CN112574355B - Active dye acid-proof agent and preparation method thereof - Google Patents

Active dye acid-proof agent and preparation method thereof Download PDF

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CN112574355B
CN112574355B CN202011278790.1A CN202011278790A CN112574355B CN 112574355 B CN112574355 B CN 112574355B CN 202011278790 A CN202011278790 A CN 202011278790A CN 112574355 B CN112574355 B CN 112574355B
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acid
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titanium carbonitride
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CN112574355A (en
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宛斌
杜尧森
王腾军
刘秀峰
袁辉
刘鹏远
陈冬冬
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Linqing Sanhe Textile Group Co ltd
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    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0014—Influencing the physical properties by treatment with a liquid, e.g. solvents
    • 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
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0072—Preparations with anionic dyes or reactive dyes
    • 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
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
    • 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
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/673—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses an active dye acid-proofing agent and a preparation method thereof, which comprises the steps of firstly taking triethylene tetramine and methyl acrylate as raw materials to react to prepare an end amino compound, then adding the end amino compound, a fluorine-containing monomer, an initiator, a cross-linking agent and a modified nano material into a mixed solution of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt and 1-hydroxyethyl-3-methylimidazolium dinitrile amine salt, and uniformly dispersing by ultrasonic waves to obtain the active dye acid-proofing agent, wherein the acid-proofing effect of active dye is greatly improved.

Description

Active dye acid-proof agent and preparation method thereof
Technical Field
The invention relates to an acid-proof agent of a reactive dye and a preparation method thereof. Belongs to the technical field of dye auxiliary agents.
Background
The reactive dye is also called reactive dye, is a novel water-soluble dye appearing in the 50 th century, contains reactive groups capable of reacting with hydroxyl in cellulose and amino in protein fiber in molecules, and generates covalent bonds with the fiber during dyeing to generate a dye-fiber compound. The reactive dye has the characteristics of bright color, good leveling property, simple and convenient dyeing method, high dyeing fastness, complete chromatogram, lower cost and the like.
Although the reactive groups in the reactive dye molecule are susceptible to covalent bonding with the fiber, the color fastness is not ideal. During the dyeing process, particularly when the fabric is dyed in dark color, a large amount of unfixed reactive dyes exist on the dyed fabric due to the fact that the dye concentration is too high, the unfixed dyes are difficult to wash off the dyed fabric, and the dyes can fade during the washing process; meanwhile, chemical bonds formed between some active groups and fibers are easy to hydrolyze, so that the wet treatment fastness is low. In addition, the reactive dye dyed fabric has poor acid resistance, so that the fabric is easy to fade and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an active dye acid-proofing agent and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an active dye acid-proofing agent comprises the steps of firstly, taking trivinyl tetramine and methyl acrylate as raw materials to react to prepare an amine-terminated compound, then adding the amine-terminated compound, a fluorine-containing monomer, an initiator, a cross-linking agent and a modified nano material into a mixed solution of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt and 1-hydroxyethyl-3-methylimidazolium dinitrile amine salt, and uniformly dispersing by ultrasonic waves to obtain the active dye acid-proofing agent; the modified nano material is prepared by using nano titanium carbonitride and selenious acid as raw materials to prepare a nano material and then performing modification treatment by using gamma-aminoethyl aminopropyl trimethoxysilane.
Preferably, the preparation method of the amine-terminated compound comprises the following steps: firstly, 1 part of triethylene tetramine is placed in a cold water bath, a mixed solution of 0.7-0.9 part of methyl acrylate and 2-3 parts of methanol is slowly dripped at a constant speed under the protection of nitrogen, after the dripping is finished, the mixed solution is stirred and reacts for 3-5 hours at 25-30 ℃, the methanol is removed under reduced pressure, the mixed solution is heated to 140-150 ℃, and the stirring and the reaction are continued for 3-4 hours, so that the terminal amino compound is obtained.
Further preferably, the dropping time is 40 to 60 minutes.
Preferably, the mass ratio of the amine-terminated compound, the fluorine-containing monomer, the initiator, the crosslinking agent, the modified nano material, the tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt and the 1-hydroxyethyl-3-methylimidazolium dinitrile amine salt is 1: 5-8: 0.5-0.7: 0.6-0.8: 0.3-0.5: 7-9: 3 to 5.
Preferably, the fluorine-containing monomer is selected from any one of trifluoroethyl methacrylate, hexafluorobutyl acrylate or dodecafluoroheptyl methacrylate; the initiator is azobisisobutyronitrile or azobisisoheptonitrile; the cross-linking agent is trimethylolpropane trimethacrylate or diacetone acrylamide.
Preferably, the process conditions of ultrasonic dispersion are as follows: ultrasonic oscillation at 600-900W for 30-40 minutes.
Preferably, the preparation method of the nano material comprises the following steps of: firstly, acidizing 1 part of nano titanium carbonitride, dispersing the acidized nano titanium carbonitride in 6-9 parts of water, adding 0.04-0.06 part of selenious acid, dispersing the selenious acid uniformly by ultrasonic waves, dropwise adding concentrated ammonia water with the mass concentration of 22-25% until the pH value is 10, freezing and crushing the mixture to prepare premixed powder; and mixing and grinding the premixed powder and 0.7-0.8 part of ascorbic acid at a low temperature to obtain the nano material.
Further preferably, the specific method of acidification treatment is as follows: and (2) uniformly stirring and mixing the nano titanium carbonitride and the concentrated nitric acid, reacting for 8-10 hours at 120-130 ℃, filtering and washing the obtained product to be neutral, and drying in vacuum to obtain the nano titanium carbonitride-concentrated nitric acid catalyst.
More preferably, the mass concentration of the concentrated nitric acid is 65%, and the mass volume ratio of the nano titanium carbonitride to the concentrated nitric acid is 1 g: 100 mL.
Further preferably, the freezing and crushing process conditions are as follows: the freezing temperature is-10 to-15 ℃, the freezing time is 10 to 12 hours, the crushing temperature is-15 to-18 ℃, and the crushing particle size is 1 to 3 mu m.
Further preferably, the process conditions of the low-temperature mixing grinding are as follows: the grinding temperature is-15 to-18 ℃, the grinding time is 24 to 48 hours, and the grinding particle size is 0.1 to 0.3 mu m.
Preferably, the specific method of the modification treatment comprises the following steps in parts by weight: firstly, dispersing 1 part of nano material in 5-8 parts of methanol by ultrasonic waves, then adding 0.3-0.5 part of gamma-aminoethyl aminopropyltrimethoxysilane, heating to reflux, stirring for 3-5 hours under heat preservation, and removing the solvent by rotary evaporation to obtain the modified nano material.
The active dye acid inhibitor is obtained by the preparation method.
The application method of the active dye acid inhibitor comprises the steps of dispersing 1 part of active dye in 8-10 parts of water by weight through ultrasonic waves, stirring and heating to 80-90 ℃, adding 0.3-0.5 part of the acid inhibitor, keeping the temperature, stirring for 5-7 hours, cooling and filtering.
The invention has the beneficial effects that:
the method comprises the steps of firstly reacting triethylene tetramine and methyl acrylate serving as raw materials to prepare an amine-terminated compound, then adding the amine-terminated compound, a fluorine-containing monomer, an initiator, a cross-linking agent and a modified nano material into a mixed solution of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt and 1-hydroxyethyl-3-methylimidazol dinitrile amine salt, and uniformly dispersing by ultrasonic waves to obtain the reactive dye acid inhibitor, wherein the acid-proof effect of the reactive dye is greatly improved.
The modified nano material is prepared by using nano titanium carbonitride and selenious acid as raw materials to prepare a nano material and then performing modification treatment by using gamma-aminoethyl aminopropyl trimethoxysilane. The modified nano material has a nano size and a large specific surface area, has a good adsorption effect on the reactive dye, and meanwhile, the amino introduced by modification can form a hydrogen bond effect with amino, fluorine and the like in the acid-proof agent, and the acid-proof agent component is attracted to the surface of the reactive dye by virtue of the hydrogen bond effect, so that the reactive dye is protected, and the acid-proof effect is improved.
The acid-proof agent is added with the fluorine-containing monomer, the initiator and the cross-linking agent, and when the acid-proof agent is used, the fluorine-containing monomer is polymerized to form a polymer film on the surface of the reactive dye, so that the acid-proof effect is further improved.
The acid-proof agent realizes the dispersion of other components through the mixed liquid of tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt and 1-hydroxyethyl-3-methylimidazolidinediamine salt, on one hand, the components are uniformly dispersed, which is beneficial to the coating of the reactive dye, on the other hand, hydroxyl and the like contained in the ionic liquid can also construct a network structure by means of hydrogen bond action, thereby further improving the acid-proof effect.
Detailed Description
The present invention will be further illustrated by the following examples, which are intended to be merely illustrative and not limitative.
The tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt and the 1-hydroxyethyl-3-methylimidazolidineamine salt are purchased from Ordoviceae New Material science and technology Limited, Qingdao.
Example 1:
a preparation method of an active dye acid-proofing agent comprises the steps of firstly, taking trivinyl tetramine and methyl acrylate as raw materials to react to prepare an amine-terminated compound, then adding the amine-terminated compound, a fluorine-containing monomer, an initiator, a cross-linking agent and a modified nano material into a mixed solution of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt and 1-hydroxyethyl-3-methylimidazolium dinitrile amine salt, and uniformly dispersing by ultrasonic waves to obtain the active dye acid-proofing agent; the modified nano material is prepared by using nano titanium carbonitride and selenious acid as raw materials to prepare a nano material and then performing modification treatment by using gamma-aminoethyl aminopropyl trimethoxysilane.
The preparation method of the amine-terminated compound comprises the following steps: firstly, 1kg of triethylene tetramine is placed in a cold water bath, a mixed solution of 0.7kg of methyl acrylate and 3kg of methanol is slowly dripped at a constant speed under the protection of nitrogen, after the dripping is finished, the mixed solution is stirred and reacts for 5 hours at 25 ℃, the methanol is removed under reduced pressure, the mixed solution is heated to 140 ℃, and the stirring and the reaction are continued for 4 hours, so that the terminal amino compound is obtained. The dropping time was 40 minutes.
The mass ratio of the amine-terminated compound, the fluorine-containing monomer, the initiator, the crosslinking agent, the modified nano material, the tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt and the 1-hydroxyethyl-3-methylimidazolium dinitrile amine salt is 1: 8: 0.5: 0.8: 0.3: 9: 3.
the fluorine-containing monomer is trifluoroethyl methacrylate; the initiator is azobisisobutyronitrile; the cross-linking agent is trimethylolpropane trimethacrylate.
The process conditions of ultrasonic dispersion are as follows: ultrasonic vibration at 900W was carried out for 30 minutes.
The preparation method of the nano material comprises the following steps: firstly, acidizing 1kg of nano titanium carbonitride, then dispersing the acidized nano titanium carbonitride in 9kg of water, then adding 0.04kg of selenious acid, uniformly dispersing the selenious acid by ultrasonic waves, dropwise adding strong ammonia water with the mass concentration of 25% until the pH value is 10, freezing and crushing the mixture to prepare premixed powder; and then mixing and grinding the premixed powder and 0.7kg of ascorbic acid at low temperature to obtain the nano material.
The specific method for acidizing comprises the following steps: stirring and mixing the nano titanium carbonitride and the concentrated nitric acid uniformly, reacting for 8 hours at 130 ℃, filtering and washing the obtained product to be neutral, and drying in vacuum to obtain the nano titanium carbonitride-concentrated nitric acid catalyst. The mass concentration of the concentrated nitric acid is 65%, and the mass volume ratio of the nano titanium carbonitride to the concentrated nitric acid is 1 g: 100 mL.
The technological conditions of freezing and crushing are as follows: freezing at-15 deg.C for 10 hr, pulverizing at-18 deg.C, and pulverizing to particle size of 1 μm.
The process conditions of the low-temperature mixing grinding are as follows: the grinding temperature is-18 ℃, the grinding time is 24 hours, and the grinding particle size is 0.3 mu m.
The specific method of modification treatment is as follows: firstly, 1kg of nano material is dispersed in 5kg of methanol by ultrasonic wave, then 0.5kg of gamma-aminoethyl aminopropyl trimethoxy silane is added, the mixture is heated to reflux, the mixture is stirred for 3 hours under the condition of heat preservation, and the solvent is removed by rotary evaporation, thus obtaining the modified nano material.
Example 2:
a preparation method of an active dye acid-proofing agent comprises the steps of firstly, taking trivinyl tetramine and methyl acrylate as raw materials to react to prepare an amine-terminated compound, then adding the amine-terminated compound, a fluorine-containing monomer, an initiator, a cross-linking agent and a modified nano material into a mixed solution of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt and 1-hydroxyethyl-3-methylimidazolium dinitrile amine salt, and uniformly dispersing by ultrasonic waves to obtain the active dye acid-proofing agent; the modified nano material is prepared by using nano titanium carbonitride and selenious acid as raw materials to prepare a nano material and then performing modification treatment by using gamma-aminoethyl aminopropyl trimethoxysilane.
The preparation method of the amine-terminated compound comprises the following steps: firstly, 1kg of triethylene tetramine is placed in a cold water bath, a mixed solution of 0.9kg of methyl acrylate and 2kg of methanol is slowly dripped at a constant speed under the protection of nitrogen, after the dripping is finished, the mixed solution is stirred and reacts for 3 hours at the temperature of 30 ℃, the methanol is removed under reduced pressure, the mixed solution is heated to the temperature of 150 ℃, and the stirring and the reaction are continued for 3 hours, so that the terminal amino compound is obtained. The dropping time was 60 minutes.
The mass ratio of the amine-terminated compound, the fluorine-containing monomer, the initiator, the crosslinking agent, the modified nano material, the tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt and the 1-hydroxyethyl-3-methylimidazolium dinitrile amine salt is 1: 5: 0.7: 0.6: 0.5: 7: 5.
the fluorine-containing monomer is hexafluorobutyl acrylate; the initiator is azobisisoheptonitrile; the cross-linking agent is diacetone acrylamide.
The process conditions of ultrasonic dispersion are as follows: ultrasonic oscillation at 600W for 40 minutes.
The preparation method of the nano material comprises the following steps: firstly, acidizing 1kg of nano titanium carbonitride, then dispersing the acidized nano titanium carbonitride in 6kg of water, then adding 0.06kg of selenious acid, uniformly dispersing the selenious acid by ultrasonic waves, dropwise adding strong ammonia water with the mass concentration of 22% until the pH value is 10, freezing and crushing the mixture to prepare premixed powder; and then mixing and grinding the premixed powder and 0.8kg of ascorbic acid at low temperature to obtain the nano material.
The specific method for acidizing comprises the following steps: stirring and mixing the nano titanium carbonitride and the concentrated nitric acid uniformly, reacting for 10 hours at 120 ℃, filtering and washing the obtained product to be neutral, and drying in vacuum to obtain the nano titanium carbonitride-concentrated nitric acid catalyst. The mass concentration of the concentrated nitric acid is 65%, and the mass volume ratio of the nano titanium carbonitride to the concentrated nitric acid is 1 g: 100 mL.
The technological conditions of freezing and crushing are as follows: freezing at-10 deg.C for 12 hr, pulverizing at-15 deg.C, and pulverizing to particle size of 3 μm.
The process conditions of the low-temperature mixing grinding are as follows: the grinding temperature is-15 ℃, the grinding time is 48 hours, and the grinding particle size is 0.1 mu m.
The specific method of modification treatment is as follows: firstly, 1kg of nano material is dispersed in 8kg of methanol by ultrasonic wave, then 0.3kg of gamma-aminoethyl aminopropyl trimethoxy silane is added, the mixture is heated to reflux, the mixture is stirred for 5 hours under the condition of heat preservation, and the solvent is removed by rotary evaporation, thus obtaining the modified nano material.
Example 3:
a preparation method of an active dye acid-proofing agent comprises the steps of firstly, taking trivinyl tetramine and methyl acrylate as raw materials to react to prepare an amine-terminated compound, then adding the amine-terminated compound, a fluorine-containing monomer, an initiator, a cross-linking agent and a modified nano material into a mixed solution of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt and 1-hydroxyethyl-3-methylimidazolium dinitrile amine salt, and uniformly dispersing by ultrasonic waves to obtain the active dye acid-proofing agent; the modified nano material is prepared by using nano titanium carbonitride and selenious acid as raw materials to prepare a nano material and then performing modification treatment by using gamma-aminoethyl aminopropyl trimethoxysilane.
The preparation method of the amine-terminated compound comprises the following steps: firstly, 1kg of triethylene tetramine is placed in a cold water bath, a mixed solution of 0.8kg of methyl acrylate and 2.5kg of methanol is slowly dripped at a constant speed under the protection of nitrogen, after the dripping is finished, the mixed solution is stirred and reacts for 4 hours at the temperature of 28 ℃, the methanol is removed under reduced pressure, the mixed solution is heated to 145 ℃, and the stirring and the reaction are continued for 3.5 hours, so that the terminal amino compound is obtained. The dropping time was 50 minutes.
The mass ratio of the amine-terminated compound, the fluorine-containing monomer, the initiator, the crosslinking agent, the modified nano material, the tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt and the 1-hydroxyethyl-3-methylimidazolium dinitrile amine salt is 1: 6: 0.6: 0.7: 0.4: 8: 4.
the fluorine-containing monomer is dodecafluoroheptyl methacrylate; the initiator is azobisisobutyronitrile; the cross-linking agent is trimethylolpropane trimethacrylate.
The process conditions of ultrasonic dispersion are as follows: ultrasonic oscillation at 700W for 35 minutes.
The preparation method of the nano material comprises the following steps: firstly, acidifying 1kg of nano titanium carbonitride, then dispersing the nano titanium carbonitride in 8kg of water, then adding 0.05kg of selenious acid, uniformly dispersing the selenious acid by ultrasonic waves, dropwise adding 23% strong ammonia water until the pH value is 10, freezing and crushing the mixture to prepare premixed powder; and then mixing and grinding the premixed powder and 0.75kg of ascorbic acid at low temperature to obtain the nano material.
The specific method for acidizing comprises the following steps: stirring and mixing the nano titanium carbonitride and the concentrated nitric acid uniformly, reacting for 9 hours at 125 ℃, filtering and washing the obtained product to be neutral, and drying in vacuum to obtain the nano titanium carbonitride-concentrated nitric acid catalyst. The mass concentration of the concentrated nitric acid is 65%, and the mass volume ratio of the nano titanium carbonitride to the concentrated nitric acid is 1 g: 100 mL.
The technological conditions of freezing and crushing are as follows: freezing at-12 deg.C for 11 hr, pulverizing at-16 deg.C, and pulverizing to particle size of 2 μm.
The process conditions of the low-temperature mixing grinding are as follows: the grinding temperature is-17 ℃, the grinding time is 30 hours, and the grinding particle size is 0.2 mu m.
The specific method of modification treatment is as follows: firstly, 1kg of nano material is dispersed in 6kg of methanol by ultrasonic wave, then 0.4kg of gamma-aminoethyl aminopropyl trimethoxy silane is added, the mixture is heated to reflux, the mixture is stirred for 4 hours under the condition of heat preservation, and the solvent is removed by rotary evaporation, thus obtaining the modified nano material.
Comparative example 1
A preparation method of an active dye acid-proofing agent comprises the steps of firstly adding a fluorine-containing monomer, an initiator, a cross-linking agent and a modified nano material into a mixed solution of tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt and 1-hydroxyethyl-3-methylimidazolium dinitrile amine salt, and uniformly dispersing by ultrasonic waves to obtain the active dye acid-proofing agent; the modified nano material is prepared by using nano titanium carbonitride and selenious acid as raw materials to prepare a nano material and then performing modification treatment by using gamma-aminoethyl aminopropyl trimethoxysilane.
The mass ratio of the fluorine-containing monomer, the initiator, the cross-linking agent, the modified nano material, the tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt and the 1-hydroxyethyl-3-methylimidazolium dinitrile amine salt is 8: 0.5: 0.8: 0.3: 9: 3.
the fluorine-containing monomer is trifluoroethyl methacrylate; the initiator is azobisisobutyronitrile; the cross-linking agent is trimethylolpropane trimethacrylate.
The process conditions of ultrasonic dispersion are as follows: ultrasonic vibration at 900W was carried out for 30 minutes.
The preparation method of the nano material comprises the following steps: firstly, acidizing 1kg of nano titanium carbonitride, then dispersing the acidized nano titanium carbonitride in 9kg of water, then adding 0.04kg of selenious acid, uniformly dispersing the selenious acid by ultrasonic waves, dropwise adding strong ammonia water with the mass concentration of 25% until the pH value is 10, freezing and crushing the mixture to prepare premixed powder; and then mixing and grinding the premixed powder and 0.7kg of ascorbic acid at low temperature to obtain the nano material.
The specific method for acidizing comprises the following steps: stirring and mixing the nano titanium carbonitride and the concentrated nitric acid uniformly, reacting for 8 hours at 130 ℃, filtering and washing the obtained product to be neutral, and drying in vacuum to obtain the nano titanium carbonitride-concentrated nitric acid catalyst. The mass concentration of the concentrated nitric acid is 65%, and the mass volume ratio of the nano titanium carbonitride to the concentrated nitric acid is 1 g: 100 mL.
The technological conditions of freezing and crushing are as follows: freezing at-15 deg.C for 10 hr, pulverizing at-18 deg.C, and pulverizing to particle size of 1 μm.
The process conditions of the low-temperature mixing grinding are as follows: the grinding temperature is-18 ℃, the grinding time is 24 hours, and the grinding particle size is 0.3 mu m.
The specific method of modification treatment is as follows: firstly, 1kg of nano material is dispersed in 5kg of methanol by ultrasonic wave, then 0.5kg of gamma-aminoethyl aminopropyl trimethoxy silane is added, the mixture is heated to reflux, the mixture is stirred for 3 hours under the condition of heat preservation, and the solvent is removed by rotary evaporation, thus obtaining the modified nano material.
Comparative example 2
A preparation method of an active dye acid-proofing agent comprises the steps of firstly, taking triethylene tetramine and methyl acrylate as raw materials to react to prepare an end amino compound, then adding the end amino compound and a modified nano material into a mixed solution of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt and 1-hydroxyethyl-3-methylimidazol dinitrile amine salt, and uniformly dispersing by ultrasonic waves to obtain the active dye acid-proofing agent; the modified nano material is prepared by using nano titanium carbonitride and selenious acid as raw materials to prepare a nano material and then performing modification treatment by using gamma-aminoethyl aminopropyl trimethoxysilane.
The preparation method of the amine-terminated compound comprises the following steps: firstly, 1kg of triethylene tetramine is placed in a cold water bath, a mixed solution of 0.7kg of methyl acrylate and 3kg of methanol is slowly dripped at a constant speed under the protection of nitrogen, after the dripping is finished, the mixed solution is stirred and reacts for 5 hours at 25 ℃, the methanol is removed under reduced pressure, the mixed solution is heated to 140 ℃, and the stirring and the reaction are continued for 4 hours, so that the terminal amino compound is obtained. The dropping time was 40 minutes.
The mass ratio of the amine-terminated compound to the modified nano material to the tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt to the 1-hydroxyethyl-3-methylimidazolium dinitrile amine salt is 1: 0.3: 9: 3.
the process conditions of ultrasonic dispersion are as follows: ultrasonic vibration at 900W was carried out for 30 minutes.
The preparation method of the nano material comprises the following steps: firstly, acidizing 1kg of nano titanium carbonitride, then dispersing the acidized nano titanium carbonitride in 9kg of water, then adding 0.04kg of selenious acid, uniformly dispersing the selenious acid by ultrasonic waves, dropwise adding strong ammonia water with the mass concentration of 25% until the pH value is 10, freezing and crushing the mixture to prepare premixed powder; and then mixing and grinding the premixed powder and 0.7kg of ascorbic acid at low temperature to obtain the nano material.
The specific method for acidizing comprises the following steps: stirring and mixing the nano titanium carbonitride and the concentrated nitric acid uniformly, reacting for 8 hours at 130 ℃, filtering and washing the obtained product to be neutral, and drying in vacuum to obtain the nano titanium carbonitride-concentrated nitric acid catalyst. The mass concentration of the concentrated nitric acid is 65%, and the mass volume ratio of the nano titanium carbonitride to the concentrated nitric acid is 1 g: 100 mL.
The technological conditions of freezing and crushing are as follows: freezing at-15 deg.C for 10 hr, pulverizing at-18 deg.C, and pulverizing to particle size of 1 μm.
The process conditions of the low-temperature mixing grinding are as follows: the grinding temperature is-18 ℃, the grinding time is 24 hours, and the grinding particle size is 0.3 mu m.
The specific method of modification treatment is as follows: firstly, 1kg of nano material is dispersed in 5kg of methanol by ultrasonic wave, then 0.5kg of gamma-aminoethyl aminopropyl trimethoxy silane is added, the mixture is heated to reflux, the mixture is stirred for 3 hours under the condition of heat preservation, and the solvent is removed by rotary evaporation, thus obtaining the modified nano material.
Comparative example 3
A preparation method of an active dye acid-proof agent comprises the steps of firstly using triethylene tetramine and methyl acrylate as raw materials to react to prepare an end amino compound, then adding the end amino compound, a fluorine-containing monomer, an initiator and a cross-linking agent into a mixed solution of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt and 1-hydroxyethyl-3-methylimidazole dinitrile amine salt, and uniformly dispersing by ultrasonic waves to obtain the active dye acid-proof agent.
The preparation method of the amine-terminated compound comprises the following steps: firstly, 1kg of triethylene tetramine is placed in a cold water bath, a mixed solution of 0.7kg of methyl acrylate and 3kg of methanol is slowly dripped at a constant speed under the protection of nitrogen, after the dripping is finished, the mixed solution is stirred and reacts for 5 hours at 25 ℃, the methanol is removed under reduced pressure, the mixed solution is heated to 140 ℃, and the stirring and the reaction are continued for 4 hours, so that the terminal amino compound is obtained. The dropping time was 40 minutes.
The mass ratio of the amine-terminated compound, the fluorine-containing monomer, the initiator, the cross-linking agent, the tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt and the 1-hydroxyethyl-3-methylimidazolium dinitrile amine salt is 1: 8: 0.5: 0.8: 9: 3.
the fluorine-containing monomer is trifluoroethyl methacrylate; the initiator is azobisisobutyronitrile; the cross-linking agent is trimethylolpropane trimethacrylate.
The process conditions of ultrasonic dispersion are as follows: ultrasonic vibration at 900W was carried out for 30 minutes.
Comparative example 4
A preparation method of an active dye acid-proofing agent comprises the steps of firstly, taking trivinyl tetramine and methyl acrylate as raw materials to react to prepare an amino-terminated compound, then adding the amino-terminated compound, a fluorine-containing monomer, an initiator, a cross-linking agent and a modified nano material into tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide, and uniformly dispersing by ultrasonic waves to obtain the active dye acid-proofing agent; the modified nano material is prepared by using nano titanium carbonitride and selenious acid as raw materials to prepare a nano material and then performing modification treatment by using gamma-aminoethyl aminopropyl trimethoxysilane.
The preparation method of the amine-terminated compound comprises the following steps: firstly, 1kg of triethylene tetramine is placed in a cold water bath, a mixed solution of 0.7kg of methyl acrylate and 3kg of methanol is slowly dripped at a constant speed under the protection of nitrogen, after the dripping is finished, the mixed solution is stirred and reacts for 5 hours at 25 ℃, the methanol is removed under reduced pressure, the mixed solution is heated to 140 ℃, and the stirring and the reaction are continued for 4 hours, so that the terminal amino compound is obtained. The dropping time was 40 minutes.
The mass ratio of the amine-terminated compound, the fluorine-containing monomer, the initiator, the cross-linking agent, the modified nano material and the tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt is 1: 8: 0.5: 0.8: 0.3: 9.
the fluorine-containing monomer is trifluoroethyl methacrylate; the initiator is azobisisobutyronitrile; the cross-linking agent is trimethylolpropane trimethacrylate.
The process conditions of ultrasonic dispersion are as follows: ultrasonic vibration at 900W was carried out for 30 minutes.
The preparation method of the nano material comprises the following steps: firstly, acidizing 1kg of nano titanium carbonitride, then dispersing the acidized nano titanium carbonitride in 9kg of water, then adding 0.04kg of selenious acid, uniformly dispersing the selenious acid by ultrasonic waves, dropwise adding strong ammonia water with the mass concentration of 25% until the pH value is 10, freezing and crushing the mixture to prepare premixed powder; and then mixing and grinding the premixed powder and 0.7kg of ascorbic acid at low temperature to obtain the nano material.
The specific method for acidizing comprises the following steps: stirring and mixing the nano titanium carbonitride and the concentrated nitric acid uniformly, reacting for 8 hours at 130 ℃, filtering and washing the obtained product to be neutral, and drying in vacuum to obtain the nano titanium carbonitride-concentrated nitric acid catalyst. The mass concentration of the concentrated nitric acid is 65%, and the mass volume ratio of the nano titanium carbonitride to the concentrated nitric acid is 1 g: 100 mL.
The technological conditions of freezing and crushing are as follows: freezing at-15 deg.C for 10 hr, pulverizing at-18 deg.C, and pulverizing to particle size of 1 μm.
The process conditions of the low-temperature mixing grinding are as follows: the grinding temperature is-18 ℃, the grinding time is 24 hours, and the grinding particle size is 0.3 mu m.
The specific method of modification treatment is as follows: firstly, 1kg of nano material is dispersed in 5kg of methanol by ultrasonic wave, then 0.5kg of gamma-aminoethyl aminopropyl trimethoxy silane is added, the mixture is heated to reflux, the mixture is stirred for 3 hours under the condition of heat preservation, and the solvent is removed by rotary evaporation, thus obtaining the modified nano material.
Test examples
Firstly, 1kg of reactive brilliant blue KN-R is dispersed in 9kg of water by ultrasonic wave, stirred and heated to 85 ℃, 0.4kg of the acid-proofing agent obtained in the examples 1-3 or the comparative examples 1-4 is added, the mixture is kept warm and stirred for 5-7 hours, and the dye is obtained by cooling and suction filtration. The acid resistance of the dye was examined by placing the dye in a conical flask, adding 50mL of a 5% hydrochloric acid solution having a mass concentration, and observing the change in the state in the conical flask after 24 hours, the results are shown in Table 1.
TABLE 1 dye acid resistance study
Change of state in conical flask
Example 1 No color change, no color, clarity and transparency
Example 2 No color change, no color, clarity and transparency
Example 3 No color change, no color, clarity and transparency
Comparative example 1 Has color and a small amount of floccules
Comparative example 2 Has color, and has lots of floccules and precipitates
Comparative example 3 Has color, and has lots of floccules and precipitates
Comparative example 4 Color, floccule
Then preparing color paste by using the obtained dye, wherein the color paste comprises the following components in percentage by mass: 21.5% of dye, 1.5% of sodium alginate, 5% of urea, 3% of sodium bicarbonate, 1% of sodium m-nitrobenzenesulfonate and 84.5% of water.
The obtained color paste is used for dyeing and drying the pure cotton fabric, the drying temperature is 140 ℃, the drying time is 2min, and the moisture content of the fabric is less than 10%. And (4) steaming, wherein the steaming temperature is 102 ℃, and the steaming time is 9 min. Washing, drying, steaming the fabric, washing with room-temperature softened water for 2 times, washing with 82 ℃ softened water for 2 times, washing with 92 ℃ softened water for one time, washing with soaping agent in an amount of 3g/L, washing with 82 ℃ softened water for 2 times, and washing with room-temperature softened water for one time; after the washing with water, the mixture is dried in an oven at 130 ℃. The color fastness to acid perspiration is examined with reference to GB/T3922-2013, and the results are shown in Table 2.
TABLE 2 color fastness to perspiration test
Figure BDA0002780024890000101
As is clear from tables 1 and 2, the reactive dyes obtained in examples 1 to 3 have good acid resistance, and the dyed fabrics have good acid perspiration fastness and good acid-proof effect.
In comparative example 1, the terminal amine compound is omitted, in comparative example 2, the fluorine-containing monomer, the initiator and the crosslinking agent are omitted, in comparative example 3, the modified nano material is omitted, in comparative example 4, the 1-hydroxyethyl-3-methylimidazolium dinitrile amine salt is omitted, the acid resistance effect of the reactive dye is obviously poor, and the terminal amine compound, the polymer, the nano material, the ionic liquid and the like synergistically improve the acid resistance effect of the reactive dye.
Although the present invention has been described with reference to the specific embodiments, it is not intended to limit the scope of the present invention, and various modifications and variations can be made by those skilled in the art without inventive changes based on the technical solution of the present invention.

Claims (8)

1. A preparation method of an active dye acid-proofing agent is characterized in that triethylene tetramine and methyl acrylate are used as raw materials to react to prepare an amine-terminated compound, then the amine-terminated compound, a fluorine-containing monomer, an initiator, a cross-linking agent and a modified nano material are added into a mixed solution of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt and 1-hydroxyethyl-3-methylimidazolium dinitrile amine salt, and ultrasonic dispersion is carried out uniformly to obtain the active dye acid-proofing agent; the modified nano material is prepared by preparing nano titanium carbonitride and selenious acid as raw materials and then performing modification treatment by utilizing gamma-aminoethyl aminopropyl trimethoxysilane;
the mass ratio of the amine-terminated compound, the fluorine-containing monomer, the initiator, the crosslinking agent, the modified nano material, the tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt and the 1-hydroxyethyl-3-methylimidazolium dinitrile amine salt is 1: 5-8: 0.5-0.7: 0.6-0.8: 0.3-0.5: 7-9: 3-5;
the fluorine-containing monomer is selected from any one of trifluoroethyl methacrylate, hexafluorobutyl acrylate or dodecafluoroheptyl methacrylate; the initiator is azobisisobutyronitrile or azobisisoheptonitrile; the cross-linking agent is trimethylolpropane trimethacrylate or diacetone acrylamide.
2. The method according to claim 1, wherein the amine-terminated compound is prepared by the following steps in parts by weight: firstly, 1 part of triethylene tetramine is placed in a cold water bath, a mixed solution of 0.7-0.9 part of methyl acrylate and 2-3 parts of methanol is slowly dripped at a constant speed under the protection of nitrogen, after the dripping is finished, the mixed solution is stirred and reacts for 3-5 hours at 25-30 ℃, the methanol is removed under reduced pressure, the mixed solution is heated to 140-150 ℃, and the stirring and the reaction are continued for 3-4 hours, so that the terminal amino compound is obtained.
3. The preparation method according to claim 1, wherein the process conditions of the ultrasonic dispersion are as follows: ultrasonic oscillation at 600-900W for 30-40 minutes.
4. The preparation method of claim 1, wherein the nano material is prepared by the following steps in parts by weight: firstly, acidizing 1 part of nano titanium carbonitride, dispersing the acidized nano titanium carbonitride in 6-9 parts of water, adding 0.04-0.06 part of selenious acid, uniformly dispersing the selenious acid by ultrasonic waves, dropwise adding concentrated ammonia water with the mass concentration of 22-25% until the pH value is =10, freezing and crushing to prepare premixed powder; and mixing and grinding the premixed powder and 0.7-0.8 part of ascorbic acid at a low temperature to obtain the nano material.
5. The preparation method according to claim 4, wherein the specific method of acidification treatment is as follows: and (2) uniformly stirring and mixing the nano titanium carbonitride and the concentrated nitric acid, reacting for 8-10 hours at 120-130 ℃, filtering and washing the obtained product to be neutral, and drying in vacuum to obtain the nano titanium carbonitride-concentrated nitric acid catalyst.
6. The preparation method according to claim 1, wherein the specific method of modification treatment comprises the following steps in parts by weight: firstly, dispersing 1 part of nano material in 5-8 parts of methanol by ultrasonic waves, then adding 0.3-0.5 part of gamma-aminoethyl aminopropyltrimethoxysilane, heating to reflux, stirring for 3-5 hours under heat preservation, and removing the solvent by rotary evaporation to obtain the modified nano material.
7. An acid inhibitor for reactive dyes obtained by the method of any one of claims 1 to 6.
8. The use method of the reactive dye acid inhibitor according to claim 7, comprising the steps of dispersing 1 part of the reactive dye in 8-10 parts of water by weight by ultrasonic wave, heating to 80-90 ℃ with stirring, adding 0.3-0.5 part of the acid inhibitor, stirring for 5-7 hours with heat preservation, cooling and filtering.
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