CN111217964B - Waterborne polyurethane-acrylate hybrid resin, preparation method thereof and application thereof in leather finishing agent - Google Patents
Waterborne polyurethane-acrylate hybrid resin, preparation method thereof and application thereof in leather finishing agent Download PDFInfo
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- CN111217964B CN111217964B CN201811429184.8A CN201811429184A CN111217964B CN 111217964 B CN111217964 B CN 111217964B CN 201811429184 A CN201811429184 A CN 201811429184A CN 111217964 B CN111217964 B CN 111217964B
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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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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- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention provides a waterborne polyurethane-acrylate hybrid resin, a preparation method thereof and application thereof in a leather finishing agent, wherein the preparation method comprises the following steps: mixing and dissolving a diluent monomer and an isocyanate-terminated prepolymer, carrying out high-speed shearing dispersion after neutralization reaction to obtain a pre-hybrid emulsion, and adding an initiator into the pre-hybrid emulsion to initiate polymerization; the isocyanate-terminated prepolymer is obtained by mixing and reacting diisocyanate, macromolecular polyol and a chain extender; the macromolecular polyol comprises at least one of polyether diol and polyester diol. The aqueous polyurethane-acrylate hybrid resin prepared by the preparation method disclosed by the invention is simple and controllable in preparation process, and the leather finishing agent prepared from the aqueous polyurethane-acrylate hybrid resin is suitable for the field of high-end leather finishing agents and has the advantages of high weather resistance, smooth hand feeling, good anti-sticking performance, good anti-whitening performance, good filler coating performance, high black transparency and good scratch resistance.
Description
Technical Field
The invention relates to the field of aqueous leather finishing agents, in particular to an aqueous polyurethane-acrylate hybrid resin for a leather finishing agent, a preparation method thereof and application thereof in a leather finishing agent.
Background
Surface finishing is one of the most important processes in leather manufacturing processes, and in order to make the appearance and hand feel of artificial leather closer to genuine leather, the surface of artificial leather is usually subjected to surface finishing treatment for brightening, delustering and hand feel improvement so as to obtain soft gloss and hand feel similar to natural leather, and the leather is subjected to surface finishing to impart necessary properties such as scratch resistance, abrasion resistance, alcohol resistance, flex resistance, high-temperature yellowing resistance, ultraviolet light resistance and the like.
In the prior art, the waterborne polyurethane resin has been widely applied to the field of leather finishing agents due to the characteristics of good film forming property, good flexibility, high gloss and fullness, elastic paint film, excellent wear resistance of the paint film and the like. CN 201410708489.8 discloses a preparation method of a waterborne polyurethane leather finishing agent, which uses diisocyanate, Cellulose Acetate Butyrate (CAB) and polyether polyol to generate a prepolymer capped by isocyanate groups, then uses triethylamine to neutralize after chain extension is carried out by hydrophilic chain extender, and finally uses ethylenediamine to carry out chain extension to form a cellulose acetate butyrate modified waterborne polyurethane dispersoid, thereby preparing the waterborne polyurethane leather finishing agent. However, the waterborne polyurethane resin obtained by the method has the advantages of high fullness, good glossiness, excellent film forming property, good wear resistance and the like, but also has the problems of low paint film hardness, poor scratch resistance, poor weather resistance of the paint film and the like, and is difficult to be applied to the fields of high-end leather, such as automotive interiors, high-grade sofas and clothes.
Polyurethane-acrylate emulsion (PUA) is prepared from Polyurethane (PU) and Polyacrylate (PA) by chemical copolymerization or physical blending, and is known as third-generation waterborne polyurethane because the polyurethane has the advantages of excellent wear resistance, toughness, adhesive force, mechanical strength of acrylate, good weather resistance and the like. CN 201510514721.9 discloses a preparation method of polybutadiene modified polyurethane-acrylate emulsion, and the modified polyurethane-acrylate emulsion prepared by the method has the advantages of low film-forming temperature, excellent water resistance, excellent flexibility resistance and high adhesive force to non-polar base materials. But the anti-sticking properties of the paint film surface and the covering properties with respect to the filler are poor. In the downstream production of leather, surface-finished leather products inevitably result in "face-to-face" stacking and pressing of the leather, so that excellent anti-blocking properties of the finish paint film are required, otherwise the product can not be used because of blocking problems. In addition, most of the coating agents are matte, and the resin has better coating capacity on the filler, so that the matte coating agent can have excellent black transmittance, and the problem of white folding after the matte coating surface is stacked and extruded can be avoided.
Therefore, the development of a high-end leather coating agent with high weather resistance, smooth hand feeling, good anti-adhesion performance and strong filler coating performance, which can meet the requirements of the performance and appearance of the high-end leather coating agent, and meet the construction requirements of anti-blocking and anti-whitening.
Disclosure of Invention
The invention provides a preparation method of the waterborne polyurethane-acrylate hybrid resin and application of the resin prepared by the preparation method in the field of leather finishing agents, which are used for making up the defects in the prior art.
According to a first aspect of the present invention, there is provided a method for preparing an aqueous polyurethane-acrylate hybrid resin, comprising the steps of,
mixing and dissolving a reactive diluent monomer and an isocyanate-terminated prepolymer, neutralizing by a neutralizer, then carrying out high-speed shearing and dispersion to obtain a pre-hybrid emulsion, and adding an initiator into the pre-hybrid emulsion to initiate polymerization;
wherein the reactive diluent monomer comprises acrylate monomers and styrene monomers (such as styrene or methyl styrene) and fluorine-containing reactive functional monomers; wherein the acrylate monomer is one or more of methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, propyl acrylate, hydroxypropyl acrylate, butyl acrylate, hydroxybutyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, propyl methacrylate, butyl methacrylate, isobornyl acrylate and isooctyl acrylate; more preferably, the acrylate monomer is butyl acrylate and/or methyl methacrylate;
the isocyanate-terminated prepolymer is prepared by mixing and reacting the following raw materials: diisocyanate, macromolecular polyol and a chain extender; the macromolecular polyol comprises at least one of polyether diol and polyester diol; wherein the chain extender comprises a micromolecular polyol chain extender and a carboxylic acid type hydrophilic chain extender.
Preferably, based on the total mass of the prepolymer for preparing the aqueous polyurethane-acrylate hybrid resin, the raw materials for preparing the isocyanate-terminated prepolymer comprise the following components in the following amounts: 15-40 wt%, preferably 20-35 wt% of diisocyanate; chain extenders in the range from 3 to 16% by weight, preferably from 5 to 12% by weight; the weight percent of the macromolecular polyol is 45-70%, preferably 55-65%, and the molar ratio of the macromolecular polyol to the diisocyanate is 1:3-1:6, and the molar ratio is more preferably 1:3.5-1: 5.
Preferably, the number average molecular weight of the polyether diol or the polyester diol is 500-3000, more preferably 1000-2000, and even more preferably 2000, which is beneficial to improving the fullness and the flex resistance of a coating film formed by the resin prepared from the resin, so as to obtain better use effect.
Preferably, the chain extender includes a small molecule polyol chain extender and a carboxylic acid type hydrophilic chain extender. Preferably, the small molecular polyol chain extender and the carboxylic acid type hydrophilic chain extender are used in an amount of 1 to 6 wt% (preferably 2 to 4 wt%), 2 to 10 wt% (preferably 4 to 8 wt%), respectively, based on the total mass of the isocyanate terminated prepolymer for preparing the aqueous polyurethane-acrylate hybrid resin; preferably, the small-molecule polyol chain extender is an active hydrogen-containing polyol chain extender, the molecular weight of the polyol chain extender is preferably 30-200g/mol, and preferably, the carboxylic acid type hydrophilic chain extender is an active hydrogen-containing carboxylic acid type hydrophilic chain extender.
Preferably, the reactive diluent monomer is used in an amount of 0.6 to 1.5 times, preferably 0.8 to 1.2 times the amount of the isocyanate-terminated prepolymer. Preferably, the solvent used in the reactive diluent monomer is an organic solvent having a boiling point of less than 100 ℃, for example, a ketone solvent such as acetone, methyl ethyl ketone, etc., preferably acetone is used. The amount of the solvent used is preferably 0.6 to 1.2 times the amount of the isocyanate terminated prepolymer.
Preferably, the amount of the acrylate monomer is 0.3 to 0.8 times, preferably 0.5 to 0.7 times of the mass of the reactive diluent monomer. The acrylate monomers include, but are not limited to, one or more of methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, propyl acrylate, hydroxypropyl acrylate, butyl acrylate, hydroxybutyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, propyl methacrylate, butyl methacrylate, isobornyl acrylate, and isooctyl acrylate; more preferably, the acrylate monomer is butyl acrylate and/or methyl methacrylate; the acrylate monomer can improve the weather resistance, gloss retention and xenon lamp aging resistance of a paint film, and can improve the polymerization initiating efficiency and stability of the three reactive diluent monomers.
Preferably, the amount of the styrene-based monomer is 0.1 to 0.5 times, preferably 0.2 to 0.3 times, the mass of the reactive diluent monomer. The styrene-based monomers include, but are not limited to, styrene or methylstyrene; more preferably, the styrene-based monomer is styrene; the styrene-based monomer can provide chemical resistance (such as ethanol wiping resistance, white gasoline wiping resistance, artificial sweat wiping resistance and the like), blackness, hardness and scratch resistance of the surface of a paint film due to the fact that a benzene ring has a special rigid structure, an extremely high refractive index and a high glass transition temperature.
The fluorine-containing reactive functional monomer comprises one or more of but is not limited to perfluoropropyl vinyl ether and perfluoroalkylethyl acrylate. The atoms connected with carbon atoms on the main chain or side chain of the perfluorinated polymerizable monomer are all fluorine atoms, and the radius of the fluorine atoms is small, so that the long bond and the short bond of the C-F bond are high, so that the polymer molecules have many special properties such as hot adhesion resistance, oil stain resistance, low surface energy, weather resistance, chemical resistance and the like, and in the resin film forming process, the fluorine atoms can migrate from the inside to the surface, and even a small amount of the fluorine atoms can be enriched, so that the special properties are provided. Preferably, the fluorine-containing reactive functional monomer is used in an amount of 0.01 to 0.2 times, preferably 0.05 to 0.1 times, the mass of the diluent monomer. When the amount of the fluorine-containing reactive functional monomer is less than 0.01 times of the mass of the diluent monomer, polymerization is difficult to initiate due to too low concentration, and the above-mentioned special properties cannot be provided; when the amount of the fluorine-containing reactive functional monomer is more than 0.2 times the mass of the diluent monomer, the surface energy of the paint film is too low, thereby affecting the recoating effect. Preferred perfluoroalkyl ethyl acrylates of the present invention have the structural formula:
wherein n is 6-12.
The reactive diluent monomer quality, the acrylate monomer, the styrene monomer and the fluorine-containing reactive functional monomer have a synergistic effect, so that the polymerization reaction efficiency is improved, and the excellent chemical resistance, blackness, hot adhesion resistance, oil stain resistance and weather resistance of a paint film are provided.
In the preparation method of the invention, preferably, the amount of the initiator is 0.05-0.3% of the mass of the reactive diluent monomer, and preferably 0.1-0.2%; preferably, the initiator comprises an oxidizing agent and a reducing agent; further preferably, the oxidizing agent comprises one or more of ammonia persulfate, sodium persulfate, potassium persulfate and tert-butyl hydroperoxide, and further preferably, the reducing agent comprises one or more of sodium hydrosulfite, sodium hydrogen sulfite and isoascorbic acid. A more preferred initiator is a combination of both t-butyl hydroperoxide and sodium hydrosulfite. The mass ratio of the oxidizing agent to the reducing agent may be 1: 0.5-1.5.
In a more preferred embodiment of the preparation method of the present invention, based on the total mass of the prepolymer for preparing the aqueous polyurethane-acrylate hybrid resin, the isocyanate-terminated prepolymer is prepared by mixing and reacting the following components in percentage by mass: 15-40 wt% of diisocyanate, 1-6 wt% of micromolecular polyol chain extender and 2-10 wt% of carboxylic acid type hydrophilic chain extender; 45-70 wt% of macromolecular polyol, wherein the molar ratio of the macromolecular polyol to diisocyanate is 1:3-1: 6; based on the total mass of the prepolymer for preparing the aqueous polyurethane-acrylate hybrid resin, the amount of the reactive diluent monomer is 0.8-1.2 times of the mass of the isocyanate-terminated prepolymer; the dosage of the acrylate monomer is 0.3 to 0.8 time, preferably 0.5 to 0.7 time of the mass of the reactive diluent monomer; the dosage of the styryl monomer is 0.1 to 0.5 times, preferably 0.2 to 0.3 times of the mass of the reactive diluent monomer; the dosage of the fluorine-containing reactive functional monomer is 0.01 to 0.2 time of the mass of the reactive diluent monomer; the using amount of the initiator is 0.05-0.3% of the mass of the monomer.
In a more preferred embodiment of the preparation method of the present invention, based on the total mass of the prepolymer for preparing the aqueous polyurethane-acrylate hybrid resin, the isocyanate-terminated prepolymer is prepared by mixing and reacting the following components in percentage by mass: 20-35 wt% of diisocyanate, 2-4 wt% of micromolecular polyol chain extender and 4-8 wt% of carboxylic acid type hydrophilic chain extender; also contains 55-65 wt% of macromolecular polyol, wherein the molar ratio of the macromolecular polyol to diisocyanate is 1:3.5-1: 5; based on the total mass of the prepolymer for preparing the aqueous polyurethane-acrylate hybrid resin, the amount of the reactive diluent monomer is 0.8-1.2 times of the mass of the isocyanate-terminated prepolymer; the dosage of the acrylate monomer is 0.5 to 0.7 time of the mass of the reactive diluent monomer; the dosage of the styrene-based monomer is 0.2 to 0.3 time of the mass of the reactive diluent monomer; the dosage of the fluorine-containing reactive functional monomer is 0.05 to 0.1 time of the mass of the reactive diluent monomer; the amount of the initiator is 0.1-0.2% of the mass of the reactive diluent monomer.
In a preferred embodiment of the preparation method of the present invention, the fluorine-containing reactive functional monomer includes, but is not limited to, one or more of perfluoropropyl vinyl ether, perfluoroalkyl ethyl acrylate. The perfluoro polymerizable monomer has the advantages that atoms connected with carbon atoms on a main chain or a side chain of the perfluoro polymerizable monomer are all fluorine atoms, and the radius of the fluorine atoms is small, so that the long bond and the short bond of a C-F bond are large, so that polymer molecules have many special properties such as hot adhesion resistance, oil stain resistance, low surface energy, weather resistance, chemical resistance and the like, during a resin film forming process, the fluorine atoms can migrate from the inside to the surface, and even a small amount of fluorine atoms can be enriched, so that the special properties are provided, the perfluoro alkyl ethyl acrylate is preferably selected, and the structural formula of the perfluoro polymerizable monomer is as follows:
the value range of n is 6-12.
In a preferred embodiment of the preparation method of the present invention, the diisocyanate includes, but is not limited to, one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane diisocyanate.
In a preferred embodiment of the preparation method of the present invention, the polyether diol or polyester diol (dihydroxy polymer) includes, but is not limited to, one or more of polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, polytetrahydrofuran ether glycol, polycaprolactone diol, polycarbonate diol, polyethylene glycol adipate diol, poly 1, 4-butylene glycol adipate diol, poly neopentyl glycol adipate diol, poly 1, 6-hexanediol adipate diol, and poly neopentyl glycol adipate 1, 6-hexanediol adipate diol, more preferably poly neopentyl glycol adipate diol, further preferably poly neopentyl glycol adipate diol having a number average molecular weight of 1000-.
In a preferred embodiment of the preparation method of the present invention, the chain extender includes a small molecule polyol chain extender and a carboxylic acid type hydrophilic chain extender; the chain extender of the small molecular weight polyol more preferably contains active hydrogen and more than two active groups capable of reacting with isocyanate, preferably comprises but is not limited to one or two of trimethylolpropane and 1, 4-butanediol, and preferably uses trimethylolpropane; the carboxylic acid type hydrophilic chain extender preferably includes, but is not limited to, a small molecule diol compound having a carboxylate group, preferably including one or more of dimethylolpropionic acid, dimethylolbutyric acid, tartaric acid, N-dimethylolmaleamic acid, more preferably dimethylolpropionic acid.
In a preferred embodiment of the production method of the present invention, the reaction temperature employed when producing the isocyanate terminated prepolymer is 75 to 85 ℃; the end point of the reaction can be determined in particular by reacting until the NCO has reached the theoretical value.
In a preferred embodiment of the production method of the present invention, the mixing and dissolving of the diluting monomer with the isocyanate terminated prepolymer is carried out at 50 to 60 ℃.
In a preferred embodiment of the preparation process of the present invention, the initiation temperature of the hybrid emulsion initiated polymerization is 30-35 ℃. In one embodiment, the time for the polymerization reaction is preferably 0.5 to 1 hour.
In a specific embodiment of the preparation method of the present invention, the neutralization reaction is performed by adding a neutralizing agent to a mixed solution of a diluted monomer and an isocyanate-terminated prepolymer for neutralization reaction, which is a conventional operation in the art and is not described in detail. The neutralizing agent added for the neutralization reaction is, for example, an organic amine, preferably a C1-C15 organic amine, more preferably an organic amine neutralizing agent containing no active hydrogen, such as Triethylamine (TEA), trimethylamine or dimethylethylamine, and is preferably 100% neutralized.
In a preferred embodiment of the production method of the present invention, the following step is further included after initiation of polymerization: the solvent in the aqueous polyurethane-acrylate hybrid resin obtained by the initiated polymerization is removed, for example, by vacuum distillation at a temperature of 55-65 ℃ under a pressure of 0.08-0.1 MPa. .
The second aspect of the invention provides the aqueous polyurethane-acrylate hybrid resin prepared by the preparation method.
The third aspect of the invention provides the use of the aqueous polyurethane-acrylate hybrid resin, which is particularly suitable for the preparation of leather finishes, preferably for the preparation of leather finishes suitable for automotive interiors, high-end sofas and high-end clothing.
As used herein, "plurality" means two and more than two.
The third aspect of the invention also provides a leather finishing agent, which comprises the aqueous polyurethane-acrylate hybrid resin prepared by the preparation method, preferably, the content of the aqueous polyurethane-acrylate hybrid resin in the leather finishing agent is 40-60 wt%.
The technical scheme provided by the invention has the following beneficial effects:
the resin prepared by the invention meets the application performance, appearance requirement and construction requirement of the high-end leather finishing agent, and compared with the traditional aqueous polyurethane resin and aqueous acrylate resin, the aqueous polyurethane-acrylate resin has obvious performance advantage, solves the problems of insufficient hardness and poor scratch resistance and weather resistance of the simple polyurethane resin, and also solves the problems of poor fullness and poor yield resistance of the simple acrylate resin.
Compared with the traditional waterborne polyurethane/acrylate resin, the resin has the advantages that by introducing the special functional monomer, the hybrid emulsion resin has obvious performance advantages, high smoothness of hand feeling, good anti-blocking performance, good coating performance on the polishing powder, excellent whitening resistance and good construction performance.
The average particle size of the resin prepared by the invention is in the range of 60-150nm, and preferably in the range of 80-120 nm.
The waterborne polyurethane-acrylate hybrid resin provided by the invention is safe and controllable in synthesis process, simple to operate and easy to realize large-scale industrial production.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the examples and comparative examples, "%" means "% by weight" unless otherwise specified.
The test methods used in the examples or comparative examples are described below:
the solid content test method comprises the following steps: weighing appropriate amount of the emulsion in a container made of tinfoil paper, weighing the weight change at 150 deg.C for 20min, and calculating the solid content.
The particle size test method comprises the following steps: a malvern particle size instrument was used.
pH test method: a pH meter was used.
Viscosity test method: the measurements were carried out using a BROOKFIELD viscometer, spindle 3/30 rpm.
The appearance test method comprises the following steps: and judging the eye sight.
The formulations of the emulsions prepared in the following examples or comparative examples used in the preparation of leather finishes are given in Table 1 below:
table 1:
the method for testing the application properties of the examples and comparative examples is described as follows:
pencil hardness test method: a set of pencils with hardness of 6B, 5B, 4B, 3B, 2B, HB, F, H, 2H, 3H, 4H and 5H are adopted, 1000 gram force is applied to the coating film in a 45-degree direction, a stroke of 10 millimeters is marked at different positions, whether obvious scratches exist in the appearance of the sample is observed, and the hardness of the pencil with the hardest pencil number which cannot scratch the coating film is taken as the hardness of the pencil of the coating film.
Xenon lamp aging resistance: cutting the leather base material treated by the surface finishing agent into square sample strips of 5cm multiplied by 10cm, reserving a sample for blank comparison, placing the rest in a xenon lamp aging test box, irradiating for 300 hours under a 30W xenon lamp, taking out after reaching the experimental time, cooling for more than 10 minutes, observing the yellowing, and comparing with the blank sample to test the color difference value.
Gloss test method: adopting a gloss instrument to test the gloss of the surface of a paint film of the finishing agent, wherein the testing angle is selected to be 85 DEG
The black transmittance test method comprises the following steps: coating agent with the thickness of 20 mu m wet film is uniformly coated on a black leather substrate, and after the paint film is completely dried, the blackness of the paint film is observed by naked eyes. The evaluation grades are referred to in table 2 below:
TABLE 2
| Grade | Degree of black penetration |
| 5 | Very black and full of color |
| 4 | Black and has certain fullness |
| 3 | Has a certain black transmittance |
| 2 | Slight whitening |
| 1 | Severe whitening |
The normal temperature adhesion resistance test method comprises the following steps: the leather substrate treated with the surface finishing agent was cut into 5cm × 10cm square sample strips, and the paint films were folded in half from the middle "face to face". The sample is pressed with a 25kg weight for 24 hours at normal temperature (25 +/-2 ℃), and then the sample is opened, the sample is easily peeled off, and the surface cannot be adhered with a paint film.
The high-temperature adhesion resistance test method comprises the following steps: the leather substrate treated with the surface finishing agent was cut into 5cm × 10cm square sample strips, and the paint films were folded in half from the middle "face to face". The sample is pressed for 24 hours at 80 +/-2 ℃ by a weight of 5kg, and then the sample strip is opened, the sample strip is easily peeled off, and the surface cannot be adhered with a paint film.
The anti-whitening test method comprises the following steps: the leather substrate treated with the surface finishing agent was cut into 5cm × 10cm square sample strips, and the paint films were folded in half from the middle "face to face". The sample is pressed for 24 hours at normal temperature (25 +/-2 ℃) by a weight of 25kg, and then the sample strip is opened, so that the whitening phenomenon at the crease position is avoided.
Recoatability: after brushing one surface coating agent, drying at 130 ℃ for 2min, then brushing one surface coating agent again, and drying at 130 ℃ for 2 min. The recoatability was reflected by testing the adhesion of the coating. The evaluation grades are referred to in table 3 below:
TABLE 3
| Grade | Recoatability |
| 5 | And (3) optimization: the paint film is not fallen off completely |
| 4 | Good: the falling area of a paint film is less than 5 percent |
| 3 | The method comprises the following steps: the falling area of a paint film is between 5 and 15 percent |
| 2 | Slightly worse: the falling area of a paint film is between 15 and 35 percent |
| 1 | Difference: the falling area of a paint film is more than 35 percent |
The stability test method comprises the following steps: and (5) placing the mixture in a constant-temperature oven at 50 ℃ for one month, and observing whether the appearance of the emulsion is layered or not.
The starting materials used in the examples or comparative examples are described below:
PNA-2000 (poly neopentyl glycol adipate diol, hydroxyl value 56mgKOH/g, number average molecular weight 2000, functionality 2, Nitschel Daichemical);
TMP (trimethylolpropane, BASF, germany);
DMPA (dimethylolpropionic acid, boston);
TEA (triethylamine, BASF, germany);
acetone (refined by Wanhua chemical group GmbH)
MMA (methyl methacrylate, zilu petrochemical);
BA (butyl acrylate, Wanhua chemical group Co., Ltd.)
St (styrene, mesopetrochemical);
perfluoroalkyl ethyl acrylate (Guangdong Wengjiang chemical reagent Co., Ltd.)
AA (acrylic acid, Wanhua chemical group, Ltd.)
APS (ammonium persulfate, chemical industry Co., Ltd.)
NaHCO3 (sodium bicarbonate, chemical Co., Ltd.)
DS-4AP (sodium dodecyl benzene sulfonate, Rodiya)
Sodium hydrosulfite (sodium hydrosulfite, available from Xiong chemical Co., Ltd.)
TBHP (tert-butyl hydroperoxide, Shigaku chemical Co., Ltd.)
Silok 8000 (wetting agent, Guangzhou siloco high molecular Polymer Co., Ltd.)
Dipropylene glycol dimethyl ether (solvent, Dow chemical)
FM-14LV (extinction powder, Japan Deshan chemical)
NXZ (antifoam, NOPPIC Japan)
Comparative example 1: aqueous polyurethane resin emulsion
To a four-necked flask equipped with a reflux condenser, a thermometer and a mechanical stirrer were added 68g
HMDI (dicyclohexylmethane diisocyanate) and 110g PNA2000 (poly neopentyl glycol adipate diol) are heated to 80 ℃ for reaction for 1h, then the temperature is reduced to about 60 ℃, 3.8g trimethylolpropane, 12.6g dimethylolpropionic acid and 48g acetone are added, the temperature is heated to 75 ℃ for reaction, samples are taken every 1h for NCO measurement, and the reaction is stopped until the NCO reaches below 2%.
Cooling to below 60 deg.C (50-60 deg.C), adding 76g acetone, mixing and dissolving.
And cooling to below 40 ℃, adding 9.5g of triethylamine, and carrying out neutralization reaction for 3 min.
Pouring the prepared prepolymer into a dispersion cup, adding 282g of water under the high-speed shearing condition of 1500r/min to obtain the waterborne polyurethane emulsion, and removing acetone from the emulsion in a reduced pressure distillation mode to obtain the semitransparent waterborne polyurethane resin emulsion with the solid content of 40% and the particle size of 30 nm.
Comparative example 2: aqueous acrylic emulsion
A jar was charged with 210g of distilled water, 22g of DS-4AP (22.5%) (sodium dodecylbenzenesulfonate), 392g of methyl methacrylate, 100g of butyl acrylate, 8g of acrylic acid, 0.8g of ammonium persulfate, and a pre-emulsion was prepared under high-speed (1000r/min) stirring.
7g of DS-4AP (22.5%) (sodium dodecylbenzenesulfonate), 1 g of sodium bicarbonate and 535g of distilled water were put into a four-neck flask equipped with a reflux condenser, a thermometer, a dropping funnel and a mechanical stirrer, and the temperature was raised to 85 ℃ to add 30g of the prepared pre-emulsion and 1.2g of ammonium persulfate to initiate a reaction.
After 20 minutes, the pre-emulsion was slowly dropped into the flask using a dropping funnel, over 4 hours, and incubated for 1 hour. Then cooling to 70 ℃, adding 1.2g of tert-butyl hydroperoxide and 0.8g of isoascorbic acid, cooling to room temperature after 1 hour, and discharging to obtain the acrylic emulsion with solid content of about 40% and particle size of 150 nm.
Comparative example 3: aqueous polyurethane acrylate emulsion
To a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was added 68g
HMDI (dicyclohexylmethane diisocyanate) and 110g PNA2000 (poly neopentyl glycol adipate diol) are heated to 80 ℃ for reaction for 1h, then the temperature is reduced to about 60 ℃, 3.8g trimethylolpropane, 12.6g dimethylolpropionic acid and 48g acetone are added, the temperature is heated to 75 ℃ for reaction, samples are taken every 1h for NCO measurement, and the reaction is stopped until the NCO reaches below 2%.
The temperature is reduced to below 60 ℃ (between 50 and 60 ℃), 76g of acetone, 39g of butyl acrylate and 156g of methyl methacrylate are added and mixed and dissolved.
And cooling to below 40 ℃, adding 9.5g of triethylamine, and carrying out neutralization reaction for 3 min.
And pouring the prepared prepolymer into a dispersion cup, and adding 585g of water under the high-speed shearing condition of 1500r/min to obtain the aqueous polyurethane-acrylate mixed emulsion.
The emulsion was transferred to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring, heated to about 32 ℃ and then charged with 0.3g of t-butyl hydroperoxide and 0.3g of sodium dithionite in order to initiate radical polymerization.
After the polymerization is finished, acetone in the emulsion is removed in a reduced pressure distillation mode to obtain the semitransparent waterborne polyurethane acrylate resin emulsion with the solid content of 40% and the particle size of 95 nm.
Example 1:
to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was added 68g
HMDI (dicyclohexylmethane diisocyanate) and 110g PNA2000 (poly neopentyl glycol adipate diol), heating to 80 ℃ for reacting for 1h, then cooling to about 60 ℃, adding 3.8g trimethylolpropane, 12.6g dimethylolpropionic acid and 48g acetone, heating to 75 ℃ for reacting, sampling every 1h to measure NCO until NCO reaches below 2%, and stopping the reaction.
Cooling to below 60 deg.C (50-60 deg.C), adding 76g acetone, 32g butyl acrylate, 104.5g methyl methacrylate, 39g styrene, and 19.5g perfluoroalkyl ethyl acrylate, mixing, and dissolving.
And cooling to below 40 ℃, adding 9.5g of triethylamine, and carrying out neutralization reaction for 3 min.
And pouring the prepared prepolymer into a dispersion cup, and adding 585g of water under the high-speed shearing condition of 1500r/min to obtain the aqueous polyurethane-acrylate mixed emulsion.
The emulsion was transferred to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring, heated to about 32 ℃ and then charged with 0.3g of t-butyl hydroperoxide and 0.3g of sodium dithionite in this order to initiate radical polymerization.
After the polymerization is finished, acetone in the emulsion is removed in a reduced pressure distillation mode, and the semitransparent water-based polyurethane-acrylate hybrid resin emulsion with the solid content of 40% and the particle size of 89nm is obtained.
Example 2:
to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was added 68g
HMDI (dicyclohexylmethane diisocyanate) and 110g PNA2000 (poly neopentyl glycol adipate diol) are heated to 80 ℃ for reaction for 1h, then the temperature is reduced to about 60 ℃, 3.8g trimethylolpropane, 12.6g dimethylolpropionic acid and 48g acetone are added, the temperature is heated to 75 ℃ for reaction, samples are taken every 1h for NCO measurement, and the reaction is stopped until the NCO reaches below 2%.
Cooling to below 60 deg.C (50-60 deg.C), adding 76g acetone, 32g butyl acrylate, 122g methyl methacrylate, 39g styrene, and 2g perfluoroalkyl ethyl acrylate, mixing, and dissolving.
And cooling to below 40 ℃, adding 9.5g of triethylamine, and carrying out neutralization reaction for 3 min.
And pouring the prepared prepolymer into a dispersion cup, and adding 585g of water under the high-speed shearing condition of 1500r/min to obtain the aqueous polyurethane-acrylate mixed emulsion.
The emulsion was transferred to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring, heated to about 32 ℃ and then charged with 0.3g of t-butyl hydroperoxide and 0.3g of sodium dithionite in this order to initiate radical polymerization.
After the polymerization is finished, acetone in the emulsion is removed in a reduced pressure distillation mode, and the semitransparent water-based polyurethane-acrylate hybrid resin emulsion with the solid content of 40% and the particle size of 83nm is obtained.
Example 3:
to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was added 68g
HMDI (dicyclohexylmethane diisocyanate) and 110g PNA2000 (poly neopentyl glycol adipate diol) are heated to 80 ℃ for reaction for 1h, then the temperature is reduced to about 60 ℃, 3.8g trimethylolpropane, 12.6g dimethylolpropionic acid and 48g acetone are added, the temperature is heated to 75 ℃ for reaction, samples are taken every 1h for NCO measurement, and the reaction is stopped until the NCO reaches below 2%.
Cooling to below 60 deg.C (50-60 deg.C), adding 76g acetone, 32g butyl acrylate, 88g methyl methacrylate, 39g styrene, 36g perfluoroalkyl ethyl acrylate, mixing and dissolving.
And cooling to below 40 ℃, adding 9.5g of triethylamine, and carrying out neutralization reaction for 3 min.
And pouring the prepared prepolymer into a dispersion cup, and adding 585g of water under the high-speed shearing condition of 1500r/min to obtain the aqueous polyurethane-acrylate mixed emulsion.
The emulsion was transferred to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring, heated to about 32 ℃ and then charged with 0.3g of t-butyl hydroperoxide and 0.3g of sodium dithionite in this order to initiate radical polymerization.
After the polymerization is finished, acetone in the emulsion is removed in a reduced pressure distillation mode, and the semitransparent water-based polyurethane-acrylate hybrid resin emulsion with the solid content of 40% and the particle size of 95nm is obtained.
Example 4:
to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was added 68g
HMDI (dicyclohexylmethane diisocyanate) and 110g PNA2000 (poly neopentyl glycol adipate diol) are heated to 80 ℃ for reaction for 1h, then the temperature is reduced to about 60 ℃, 3.8g trimethylolpropane, 12.6g dimethylolpropionic acid and 48g acetone are added, the temperature is heated to 75 ℃ for reaction, samples are taken every 1h for NCO measurement, and the reaction is stopped until the NCO reaches below 2%.
Cooling to below 60 deg.C (50-60 deg.C), adding 76g acetone, 25.6g butyl acrylate, 83.6g methyl methacrylate, 31.2g styrene, and 15.6g perfluoroalkyl ethyl acrylate, mixing, and dissolving.
And cooling to below 40 ℃, adding 9.5g of triethylamine, and carrying out neutralization reaction for 3 min.
The prepared prepolymer is poured into a dispersion cup, and 526.5g of water is added under the high-speed shearing condition of 1500r/min to obtain the aqueous polyurethane-acrylate mixed emulsion.
The emulsion was transferred to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring, heated to about 32 ℃ and then charged with 0.3g of t-butyl hydroperoxide and 0.3g of sodium dithionite in this order to initiate radical polymerization.
After the polymerization is finished, acetone in the emulsion is removed in a reduced pressure distillation mode, and the semitransparent water-based polyurethane-acrylate hybrid resin emulsion with the solid content of 40% and the particle size of 82nm is obtained.
Example 5:
to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was added 68g
HMDI (dicyclohexylmethane diisocyanate), 110g PNA2000 (poly neopentyl glycol adipate diol), heating to 80 ℃ for reaction for 1h, then cooling to about 60 ℃, adding 3.8g of trimethylolpropane, 12.6g of dimethylolpropionic acid and 48g of acetone, heating to 75 ℃ for reaction, sampling every 1h, measuring NCO, and stopping the reaction until the NCO reaches below 2%.
Cooling to below 60 deg.C (50-60 deg.C), adding 76g acetone, 38.4g butyl acrylate, 125.4g methyl methacrylate, 46.8g styrene, and 23.4g perfluoroalkyl ethyl acrylate, mixing, and dissolving.
And cooling to below 40 ℃, adding 9.5g of triethylamine, and carrying out neutralization reaction for 3 min.
The prepared prepolymer is poured into a dispersion cup, and 643.5g of water is added under the high-speed shearing condition of 1500r/min to obtain the aqueous polyurethane-acrylate mixed emulsion.
The emulsion was transferred to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring, heated to about 32 ℃ and then charged with 0.3g of t-butyl hydroperoxide and 0.3g of sodium dithionite in this order to initiate radical polymerization.
After the polymerization is finished, acetone in the emulsion is removed in a reduced pressure distillation mode, and the semitransparent water-based polyurethane-acrylate hybrid resin emulsion with the solid content of 40% and the particle size of 92nm is obtained.
The emulsions prepared in the examples and comparative examples were used to prepare leather finishes according to the formulations provided above and were tested for properties. The results of the performance tests of the obtained leather finishing agent are shown in Table 3 below
TABLE 3
From the above results, it can be seen that the resin obtained in the examples of the present invention has higher pencil hardness than that of comparative example 1, so that higher scratch resistance can be obtained, and the resin has better extinction efficiency, lower glossiness, better black transmittance, higher xenon lamp aging resistance and better comprehensive performance; compared with the comparative example 2, the embodiment of the invention has obvious performance advantages of normal temperature adhesion resistance, high temperature adhesion resistance and whitening resistance; compared with the comparative example 3, the embodiment of the invention has the advantages of higher scratch resistance, higher normal temperature adhesion resistance, higher high temperature adhesion resistance, higher folding and whitening resistance, better xenon lamp aging resistance, better black transmittance and better comprehensive performance.
From the embodiment 1 and the embodiment 2, the perfluoroalkyl ethyl acrylate with higher content is added into the formula system in the embodiment 1, and the high-temperature blocking resistance of the surface of the coating agent paint film is more excellent than that of the embodiment 2;
example 3 further increased the perfluoroalkyl ethyl acrylate content compared to example 1, and the hardness and scratch resistance of the paint film were further improved, but the recoatability was slightly reduced.
From production practice, the preparation method of the waterborne polyurethane-acrylate hybrid resin emulsion has the advantages of simple and controllable preparation process, high weather resistance, smooth hand feeling, good anti-sticking performance, good anti-whitening performance, good filler coating performance, high black transmittance and good scratch resistance, and has great practical use value.
It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (28)
1. A preparation method of aqueous polyurethane-acrylate hybrid resin is characterized by comprising the following steps:
mixing and dissolving a reactive diluent monomer and an isocyanate-terminated prepolymer, neutralizing by a neutralizer, then carrying out high-speed shearing and dispersion to obtain a pre-hybrid emulsion, and adding an initiator into the pre-hybrid emulsion to initiate polymerization;
wherein the reactive diluent monomer comprises an acrylate monomer, a styrene monomer and a fluorine-containing reactive functional monomer; wherein the acrylate monomer is one or more of methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, propyl acrylate, hydroxypropyl acrylate, butyl acrylate, hydroxybutyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, propyl methacrylate, butyl methacrylate, isobornyl acrylate and isooctyl acrylate;
the fluorine-containing reactive functional monomer is selected from one or more of perfluoroalkyl ethyl acrylate, and the structural formula of the fluorine-containing reactive functional monomer is as follows:
wherein n is 6-12;
the dosage of the acrylate monomer is 0.3 to 0.8 time of the mass of the reactive diluent monomer, the dosage of the styryl monomer is 0.1 to 0.5 time of the mass of the reactive diluent monomer, the dosage of the fluorine-containing reactive functional monomer is 0.01 to 0.2 time of the mass of the reactive diluent monomer,
the isocyanate-terminated prepolymer is prepared by mixing and reacting the following raw materials: diisocyanate, macromolecular polyol and a chain extender; the macromolecular polyol comprises at least one of polyether diol and polyester diol; wherein the chain extender comprises a micromolecular polyol chain extender and a carboxylic acid type hydrophilic chain extender.
2. The method according to claim 1, wherein the raw materials for preparing the isocyanate-terminated prepolymer comprise the following components in the following amounts, based on the total mass of the isocyanate-terminated prepolymer for preparing the aqueous polyurethane-acrylate hybrid resin: 15-40 wt% of diisocyanate; 3-16 wt% of a chain extender; 45-70 wt% of macromolecular polyol.
3. The method according to claim 2, wherein the molar ratio of the macropolyol to the diisocyanate is 1:3 to 1: 6.
4. The method according to claim 1, wherein the acrylate monomer is butyl acrylate and/or methyl methacrylate.
5. The production method according to any one of claims 1 to 4, characterized in that the polyether diol or polyester diol has a number average molecular weight of 500-3000; the polyether diol or polyester diol is selected from one or more of polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, polytetrahydrofuran ether glycol, polycaprolactone diol, polycarbonate diol, polyethylene glycol adipate diol, poly 1, 4-butanediol adipate diol, poly neopentyl glycol adipate diol, poly 1, 6-hexanediol adipate diol and poly 1, 6-hexanediol adipate diol;
the diisocyanate includes one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane diisocyanate.
6. The method as claimed in claim 5, wherein the polyether diol or polyester diol has a number average molecular weight of 1000-2000.
7. The method as claimed in claim 5, wherein the polyester diol is selected from the group consisting of neopentyl glycol adipate diol having a number average molecular weight of 1000-2000.
8. The preparation method according to any one of claims 1 to 4, characterized in that the small molecule polyol chain extender is used in an amount of 1 to 6 wt% based on the total mass of the prepolymer for preparing the aqueous polyurethane-acrylate hybrid resin; the dosage of the carboxylic acid type hydrophilic chain extender is 2-10 wt%.
9. The preparation method of claim 8, wherein the small molecule polyol chain extender is used in an amount of 2 to 4 wt% based on the total mass of the prepolymer for preparing the aqueous polyurethane-acrylate hybrid resin; the dosage of the carboxylic acid type hydrophilic chain extender is 4-8 wt%.
10. The preparation method of claim 8, wherein the small molecule polyol chain extender is a polyol chain extender containing active hydrogen, and the molecular weight of the polyol chain extender is 30-200 g/mol;
the carboxylic acid type hydrophilic chain extender is a carboxylic acid type hydrophilic chain extender containing active hydrogen.
11. The preparation method of claim 10, wherein the small-molecule polyol chain extender is a polyol chain extender containing active hydrogen and more than two reactive groups capable of reacting with isocyanate,
the carboxylic acid type hydrophilic chain extender is a micromolecular diol compound with a carboxylate radical.
12. The preparation method according to claim 11, wherein the small-molecule polyol chain extender is one or both of trimethylolpropane and 1, 4-butanediol,
the carboxylic acid type hydrophilic chain extender is one or more of dimethylolpropionic acid, dimethylolbutyric acid, tartaric acid and N, N-dimethylolmaleamic acid.
13. The method of any of claims 1-4, wherein the reactive diluent monomer is used in an amount of 0.6 to 1.5 times the amount of the isocyanate-terminated prepolymer.
14. The method of claim 13, wherein the reactive diluent monomer is used in an amount of 0.8 to 1.2 times the amount of the isocyanate-terminated prepolymer.
15. The method of claim 13, wherein the solvent used in the reactive diluent monomer is an organic solvent having a boiling point of less than 100 ℃ and is used in an amount of 0.6 to 1.2 times the amount of the isocyanate terminated prepolymer.
16. The method according to claim 15, wherein the solvent used in the reactive diluent monomer is acetone or methyl ethyl ketone.
17. The production method according to any one of claims 1 to 4,
the styrene-based monomer is selected from styrene or methyl styrene.
18. The method according to any one of claims 1 to 4, wherein the acrylic monomer is used in an amount of 0.5 to 0.7 times the mass of the reactive diluent monomer,
the dosage of the styrene-based monomer is 0.2 to 0.3 time of the mass of the reactive diluent monomer;
the dosage of the fluorine-containing reactive functional monomer is 0.05-0.1 time of the mass of the reactive diluent monomer.
19. The process according to any one of claims 1 to 4, wherein the initiator is used in an amount of 0.05 to 0.3% by mass based on the mass of the reactive diluent monomer;
the initiator comprises an oxidizing agent and a reducing agent;
the oxidant comprises one or more of ammonium persulfate, sodium persulfate, potassium persulfate and tert-butyl hydroperoxide,
the reducing agent comprises one or more of sodium hydrosulfite, sodium formaldehyde sulfoxylate, sodium hydrogen sulfite and isoascorbic acid.
20. A method as claimed in claim 19, wherein said initiator is used in an amount of 0.1 to 0.2% by mass of the reactive diluent monomer.
21. The preparation method according to any one of claims 1 to 4, wherein the isocyanate terminated prepolymer is prepared by mixing and reacting the following components in percentage by mass based on the total mass of the isocyanate terminated prepolymer for preparing the aqueous polyurethane-acrylate hybrid resin: 15-40 wt% of diisocyanate, 1-6 wt% of micromolecular polyol chain extender, 2-10 wt% of carboxylic acid type hydrophilic chain extender and 45-70 wt% of macromolecular polyol, wherein the molar ratio of the macromolecular polyol to the diisocyanate is 1:3-1: 6.
22. The production method according to any one of claims 1 to 4, characterized in that the reaction temperature employed in producing the isocyanate terminated prepolymer is 75 to 85 ℃.
23. The method according to claim 22, wherein the mixing and dissolving of the reactive diluent monomer and the isocyanate-terminated prepolymer are carried out at 50 to 60 ℃.
24. The method as claimed in claim 22, wherein the initiation temperature of the hybrid emulsion initiated polymerization is 30-35 ℃.
25. The production method according to any one of claims 1 to 4, further comprising, after the initiation of polymerization, the steps of: the solvent is removed from the product obtained by initiating the polymerization.
26. An aqueous polyurethane-acrylate hybrid resin obtained by the preparation method according to any one of claims 1 to 25.
27. Use of the aqueous polyurethane-acrylic hybrid resin of claim 26 for preparing a leather finish.
28. A leather finish characterized by comprising the aqueous polyurethane-acrylic hybrid resin of claim 26.
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