CN114045107A - Environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion and preparation method and application thereof - Google Patents
Environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion and preparation method and application thereof Download PDFInfo
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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract
The invention provides an environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion, and a preparation method and application thereof. The environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion comprises functional layered silicate, wherein the functional layered silicate is modified by anionic surfactant, cationic surfactant and hydroxyl-rich water-soluble polymer composite intercalation. The preparation method comprises the following steps: (1) mixing materials: uniformly mixing the functional montmorillonite-modified polyurethane acrylate oligomer, the acrylate monomer and water, heating, stirring by a stirrer, and naturally cooling to room temperature to obtain a component A; (2) uniformly stirring the photoinitiator, the flatting agent and water at normal temperature to obtain a component B; (3) and (3) mixing the component A and the component B, stirring uniformly at normal temperature, standing for defoaming, and storing in a dark place to obtain the environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion. The invention can be used for adhesives or coatings.
Description
Technical Field
The invention relates to the field of composite materials, in particular to an environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion, and a preparation method and application thereof.
Background
At present, the waterborne polyurethane acrylate resin is a novel safe and environment-friendly green resin which is developed rapidly in recent years, and with the enhancement of environmental awareness and the tightening of environmental policies of people, the waterborne polyurethane acrylate resin which is an environment-friendly material with low VOC has a wide development prospect, and is widely applied to the fields of coatings, adhesives, printing ink, wind power and the like. However, the water resistance, mechanical strength, heat resistance and barrier property of the aqueous urethane acrylate resin are poor, so that a layered inorganic silicate filler such as montmorillonite is often used for reinforcing modification, but it is the direction of research in the art how to achieve high degree of extension of interlayer spacing of the layered inorganic silicate to improve dispersion in a matrix, and how to achieve compatibility or grafting reaction between the urethane acrylate and the layered inorganic silicate to fully exert the modification effect.
Disclosure of Invention
The invention aims to provide an environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion and a preparation method thereof, which increase the interlayer spacing and the dispersity of phyllosilicates such as montmorillonite and the like, improve the compatibility between phyllosilicates and polyurethane acrylate, and generate a grafting reaction, thereby realizing that the modified polyurethane acrylate composite material has excellent water resistance, mechanical strength, heat resistance, gas barrier property and other properties.
In order to achieve the aim, the invention provides an environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion, which comprises functional layered silicate, wherein the functional layered silicate is a layered silicate modified by composite intercalation of an anionic surfactant, a cationic surfactant and a water-soluble polymer rich in hydroxyl.
Further, the phyllosilicate is one or a combination of bentonite, talcum powder and montmorillonite; montmorillonite is preferred.
Further, the water-soluble polymer rich in hydroxyl groups is polyvinyl alcohol.
Further, comprising components a and B; the component A comprises the following components in parts by weight:
the component B comprises:
3-5 parts of photoinitiator
0.2 to 0.5 portion of flatting agent
5-10 parts of water.
Further, the preparation method of the functional montmorillonite modified polyurethane acrylate oligomer comprises the following steps: (1) weighing 10-20 parts of sodium montmorillonite by mass, dispersing in 50 parts of water, adding 2-4 parts of dodecyl trimethyl ammonium chloride, stirring and heating in a stirrer for 1-2 hours at the rotation speed of 500-; (2) dispersing the primary intercalated montmorillonite in 50 parts of water, adding 6-8 parts of methacryloyloxyethyl trimethyl ammonium chloride according to parts by weight, stirring and heating in a stirrer for 1-2 hours at the rotation speed of 500-; (3) dispersing the secondary intercalation montmorillonite in 50 parts of aqueous solution of 6 wt% polyvinyl alcohol, stirring and heating in a stirrer for 2-3h at the rotation speed of 100-; (4) adding 10 parts of the exfoliated functional montmorillonite into 20 parts of first batch of diisocyanate, heating to 50-90 ℃, adding diol with the molar ratio of 1:1 to the first batch of diisocyanate and 0.1-0.6 part of catalyst after 1-2h, then continuously adding 20 parts of second batch of diisocyanate, and finally blocking with hydroxyl acrylate, wherein the molar ratio of the hydroxyl acrylate to the total amount of the diisocyanate is 0.5-0.55: 1; and heating the reaction system to 80-100 ℃, reacting for 5-7h, washing and drying to obtain the functional montmorillonite-modified polyurethane acrylate oligomer.
Further, the diisocyanate is one or a combination of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate; the dihydric alcohol is one or a combination of butanediol, neopentyl glycol, hexanediol, 3-methyl-1, 5-pentanediol and polycaprolactone diol; the catalyst is one of stannous octoate, dibutyltin dilaurate and triethanolamine.
Further, the acrylate monomer is one or a combination of amino acrylate, organic silicon acrylate, 2-hydroxy acrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate and sulfobetaine methacrylate; the photoinitiator is one or a combination of 1-hydroxy-cyclohexyl benzophenone, 2, 4, 6-trimethyl benzoyl-diphenyl phosphine oxide, benzophenone and 2, 2-diethoxy phenyl ethyl ketone.
Further, the leveling agent is any one of BYK373, BYK325 or BYK 331.
The invention also provides a preparation method of the environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion, which comprises the following steps: (1) mixing materials: uniformly mixing the functional montmorillonite modified polyurethane acrylate oligomer, the acrylate monomer and water, heating to 60-65 ℃, stirring for 30min at 800r/min by a stirrer, and naturally cooling to room temperature to obtain a component A; (2) uniformly stirring the photoinitiator, the flatting agent and water at normal temperature to obtain a component B; (3) and (3) mixing the component A and the component B, stirring uniformly at normal temperature, standing for defoaming, and storing in a dark place to obtain the environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion.
The invention also provides application of the environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion, which can be used for adhesives or coatings.
The invention has the following beneficial effects:
1. according to the method, firstly, dodecyl trimethyl ammonium chloride is used for intercalating montmorillonite, the interlayer spacing is preliminarily enlarged, then methacryloyloxyethyl trimethyl ammonium chloride is further intercalated, the interlayer spacing is continuously enlarged, the polarity degree of an interlayer microenvironment is further adjusted, and finally polyvinyl alcohol is intercalated to endow the montmorillonite with a reactive group-hydroxyl. And then taking the modified montmorillonite as a template for in-situ polymerization, adding diisocyanate, carrying out grafting reaction on a group-NCO of the diisocyanate and hydroxyl on the surface of the organically modified montmorillonite, sequentially adding dihydric alcohol and diisocyanate for chain extension, and finally, terminating the hydroxyl acrylate to prepare the polyurethane acrylate with sufficient compatibility and graft modification of the montmorillonite.
2. The invention creatively combines different properties of three intercalation agents, firstly utilizes the easy intercalation property of dodecyl trimethyl ammonium chloride to generate cation exchange effect with montmorillonite, increases the interlayer spacing of the montmorillonite, changes the non-polarity of the interlayer, makes the polarity of the interlayer close to that of the subsequent intercalation agent, is beneficial to further performing cation exchange on the subsequent intercalation agent of methacryloyloxyethyl trimethyl ammonium chloride to change the microenvironment between layers of the organic modified montmorillonite, makes the intercalation agent have high-activity methacrylic acid groups, has the non-polarity weaker than long-chain alkyl, can further expand the interlayer spacing of the montmorillonite, and then provides proper conditions for the intercalation of polyvinyl alcohol.
3. The modified montmorillonite is used as an in-situ polymerization template to obtain the layered montmorillonite graft modified polyurethane acrylate oligomer, and the layered montmorillonite graft modified polyurethane acrylate oligomer participates in subsequent polymerization reaction, fully exerts the 'sea island' effect of the layered montmorillonite in matrix resin, not only improves the mechanical strength, but also fully exerts the oxygen and moisture barrier effect of the layered montmorillonite, and further improves the water resistance, the gas barrier property and the heat resistance of polyurethane acrylate.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to make the aforementioned objects, features and advantages of the invention more comprehensible.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
The environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion comprises functional layered silicate, wherein the functional layered silicate is modified by anionic surfactant, cationic surfactant and hydroxyl-rich water-soluble polymer composite intercalation. Wherein the phyllosilicate can be one or a combination of bentonite, talcum powder and montmorillonite; montmorillonite is preferred. The hydroxyl-rich water-soluble polymer may be polyvinyl alcohol.
The environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion comprises components A and B; the component A comprises the following components in parts by weight:
the component B comprises:
3-5 parts of photoinitiator
0.2 to 0.5 portion of flatting agent
5-10 parts of water.
The preparation method of the functional montmorillonite modified polyurethane acrylate oligomer comprises the following steps: (1) weighing 10-20 parts of sodium montmorillonite by mass, dispersing in 50 parts of water, adding 2-4 parts of dodecyl trimethyl ammonium chloride, stirring and heating in a stirrer for 1-2 hours at the rotation speed of 500-; (2) dispersing the primary intercalated montmorillonite in 50 parts of water, adding 6-8 parts of methacryloyloxyethyl trimethyl ammonium chloride according to parts by weight, stirring and heating in a stirrer for 1-2 hours at the rotation speed of 500-; (3) dispersing the secondary intercalation montmorillonite in 50 parts of aqueous solution of 6 wt% polyvinyl alcohol, stirring and heating in a stirrer for 2-3h at the rotation speed of 100-; (4) adding 10 parts of the exfoliated functional montmorillonite into 20 parts of first batch of diisocyanate, heating to 50-90 ℃, adding diol with the molar ratio of 1:1 to the first batch of diisocyanate and 0.1-0.6 part of catalyst after 1-2h, then continuously adding 20 parts of second batch of diisocyanate, and finally blocking with hydroxyl acrylate, wherein the molar ratio of the hydroxyl acrylate to the total amount of the diisocyanate is 0.5-0.55: 1; and heating the reaction system to 80-100 ℃, reacting for 5-7h, washing and drying to obtain the functional montmorillonite-modified polyurethane acrylate oligomer.
Wherein the diisocyanate is one or a combination of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate; the dihydric alcohol is one or a combination of butanediol, neopentyl glycol, hexanediol, 3-methyl-1, 5-pentanediol and polycaprolactone diol; the catalyst is one of stannous octoate, dibutyltin dilaurate and triethanolamine. The acrylate monomer is one or a combination of amino acrylate, organic silicon acrylate, 2-hydroxy acrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate and sulfobetaine methacrylate; the photoinitiator is one or a combination of 1-hydroxy-cyclohexyl benzophenone, 2, 4, 6-trimethyl benzoyl-diphenyl phosphine oxide, benzophenone and 2, 2-diethoxy phenyl ethyl ketone. The leveling agent is any one of BYK373, BYK325 or BYK 331.
The preparation method of the environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion comprises the following steps of: (1) mixing materials: uniformly mixing the functional montmorillonite modified polyurethane acrylate oligomer, the acrylate monomer and water, heating to 60-65 ℃, stirring for 30min at 800r/min by a stirrer, and naturally cooling to room temperature to obtain a component A; (2) uniformly stirring the photoinitiator, the flatting agent and water at normal temperature to obtain a component B; (3) and (3) mixing the component A and the component B, stirring uniformly at normal temperature, standing for defoaming, and storing in a dark place to obtain the environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion.
The environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion can be used for adhesives or coatings.
The environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion of the present invention, and the preparation method and use thereof are specifically described below with reference to specific examples.
Example 1
Preparing functional montmorillonite modified polyurethane acrylate oligomer:
(1) weighing 10 parts of sodium-based montmorillonite according to parts by mass, dispersing in 50 parts of water, adding 2 parts of dodecyl trimethyl ammonium chloride, stirring and heating for 1 hour in a stirrer at the rotation speed of 500 revolutions per minute and the temperature of 70 ℃, performing suction filtration, washing with deionized water, and drying to obtain primary intercalated montmorillonite;
(2) dispersing the primary intercalated montmorillonite in 50 parts of water, adding 6 parts of methacryloyloxyethyl trimethyl ammonium chloride according to parts by weight, stirring and heating for 1 hour in a stirrer at the rotation speed of 500 revolutions per minute and the temperature of 60 ℃, carrying out suction filtration, washing with deionized water, and drying to obtain secondary intercalated montmorillonite;
(3) dispersing the secondary intercalation montmorillonite in 50 parts of aqueous solution of polyvinyl alcohol with the concentration of 6 wt%, stirring and heating for 2 hours in a stirrer at the rotation speed of 100 r/min and the temperature of 50 ℃, carrying out suction filtration, washing with deionized water, and drying to obtain layered stripped functional montmorillonite;
(4) adding 10 parts of the exfoliated functional montmorillonite into 20 parts of first diphenylmethane diisocyanate, heating to 50 ℃, adding 3-methyl-1, 5-pentanediol with a molar ratio of 1:1 to the first diphenylmethane diisocyanate and 0.1 part of dibutyltin dilaurate after 1 hour, continuing to add 20 parts of second diphenylmethane diisocyanate, and finally blocking with hydroxy acrylate, wherein the molar ratio of the hydroxy acrylate to the total amount of the diphenylmethane diisocyanate is 0.5: 1; and (3) heating the reaction system to 80 ℃, reacting for 5h, washing and drying to obtain the functional montmorillonite-modified polyurethane acrylate oligomer.
(II) preparing environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion:
(1) weighing materials, wherein the component A comprises the following components in parts by weight:
the component B comprises:
3 parts of 2, 2-diethoxyphenylethanone
BYK 3310.2 parts
5 parts of water;
(2) mixing materials: uniformly mixing the functional montmorillonite-modified polyurethane acrylate oligomer, the acrylate monomer and water, heating to 60 ℃, stirring for 30min at 500 revolutions per minute by a stirrer, and naturally cooling to room temperature to obtain a component A;
(3) uniformly stirring 2, 2-diethoxyphenylethanone, BYK331 and water at normal temperature to obtain a component B;
(4) and (3) mixing the component A and the component B, stirring uniformly at normal temperature, standing for defoaming, and storing in a dark place to obtain the environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion.
Example 2
Preparing functional montmorillonite modified polyurethane acrylate oligomer:
(1) weighing 20 parts of sodium-based montmorillonite according to parts by mass, dispersing in 50 parts of water, adding 4 parts of dodecyl trimethyl ammonium chloride, stirring and heating in a stirrer for 2 hours at the rotating speed of 800 revolutions per minute and the temperature of 80 ℃, filtering, washing with deionized water, and drying to obtain primary intercalated montmorillonite;
(2) dispersing the primary intercalated montmorillonite in 50 parts of water, adding 8 parts of methacryloyloxyethyl trimethyl ammonium chloride according to parts by weight, stirring and heating for 2 hours in a stirrer at the rotating speed of 800 revolutions per minute and the temperature of 70 ℃, filtering, washing with deionized water, and drying to obtain secondary intercalated montmorillonite;
(3) dispersing the secondary intercalation montmorillonite in 50 parts of aqueous solution of polyvinyl alcohol with the concentration of 6 wt%, stirring and heating in a stirrer for 3 hours at the rotation speed of 200 r/min and the temperature of 60 ℃, carrying out suction filtration, washing with deionized water, and drying to obtain layered stripped functional montmorillonite;
(4) adding 10 parts of the layered exfoliated functional montmorillonite into 20 parts of first toluene diisocyanate, heating to 90 ℃, adding butanediol with the molar ratio of 1:1 to the first toluene diisocyanate and 0.6 part of stannous octoate after 2 hours, then continuously adding 20 parts of second toluene diisocyanate, and finally blocking with hydroxyl acrylate, wherein the molar ratio of the hydroxyl acrylate to the total amount of the toluene diisocyanate is 0.55: 1; and (3) heating the reaction system to 100 ℃, reacting for 7h, washing and drying to obtain the functional montmorillonite-modified polyurethane acrylate oligomer.
(II) preparing environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion:
(1) weighing materials, wherein the component A comprises the following components in parts by weight:
the component B comprises:
5 parts of 1-hydroxy-cyclohexyl benzophenone
BYK 3730.5 parts
10 parts of water;
(2) mixing materials: uniformly mixing the functional montmorillonite modified polyurethane acrylate oligomer, the 2-hydroxy acrylate and water, heating to 65 ℃, stirring for 30min at 800r/min by a stirrer, and naturally cooling to room temperature to obtain a component A;
(3) uniformly stirring 1-hydroxy-cyclohexyl benzophenone, BYK373 and water at normal temperature to obtain a component B;
(4) and (3) mixing the component A and the component B, stirring uniformly at normal temperature, standing for defoaming, and storing in a dark place to obtain the environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion.
Example 3
Preparing functional montmorillonite modified polyurethane acrylate oligomer:
(1) weighing 15 parts of sodium-based montmorillonite according to parts by mass, dispersing in 50 parts of water, adding 3 parts of dodecyl trimethyl ammonium chloride, stirring and heating for 1.5 hours in a stirrer at the rotating speed of 650 revolutions per minute and the temperature of 75 ℃, performing suction filtration, washing with deionized water, and drying to obtain primary intercalation montmorillonite;
(2) dispersing the primary intercalated montmorillonite in 50 parts of water, adding 7 parts of methacryloyloxyethyl trimethyl ammonium chloride according to parts by weight, stirring and heating for 1.5 hours in a stirrer at the rotating speed of 600 revolutions per minute and the temperature of 65 ℃, carrying out suction filtration, washing with deionized water, and drying to obtain secondary intercalated montmorillonite;
(3) dispersing the secondary intercalation montmorillonite in 50 parts of aqueous solution of polyvinyl alcohol with the concentration of 6 wt%, stirring and heating in a stirrer for 2.5h at the rotation speed of 150 r/min and the temperature of 55 ℃, carrying out suction filtration, washing with deionized water, and drying to obtain layered stripped functional montmorillonite;
(4) adding 10 parts of the delaminated functional montmorillonite into 20 parts of first isophorone diisocyanate, heating to 70 ℃, adding polycaprolactone diol with a molar ratio of 1:1 to the first isophorone diisocyanate and 0.3 part of triethanolamine after 1.5h, then continuously adding 20 parts of second isophorone diisocyanate, and finally blocking with hydroxy acrylate, wherein the molar ratio of the hydroxy acrylate to the total amount of isophorone diisocyanate is 0.5: 1; and (3) heating the reaction system to 90 ℃, reacting for 6h, washing and drying to obtain the functional montmorillonite-modified polyurethane acrylate oligomer.
(II) preparing environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion:
(1) weighing materials, wherein the component A comprises the following components in parts by weight:
the component B comprises:
4 portions of benzophenone
BYK 3250.3 parts
6 parts of water;
(2) mixing materials: uniformly mixing the functional montmorillonite modified polyurethane acrylate oligomer, the polyurethane acrylate oligomer, trimethylolpropane triacrylate and water, heating to 62 ℃, stirring for 30min at 650r/min by a stirrer, and naturally cooling to room temperature to obtain a component A;
(3) uniformly stirring benzophenone, BYK325 and water at normal temperature to obtain a component B;
(4) and (3) mixing the component A and the component B, stirring uniformly at normal temperature, standing for defoaming, and storing in a dark place to obtain the environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion.
Comparative example 1
The procedure is as in example 3 except that cetyltrimethylammonium bromide is used in place of methacryloyloxyethyltrimethylammonium chloride.
Comparative example 2
The procedure of example 3 was repeated except that polyvinyl alcohol was not used in the production of the functional montmorillonite.
Comparative example 3
The procedure for preparing functional montmorillonite was the same as in example 3 except that methacryloyloxyethyl trimethyl ammonium chloride and polyvinyl alcohol were not used.
Performance testing
1. Coating material
(1) Sample (I)
The components A and B of each example and comparative example are uniformly mixed according to the parts by weight, vacuumed, defoamed, coated on a glass sheet subjected to electrostatic dust removal, and cured by ultraviolet irradiation at 45 ℃ to obtain a film sample with the film thickness of 0.3 mm.
(2) Testing
Adhesion force: one hundred lattice method (3M600,3 times);
pencil hardness: mitsubishi pencil (1KG force);
boiling resistance: soaking the sample at 100 deg.c for 1 hr;
wear resistance: testing according to a standard rotating rubber grinding wheel method for measuring the wear resistance of colored paint and varnish (GB/T1768-2006);
gas barrier properties: the equipment is a differential pressure gas permeameter, and the gas pressure in a high-pressure chamber is 1.0 × 105Pa; the equipment is a differential pressure gas permeation instrument.
2. Film(s)
Uniformly mixing the components A and B in the examples and the comparative examples according to the mass parts, removing bubbles in vacuum, pouring the mixture into a mold coated with a release agent, irradiating and curing the mixture by ultraviolet light at 60 ℃ to obtain a film with the thickness of 1mm, and cutting the film into dumbbell-shaped sample strips; the tensile strength of the film was measured at a tensile speed of 1 m/min.
Performance comparison table
The embodiments show that the environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion prepared by the invention is used for adhesives or coatings, is relatively unmodified, has higher adhesive force, hardness, water boiling resistance and wear resistance, has good gas barrier property, and can reduce the contact between air and metal base materials, thereby improving the corrosion resistance; can also be used for preparing composite materials, has good mechanical properties and completely meets the industrial application requirements.
Although some specific embodiments of the present invention have been described in detail by way of illustration, it should be understood by those skilled in the art that the above illustration is only for the purpose of illustration and is not intended to limit the scope of the invention. It will be appreciated by those skilled in the art that modifications may be made to the above embodiments without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. The environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion is characterized by comprising functional layered silicate, wherein the functional layered silicate is modified by the composite intercalation of an anionic surfactant, a cationic surfactant and a water-soluble polymer rich in hydroxyl.
2. The environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion according to claim 1, wherein the phyllosilicate is one or a combination of bentonite, talcum powder and montmorillonite; montmorillonite is preferred.
3. The environmentally friendly high solid content aqueous urethane acrylate composite emulsion of claim 1, wherein the water-soluble polymer rich in hydroxyl groups is polyvinyl alcohol.
4. The environmentally friendly high solid content aqueous urethane acrylate composite emulsion according to claim 2 or 3, comprising components A and B; the component A comprises the following components in parts by weight:
the component B comprises:
3-5 parts of photoinitiator
0.2 to 0.5 portion of flatting agent
5-10 parts of water.
5. The environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion according to claim 4, wherein the preparation method of the functional montmorillonite-modified polyurethane acrylate oligomer comprises the following steps:
(1) weighing 10-20 parts of sodium montmorillonite by mass, dispersing in 50 parts of water, adding 2-4 parts of dodecyl trimethyl ammonium chloride, stirring and heating in a stirrer for 1-2 hours at the rotation speed of 500-;
(2) dispersing the primary intercalated montmorillonite in 50 parts of water, adding 6-8 parts of methacryloyloxyethyl trimethyl ammonium chloride according to parts by weight, stirring and heating in a stirrer for 1-2 hours at the rotation speed of 500-;
(3) dispersing the secondary intercalation montmorillonite in 50 parts of aqueous solution of 6 wt% polyvinyl alcohol, stirring and heating in a stirrer for 2-3h at the rotation speed of 100-;
(4) adding 10 parts of the exfoliated functional montmorillonite into 20 parts of first batch of diisocyanate, heating to 50-90 ℃, adding diol with the molar ratio of 1:1 to the first batch of diisocyanate and 0.1-0.6 part of catalyst after 1-2h, then continuously adding 20 parts of second batch of diisocyanate, and finally blocking with hydroxyl acrylate, wherein the molar ratio of the hydroxyl acrylate to the total amount of the diisocyanate is 0.5-0.55: 1; and heating the reaction system to 80-100 ℃, reacting for 5-7h, washing and drying to obtain the functional montmorillonite-modified polyurethane acrylate oligomer.
6. The environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion according to claim 5, wherein the diisocyanate is one or a combination of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate; the dihydric alcohol is one or a combination of butanediol, neopentyl glycol, hexanediol, 3-methyl-1, 5-pentanediol and polycaprolactone diol; the catalyst is one of stannous octoate, dibutyltin dilaurate and triethanolamine.
7. The environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion according to claim 4, wherein the acrylate monomer is one or a combination of amino acrylate, silicone acrylate, 2-hydroxy acrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate and sulfobetaine methacrylate; the photoinitiator is one or a combination of 1-hydroxy-cyclohexyl benzophenone, 2, 4, 6-trimethyl benzoyl-diphenyl phosphine oxide, benzophenone and 2, 2-diethoxy phenyl ethyl ketone.
8. The environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion as claimed in claim 4, wherein the leveling agent is any one of BYK373, BYK325 or BYK 331.
9. The method for preparing the environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion according to any one of claims 4 to 8, comprising the following steps:
(1) mixing materials: uniformly mixing the functional montmorillonite modified polyurethane acrylate oligomer, the acrylate monomer and water, heating to 60-65 ℃, stirring for 30min at 800r/min by a stirrer, and naturally cooling to room temperature to obtain a component A;
(2) uniformly stirring the photoinitiator, the flatting agent and water at normal temperature to obtain a component B;
(3) and (3) mixing the component A and the component B, stirring uniformly at normal temperature, standing for defoaming, and storing in a dark place to obtain the environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion.
10. Use of the environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion according to any one of claims 1 to 8, wherein the environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion can be used for adhesives or coatings.
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