CN115353751A - Preparation method of monoazo disperse dye - Google Patents
Preparation method of monoazo disperse dye Download PDFInfo
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- CN115353751A CN115353751A CN202211034982.7A CN202211034982A CN115353751A CN 115353751 A CN115353751 A CN 115353751A CN 202211034982 A CN202211034982 A CN 202211034982A CN 115353751 A CN115353751 A CN 115353751A
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- disperse dye
- temperature
- reaction product
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- sulfuric acid
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- 239000000986 disperse dye Substances 0.000 title claims abstract description 84
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 105
- 238000005859 coupling reaction Methods 0.000 claims abstract description 89
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims abstract description 60
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000008878 coupling Effects 0.000 claims abstract description 25
- 238000010168 coupling process Methods 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 16
- 230000009466 transformation Effects 0.000 claims abstract description 15
- 230000002378 acidificating effect Effects 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 105
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 37
- 239000000047 product Substances 0.000 claims description 30
- 239000005457 ice water Substances 0.000 claims description 29
- 238000001179 sorption measurement Methods 0.000 claims description 19
- 238000010790 dilution Methods 0.000 claims description 16
- 239000012895 dilution Substances 0.000 claims description 16
- 239000003463 adsorbent Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- 238000001816 cooling Methods 0.000 description 24
- 238000005406 washing Methods 0.000 description 18
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 16
- NSVHSAUVIFTVPN-UHFFFAOYSA-N 3-[n-(2-cyanoethyl)anilino]propanenitrile Chemical compound N#CCCN(CCC#N)C1=CC=CC=C1 NSVHSAUVIFTVPN-UHFFFAOYSA-N 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- 230000007935 neutral effect Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000975 dye Substances 0.000 description 11
- LOCWBQIWHWIRGN-UHFFFAOYSA-N 2-chloro-4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1Cl LOCWBQIWHWIRGN-UHFFFAOYSA-N 0.000 description 10
- UJTRMFNKHYGXDI-UHFFFAOYSA-N 2-[n-(2-cyanoethyl)anilino]ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCN(CCC#N)C1=CC=CC=C1 UJTRMFNKHYGXDI-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- CWCYJRVQCBCDTJ-UHFFFAOYSA-N methyl 3-[n-(2-cyanoethyl)anilino]propanoate Chemical compound COC(=O)CCN(CCC#N)C1=CC=CC=C1 CWCYJRVQCBCDTJ-UHFFFAOYSA-N 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- LLFYBLBUVUYAQU-UHFFFAOYSA-N 2-[3-acetamido-n-(2-cyanoethyl)anilino]ethyl acetate Chemical compound CC(=O)NC1=CC=CC(N(CCOC(C)=O)CCC#N)=C1 LLFYBLBUVUYAQU-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- RRGWFPOSTSQIQE-UHFFFAOYSA-N 2-[n-(2-cyanoethyl)anilino]ethyl acetate Chemical compound CC(=O)OCCN(CCC#N)C1=CC=CC=C1 RRGWFPOSTSQIQE-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- BZQVBRPPYCAVSE-UHFFFAOYSA-N [N-(2-cyanoethyl)-2-ethylanilino] acetate Chemical compound C(#N)CCN(C1=C(C=CC=C1)CC)OC(C)=O BZQVBRPPYCAVSE-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 2
- BIXZHMJUSMUDOQ-UHFFFAOYSA-N dichloran Chemical compound NC1=C(Cl)C=C([N+]([O-])=O)C=C1Cl BIXZHMJUSMUDOQ-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- ZXRCAYWYTOIRQS-UHFFFAOYSA-N hydron;phenol;chloride Chemical compound Cl.OC1=CC=CC=C1 ZXRCAYWYTOIRQS-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- YGGXZTQSGNFKPJ-UHFFFAOYSA-N methyl 2-naphthalen-1-ylacetate Chemical compound C1=CC=C2C(CC(=O)OC)=CC=CC2=C1 YGGXZTQSGNFKPJ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber 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
- C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
-
- 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
- C09B29/0805—Amino benzenes free of acid groups
- C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
- C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
- C09B29/0811—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino
-
- 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
- C09B29/0805—Amino benzenes free of acid groups
- C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
- C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
- C09B29/0811—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino
- C09B29/0823—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino substituted by CN
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of a monoazo disperse dye. The preparation method comprises the following steps: step 1): diazotizing a compound shown as a formula (I) and nitrosyl sulfuric acid under an acidic condition to obtain a diazo reaction product; step 2): carrying out coupling reaction on the diazo reaction product and a coupling component shown in a formula (II) to obtain a coupling reaction product; step 3): and (3) carrying out crystal transformation on the coupling reaction product to obtain the monoazo disperse dye. The monoazo disperse dye prepared by the preparation method has the characteristics of environment-friendly process, excellent dyeing property and high purity and yield. Furthermore, the preparation method of the monoazo disperse dye is simple and easy to implement, and raw materials are easy to obtain, so that the monoazo disperse dye is suitable for mass production.
Description
Technical Field
The invention relates to a preparation method of a monoazo disperse dye, belonging to the field of dye synthesis.
Background
The disperse dye is the most important variety in the dye industry, not only is the special dye for terylene, but also can be applied to printing and dyeing of synthetic fibers such as acetate fiber, acrylic fiber, polypropylene fiber and the like, and has a large market proportion in the dye. The monoazo disperse dye is widely applied due to simple preparation process and low cost, has large market proportion and wide application prospect.
Chinese patent CN 101117446A discloses a synthesis method of an azo disperse dye monomer compound, which solves the problems of high cost and energy consumption of the old process by improving the preparation process, but the diazo liquid of the azo disperse dye monomer compound directly participates in the coupling reaction after being prepared, the coupling reaction is completed by dripping the diazo liquid into the coupling liquid, and the coupling reaction product is not subjected to crystal transformation and direct washing, so that the yield and the purity of the final product are low, organic chlorine and the like in the product exceed standards, the azo disperse dye monomer compound is not environment-friendly, and the dyeing fastness of the product is poor.
Therefore, the research of a clean, high-quality and good-color-fastness preparation method of the monoazo disperse dye is a technical problem to be solved urgently.
Disclosure of Invention
Problems to be solved by the invention
In view of the technical problems in the prior art, the invention provides a preparation method of a monoazo disperse dye, and the monoazo disperse dye prepared by the method has the characteristics of environment-friendly process, excellent dyeing performance, and high product quality and yield.
Means for solving the problems
The invention provides a preparation method of a monoazo disperse dye, which comprises the following steps:
step 1): diazotizing a compound shown as a formula (I) and nitrosyl sulfuric acid under an acidic condition to obtain a diazo reaction product;
in the formula (I), R 1 And R 2 Each independently is hydrogen or halogen;
step 2): carrying out coupling reaction on the diazo reaction product and a coupling component shown in a formula (II) to obtain a coupling reaction product;
in the formula (II), M 1 Is hydrogen or C 1 ～C 4 Alkanoylamino of (a), M 2 、M 3 Each independently is C substituted or unsubstituted by a substituent 1 ～C 4 The substituent is cyano, C 1 -C 4 Alkanoyloxy or benzoyloxy of (a);
and step 3): and (3) carrying out crystal transformation on the coupling reaction product to obtain the monoazo disperse dye.
The preparation method of the monoazo disperse dye comprises the following steps of 1) adding a compound shown as a formula (I) into a mixed solution of nitrosyl sulfuric acid and concentrated sulfuric acid for reaction; preferably, the temperature of the mixed solution of nitrosyl sulfuric acid and concentrated sulfuric acid is-5-20 ℃, and the input time of the compound shown in the formula (I) is 1.5-5 h; more preferably, the concentrated sulfuric acid is sulfuric acid having a concentration of 90% or more.
The preparation method of the monoazo disperse dye provided by the invention is characterized in that the reaction temperature in the step 1) is-2-35 ℃, and the reaction time is 2-24 h.
The preparation method of the monoazo disperse dye according to the invention, wherein the step 2) comprises adding the coupling component shown in the formula (II) into the diazo reaction product, preferably, the coupling component shown in the formula (II) is added in the form of a coupling component solution shown in the formula (II), and more preferably, the coupling reaction temperature is-5-45 ℃; the reaction time is 3-8 h.
According to the preparation method of the monoazo disperse dye, the monoazo disperse dye is obtained by heating the coupling reaction product to 100-120 ℃ and pressurizing to 0.1-0.2 Mpa for heat preservation and crystal transformation.
According to the preparation method of the monoazo disperse dye, the temperature of the coupling reaction product is raised to 100-120 ℃ in a stepped temperature raising mode; preferably, the stepwise temperature rise comprises keeping the temperature at less than 40 ℃ for 4-12h; then heating to 40-55 ℃ and preserving heat for 4-12h; finally, the temperature is raised to 100-120 ℃ and the temperature is preserved for 1-10h.
The preparation method of the monoazo disperse dye, provided by the invention, comprises an adsorption step between the step 1) and the step 2), wherein the adsorption step comprises adsorbing the diazo reaction product by using an adsorbent and then removing solid matters to obtain an adsorbed product;
and then carrying out coupling reaction on the adsorption product and a coupling component shown in a formula (II) to obtain a coupling reaction product.
The preparation method of the monoazo disperse dye provided by the invention is characterized in that the addition amount of the adsorbent is 3-4% of the compound shown in the formula (I) in percentage by mass.
According to the preparation method of the monoazo disperse dye, the solid matter is removed after the adsorption is finished and the mixture is diluted by using an ice-water mixture; preferably, the amount of the ice-water mixture added is 1.5 to 5 times the amount of the compound of formula (I).
The invention also provides a monoazo disperse dye, which is prepared by the preparation method; wherein the yield of the monoazo disperse dye is more than 95%, and the purity of the monoazo disperse dye is more than 96%.
ADVANTAGEOUS EFFECTS OF INVENTION
The monoazo disperse dye prepared by the preparation method has the characteristics of environment-friendly process, excellent dyeing property and high purity and yield.
Furthermore, the preparation method of the monoazo disperse dye is simple and easy to implement, and raw materials are easy to obtain, so that the monoazo disperse dye is suitable for mass production.
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, methods, means, devices and steps which are well known to those skilled in the art have not been described in detail so as not to obscure the invention.
It should be noted that:
in the present specification, the numerical range represented by "a value a to B value" means a range including the endpoint value A, B. All units used in the invention are international standard units unless otherwise stated, and numerical values and numerical ranges appearing in the invention should be understood to include errors allowed in industrial production.
Reference in the specification to "some specific/preferred embodiments," "other specific/preferred embodiments," "embodiments," and so forth, means that a particular element (e.g., feature, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
The invention firstly provides a preparation method of a monoazo disperse dye, which comprises the following steps:
step 1): diazotizing a compound shown as a formula (I) and nitrosyl sulfuric acid under an acidic condition to obtain a diazo reaction product;
in the formula (I), R 1 And R 2 Each independently hydrogen or halogen;
step 2): carrying out coupling reaction on the diazo reaction product and a coupling component shown in a formula (II) to obtain a coupling reaction product;
in the formula (II), M 1 Is hydrogen or C 1 ～C 4 Alkanoylamino of (a), M 2 、M 3 Each independently is C substituted or unsubstituted by a substituent 1 ～C 4 The substituent is cyano, C 1 -C 4 Alkanoyloxy or benzoyloxy of (a);
step 3): and (3) carrying out crystal transformation on the coupling reaction product to obtain the monoazo disperse dye.
The monoazo disperse dye prepared by the preparation method has the characteristics of environment-friendly process, excellent dyeing property and high purity and yield. Furthermore, the preparation method of the monoazo disperse dye is simple and easy to implement, and raw materials are easy to obtain, so that the monoazo disperse dye is suitable for mass production.
In some specific embodiments, the step 1) comprises adding the compound represented by the formula (I) into a mixed solution of nitrosyl sulfuric acid and concentrated sulfuric acid to react; preferably, the temperature of the mixed solution of nitrosyl sulfuric acid and concentrated sulfuric acid is-5 to 20 ℃, for example: -2 ℃, 0 ℃, 2 ℃, 5 ℃, 8 ℃, 10 ℃, 12 ℃, 15 ℃, 18 ℃ and the like; the compound of formula (I) is dosed for 1.5 to 5 hours, for example: 2h, 2.5h, 3h, 3.5h, 4h, 4.5h and the like. The nitrosyl sulfuric acid used in the reaction process can replace sodium nitrite, so that the reaction cost is reduced, the salt content in the product is reduced, and the product quality is improved.
Further, in the present invention, the concentrated sulfuric acid used in the step 1) is sulfuric acid having a concentration of 90% or more, and some water may be appropriately added when preparing a mixed solution of nitrosyl sulfuric acid and sulfuric acid. Specifically, the mass ratio of the concentrated sulfuric acid to the nitrosyl sulfuric acid may be 1.5 to 2.5, for example: 1.8, 1:2, 1.
Further, in some specific embodiments, the reaction temperature of step 1) is from-2 to 35 ℃, for example: 0 deg.C, 5 deg.C, 10 deg.C, 15 deg.C, 20 deg.C, 25 deg.C, 30 deg.C, etc.; the reaction time is 2 to 24 hours, for example: 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h and the like. When the reaction temperature of the step 1) is-2-35 ℃ and the reaction time is 2-24 h, the reaction can be completed to obtain the required diazo reaction product.
In some specific embodiments, the step 2) comprises adding the coupling component represented by formula (II) to the diazo reaction product, preferably at a temperature of-5 to 45 ℃, for example: 0 deg.C, 5 deg.C, 10 deg.C, 15 deg.C, 20 deg.C, 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, etc.; the coupling reaction time is 3 to 8 hours, for example: 4h, 5h, 6h, 7h and the like. The coupling reaction temperature is-5-45 ℃; when the coupling reaction time is 3-8 h, the coupling reaction can be completed, and the required coupling reaction product is obtained.
Specifically, the coupling component represented by the formula (II) is added in the form of a coupling component solution represented by the formula (II). In particular, it may be carried out at a temperature of from-5 to 15 ℃, for example: dropwise adding the coupling component solution shown in the formula (II) into the diazo reaction product at the temperature of-2 ℃, 0 ℃, 2 ℃, 4 ℃,6 ℃, 8 ℃, 10 ℃, 12 ℃ and the like.
Specifically, the coupling component represented by the formula (II) is mixed with concentrated sulfuric acid in the presence of an ice-water mixture to obtain a coupling component solution represented by the formula (II). The temperature and time of mixing are not particularly limited in the present invention, and the temperature of mixing is preferably 20 ℃ or less, for example: 0 ℃, 2 ℃, 4 ℃,6 ℃, 8 ℃, 10 ℃, 12 ℃, 14 ℃, 16 ℃, 18 ℃ and the like; the mixing time is 0.1-2h, for example: 0.5h, 0.8h, 1h, 1.5h, 1.8h and the like.
Further, in the present invention, the concentrated sulfuric acid used in the step 2) is sulfuric acid having a concentration of 90% or more. Specifically, the mass ratio of the coupling component represented by the formula (II) to the concentrated sulfuric acid may be 1:1.
The method of adding the coupling component shown in the formula (II) to the diazo reaction product replaces the traditional mode of dropwise adding the diazo reaction product to the coupling component, so that the recrystallized and precipitated coupling component with small particle size can be fully reacted, and the quality and the yield of the product are improved.
Further, in some embodiments, the coupling reaction product is heated to a temperature of 100 to 120 ℃, for example: 102 ℃, 105 ℃, 108 ℃, 110 ℃, 112 ℃, 115 ℃, 118 ℃ and the like; and pressurizing 0.1 to 0.2MPa, for example: 0.12Mpa, 0.14Mpa, 0.16Mpa, 0.18Mpa, etc., and carrying out heat preservation and crystal transformation to obtain the monoazo disperse dye. According to the invention, the crystal form of the product is changed through crystal transformation, so that the fastness of the monoazo disperse dye is more excellent.
Generally, the coupling reaction product starts to be subjected to crystal transformation when the temperature is raised to 90 ℃, but the temperature is set to be 100-120 ℃ in the invention, so that the crystal transformation can be performed more completely, and the fastness of the obtained monoazo disperse dye is more excellent.
Specifically, heating the coupling reaction product to 100-120 ℃ in a step heating mode; preferably, said stepwise increasing of temperature comprises increasing the temperature of the reaction mixture at less than 40 ℃, for example: keeping the temperature at 20 deg.C, 22 deg.C, 25 deg.C, 28 deg.C, 30 deg.C, 32 deg.C, 35 deg.C, 38 deg.C for 4-12h, such as: 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h and the like; then the temperature is raised to 40-55 ℃, for example: keeping the temperature at 42 deg.C, 45 deg.C, 48 deg.C, 50 deg.C, 52 deg.C for 4-16h, such as: 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h and the like; finally, the temperature is raised to 100-120 ℃, for example: preserving the heat at 102 ℃, 105 ℃, 108 ℃, 110 ℃, 112 ℃, 115 ℃, 118 ℃ and the like for 1-10h, for example: 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, and the like.
The common one-step temperature rise is to directly raise the temperature to the crystal transformation temperature, while the step temperature rise mode of the invention is to divide the temperature into a plurality of sections, and the temperature is preserved in each temperature section after the temperature is raised to a certain temperature, and the step temperature rise is favorable for complete crystallization of the disperse dye, favorable for complete crystal transformation of the dye after 100 ℃ and favorable for improving the high-temperature dispersion stability of the dye.
Further, in other specific embodiments, between the step 1) and the step 2), an adsorption step is further included, wherein the adsorption step includes removing solid substances after adsorbing the diazo reaction product by using an adsorbent to obtain an adsorbed product; and then carrying out coupling reaction on the adsorption product and a coupling component shown in a formula (II) to obtain a coupling reaction product.
The adsorbent is used for adsorbing the diazo reaction product, so that waste residues in the diazo reaction product can be adsorbed, the content of pollutants such as organic chlorine, phenol and the like in a finished product is reduced, and the obtained product is more environment-friendly. The adsorbent used includes, but is not limited to, activated carbon, diatomaceous earth, molecular sieves, and the like.
Specifically, the adding amount of the adsorbent is 3% -4% of the compound of the formula (I) in percentage by mass, for example: 3.2%, 3.5%, 3.8%, etc. When the addition amount of the adsorbent is 3-4% of that of the compound shown in the formula (I), the waste residue in the diazo reaction product can be effectively adsorbed, and the content of pollutants such as organic chlorine, phenol and the like in a finished product is reduced.
In some embodiments, after adsorption is complete, dilution is performed with an ice water mixture, and then the solid material is removed; preferably, the ice-water mixture is added in an amount of 1.5 to 5 times the amount of the compound of formula (I), for example: 2 times, 2.5 times, 3 times, 3.5 times, 4 times, 4.5 times, etc.
In the invention, the purpose of adding the ice-water mixture for dilution is to reduce the concentration of the diazonium liquid so as to ensure that the diazonium liquid and the coupling reactant react more fully; meanwhile, the acidity of the diazo liquid can be improved, and incomplete reaction of coupling reaction products caused by over-low precipitation of the acidity of the diazo liquid is prevented.
Further, the invention also provides a monoazo disperse dye, which is prepared by the preparation method; wherein the yield of the monoazo disperse dye is 95% or more, and the purity of the monoazo disperse dye is 96% or more.
The structural general formula of the monoazo disperse dye is shown as follows:
wherein R is 1 And R 2 Each independently of the other being hydrogen or halogen, M 1 Is hydrogen or C 1 ～C 4 Alkanoylamino of (a), M 2 、M 3 Each independently substituted or unsubstituted C 1 ～C 4 The substituent is cyano, C 1 -C 4 Alkanoyloxy or benzoyloxy of (a).
In addition, the monoazo disperse dye prepared by the preparation method can be used for dyeing and printing fabrics.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by manufacturers, and are all conventional products which can be obtained commercially or prepared conventionally.
Example 1:
respectively taking 26g of water and 80g of sulfuric acid with the concentration of 98%, placing the water and the sulfuric acid into a three-neck flask, starting stirring and cooling, adding 163g of nitrosyl sulfuric acid when the temperature is reduced to 10 ℃, uniformly stirring, adding 60g of 2-chloro-4-nitroaniline, controlling the temperature at 15 ℃ during feeding, controlling the feeding time to be 1.5h, keeping the temperature of a reaction system at 25 ℃ after the feeding is finished, and reacting for 6h to obtain a diazo reaction product.
And after the reaction is finished, adding 2g of activated carbon into the diazo reaction product, stirring for 1.5h, adding 260g of ice-water mixture for dilution, and performing suction filtration after the dilution is finished to obtain an adsorption product.
100g of the ice-water mixture and 98% sulfuric acid are respectively put into a flask, the temperature is reduced to 10 ℃, 70g of N, N-dicyanoethylaniline is added, the temperature is kept at 10 ℃, stirring is carried out for 0.5h until the N, N-dicyanoethylaniline is completely dissolved, and then the N, N-dicyanoethylaniline solution is obtained and stands for standby.
And (3) cooling the obtained N, N-dicyanoethylaniline solution to 2 ℃, slowly dripping the solution into the diazo reaction product, and keeping the system temperature at 0 ℃ for reaction for 5 hours after dripping to obtain a coupling reaction product.
Slowly heating the obtained coupling reaction product to 33 ℃, preserving heat for 8h, slowly heating to 40 ℃, preserving heat for 8h, heating to 55 ℃, reacting for 4h, heating to 110 ℃ under the condition of 0.1Mpa vapor pressure, preserving heat for 2h, heating to 120 ℃ under the condition of 0.2Mpa vapor pressure, preserving heat for 2h, washing with 70 ℃ hot water until the pH value is neutral, and drying to obtain the monoazo disperse dye, wherein the structural formula is shown as (III-1) and is marked as S1.
Example 2:
respectively taking 26g of water and 80g of sulfuric acid with the concentration of 98 percent, putting the water and the sulfuric acid into a three-neck flask, starting stirring and cooling, adding 163g of nitrosyl sulfuric acid when the temperature is reduced to 15 ℃, uniformly stirring, adding 60g of 2-chloro-4-nitroaniline, controlling the temperature at 15 ℃ during feeding, feeding for 2h, and keeping the temperature of a reaction system at 20 ℃ after the feeding for reacting for 6h to obtain a diazo reaction product.
And after the reaction is finished, adding 2g of molecular sieve into the diazo reaction product, stirring for 4h, adding 300g of ice-water mixture, diluting, and performing suction filtration to obtain an adsorption product after dilution is finished.
100g of the ice-water mixture and 98% sulfuric acid are respectively put into a flask, the temperature is reduced to 10 ℃, 80g of N-cyanoethyl-N-acetoxyethylaniline is added, the temperature is kept at 10 ℃, stirring is carried out for 0.5h until the N-cyanoethyl-N-acetoxyethylaniline is completely dissolved, and then the N-cyanoethyl-N-acetoxyethylaniline solution is obtained and stands for standby.
And (3) cooling the obtained N-cyanoethyl-N-acetoxyethylaniline solution to 5 ℃, slowly dripping the solution into the diazo reaction product, and keeping the system temperature at 10 ℃ after dripping is finished to react for 8 hours to obtain a coupling reaction product.
Slowly heating the obtained coupling reaction product to 33 ℃, preserving heat for 8h, slowly heating to 40 ℃, preserving heat for 8h, heating to 55 ℃, reacting for 4h, heating to 110 ℃ under the condition of 0.1Mpa vapor pressure, preserving heat for 2h, heating to 120 ℃ under the condition of 0.2Mpa vapor pressure, preserving heat for 2h, washing with 70 ℃ hot water until the pH value is neutral, and drying to obtain the monoazo disperse dye, wherein the structural formula (III-2) is shown as S2.
Example 3:
respectively taking 26g of water and 80g of sulfuric acid with the concentration of 98 percent, putting the water and the sulfuric acid into a three-neck flask, starting stirring and cooling, adding 163g of nitrosyl sulfuric acid when the temperature is reduced to 15 ℃, uniformly stirring, adding 60g of 2-chloro-4-nitroaniline, controlling the temperature at 20 ℃ during feeding, feeding for 3h, and keeping the temperature of a reaction system at 20 ℃ after the feeding for reacting for 6h to obtain a diazo reaction product.
After the reaction is finished, 2g of diatomite is added into the diazo reaction product, the mixture is stirred for 3h, 280g of ice-water mixture is added for dilution, and after the dilution is finished, suction filtration is carried out to obtain an adsorption product.
100g of the ice-water mixture and 98% sulfuric acid are respectively put into a flask, the temperature is reduced to 15 ℃, 85g of N-cyanoethyl-N-methoxycarbonylethylaniline is added, the temperature is kept at 10 ℃, the mixture is stirred for 1 hour until the mixture is completely dissolved to obtain N-cyanoethyl-N-methoxycarbonylethylaniline solution, and the solution is kept stand for standby.
And (3) cooling the obtained N-cyanoethyl-N-methoxycarbonylethylaniline solution to 10 ℃, slowly dripping the solution into the diazo reaction product, and keeping the system temperature at 15 ℃ after dripping is finished to react for 12 hours to obtain a coupling reaction product.
Slowly heating the obtained coupling reaction product to 33 ℃, preserving heat for 8h, slowly heating to 40 ℃, preserving heat for 8h, heating to 55 ℃, reacting for 4h, heating to 110 ℃ under the condition of 0.1Mpa vapor pressure, preserving heat for 2h, heating to 120 ℃ under the condition of 0.2Mpa vapor pressure, preserving heat for 2h, washing with 70 ℃ hot water until the pH value is neutral, and drying to obtain the monoazo disperse dye, wherein the structural formula (III-3) is shown as S3.
Example 4:
respectively taking 26g of water and 85g of 98% sulfuric acid, placing the water and the sulfuric acid into a three-neck flask, starting stirring and cooling, adding 163g of nitrosyl sulfuric acid when the temperature is reduced to 20 ℃, uniformly stirring, adding 60g of 2-chloro-4-nitroaniline, controlling the temperature at 20 ℃ during feeding, controlling the feeding time to be 1.5h, keeping the temperature of a reaction system at 35 ℃ after the feeding is finished, and reacting for 12h to obtain a diazo reaction product.
And after the reaction is finished, adding 2g of activated carbon into the diazo reaction product, stirring for 5h, adding 260g of ice-water mixture for dilution, and performing suction filtration after the dilution is finished to obtain an adsorption product.
And (3) putting 100g of the ice-water mixture and 98% sulfuric acid into a flask, cooling to 15 ℃, adding 42g of N, N-dimethylaniline, keeping the temperature at 15 ℃, stirring for 1 hour until the N, N-dimethylaniline is completely dissolved to obtain an N, N-dimethylaniline solution, and standing for later use.
And (3) cooling the obtained N, N-dimethylaniline solution to 8 ℃, slowly dripping the solution into the diazo reaction product, and keeping the system temperature at 10 ℃ after dripping is finished to react for 15 hours to obtain a coupling reaction product.
Slowly heating the obtained coupling reaction product to 33 ℃, preserving heat for 8h, slowly heating to 40 ℃, preserving heat for 8h, heating to 55 ℃, reacting for 4h, heating to 110 ℃ under the condition of 0.1Mpa vapor pressure, preserving heat for 2h, heating to 120 ℃ under the condition of 0.2Mpa vapor pressure, preserving heat for 2h, washing with 70 ℃ hot water until the pH value is neutral, and drying to obtain the monoazo disperse dye, wherein the structural formula is shown as (III-4) and is marked as S4.
Example 5:
respectively taking 26g of water and 85g of 98% sulfuric acid, placing the water and the sulfuric acid into a three-neck flask, starting stirring and cooling, adding 163g of nitrosyl sulfuric acid when the temperature is reduced to 20 ℃, uniformly stirring, adding 55g of 2,6-dichloro-4-nitroaniline, controlling the temperature at 20 ℃ during feeding, feeding for 3h, and keeping the temperature of a reaction system at 20 ℃ after feeding for 6h to obtain a diazo reaction product.
And after the reaction is finished, adding 2g of molecular sieve into the diazo reaction product, stirring for 2h, adding 260g of ice-water mixture for dilution, and performing suction filtration after the dilution is finished to obtain an adsorption product.
100g of the ice-water mixture and 98% sulfuric acid are respectively put into a flask, the temperature is reduced to 15 ℃, 53g of N, N-dicyanoethylaniline is added, the temperature is kept at 15 ℃, the mixture is stirred for 1 hour until the mixture is completely dissolved to obtain N, N-dicyanoethylaniline solution, and the solution is kept stand for standby.
And (3) cooling the obtained N, N-dicyanoethylaniline solution to 15 ℃, slowly dripping the solution into the diazo reaction product, and keeping the system temperature at 15 ℃ after dripping is finished to react for 12 hours to obtain a coupling reaction product.
Slowly heating the obtained coupling reaction product to 33 ℃, preserving heat for 8h, slowly heating to 40 ℃, preserving heat for 8h, heating to 55 ℃, reacting for 4h, heating to 110 ℃ under the condition of 0.1Mpa vapor pressure, preserving heat for 2h, heating to 120 ℃ under the condition of 0.2Mpa vapor pressure, preserving heat for 2h, washing with 70 ℃ hot water until the pH value is neutral, and drying to obtain the monoazo disperse dye, wherein the structural formula is shown as (III-5) and is marked as S5.
Example 6:
respectively taking 26g of water and 85g of 98% sulfuric acid, placing the water and the sulfuric acid into a three-neck flask, starting stirring and cooling, adding 163g of nitrosyl sulfuric acid when the temperature is reduced to 20 ℃, uniformly stirring, adding 55g of 2-chloro-4-nitroaniline, controlling the temperature at 15 ℃ during feeding, feeding for 2h, and keeping the temperature of a reaction system at 20 ℃ after feeding for reaction for 6h to obtain a diazo reaction product.
And after the reaction is finished, adding 2g of diatomite into the diazo reaction product, stirring for 2h, adding 260g of ice-water mixture for dilution, and performing suction filtration after the dilution is finished to obtain an adsorption product.
100g of ice-water mixture and 98% sulfuric acid are respectively put into a flask, the temperature is reduced to 15 ℃, 96g of 3-acetamido-N-cyanoethyl-N-acetoxyethyl aniline is added, the temperature is maintained at 15 ℃, stirring is carried out for 1h until the 3-acetamido-N-cyanoethyl-N-acetoxyethyl aniline is completely dissolved, and then 3-acetamido-N-cyanoethyl-N-acetoxyethyl aniline solution is obtained and stands for standby.
And (3) cooling the obtained 3-acetamido-N-cyanoethyl-N-acetoxyethylaniline solution to 15 ℃, slowly dripping the solution into the diazo reaction product, and keeping the system temperature at 15 ℃ after dripping is finished to react for 10 hours to obtain a coupling reaction product.
Slowly heating the obtained coupling reaction product to 33 ℃, preserving heat for 8h, slowly heating to 40 ℃, preserving heat for 8h, heating to 55 ℃, reacting for 4h, heating to 110 ℃ under the condition of 0.1Mpa vapor pressure, preserving heat for 2h, heating to 120 ℃ under the condition of 0.2Mpa vapor pressure, preserving heat for 2h, washing with 70 ℃ hot water until the pH value is neutral, and drying to obtain the monoazo disperse dye, wherein the structural formula is shown as (III-6) and is marked as S6.
Example 7:
respectively taking 26g of water and 85g of sulfuric acid with the concentration of 98% to place in a three-neck flask, starting stirring and cooling, adding 163g of nitrosyl sulfuric acid when the temperature is reduced to 20 ℃, uniformly stirring, adding 55g of p-nitroaniline, controlling the temperature at 0 ℃ during feeding for 2h, keeping the temperature of a reaction system at 0 ℃ after feeding, and reacting for 6h to obtain a diazo reaction product.
And after the reaction is finished, adding 2g of diatomite into the diazo reaction product, stirring for 2h, adding 260g of ice-water mixture for dilution, and performing suction filtration after the dilution is finished to obtain an adsorption product.
100g of the ice-water mixture and 98% sulfuric acid are respectively put into a flask, the temperature is reduced to 8 ℃, 122g of N-cyanoethyl-N-benzoyloxyethylaniline is added, the temperature is kept at 8 ℃, stirring is carried out for 1 hour until the N-cyanoethyl-N-benzoyloxyethylaniline is completely dissolved, and then the N-cyanoethyl-N-benzoyloxyethylaniline solution is obtained and stands for standby.
And (3) cooling the obtained N-cyanoethyl-N-benzoyl oxyethylaniline solution to 5 ℃, slowly dripping the solution into the diazo reaction product, and keeping the system temperature at 5 ℃ for reaction for 10 hours after dripping to obtain a coupling reaction product.
Slowly heating the obtained coupling reaction product to 33 ℃, preserving heat for 8h, slowly heating to 40 ℃, preserving heat for 8h, heating to 55 ℃, reacting for 4h, heating to 110 ℃ under the condition of 0.1Mpa vapor pressure, preserving heat for 2h, heating to 120 ℃ under the condition of 0.2Mpa vapor pressure, preserving heat for 2h, washing with 70 ℃ hot water until the pH value is neutral, and drying to obtain the monoazo disperse dye, wherein the structural formula is shown as (III-7) and is marked as S7.
Comparative example 1
Respectively taking 26g of water and 80g of sulfuric acid with the concentration of 98 percent, putting the water and the sulfuric acid into a three-neck flask, starting stirring and cooling, adding 163g of nitrosyl sulfuric acid when the temperature is reduced to 10 ℃, uniformly stirring, adding 60g of 2-chloro-4-nitroaniline, controlling the temperature at 15 ℃ during feeding, feeding for 1.5h, and keeping the temperature of a reaction system at 25 ℃ for reacting for 6h after the feeding is finished to obtain a diazo reaction product.
100g of the ice-water mixture and 98% sulfuric acid are respectively put into a flask, the temperature is reduced to 10 ℃, 70g of N, N-dicyanoethylaniline is added, the temperature is kept at 10 ℃, stirring is carried out for 0.5h until the N, N-dicyanoethylaniline is completely dissolved, and then the N, N-dicyanoethylaniline solution is obtained and stands for standby.
And dropwise adding the obtained diazo reaction product into the N, N-dicyanoethylaniline solution, and after dropwise adding, carrying out heat preservation reaction for 3 hours to obtain a coupling reaction product.
And filtering the obtained coupling reaction product, washing until the pH value is neutral, and drying to obtain the monoazo disperse dye, wherein the structural formula of the monoazo disperse dye is shown as (III-1) and is marked as D1.
Comparative example 2:
respectively taking 26g of water and 80g of sulfuric acid with the concentration of 98%, placing the water and the sulfuric acid into a three-neck flask, starting stirring and cooling, adding 163g of nitrosyl sulfuric acid when the temperature is reduced to 15 ℃, uniformly stirring, adding 60g of 2-chloro-4-nitroaniline, controlling the temperature at 15 ℃ during feeding, controlling the feeding time to be 2h, and keeping the temperature of a reaction system at 20 ℃ after the feeding is finished to react for 6h to obtain a diazo reaction product.
100g of ice-water mixture and 98% sulfuric acid are respectively put into a flask, the temperature is reduced to 10 ℃, 80g of N-cyanoethyl-N-acetoxyl ethyl aniline is added, the temperature is kept at 10 ℃, stirring is carried out for 0.5h until the N-cyanoethyl-N-acetoxyl ethyl aniline is completely dissolved to obtain N-cyanoethyl-N-acetoxyl ethyl aniline solution, and the solution is kept stand for standby.
Slowly dripping the obtained diazo reaction product into N-cyanoethyl-N-acetoxyl ethylaniline solution, and keeping the system temperature at 10 ℃ for reacting for 8h after finishing dripping to obtain a coupling reaction product.
And filtering the obtained coupling reaction product, washing until the pH value is neutral, and drying to obtain the monoazo disperse dye, wherein the structural formula of the monoazo disperse dye is shown as (III-2) and is marked as D2.
Comparative example 3:
respectively taking 26g of water and 80g of sulfuric acid with the concentration of 98 percent, putting the water and the sulfuric acid into a three-neck flask, starting stirring and cooling, adding 163g of nitrosyl sulfuric acid when the temperature is reduced to 15 ℃, uniformly stirring, adding 60g of 2-chloro-4-nitroaniline, controlling the temperature at 20 ℃ during feeding, reacting for 3h, keeping the temperature of a reaction system at 20 ℃ after the feeding is finished, and reacting for 6h to obtain a diazo reaction product after the reaction is finished.
100g of the ice-water mixture and 98% sulfuric acid are respectively put into a flask, the temperature is reduced to 15 ℃, 85g of N-cyanoethyl-N-methoxycarbonylethylaniline is added, the temperature is kept at 10 ℃, stirring is carried out for 1h until the N-cyanoethyl-N-methoxycarbonylethylaniline is completely dissolved, and then the N-cyanoethyl-N-methoxycarbonylethylaniline solution is obtained and stands for standby.
Slowly dripping the obtained diazo reaction product into N-cyanoethyl-N-methoxycarbonylethylaniline solution, and keeping the temperature for reaction for 12 hours after finishing dripping to obtain a coupling reaction product.
And filtering the obtained coupling reaction product, washing until the pH value is neutral, and drying to obtain the monoazo disperse dye, wherein the structural formula of the monoazo disperse dye is shown as (III-3) and is marked as D3.
Comparative example 4:
respectively taking 26g of water and 85g of 98% sulfuric acid, placing the water and the sulfuric acid into a three-neck flask, starting stirring and cooling, adding 163g of nitrosyl sulfuric acid when the temperature is reduced to 20 ℃, uniformly stirring, adding 60g of 2-chloro-4-nitroaniline, controlling the temperature at 20 ℃ during feeding, controlling the feeding time to be 1.5h, keeping the temperature of a reaction system at 35 ℃ after the feeding is finished, reacting for 12h, and obtaining a diazo reaction product after the reaction is finished.
And (3) putting 100g of the ice-water mixture and 98% sulfuric acid into a flask, cooling to 15 ℃, adding 42g of N, N-dimethylaniline, keeping the temperature at 15 ℃, stirring for 1 hour until the N, N-dimethylaniline is completely dissolved to obtain an N, N-dimethylaniline solution, and standing for later use.
Slowly dripping the obtained diazo reaction product into N, N-dimethylaniline solution, and keeping the system temperature at 10 ℃ for reacting for 15h after finishing dripping to obtain a coupling reaction product.
And filtering the obtained coupling reaction product, washing until the pH value is neutral, and drying to obtain the monoazo disperse dye, wherein the structural formula of the monoazo disperse dye is shown as (III-4) and is marked as D4.
Comparative example 5:
respectively taking 26g of water and 85g of 98% sulfuric acid, placing the water and the sulfuric acid into a three-neck flask, starting stirring and cooling, adding 163g of nitrosyl sulfuric acid when the temperature is reduced to 20 ℃, adding 55g of 2,6-dichloro-4-nitroaniline after uniformly stirring, controlling the temperature at 20 ℃ during feeding, controlling the feeding time to be 3h, keeping the temperature of a reaction system at 20 ℃ after feeding, reacting for 6h, and obtaining a diazo reaction product after the reaction is finished.
100g of the ice-water mixture and 98% sulfuric acid are respectively put into a flask, the temperature is reduced to 15 ℃, 53g of N, N-dicyanoethylaniline is added, the temperature is kept at 15 ℃, the mixture is stirred for 1 hour until the N, N-dicyanoethylaniline is completely dissolved, and then the N, N-dicyanoethylaniline solution is obtained and stands for standby.
Slowly dripping the obtained diazo reaction product into the N, N-dicyanoethylaniline solution, and preserving the temperature for reaction for 12 hours after finishing dripping to obtain a coupling reaction product.
And filtering the obtained coupling reaction product, washing until the pH value is neutral, and drying to obtain the monoazo disperse dye, wherein the structural formula of the monoazo disperse dye is shown as (III-5) and is marked as D5.
Comparative example 6:
respectively taking 26g of water and 85g of 98% sulfuric acid, placing the water and the sulfuric acid into a three-neck flask, starting stirring and cooling, adding 163g of nitrosyl sulfuric acid when the temperature is reduced to 20 ℃, uniformly stirring, adding 55g of 2-chloro-4-nitroaniline, controlling the temperature at 15 ℃ during feeding, reacting for 2h, keeping the temperature of a reaction system at 20 ℃ after feeding, and obtaining a diazo reaction product after the reaction is finished.
100g of ice-water mixture and 98% sulfuric acid are respectively put into a flask, the temperature is reduced to 15 ℃, 96g of 3-acetamido-N-cyanoethyl-N-acetoxyethylaniline is added, the temperature is kept at 15 ℃, stirring is carried out for 1h until the mixture is completely dissolved, and then 3-acetamido-N-cyanoethyl-N-acetoxyethylaniline solution is obtained and stands for standby.
Slowly dripping the obtained diazo reaction product into a 3-acetamido-N-cyanoethyl-N-acetoxyl ethyl aniline solution, and keeping the temperature for reaction for 10 hours after the dripping is finished to obtain a coupling reaction product.
And filtering the obtained coupling reaction product, washing until the pH value is neutral, and drying to obtain the monoazo disperse dye, wherein the structural formula of the monoazo disperse dye is shown as (III-6) and is marked as D6.
Comparative example 7
Respectively taking 26g of water and 85g of 98% sulfuric acid, placing the water and the sulfuric acid into a three-neck flask, starting stirring and cooling, adding 163g of nitrosyl sulfuric acid when the temperature is reduced to 20 ℃, uniformly stirring, adding 55g of p-nitroaniline, controlling the temperature at 0 ℃ during feeding and the feeding time at 2h, keeping the temperature of a reaction system at 0 ℃ after feeding, reacting for 6h, and obtaining a diazo reaction product after the reaction is finished.
100g of the ice-water mixture and 98% sulfuric acid are respectively put into a flask, the temperature is reduced to 8 ℃, 122g of N-cyanoethyl-N-benzoyloxyethylaniline is added, the temperature is kept at 8 ℃, stirring is carried out for 1h until the N-cyanoethyl-N-benzoyloxyethylaniline is completely dissolved, and then the N-cyanoethyl-N-benzoyloxyethylaniline solution is obtained and stands for standby.
And (3) cooling the obtained diazo reaction product to 5 ℃, slowly dripping the product into the N-cyanoethyl-N-benzoyloxyethylaniline solution, and keeping the system temperature at 5 ℃ for reaction for 10 hours after dripping is finished to obtain a coupling reaction product.
Washing the obtained coupling reaction product with hot water at 70 ℃ until the pH value is neutral, and drying to obtain the monoazo disperse dye, wherein the structural formula is shown as (III-7) and is marked as D7.
Dyeing method
0.5g of the monoazo disperse dyes obtained in the examples 1-7 and the comparative examples 1-7 and 1.2g of a dispersant are respectively placed in a dye vat, 50g of terylene is uniformly stirred and added, the temperature is raised to 70 ℃ at the speed of 1 ℃/min, then the dyeing is carried out for 10min, the temperature is raised to 100 ℃ at the speed of 1 ℃/min, then the dyeing is carried out for 10min, finally the temperature is raised to 130 ℃ at the speed of 1 ℃/min, the temperature is kept for 60min, then the washing is carried out after high-temperature water drainage, then the washing is carried out after 30min at the temperature of 100 ℃, 1.2g of glacial acetic acid is added, the antistatic agent stearyl trimethyl ammonium chloride is added after uniform stirring, and finally the fabric which is successfully dyed is obtained after dehydration and drying.
Performance testing
And measuring the ironing resistance, the washing resistance, the perspiration resistance and the light fastness of the dried dyed fabric by taking the dried dyed fabric, wherein the adopted methods refer to GB/T6152-1997, GB/T3921-2008, GB/T3922-2013 and GB/T8426-1998 respectively. Then, the contents of chlorinated phenol, chlorinated benzene and toluene in the dyed fabric are respectively measured by methods of GB/T18414.1-2006, GB/T18414.2-2006 and GB/T20384-2006, the high-temperature dispersion stability of the dye is measured by GB/T5541-2017, and finally the purity of the obtained monoazo dispersion dye is measured by liquid chromatography and the product yield is calculated (wherein, the product yield = the raw material amount of the generated target product/raw material feeding amount x 100%). The properties of the monoazo dispersion dyes prepared in the examples and comparative examples are shown in table 1 below:
TABLE 1
Note: "-" indicates that no detection was made
As can be seen from Table 1, the monoazo disperse dyes obtained in examples 1 to 7 have high purity and excellent dyeing property, while the dyes in the comparative examples have low purity and poor dyeing property; in the aspect of environmental protection, the products synthesized by the method of the invention are not detected in the aspects of benzene chloride, phenol chloride and toluene, while the products in the comparative examples are detected, which shows that the method of the invention can be used for preparing the monoazo disperse dye with higher purity and yield, more excellent dyeing performance and more environmental protection. And finally, in the aspect of high-temperature dispersion stability, the performances of the S1-S7 subjected to the step-type temperature-rise crystal transformation are remarkably better than those of D1-D7 subjected to the common temperature-rise crystal transformation.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a monoazo disperse dye is characterized by comprising the following steps:
step 1): diazotizing a compound shown in a formula (I) and nitrosyl sulfuric acid under an acidic condition to obtain a diazo reaction product;
in the formula (I), R 1 And R 2 Each independently is hydrogen or halogen;
step 2): performing a coupling reaction on the diazo reaction product and a coupling component shown in a formula (II) to obtain a coupling reaction product;
in the formula (II), M 1 Is hydrogen or C 1 ～C 4 Alkanoylamino of (a), M 2 、M 3 Each independently is C substituted or unsubstituted by a substituent 1 ～C 4 The substituent is cyano, C 1 -C 4 Alkanoyloxy or benzoyloxy of (a);
step 3): and (3) carrying out crystal transformation on the coupling reaction product to obtain the monoazo disperse dye.
2. The method for preparing a monoazo disperse dye according to claim 1, wherein the step 1) comprises adding the compound represented by the formula (I) to a mixed solution of nitrosyl sulfuric acid and concentrated sulfuric acid to perform a reaction; preferably, the temperature of the mixed solution of nitrosyl sulfuric acid and concentrated sulfuric acid is-5-20 ℃, and the input time of the compound shown in the formula (I) is 1.5-5 h; more preferably, the concentrated sulfuric acid is sulfuric acid having a concentration of 90% or more.
3. The method for preparing a monoazo disperse dye according to claim 1 or 2, wherein the reaction temperature in the step 1) is-2 to 35 ℃ and the reaction time is 2 to 24 hours.
4. A process for preparing a monoazo disperse dye according to any one of claims 1 to 3, wherein the step 2) comprises adding a coupling component of formula (II) to the diazo reaction product, preferably wherein the coupling component of formula (II) is added as a solution of the coupling component of formula (II), more preferably wherein the coupling reaction temperature is from-5 to 45 ℃; the reaction time is 3-8 h.
5. The method for preparing a monoazo disperse dye according to any one of claims 1 to 4, wherein the monoazo disperse dye is obtained by subjecting the coupling reaction product to temperature increase to 100 to 120 ℃ and pressure increase to 0.1 to 0.2MPa, followed by crystal transformation under heat.
6. The method for preparing a monoazo disperse dye according to claim 5, wherein the temperature of the coupling reaction product is raised to 100-120 ℃ in a stepwise manner; preferably, the stepwise temperature rise comprises keeping the temperature at less than 40 ℃ for 4-12h; then heating to 40-55 ℃ and preserving the heat for 4-12h; finally, the temperature is raised to 100-120 ℃ and the temperature is preserved for 1-10h.
7. The method for preparing a monoazo disperse dye according to any one of claims 1-6, wherein between the steps 1) and 2), an adsorption step is further included, and the adsorption step comprises adsorbing the diazo reaction product by using an adsorbent and then removing solid substances to obtain an adsorbed product;
and then carrying out coupling reaction on the adsorption product and a coupling component shown in a formula (II) to obtain a coupling reaction product.
8. The method for preparing a monoazo disperse dye according to claim 7, wherein the adsorbent is added in an amount of 3% to 4% by mass of the compound of formula (I).
9. The method for preparing a monoazo disperse dye according to claim 7 or 8, wherein after completion of the adsorption, the solid matter is removed after dilution with an ice-water mixture; preferably, the amount of the ice-water mixture added is 1.5 to 5 times the amount of the compound of formula (I).
10. A monoazo disperse dye, which is prepared by the preparation method according to any one of claims 1 to 9; wherein the yield of the monoazo disperse dye is 95% or more, and the purity of the monoazo disperse dye is 96% or more.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955683A (en) * | 2009-07-16 | 2011-01-26 | 姚涌 | Preparation method of high-performance organic pigment C.I.P.R.185 |
| CN103374238A (en) * | 2012-04-28 | 2013-10-30 | 高邮市华宝颜料有限公司 | Method of preparing transparent pigment yellow 180 |
| CN105418453A (en) * | 2015-12-01 | 2016-03-23 | 浙江闰土研究院有限公司 | Process for diazotizing azo-dye intermediate |
| CN105440737A (en) * | 2014-08-29 | 2016-03-30 | 浙江迪邦化工有限公司 | Preparation method of energy-efficient and environmentally-friendly disperse dye |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955683A (en) * | 2009-07-16 | 2011-01-26 | 姚涌 | Preparation method of high-performance organic pigment C.I.P.R.185 |
| CN103374238A (en) * | 2012-04-28 | 2013-10-30 | 高邮市华宝颜料有限公司 | Method of preparing transparent pigment yellow 180 |
| CN105440737A (en) * | 2014-08-29 | 2016-03-30 | 浙江迪邦化工有限公司 | Preparation method of energy-efficient and environmentally-friendly disperse dye |
| CN105418453A (en) * | 2015-12-01 | 2016-03-23 | 浙江闰土研究院有限公司 | Process for diazotizing azo-dye intermediate |
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