CN114164663A - High-performance durable polyurethane polyacrylate waterproof agent and preparation method thereof - Google Patents
High-performance durable polyurethane polyacrylate waterproof agent and preparation method thereof Download PDFInfo
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- CN114164663A CN114164663A CN202111570226.1A CN202111570226A CN114164663A CN 114164663 A CN114164663 A CN 114164663A CN 202111570226 A CN202111570226 A CN 202111570226A CN 114164663 A CN114164663 A CN 114164663A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/2845—Monohydroxy epoxy compounds
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
- D06M15/29—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing a N-methylol group or an etherified N-methylol group; containing a N-aminomethylene group; containing a N-sulfidomethylene group
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
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- D—TEXTILES; PAPER
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
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Abstract
The invention discloses a high-performance durable polyurethane polyacrylic acid ester waterproof agent and a preparation method thereof, the waterproof agent comprises a water-based dispersion compounded by a component A and a component B, the component A is a copolymer of a monomer structure a, a comonomer B and a crosslinking monomer C, the monomer structure a is fluorine-free acrylate with a general formula of R1COOC (R2) ═ CH2 structure, the comonomer B is a cationic monomer with C ═ C bond, the crosslinking monomer C is a polymerizable monomer with reactive groups, the component B is a copolymer of a monomer structural unit d and a structural unit e, the waterproof effect of the prepared agent is improved by the combined compounding of the specific groups in the component A and the component B, the prepared agent still has excellent waterproof effect after being washed for 20 times, the waterproof effect, the stability and the sustainability are effectively considered, on the premise of greatly improving the surface adsorption capacity of the waterproof agent and a substrate, also improves the waterproof effect and the washing resistance persistence of the waterproof agent and comprehensively enhances the service performance of the waterproof agent.
Description
Technical Field
The invention particularly relates to the field of textile auxiliaries, and particularly relates to a high-performance durable polyurethane polyacrylate waterproof agent and a preparation method thereof.
Background
With the improvement of production and living standards, people have higher and higher requirements on the functionality of fabrics, waterproof fabrics are one of the fabrics, and in order to impart waterproof performance to textiles, fluorine-containing acrylate polymers are widely applied to the surfaces of textile substrates. The fluorine-containing acrylate polymer has a unique long-chain C-F structure, and the surface tension of the textile fabric substrate is far lower than that of water, so that excellent waterproof performance is achieved.
However, the use of the fluorine-containing acrylate polymer is limited because the fluorine-containing acrylate polymer generates substances harmful to human bodies and ecological environment in the use process, and the fluorine-containing acrylate polymer is relatively expensive.
The fluoride-free waterproof agent is more and more popular among people because of no harm to the environment, high cost performance and good waterproof effect. The existing fluorine-free waterproof agent is of alkane long-chain type; an acrylate polymer; organopolysiloxanes and polyurethanes. The fluoride-free water repellent has the characteristics of acrylic ester fluoride-free water repellent, wherein the acrylic ester fluoride-free water repellent has excellent water resistance, high cost performance and relatively easy preparation method, and the polyurethane water repellent has excellent crosslinking performance, washing resistance and high cost performance, so that the two water repellents are widely applied by people at present.
It is known that an acrylate water repellent has excellent water repellent effect and stability but its persistence effect is not satisfactory, and a polyurethane water repellent has excellent persistence but its water repellent effect and stability effect are not satisfactory.
Disclosure of Invention
The invention aims to provide a high-performance durable polyurethane polyacrylate waterproof agent and a preparation method thereof, and aims to solve the problems in the background art.
In order to achieve the purpose, the invention provides the following technical scheme:
a high-performance durable polyurethane polyacrylate waterproof agent comprises a water-based dispersion compounded by a component A and a component B;
the component A is a copolymer of a monomer structure a, a comonomer b and a crosslinking monomer C, wherein the monomer structure a is a fluorine-free acrylate with a general formula of R1COOC (R2) ═ CH2, the comonomer b is a cationic monomer with a C ═ C bond, and the crosslinking monomer C is a polymerizable monomer with a reactive group;
the component B is a copolymer of a monomer structural unit d having a Q-NHC (O) -X-like structure and a structural unit e having a HO- (SiO (CH3)2) n-OH-like structure.
Further scheme: the component A accounts for 10-90% of the weight of the formula, and the component B accounts for 5-50% of the weight of the formula.
Further scheme: the component A accounts for 20-80% of the weight of the formula, and the component B accounts for 10-40% of the weight of the formula.
Further scheme: the component A accounts for 30-70% of the weight of the formula, and the component B accounts for 10-30% of the weight of the formula.
Further scheme: 1 of the monomeric structure a is an alkyl group containing 1 to 24 carbon atoms; r2 is H, CH3 or CH2CH 3.
Further scheme: the polymerizable monomer of the crosslinking monomer C is a monomer which does not contain an F atom and has at least one reactive group which can react with an acrylate or a C ═ C bond.
Further scheme: q of said structural unit d is a monovalent, divalent or polyvalent moiety selected from linear or linear, cyclic or acyclic alkylene groups, said alkylene groups optionally containing at least one group selected from alkoxy, phenyl, alkylene oxide, urethane, urea, biuret, uretdione, cyclized isocyanate, allophanate or isocyanurate.
Further scheme: x of the structural unit d is a residue of a cyclic or acyclic sugar alcohol substituted with at least one of the following groups: -R1; -c (O) R1, - (CH 2O) n (CH3) CH2O) mR2, - (CH 2O) n (CH3) CH2O) m C (O) R1, or mixtures thereof.
Further scheme: each n is independently 0 to 20, each m is independently 0 to 20, and m + n is greater than 0, each R1 is independently a linear or branched hydrocarbyl group having 5-29 carbons optionally including at least 1 unsaturated bond, each R2 is independently-H, and a linear or branched hydrocarbyl group having 6 to 30 carbons optionally including at least 1 unsaturated bond, or mixtures thereof.
Another objective of the present application is to provide a preparation method of the high-performance durable polyurethane polyacrylate waterproof agent, which comprises the following steps:
1. preparation of component A: adding a surfactant and a water-soluble organic solvent into dispersion water, uniformly stirring, adding a monomer structure a, a comonomer b and a crosslinking monomer c, heating to 40-70 ℃, uniformly stirring, mixing and emulsifying the monomers, the surfactant and the water-based medium by using a homomixer or a high-pressure emulsifier uniformly, heating to 40-90 ℃ in the presence of a polymerization initiator and a protective gas, and reacting and polymerizing uniformly;
2. preparing a component B: adding sugar alcohol into a flask, heating to 100-150 ℃, distilling under reduced pressure for dehydration, then cooling to room temperature, adding isocyanate and a solvent, stirring uniformly, heating to 40-90 ℃, adding a catalyst, preserving heat for a plurality of hours, adding a compound II, supplementing the catalyst, and continuing preserving heat for a plurality of hours at 40-90 ℃; adding water and surfactant, stirring to mix thoroughly, homogenizing or ultrasonic treating, and removing organic solvent;
3. and compounding the component A and the component B according to the proportion to obtain the waterproof agent.
Compared with the prior art, the invention has the beneficial effects that:
through the combination and compounding of the specific groups in the component A and the component B, the waterproof effect of the prepared reagent is improved, the prepared reagent still has excellent waterproof effect after being washed for 20 times, the waterproof effect, the stability and the durability are effectively considered, the waterproof effect and the washing durability of the waterproof agent are also improved on the premise of greatly improving the surface adsorption capacity of the waterproof agent and a base material, and the use performance of the waterproof agent is comprehensively enhanced.
Drawings
Fig. 1 is a schematic view of a water-repellent picture grade.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention discloses a high-performance durable polyurethane polyacrylate waterproof agent, which comprises a water-based dispersion compounded by a component A and a component B.
Wherein component A is a copolymer of monomer structure a, comonomer b and crosslinking monomer c, wherein component A accounts for 10-90% of the total formula weight, preferably: 20-80%, more preferably 30-70%;
monomer structure a is a non-fluorinated acrylate of the general formula R1COOC (R2) ═ CH2, where R1 is an alkyl group containing 1 to 24 carbon atoms; r2 is H, CH3 or CH2CH 3;
as the monomer structure a, from the viewpoint of water-repellent effect, it is preferable to use an alkyl (meth) acrylate or cycloalkyl (meth) acrylate having a saturated or unsaturated linear or branched alkyl group having 1 to 24 carbon atoms, such as, for example: isobornyl (meth) acrylate, tetradecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, etc., with hexadecyl (meth) acrylate and octadecyl (meth) acrylate being preferred.
The monomer structure a constitutes about 5 to 60% by weight, preferably about 10 to 50% by weight, and more preferably about 15 to 30% by weight of component A;
the comonomer b is a cationic monomer having C ═ C bond, such a substance contains at least one or more cationic monomers having C ═ C bond, and the cationic monomer having C ═ C bond includes, but is not limited to, methacryloyloxyethyl trimethyl ammonium chloride; dimethyldiallylammonium chloride, octadecyldimethylammonium chloride, methacrylamidopropyltrimethylammonium chloride, preferably: dimethyldiallylammonium chloride;
the monomer b is contained in the component A at about 0.1 to 10% by weight, preferably about 0.1 to 5% by weight, and more preferably about 0.1 to 3% by weight
The crosslinking monomer c is a polymerizable monomer having a reactive group; the polymerizable monomer is a monomer which does not contain an F atom and has at least one reactive group which can react with an acrylate or a C ═ C bond;
crosslinking monomers c include, but are not limited to, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylate, N-dimethyl (meth) acrylamide, poly (ethylene/propylene glycol) mono (meth) acrylate, glycidyl (meth) acrylate, with N-methylol (meth) acrylamide and glycidyl (meth) acrylate being preferred; preferably: n-methylolacrylamide;
the crosslinking monomer c is contained in the component A in an amount of about 0.1 to 20% by weight, preferably about 1 to 15% by weight, and more preferably about 2 to 10% by weight.
Furthermore, the present invention contains component B, which is a copolymer of monomeric structural units d and structural units e, wherein component B accounts for 5 to 50% by weight of the entire invention, and preferably: 10-40%, more preferably 10-30%;
wherein structural unit d has the structure Q-nhc (o) -X-, wherein Q is a monovalent, divalent or polyvalent moiety selected from linear or straight chain, cyclic or acyclic alkylene groups optionally containing at least one group selected from alkoxy, phenyl, alkylene oxide, urethane, urea, biuret, uretdione, cyclized isocyanate, allophanate or isocyanurate;
wherein X is the residue of a cyclic or acyclic sugar alcohol substituted with at least one of the following groups: -R1; -c (O) R1, - (CH 2O) n (CH3) CH2O) mR2, - (CH 2O) n (CH3) CH2O) m C (O) R1, or mixtures thereof;
wherein the cyclic or acyclic sugar alcohol is selected from a sugar, a reducing sugar, an amino sugar, an aldonic acid, or an aldonic lactone;
wherein each n is independently 0 to 20, each m is independently 0 to 20, and m + n is greater than 0;
each R1 is independently a straight or branched chain hydrocarbyl group having 5-29 carbons optionally including at least 1 unsaturated bond; and each R2 is independently-H; a linear or branched hydrocarbyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond or mixtures thereof;
such compounds include, but are not limited to: hexamethylene diisocyanate biuret, hexamethylene diisocyanate homopolymer, toluene diisocyanate trimer and trimer of 3-isocyanato and methyl-3, 4, 4-trimethylcyclohexyl isocyanate, preferably DESMODUR N-3300, DESMODUR N-3600, DESMODUR N100, DESMODUR N-75D, etc. available from Bayer corporation; preferably DESMODUR N100;
wherein the compound constitutes 5-50% by weight of component B, preferably: 5-30 wt%, more preferably 5-20 wt%;
the structural unit e has the following structure HO- (SiO (CH3)2) n-OH;
wherein each n is independently 0 to 1000, compounds including but not limited to: linear body, hydroxyl silicone oil, 10 viscosity 107 glue, 50 million viscosity 107 glue polysiloxane or silicone containing reactive hydroxyl; among them, 10-viscosity 107 glue is preferred, and among them, the compound is preferably 1 to 70% by weight, preferably 1 to 30% by weight, more preferably 1 to 20% by weight, based on the component B;
the polymer component A and the component B are compounded according to different proportions by different polymerization methods;
the component A polymerization method preferably comprises the steps of adding a surfactant and a water-soluble organic solvent into dispersion water, uniformly stirring, adding a monomer structure a, a comonomer b and a crosslinking monomer c, heating to 40-70 ℃, uniformly stirring, mixing and emulsifying the monomer, the surfactant and an aqueous medium by using a homomixer or a high-pressure emulsifier, heating to 40-90 ℃ in the presence of a polymerization initiator and a protective gas, and uniformly reacting and polymerizing.
Water-soluble or oil-soluble radical polymerization initiators are preferred in the present invention.
Common free radical polymerization initiators include azo initiators, peroxide initiators, redox system initiators and the like, the azo initiators are preferred in the invention, water-soluble azo initiators are particularly preferred, and azodiisobutyl amidine hydrochloride is particularly preferred;
the polymerization initiator is present in an amount of 0.05 to 10% by weight, preferably about 0.1 to 5% by weight, based on the weight of component A.
Wherein, the polymerization method of the component B preferably comprises the steps of adding sugar alcohol into a flask, heating to 100-150 ℃, distilling under reduced pressure for dehydration, then cooling to room temperature, adding isocyanate and a solvent, stirring uniformly, heating to 40-90 ℃, adding a catalyst, preserving heat for a plurality of hours, adding a compound II, supplementing the catalyst, and preserving heat for a plurality of hours at 40-90 ℃; adding water and surfactant, stirring, homogenizing or ultrasonic treating, and removing organic solvent.
The component A and the component B are used according to the required proportion, so that excellent waterproof and washable performances can be obtained.
The polymer of the invention is diluted to the solid content concentration of about 0.1-10 wt% in water, and is suitable for various fabrics such as natural fibers, synthetic fibers, artificial fibers and other fabrics. As the application method, coating, dipping, spraying, padding, roll coating or a combination thereof may be used. The specific method comprises the following steps:
the solid content concentration is set to 0.1 to 10 wt% to be used as a padding bath, the material to be treated is padded in the padding bath, and then excess liquid is removed by a squeeze roll and dried. The material to be treated is dried at a temperature of about 80 to 120 ℃ for about 1 minute to 1 hour, and then cured at a temperature of about 150 to 180 ℃ for about 1 to 3 minutes, preferably 150 to 170 ℃ for about 1 to 3 minutes, and particularly preferably 170 ℃ for about 1 minute, to complete the water repellent treatment.
Example 1: (preparation A1)
A dry four-neck round-bottom flask, a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser and a gas outlet were assembled together, 58.75g of water, 10.5g of tripropylene glycol, 1.5g of sorbitan monostearate (span 60), 0.8g of isotridecanol polyoxyethylene ether 8EO,1.0g of dodecatetraol polyoxyethylene ether 7EO,6g of diallylaminomethylammonium chloride (60% content), heated to 60 ℃, stirred and dissolved uniformly for 30 minutes, 20.7g of stearyl acrylate, 0.6g of N-methylolacrylamide, 0.15g of dodecylmercaptan were continuously added, and stirred uniformly for 60 minutes at 60 ℃.
Treating the mixed solution at 60 deg.C under 40MPa for 30min with high pressure emulsifying machine to obtain uniform emulsion. The emulsion was added to a glass flask, heated to 40 ℃ to displace nitrogen gas for 30min, heated to 70 ℃ to add azobisisobutyryl ether hydrochloride (dissolved in 10g of water) in an amount of 0.3g, and polymerized at 80 ℃ for 5 hours to obtain a fine and uniform emulsion, A1 was obtained.
Example a 2: (preparation A2)
A dry four-neck round-bottom flask, a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser and a gas outlet were assembled together, 52.75g of water, 10.5g of tripropylene glycol, 1.5g of sorbitan monostearate (span 60), 0.8g of isotridecanol polyoxyethylene ether 8EO,1.0g of dodecatetraol polyoxyethylene ether 7EO,12g of diallylaminomethylammonium chloride (60% content), heated to 60 ℃, stirred and dissolved uniformly for 30 minutes, 20.7g of stearyl acrylate, 0.6g of N-methylolacrylamide, 0.15g of dodecylmercaptan were continuously added, and stirred uniformly for 60 minutes at 60 ℃.
Treating the mixed solution at 60 deg.C under 40MPa for 30min with high pressure emulsifying machine to obtain uniform emulsion. The emulsion was added to a glass flask, heated to 40 ℃ to displace nitrogen gas for 30min, heated to 70 ℃ to add azobisisobutyryl ether hydrochloride (dissolved in 10g of water) in an amount of 0.3g, and polymerized at 80 ℃ for 5 hours to obtain a fine and uniform emulsion, A2 was obtained.
Example 3: (preparation B1)
Assembling a dry four-mouth round-bottom flask, a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser and a gas outlet together, adding 23g of sorbitan trioleate into the flask, heating to 110 ℃, distilling under reduced pressure for 1.5 hours, cooling to 40 ℃, continuously adding 14g of DESMODUR N100 and 100g of MIBK, heating the reaction mixture to 70 ℃, adding 0.1g of dibutyltin dilaurate, preserving heat at 75 ℃ for 2 hours, adding 10g of a linear body and 0.1g of dibutyltin dilaurate, preserving heat at 75 ℃ for 2 hours, adding 5g of polyethylene glycol 400, and continuously preserving heat at 75 ℃ for 4 hours;
when the reaction was tested negative for reactive isocyanate, 100g of deionized water, 10g of octadecyl dimethyl ammonium chloride, 5g of AEO7 were added and the mixture was stirred at 65 ℃ for 1 hour each, then the mixture was homogenized 2 times at 4000psi, MIBK was removed by distillation, the product was filtered and diluted to 25% solids to give B1.
Example 4 (preparation B2)
Assembling a dry four-mouth round-bottom flask, a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser and a gas outlet together, adding 23g of sorbitan trioleate into the flask, heating to 110 ℃, distilling under reduced pressure for 1.5 hours, cooling to 40 ℃, continuously adding 14g of DESMODUR N100 and 100g of MIBK, heating the reaction mixture to 70 ℃, adding 0.1g of dibutyltin dilaurate, preserving heat at 75 ℃ for 2 hours, adding 10g of 10g of CS107 glue and 0.1g of dibutyltin dilaurate, preserving heat at 75 ℃ for 2 hours, adding 5g of polyethylene glycol 400, and continuously preserving heat at 70-75 ℃ for 4 hours;
when the reaction was tested negative for reactive isocyanate, 100g of deionized water, 10g of octadecyl dimethyl ammonium chloride, 5g of AEO7 were added and the mixture was stirred at 65 ℃ for 1 hour each, then the mixture was homogenized 2 times at 4000psi, MIBK was removed by distillation, the product was filtered and diluted to 25% solids to give B2.
The compounds A1, A2, B1 and B2 prepared in example 1, example 2, example 3 and example 4 respectively are compounded according to the following proportion to obtain 6 groups of compounded reagents, wherein the compounding ratio of examples 5 to example 10 is shown in Table 1:
table 1: examples 5 to 10 compounding ratios
Comparative example C
A dry four-neck round-bottom flask, a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser and a gas outlet were assembled together, 62.75g of water, 10.5g of tripropylene glycol, 1.5g of sorbitan monostearate (span 60), 0.8g of isomeric tridecanol polyoxyethylene ether 8EO,1.0g of dodecadecyl alcohol polyoxyethylene ether 7EO,2.0g of cetyltrimethylammonium chloride were added to the flask, the temperature was raised to 60 ℃, stirred and dissolved uniformly for 30 minutes, 20.7g of stearyl acrylate, 0.6g of N-methylolacrylamide, 0.15g of dodecylmercaptan were further added, and stirred uniformly for 60 minutes at constant temperature of 60 ℃.
Treating the mixed solution at 60 deg.C under 40MPa for 30min with high pressure emulsifying machine to obtain uniform emulsion. Adding the emulsion into a glass flask, heating to 40 ℃, carrying out nitrogen replacement on gas for 30min, heating to 70 ℃, adding 0.3g of azobisisobutyryl ether hydrochloride (dissolved by 10g of water), and carrying out polymerization reaction for 5 hours at 80 ℃ to obtain fine and uniform emulsion.
Washing durability test for water repellency:
washing with a washing solution at 40 ℃ for 25 minutes (5 minutes HL, 4 times in succession), dehydrating for 3 minutes, rinsing for 2 minutes, decoloring for 3 minutes, roller drying was carried out in accordance with JIS L-0217-;
test of Water-proof Effect
The water repellent effect (according to AATCC 22) was measured for a water repellent test. The water repellency was expressed as water repellency No. (as shown in table 1 below, the suffix "+" attached to the numerical value indicates a slightly better performance than that indicated by the numerical value.
| Water repellency NO. | Status of state |
| 100(5 level) | The surface of the shower is not wet and is not stained with water drops |
| 90 (4-grade) | The surface of the drenched liquid is not wetted, but the surface occupies water drops |
| 80 (grade 3) | With only unlinked small-area wetting of the showered surface |
| 70 (2-grade) | The surface of the drenched liquid is half wet |
| 50 (level 1) | The drenched surface is totally wetted |
Water repellent picture grade (as shown in figure 1)
ISO 5-the upper layer surface is not wetted and wetted; ISO 4-there is a small amount of irregular wetting or wetting on the upper surface; ISO 3-wetting the upper layer surface at the showering position; ISO 2-partial wetting of the entire upper surface; ISO 1-complete wetting of all upper surface. ISO water spray test grade chart based on AATCC picture grade.
The evaluation of the water repellency of the emulsion thus obtained in the above example is shown in Table 2 below
As can be seen from table 2, a1 and a2 prepared in example 1 and example 2 have excellent waterproofing effect, but the waterproofing effect is reduced after 20 times of washing resistance;
the waterproof effects of B1 and B2 prepared in examples 3 and 4 are not ideal, but the waterproof effect is not greatly reduced after 20 times of washing resistance;
the waterproof effect of the comparative example C is relatively poor, and the waterproof effect is basically not achieved after the washing is carried out for 5 times;
examples 5 to 10 show that the waterproof effect of the agent prepared by compounding A1.A2, B1 and B2 is improved, and the agent still has excellent waterproof effect after being washed for 20 times, so that the waterproof effect, the stability and the durability are effectively considered, the waterproof effect and the washing durability of the waterproof agent are improved on the premise of greatly improving the surface adsorption capacity of the waterproof agent and a base material, and the use performance of the waterproof agent is comprehensively enhanced.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art will be able to make the description as a whole, and the embodiments in each example may be appropriately combined to form other embodiments that may be understood by those skilled in the art.
Claims (10)
1.A high-performance durable polyurethane polyacrylate waterproof agent is characterized by comprising a water-based dispersion compounded by a component A and a component B:
wherein the component A is a copolymer of a monomer structure a which is a fluorine-free acrylate having a general formula of R1COOC (R2) ═ CH2, a comonomer b which is a cationic monomer having a C ═ C bond, and a crosslinking monomer C which is a polymerizable monomer having a reactive group;
the component B is a copolymer of a monomer structural unit d having a Q-NHC (O) -X-like structure and a structural unit e having a HO- (SiO (CH3)2) n-OH-like structure.
2. The high-performance durable polyurethane polyacrylate waterproofing agent according to claim 1 wherein component a is 10-90% by weight of the formulation and component B is 5-50% by weight of the formulation.
3. The high-performance durable polyurethane polyacrylate waterproofing agent according to claim 1, wherein the component A accounts for 20-80% of the weight of the formula, and the component B accounts for 10-40% of the weight of the formula.
4. The high-performance durable polyurethane polyacrylate waterproofing agent according to claim 1, wherein the component A accounts for 30-70% of the weight of the formula, and the component B accounts for 10-30% of the weight of the formula.
5. The high performance durable polyurethane polyacrylate waterproofing agent according to claim 1 wherein 1 of the monomer structure a is an alkyl group containing 1 to 24 carbon atoms; r2 is H, CH3 or CH2CH 3.
6. The high-performance permanent polyurethane polyacrylate waterproofing agent according to claim 1 wherein the polymerizable monomer of the crosslinking monomer C is free of F atom and has at least one reactive group that can react with acrylates or C ═ C bond.
7. The high performance permanent polyurethane polyacrylate waterproofing agent according to claim 1 characterized in that Q of the structural unit d is a monovalent, divalent or polyvalent moiety selected from linear or linear, cyclic or acyclic alkylene group optionally containing at least one group selected from alkoxy, phenyl, alkylene oxide, urethane, urea, biuret, uretdione, cyclized isocyanate, allophanate or isocyanurate.
8. The high-performance permanent polyurethane polyacrylate waterproofing agent according to claim 1 wherein X of the structural unit d is the residue of a cyclic or acyclic sugar alcohol substituted with at least one of the following groups: -R1; -c (O) R1, - (CH 2O) n (CH3) CH2O) mR2, - (CH 2O) n (CH3) CH2O) m C (O) R1, or mixtures thereof.
9. The high performance durable polyurethane polyacrylate waterproofing agent according to claim 8 wherein each n is independently 0 to 20, each m is independently 0 to 20, and m + n is greater than 0, each R1 is independently a linear or branched hydrocarbyl group having 5-29 carbons optionally including at least 1 unsaturated bond, each R2 is independently-H, and a linear or branched hydrocarbyl group having 6 to 30 carbons optionally including at least 1 unsaturated bond, or mixtures thereof.
10. A process for the preparation of a high performance durable polyurethane polyacrylate waterproofing agent comprising any of claims 1 to 9 comprising the steps of:
1) and preparation of component A: adding a surfactant and a water-soluble organic solvent into dispersion water, uniformly stirring, adding a monomer structure a, a comonomer b and a crosslinking monomer c, heating to 40-70 ℃, uniformly stirring, mixing and emulsifying the monomers, the surfactant and the water-based medium by using a homomixer or a high-pressure emulsifier uniformly, heating to 40-90 ℃ in the presence of a polymerization initiator and a protective gas, and reacting and polymerizing uniformly;
2) and the component B is prepared by the following steps: adding sugar alcohol into a flask, heating to 100-150 ℃, distilling under reduced pressure for dehydration, then cooling to room temperature, adding isocyanate and a solvent, stirring uniformly, heating to 40-90 ℃, adding a catalyst, preserving heat for a plurality of hours, adding a compound II, supplementing the catalyst, and continuing preserving heat for a plurality of hours at 40-90 ℃; adding water and surfactant, stirring to mix thoroughly, homogenizing or ultrasonic treating, and removing organic solvent;
3) and compounding the component A and the component B according to the proportion to obtain the waterproof agent.
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