ℃, 20 ℃ and 25 ℃, the reaction time is 1-5h, and the typical but non-limiting reaction time is, for example, 1h, 2h, 3h, 4h and 5h (the progress of the coupling reaction of the invention can be monitored by a conventional test method in the field (such as a color penetration ring developing method), and the color development of the alkylaniline compound in slight excess is taken as a reaction end point);
the acid solution in step B of the present invention includes, but is not limited to, an aqueous solution of concentrated sulfuric acid, and the volume ratio of concentrated sulfuric acid to water is 1: 50 to 100, typically but not exclusively in a molar ratio of, for example, 1: 50. 1: 60. 1: 70. 1: 80. 1: 90.
in a preferred embodiment, the molar ratio of the alkylaniline compound of the invention to the halo-p-nitroaniline compound is 1 to 1.2:1, with typical but non-limiting molar ratios being, for example, 1: 1. 1.1: 1. 1.2: 1;
the alkylaniline compounds of the present invention include, but are not limited to, N-ethyl-N-benzoyloxyethyl-m-toluidine, N-methyl-N-propionyloxyethyl-m-toluidine, and N-ethyl-N-propionyloxyethyl-m-toluidine;
the halogenated p-nitroaniline compounds of the present invention include, but are not limited to, 2, 6-dibromop-nitroaniline, 2, 6-dichlorop-nitroaniline, o-chloro-p-nitroaniline and 2-bromo-6-chloro-4-nitroaniline.
In a preferred embodiment, the process for preparing an alkylaniline compound of the present invention comprises the steps of:
carrying out esterification reaction on a hydroxyalkyl aniline compound and an acyl halide compound in a solvent to obtain an alkylaniline compound;
wherein the hydroxyalkyl aniline compound of the present invention has a structure represented by formula (6):
t is an integer from 1 to 6, t is 1, 2, 3, 4, 5 or 6;
R13、R14、R15、R16、R17independently is hydrogen, C1～C6Alkyl of (C)6～C10Substituted or unsubstituted aryl of, R13、R14、R15、R16、R17May be the same or different, and R13、R14、R15、R16When not simultaneously hydrogen, the alkyl group may be straight or branched, including but not limited to methyl (CH)3-, ethyl (C)2H5-) n-propyl (-CH)2CH2CH3) Isopropyl (-CH (CH)3)2) N-butyl (-CH)2CH2CH2CH3) Isobutyl (-CH)2CH(CH3)CH3) Sec-butyl (-CH (CH)3)CH2CH3) And tert-butyl (-C (CH)3)2CH3) Substituted or unsubstituted aryl includes, but is not limited to, phenyl, benzyl, benzeneEthyl and phenylpropyl;
the acyl halide compound of the present invention has a structure represented by formula (7):
x is halo, which is a halogen element including, but not limited to, fluorine, chlorine, and bromine;
R18is hydrogen, C1～C6Alkyl of (C)6～C10Substituted or unsubstituted aryl of (a), alkyl may be straight or branched, and alkyl includes, but is not limited to, methyl (CH)3-, ethyl (C)2H5-) n-propyl (-CH)2CH2CH3) Isopropyl (-CH (CH)3)2) N-butyl (-CH)2CH2CH2CH3) Isobutyl (-CH)2CH(CH3)CH3) Sec-butyl (-CH (CH)3)CH2CH3) And tert-butyl (-C (CH)3)2CH3) Substituted or unsubstituted aryl groups include, but are not limited to, phenyl, benzyl, phenylethyl, and phenylpropyl;
wherein the molar ratio of the hydroxyalkyl aniline compound to the acyl halide compound is 1-1.3: 1, in a typical but non-limiting molar ratio, for example 1: 1. 1.1: 1. 1.2: 1. 1.3: 1; the esterification reaction of the present invention is carried out at a temperature of 50 to 100 deg.C, typically but not limited to, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C, for a reaction time of 1 to 4 hours, typically but not limited to, for a reaction time of 1 to 4 hours (the progress of the esterification reaction of the present invention can be monitored by a conventional test method in the art such as HPLC, with the hydroxyalkyl aniline compound ≦ 1% as the reaction end point); the solvent for the esterification reaction of the present invention includes, but is not limited to, at least one of methanol, acetone, acetic acid, and water.
In a preferred embodiment, the hydroxyalkyl aniline compounds of the present invention include, but are not limited to, N-ethyl-N-hydroxyethyl m-toluidine and N-methyl-N-hydroxyethyl m-toluidine; the acyl halide compounds of the present invention include, but are not limited to, benzoyl chloride and propionyl chloride.
A typical preparation method of dispersed brown comprises the following steps:
(a) carrying out esterification reaction on a hydroxyalkyl aniline compound and an acyl halide compound in a solvent to obtain an alkyl aniline compound, wherein the molar ratio of the hydroxyalkyl aniline compound to the acyl halide compound is 1-1.3, the temperature of the esterification reaction is 50-100 ℃, the reaction time is 1-4h, and the solvent of the esterification reaction comprises at least one of methanol, acetone, acetic acid and water;
(b) carrying out diazotization reaction on halogenated p-nitroaniline compounds and a diazotization agent in an acid solution to obtain a diazotized solution, wherein the temperature of the diazotization reaction is 0-50 ℃, the reaction time is 1-6 h, the diazotization agent comprises nitrosyl sulfuric acid, the molar ratio of the diazotization agent to the halogenated p-nitroaniline compounds is 1-1.5: 1, the acid solution comprises a solution of sulfuric acid, and the molar ratio of the sulfuric acid to the halogenated p-nitroaniline compounds is 1-8: 1;
(c) performing coupling reaction on the diazo liquid obtained in the step (b) and the alkylaniline compound obtained in the step (a) in an acid solution to obtain dispersed brown, wherein the molar ratio of the alkylaniline compound to the halogenated p-nitroaniline compound in the diazo liquid is 1-1.2: 1, the coupling reaction temperature is 0-25 ℃, the reaction time is 1-5h, the acid solution comprises an aqueous solution of concentrated sulfuric acid, and the volume ratio of the concentrated sulfuric acid to water is 1: 50 to 100.
The preparation method of the disperse brown is simple and easy to implement, convenient to operate, high in yield and low in cost.
According to a third aspect of the invention, there is provided the use of the above-mentioned dispersed palm for dyeing a fibrous article.
The invention provides the application of the disperse brown as the disperse dye, which can be treated according to the conventional treatment method in the field (such as sanding) to obtain the disperse dye, and the disperse dye can be applied to the dyeing and printing of polyester fibers and blended fiber products thereof according to the conventional dyeing method of the disperse dye in the field, wherein the polyester fibers, namely polyethylene terephthalate fibers (terylene) and the blended fiber products thereof, such as terylene/cotton and terylene/viscose are the conventional polyester fibers in the field and the blended fiber products thereof, and the blended fiber products can be in the conventional existing form in the field, such as fibers, yarns, woven fabrics, knitted fabrics, non-woven fabrics and the like.
The application of the disperse brown in the fiber product dyeing has the characteristics of high fastness and good dyeing performance.
The invention is further illustrated by the following examples. The materials in the examples are prepared according to known methods or are directly commercially available, unless otherwise specified.
Example 1
(1) A process for the preparation of an alkylaniline compound comprising the steps of:
weighing 27g of N-ethyl-N-hydroxyethyl m-toluidine into a 100ml four-neck flask, and slowly adding 30ml of acetic acid under the stirring condition; then slowly heating to 65-70 ℃, and slowly dripping 24g of benzoyl chloride from a constant-pressure dropping funnel at the temperature of 65-70 ℃ for about 2 hours; slowly heating to 70-75 ℃ after adding, preserving heat for reaction, sampling after the reaction is preserved for 1h, detecting by HPLC (high performance liquid chromatography), and finishing the reaction when the reactant N-ethyl-N-hydroxyethyl m-toluidine is less than or equal to 1 percent to obtain a product
83g of acetic acid solution with the purity of about 97 percent, and the product is determined to be [ M + H ] by LC-MS (liquid chromatography-mass spectrometry)]+284.2，[M+Na]+306.2。
(2) The preparation method of the dispersed brown comprises the following steps:
weighing 6g of concentrated sulfuric acid into a dry 100ml three-neck flask, cooling the concentrated sulfuric acid in a water bath to below 20 ℃, adding 8.7g of nitrosyl sulfuric acid, uniformly stirring, cooling the nitrosyl sulfuric acid in an ice-water bath to about 20 ℃, slowly adding 7.4g of 2, 6-dibromo-p-nitroaniline at about 20 ℃, adding the mixture for about 1 hour, and keeping the temperature at about 20 ℃ for 3-4 hours after the addition to obtain a transparent diazonium solution; then, dropwise adding the mixture into the mixture within 1h to perform coupling reaction with the product obtained in the step A, adding ice to control the reaction temperature to be 0-5 ℃, preserving the temperature at 0-5 ℃ for 2h to complete the coupling reaction, then naturally stirring the mixture to room temperature, filtering the mixture, washing the mixture with water,drying again to obtain disperse brown
The yield was about 83.4% and the purity by HPLC was 96.3%. The product was determined by LC-MS to be [ M + H]+591.3，[M+Na]+613.4, LC-MS data are obtained by Waters UPLC-SQD LC-MS (mobile phase is acetonitrile/water system, 60% -90% acetonitrile V/V, column temperature 40 ℃ C.).
Examples 2 to 8
The dispersed brown of examples 2 to 8 was prepared according to the method of example 1, and the relevant experimental data and structural identification data of the alkylaniline compounds of examples 2 to 8 and the dispersed brown prepared therefrom are shown in tables 1 and 2;
table 1 shows the data on the experiments and the structural identification of the alkylaniline compounds obtained in step (1) of examples 2 to 8.
Table 2 shows the data of the experiments and the structural identification data of the dispersed brown obtained in step (2) of examples 2 to 8.
TABLE 1
TABLE 2
Example 9
Dispersing and grinding 10 g of the disperse brown obtained in the example 1, 12 g of a dispersing agent MF, 3g of sodium lignosulfonate and 37.5 g of water by using a sand mill, and performing spray drying after the dispersing and grinding treatment to obtain the brown disperse dye.
Examples 10 to 16
The disperse brown of examples 2 to 8 was subjected to a disperse milling treatment in accordance with the procedure of example 9 to give brown disperse dyes of examples 10 to 16.
Comparative example 1
C.i. disperse brown 19 commercial dye (structure as follows):
comparative example 2
C.i. disperse orange 30 commercial dye (structure as follows):
examples of the experiments
The disperse dye of example 9 is subjected to contrast dyeing in dye baths of different pH values, respectively, and comprises the following steps:
0.5 g of the disperse dye of example 9 is respectively dispersed in 500 ml of water to form dye suspension, 25 ml of the suspension is absorbed and mixed with 25 ml of water, the pH values of the dye baths are respectively 4, 5, 9, 11, 12 and 13, 6g/L of 30 percent hydrogen peroxide is respectively added, the temperature is raised to 60 ℃, 2.5 g of polyester fiber cloth is respectively put into the dye baths, the temperature is raised to 130 ℃ within 30 minutes, the temperature is kept for 50 minutes, the temperature is lowered, the dye baths are fully washed with water and dried by blowing, and dyed cloth samples are obtained.
The disperse dyes of examples 10 to 16 were subjected to comparative dyeing in baths of different pH values, respectively, at pH values of 4, 5, 9, 11, 12 and 13, according to the above-described method, to give dyed cloth samples.
The disperse dyes of comparative examples 1 to 2 were subjected to comparative dyeing in dye baths of different pH values, respectively, of 4, 5, 9, 11, 12 and 13, respectively, in accordance with the above-described method, to give dyed cloth samples.
The cloth specimens dyed with the dyes of examples 9-16 and comparative examples 1-2 were tested for fastness to washing, rubbing, sunlight and sublimation according to ISO 105C 10C (3), GB/T3920-2008, ISO 105B02, GB/T5718 1997, respectively. The test results are shown in Table 3, wherein the dyeing bath pH value is 5, and the dyeing cloth samples without adding hydrogen peroxide are taken as the standard.
TABLE 3
As can be seen from the table above, the brown disperse dye disclosed by the invention presents special reddish brown after being dyed on fibers, can be used under an alkaline condition that the pH is less than or equal to 13, is good in stability of resisting oxidation of hydrogen peroxide, and is good in washing resistance, friction resistance, sunlight resistance and sublimation color fastness.
The dye of the comparative example 1 is yellow brown after dyeing fibers, and because the structure of the dye contains methyl carboxylate, the methyl carboxylate belongs to simple ester, under alkaline conditions, the methyl carboxylate is decomposed into carboxylic acid and methanol, and the carboxylic acid can further generate acid-base reaction to generate carboxylate, so that the equilibrium of the hydrolysis reaction is promoted to be carried out in a forward direction. Therefore, the dye of the comparative example 1 has extremely weak alkali resistance in structure and poor oxidation resistance stability under a strong alkaline condition, when the pH value of a dye bath is more than or equal to 9, the dyeing effect is poor, and the fastness and the dyeing performance are integrally inferior to those of the disperse dye.
The dye of comparative example 2 is different from the present invention in the chromophoric group in its structure, cyanoethyl is weaker in chromophoric strength, it only appears orange after dyeing fiber, and the ester group contained in its structure is a bulky ester, which is highly similar to the present invention and different from the ester group in c.i. disperse brown 19 of comparative example 1, and generally, the bulky ester is not easy to attack the ester group by alkali due to steric hindrance, so that the reaction is generally slower and difficult to hydrolyze. Thus, the dye of comparative example 2 has a certain alkali resistance. However, the structure of comparative example 2 is different from that of the present invention, and not only the difference in color light of the dye is large, but also the difference in alkali resistance is large. Although the dye of comparative example 2 has a certain alkali resistance, it is only suitable for the dyeing bath with pH < 9, but cannot be used in the alkali scouring dyeing one-bath process.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. Dispersed brown, characterized in that it has the structure of formula (1):
wherein m is an integer from 1 to 6;
X1、X2、X3、X4independently is halo or hydrogen, and X1、X2、X3、X4Not hydrogen at the same time;
R1、R2、R3、R4、R5、R6independently is hydrogen, C1～C6Alkyl of (C)6～C10Substituted or unsubstituted aryl of (a), and R1、R2、R3、R4Not hydrogen at the same time.
2. Dispersed brown according to claim 1, characterized in that it has the structure of formula (2):
wherein m is an integer from 1 to 3;
X3、X4independently fluorine, chlorine, bromine or iodine;
R2、R5、R6independently is C1～C3Alkyl of (C)6～C8Substituted or unsubstituted aryl of (a).
3. Dispersed brown according to claim 2, characterized in that it has the structure of formula (3):
wherein, X3、X4Independently is chlorine or bromine;
R2、R5independently methyl or ethyl;
R6is ethyl, propyl or phenyl.
4. Dispersed brown according to any of claims 1-3, characterized in that it is any of the following compounds:
5. a process for the preparation of dispersed brown according to any of claims 1 to 4, characterized in that it comprises the following steps:
carrying out diazotization-coupling reaction on a halogenated p-nitroaniline compound and an alkyl aniline compound to obtain the disperse brown;
wherein the halogenated p-nitroaniline compound has a structure shown in a formula (4):
X5、X6、X7、X8independently is halo or hydrogen, and X5、X6、X7、X8Not hydrogen at the same time;
the alkylaniline compound has a structure represented by formula (5):
n is an integer from 1 to 6;
R7、R8、R9、R10、R11、R12independently is hydrogen, C1～C6Alkyl of (C)6～C10Substituted or unsubstituted aryl of (a), and R7、R8、R9、R10Not hydrogen at the same time.
6. The method of claim 5, comprising the steps of:
A. carrying out diazotization reaction on halogenated p-nitroaniline compound and diazotization agent in acid liquor to obtain diazotized solution;
wherein the temperature of the diazotization reaction is 0-50 ℃, and the reaction time is 1-6 h;
the diazotizing agent comprises nitrosyl sulfuric acid;
the molar ratio of the diazotization agent to the halogenated p-nitroaniline compound is 1-1.5: 1;
the acid solution comprises a solution of sulfuric acid;
preferably, the molar ratio of the sulfuric acid to the halogenated p-nitroaniline compound is 1-8: 1;
B. carrying out coupling reaction on the diazo liquid obtained in the step A and an alkyl aniline compound in an acid solution to obtain the dispersed brown;
wherein the temperature of the coupling reaction is 0-25 ℃, and the reaction time is 1-5 h;
the acid solution comprises an aqueous solution of concentrated sulfuric acid;
preferably, the volume ratio of the concentrated sulfuric acid to the water is 1: 50 to 100.
7. The preparation method according to claim 6, wherein the molar ratio of the alkylaniline compound to the halogenated p-nitroaniline compound is 1-1.2: 1, preferably 1.01-1.1: 1;
preferably, the alkylaniline compound comprises at least one of N-ethyl-N-benzoyloxyethyl-m-toluidine, N-methyl-N-propionyloxyethyl-m-toluidine, and N-ethyl-N-propionyloxyethyl-m-toluidine;
preferably, the halogenated p-nitroaniline compound comprises at least one of 2, 6-dibromo-p-nitroaniline, 2, 6-dichloro-p-nitroaniline, o-chloro-p-nitroaniline and 2-bromo-6-chloro-4-nitroaniline;
preferably, the temperature of the diazotization reaction is 10-30 ℃, and the reaction time is 2-5 h;
preferably, the molar ratio of the diazotizing agent to the halogenated p-nitroaniline compound is 1.01-1.1: 1;
preferably, the molar ratio of the sulfuric acid to the halogenated p-nitroaniline compound is 1.01-5: 1;
preferably, the temperature of the coupling reaction is 0-10 ℃, and the reaction time is 1-3 h;
preferably, the volume ratio of the concentrated sulfuric acid to the water is 1: 55-85.
8. The method according to claim 5, wherein the method for producing an alkylaniline compound comprises the steps of:
carrying out esterification reaction on a hydroxyalkyl aniline compound and an acyl halide compound in a solvent to obtain the alkyl aniline compound;
wherein the hydroxyalkyl aniline compound has a structure represented by formula (6):
t is selected from an integer of 1 to 6;
R13、R14、R15、R16、R17independently is hydrogen, C1～C6Alkyl of (C)6～C10Substituted or unsubstituted aryl of (a), and R13、R14、R15、R16Not hydrogen at the same time;
the acid halide compound has a structure represented by formula (7):
x is a halogen group;
R18is hydrogen,C1～C6Alkyl of (C)6～C10Substituted or unsubstituted aryl of (a);
preferably, the molar ratio of the hydroxyalkyl aniline compound to the acyl halide compound is 1-1.3: 1;
preferably, the molar ratio of the hydroxyalkyl aniline compound to the acyl halide compound is 1-1.1: 1;
preferably, the temperature of the esterification reaction is 50-100 ℃, and the reaction time is 1-4 h;
preferably, the temperature of the esterification reaction is 60-90 ℃, and the reaction time is 2-3 h;
preferably, the solvent comprises at least one of methanol, acetone, acetic acid and water.
9. The method according to claim 8, wherein the hydroxyalkyl aniline compound comprises at least one of N-ethyl-N-hydroxyethyl m-toluidine and N-methyl-N-hydroxyethyl m-toluidine;
the acid halide compound includes at least one of benzoyl chloride and propionyl chloride.
10. Use of a dispersed brown according to any of claims 1 to 4 for dyeing fibre products.
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| CN116178982A (en) * | 2022-12-28 | 2023-05-30 | 浙江龙盛集团股份有限公司 | Disperse dye compound containing benzoate groups and heterocyclic rings and application thereof |
| CN116200048A (en) * | 2022-12-28 | 2023-06-02 | 浙江龙盛集团股份有限公司 | Disperse dye compound containing benzoate groups and application thereof |
| CN116200050A (en) * | 2022-12-28 | 2023-06-02 | 浙江龙盛集团股份有限公司 | Disperse blue-to-black dye composition and dye product thereof |
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| GB1324367A (en) * | 1970-11-24 | 1973-07-25 | Yorkshire Chemicals Ltd | Disperse dyes |
| EP0330967A2 (en) * | 1988-02-26 | 1989-09-06 | Bayer Ag | Process for dyeing synthetic fibrous materials |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116178982A (en) * | 2022-12-28 | 2023-05-30 | 浙江龙盛集团股份有限公司 | Disperse dye compound containing benzoate groups and heterocyclic rings and application thereof |
| CN116200048A (en) * | 2022-12-28 | 2023-06-02 | 浙江龙盛集团股份有限公司 | Disperse dye compound containing benzoate groups and application thereof |
| CN116200050A (en) * | 2022-12-28 | 2023-06-02 | 浙江龙盛集团股份有限公司 | Disperse blue-to-black dye composition and dye product thereof |
| CN116178982B (en) * | 2022-12-28 | 2024-04-05 | 浙江龙盛集团股份有限公司 | Disperse dye compound containing benzoate groups and heterocyclic rings and application thereof |
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Application publication date: 20211102 |