CN110527465B - Flocking adhesive for spinning and preparation method thereof - Google Patents
Flocking adhesive for spinning and preparation method thereof Download PDFInfo
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- CN110527465B CN110527465B CN201910655010.1A CN201910655010A CN110527465B CN 110527465 B CN110527465 B CN 110527465B CN 201910655010 A CN201910655010 A CN 201910655010A CN 110527465 B CN110527465 B CN 110527465B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a spinning flocking adhesive which is characterized by comprising the following components in parts by weight: 30-40 parts of hyperbranched waterborne polyurethane acrylate, 10-20 parts of O- (ethyleneoxybutyl) -N- (triethoxysilylpropyl) urethane, 8-12 parts of acrylic acid-L-menthyl ester, 5-10 parts of polynorbornene-2, 3-dicarboxylic acid polytetrahydrofurandiol ester, 10-15 parts of acrylic acid-2, 3-epoxypropyl ester modified 1-aminobenzotriazole, 5-8 parts of acrylic acid hexahydro-4, 7-methylene-1H-indenyl ester, 1-4 parts of emulsifier, 0.3-0.6 part of initiator, 5-10 parts of ethanol and 50-60 parts of water. The invention also discloses a preparation method of the flocking adhesive for spinning. The flocking adhesive for spinning disclosed by the invention is good in wear resistance, moisture resistance, water resistance, solvent resistance and heat resistance, good in flocking effect, excellent in performance stability and high in peel strength.
Description
Technical Field
The invention relates to the technical field of textile auxiliaries, in particular to a flocking adhesive for spinning and a preparation method thereof.
Background
With the progress and development of society, environment-friendly and fashionable textile fabrics are more and more popular with people, and flocking fabrics are more and more widely applied to the fields of flexible and changeable patterns and gorgeous colors and are mainly applied to the aspects of clothes, shoe materials, automotive interiors, decorative cloth and the like. The flocking fabric in the prior art is mostly prepared by electrostatic flocking, and the principle is that after the flocking is processed by electro-chemical treatment, the original disorder state is changed under the action of an electric field generated by a high-voltage electrostatic generator, the flocking is evenly and regularly implanted into the flocking adhesive in a wet state in a certain direction, and the flocking adhesive forms the flocking on the surface after solidification. The quality of the flocking effect is determined by the quality of the flocking adhesive to a certain extent, and therefore, it is important to develop a flocking adhesive with excellent performance.
At present, the most common flocking adhesive is polyacrylate flocking adhesive which is non-toxic and harmless and easy to prepare, but the flocking adhesive has many defects in the aspects of wear resistance, hand feeling, moisture resistance, antibiosis and the like, and the phenomena of fluff falling and the like are easy to occur in the using process of fabrics, particularly in the washing process. Other types of flocking adhesives also have the defects of low bonding strength, poor stability, easy melting at high temperature, poor heat resistance, easy combustion, easy oxidation after long-time bonding, easy falling-off, poor water resistance, hand feeling, air permeability and moisture permeability, and the defects of unsafe use, high baking temperature, serious environmental protection problem and the like of partial adhesives generally.
Chinese patent CN101343525A discloses a water-based adhesive used in products of artificial leather electrostatic flocking genuine leather fiber and a preparation method thereof, the invention patent application is a composite water-based adhesive, interpenetrating network polymer emulsion taking polyurethane as a shell and polyacrylic ester as a core is synthesized into acrylate polymer emulsion containing epoxy group, which can seal carboxyl in water-based polyurethane, and the two are chemically blended according to a certain proportion. It can only be used for the products of artificial leather and electrostatic leather-planting fiber, is not suitable for various fiber fluff, and has no cold resistance and solvent resistance.
Therefore, there is a need to develop a flocking adhesive for textile having excellent comprehensive performance, safe and environment-friendly use and good flocking effect.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the spinning flocking adhesive and the preparation method thereof, the preparation method is simple and easy to operate, has small dependence on equipment, mild reaction conditions, safe, environment-friendly and harmless preparation process, is suitable for large-scale production requirements, and has higher popularization and application values; the prepared spinning flocking adhesive is good in wear resistance, moisture resistance, water resistance, solvent resistance and heat resistance, good in flocking effect, excellent in performance stability and high in peel strength.
In order to achieve the aim, the invention adopts the technical scheme that the flocking adhesive for spinning comprises the following components in parts by weight: 30-40 parts of hyperbranched waterborne polyurethane acrylate, 10-20 parts of O- (ethyleneoxybutyl) -N- (triethoxysilylpropyl) urethane, 8-12 parts of acrylic acid-L-menthyl ester, 5-10 parts of polynorbornene-2, 3-dicarboxylic acid polytetrahydrofurandiol ester, 10-15 parts of acrylic acid-2, 3-epoxypropyl ester modified 1-aminobenzotriazole, 5-8 parts of acrylic acid hexahydro-4, 7-methylene-1H-indenyl ester, 1-4 parts of emulsifier, 0.3-0.6 part of initiator, 5-10 parts of ethanol and 50-60 parts of water.
Further, the emulsifier is at least one of sodium dodecyl sulfate, secondary alcohol fatty alcohol polyoxyethylene ether, castor oil polyoxyethylene ether and alkylphenol ether sodium sulfosuccinate.
Further, the initiator is at least one of potassium persulfate, sodium persulfate, ammonium persulfate and azodiisopropyl imidazoline hydrochloride.
Further, the preparation method of the polytetrahydrofurandiol ester of polynorbornene-2, 3-dicarboxylic acid comprises the following steps: adding norbornene-2, 3-dicarboxylic acid, polytetrahydrofuran diol and high boiling point solvent into a polymerization reaction kettle, sealing, carrying out a reflux reaction at 245-265 ℃ for 2-3 hours to carry out an esterification reaction, then adding a catalyst, reducing the pressure to 300-500Pa, carrying out a polycondensation reaction at 230-250 ℃ for 15-18 hours, precipitating in water after the reaction is finished, and then washing and drying to obtain the polynorbornene-2, 3-dicarboxylic acid polytetrahydrofuran diol ester.
Preferably, the ratio of the amounts of the norbornene-2, 3-dicarboxylic acid, the polytetrahydrofuran diol, the high boiling point solvent and the catalyst is 1:1 (6-10) to (0.3-0.5).
Preferably, the high boiling point solvent is selected from at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Preferably, the catalyst is selected from one or more of antimony trioxide, antimony acetate and ethylene glycol antimony.
Further, the preparation method of the acrylic acid-2, 3-epoxypropyl ester modified 1-aminobenzotriazole comprises the following steps: adding acrylic acid-2, 3-epoxypropyl ester, 1-aminobenzotriazole and an alkaline catalyst into an organic solvent, stirring and reacting for 4-6 hours at the temperature of 30-40 ℃, filtering to remove insoluble substances, and removing the organic solvent by rotary evaporation to obtain the acrylic acid-2, 3-epoxypropyl ester modified 1-aminobenzotriazole.
Preferably, the mass ratio of the acrylic acid-2, 3-epoxypropyl ester to the 1-aminobenzotriazole to the alkaline catalyst to the organic solvent is 1:1.05 (0.3-0.5) to 6-10.
Preferably, the alkaline catalyst is at least one of sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.
Preferably, the organic solvent is at least one of dichloromethane, acetone and tetrahydrofuran.
Further, the preparation method of the flocking adhesive for spinning comprises the following steps:
step S1: adding hyperbranched waterborne polyurethane acrylate, O- (ethyleneoxybutyl) -N- (triethoxysilylpropyl) urethane, acrylic acid-L-menthyl, polynorbornene-2, 3-dicarboxylic acid polytetrahydrofuran diol ester, acrylic acid-2, 3-epoxypropyl modified 1-aminobenzotriazole, acrylic acid hexahydro-4, 7-methylene-1H-indenyl ester, an emulsifier and ethanol into a part of water in a reaction kettle, and stirring until the mixture is uniformly mixed; the adding amount of the water accounts for 60-70% of the total mass;
s2, adding the rest water into the mixture prepared in the step S1, slowly adding the mixture into a reaction kettle under the protection of nitrogen or inert gas at the temperature of 60-70 ℃, simultaneously slowly adding an initiator, and reacting at constant temperature for 4-6 hours to obtain the flocking adhesive for spinning.
Further, the inert gas is selected from one of helium, neon and argon.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
(1) the spinning flocking adhesive provided by the invention is simple and easy to operate in a preparation method, small in equipment dependence, mild in reaction conditions, safe, environment-friendly and harmless in a preparation process, suitable for large-scale production requirements, and high in popularization and application value.
(2) The flocking adhesive for spinning overcomes the defects that the traditional flocking adhesive for spinning is low in bonding strength, poor in stability, easy to melt at high temperature, poor in heat resistance, easy to burn, easy to oxidize and fall off after being bonded for a long time, and poor in water resistance, hand feeling, air permeability and moisture permeability, overcomes the defects that part of the adhesive is unsafe to use, high in baking temperature, serious in environmental protection problem and the like, and has the advantages of wear resistance, moisture resistance, water resistance, solvent resistance, good heat resistance, good flocking effect, excellent performance stability, high peeling strength, and safety and environmental protection in the production and use processes.
(3) According to the surface treating agent for synthetic leather, added hyperbranched waterborne polyurethane acrylate, O- (ethyleneoxybutyl) -N- (triethoxysilylpropyl) urethane, acrylic acid-L-menthyl ester, polynorbornene-2, 3-dicarboxylic acid polytetrahydrofurandiol ester, acrylic acid-2, 3-epoxypropyl ester modified 1-aminobenzotriazole and acrylic acid hexahydro-4, 7-methylene-1H-indenyl ester form a three-dimensional network structure at the curing and forming stage of the flocking adhesive, so that the comprehensive performance of the flocking adhesive is improved, and particularly the weather resistance and the waterproofness are improved to a greater extent; the introduction of the hyperbranched waterborne polyurethane acrylate not only combines the advantages of polyurethane and acrylate adhesives, but also introduces double bonds to provide reaction sites for subsequent curing and crosslinking; on the other hand, due to the introduction of the hyperbranched structure, the viscosity, the dissolving capacity, the film forming performance, the water resistance and the thermal stability of the flocking adhesive can be improved; the introduced O- (ethyleneoxybutyl) -N- (triethoxysilylpropyl) urethane can improve the cohesiveness of the flocking adhesive due to the bridging action of siloxane and the introduction of a urethane structure, so that the stripping strength of the flocking adhesive is higher, and the hardness of the adhesive layer can be enhanced due to the introduction of the acrylic acid-L-menthyl. The introduction of the poly (norbornene-2, 3-dicarboxylic acid) polytetrahydrofurandiol ester can be used for conditioning the viscosity of the flocking adhesive, introducing the norbornyl structure and the polytetrahydrofuran structure on a polymer molecular chain for the first time, and combining the advantages of the furan resin and the norbornyl structure and the synergistic effect, so that the adhesive property of the polynorbornene-2, 3-dicarboxylic acid to a base material and fluff is enhanced. The introduction of acrylic acid-2, 3-epoxypropyl ester modified 1-aminobenzotriazole can obviously improve the weather resistance of the adhesive layer due to the action of benzotriazole, and hydroxyl is formed through the interaction of amino and epoxy, so that the hydrophilicity can be enhanced, and the performance stability of the flocking adhesive is facilitated. The addition of acrylic acid hexahydro-4, 7-methylene-1H-indenyl ester can further improve the peel strength of the flocking adhesive. The components and the structure are synergistic, so that the flocking adhesive has excellent comprehensive performance.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The hyperbranched waterborne polyurethane acrylate used in the following examples of the invention is prepared in advance, and the preparation method refers to: research on synthesis of hyperbranched aqueous urethane acrylate, von swimming test, university of southern China, 2016; other raw materials were all purchased commercially.
Example 1
The flocking adhesive for spinning comprises the following components in parts by weight: 30 parts of hyperbranched waterborne polyurethane acrylate, 10 parts of O- (ethyleneoxybutyl) -N- (triethoxysilylpropyl) urethane, 8 parts of acrylic acid-L-menthyl ester, 5 parts of polynorbornene-2, 3-dicarboxylic acid polytetrahydrofurandiol ester, 10 parts of acrylic acid-2, 3-epoxypropyl ester modified 1-aminobenzotriazole, 5 parts of acrylic acid hexahydro-4, 7-methylene-1H-indenyl ester, 1 part of sodium dodecyl sulfate, 0.3 part of potassium persulfate, 5 parts of ethanol and 50 parts of water.
The preparation method of the polytetrahydrofurandiol ester of the polynorbornene-2, 3-dicarboxylic acid comprises the following steps: adding norbornene-2, 3-dicarboxylic acid, polytetrahydrofuran diol and dimethyl sulfoxide into a polymerization reaction kettle, sealing, carrying out reflux reaction at 245 ℃ for 2 hours to carry out esterification reaction, then adding antimony trioxide, reducing the pressure to 300Pa, carrying out polycondensation reaction at 230 ℃ for 15 hours, precipitating in water after the reaction is finished, and washing and drying to obtain the polytetrahydrofuran diol ester of polynorbornene-2, 3-dicarboxylic acid; the weight ratio of the norbornene-2, 3-dicarboxylic acid, the polytetrahydrofuran diol, the dimethyl sulfoxide and the antimony trioxide is 1:1:6: 0.3.
The preparation method of the acrylic acid-2, 3-epoxypropyl ester modified 1-aminobenzotriazole comprises the following steps: 10g of 2, 3-epoxypropyl acrylate, 10.5g of 1-aminobenzotriazole and 3g of sodium carbonate are added into 60g of dichloromethane, stirred and reacted for 4 hours at 30 ℃, insoluble substances are removed by filtration, and dichloromethane is removed by rotary evaporation to obtain the 2, 3-epoxypropyl acrylate modified 1-aminobenzotriazole.
The preparation method of the flocking adhesive for spinning comprises the following steps:
step S1: adding hyperbranched waterborne polyurethane acrylate, O- (ethyleneoxybutyl) -N- (triethoxysilylpropyl) urethane, acrylic acid-L-menthyl, polynorbornene-2, 3-dicarboxylic acid polytetrahydrofuran diol ester, acrylic acid-2, 3-epoxypropyl modified 1-aminobenzotriazole, acrylic acid hexahydro-4, 7-methylene-1H-indenyl ester, sodium dodecyl sulfate and ethanol into partial water in a reaction kettle, and stirring until the mixture is uniformly mixed; the adding amount of the water accounts for 60 percent of the total mass;
and S2, adding the rest water into the mixture prepared in the step S1, slowly adding the mixture into a reaction kettle under the protection of nitrogen at the temperature of 60 ℃, simultaneously slowly adding potassium persulfate, and reacting at constant temperature for 4 hours to obtain the flocking adhesive for spinning.
Example 2
The flocking adhesive for spinning comprises the following components in parts by weight: 32 parts of hyperbranched waterborne polyurethane acrylate, 12 parts of O- (ethyleneoxybutyl) -N- (triethoxysilylpropyl) urethane, 9 parts of acrylic acid-L-menthyl ester, 6 parts of polynorbornene-2, 3-dicarboxylic acid polytetrahydrofurandiol ester, 11 parts of acrylic acid-2, 3-epoxypropyl ester modified 1-aminobenzotriazole, 6 parts of acrylic acid hexahydro-4, 7-methylene-1H-indenyl ester, 2 parts of secondary alcohol fatty alcohol polyoxyethylene ether, 0.4 part of sodium persulfate, 6 parts of ethanol and 52 parts of water.
The preparation method of the polytetrahydrofurandiol ester of the polynorbornene-2, 3-dicarboxylic acid comprises the following steps: adding norbornene-2, 3-dicarboxylic acid, polytetrahydrofuran diol and N, N-dimethylformamide into a polymerization reaction kettle, sealing, carrying out a reflux reaction at 250 ℃ for 2.3 hours to carry out an esterification reaction, then adding antimony acetate, reducing the pressure to 350Pa, carrying out a polycondensation reaction at 235 ℃ for 16 hours, precipitating in water after the reaction is finished, and then washing and drying to obtain the polytetrahydrofuran diol ester of polynorbornene-2, 3-dicarboxylic acid; the weight ratio of the norbornene-2, 3-dicarboxylic acid, the polytetrahydrofuran diol, the N, N-dimethylformamide and the antimony acetate is 1:1:7: 0.35.
The preparation method of the acrylic acid-2, 3-epoxypropyl ester modified 1-aminobenzotriazole comprises the following steps: 100g of 2, 3-epoxypropyl acrylate, 105g of 1-aminobenzotriazole and 35g of potassium carbonate are added into 700g of acetone, stirred and reacted for 4.5 hours at 33 ℃, insoluble substances are removed by filtration, and the acetone is removed by rotary evaporation to obtain the 2, 3-epoxypropyl acrylate modified 1-aminobenzotriazole.
The preparation method of the flocking adhesive for spinning comprises the following steps:
step S1: adding hyperbranched waterborne polyurethane acrylate, O- (ethyleneoxybutyl) -N- (triethoxysilylpropyl) urethane, acrylic acid-L-menthyl, polynorbornene-2, 3-dicarboxylic acid polytetrahydrofuran diol ester, acrylic acid-2, 3-epoxypropyl modified 1-aminobenzotriazole, acrylic acid hexahydro-4, 7-methylene-1H-indenyl ester, secondary alcohol fatty alcohol polyoxyethylene ether and ethanol into partial water in a reaction kettle, and stirring until the mixture is uniformly mixed; the adding amount of the water accounts for 63% of the total mass;
and S2, adding the rest water into the mixture prepared in the step S1, slowly adding the mixture into a reaction kettle under the protection of helium and at the temperature of 63 ℃, simultaneously slowly adding sodium persulfate, and reacting at constant temperature for 4.5 hours to obtain the flocking adhesive for spinning.
Example 3
The flocking adhesive for spinning comprises the following components in parts by weight: 35 parts of hyperbranched waterborne polyurethane acrylate, 15 parts of O- (ethyleneoxybutyl) -N- (triethoxysilylpropyl) urethane, 10 parts of acrylic acid-L-menthyl ester, 8 parts of polynorbornene-2, 3-dicarboxylic acid polytetrahydrofuran diol ester, 13 parts of acrylic acid-2, 3-epoxypropyl ester modified 1-aminobenzotriazole, 6.5 parts of acrylic acid hexahydro-4, 7-methylene-1H-indenyl ester, 2.5 parts of castor oil polyoxyethylene ether, 0.45 part of ammonium persulfate, 7.5 parts of ethanol and 55 parts of water.
The preparation method of the polytetrahydrofurandiol ester of the polynorbornene-2, 3-dicarboxylic acid comprises the following steps: adding norbornene-2, 3-dicarboxylic acid, polytetrahydrofuran diol and N, N-dimethylacetamide into a polymerization reaction kettle, sealing, carrying out a reflux reaction at 255 ℃ for 2.5 hours to carry out an esterification reaction, then adding ethylene glycol antimony, reducing the pressure to 400Pa, carrying out a polycondensation reaction at 240 ℃ for 16.5 hours, precipitating in water after the reaction is finished, and washing and drying to obtain the polynorbornene-2, 3-dicarboxylic acid polytetrahydrofuran diol ester; the weight ratio of the norbornene-2, 3-dicarboxylic acid, the polytetrahydrofuran diol, the N, N-dimethylacetamide and the ethylene glycol antimony is 1:1:8: 0.4.
The preparation method of the acrylic acid-2, 3-epoxypropyl ester modified 1-aminobenzotriazole comprises the following steps: 100g of 2, 3-epoxypropyl acrylate, 105g of 1-aminobenzotriazole and 40g of sodium hydroxide are added into 800g of tetrahydrofuran, stirred and reacted for 5 hours at the temperature of 35 ℃, insoluble substances are removed by filtration, and organic solvent is removed by rotary evaporation to obtain the 2, 3-epoxypropyl acrylate modified 1-aminobenzotriazole.
The preparation method of the flocking adhesive for spinning comprises the following steps:
step S1: adding hyperbranched waterborne polyurethane acrylate, O- (ethyleneoxybutyl) -N- (triethoxysilylpropyl) urethane, acrylic acid-L-menthyl, polynorbornene-2, 3-dicarboxylic acid polytetrahydrofuran diol ester, acrylic acid-2, 3-epoxypropyl modified 1-aminobenzotriazole, acrylic acid hexahydro-4, 7-methylene-1H-indenyl ester, castor oil polyoxyethylene ether and ethanol into a part of water in a reaction kettle, and stirring until the mixture is uniformly mixed; the adding amount of the water accounts for 65% of the total mass;
and S2, adding the rest water into the mixture prepared in the step S1, slowly adding the mixture into a reaction kettle under the protection of neon at the temperature of 65 ℃, simultaneously slowly adding ammonium persulfate, and reacting at constant temperature for 5 hours to obtain the flocking adhesive for spinning.
Example 4
The flocking adhesive for spinning comprises the following components in parts by weight: 38 parts of hyperbranched waterborne polyurethane acrylate, 18 parts of O- (ethyleneoxybutyl) -N- (triethoxysilylpropyl) urethane, 11 parts of acrylic acid-L-menthyl ester, 9 parts of polynorbornene-2, 3-dicarboxylic acid polytetrahydrofurandiol ester, 14 parts of acrylic acid-2, 3-epoxypropyl ester modified 1-aminobenzotriazole, 7.5 parts of acrylic acid hexahydro-4, 7-methylene-1H-indenyl ester, 3.5 parts of emulsifier, 0.55 part of initiator, 9 parts of ethanol and 58 parts of water; the emulsifier is formed by mixing sodium dodecyl sulfate, secondary alcohol fatty alcohol polyoxyethylene ether, castor oil polyoxyethylene ether and alkylphenol ether sodium sulfosuccinate according to the mass ratio of 1:1:2: 3; the initiator is formed by mixing potassium persulfate, sodium persulfate, ammonium persulfate and azodiisopropyl imidazoline hydrochloride according to the mass ratio of 1:1:3: 2.
The preparation method of the polytetrahydrofurandiol ester of the polynorbornene-2, 3-dicarboxylic acid comprises the following steps: adding norbornene-2, 3-dicarboxylic acid, polytetrahydrofuran diol and a high-boiling point solvent into a polymerization reaction kettle, sealing, carrying out a reflux reaction at 260 ℃ for 2.8 hours to carry out an esterification reaction, then adding a catalyst, reducing the pressure to 480Pa, carrying out a polycondensation reaction at 245 ℃ for 17 hours, precipitating in water after the reaction is finished, and washing and drying to obtain the polytetrahydrofuran diol ester of polynorbornene-2, 3-dicarboxylic acid; the ratio of the norbornene-2, 3-dicarboxylic acid, the polytetrahydrofuran diol, the high-boiling point solvent and the catalyst is 1:1:9: 0.45; the high boiling point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 1:2:1: 3; the catalyst is prepared by mixing antimony trioxide, antimony acetate and ethylene glycol antimony in a mass ratio of 1:3: 4.
The preparation method of the acrylic acid-2, 3-epoxypropyl ester modified 1-aminobenzotriazole comprises the following steps: adding 100g of 2, 3-epoxypropyl acrylate, 105g of 1-aminobenzotriazole and 47g of basic catalyst into 960g of organic solvent, stirring and reacting for 5.6 hours at 38 ℃, filtering to remove insoluble substances, and removing the organic solvent by rotary evaporation to obtain 2, 3-epoxypropyl acrylate modified 1-aminobenzotriazole; the alkaline catalyst is formed by mixing sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide according to the mass ratio of 1:1:3: 2; the organic solvent is formed by mixing dichloromethane, acetone and tetrahydrofuran according to a mass ratio of 1:3: 5.
The preparation method of the flocking adhesive for spinning comprises the following steps:
step S1: adding hyperbranched waterborne polyurethane acrylate, O- (ethyleneoxybutyl) -N- (triethoxysilylpropyl) urethane, acrylic acid-L-menthyl, polynorbornene-2, 3-dicarboxylic acid polytetrahydrofuran diol ester, acrylic acid-2, 3-epoxypropyl modified 1-aminobenzotriazole, acrylic acid hexahydro-4, 7-methylene-1H-indenyl ester, an emulsifier and ethanol into a part of water in a reaction kettle, and stirring until the mixture is uniformly mixed; the adding amount of the water accounts for 68 percent of the total mass;
and S2, adding the rest water into the mixture prepared in the step S1, slowly adding the mixture into a reaction kettle under the protection of nitrogen or inert gas at the temperature of 68 ℃, simultaneously slowly adding an initiator, and reacting at constant temperature for 5.8 hours to obtain the flocking adhesive for spinning.
Example 5
The flocking adhesive for spinning comprises the following components in parts by weight: 40 parts of hyperbranched waterborne polyurethane acrylate, 20 parts of O- (ethyleneoxybutyl) -N- (triethoxysilylpropyl) urethane, 12 parts of acrylic acid-L-menthyl ester, 10 parts of polynorbornene-2, 3-dicarboxylic acid polytetrahydrofurandiol ester, 15 parts of acrylic acid-2, 3-epoxypropyl ester modified 1-aminobenzotriazole, 8 parts of acrylic acid hexahydro-4, 7-methylene-1H-indenyl ester, 4 parts of alkylphenol ether sulfosuccinic acid sodium salt, 0.6 part of azodiisopropyl imidazoline hydrochloride, 10 parts of ethanol and 60 parts of water.
The preparation method of the polytetrahydrofurandiol ester of the polynorbornene-2, 3-dicarboxylic acid comprises the following steps: adding norbornene-2, 3-dicarboxylic acid, polytetrahydrofuran diol and N-methyl pyrrolidone into a polymerization reaction kettle, sealing, carrying out a reflux reaction at 265 ℃ for 3 hours to carry out an esterification reaction, then adding antimony acetate, reducing the pressure to 500Pa, carrying out a polycondensation reaction at 250 ℃ for 18 hours, precipitating in water after the reaction is finished, and then washing and drying to obtain the polynorbornene-2, 3-dicarboxylic acid polytetrahydrofuran diol ester; the ratio of the amounts of the norbornene-2, 3-dicarboxylic acid, the polytetrahydrofuran diol, the N-methyl pyrrolidone and the antimony acetate is 1:1:10: 0.5.
The preparation method of the acrylic acid-2, 3-epoxypropyl ester modified 1-aminobenzotriazole comprises the following steps: 100g of 2, 3-epoxypropyl acrylate, 105g of 1-aminobenzotriazole and 50g of potassium hydroxide were added to 1000g of dichloromethane, stirred and reacted at 40 ℃ for 6 hours, then insoluble substances were removed by filtration, and dichloromethane was removed by rotary evaporation to obtain 2, 3-epoxypropyl acrylate-modified 1-aminobenzotriazole.
The preparation method of the flocking adhesive for spinning comprises the following steps:
step S1: adding hyperbranched waterborne polyurethane acrylate, O- (ethyleneoxybutyl) -N- (triethoxysilylpropyl) urethane, acrylic acid-L-menthyl, polynorbornene-2, 3-dicarboxylic acid polytetrahydrofuran diol ester, acrylic acid-2, 3-epoxypropyl modified 1-aminobenzotriazole, acrylic acid hexahydro-4, 7-methylene-1H-indenyl ester, an emulsifier and ethanol into a part of water in a reaction kettle, and stirring until the mixture is uniformly mixed; the adding amount of the water accounts for 70% of the total mass;
and S2, adding the rest water into the mixture prepared in the step S1, slowly adding the mixture into a reaction kettle under the protection of nitrogen at the temperature of 70 ℃, simultaneously slowly adding an initiator, and reacting at constant temperature for 6 hours to obtain the flocking adhesive for spinning.
Comparative example 1
A spinning flocking adhesive, the preparation method and the formula are basically the same as the example 1, except that polyurethane is used for replacing hyperbranched water-based polyurethane acrylate.
Comparative example 2
A flocking adhesive for textile was prepared in substantially the same manner as in example 1 except that O- (vinyloxybutyl) -N- (triethoxysilylpropyl) urethane was not added.
Comparative example 3
A flocking adhesive for textile was prepared in substantially the same manner as in example 1 except that L-menthyl acrylate was not added.
Comparative example 4
A flocking adhesive for textile was prepared in substantially the same manner as in example 1 except that no polytetrahydrofurandiol polynorbornene-2, 3-dicarboxylate was added.
Comparative example 5
A flocking adhesive for textile use, which is prepared in substantially the same manner and formulation as in example 1, except that 2, 3-epoxypropyl acrylate-modified 1-aminobenzotriazole is not added.
Comparative example 6
A flocking adhesive for textile was prepared in substantially the same manner as in example 1 except that hexahydro-4, 7-methylene-1H-indenyl acrylate was not added.
Comparative example 7
Polyurethane flocking glue is sold in the market.
In order to further illustrate the technical effects of the flocking adhesive in the embodiments of the present invention, the flocking adhesive in each of the above-mentioned embodiments is coated on a plant to be treated at 60 ℃, after curing, the flocking adhesive is tested for washing fastness, dry grinding fastness, solvent resistance, flexibility and hand feeling, and the results are shown in table 1, wherein the washing fastness is tested according to GB/T8629-2001, home washing and drying procedure for textile testing, and the abrasion resistance is tested according to GB/T21196-2007, determination of abrasion resistance of textile by martindale method.
TABLE 1
| Test items | Fastness to washing | Fastness to dry grinding | Solvent resistance | Flexibility | Hand feeling |
| Unit of | Stage | Next time | — | — | — |
| Example 1 | 5 | ≥11300 | Good taste | Good taste | Softness |
| Example 2 | 5 | ≥11400 | Good taste | Good taste | Softness |
| Example 3 | 5 | ≥11600 | Good taste | Good taste | Softness |
| Example 4 | 5 | ≥11700 | Good taste | Good taste | Softness |
| Example 5 | 5 | ≥12000 | Good taste | Good taste | Softness |
| Comparative example 1 | 4-5 | ≥9000 | In general | In general | In general |
| Comparative example 2 | 4 | ≥8000 | In general | In general | In general |
| Comparative example 3 | 4-5 | ≥7400 | In general | Good taste | In general |
| Comparative example 4 | 4 | ≥7200 | In general | Good taste | In general |
| Comparative example 5 | 4 | ≥7000 | In general | In general | In general |
| Comparative example 6 | 4 | ≥7100 | In general | In general | In general |
| Comparative example 7 | 3 | ≤6000 | In general | In general | In general |
As can be seen from table 1, the flocking adhesives in examples 1 to 5 have significantly better performance than the prior art (comparative example 7), and are more excellent in washing fastness, dry grinding fastness, solvent resistance, flexibility and hand feeling, which is a result of the synergistic effect of the components.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. The flocking adhesive for spinning is characterized by comprising the following components in parts by weight: 30-40 parts of hyperbranched waterborne polyurethane acrylate, 10-20 parts of O- (ethyleneoxybutyl) -N- (triethoxysilylpropyl) urethane, 8-12 parts of acrylic acid-L-menthyl ester, 5-10 parts of polynorbornene-2, 3-dicarboxylic acid polytetrahydrofurandiol ester, 10-15 parts of acrylic acid-2, 3-epoxypropyl ester modified 1-aminobenzotriazole, 5-8 parts of acrylic acid hexahydro-4, 7-methylene-1H-indenyl ester, 1-4 parts of emulsifier, 0.3-0.6 part of initiator, 5-10 parts of ethanol and 50-60 parts of water;
the preparation method of the polytetrahydrofurandiol ester of the polynorbornene-2, 3-dicarboxylic acid comprises the following steps: adding norbornene-2, 3-dicarboxylic acid, polytetrahydrofuran diol and a high-boiling point solvent into a polymerization reaction kettle, sealing, carrying out a reflux reaction at the temperature of 245-265 ℃ for 2-3 hours to carry out an esterification reaction, then adding a catalyst, reducing the pressure to 300-500Pa, carrying out a polycondensation reaction at the temperature of 230-250 ℃ for 15-18 hours, precipitating in water after the reaction is finished, and then washing and drying to obtain the polytetrahydrofuran diol ester of polynorbornene-2, 3-dicarboxylic acid;
the preparation method of the acrylic acid-2, 3-epoxypropyl ester modified 1-aminobenzotriazole comprises the following steps: adding acrylic acid-2, 3-epoxypropyl ester, 1-aminobenzotriazole and an alkaline catalyst into an organic solvent, stirring and reacting for 4-6 hours at the temperature of 30-40 ℃, filtering to remove insoluble substances, and removing the organic solvent by rotary evaporation to obtain the acrylic acid-2, 3-epoxypropyl ester modified 1-aminobenzotriazole.
2. The flocking adhesive for textile according to claim 1, wherein said emulsifier is at least one of sodium dodecyl sulfate, secondary alcohol fatty alcohol polyoxyethylene ether, castor oil polyoxyethylene ether and sodium alkyl phenol ether sulfosuccinate.
3. The flocking glue for textile according to claim 1, wherein said initiator is at least one of potassium persulfate, sodium persulfate, ammonium persulfate, azodiisopropyl imidazoline hydrochloride.
4. The flocking adhesive for textile according to claim 1, wherein the amount ratio of the norbornene-2, 3-dicarboxylic acid, polytetrahydrofuran diol, high boiling point solvent, catalyst is 1:1 (6-10) to (0.3-0.5).
5. The flocking glue for textile according to claim 1, wherein the said high boiling point solvent is selected from at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone; the catalyst is selected from one or more of antimony trioxide, antimony acetate and ethylene glycol antimony.
6. The flocking adhesive for textile according to claim 1, wherein the mass ratio of acrylic acid-2, 3-epoxypropyl ester, 1-aminobenzotriazole, alkaline catalyst and organic solvent is 1:1.05 (0.3-0.5) to (6-10).
7. The flocking glue for textile according to claim 1, wherein the alkaline catalyst is at least one of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide; the organic solvent is at least one of dichloromethane, acetone and tetrahydrofuran.
8. The flocking glue for textile according to any one of claims 1 to 7, wherein the preparation method of the flocking glue for textile comprises the following steps:
step S1: adding hyperbranched waterborne polyurethane acrylate, O- (ethyleneoxybutyl) -N- (triethoxysilylpropyl) urethane, acrylic acid-L-menthyl, polynorbornene-2, 3-dicarboxylic acid polytetrahydrofuran diol ester, acrylic acid-2, 3-epoxypropyl modified 1-aminobenzotriazole, acrylic acid hexahydro-4, 7-methylene-1H-indenyl ester, an emulsifier and ethanol into a part of water in a reaction kettle, and stirring until the mixture is uniformly mixed;
step S2: and adding the rest water into the mixture prepared in the step S1, slowly adding the mixture into a reaction kettle under the protection of nitrogen or inert gas at the temperature of 60-70 ℃, simultaneously slowly adding an initiator, and reacting at constant temperature for 4-6 hours to obtain the flocking adhesive for spinning.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110000504.3A CN112812073A (en) | 2019-07-19 | 2019-07-19 | Weather-resistant auxiliary agent for car mat flocking adhesive |
| CN201910655010.1A CN110527465B (en) | 2019-07-19 | 2019-07-19 | Flocking adhesive for spinning and preparation method thereof |
| CN202110000503.9A CN112831312A (en) | 2019-07-19 | 2019-07-19 | Anti-stripping adhesive auxiliary agent for flocking adhesive |
| CN202110000511.3A CN112724892A (en) | 2019-07-19 | 2019-07-19 | Preparation method of flocking adhesive for spinning |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910655010.1A CN110527465B (en) | 2019-07-19 | 2019-07-19 | Flocking adhesive for spinning and preparation method thereof |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202110000511.3A Division CN112724892A (en) | 2019-07-19 | 2019-07-19 | Preparation method of flocking adhesive for spinning |
| CN202110000504.3A Division CN112812073A (en) | 2019-07-19 | 2019-07-19 | Weather-resistant auxiliary agent for car mat flocking adhesive |
| CN202110000503.9A Division CN112831312A (en) | 2019-07-19 | 2019-07-19 | Anti-stripping adhesive auxiliary agent for flocking adhesive |
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| CN110527465A CN110527465A (en) | 2019-12-03 |
| CN110527465B true CN110527465B (en) | 2021-11-30 |
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| CN202110000504.3A Withdrawn CN112812073A (en) | 2019-07-19 | 2019-07-19 | Weather-resistant auxiliary agent for car mat flocking adhesive |
| CN202110000511.3A Withdrawn CN112724892A (en) | 2019-07-19 | 2019-07-19 | Preparation method of flocking adhesive for spinning |
| CN202110000503.9A Withdrawn CN112831312A (en) | 2019-07-19 | 2019-07-19 | Anti-stripping adhesive auxiliary agent for flocking adhesive |
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| CN202110000504.3A Withdrawn CN112812073A (en) | 2019-07-19 | 2019-07-19 | Weather-resistant auxiliary agent for car mat flocking adhesive |
| CN202110000511.3A Withdrawn CN112724892A (en) | 2019-07-19 | 2019-07-19 | Preparation method of flocking adhesive for spinning |
| CN202110000503.9A Withdrawn CN112831312A (en) | 2019-07-19 | 2019-07-19 | Anti-stripping adhesive auxiliary agent for flocking adhesive |
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| CN110835509A (en) * | 2019-12-12 | 2020-02-25 | 杨国亭 | Flame-retardant adhesive for power battery |
| CN114892421A (en) * | 2021-06-26 | 2022-08-12 | 上海九裕纺织科技有限公司 | Production process based on flocking on film and application thereof |
| CN117645854B (en) * | 2024-01-30 | 2024-04-05 | 赢胜节能集团股份有限公司 | Multi-component polyacrylate adhesive and production method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999031159A1 (en) * | 1997-12-15 | 1999-06-24 | Lord Corporation | Polyurethane compositions |
| CN102399525A (en) * | 2010-09-10 | 2012-04-04 | 宏峰行化工(深圳)有限公司 | Flexible package composite membrane ultraviolet cured water-based adhesive and preparation method thereof |
| CN106256868A (en) * | 2015-06-16 | 2016-12-28 | 现代自动车株式会社 | The method that high elastic aqueous adhesive composition and surface thereof process products formed |
| CN108867113A (en) * | 2018-06-06 | 2018-11-23 | 苏州印丝特纺织数码科技有限公司 | A kind of pigment printing adhesive and preparation method thereof |
-
2019
- 2019-07-19 CN CN201910655010.1A patent/CN110527465B/en active Active
- 2019-07-19 CN CN202110000504.3A patent/CN112812073A/en not_active Withdrawn
- 2019-07-19 CN CN202110000511.3A patent/CN112724892A/en not_active Withdrawn
- 2019-07-19 CN CN202110000503.9A patent/CN112831312A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999031159A1 (en) * | 1997-12-15 | 1999-06-24 | Lord Corporation | Polyurethane compositions |
| CN102399525A (en) * | 2010-09-10 | 2012-04-04 | 宏峰行化工(深圳)有限公司 | Flexible package composite membrane ultraviolet cured water-based adhesive and preparation method thereof |
| CN106256868A (en) * | 2015-06-16 | 2016-12-28 | 现代自动车株式会社 | The method that high elastic aqueous adhesive composition and surface thereof process products formed |
| CN108867113A (en) * | 2018-06-06 | 2018-11-23 | 苏州印丝特纺织数码科技有限公司 | A kind of pigment printing adhesive and preparation method thereof |
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| CN112724892A (en) | 2021-04-30 |
| CN112812073A (en) | 2021-05-18 |
| CN112831312A (en) | 2021-05-25 |
| CN110527465A (en) | 2019-12-03 |
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