CN110408234B - Environment-friendly disazo acid red dye and preparation method thereof - Google Patents
Environment-friendly disazo acid red dye and preparation method thereof Download PDFInfo
- Publication number
- CN110408234B CN110408234B CN201910726501.0A CN201910726501A CN110408234B CN 110408234 B CN110408234 B CN 110408234B CN 201910726501 A CN201910726501 A CN 201910726501A CN 110408234 B CN110408234 B CN 110408234B
- Authority
- CN
- China
- Prior art keywords
- acid red
- hydrogen
- red dye
- disazo
- independently
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002253 acid Substances 0.000 title claims abstract description 98
- 239000001044 red dye Substances 0.000 title claims abstract description 87
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 67
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 66
- 239000000975 dye Substances 0.000 claims abstract description 44
- 238000004043 dyeing Methods 0.000 claims abstract description 40
- 239000000126 substance Substances 0.000 claims abstract description 18
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 15
- -1 methoxy, ethoxy Chemical group 0.000 claims abstract description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 46
- 238000005859 coupling reaction Methods 0.000 claims description 38
- 230000008878 coupling Effects 0.000 claims description 29
- 238000010168 coupling process Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- JWAZRIHNYRIHIV-UHFFFAOYSA-N beta-hydroxynaphthyl Natural products C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229950011260 betanaphthol Drugs 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- 239000012954 diazonium Substances 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001989 diazonium salts Chemical class 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- 238000005121 nitriding Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000004744 fabric Substances 0.000 abstract description 14
- 239000002932 luster Substances 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 3
- 239000007788 liquid Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- WTRVMTQZFCLTOR-UHFFFAOYSA-N 5,5-diamino-2-phenylcyclohex-2-ene-1,1-disulfonic acid Chemical compound OS(=O)(=O)C1(S(O)(=O)=O)CC(N)(N)CC=C1C1=CC=CC=C1 WTRVMTQZFCLTOR-UHFFFAOYSA-N 0.000 description 4
- 230000000711 cancerogenic effect Effects 0.000 description 4
- 231100000315 carcinogenic Toxicity 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000987 azo dye Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000000980 acid dye Substances 0.000 description 2
- 230000002009 allergenic effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 description 1
- AQYMRQUYPFCXDM-UHFFFAOYSA-N 3-hydroxy-n-(2-methoxyphenyl)naphthalene-2-carboxamide Chemical compound COC1=CC=CC=C1NC(=O)C1=CC2=CC=CC=C2C=C1O AQYMRQUYPFCXDM-UHFFFAOYSA-N 0.000 description 1
- FBLAHUMENIHUGG-UHFFFAOYSA-N 3-hydroxy-n-(2-methylphenyl)naphthalene-2-carboxamide Chemical compound CC1=CC=CC=C1NC(=O)C1=CC2=CC=CC=C2C=C1O FBLAHUMENIHUGG-UHFFFAOYSA-N 0.000 description 1
- DTVQPYOIEBOPAA-UHFFFAOYSA-N 5-amino-2-(4-aminophenyl)-4,4-dimethoxycyclohexa-2,5-diene-1,1-disulfonic acid Chemical compound COC1(C(=CC(C(=C1)C1=CC=C(N)C=C1)(S(=O)(=O)O)S(=O)(=O)O)N)OC DTVQPYOIEBOPAA-UHFFFAOYSA-N 0.000 description 1
- GECICDVEVFIQJA-UHFFFAOYSA-N 5-amino-2-(4-aminophenyl)-4,4-dimethylcyclohexa-2,5-diene-1,1-disulfonic acid Chemical compound CC1(C(=CC(C(=C1)C1=CC=C(N)C=C1)(S(=O)(=O)O)S(=O)(=O)O)N)C GECICDVEVFIQJA-UHFFFAOYSA-N 0.000 description 1
- VVPHSMHEYVOVLH-UHFFFAOYSA-N 6-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=CC2=CC(O)=CC=C21 VVPHSMHEYVOVLH-UHFFFAOYSA-N 0.000 description 1
- HUYJTJXLNBOVFO-UHFFFAOYSA-N 7-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(O)=CC=C21 HUYJTJXLNBOVFO-UHFFFAOYSA-N 0.000 description 1
- MVEOHWRUBFWKJY-UHFFFAOYSA-N 7-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=CC(S(O)(=O)=O)=CC2=CC(O)=CC=C21 MVEOHWRUBFWKJY-UHFFFAOYSA-N 0.000 description 1
- 229920006052 Chinlon® Polymers 0.000 description 1
- FYJKEJZGNQVNLC-UHFFFAOYSA-N N-(4-ethoxyphenyl)-3-hydroxy-2-naphthalenecarboxamide Chemical compound C1=CC(OCC)=CC=C1NC(=O)C1=CC2=CC=CC=C2C=C1O FYJKEJZGNQVNLC-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
- 150000001448 anilines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HNBQFKZSMFFZQY-UHFFFAOYSA-L chembl1559341 Chemical compound [Na+].[Na+].C1=CC(C)=CC=C1S(=O)(=O)OC1=CC=C(N=NC=2C(=CC(=CC=2)C=2C=C(C)C(N=NC=3C4=C(C=C(C=C4C=CC=3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=2)C)C=C1 HNBQFKZSMFFZQY-UHFFFAOYSA-L 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- OHAXNCGNVGGWSO-UHFFFAOYSA-N n-(4-chlorophenyl)-3-hydroxynaphthalene-2-carboxamide Chemical compound OC1=CC2=CC=CC=C2C=C1C(=O)NC1=CC=C(Cl)C=C1 OHAXNCGNVGGWSO-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 239000000979 synthetic dye Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
- C09B35/02—Disazo dyes
- C09B35/037—Disazo dyes characterised by two coupling components of different types
-
- 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
- C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
- C09B35/02—Disazo dyes
- C09B35/039—Disazo dyes characterised by the tetrazo component
- C09B35/08—Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of biphenyl
- C09B35/20—Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of biphenyl from two coupling compounds of different types
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Abstract
The invention relates toThe field of organic dyes for fabrics discloses an environment-friendly disazo acid red dye which has a chemical structure shown in a general formula (I):
R1and R2Each independently is: hydrogen, C1～C5Alkyl of (C)1～C5One of alkoxy and chloro of (1); r3Each independently is: one of hydrogen, sulfonic acid group and carboxyl group; r4Each independently is: one of hydrogen, methyl, methoxy, ethoxy, nitro and chloro; the dyed fabric has thick and full color and luster, and the dyeing promotion rate of the dye is improved.
Description
Technical Field
The invention relates to the field of organic dyes for fabrics, in particular to an environment-friendly disazo acid red dye and a preparation method thereof.
Background
Azo dyes are the most widely used synthetic dyes in textile apparel in printing and dyeing processes, for dyeing and printing a wide variety of natural and synthetic fibers, and also for coloring paints, plastics, rubbers, and the like.
The acid dye is a water-soluble dye with an acid group in the structure, and dyeing is carried out in an acid medium. The azo acid red dye is mainly used for dyeing wool, silk, chinlon and the like, and can also be used for dyeing leather, paper, ink and the like, wherein the azo acid red dye belongs to azo dyes and acid dyes. With the existing environmental awareness and the increasing requirements of people on health, a large amount of azo dyes and the use of raw materials thereof in the dye field are forbidden in the existing Chinese standard and foreign standard, wherein the forbidden azo acid red dyes have more restricted dyes, such as acid red 114# and the like. However, the conventional substitute dyes have defects in the using process and effect, and have certain defects such as darker dyeing color, low dyeing improvement rate and difficult coloring compared with the conventional forbidden original dyes in the dyeing effect, so that the acid red dye which is environment-friendly and healthy and has the dyeing performance comparable to that of the original dye is needed.
Disclosure of Invention
Aiming at the defects in the prior art, the first purpose of the invention is to provide the environment-friendly disazo acid red dye, the dyed fabric is thick and full in color and luster, and the dyeing promotion rate of the dye is improved.
The technical purpose of the invention is realized by the following technical scheme:
an environment-friendly disazo acid red dye has a chemical structure shown in a general formula (I):
R1and R2Each independently is: hydrogen, C1～C5Alkyl of (C)1～C5One of alkoxy and chloro of (1);
R3each independently is: one of hydrogen, sulfonic acid group and carboxyl group;
R4each independently is: hydrogen, methyl, methoxy, ethoxy, nitro and chloro.
By adopting the technical scheme, the disazo acid red dye comprises a conjugated planar structure formed by a plurality of N-N bonds and benzene rings, wherein the conjugated planar structure is a structure (VI) as shown in the specification,
the conjugated degree of the chromophoric group is extended, the chromophoric coefficient of the disazo acid red dye is increased, the dyed fabric is thick and full in color, and the dyeing promotion rate of the dye is improved.
The invention is further configured to: the R is4Each independently is chloro or hydrogen.
Through adopting above-mentioned technical scheme, this application dye dyeing effect and dyed fabric's light fastness and wet processing fastness are more excellent.
The invention is further configured to: the R is1And R2Each independently is methyl, methoxy or hydrogen.
Through adopting above-mentioned technical scheme, this application dye dyeing effect and dyed fabric's light fastness and wet processing fastness are more excellent.
The invention is further configured to: the R is3Each independently is a sulfonic acid group or hydrogen.
By adopting the technical scheme, the dye has excellent dyeing effect, excellent light fastness and wet treatment fastness of dyed fabrics, more stable dye property and improved high temperature resistance and water immersion resistance of dye and dye dyeing.
The invention is further configured to: the raw materials of the material comprise a main body A, a coupling component B and a coupling component C, wherein the main body A has a general formula (II):
the disazo acid red dye is obtained by performing double nitridation on a main body A and then sequentially coupling the main body A with a first coupling component B and a second coupling component C.
By adopting the technical scheme, the main body A with the general formula (II) does not belong to national standards of China and anilines forbidden by European Union dyes, and when the disazo acid red dye disclosed by the application is in long-term contact with human skin, the main body A with the general formula (II) is mixed with components released in a metabolic process and cannot react to form a carcinogenic aromatic amine compound, so that the existing scarce or other disazo acid red dyes with high replacement cost are obtained.
Aiming at the defects in the prior art, the second purpose of the invention is to provide the preparation method of the environmentally-friendly disazo acid red dye, which is convenient to produce and control and has high dye preparation yield.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of an environment-friendly disazo acid red dye comprises the following steps,
s1: the 4, 4-diamino-2, 2-disulfonic acid biphenyl derivatives with the general formula (II) are subjected to double nitridation, wherein the general formula (II) is as follows,
R1and R2Each independently is: hydrogen, C1～C5Alkyl of (C)1～C5One of alkoxy and chloro of (1);
s2: coupling reaction of the diazonium salt product obtained in S1 with a 2-naphthol compound having the general formula (III),
R3each independently is: hydrogen, sulfonic group and carboxyl to obtain a primary coupling compound of a general formula (IV),
s3: subjecting the primary conjugate obtained in S2 to a coupling reaction with a coupling component having the general formula (V) shown below,
R4each independently is: hydrogen, methyl, methoxy, ethoxy, nitro and chlorine radical to obtain the secondary coupling compound of the general formula (I),
s4: and separating or enriching the secondary coupling compound obtained in the S3 to obtain the disazo acid red dye.
By adopting the technical scheme, the process is simple, the negative effects of products and the like generated by side reactions on the chromaticity of the dye and the dyeing improvement rate are small, the production control is convenient, and the production yield of the product dye is high.
The invention is further configured to: the reaction environment temperature of the double nitriding reaction in S1 is 0-40 ℃.
The invention is further configured to: the pH of the reaction environment for the coupling reaction in S3 is 5-10, and the temperature of the reaction environment is 15-35 ℃.
Through adopting above-mentioned technical scheme, the reaction environment temperature of double nitriding reaction is 0 ~ 40 ℃ in S1, the reaction environment pH of coupling reaction is 5 ~ 10 in S3, when reaction environment temperature is 15 ~ 35 ℃, this application disazo acid red dyestuff 'S preparation yield is higher, and product dyestuff colourity and dyeing promotion rate are high, simultaneously this application disazo acid red dyestuff preparation' S preferred environment, its requirement is simply easily reached, and control is convenient, be convenient for this application disazo acid red dyestuff production.
Aiming at the defects in the prior art, the third purpose of the invention is to provide the application of the disazo acid red dye as an environment-friendly dye in clothes dyeing, daily necessity dyeing and paper dyeing.
By adopting the technical scheme, the disazo acid red dye is used as a safe, carcinogenic, non-allergenic and environment-friendly dye in clothes dyeing, daily article dyeing and paper dyeing.
In conclusion, the invention has the following beneficial effects:
1. the disazo acid red dye has a conjugated planar structure with a structure (VI) formed by a plurality of N-N bonds and benzene rings, extends the conjugation degree of a chromophoric group, increases the chromophoric coefficient of the disazo acid red dye, ensures that dyed fabrics have thick and full color and luster, and improves the dyeing lifting rate of the dye;
2. the acid red dyeing is optimized in coupling components, coupling components of a naphthol series are introduced, the color development and dyeing effect of the dye is improved, the adjustment of the chromaticity of the dye is convenient, and meanwhile, the coupling components of the naphthol series are introduced when a conjugate plane structure of a structure (VI) exists, so that dyed fabrics dyed by the dye are thick and full in color, and the light fastness and the wet processing fastness are improved;
3.R1and R2Each independently of the other being methyl, methoxy or hydrogen, R4When the dyes are respectively carboxyl or hydrogen, the dyeing effect of the dye and the light fastness and wet processing fastness of dyed fabrics are better, and when R is carboxyl or hydrogen3When the dyes are respectively independent sulfonic acid groups or hydrogen, the properties of the dyes are more stable besides the improvement of light fastness and wet treatment fastness, and the high temperature resistance and the water immersion resistance of the dyes and the dyes are improved;
4. in the long-term contact of the disazo acid red dye with human skin, the main body A with the chemical structure of the general formula (II) is mixed with the components released in the metabolic process and does not react to form a carcinogenic aromatic amine compound, so that the disazo acid red dye which is scarce or expensive in other replacement costs is obtained;
5. the disazo acid red dye provided by the application has the advantages that the preparation process is simple, the negative effects of products and the like generated by side reactions on the chromaticity and the dyeing improvement rate of the dye are small, the production control reaction is realized, the dye preparation yield of the product is high, meanwhile, the requirement of the preparation of the disazo acid red dye is simple and easy to achieve, the control is convenient, and the production of the disazo acid red dye is convenient;
6. the disazo acid red dye is used as a safe, carcinogenic, non-allergenic and environment-friendly dye in clothes dyeing, daily article dyeing and paper dyeing.
Detailed Description
An environment-friendly disazo acid red dye has a chemical structure of a general formula (I):
R1and R2Each independently is: hydrogen, C1～C5Alkyl of (C)1～C5One of alkoxy and chloro of (1);
R3each independently is: one of hydrogen, sulfonic acid group and carboxyl group;
R4each independently is: hydrogen, methyl, methoxy, ethoxy, nitro and chloro.
Which comprises a conjugated structure consisting of a plurality of N ═ N bonds and benzene rings, the conjugated planar structure being structure (vi), as shown below,
the conjugated degree of the chromophoric group is extended, the chromophoric coefficient of the disazo acid red dye is increased, the dyed fabric is thick and full in color, and the dyeing promotion rate of the dye is improved.
The preparation method of the disazo acid red dye comprises the following steps:
s1: the 4, 4-diamino-2, 2-disulfonic acid biphenyl derivatives with the general formula (II) are subjected to double nitridation, the general formula (II) is shown as follows,
R1and R2Each independently is: hydrogen, C1～C5Alkyl of (C)1～C5One of substituted or unsubstituted sulfonamide, hydroxyl, halogen, and substituted or unsubstituted carboxyl;
s2: coupling reaction of the diazonium salt product obtained in S1 with a 2-naphthol compound having the general formula (III),
R3each independently is: hydrogen, sulfonic group and carboxyl to obtain a primary coupling compound of a general formula (IV),
s3: subjecting the primary conjugate obtained in S2 to a coupling reaction with a coupling component having the general formula (V) shown below,
R4each independently is: hydrogen, methyl, methoxy, ethoxy, nitro and chlorine radical to obtain the secondary coupling compound of the general formula (I),
s4: and separating or enriching the secondary coupling compound obtained in the S3 to obtain the disazo acid red dye.
In the first embodiment, the first step is,
an environment-friendly disazo acid red dye has a chemical structure of a general formula (I), wherein R1Is hydrogen, R2Is hydrogen, R3Is hydrogen, R4Is hydrogen.
The preparation method of the disazo acid red dye of the first embodiment comprises the following steps,
t1: taking 150ml of deionized water, adding 17.2g of 4, 4-diaminobiphenyl-2, 2-disulfonic acid, heating to 60 ℃, adding 30 wt% of liquid caustic soda solution (sodium hydroxide solution), fully stirring, and adding 3.55g of sodium nitrite for later use to prepare a part of solution prepared in advance;
t1: taking 100ml of ice-water mixture, adding 10g of hydrochloric acid, starting a stirrer to stir and mix the mixture, cooling to 0-5 ℃, maintaining the temperature to be 0-5 ℃, adding a portion of pre-prepared solution into a beaker for 5 minutes, keeping the temperature of the mixed solution at 5-8 ℃, and carrying out heat preservation reaction for 4-5 hours to obtain diazonium solution;
t3: mixing 80ml of deionized water with 9g of 30 wt% of liquid caustic soda, heating to 80 ℃, adding 7.2g of 2-naphthol, fully stirring to dissolve the 2-naphthol, adding ice, and cooling to 20-30 ℃ to obtain a portion of first coupling component liquid;
t4: adding one portion of the first coupling component liquid into reacted 500ml of diazo liquid for 20 minutes, adjusting the temperature of the added mixed liquid to be 10-15 ℃, adjusting the pH value of the mixed liquid to be 6-9 by using 30 wt% of liquid alkali, and reacting at 10-20 ℃ for 3-4 hours to obtain one portion of primary coupling liquid;
t5: taking 120ml of deionized water, adding 9g of 30 wt% of liquid alkali, mixing, heating to 60-90 ℃, adding 13.3g of naphthol, continuously stirring, mixing and stirring for 2 hours until the naphthol is dissolved and mixed uniformly, adding ice, and cooling to 10-25 ℃ to obtain a portion of second coupling component liquid;
t6: and adding one part of the second coupling component liquid into one part of the first coupling liquid, adjusting the pH value of the mixed liquid to 5-10 by using 30 wt% liquid alkali at the temperature of 10-20 ℃, controlling the temperature to be 10-30 ℃ and reacting for 5 hours to obtain the disazo acid red dye (P1), and filtering and drying to obtain the product, namely the disazo acid red dye (P1).
In the second embodiment, the first embodiment of the method,
an environment-friendly disazo acid red dye has a chemical structure of a general formula (I), wherein R1Is methyl, R2Is methyl, R3Is hydrogen, R4Is hydrogen.
Example two a disazo acid red dye was prepared by following the procedure of example one and differing therefrom in that the product disazo acid red dye (P2) was prepared synthetically in T1 by replacing 4, 4-diaminobiphenyl-2, 2-disulfonic acid with an equimolar amount of 5, 5-dimethylbenzidine-2, 2-disulfonic acid.
In the third embodiment, the first step is that,
an environment-friendly disazo acid red dye has a chemical structure of a general formula (I), wherein R1Is methoxy, R2Is methoxy, R3Is hydrogen, R4Is hydrogen.
Example iii the procedure for the preparation of disazo acid red dye is based on example one, with the difference that the product disazo acid red dye (P3) is prepared synthetically in T1 by replacing 4, 4-diaminobiphenyl-2, 2-disulfonic acid with an equimolar amount of 5, 5-dimethoxybenzidine-2, 2-disulfonic acid.
In the fourth embodiment, the first step is that,
an environment-friendly disazo acid red dye has a chemical structure of a general formula (I), wherein R1Is a chlorine atom, R2Is a chlorine atom, R3Is hydrogen, R4Is hydrogen.
Example four the procedure for the preparation of disazo acid red dye is based on example one, with the difference that the product disazo acid red dye (P4) was prepared synthetically in T1 by replacing 4, 4-diaminobiphenyl-2, 2-disulfonic acid with an equimolar amount of 5, 5-dichlorobenzidine-2, 2-disulfonic acid.
In the fifth embodiment, the first step is,
an environment-friendly disazo acid red dye has a chemical structure of a general formula (I), wherein R1Is hydrogen, R2Is hydrogen, R3Is a sulfonic acid group, R4Is hydrogen.
The preparation method of the disazo acid red dye of the fifth embodiment is based on the first embodiment, and is characterized in that: t3: 80ml of deionized water and 9g of 30 wt% of liquid alkali are mixed, after the temperature is raised to 40 ℃, 11.2g of 2-naphthol-6-sulfonic acid (Schumar's acid) is added, the mixture is fully stirred to dissolve the 2-naphthol, and then ice is added to reduce the temperature to 20-30 ℃ to obtain a portion of first coupling component liquid. The rest of the steps are the same as the first embodiment. Finally, the product of the disazo acid red dye (P5) is obtained.
In the sixth embodiment, the process is carried out,
an environment-friendly disazo acid red dye has a chemical structure of a general formula (I), wherein R1Is hydrogen, R2Is hydrogen, R3Is a sulfonic acid group, R4Is hydrogen.
EXAMPLE six preparation of disazo acid red dye the procedure was based on example one, except that 2-naphthol was replaced by an equimolar amount of 2-naphthol-7-sulfonic acid in T3 to prepare the disazo acid red dye (P6).
In the seventh embodiment, the process is carried out,
an environment-friendly disazo acid red dye has a chemical structure of a general formula (I), wherein R1Is hydrogen, R2Is hydrogen, R3Is a sulfonic acid group, R4Is hydrogen.
EXAMPLE seven preparation of disazo acid red dye the procedure was based on example one, except that 2-naphthol was replaced by an equimolar amount of 2-naphthol-8-sulfonic acid in T3 to prepare the product disazo acid red dye (P7).
In the eighth embodiment, the method comprises the following steps of,
an environment-friendly disazo acid red dye has a chemical structure of a general formula (I), wherein R1Is hydrogen, R2Is hydrogen, R3Is a carboxyl group, R4Is hydrogen.
EXAMPLE eight preparation of disazo acid red dye procedure is based on example one, except that 2-naphthol is replaced with an equimolar amount of 2-hydroxy-3-naphthoic acid in T3 to prepare the product disazo acid red dye (P8).
In the ninth embodiment, the method of the present invention,
an environment-friendly disazo acid red dye has a chemical structure of a general formula (I), wherein R1Is hydrogen, R2Is hydrogen, R3Is a carboxyl group, R4Is nitro.
The procedure for the preparation of disazo acid red dye of example nine is based on example one and differs therefrom in that T5: taking 120ml of deionized water, adding 9g of 30 wt% of liquid alkali, mixing, heating to 60-90 ℃, wherein the temperature is 75 ℃, adding 15.5g of naphthol AS-BSs, continuously stirring, mixing and stirring for 2 hours until the naphthol is dissolved and uniformly mixed, adding ice, cooling to 10-25 ℃, wherein the temperature is 18 ℃, obtaining a portion of second coupling component liquid, and synthesizing to prepare the product bisazo acid red dye (P9) by the same steps AS the first embodiment.
In the embodiment example ten, the method comprises the following steps of,
an environment-friendly disazo acid red dye has a chemical structure of a general formula (I), wherein R1Is hydrogen, R2Is hydrogen, R3Is hydrogen, R4Is methoxy.
EXAMPLE ten procedures for the preparation of disazo acid red dye based on example one, except that the product disazo acid red dye (P10) was prepared synthetically by substituting an equimolar amount of naphthol AS-OL for the naphthol in T5.
In the eleventh embodiment, the method comprises the following steps of,
an environment-friendly disazo acid red dye has a chemical structure of a general formula (I), wherein R1Is hydrogen, R2Is hydrogen, R3Is hydrogen, R4Is a chlorine atom.
EXAMPLE ten procedures for the preparation of disazo acid red dye based on example one, except that the naphthol was replaced with an equimolar amount of naphthol AS-E in T5, the synthesis was carried out to prepare disazo acid red dye (P11).
In the case of the twelfth embodiment, the following examples are given,
an environment-friendly disazo acid red dye has a chemical structure of a general formula (I), wherein R1Is hydrogen, R2Is hydrogen, R3Is hydrogen, R4Is methyl.
EXAMPLE ten procedures for the preparation of disazo acid red dye based on example one, except that the synthesis was carried out in T5 with an equimolar amount of naphthol AS-D in place of the naphthol to prepare the disazo acid red dye product (P12).
In the thirteenth embodiment, the process is carried out,
an environment-friendly disazo acid red dye has a chemical structure of a general formula (I), wherein R1Is hydrogen, R2Is hydrogen, R3Is hydrogen, R4Is ethoxy.
The preparation method of the disazo acid red dye in example ten is based on example one, and is characterized in that the product disazo acid red dye (P13) is prepared by synthesizing T5 by using naphthol AS-VL instead of naphthol.
The performance of the disazo acid red dye and the currently forbidden 114# acid red dye obtained in the first to the thirteenth embodiments are tested, and the dyeing performance is tested, and the test results are shown in table one. Wherein the light fastness is tested according to the test method recorded in the standard ISO 105-B02, and the wet treatment fastness is finely tested by the test method recorded in the standard ISO 105-C06-B2S and the solubility GB/T21879-2015.
Table one, example one to example thirteen and table of test results of 114# acid red dye
Compared with the performance and dyeing performance of the existing 14# acid red dye, the performance and dyeing performance of products P1-P14 are compared, and the ' molar light absorption coefficient ratio ' and the product of solubility and the molar light absorption coefficient ratio ' can be used for knowing that the color development coefficient of the disazo acid red dye is increased, the dyed fabric is thick and full in color, the dyeing improvement rate of the dye is improved, and meanwhile, the dyed fabric dyed by the dye is thick and full in color, and the light fastness and the wet processing fastness are improved.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, 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 invention.
Claims (9)
1. An environment-friendly disazo acid red dye has a chemical structure shown in a general formula (I):
R1and R2Each independently is: hydrogen, C1～C5Alkyl of (C)1～C5One of alkoxy and chloro of (1);
R3each independently is: one of hydrogen, sulfonic acid group and carboxyl group;
R4each independently is: hydrogen, methyl, methoxy, ethoxy, nitro and chloro.
2. The environmentally friendly disazo acid red according to claim 1Dye, characterized in that R is4Each independently is chloro or hydrogen.
3. The environmentally friendly disazo acid red dye according to claim 1, wherein R is selected from the group consisting of1And R2Each independently is methyl, methoxy or hydrogen.
4. The environmentally friendly disazo acid red dye according to claim 1, wherein R is selected from the group consisting of3Each independently is a sulfonic acid group or hydrogen.
5. The environmentally friendly disazo acid red dye according to claim 1, wherein the raw material comprises a main body A, and the main body A has a general formula (II):
the disazo acid red dye is obtained by performing double nitridation on a main body A and then performing coupling.
6. The method for preparing the environmentally friendly disazo acid red dye according to any one of claims 1 or 5, comprising the steps of,
s1: the 4, 4-diamino-2, 2-disulfonic acid biphenyl derivatives with the general formula (II) are subjected to double nitridation, wherein the general formula (II) is as follows,
R1and R2Each independently is: hydrogen, C1～C5Alkyl of (C)1～C5One of alkoxy and chloro of (1);
s2: coupling reaction of the diazonium salt product obtained in S1 with a 2-naphthol compound having the general formula (III),
R3each independently is: hydrogen, sulfonic group and carboxyl to obtain a primary coupling compound of a general formula (IV),
s3: subjecting the primary conjugate obtained in S2 to a coupling reaction with a coupling component having the general formula (V) shown below,
R4each independently is: hydrogen, methyl, methoxy, ethoxy, nitro and chlorine radical to obtain the secondary coupling compound of the general formula (I),
s4: and separating or enriching the secondary coupling compound obtained in the S3 to obtain the disazo acid red dye.
7. The method for preparing the environmentally friendly disazo acid red dye according to claim 6, wherein the reaction environment temperature of the double nitriding reaction in S1 is 0-40 ℃.
8. The method for preparing the environmentally friendly disazo acid red dye according to claim 6, wherein the pH of the coupling reaction environment in S3 is 5-10, and the temperature of the reaction environment is 15-35 ℃.
9. The use of the environmentally friendly disazo acid red dye according to any one of claims 1 to 5 as an environmentally friendly dye in the dyeing of clothing, in the dyeing of household goods, and in the dyeing of paper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910726501.0A CN110408234B (en) | 2019-08-07 | 2019-08-07 | Environment-friendly disazo acid red dye and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910726501.0A CN110408234B (en) | 2019-08-07 | 2019-08-07 | Environment-friendly disazo acid red dye and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110408234A CN110408234A (en) | 2019-11-05 |
| CN110408234B true CN110408234B (en) | 2020-12-08 |
Family
ID=68366360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910726501.0A Active CN110408234B (en) | 2019-08-07 | 2019-08-07 | Environment-friendly disazo acid red dye and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110408234B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4307167A (en) * | 1980-03-03 | 1981-12-22 | International Business Machines Corporation | Layered electrophotographic plate having tetramethyl benzidene based disazo dye |
| CN1505665A (en) * | 2001-05-23 | 2004-06-16 | 科莱恩有限公司 | colorant combination |
| WO2014065335A1 (en) * | 2012-10-26 | 2014-05-01 | 日本化薬株式会社 | Ink for inkjet textile printing and textile printing method using same |
| JP2014185201A (en) * | 2013-03-22 | 2014-10-02 | Nippon Kayaku Co Ltd | Ink used for inkjet printing and printing method of fiber using the same |
-
2019
- 2019-08-07 CN CN201910726501.0A patent/CN110408234B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4307167A (en) * | 1980-03-03 | 1981-12-22 | International Business Machines Corporation | Layered electrophotographic plate having tetramethyl benzidene based disazo dye |
| CN1505665A (en) * | 2001-05-23 | 2004-06-16 | 科莱恩有限公司 | colorant combination |
| WO2014065335A1 (en) * | 2012-10-26 | 2014-05-01 | 日本化薬株式会社 | Ink for inkjet textile printing and textile printing method using same |
| JP2014185201A (en) * | 2013-03-22 | 2014-10-02 | Nippon Kayaku Co Ltd | Ink used for inkjet printing and printing method of fiber using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110408234A (en) | 2019-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101265369A (en) | A kind of azo dye composition and its application | |
| CN104710813B (en) | Bright yellow disperse dye capable of alkaline dyeing | |
| CN110408234B (en) | Environment-friendly disazo acid red dye and preparation method thereof | |
| US2662074A (en) | Copper complexes of monosulfonamido formazyl dyes | |
| US2022579A (en) | 2,3-hydroxy-naphthoic acid arylamide | |
| Szadowski et al. | Synthesis and properties of disazo dyes derived from water-soluble derivatives of benzidine and 4, 4'-diaminodiphenylurea | |
| CN101519537A (en) | Asymmetric azo complex dyes and process for their preparation | |
| CN108929558B (en) | A kind of disperse scarlet dye compound and its preparation method and application | |
| CN104710812B (en) | Preparation method of disperse dye capable of alkaline dyeing | |
| JP2534908B2 (en) | Azo compound and dyeing method using the same | |
| CN112876875B (en) | Disazo reactive yellow dye and preparation method and application thereof | |
| CN111484752A (en) | Dye compound, dye composition, and preparation method and application thereof | |
| US2590346A (en) | Cupriferous disazo-dyestuffs | |
| US1363886A (en) | Disazo dye | |
| CN115521637B (en) | Compound thick and deep bright printing reactive scarlet dye | |
| CN111500088B (en) | Disperse yellow dye composition, dye product and application | |
| US2392181A (en) | Diphenylamine azo dyestuffs | |
| US2050811A (en) | Primary disazo compounds | |
| US2066986A (en) | Water-insoluble azodyestuffs | |
| US1145072A (en) | Azo dyestuffs insoluble in water and process of making them. | |
| US2394246A (en) | Disazo dyestuffs | |
| KR960005658B1 (en) | Process for producing reactive azo-dye | |
| US1815133A (en) | New azo dyestuffs and process of preparing them | |
| CN114085547A (en) | Green intermediate-temperature reactive dye and preparation method thereof | |
| US1122564A (en) | Condensation products from the arylamids of 2.3-oxynaphthoic acid and formaldehyde and azo dyestuffs therefrom and process of making same. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |