CN114058194A - Preparation process of purple reactive dye - Google Patents
Preparation process of purple reactive dye Download PDFInfo
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- CN114058194A CN114058194A CN202111386022.2A CN202111386022A CN114058194A CN 114058194 A CN114058194 A CN 114058194A CN 202111386022 A CN202111386022 A CN 202111386022A CN 114058194 A CN114058194 A CN 114058194A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000985 reactive dye Substances 0.000 title claims description 22
- 239000007788 liquid Substances 0.000 claims abstract description 80
- 239000000243 solution Substances 0.000 claims abstract description 71
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 238000005859 coupling reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000008878 coupling Effects 0.000 claims abstract description 25
- 238000010168 coupling process Methods 0.000 claims abstract description 25
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 19
- MJNYPLCGWXFYPD-UHFFFAOYSA-N 2-amino-5-sulfobenzoic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1C(O)=O MJNYPLCGWXFYPD-UHFFFAOYSA-N 0.000 claims abstract description 16
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006482 condensation reaction Methods 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 14
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004537 pulping Methods 0.000 claims abstract description 12
- 239000012954 diazonium Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 9
- 150000001989 diazonium salts Chemical class 0.000 claims abstract description 7
- 238000006193 diazotization reaction Methods 0.000 claims abstract description 7
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 14
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 14
- 235000017550 sodium carbonate Nutrition 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 210000000805 cytoplasm Anatomy 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000007639 printing Methods 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 29
- 239000000047 product Substances 0.000 description 12
- 238000001816 cooling Methods 0.000 description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005185 salting out Methods 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 6
- SGDPNXUHAPTFNC-UHFFFAOYSA-N (4-aminophenoxy)methanediazonium Chemical class C(OC1=CC=C(C=C1)N)[N+]#N SGDPNXUHAPTFNC-UHFFFAOYSA-N 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical group C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 4
- -1 para-anisidine diazonium salt Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000033764 rhythmic process Effects 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000861 blow drying Methods 0.000 description 2
- 239000000337 buffer salt Substances 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000001047 purple dye Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007974 sodium acetate buffer Substances 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- DLPITEUCXDBWSF-UHFFFAOYSA-K trisodium N-[8-oxido-7-[[2-oxido-4-(2-sulfooxyethylsulfonyl)phenyl]diazenyl]-3,6-disulfonaphthalen-1-yl]ethanimidate Chemical compound CC(=NC1=C2C(=CC(=C1)S(=O)(=O)O)C=C(C(=C2[O-])N=NC3=C(C=C(C=C3)S(=O)(=O)CCOS(=O)(=O)O)[O-])S(=O)(=O)O)[O-].[Na+].[Na+].[Na+] DLPITEUCXDBWSF-UHFFFAOYSA-K 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 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
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
- C09B62/08—Azo dyes
- C09B62/085—Monoazo dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
- Coloring (AREA)
Abstract
The invention discloses a preparation process of a purple reactive printing dye, which comprises the following steps: 1) adding H acid monosodium salt into water, adjusting the pH value, and dissolving to obtain H acid solution clear liquid; 2) after pulping and dispersing cyanuric chloride in an ice bath, carrying out primary condensation reaction with the H acid solution to obtain a primary condensate; 3) carrying out diazotization reaction on anisidine and sodium nitrite in the presence of mixed acid to obtain a diazonium salt solution after complete reaction; 4) performing coupling reaction on the diazo liquid and a condensate for alkali adjustment to obtain a coupling liquid after the reaction is completed; 5) adding water into 2-amino-5-sulfobenzoic acid to adjust alkali to obtain a neutralized solution; 6) and (4) carrying out secondary condensation reaction on the coupling solution and the neutralization solution for alkali adjustment, and obtaining the violet dye raw stock after complete reaction. The preparation process optimizes the reaction flow, refines the specific operation steps, shortens the production time, reduces the energy consumption and the wastewater discharge, and improves the color fixing rate, the yield, the solubility and the like of the product; meanwhile, the mixed acid is adopted to replace the process, the condensation reaction is alleviated, and the storage and application stability of the dye is enhanced.
Description
Technical Field
The invention belongs to the field of reactive dye synthesis, and particularly relates to a preparation process of a purple reactive dye.
Background
Reactive dyes are an important branch of the dye industry, and the dyes mainly comprise dye matrixes, linking groups and reactive groups, and the reactive groups can perform nucleophilic substitution reaction with cellulose fibers such as cotton, wool, hemp and the like to form stable covalent bonds, so the dyes are also called as reactive dyes. Since the 50 s of the last century, the development and exploration of reactive dyes never stopped, and with the deep research, the advantages of reactive dyes, including bright color, wide color spectrum, high solubility, simple dyeing process, wide application range and the like, are continuously exploited, and gradually meet the requirements of most fibers and fabrics in the market.
Reactive Violet 46, Chinese alias active Violet 46, active Violet RRN, formula C27H16ClN7Na4O13S3The molecular weight of 870.07 is one of the representatives of purple active printing dyes, can be directly applied to the printing of cotton, nylon, silk, wool and other fabrics, and can be further processed into liquid dyes and ink-jet printing dyes, thereby improving the added value of products.
The structural formula is as follows:
the traditional synthesis method of the active violet RRN comprises the steps of carrying out alkaline coupling on p-anisidine diazonium salt and an H acid solution to obtain a coupling solution, adding sodium chloride and potassium chloride salt into the coupling solution for separation and refining to obtain a chromophore, carrying out primary condensation on the chromophore and cyanuric chloride, then adding 2-amino-5-sulfobenzoic acid for secondary condensation, finally adding potassium chloride for salting out, carrying out filter pressing to obtain a filter cake, and dissolving the filter cake to obtain the protoplasm. The traditional process has the advantages that the color light is stable, the solid content of the primary pulp can be controlled within a certain range, and the spray drying cost is reduced. The disadvantages are obvious, firstly, two salting-out procedures are needed to generate a large amount of high-salinity high-COD colored wastewater, meanwhile, the salting-out loss is large, the product yield is not high, and the raw material cost is not low; secondly, in order to ensure the stable reaction, one or two kinds of sodium phosphate are blended into buffer salt to participate in the condensation reaction, the synthesized product can generate phosphorus-containing wastewater in the printing and dyeing process, and phosphorus element residues also exist on the fabric; thirdly, the solubility of the dye is not high and generally not more than 100g/L, a large amount of cosolvent is required to be added in the deep processing process of the dye into liquid dye, the cost is increased, the storage stability is poor, and the risks of precipitation of thick substances, reduction of color fixing rate and the like are avoided after the dye is placed for a long time; finally, the production period is long, the time required for producing each batch of products is over 65 hours, and both the chromophore preparation and salting-out refining need to consume a large amount of manpower and material resources, occupy production resources and limit the productivity of a company.
Domestic and foreign market analysis: active Violet with a vinyl sulfone structure is basically selected for low-end products, such as C.I. reactive Violet 5, also named as active Violet 5 and active Violet KN-4R in Chinese, active Violet printing paste with the vinyl sulfone structure can be hydrolyzed in the preparation and storage processes, the fixation rate of dye on the fabric is low in the printing process, and colored patterns are easily caused; the vinyl sulfone structure of a high-end product cannot meet the market demand, the purple RRN manufactured by the traditional process has high cost and is in a disadvantage of competing with similar products abroad, and the demand in the field is maintained by basically depending on imported purple RRN.
Disclosure of Invention
The invention aims to provide a preparation process of a purple reactive dye aiming at the defects of the prior art, the preparation process can reduce a large amount of high-COD and high-salinity colored wastewater generated by the traditional salting-out refining method, and the synthesized dye has good solubility, good dyeing fastness, high fixation rate, no phosphorus residue on cloth surface, bright color, excellent thermal stability and good storage property when being processed into liquid dye.
The technical scheme provided by the invention is as follows:
a preparation process of a purple reactive printing dye comprises the following steps:
1) adding the monosodium salt of H acid into water, pulping, adjusting the pH value to 6.5-7.2, stirring and dissolving to obtain a clear solution of H acid;
2) after pulping and dispersing cyanuric chloride in an ice bath, dropwise adding the H acid solution obtained in the step 1), controlling the temperature to be 3-8 ℃ and the pH value to be 1.5-1.8, carrying out primary condensation reaction, and obtaining a condensate after the reaction is completed;
3) carrying out diazotization reaction on anisidine and sodium nitrite in the presence of mixed acid to obtain a diazonium salt solution after complete reaction;
4) adding the diazo liquid obtained in the step 3) into the primary condensed liquid obtained in the step 2) for coupling reaction, controlling the temperature to be 2-6 ℃, adjusting the pH value to be 6.8-7.0, and obtaining the coupling liquid after the reaction is completed;
5) adding water into 2-amino-5-sulfobenzoic acid, adjusting the pH value to 7.0-7.5, and stirring for dissolving to obtain a neutralized solution;
6) and (3) adding the neutralization solution obtained in the step (5) into the coupling solution obtained in the step (4), heating to 50-55 ℃, maintaining the pH value at 7.3-7.5, and carrying out secondary condensation reaction to obtain the violet dye protoplasm after complete reaction.
The dissolving reaction process of the H acid monosodium salt in the step 1) is as follows:
in the step 1), the monosodium H acid is extremely insoluble in water, and the monosodium H acid is dissolved and then participates in a condensation reaction in an alkali adjusting mode, so that the material contact effect can be improved, the conversion rate can be improved, and the reaction time can be shortened.
Preferably, in the step 1), industrial grade 30% liquid alkali is used for adjusting the pH value, and the mass fraction of the obtained H acid clear solution is controlled to be 25-30%.
Preferably, in the step 1), after the dissolution is completed, the temperature is reduced and maintained at 2-6 ℃.
The primary condensation reaction process in the step 2) is as follows:
in the step 2), the pulping progress is controlled by detecting the pH value, and the completion of pulping is indicated when the pH value is within a calibration range; the condensation reaction of cyanuric chloride and H acid is actually the first step of synthesis reaction of the product, the steric hindrance is small, the reaction is easy to carry out, buffer salt is not needed, the reaction can be stabilized by adjusting with sodium bicarbonate, the other condensation reaction is a process of slowing, then speeding and then slowing, so in the process of actually dripping H acid solution, the dripping rhythm needs to be controlled, the reaction is ensured to be in the best state, and meanwhile, the reaction temperature is controlled, so that cyanuric chloride hydrolysis caused by local overheating is prevented; finally, the reaction time was controlled and the end point of the reaction was determined by HPLC.
Preferably, in the step 2), after the cyanuric chloride is pulped, when the pH value is 2.0-2.5, the pulping effect is optimal, and the H acid solution is dripped.
Preferably, in the step 2), the total dropping time of the H acid soluble clear liquid is 75-90min, the first 25-30min is controlled to be 1/4 of the total volume of the H acid soluble clear liquid, the middle 25-30min is controlled to be 1/2 of the total volume of the H acid soluble clear liquid, and the last 25-30min is controlled to be 1/4 of the total volume of the H acid soluble clear liquid.
Preferably, in the step 2), the pH value is maintained by using baking soda in the process of dripping and reacting the H acid clear solution, and the molar ratio of the baking soda to the H acid is (0.9-1.2): 1.
Preferably, in the step 2), the reaction time is controlled to be 3-4h, and the reaction end point is > 97% of the purity of the condensate detected by HPLC.
The diazotization reaction process in the step 3) is as follows:
in the step 3), the diazo reaction needs to be carried out under a strong acid condition, acetic acid is adopted to replace a part of hydrochloric acid to form mixed acid to participate in the diazo reaction, and the acetic acid has a good dissolving effect on the p-anisidine, so that the p-anisidine is more hydrophilic to a water phase, the diazo reaction with sodium nitrite is more facilitated, and the yield of the diazo reaction is improved; an acetic acid-sodium acetate buffer system is also added for the subsequent reaction. The buffer system can replace phosphate to play a role in maintaining stability in a secondary condensation reaction, can also inhibit hydrolysis in the storage and printing and dyeing processes of the dye, and improves the stability.
Preferably, in the step 3), the mixed acid is a mixed solution of hydrochloric acid and acetic acid.
Preferably, the molar ratio of the hydrochloric acid, the acetic acid, the sodium nitrite and the p-anisidine in the step 3) is (0.5-1.0) to (0.5-1.0): (1.0-1.05): 1.
preferably, the diazotization reaction temperature in the step 3) is controlled to be 0-5 ℃, and the reaction time is controlled to be 4-5 h.
The reaction process of the coupling reaction in the step 4) is as follows:
in the step 4) of the invention, the coupling reaction mainly occurs at the ortho-position of the amino group and the ortho-position of the hydroxyl group of the H acid, and the product needs the coupling product at the ortho-position of the hydroxyl group of the H acid. Therefore, the calcined soda is added into the primary condensed liquid before the coupling, the activity of the amino ortho position of the H acid is reduced, meanwhile, the pH value is maintained well in the process of dropwise adding the diazonium salt, the diazonium salt can be rapidly coupled at the hydroxyl ortho position of the H acid, the coupling time is reduced, byproducts are reduced, the purity of the coupling liquid is improved, and the relative color fixing rate of the dye is improved. If baking soda is used to adjust the pH, the coupling yield will decrease by 10-15% because the baking soda is too weak in alkalinity and too slow a coupling rate will lead to hydrolysis of some of the diazonium salt; if liquid alkali or dilute liquid alkali is used for adjusting the pH value, the coupling yield can be reduced by 5-8%, the relative fixation rate is reduced by 10-12%, and the reason that the yield is low is that no buffer system exists in the process of using a strong base for coupling and adjusting the pH value, so that the strong base is directly contacted with the diazonium salt to lose the coupling capacity, and the yield is low; the reason of low relative fixation rate is that the buffering capacity of the system is poor, and the second chlorine in the structure is hydrolyzed into hydroxyl by the first condensate when the first condensate meets strong alkali, so that the second condensate cannot participate in secondary condensation subsequently, and the relative fixation rate is reduced.
Preferably, before the diazo liquid is added into the first condensed liquid in the step 4), a process amount of sodium carbonate is added into the first condensed liquid.
Further preferably, before the diazo liquid is added into the first condensed liquid in the step 4), soda ash is added into the first condensed liquid, wherein the mass of the soda ash is 10-15% of that of the cyanuric chloride.
Preferably, the time for adding the diazo liquid into the first liquid condensation in the step 4) is controlled to be 20-30min, and the pH value is controlled to be more than 6.5 and the temperature is controlled to be less than 6 ℃ in the adding process.
Preferably, after the diazo liquid is added in the step 4), 20% sodium carbonate solution is prepared to maintain the pH value, and the reaction time is maintained to be 2-3 h.
The reaction process of the neutralization reaction of the 2-amino-5-sulfobenzoic acid in the step 5) is as follows:
preferably, the pH value is adjusted by using industrial grade 30% liquid alkali in the step 5), and the mass fraction of the obtained 2-amino-5-sulfobenzoic acid neutralization solution is 20-30%.
The secondary condensation reaction process in the step 6) is as follows:
preferably, after the neutralization solution is added in the step 6), 20% of soda ash solution is prepared to maintain the pH value, and the reaction time is maintained to be 4-5 h.
Preferably, in the steps 1) to 6), the molar ratio of cyanuric chloride, the monosodium salt of H acid, the p-anisidine and the 2-amino-5-sulfobenzoic acid is 1 (0.98-1.03): (0.97-1.02): 0.96-1.01).
Compared with the prior art, the invention has the beneficial effects that:
(1) the reaction flow is optimized, the salting-out of a chromophore and the salting-out of a secondary condensate are omitted, the yield is improved, the discharge of high-COD colored wastewater is reduced, the biochemical degradation pressure is reduced, and the method is green and environment-friendly;
(2) the production period is short, the energy consumption is low, and the energy utilization efficiency is high;
(3) the color fixing rate is high, the solubility is good, the high-concentration liquid dye can be processed, and the product return rate is high;
(4) the performance is stable, the storage is convenient, and the product thermal stability detection performance is excellent;
(5) the dye has no phosphorization, and can not cause water eutrophication after being applied.
Detailed Description
Example 1:
adding 1000kg of bottom water into a 5-square reaction kettle, adding 430kg of monosodium H acid, stirring for 30min, dropwise adding 140kg of 30% industrial liquid alkali, adjusting the pH value to 6.5-7.2, dissolving the H acid to obtain a clear solution, cooling to 2-6 ℃, and preserving heat for later use.
Adding 600kg of bottom water and 1000kg of crushed ice into a 15-square reaction kettle, adding 200kg of cyanuric chloride, stirring and pulping, measuring the volume of the standby H acid solution clear liquid when the pH value is 2.0-2.5, then beginning to dropwise add the H acid solution clear liquid, controlling the dropping rhythm, controlling the dropwise adding amount to be 1/4 of the total volume of the H acid solution clear liquid in the first 25-30min, controlling the dropwise adding amount to be 1/2 of the total volume of the H acid solution clear liquid in the middle 25-30min, controlling the dropwise adding amount to be 1/4 of the total volume of the H acid solution clear liquid in the last 25-30min, keeping the pH value to be 1.5-1.8 by using baking soda in the dropwise adding process, keeping the pH value to be 1.5-1.8 by using the baking soda after the dropwise adding is finished, keeping the temperature to be 3-8 ℃, reacting for 3-4H by HPLC, and obtaining a condensate when the purity is detected to be more than 97%.
Adding 600kg of bottom water into a 5-square diazo pot, heating to 40 ℃, adding 125kg of p-anisidine, stirring for 20min, adding 100kg of 30% industrial hydrochloric acid and 40kg of 99.5% industrial acetic acid, continuing to stir for 10min, adding crushed ice, cooling to 0-5 ℃, dropwise adding 250kg of 30% sodium nitrite solution, keeping the temperature at 0-5 ℃ after dropwise adding, continuing to react for 4-5h, and eliminating excessive sodium nitrite by using sulfamic acid to obtain p-anisidine diazonium salt for later use.
Adding 25kg of soda into the first condensed liquid, transferring the para-anisidine diazonium salt in a 5-square diazo pot into the first condensed liquid, controlling the transfer time to be 20-30min, keeping the pH value to be more than 6.5 and the temperature to be less than 6 ℃, continuing to use 20% soda liquid to maintain the pH value to be 6.8-7.0 after the transfer is finished, preserving the temperature to be 2-6 ℃, reacting for 2-3h, and obtaining the coupling liquid after the reaction is completed.
Adding 500kg of bottom water into a 5-square reaction kettle, adding 230kg of 2-amino-5-sulfobenzoic acid, stirring for 30min, dropwise adding 285kg of 30% industrial liquid alkali, adjusting the pH value to 7.0-7.5, and stirring for dissolving to obtain a neutralized solution.
And (3) quickly transferring the neutralized solution of 2-amino-5-sulfobenzoic acid into the coupling solution, heating to 50-55 ℃, maintaining the pH value at 7.3-7.5 by using 20% soda ash solution, continuously preserving the heat at 50-55 ℃, reacting for 4-5h, and obtaining the violet dye protoplasm after the reaction is completed.
Standardizing the primary pulp, and spray-drying to obtain the active purple RRN dye dry powder.
Example 2:
adding 1000kg of bottom water into a 5-square reaction kettle, adding 440kg of monosodium H acid, stirring for 30min, dropwise adding 143kg of 30% industrial liquid alkali, adjusting the pH value to 6.5-7.2, dissolving the H acid to obtain a clear solution, cooling to 2-6 ℃, and preserving heat for later use.
Adding 600kg of bottom water and 1000kg of crushed ice into a 15-square reaction kettle, adding 200kg of cyanuric chloride, stirring and pulping, measuring the volume of the standby H acid solution clear liquid when the pH value is 2.0-2.5, then beginning to dropwise add the H acid solution clear liquid, controlling the dropping rhythm, controlling the dropwise adding amount to be 1/4 of the total volume of the H acid solution clear liquid in the first 25-30min, controlling the dropwise adding amount to be 1/2 of the total volume of the H acid solution clear liquid in the middle 25-30min, controlling the dropwise adding amount to be 1/4 of the total volume of the H acid solution clear liquid in the last 25-30min, keeping the pH value to be 1.5-1.8 by using baking soda in the dropwise adding process, keeping the pH value to be 1.5-1.8 by using the baking soda after the dropwise adding is finished, keeping the temperature to be 3-8 ℃, reacting for 3-4H by HPLC, and obtaining a condensate when the purity is detected to be more than 97%.
Adding 600kg of bottom water into a 5-square diazo pot, heating to 40 ℃, adding 128kg of p-anisidine, stirring for 20min, adding 110kg of 30% industrial hydrochloric acid and 35kg of 99.5% industrial acetic acid, continuing stirring for 10min, adding crushed ice, cooling to 0-5 ℃, dropwise adding 256kg of 30% sodium nitrite solution, keeping the temperature at 0-5 ℃ after dropwise adding, continuing to react for 4-5h, and eliminating excessive sodium nitrite by using sulfamic acid to obtain p-anisidine diazonium salt for later use.
Adding 25kg of soda into the first condensed liquid, transferring the para-anisidine diazonium salt in a 5-square diazo pot into the first condensed liquid, controlling the transfer time to be 20-30min, keeping the pH value to be more than 6.5 and the temperature to be less than 6 ℃, continuing to use 20% soda liquid to maintain the pH value to be 6.8-7.0 after the transfer is finished, preserving the temperature to be 2-6 ℃, reacting for 2-3h, and obtaining the coupling liquid after the reaction is completed.
Adding 500kg of bottom water into a 5-square reaction kettle, adding 232kg of 2-amino-5-sulfobenzoic acid, stirring for 30min, dropwise adding 290kg of 30% industrial liquid alkali, adjusting the pH value to 7.0-7.5, and stirring for dissolving to obtain a neutralized solution.
And (3) quickly transferring the neutralized solution of 2-amino-5-sulfobenzoic acid into the coupling solution, heating to 50-55 ℃, maintaining the pH value at 7.3-7.5 by using 20% soda ash solution, continuously preserving the heat at 50-55 ℃, reacting for 4-5h, and obtaining the violet dye protoplasm after the reaction is completed.
Standardizing the primary pulp, and spray-drying to obtain the active purple RRN dye dry powder.
Example 3:
adding 1000kg of bottom water into a 5-square reaction kettle, adding 430kg of monosodium H acid, stirring for 30min, dropwise adding 140kg of 30% industrial liquid alkali, adjusting the pH value to 6.5-7.2, dissolving the H acid to obtain a clear solution, cooling to 2-6 ℃, and preserving heat for later use.
Adding 600kg of bottom water and 1000kg of crushed ice into a 15-square reaction kettle, adding 200kg of cyanuric chloride, stirring and pulping, measuring the volume of the standby H acid solution clear liquid when the pH value is 2.0-2.5, then beginning to dropwise add the H acid solution clear liquid, controlling the dropping rhythm, controlling the dropwise adding amount to be 1/4 of the total volume of the H acid solution clear liquid in the first 25-30min, controlling the dropwise adding amount to be 1/2 of the total volume of the H acid solution clear liquid in the middle 25-30min, controlling the dropwise adding amount to be 1/4 of the total volume of the H acid solution clear liquid in the last 25-30min, keeping the pH value to be 1.5-1.8 by using baking soda in the dropwise adding process, keeping the pH value to be 1.5-1.8 by using the baking soda after the dropwise adding is finished, keeping the temperature to be 3-8 ℃, reacting for 3-4H by HPLC, and obtaining a condensate when the purity is detected to be more than 97%.
Adding 600kg of bottom water into a 5-square diazo pot, heating to 40 ℃, adding 125kg of p-anisidine, stirring for 20min, adding 100kg of 30% industrial hydrochloric acid and 40kg of 99.5% industrial acetic acid, continuing to stir for 10min, adding crushed ice, cooling to 0-5 ℃, dropwise adding 250kg of 30% sodium nitrite solution, keeping the temperature at 0-5 ℃ after dropwise adding, continuing to react for 4-5h, and eliminating excessive sodium nitrite by using sulfamic acid to obtain p-anisidine diazonium salt for later use.
28kg of calcined soda is added into the first condensed liquid, the para-anisidine diazonium salt in a 5-square diazo pot is transferred into the first condensed liquid, the transfer time is controlled to be 20-30min, the pH value is greater than 6.5, the temperature is less than 6 ℃, after the transfer is finished, 20% calcined soda liquid is continuously used for maintaining the pH value to be 6.8-7.0, the temperature is kept to be 2-6 ℃, the reaction lasts for 2-3h, and the coupling liquid is obtained after the reaction is completed.
Adding 500kg of bottom water into a 5-square reaction kettle, adding 230kg of 2-amino-5-sulfobenzoic acid, stirring for 30min, dropwise adding 285kg of 30% industrial liquid alkali, adjusting the pH value to 7.0-7.5, and stirring for dissolving to obtain a neutralized solution.
And (3) quickly transferring the neutralized solution of 2-amino-5-sulfobenzoic acid into the coupling solution, heating to 50-55 ℃, maintaining the pH value at 7.3-7.5 by using 20% soda ash solution, continuously preserving the heat at 50-55 ℃, reacting for 4-5h, and obtaining the violet dye protoplasm after the reaction is completed.
Standardizing the primary pulp, and spray-drying to obtain the active purple RRN dye dry powder.
Comparative example 1:
adding 600kg of bottom water into a 5-square diazo pot, heating to 40 ℃, adding 125kg of p-anisidine, stirring for 20min, adding 160kg of 30% industrial hydrochloric acid, continuing stirring for 10min, adding crushed ice, cooling to 0-5 ℃, dropwise adding 245kg of 30% sodium nitrite solution, keeping the temperature at 3-8 ℃ after dropwise adding, continuing to react for 4-5h, and removing excessive sodium nitrite by using sulfamic acid to obtain p-anisidine diazonium salt for later use.
Adding 900kg of bottom water into a 5-square reaction kettle, adding 420kg of H acid monosodium salt, stirring for 30min, dropwise adding 138kg of 30% industrial liquid alkali, adjusting the pH value to 6.5-7.2, and dissolving the H acid to obtain a clear solution for later use.
Transferring the H acid solution into para-anisidine diazonium salt, adjusting the pH value to 6-6.5 by using baking soda after the transfer is finished, cooling to 5-10 ℃, and carrying out heat preservation reaction for 6-7H. After the end point is reached, the temperature is raised to 45-50 ℃, the volume is measured, 10% of NaCl and 10% of KCl are added, stirring is carried out at a low speed, a large amount of materials are separated out after 3-4 hours, spots on qualitative filter paper are clear, seepage rings are clean, filter pressing and blow drying are carried out, a filter cake is collected, 800kg of bottom water is added into a 5-square reaction pot, the filter cake is added, stirring and dissolving are carried out, a color base is obtained, and 10kg of sodium dihydrogen phosphate and 20kg of disodium hydrogen phosphate are added for later use.
Adding 600kg of bottom water and 1000kg of crushed ice into a 15-square reaction kettle, adding 200kg of cyanuric chloride, stirring and pulping for 2h, adding a chromophore, adjusting the pH value to 5.5-6 with sodium bicarbonate after the addition, preserving the temperature at 10-15 ℃, and reacting for 6-7 h. After the end of the first condensation, 232kg of 2-amino-5-sulfobenzoic acid, 10kg of sodium dihydrogen phosphate and 20kg of disodium hydrogen phosphate are directly added, the temperature is raised, the temperature is kept at 50-55 ℃, the pH value is maintained at 7.5-8.0 by 15% industrial liquid alkali, and the reaction is carried out for 4-5 h. And after the secondary shrinkage end point is reached, measuring the volume, adding 18% of KCl in volume ratio, stirring at a low speed, separating out a large amount of dye after 3-4h, determining the spots on the qualitative filter paper to be clear and permeating the ring to be light in color, performing filter pressing and blow drying, and collecting a filter cake.
6000kg of bottom water is added into a 15-square reaction kettle, filter cakes are added, stirring is carried out, and the pH value is adjusted back to 6.5-7.0 by using a small amount of industrial hydrochloric acid, so as to obtain the purple dye raw pulp.
Standardizing the primary pulp, and spray-drying to obtain the active purple RRN dye dry powder.
Comparative example 2:
preparing vinyl sulfone structure reactive purple dye according to synthesis process of page 306 reactive brilliant purple KN-4R in dye production process compilation (compilation: Shanghai organic chemical industry Co., 1976, 2 months) to obtain comparative sample 2
Comparing the purple reactive dye products respectively prepared in examples 1-3 with the purple reactive dye product of comparative example 1 synthesized by the traditional process and the disclosed purple comparative example 2 with a vinyl sulfone structure, the color light, the relative strength, the relative fixation rate, the relative yield and the solubility (taking the enterprise as a standard) are compared in the table 1; table 2 shows the relative fixation change of the standardized samples stored at 72 ℃ for 3 days, and the relative fixation of the printing color pastes prepared in the same concentration at 35 ℃ compared with 1 st, 3 th, 5 th and 7 th days.
Comparative example 3:
in example 1, acetic acid was not used in the diazotization step, and an equimolar amount of the acid was replaced with hydrochloric acid, but the rest was not changed.
Comparative example 4:
in example 1, soda ash was not used in the coupling step, and 15 to 30% caustic soda lye was used in place of soda ash, but the rest was not changed.
TABLE 1
TABLE 2
Claims (10)
1. A preparation process of a purple reactive dye is characterized by comprising the following steps:
1) adding the monosodium salt of H acid into water, pulping, adjusting the pH value to 6.5-7.2, stirring and dissolving to obtain a clear solution of H acid;
2) after pulping and dispersing cyanuric chloride in an ice bath, dropwise adding the H acid solution obtained in the step 1), controlling the temperature to be 3-8 ℃ and the pH value to be 1.5-1.8, carrying out primary condensation reaction, and obtaining a condensate after the reaction is completed;
3) carrying out diazotization reaction on anisidine and sodium nitrite in the presence of mixed acid to obtain a diazonium salt solution after complete reaction;
4) adding the diazo liquid obtained in the step 3) into the primary condensed liquid obtained in the step 2) for coupling reaction, controlling the temperature to be 2-6 ℃, adjusting the pH value to be 6.8-7.0, and obtaining the coupling liquid after the reaction is completed;
5) adding water into 2-amino-5-sulfobenzoic acid, adjusting the pH value to 7.0-7.5, and stirring for dissolving to obtain a neutralized solution;
6) and (3) adding the neutralization solution obtained in the step (5) into the coupling solution obtained in the step (4), heating to 50-55 ℃, maintaining the pH value at 7.3-7.5, carrying out secondary condensation reaction, and obtaining the purple reactive dye protoplasm after complete reaction.
2. The process for preparing the purple reactive dye according to claim 1, wherein the pH value of the industrial grade 30% liquid alkali is used for adjusting the pH value in the step 1), and the mass fraction of the obtained H acid solution is controlled to be 25-30%.
3. The process for preparing a purple reactive dye according to claim 1, wherein after the cyanuric chloride is pulped in the step 2), H acid solution is added dropwise when the pH value is 2.0-2.5;
the total dropping time of the H acid soluble clear liquid in the step 2) is 75-90min, the dropping amount is controlled to be 1/4 of the total volume of the H acid soluble clear liquid in the first 25-30min, the dropping amount is controlled to be 1/2 of the total volume of the H acid soluble clear liquid in the middle 25-30min, and the dropping amount is controlled to be 1/4 of the total volume of the H acid soluble clear liquid in the last 25-30 min;
in the step 2), during the dropping and reaction of the H acid solution, the pH value is maintained by using baking soda, and the molar ratio of the baking soda to the H acid is (0.9-1.2): 1.
4. The process for preparing a purple reactive dye according to claim 1, wherein the mixed acid in the step 3) is a mixed solution of hydrochloric acid and acetic acid.
5. The process for preparing a violet reactive dye according to claim 1 and claim 4, wherein the molar ratio of hydrochloric acid, acetic acid, sodium nitrite and p-anisidine in the step 3) is (0.5-1.0) to (0.5-1.0): (1.0-1.05): 1.
6. the process for preparing the purple reactive dye according to claim 1, wherein the diazotization reaction temperature in the step 3) is controlled to be 0-5 ℃, and the reaction time is controlled to be 4-5 h.
7. The process for preparing a purple reactive dye according to claim 1, wherein a process amount of sodium carbonate is added to the first condensed liquid before the diazo liquid is added to the first condensed liquid in the step 4);
in the step 4), the time for adding the first condensed liquid into the diazo liquid is controlled to be 20-30min, the pH value is controlled to be more than 6.5 in the adding process, and the temperature is controlled to be less than 6 ℃;
after the diazo liquid is added in the step 4), 20 percent of soda solution is prepared to maintain the pH value, and the reaction time is maintained for 2-3 h.
8. The process for preparing the purple reactive dye according to claim 1, wherein the pH is adjusted by using industrial grade 30% liquid alkali in the step 5), and the mass fraction of the 2-amino-5-sulfobenzoic acid in the obtained neutralized liquid is 20-30%.
9. The process for preparing the purple reactive dye according to claim 1, wherein after the neutralization solution is added in the step 6), 20% soda ash solution is prepared to maintain the pH value, and the reaction time is maintained to be 4-5 h.
10. The process for preparing a violet reactive dye according to claim 1, wherein in the steps 1) to 6), the molar ratio of cyanuric chloride, monosodium H acid, p-anisidine and 2-amino-5-sulfobenzoic acid is 1 (0.98-1.03): (0.97-1.02): 0.96-1.01).
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