CN118027704A - Environment-friendly papermaking dye and preparation method thereof - Google Patents
Environment-friendly papermaking dye and preparation method thereof Download PDFInfo
- Publication number
- CN118027704A CN118027704A CN202410144667.2A CN202410144667A CN118027704A CN 118027704 A CN118027704 A CN 118027704A CN 202410144667 A CN202410144667 A CN 202410144667A CN 118027704 A CN118027704 A CN 118027704A
- Authority
- CN
- China
- Prior art keywords
- dye
- reaction
- environment
- temperature
- raw materials
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006482 condensation reaction Methods 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 19
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 amine cationic bipyridine heterocyclic compounds Chemical class 0.000 claims abstract description 14
- 239000000123 paper Substances 0.000 claims abstract description 14
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005859 coupling reaction Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 229940105325 3-dimethylaminopropylamine Drugs 0.000 claims abstract description 11
- 125000002091 cationic group Chemical group 0.000 claims abstract description 11
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims abstract description 11
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims abstract description 6
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 6
- 230000005494 condensation Effects 0.000 claims abstract description 5
- 230000008878 coupling Effects 0.000 claims abstract description 5
- 238000010168 coupling process Methods 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 239000000975 dye Substances 0.000 claims description 61
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 239000012954 diazonium Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 238000007098 aminolysis reaction Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 9
- 239000012362 glacial acetic acid Substances 0.000 claims description 9
- 235000010288 sodium nitrite Nutrition 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 238000005576 amination reaction Methods 0.000 claims description 4
- 239000000987 azo dye Substances 0.000 claims description 4
- 238000005956 quaternization reaction Methods 0.000 claims description 4
- 238000010009 beating Methods 0.000 claims description 3
- 239000007859 condensation product Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000004043 dyeing Methods 0.000 abstract description 7
- 239000012752 auxiliary agent Substances 0.000 abstract description 5
- 239000010865 sewage Substances 0.000 abstract description 5
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 2
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 abstract description 2
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000004040 coloring Methods 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 238000009967 direct dyeing Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 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 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material 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
- C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
- C09B35/02—Disazo dyes
- C09B35/039—Disazo dyes characterised by the tetrazo component
- C09B35/08—Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of biphenyl
- C09B35/10—Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of biphenyl from two coupling components of the same type
- C09B35/18—Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of biphenyl from two coupling components of the same type from heterocyclic compounds
- C09B35/185—Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of biphenyl from two coupling components of the same type from heterocyclic compounds from pyridine or pyridone components
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
- C09B35/02—Disazo dyes
- C09B35/021—Disazo dyes characterised by two coupling components of the same type
- C09B35/03—Disazo dyes characterised by two coupling components of the same type in which the coupling component is a heterocyclic compound
- C09B35/031—Disazo dyes characterised by two coupling components of the same type in which the coupling component is a heterocyclic compound containing a six membered ring with one nitrogen atom as the only ring hetero atom
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/28—Colorants ; Pigments or opacifying agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
Abstract
The invention discloses an environment-friendly papermaking dye and a preparation method thereof, wherein the dye is prepared by taking pyridine, methyl monochloroacetate, 3-dimethylaminopropylamine and methyl acetoacetate as raw materials, and respectively carrying out condensation and cyclization reactions of three steps in a methanol solvent under different temperature conditions and under the action of alkali to synthesize quaternary amine cationic bipyridine heterocyclic compounds; the yellow cationic liquid dye for cardboard paper is synthesized by taking the bipyridine heterocyclic compound as a coupling component and 4,4' -diaminodiphenyl methane as a diazo component. The heterocyclic pyridone dye intermediate adopted by the invention can synthesize yellow cationic dye with excellent performance into high water-solubility liquid dye, and has the advantages of good substantivity, stable dye hue, high dye-uptake, high light fastness, no dye auxiliary agent and less sewage residue after dyeing, thus being a high-quality environment-friendly dye variety.
Description
[ Field of technology ]
The invention relates to the technical field of dyes, in particular to a preparation method of an environment-friendly papermaking dye for coloring in secondary fiber papermaking paper pulp.
[ Background Art ]
At present, powdery solid dyes are mainly used for water dissolution or water dispersion to form liquid dyes for coloring in cardboard paper pulp manufactured by secondary fibers, and due to poor water solubility of the powdery dyes, water dispersion stability needs to be improved by dye auxiliary agents, meanwhile, the dyes have poor direct dyeing property, complex dyeing operation process, difficult hue control, slow color adjustment speed, and high residual sewage after dyeing, and cannot meet the use requirement of a high-speed paper machine.
Therefore, the development of the environment-friendly dye which does not need to add dye auxiliary agents has high water solubility, good direct dyeing property, quick coloring, high dye-uptake, stable hue and less sewage residue after dyeing meets the current environment-friendly requirement and the clean production trend. Based on this, the present inventors have proposed the following technical means.
[ Invention ]
The invention aims to overcome the defects of the prior art and provide an environment-friendly papermaking dye and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme that the environment-friendly papermaking dye is prepared by taking pyridine, methyl monochloroacetate, 3-dimethylaminopropylamine and methyl acetoacetate as raw materials, and respectively carrying out condensation and cyclization reactions of three steps in a methanol solvent under different temperature conditions and under the action of alkali to synthesize quaternary amine cationic bipyridine heterocyclic compounds; the bipyridine heterocyclic compound is used as a coupling component, 4' -diaminodiphenyl methane is used as a diazo component, and a yellow cationic liquid dye for cardboard paper is synthesized; the molecular formula of the bipyridine heterocyclic compound is as follows: 3-pyridinyl-4-methyl-5- (H) -6-hydroxy-N (N ', N' -dimethylaminopropyl) -pyridin-2-one.
The invention adopts heterocyclic pyridone dye intermediate (molecular formula: 3-pyridyl-4-methyl-5- (H) -6-hydroxy-N (N ', N' -dimethylaminopropyl) -pyridin-2-one is abbreviated as DPY) to synthesize yellow cationic dye with excellent performance as high water-soluble liquid dye, and has good direct dyeing property, stable dye hue, high dye-uptake, high light fastness, no dye auxiliary agent, less residual sewage after dyeing, and is a high-quality environment-friendly dye variety.
The preparation method adopts the following technical scheme: the azo compound synthesized by reacting the synthesized dye intermediate with 4,4' -diaminodiphenyl methane is the environment-friendly papermaking dye; wherein, the dye intermediate DPY synthesis comprises the following steps: 1-1, quaternized condensation reaction: the condensation reaction of pyridine and methyl monochloroacetate in methanol solvent is carried out to separate out crystallization; 1-2, quaternization condensation product aminolysis condensation reaction: cooling the quaternized product in the step 1-1 to 0 ℃ in the same container, and dropwise adding 3-dimethylaminopropylamine at the temperature of 0-5 ℃ for condensation reaction, wherein the reaction is aminolysis reaction; 1-3, adding 50% potassium hydroxide solution into the product obtained in the step 1-2 at the temperature of 0 ℃, and dropwise adding methyl acetoacetate at the temperature of 0 ℃ to generate a dye intermediate DPY; the prepared dye intermediate reacts with 4,4' -diaminodiphenyl methane to synthesize azo compound, and the product is the paper-making dye, which comprises the following steps: diazotizing 2-1, 4' -diaminodiphenyl methane, fully dissolving the diazotizing component 4,4' -diaminodiphenyl methane in concentrated hydrochloric acid solution, adding ice cubes, dropwise adding 30% sodium nitrite solution and 4,4' -diaminodiphenyl methane at the temperature of 5-10 ℃ for diazotizing, and obtaining diazonium solution after diazotizing; 2-2, coupling reaction to synthesize dye, regulating pH value of the dye intermediate aqueous solution to 7 by glacial acetic acid, cooling to about 15 ℃, dripping heavy nitrogen solution at about 20 ℃ and dripping within 1 hour to obtain azo dye, namely the environment-friendly papermaking dye.
In the technical scheme, in the reaction system of the step 1-1, the weight ratio of the components of the raw materials is as follows: 29.89% of solvent, 29.56% of pyridine and 40.54% of methyl monochloroacetate, wherein the reaction temperature is 70 ℃, the temperature is reduced to 50 ℃ after the reaction is carried out for 5 hours, the temperature is increased to 70 ℃ after crystallization is separated out, and the reaction is continued for 2 hours.
In the technical scheme, in the step 1-2 reaction system, the weight ratio of the components of the raw materials is as follows: 72.37% of quaternary amination product and 27.63% of 3-dimethylaminopropylamine.
In the technical scheme, in the reaction system of the step 1-3, the weight ratio of the components of the raw materials is as follows: 60.65% of aminolysis reaction products, 18.40% of 50% KOH solution and 20.95% of methyl acetoacetate.
In the technical scheme, in the step 2-1 reaction system, the weight ratio of the components of the raw materials is as follows: 16.51% of hydrochloric acid, 25.56% of beating water, 17.47% of 4,4' -diaminodiphenyl methane, 12.13% of sodium nitrite and 28.33% of water are added dropwise.
In the technical scheme, in the step 2-2 reaction system, the weight ratio of the components of the raw materials is as follows: diazonium reaction diazonium liquor 44.63%, glacial acetic acid 2.14% and dye intermediate 53.23%.
Compared with the prior art, the invention has the following advantages:
1. The invention is a high-concentration yellow cationic dye aqueous solution, is suitable for dyeing in the pulp of the cardboard paper manufactured by secondary fibers, does not need dye auxiliary agents, has good substantivity, is simple to use and operate, and can be automatically and accurately added.
2. The dye molecule of the invention is a cationic macromolecular plane structure, is easy to quickly and firmly adsorb the cellulose surface, has the advantages of quick coloring, high absorptivity and less residue after dyeing, can reduce the load of a sewage treatment system, and is suitable for the production of a high-speed paper machine.
3. The invention has simple production process, normal temperature and normal pressure synthesis conditions, and reduces the production safety risk; the production process has low energy consumption and less three wastes, and is an environment-friendly product. Has important significance for energy conservation and emission reduction.
[ Detailed description ] of the invention
The invention takes pyridine, methyl monochloroacetate, 3-dimethylaminopropylamine and methyl acetoacetate as raw materials and respectively carries out condensation and cyclization reactions of three steps in methanol solvent under different temperature conditions and alkali effects to synthesize quaternary amine cationic bipyridine heterocyclic compounds, and the molecular formula is as follows: 3-pyridinyl-4-methyl-5- (H) -6-hydroxy-N (N ', N' -dimethylaminopropyl) -pyridin-2 v-one, (hereinafter DPY). Taking the DPY intermediate compound as a coupling component; the yellow cationic liquid dye special for the cardboard paper is synthesized by taking 4,4' -diaminodiphenyl methane as a diazo component.
In preparing the present invention, the dye intermediate DPY synthesis comprises the steps of:
1-1, quaternized condensation reaction: the condensation reaction of pyridine and methyl monochloroacetate in methanol solvent is carried out at 70 deg.c for 5 hr, and then cooled to 50 deg.c for crystallization to separate out, and the temperature is raised to 70 deg.c for 2 hr to complete the condensation reaction. In the reaction system of the step 1-1, the weight ratio of the components of the raw materials is as follows:
solvent 29.89%
29.56% Of pyridine
Methyl monochloroacetate 40.54
1-2, Quaternization condensation product aminolysis condensation reaction: and cooling the quaternary amination product to 0 ℃ in the same container, dropwise adding 3-dimethylaminopropylamine at the temperature of 0-5 ℃ for condensation reaction, wherein the reaction is an aminolysis reaction, heating to 10 ℃ after the dropwise adding is finished, and continuously preserving the heat for 11 hours. In the reaction system of the step 1-2, the weight ratio of the components of the raw materials is as follows:
quaternary amination product 72.37%
3-Dimethylaminopropylamine 27.63%
1-3, Cyclizing reaction of the aminolysis reaction product to form a dye intermediate: adding 50% potassium hydroxide solution into the product obtained in the step 1-2 at about 0 ℃, dropwise adding methyl acetoacetate at the temperature of 0 ℃, carrying out a series of reactions such as nucleophilic addition, condensation, dehydration, demethanol cyclization and the like on the aminolysis reaction product and methyl acetoacetate under the action of 50% potassium hydroxide solution, closing the loop to generate a dye intermediate DPY, and supplementing the potassium hydroxide solution at any time in the dropwise adding process. And naturally heating to 30 ℃ in the later stage of the reaction, and distilling under reduced pressure to the distillation end point under the condition of the temperature. The distilled methanol is recovered and reused, the final product is DPY intermediate water solution, and a proper amount of water is added to adjust the content. And adjusting the pH value of the DPY aqueous solution to about 9.5 by glacial acetic acid. In the reaction system of the step 1-3, the weight ratio of the components of the raw materials is as follows:
Ammonolysis reaction product 60.65%
50% KOH solution 18.40%
Methyl acetoacetate 20.95%
The DPY intermediate prepared by the method is reacted with 4,4' -diaminodiphenyl methane to synthesize an azo compound, and the product is the yellow cationic liquid dye special for the cardboard paper.
Diazotizing 2-1, 4' -diaminodiphenyl methane, fully dissolving the diazotizing component 4,4' -diaminodiphenyl methane in concentrated hydrochloric acid (20%) solution (commonly called pulping), adding ice cubes, dropwise adding 30% sodium nitrite solution and 4,4' -diaminodiphenyl methane at the temperature of 5-10 ℃ for diazotizing, and obtaining diazonium liquid after the diazotizing reaction is completed. In the reaction system of the step 2-1, the weight ratio of the components of the raw materials is as follows:
2-2, synthesizing dye by coupling reaction, regulating the pH value of the DPY intermediate aqueous solution to about 7 by glacial acetic acid, cooling to about 15 ℃, dripping heavy nitrogen liquid at about 20 ℃, and dripping within 1 hour. The diazo component and the DPY coupling component are subjected to coupling reaction to obtain the azo dye, and the azo dye is the yellow liquid cationic dye special for the cardboard paper.
The chemical structural formula of the reaction system in the step 2-2 is as follows
In the reaction system of the step 2-2, the proportions (weight) of the components of the raw materials are as follows:
diazonium reaction diazonium liquor 44.63%
Glacial acetic acid 2.14%
DPY intermediate 53.23%
The product obtained by the above reaction is the dye of the invention, which has the following indexes:
Preferred embodiments
Dye intermediate DPY synthesis: 79.1g of pyridine, 108.52 g of methyl monochloroacetate and 80g of methanol are sequentially added into a 500ml four-necked flask provided with a stirrer and a thermometer; sealing and heating to 71 ℃, preserving heat and reacting for 5 hours, and cooling the materials to 50 ℃ until solid is separated out. And then heating to 71 ℃, and preserving heat for 2 hours to fully complete the quaternization condensation reaction. Cooling the reaction product in the bottle to 0 ℃ in the same reaction flask, dropwise adding 102.18g of 3-dimethylaminopropylamine, controlling the temperature to be about 0 ℃ in the dropwise adding process, naturally heating to 10 ℃ after the dropwise adding is finished, and keeping the temperature for continuous reaction for 11 hours, thus finishing the aminolysis condensation reaction. Cooling the reaction product in the bottle to 0 ℃, adding 112.2g of 50% potassium hydroxide solution, slowly dropwise adding 127.73g of methyl acetoacetate at low temperature for 12 hours, adding about 50g of potassium hydroxide solution at any time along with dropwise adding of the methyl acetoacetate, and naturally heating to 30 ℃ after the dropwise adding is finished, so that a series of reactions such as nucleophilic addition, dehydration, methanol removal cyclization and the like occur in the bottle. Sampling and detecting the content of the DPY intermediate in the product, performing reduced pressure distillation operation and condensing and recovering methanol when the content of the DPY intermediate in the product is not increased any more until the specific gravity of the materials in the system reaches 1.13-1.136 as a distillation end point, adding water to adjust the content and glacial acetic acid to adjust the PH value of the DPY intermediate to about 9.5 and the content of the DPY intermediate to about 28-30%, thus obtaining DPY intermediate aqueous solution for the next step.
The diazo and coupling reaction operation is carried out between 4,4' -diaminodiphenyl methane and an intermediate DPY to synthesize the dye: 38.75g of hydrochloric acid (calculated by HCl), 60g of water and 41g of 4,4' -diaminodiphenyl methane are respectively added into a 500ml four-neck flask with a stirrer and a thermometer, the stirring and the mixing start to react and release heat, the temperature in the flask naturally rises to 50 ℃, and the solution and the slurry are continuously dissolved and pulped for 12 hours under the heat preservation, and the process is commonly called pulping operation. When beating is fully completed, adding a proper amount of water and ice cubes, and reducing the temperature to 0 ℃. 28.5g of sodium nitrite was dissolved in 66.5g of water to give 95930% sodium nitrite solution. The sodium nitrite solution was added dropwise to the slurry mixture of 4,4' -diaminodiphenylmethane for a diazotization reaction for 50 minutes. The temperature of the reaction system is controlled at 5-10 ℃ and the PH value is lower than 3. As the diazonium reaction rapidly releases heat to heat the system, ice cubes are continuously added in the operation process, and the reaction bottle is placed in a low-temperature constant-temperature tank at 4 ℃, so that side reactions caused by the excessively rapid temperature rise of the system are prevented. And in the operation process of the diazonium reaction, using starch potassium iodide test paper to test whether the reactant reaches a diazonium end point, when the test result of the starch potassium iodide test paper just turns blue after the dripping is finished, adding a little excessive sodium nitrite solution, and simultaneously using Congo red test paper to test whether the PH value of the reactant is lower than 3, and adding hydrochloric acid when the PH value is higher than 3. And (3) maintaining the condition of slightly excessive nitrous acid in the system at the end point of the diazonium reaction, and continuing the constant-temperature reaction for 2 hours for standby. DPY intermediate 113g was placed in a 1000mL four-necked flask equipped with a stirrer and a thermometer, and the pH was adjusted to about 7 with glacial acetic acid. And cooling to below 15 ℃, beginning to drop the diazonium solution for coupling reaction, and destroying excessive nitrous acid in the diazonium solution by sulfamic acid before dropping, wherein the dosage is just colorless when tested by using starch potassium iodide test paper. The coupling reaction is carried out at 15-20 ℃, the coupling reaction is completed within 1 hour, and water is added to adjust the content, so that about 1000 g of yellow cationic liquid dye special for the cardboard paper is finally obtained.
The foregoing is merely illustrative of the technical solution of the embodiments of the present invention, and is not meant to be limiting, and those skilled in the art will understand that the technical solution of the embodiments of the present invention may be modified or equivalently replaced, and that the modified or equivalent replacement does not deviate from the scope of the technical solution of the embodiments of the present invention.
Claims (7)
1. An environment-friendly papermaking dye is characterized in that pyridine, methyl monochloroacetate, 3-dimethylaminopropylamine and methyl acetoacetate are used as raw materials, and condensation and cyclization reactions of three steps are respectively carried out in a methanol solvent under different temperature conditions and under the action of alkali to synthesize quaternary amine cation bipyridine heterocyclic compounds; the bipyridine heterocyclic compound is used as a coupling component, 4' -diaminodiphenyl methane is used as a diazo component, and a yellow cationic liquid dye for cardboard paper is synthesized;
The molecular formula of the bipyridine heterocyclic compound is as follows: 3-pyridinyl-4-methyl-5- (H) -6-hydroxy-N (N ', N' -dimethylaminopropyl) -pyridin-2-one.
2. The preparation method of the environment-friendly papermaking dye is characterized in that the azo compound synthesized by reacting the synthesized dye intermediate with 4,4' -diaminodiphenyl methane is the environment-friendly papermaking dye; wherein, the dye intermediate DPY synthesis comprises the following steps:
1-1, quaternized condensation reaction: the condensation reaction of pyridine and methyl monochloroacetate in methanol solvent is carried out to separate out crystallization;
1-2, quaternization condensation product aminolysis condensation reaction: cooling the quaternized product in the step 1-1 to 0 ℃ in the same container, and dropwise adding 3-dimethylaminopropylamine at the temperature of 0-5 ℃ for condensation reaction, wherein the reaction is aminolysis reaction;
1-3, adding 50% potassium hydroxide solution into the product obtained in the step 1-2 at the temperature of 0 ℃, and dropwise adding methyl acetoacetate at the temperature of 0 ℃ to generate a dye intermediate DPY;
The prepared dye intermediate reacts with 4,4' -diaminodiphenyl methane to synthesize azo compound, and the product is the paper-making dye, which comprises the following steps:
Diazotizing 2-1, 4' -diaminodiphenyl methane, fully dissolving the diazotizing component 4,4' -diaminodiphenyl methane in concentrated hydrochloric acid solution, adding ice cubes, dropwise adding 30% sodium nitrite solution and 4,4' -diaminodiphenyl methane at the temperature of 5-10 ℃ for diazotizing, and obtaining diazonium solution after diazotizing;
2-2, coupling reaction to synthesize dye, regulating pH value of the dye intermediate aqueous solution to 7 by glacial acetic acid, cooling to about 15 ℃, dripping heavy nitrogen solution at about 20 ℃ and dripping within 1 hour to obtain azo dye, namely the environment-friendly papermaking dye.
3. The method for preparing the environment-friendly papermaking dye according to claim 2, wherein in the reaction system of the step 1-1, the weight ratio of the components of the raw materials is as follows: 29.89% of solvent, 29.56% of pyridine and 40.54% of methyl monochloroacetate, wherein the reaction temperature is 70 ℃, the temperature is reduced to 50 ℃ after the reaction is carried out for 5 hours, the temperature is increased to 70 ℃ after crystallization is separated out, and the reaction is continued for 2 hours.
4. The method for preparing the environment-friendly papermaking dye according to claim 2, wherein in the reaction system of the step 1-2, the weight ratio of the components of the raw materials is as follows: 72.37% of quaternary amination product and 27.63% of 3-dimethylaminopropylamine.
5. The method for preparing the environment-friendly papermaking dye according to claim 2, wherein in the reaction system of the step 1-3, the weight ratio of the components of the raw materials is as follows: 60.65% of aminolysis reaction products, 18.40% of 50% KOH solution and 20.95% of methyl acetoacetate.
6. The method for preparing the environment-friendly papermaking dye according to claim 2, wherein in the reaction system of the step 2-1, the weight ratio of the components of the raw materials is as follows: 16.51% of hydrochloric acid, 25.56% of beating water, 17.47% of 4,4' -diaminodiphenyl methane, 12.13% of sodium nitrite and 28.33% of water are added dropwise.
7. The method for preparing the environment-friendly papermaking dye according to claim 2, wherein in the reaction system of the step 2-2, the weight ratio of the components of the raw materials is as follows: diazonium reaction diazonium liquor 44.63%, glacial acetic acid 2.14% and dye intermediate 53.23%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410144667.2A CN118027704A (en) | 2024-02-01 | 2024-02-01 | Environment-friendly papermaking dye and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410144667.2A CN118027704A (en) | 2024-02-01 | 2024-02-01 | Environment-friendly papermaking dye and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118027704A true CN118027704A (en) | 2024-05-14 |
Family
ID=90990622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410144667.2A Pending CN118027704A (en) | 2024-02-01 | 2024-02-01 | Environment-friendly papermaking dye and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118027704A (en) |
-
2024
- 2024-02-01 CN CN202410144667.2A patent/CN118027704A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103228739B (en) | Azo dye | |
| US4257770A (en) | Disazo dye composition | |
| EP2049599B1 (en) | Basic bisazo compounds | |
| CN102838883A (en) | Preparation method for C.I. paratonere 49:1 | |
| CN111217764B (en) | Method for preparing 6-nitro-1, 2, 4-acid oxygen | |
| CN118027704A (en) | Environment-friendly papermaking dye and preparation method thereof | |
| CN107828240B (en) | A kind of preparation method and application of dark blue reactive dye mill base | |
| US6719906B1 (en) | Process for the preparation of solutions of anionic organic compounds | |
| CN108997774B (en) | Method for producing organic cobalt complex | |
| KR100270403B1 (en) | Reactive red dyes containing monochlorotriazine and acetoxyethyl sulfone groups | |
| CN111100478A (en) | Preparation method and application of blue dye with three active groups | |
| CN112322073B (en) | Monoazo lake pigment and preparation method thereof | |
| CN112322068B (en) | Monoazo yellow organic pigment and preparation method thereof | |
| CN112409812A (en) | Preparation method of novel heterocyclic nitrogen-coupled disperse dye | |
| US4699628A (en) | Process for the preparation of a water soluble direct green polyazo dyestuffs mixture in situ and water soluble direct green polyazo dyestuffs mixture obtained thereby | |
| CN102351792A (en) | Azonaphthalene dicarboximide compound and composition, preparation and application thereof | |
| CN106634042B (en) | A kind of one-step method for synthesizing of active black dye | |
| CN101481521A (en) | Bright yellow reactive dye for fur and preparation thereof | |
| CN112226098A (en) | Direct dye and preparation method thereof | |
| CN107805403A (en) | A kind of preparation method of faintly acid orchil | |
| CN113121447B (en) | Synthetic method for preparing 5-aminobenzimidazolone | |
| CA1181066A (en) | Monoazo and disazo dyestuffs containing aminoalkylenesulfonamido moieties | |
| CN114085547B (en) | Green medium-temperature reactive dye and preparation method thereof | |
| CN112679979B (en) | Preparation method of benzotriazole ultraviolet absorber intermediate azo dye | |
| CN110878176B (en) | Reactive dye compound and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |