CN116463868A - Aldehyde-free color fixing agent and preparation method thereof - Google Patents
Aldehyde-free color fixing agent and preparation method thereof Download PDFInfo
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- CN116463868A CN116463868A CN202310375602.4A CN202310375602A CN116463868A CN 116463868 A CN116463868 A CN 116463868A CN 202310375602 A CN202310375602 A CN 202310375602A CN 116463868 A CN116463868 A CN 116463868A
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- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 67
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 58
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical group [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 23
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 96
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical group NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 33
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 2
- 230000002035 prolonged effect Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 239000004744 fabric Substances 0.000 abstract description 5
- 125000002091 cationic group Chemical group 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001450 anions Chemical class 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000269 nucleophilic effect Effects 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000007888 film coating Substances 0.000 abstract 1
- 238000009501 film coating Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000975 dye Substances 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- -1 cationic ammonium salt Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
- D06P5/08—After-treatment with organic compounds macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The application discloses an aldehyde-free color fixing agent and a preparation method thereof, and relates to the technical field of color fixing agents; the formaldehyde-free fixing agent is prepared from the following components in parts by weight: 130-140 parts of monomer; 8-11 parts of cross-linking agent; initiator 4-5.5 parts: 290-300 parts of deionized water; wherein the monomer is a dimethyl diallyl ammonium chloride aqueous solution with the mass percentage concentration of 60% or more. The nucleophilic group-NH-contained in the polydimethyl diallyl ammonium chloride polymer can be covalently bonded with active chlorine in active dye molecules, so that the water solubility of the dye is reduced, the strong cationic property of the copolymer is combined with anions to form color lake by ionic bonds, a network structure formed by a long chain structure can form a film coating dye molecule on the surface of the fabric to prevent loss of the dye molecules, the color fixing effect is achieved, the utilization rate of diallyl amine is improved under the action of equivalent diallyl amine, and the cost is saved.
Description
Technical Field
The application relates to the technical field of color fixing agents, in particular to an aldehyde-free color fixing agent and a preparation method thereof.
Background
Currently, the fixing agent is one of important auxiliary agents in the printing and dyeing industry, and forms insoluble colored matters with dyes on fabrics so as to improve the washing and perspiration fastness of the colors, and the like. In the current market, the color fixing agent is various, contains formaldehyde in many ways, and the color fixing effect is not ideal. Along with the development of scientific technology, the living standard and environmental awareness of people are improved, laws and regulations are perfected successively, and the development of the formaldehyde-free color fixing agent meets the demands of people.
Diallyl amine is used as one of important raw materials for industrial production of aldehyde-free fixing agents, however, few domestic manufacturers and only a few foreign manufacturers produce the diallyl amine, and the yield is difficult to reach the market demand.
In the market at present, the formaldehyde-free color fixing agent obtained by copolymerizing diallyl amine and dimethyl diallyl ammonium chloride has high cost; and the temperature is higher during the preparation, which is easy to cause the following conditions: the toxic substances of the diallylamine volatilize, so that potential safety hazards exist; the viscosity is too large, so that the motor load is too large and the energy consumption is high; the dispersibility of the copolymer is affected, and the color fixing effect is poor.
Disclosure of Invention
In order to solve at least one technical problem, an aldehyde-free fixing agent which is environment-friendly, low in cost and good in fixing effect is developed.
On the one hand, the formaldehyde-free fixing agent provided by the application is prepared from the following components in parts by weight: 130-140 parts of monomer; 8-11 parts of cross-linking agent; initiator 4-5.5 parts: 290-300 parts of deionized water; wherein the monomer is a dimethyl diallyl ammonium chloride aqueous solution with the mass percentage concentration of 60% or more.
Through adopting above-mentioned technical scheme, the aldehyde-free fixing agent of this application design, in the nucleophilic group-NH-that polydimethyl diallyl ammonium chloride polymer contained, can take place covalent bond with the active chlorine in the active dye molecule and combine, the water solubility of dyestuff has been reduced, in addition, the strong cationic nature of copolymer, can combine with the anion with the ionic bond and produce the laked lake, and the network structure that long-chain structure formed can form film cladding dyestuff molecule on the fabric surface and prevent the loss of dyestuff molecule, thereby reach the fixation effect, and through this formula, make under the effect of equivalent diallylamine, the monomer conversion reaches the highest, greatly improved the utilization ratio of diallylamine, the cost of producing aldehyde-free fixing agent has been practiced thrift.
Optionally, the cross-linking agent is diallylamine.
Optionally, the initiator is a sodium persulfate solution with a mass percent concentration of 15%.
In a second aspect, the present application provides a method for preparing the formaldehyde-free fixing agent, including the following steps:
s1: adding deionized water into a reaction kettle, adding a crosslinking agent and 30-50wt% of monomer, and stirring for reaction;
s2: dropwise adding hydrochloric acid into the reaction kettle, and adjusting the pH;
s3: heating, dropwise adding 30-50wt% of initiator under stirring, heating, and keeping the temperature of the reaction kettle for continuous reaction;
s4: keeping the temperature in the reaction kettle unchanged, dropwise adding the rest initiator and monomer into the reaction kettle, and keeping the temperature for continuous reaction after the completion of dropwise adding;
s5: cooling, adding liquid alkali to regulate pH and sugar degree to obtain the target product.
By adopting the technical scheme, the whole preparation process of the formaldehyde-free color fixing agent is simple, easy to prepare, mild in process condition and optimal in color fixing effect.
Optionally, the mass percentage concentration of hydrochloric acid in the S2 is 37%; the liquid alkali in the step S5 is sodium hydroxide aqueous solution with the mass percentage concentration of 48-51%.
By adopting the technical scheme, the pH value environment suitable for copolymerization of the monomer and the crosslinking agent is created under the neutralization action of the specific hydrochloric acid and the specific liquid alkali, the pH value of the product can be efficiently regulated, and the reaction is facilitated.
Optionally, in the step S2, hydrochloric acid is dropwise added until the pH value in the reaction kettle is 2.0-3.0; the dripping time is 1-1.5h.
By adopting the technical scheme, the dropping rate of hydrochloric acid is controlled, the reaction heat release is controlled, volatilization of diallylamine toxic substances is avoided, poisoning is avoided, and meanwhile, the damage caused by material overflow or equipment pressure holding caused by that equipment is not sealed or a pressure release device is not arranged is avoided.
Optionally, in S3, after heating to 40 ℃, an initiator is added dropwise.
By adopting the technical scheme, when the temperature is heated to 40 ℃, the exothermic mechanism of the reaction is controlled by adding the initiator, so that the reaction temperature of the reaction is reached, the production cost is saved, and the energy consumption is reduced.
Optionally, in the step S3, after the initiator is added dropwise, the temperature in the reaction kettle is raised to 65-75 ℃, and the temperature in the reaction kettle is kept at 65-75 ℃ for continuous reaction.
Optionally, in the step S4, the monomer and the initiator are added dropwise at the same time, and the adding time of the monomer is 3-4h; the dripping time of the initiator is prolonged by 10-15min based on the monomer dripping time, and the heat preservation time is 2h.
By adopting the scheme, the exothermic reaction is controlled by controlling the dropping rate of the monomer and the initiator, so that the product is kept in a better viscosity range, and the color fixing effect is optimal.
Optionally, in the step S5, the temperature is reduced to 40-50 ℃, the pH value is adjusted to 4.0-6.0, and the sugar degree is adjusted to 42.0-43.0.
The environment is regulated to be an acidic environment, under the environment, the amine in the product exists in the form of cationic ammonium salt, positive-charged amine or ammonium ions are densely distributed on long molecular chains, the neutral dye ionizes in aqueous solution to enable dye parent body to be negatively charged, and insoluble solid precipitate is formed under the interaction of the positive-charged amine and the ammonium salt to be deposited on the surface of the fabric, so that loss of dye molecules is prevented.
In summary, the present invention includes at least one of the following beneficial technical effects:
1. the formaldehyde-free color fixing agent improves the utilization rate of diallylamine, saves the raw material cost for producing the formaldehyde-free color fixing agent, and has good color fixing effect;
2. the formaldehyde-free color fixing agent is simple in preparation process, exothermic reaction is controlled by controlling the addition of the crosslinking agent and the initiator, so that the reaction temperature is controlled, the energy consumption is reduced, the viscosity range of the color fixing agent is ensured, the load of a motor is reduced, and the production cost for producing the formaldehyde-free color fixing agent is saved;
3. the formaldehyde-free color fixing agent has safe production process and reduces potential safety hazards.
Detailed Description
The present application is described in further detail below with reference to examples.
The application designs an aldehyde-free color fixing agent which is prepared from the following components in parts by weight: 130-140 parts of monomer; 8-11 parts of cross-linking agent; 4-5.5 parts of an initiator; 290-300 parts of deionized water; wherein the monomer is a dimethyl diallyl ammonium chloride aqueous solution with the mass percentage concentration of 60% or more.
Prior to this application, the existing fixing agents were mainly divided into cationic fixing agents and resin fixing agents, whereas most of resin fixing agents contained formaldehyde fixing agents, which did not meet the existing law, green and environmental protection concepts. Furthermore, the formaldehyde-free color fixing agent is developed, and the diallylamine is used as one of important raw materials of the formaldehyde-free color fixing agent, so that the production of the formaldehyde-free color fixing agent is less in manufacturers, the yield of the formaldehyde-free color fixing agent does not meet the market demand, and the cost is high.
The inventor of the application finds in experiments that after a specific formula is selected, the monomer conversion rate can be optimized, the utilization rate of the diallylamine is highest, the raw material cost is greatly saved, and the produced formaldehyde-free color fixing agent has excellent color fixing performance. Based on the above findings, the inventors of the present application devised the formaldehyde-free fixing agent of the present application.
The formaldehyde-free fixing agent is prepared by the following method and comprises the following steps:
s1: adding deionized water into a reaction kettle, adding a crosslinking agent and 30-50wt% of monomer, and stirring for reaction;
s2: dropwise adding hydrochloric acid into the reaction kettle, and adjusting the pH;
s3: heating, dropwise adding 30-50wt% of initiator under stirring, heating, and keeping the temperature of the reaction kettle for continuous reaction;
s4: keeping the temperature in the reaction kettle unchanged, dropwise adding the rest initiator and monomer into the reaction kettle, and keeping the temperature for continuous reaction after the completion of dropwise adding;
s5: cooling, adding liquid alkali to regulate pH and sugar degree to obtain the target product.
The components referred to in the formulations of the present application are commercially available, unless specified otherwise.
Dimethyl diallyl ammonium chloride: purity was not less than 99% from the company limited by chemical technology, eastern, hubei;
diallylamine purchased from Pingming chemical industry Co., ltd, purity not lower than 99%;
sodium persulfate: the purity is not lower than 99% and is purchased from Jinan Jin chemical industry Co., ltd;
hydrochloric acid: purchased from national medicine reagent net, brand of Shanghai test, concentration of 37%;
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
29.5kg of deionized water is added into a reaction kettle, 0.8kg of diallylamine and 3.9kg of dimethyl diallyl ammonium chloride aqueous solution with the mass percentage concentration of 60 percent are added, and stirring reaction is carried out; dropwise adding hydrochloric acid into the reaction kettle within 1h, and adjusting the pH to 2; raising the temperature in the reaction kettle to 40 ℃, dropwise adding 0.225kg of sodium persulfate aqueous solution (the mass percentage concentration of the sodium persulfate aqueous solution is 15%) under stirring, raising the temperature to 65 ℃, and keeping the temperature of the reaction kettle for continuous reaction.
The temperature in the reaction kettle is kept unchanged, 0.225kg of sodium persulfate aqueous solution (15% of the mass percentage concentration of the sodium persulfate aqueous solution) and 9.1kg of dimethyl diallyl ammonium chloride aqueous solution (60% of the mass percentage concentration) are simultaneously added into the reaction kettle, the adding time of the dimethyl diallyl ammonium chloride aqueous solution is 3 hours, and the adding time of the sodium persulfate aqueous solution is 10 minutes longer than the adding time of the dimethyl diallyl ammonium chloride aqueous solution; after the completion of the dropping, the reaction was continued for 2 hours while maintaining the temperature.
Cooling to 40 ℃, adding a sodium hydroxide aqueous solution with the mass percent concentration of 48% to adjust the pH to 4, and adjusting the sugar degree to 42 to obtain the formaldehyde-free color fixing agent.
Example 2
Adding 30kg of deionized water into a reaction kettle, adding 0.9kg of diallylamine and 5.28kg of dimethyl diallyl ammonium chloride aqueous solution with the mass percentage concentration of 65%, and stirring for reaction; dropwise adding hydrochloric acid into the reaction kettle within 1.2h, and adjusting the pH to 2.2; raising the temperature in the reaction kettle to 40 ℃, dropwise adding 0.165kg of sodium persulfate aqueous solution (the mass percentage concentration of the sodium persulfate aqueous solution is 15%) under stirring, raising the temperature to 67 ℃, and keeping the temperature of the reaction kettle to continue the reaction.
The temperature in the reaction kettle is kept unchanged, 0.385kg of sodium persulfate aqueous solution (15% of the mass percentage concentration of the sodium persulfate aqueous solution) and 7.92kg of dimethyl diallyl ammonium chloride aqueous solution (65% of the mass percentage concentration) are simultaneously added into the reaction kettle, the adding time of the dimethyl diallyl ammonium chloride aqueous solution is 3.5h, and the adding time of the sodium persulfate aqueous solution is 12min longer than the adding time of the dimethyl diallyl ammonium chloride aqueous solution; after the completion of the dropping, the reaction was continued for 2 hours while maintaining the temperature.
Cooling to 45 ℃, adding a sodium hydroxide aqueous solution with the mass percent concentration of 49% to adjust the pH to 5, and adjusting the sugar degree to 42 to obtain the formaldehyde-free color fixing agent.
Example 3
29kg of deionized water is added into a reaction kettle, 1kg of diallylamine and 6.7kg of dimethyl diallyl ammonium chloride aqueous solution with the mass percent concentration of 70% are added, and the mixture is stirred for reaction; dropwise adding hydrochloric acid into the reaction kettle within 1.3h, and adjusting the pH to 2.4; raising the temperature in the reaction kettle to 40 ℃, dropwise adding 0.2kg of sodium persulfate aqueous solution (the mass percentage concentration of the sodium persulfate aqueous solution is 15%) under stirring, raising the temperature to 69 ℃, and keeping the temperature of the reaction kettle for continuous reaction.
The temperature in the reaction kettle is kept unchanged, 0.3kg of sodium persulfate aqueous solution (15% of the mass percentage concentration of the sodium persulfate aqueous solution) and 6.7kg of dimethyl diallyl ammonium chloride aqueous solution (70% of the mass percentage concentration) are simultaneously added into the reaction kettle, the adding time of the dimethyl diallyl ammonium chloride aqueous solution is 3.7h, and the adding time of the sodium persulfate aqueous solution is 13min longer than the adding time of the dimethyl diallyl ammonium chloride aqueous solution; after the completion of the dropping, the reaction was continued for 2 hours while maintaining the temperature.
Cooling to 47 ℃, adding a sodium hydroxide aqueous solution with the mass percent concentration of 50% to adjust the pH to 5.2, and adjusting the sugar degree to 42 to obtain the formaldehyde-free color fixing agent.
Example 4
29.5kg of deionized water is added into a reaction kettle, 1.1kg of diallylamine and 5.44kg of dimethyl diallyl ammonium chloride aqueous solution with the mass percentage concentration of 75% are added, and the mixture is stirred for reaction; dropwise adding hydrochloric acid into the reaction kettle within 1.5h, and adjusting the pH to 2.5; raising the temperature in the reaction kettle to 40 ℃, dropwise adding 0.2kg of sodium persulfate aqueous solution (the mass percentage concentration of the sodium persulfate aqueous solution is 15%) under stirring, raising the temperature to 72 ℃, and keeping the temperature of the reaction kettle for continuous reaction.
The temperature in the reaction kettle is kept unchanged, 0.2kg of sodium persulfate aqueous solution (15% of the mass percentage concentration of the sodium persulfate aqueous solution) and 8.16kg of dimethyl diallyl ammonium chloride aqueous solution (75% of the mass percentage concentration) are simultaneously added into the reaction kettle, the adding time of the dimethyl diallyl ammonium chloride aqueous solution is 3.9h, and the adding time of the sodium persulfate aqueous solution is 15min longer than the adding time of the dimethyl diallyl ammonium chloride aqueous solution; after the completion of the dropping, the reaction was continued for 2 hours while maintaining the temperature.
Cooling to 50 ℃, adding a sodium hydroxide aqueous solution with the mass percent concentration of 51% to adjust the pH to 5.5, and adjusting the sugar degree to 43 to obtain the formaldehyde-free color fixing agent.
Example 5
Adding 30kg of deionized water into a reaction kettle, adding 0.8kg of diallylamine and 4.14kg of dimethyl diallyl ammonium chloride aqueous solution with the mass percent concentration of 80%, and stirring for reaction; dropwise adding hydrochloric acid into the reaction kettle within 1.2h, and adjusting the pH to 2.7; raising the temperature in the reaction kettle to 40 ℃, dropwise adding 0.2kg of sodium persulfate aqueous solution (the mass percentage concentration of the sodium persulfate aqueous solution is 15%) under stirring, raising the temperature to 75 ℃, and keeping the temperature of the reaction kettle to continue the reaction.
The temperature in the reaction kettle is kept unchanged, 0.3kg of sodium persulfate aqueous solution (15% of the mass percentage concentration of the sodium persulfate aqueous solution) and 9.66kg of dimethyl diallyl ammonium chloride aqueous solution (80% of the mass percentage concentration) are simultaneously added into the reaction kettle, the adding time of the dimethyl diallyl ammonium chloride aqueous solution is 4 hours, and the adding time of the sodium persulfate aqueous solution is 12 minutes longer than the adding time of the dimethyl diallyl ammonium chloride aqueous solution; after the completion of the dropping, the reaction was continued for 2 hours while maintaining the temperature.
Cooling to 45 ℃, adding a sodium hydroxide aqueous solution with the mass percent concentration of 49% to adjust the pH to 5.8, and adjusting the sugar degree to 43 to obtain the formaldehyde-free color fixing agent.
Example 6
29kg of deionized water is added into a reaction kettle, 1kg of diallylamine and 7kg of dimethyl diallyl ammonium chloride aqueous solution with the mass percentage concentration of 85 percent are added, and the mixture is stirred for reaction; dropwise adding hydrochloric acid into the reaction kettle within 1h, and adjusting the pH to 3; raising the temperature in the reaction kettle to 40 ℃, dropwise adding 0.12kg of sodium persulfate aqueous solution (the mass percentage concentration of the sodium persulfate aqueous solution is 15%) under stirring, raising the temperature to 73 ℃, and keeping the temperature of the reaction kettle to continue the reaction.
The temperature in the reaction kettle is kept unchanged, 0.28kg of sodium persulfate aqueous solution (15% of the mass percentage concentration of the sodium persulfate aqueous solution) and 7kg of dimethyl diallyl ammonium chloride aqueous solution (85% of the mass percentage concentration) are simultaneously added into the reaction kettle, the adding time of the dimethyl diallyl ammonium chloride aqueous solution is 3.8h, and the adding time of the sodium persulfate aqueous solution is 15min longer than the adding time of the dimethyl diallyl ammonium chloride aqueous solution; after the completion of the dropping, the reaction was continued for 2 hours while maintaining the temperature.
Cooling to 50 ℃, adding a sodium hydroxide aqueous solution with the mass percent concentration of 50% to adjust the pH to 6, and adjusting the sugar degree to 42 to obtain the formaldehyde-free color fixing agent.
Comparative example 1
The comparative example used a T-21 formaldehyde-free fixing agent from Ningbo Aoxing fine chemical Co.
Comparative example 2
The comparative example uses a dye fixing agent (RD) of the Xinrun chemical industry.
Comparative example 3
The comparative example used a dye fixing agent (26062-79-3) in the constant chemical industry.
Performance tests were performed on examples 1-6 and comparative examples 1-3, experimental fabrics: 100% cotton knit (reddish-colored); the experimental process comprises the following steps: 40 ℃ x 20';
the rubbing fastness testing method is measured according to the method of GB/T3920-2008 "rubbing fastness to textile color fastness test";
the washing fastness testing method is measured according to the method of GB/T3921-2008 washing fastness test of textile color fastness;
the experimental results are shown in table 1:
TABLE 1 results of Performance test of examples 1-6 and comparative examples 1-3
As can be seen from examples 1-6, comparative examples 1-3 and Table 1, the formaldehyde-free fixing agent prepared by the formulation of the present application has a dry friction grade not lower than the prior art, a wet friction grade not lower than the prior art, a staining grade not lower than the prior art, and the formaldehyde-free fixing agent prepared by the formulation of the present application has an addition of 0.4g/L, an addition of 0.5g/L lower than that of comparative example 1, but has an effect not lower than that of comparative example 1, superior to that of comparative examples 2-3; therefore, the formaldehyde-free color fixing agent prepared by the formula has high efficiency and good color fixing effect.
The foregoing are all preferred embodiments of the present application, and are not intended to limit the scope of the present application in any way, therefore: all equivalent changes in structure, shape and principle of this application should be covered in the protection scope of this application.
Claims (10)
1. The formaldehyde-free color fixing agent is characterized by being prepared from the following components in parts by weight: 130-140 parts of monomer; 8-11 parts of cross-linking agent; initiator 4-5.5 parts: 290-300 parts of deionized water; wherein the monomer is a dimethyl diallyl ammonium chloride aqueous solution with the mass percentage concentration of 60% or more.
2. The formaldehyde-free fixing agent of claim 1 wherein the crosslinking agent is diallylamine.
3. The formaldehyde-free fixing agent according to claim 1, wherein the initiator is a sodium persulfate solution with a mass percent concentration of 15%.
4. A method of preparing the formaldehyde-free fixing agent of claim 1, comprising the steps of:
s1: adding deionized water into a reaction kettle, adding a crosslinking agent and 30-50wt% of monomer, and stirring for reaction;
s2: dropwise adding hydrochloric acid into the reaction kettle, and adjusting the pH;
s3: heating, dropwise adding 30-50wt% of initiator under stirring, heating, and keeping the temperature of the reaction kettle for continuous reaction;
s4: keeping the temperature in the reaction kettle unchanged, dropwise adding the rest initiator and monomer into the reaction kettle, and keeping the temperature for continuous reaction after the completion of dropwise adding;
s5: cooling, adding liquid alkali to regulate pH and sugar degree to obtain the target product.
5. The method for preparing the formaldehyde-free fixing agent according to claim 4, wherein the mass percentage concentration of hydrochloric acid in the S2 is 37%; the liquid alkali in the step S5 is sodium hydroxide aqueous solution with the mass percentage concentration of 48-51%.
6. The method for preparing aldehyde-free fixing agent according to claim 4, wherein in S2, hydrochloric acid is added dropwise to the inside of the reaction kettle until the pH value is 2.0-3.0; the dripping time is 1-1.5h.
7. The process for preparing an aldehyde-free fixing agent according to claim 4, wherein in S3, an initiator is added dropwise after the temperature is raised to 40 ℃.
8. The process for preparing aldehyde-free fixing agents according to claim 4, wherein in S3, after the initiator is added dropwise, the temperature in the reaction vessel is raised to 65 to 75 ℃ and the reaction is continued while maintaining the temperature in the reaction vessel at 65 to 75 ℃.
9. The method for preparing aldehyde-free fixing agent according to claim 4, wherein in S4, the monomer and the initiator are added dropwise at the same time, and the monomer is added dropwise for 3-4 hours; the dripping time of the initiator is prolonged by 10-15min based on the monomer dripping time, and the heat preservation time is 2h.
10. The process for preparing aldehyde-free fixing agents according to claim 4, wherein in S5, the temperature is lowered to 40-50 ℃, the pH is adjusted to 4.0-6.0, and the sugar degree is adjusted to 42.0-43.0.
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