CN112662256A - Nano-modified water-based acrylic resin and preparation method thereof - Google Patents
Nano-modified water-based acrylic resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nano modified water-based acrylic resin and a preparation method thereof, wherein the water-based acrylic resin comprises the following components in percentage by mass: 60-80% of polymer solution; 2-8% of nano dispersion liquid; 20-30% of deionized water; the sum of the mass percentages of the components is 100 percent. The invention adopts a nano material modification method to prepare the water-based acrylic resin, and the components do not contain an emulsifier and introduce high-content hydrophilic groups. The reverse phase initial stage is a water-in-oil state, and the nano material has a hydrophilic-lipophilic effect and can rapidly enter the surface of oil-water so as to coat the water into small droplets. With the addition of water, the water droplets increase until a continuous water phase is formed, and the nano material coats the resin into oil droplets to form a stable emulsion in an oil-in-water state. In addition, the used nano dispersion liquid can be self-cured to form insoluble substances with excellent water resistance, and the insoluble substances are uniformly distributed in a paint film after the paint film is dried, so that the water resistance, the chemical medium resistance and the salt spray resistance of the paint film can be improved.
Description
Technical Field
The invention belongs to the field of water-based paint, and particularly relates to nano modified water-based acrylic resin and a preparation method thereof.
Background
There are generally two synthetic methods for aqueous acrylic resins, namely emulsion and dispersion methods. The emulsion method adopts an emulsifier with a surface active structure as a stabilizer, and the emulsifier coats the resin to ensure that the resin is dispersed in water in a granular form. The content of the emulsifier adopted in the acrylic ester emulsion polymerization is generally 1-5% of the total amount of the monomers, and when a paint film is prepared, the emulsifier is remained in the paint film to cause the reduction of water resistance and chemical medium resistance; the dispersion method is that free radical polymerization of vinyl and acrylate monomers is firstly carried out in a solvent, higher content of hydrophilic groups such as carboxyl, sulfonic group, amide group and the like are needed in the formula, the content is generally 5% -10% of the total amount of the monomers, then amine substances are added for neutralization to form an anion structure, and finally water is added for dispersion to form the water dispersible resin. The water-based acrylic resin prepared by the dispersion method has high hydrophilic group content, so that a paint film prepared from the self-drying paint has poor water resistance and salt fog resistance.
Disclosure of Invention
The invention aims to solve the problems and provide a nano modified water-based acrylic resin and a preparation method thereof, wherein an emulsifier is not used, a high-content hydrophilic group is not introduced, the nano modified water-based acrylic resin is uniformly distributed on the interface of water-polymer colloidal particles by utilizing the special water-oil balance effect of a nano material, so that a polymer is uniformly and stably dispersed in water, a used nano dispersion liquid is a self-curable material, a paint film is dried and cured to form a water-insoluble deposit, and the water resistance, the chemical medium resistance and the salt fog resistance of the paint film can be improved by uniformly distributing the water-insoluble deposit in the paint film.
The purpose of the invention is realized as follows:
the nano modified water-based acrylic resin comprises the following components in percentage by mass:
60-80% of polymer solution;
2-8% of nano dispersion liquid;
20-30% of deionized water;
the sum of the mass percentages of the components is 100 percent;
wherein the content of the first and second substances,
the polymer solution is prepared from the following components in percentage by mass through a free radical polymerization mode:
40-60% of solvent, 10-20% of vinyl monomer, 20-35% of acrylate monomer, 0.5-1.1% of functional monomer and 1.2-2.2% of initiator, wherein the sum of the mass percentages of the components is 100%;
the solvent is at least one of ethanol, isopropanol, butanol, isobutanol and acetone;
the functional monomer is at least one selected from acrylic acid, methacrylic acid, diacetone acrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and acryloyl morpholine;
the initiator is selected from at least one of benzoyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile;
the nano dispersion liquid comprises the following components in parts by weight:
the main element precursor is selected from at least one of sodium chloride, calcium chloride, magnesium chloride, titanium tetrachloride, aluminum trichloride, ferrous chloride, copper chloride, beryllium chloride, strontium chloride, barium chloride, boron chloride, germanium chloride, tin chloride, lead chloride, arsenic chloride, strontium chloride, nickel chloride, vanadium chloride and gallium chloride;
the doping element precursor is selected from at least one of sodium dihydrogen phosphate, tripotassium phosphate, potassium nitrate, sodium sulfate and potassium sulfate;
the lipophilic donor is at least one selected from n-hexyltrichlorosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrichlorosilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, dodecyltrichlorosilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, dodecylcarboxylic acid, hexadecylcarboxylic acid, and dodecylsulfonic acid.
The pH value of the nano dispersion liquid in the nano modified water-based acrylic resin is 2-5, and/or the solid content is 15% -25%, and/or the viscosity value is controlled to be 10-25s when the nano modified water-based acrylic resin is coated in a 4-cup mode at 25 ℃.
The particle size of the nano material in the nano dispersion liquid in the nano modified water-based acrylic resin is 15nm-200 nm.
The preparation method of the nano dispersion liquid in the nano modified water-based acrylic resin comprises the following steps:
(1) hydrolysis:
sequentially adding 20-30 parts of deionized water, an alkali neutralizing agent and 4-7 parts of lower alcohol into a reaction kettle, and starting stirring; adding the rest deionized water and the rest lower alcohol into a head tank, stirring at the speed of 300-; dropwise adding the solution in the elevated tank into the reaction kettle at a constant speed for 2-5h, continuously reacting for 1-5h after dropwise adding, heating to 80-120 ℃, reacting for 2-8h, and cooling to room temperature;
(2) centrifugal separation:
introducing the liquid in the reactor into a centrifuge for centrifugal separation at the speed of 3000-5000r/min for 30-60 min;
(3) and (3) suction filtration:
and (3) carrying out suction filtration on the liquid after centrifugal separation under the vacuum pressure of-0.4 Mpa to-0.9 Mpa, and filtering out solid matters to obtain clear liquid, namely the nano dispersion liquid for emulsion polymerization.
The vinyl monomer in the nano modified water-based acrylic resin is selected from at least one of styrene, methyl styrene, vinyl chloride, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, vinyl trimethoxy silane and vinyl triethoxy silane.
The acrylate monomer in the nano-modified water-based acrylic resin is at least one selected from methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate, isobornyl (meth) acrylate, and glycidyl (meth) acrylate.
The alkali neutralizing agent in the nano modified water-based acrylic resin is at least one selected from potassium hydroxide, lithium hydroxide, ammonia water, monoethanolamine, diethanolamine, triethanolamine, N-dimethylethanolamine and triethylamine.
The lower alcohol in the nano modified water-based acrylic resin is at least one selected from methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol and pentanol
The invention also provides a preparation method of the nano modified water-based acrylic resin, which comprises the following steps:
(1) adding a vinyl monomer, an acrylate monomer and a functional monomer into a solvent, and carrying out free radical polymerization reaction at the temperature of 70-80 ℃ to obtain a polymer solution;
(2) transferring the polymer solution prepared in the step (1) to a dispersion kettle, then dropwise adding the nano dispersion liquid under high-speed dispersion for 30-60min, and then dropwise adding deionized water for 60-90min until a water continuous phase is formed;
(3) distilling under reduced pressure at the vacuum degree of-0.4 Mpa to-0.9 Mpa and the temperature of 60 ℃ to 80 ℃, removing the solvent, and obtaining the nano modified waterborne acrylic resin
The free radical polymerization reaction process in the step (1) comprises the following steps: adding a solvent into a reaction kettle, heating to 70-80 ℃, preparing a vinyl monomer, an acrylate monomer, a functional monomer and an initiator in an overhead tank, stirring to dissolve the initiator uniformly, dropwise adding a mixture of the vinyl monomer, the acrylate monomer, the functional monomer and the initiator into the reaction kettle at a constant speed for 3 hours, and preserving heat for 1 hour after dropwise adding is finished.
The invention adopts a method of modifying nano materials to prepare the water-based acrylic resin, the components do not contain emulsifier, and high-content hydrophilic groups are not introduced, the reverse phase initial stage is a water-in-oil state, and the nano materials have hydrophilic-lipophilic effect and can rapidly enter the surface of oil-water so as to coat the water into small droplets. With the addition of water, the water droplets increase until a continuous water phase is formed, and the nano material coats the resin into oil droplets to form a stable emulsion in an oil-in-water state. In addition, the used nano dispersion liquid can be self-cured to form insoluble substances with excellent water resistance, and the insoluble substances are uniformly distributed in a paint film after the paint film is dried, so that the water resistance, the chemical medium resistance and the salt spray resistance of the paint film can be improved.
Detailed Description
The present invention will be further described with reference to the following examples.
The invention discloses a nano modified water-based acrylic resin which comprises the following components in percentage by mass:
60-80% of polymer solution;
2-8% of nano dispersion liquid;
20-30% of deionized water;
the sum of the mass percentages of the components is 100 percent;
wherein the content of the first and second substances,
the polymer solution is prepared from the following components in percentage by mass through a free radical polymerization mode:
40-60% of solvent, 10-20% of vinyl monomer, 20-35% of acrylate monomer, 0.5-1.1% of functional monomer and 1.2-2.2% of initiator, wherein the sum of the mass percentages of the components is 100%;
wherein the content of the first and second substances,
the solvent is at least one of ethanol, isopropanol, butanol, isobutanol and acetone;
the vinyl monomer is selected from at least one of styrene, methyl styrene, vinyl chloride, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, vinyl trimethoxy silane and vinyl triethoxy silane;
the acrylate monomer is at least one selected from methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate, isobornyl (meth) acrylate and glycidyl (meth) acrylate;
the functional monomer is at least one selected from (methyl) acrylic acid, diacetone acrylamide, hydroxyethyl (methyl) acrylate, hydroxypropyl (methyl) acrylate and acryloyl morpholine;
the initiator is selected from at least one of benzoyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile;
the nano dispersion liquid comprises the following components in parts by weight:
the main element precursor is selected from at least one of sodium chloride, calcium chloride, magnesium chloride, titanium tetrachloride, aluminum trichloride, ferrous chloride, copper chloride, beryllium chloride, strontium chloride, barium chloride, boron chloride, germanium chloride, tin chloride, lead chloride, arsenic chloride, strontium chloride, nickel chloride, vanadium chloride and gallium chloride;
the doping element precursor is selected from at least one of sodium dihydrogen phosphate, tripotassium phosphate, potassium nitrate, sodium sulfate and potassium sulfate;
the lipophilic donor is at least one selected from n-hexyltrichlorosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrichlorosilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, dodecyltrichlorosilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, dodecylcarboxylic acid, hexadecylcarboxylic acid and dodecylsulfonic acid;
the alkali neutralizing agent is at least one selected from potassium hydroxide, lithium hydroxide, ammonia water, monoethanolamine, diethanolamine, triethanolamine, N-dimethylethanolamine and triethylamine.
The lower alcohol is selected from at least one of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, and pentanol.
The pH value of the nano dispersion liquid is 2-5, the solid content is 15% -25%, the viscosity value is controlled to be 10-25s when the nano dispersion liquid is coated in 4 cups at 25 ℃, and the particle size of the nano material is 15nm-200 nm;
the preparation method of the nano dispersion liquid comprises the following steps:
(1) hydrolysis:
sequentially adding 20-30 parts of deionized water, an alkali neutralizing agent and 4-7 parts of lower alcohol into a reaction kettle, and starting stirring; adding the rest deionized water and the rest lower alcohol into a head tank, stirring at the speed of 300-; dropwise adding the solution in the elevated tank into the reaction kettle at a constant speed for 2-5h, continuously reacting for 1-5h after dropwise adding, heating to 80-120 ℃, reacting for 2-8h, and cooling to room temperature;
(2) centrifugal separation:
introducing the liquid in the reactor into a centrifuge for centrifugal separation at the speed of 3000-5000r/min for 30-60 min;
(3) and (3) suction filtration:
and (3) carrying out suction filtration on the liquid after centrifugal separation under the vacuum pressure of-0.4 Mpa to-0.9 Mpa, and filtering out solid matters to obtain clear liquid, namely the nano dispersion liquid for emulsion polymerization.
The preparation method of the nano modified water-based acrylic resin comprises the following steps:
(1) adding a vinyl monomer, an acrylate monomer and a functional monomer into a solvent, and carrying out free radical polymerization reaction at the temperature of 70-80 ℃ to obtain a polymer solution;
(2) transferring the polymer solution prepared in the step (1) to a dispersion kettle, and then dropwise adding the nano dispersion liquid under high-speed dispersion for 30-60 min; then, dropwise adding deionized water for 60-90min until a water continuous phase is formed;
(3) distilling under reduced pressure at the vacuum degree of-0.4 Mpa to-0.9 Mpa and the temperature of 60 ℃ to 80 ℃, removing the solvent, and obtaining the nano modified waterborne acrylic resin
The free radical polymerization reaction process in the step (1) comprises the following steps: adding a solvent into a reaction kettle, heating to 70-80 ℃, preparing a vinyl monomer, an acrylate monomer, a functional monomer and an initiator in an overhead tank, stirring to dissolve the initiator uniformly, dropwise adding a mixture of the vinyl monomer, the acrylate monomer, the functional monomer and the initiator into the reaction kettle at a constant speed for 3 hours, and preserving heat for 1 hour after dropwise adding is finished.
Example 1:
free radical polymerization of the monomers in ethanol was carried out, the formulation being shown in table 1:
TABLE 1 Components and proportions of example 1
The polymerization process comprises the following steps: adding ethanol into a reaction kettle, and heating to 78 ℃. And (3) dropwise adding a mixture of a monomer and an initiator which are dissolved in advance for 3h, and preserving heat for 1h after the dropwise adding is finished to obtain a polymer solution.
Preparing raw materials according to the following mixture ratio:
polymer solution 65%
3 percent of nano dispersion liquid
32 percent of deionized water
And transferring the polymer solution into a dispersion kettle, dropwise adding the nano dispersion liquid for 30min, and then dropwise adding deionized water for 60min to enable the polymer solution to form an aqueous continuous phase. The nano dispersion liquid comprises the following components in parts by weight:
adding 26 parts of deionized water and 2 parts of ethanol into a head tank, then slowly adding 28 parts of titanium tetrachloride, 1.2 parts of sodium dihydrogen phosphate and 4.8 parts of dodecyl trimethoxy silane in sequence, and uniformly stirring for later use. 30 parts of deionized water, 5 parts of ethanol and 3 parts of ammonia water are added into a reaction kettle, and the mixture is stirred at the speed of 500 r/min. And (5) dropwise adding the solution in the head tank, finishing dropwise adding for 3 hours, and reacting for 2 hours after dropwise adding. Then the temperature is increased to 90 ℃, the reaction is carried out for 3 hours, and then the temperature is reduced to the room temperature.
Centrifuging the reaction solution for 45min at 4000r/min by using a centrifuge, then performing suction filtration under the vacuum pressure of-0.4 Mpa to-0.9 Mpa, and filtering out solids to obtain clear liquid, namely the nano dispersion liquid of the embodiment 1. The dispersion had a solids content of 20%, a pH of 3.2, an average particle size of 35nm and a viscosity of 12s at 25 ℃ over-4 cups.
Heating to 78 deg.C, controlling vacuum degree at-0.85 Mpa, and extracting ethanol under reduced pressure to obtain nanometer modified water-based acrylic resin.
Example 2:
free radical polymerization of the monomers in acetone was carried out, the formulation being shown in Table 2:
TABLE 2 Components and proportions of example 2
The polymerization process comprises the following steps: adding acetone into a reaction kettle, and heating to 65 ℃. And (3) dropwise adding a mixture of a monomer and an initiator which are dissolved in advance for 3h, and preserving heat for 1h after the dropwise adding is finished to obtain a polymer solution.
Preparing raw materials according to the following mixture ratio:
62 parts of a polymer solution;
5 parts of nano dispersion liquid;
33 parts of deionized water;
and transferring the polymer solution into a dispersion kettle, dropwise adding the nano dispersion liquid for 45min, and then dropwise adding deionized water for 60min to enable the polymer solution to form an aqueous continuous phase.
The nano dispersion liquid comprises the following components in parts by weight:
adding 25 parts of deionized water and 3 parts of isopropanol into a head tank, then slowly adding 22 parts of titanium tetrachloride, 10 parts of aluminum chloride, 2.5 parts of sodium dihydrogen phosphate and 7 parts of dodecyl trimethoxy silane in sequence, and uniformly stirring for later use. 20 parts of deionized water, 6 parts of isopropanol and 4.5 parts of N, N-dimethylethanolamine are added into a reaction kettle, and stirring is started. And dropwise adding the solution in the head tank, finishing dropwise adding for 2.5 hours, and reacting for 3 hours after dropwise adding. Then the temperature is increased to 80 ℃, the reaction is carried out for 4 hours, and then the temperature is reduced to the room temperature. The reaction solution was centrifuged by a centrifuge, and then filtered to remove the solid, to obtain a clear solution, i.e., the nanodispersion of example 2, having a solid content of 23%, a pH of 3, an average particle diameter of 60nm, and a viscosity of 13s in 4 cups at 25 ℃.
Heating to 64 ℃, controlling the vacuum degree to be-0.8 Mpa, and extracting acetone under reduced pressure to obtain the nano modified waterborne acrylic resin.
Example 3:
the monomer free radical polymerization is carried out in isopropanol, and the formula and the process are as follows:
table 3 composition and proportions of example 3
The polymerization process comprises the following steps: adding isopropanol into a reaction kettle, heating to 80 ℃, dropwise adding a mixture of a monomer and an initiator which are dissolved in advance for 3 hours, and preserving heat for 1 hour after dropwise adding is finished to obtain a polymer solution.
Preparing raw materials according to the following mixture ratio:
72 parts of a polymer solution obtained in the first step;
4.5 parts of nano dispersion liquid;
23.5 parts of deionized water;
and transferring the polymer solution into a dispersion kettle, dropwise adding the nano dispersion liquid for 60min, and then dropwise adding deionized water for 90min to enable the polymer solution to form an aqueous continuous phase. The nano dispersion liquid comprises the following components in parts by weight:
adding 24.3 parts of deionized water and 4 parts of propanol into a head tank, then slowly adding 20 parts of titanium tetrachloride, 11 parts of strontium chloride, 2.2 parts of tripotassium phosphate and 6 parts of dodecyl trimethoxy silane in sequence, and uniformly stirring for later use. 25 parts of deionized water, 4 parts of propanol and 3.5 parts of monoethanolamine are added to the reaction kettle and stirred at a speed of 800 r/min. And dropwise adding the solution in the head tank, finishing dropwise adding for 3.5 hours, and reacting for 4 hours after dropwise adding. Then the temperature is increased to 95 ℃, the reaction is carried out for 5 hours, and then the temperature is reduced to the room temperature.
The reaction solution was centrifuged at 4500r/min for 45min, and then vacuum filtered at-0.4 MPa to-0.9 MPa, and the solid was filtered off to obtain the clear solution, i.e., the nanodispersion of example 3. The nano dispersion has a solid content of 21.7%, a pH of 2.9, an average particle diameter of 49nm, and a viscosity of 17s at 25 ℃ after coating in 4 cups.
Heating to 80 ℃, controlling the vacuum degree to be-0.8 Mpa, and extracting acetone under reduced pressure to obtain the nano modified waterborne acrylic resin.
TABLE 4 comparison of the Performance of examples 1-3 with comparative example 1
Comparative example PRIML in DOW chemistryTM APR-968LO
The above embodiments are provided only for illustrating the present invention and not for limiting the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and therefore all equivalent technical solutions should also fall within the scope of the present invention, and should be defined by the claims.
Claims (10)
1. The nano modified water-based acrylic resin is characterized by comprising the following components in percentage by mass:
60-80% of polymer solution;
2-8% of nano dispersion liquid;
20-30% of deionized water;
the sum of the mass percentages of the components is 100 percent;
wherein the content of the first and second substances,
the polymer solution is prepared from the following components in percentage by mass through a free radical polymerization mode:
40-60% of solvent, 10-20% of vinyl monomer, 20-35% of acrylate monomer, 0.5-1.1% of functional monomer and 1.2-2.2% of initiator, wherein the sum of the mass percentages of the components is 100%;
the solvent is at least one of ethanol, isopropanol, butanol, isobutanol and acetone;
the functional monomer is at least one selected from acrylic acid, methacrylic acid, diacetone acrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and acryloyl morpholine;
the initiator is selected from at least one of benzoyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile;
the nano dispersion liquid comprises the following components in parts by weight:
the main element precursor is selected from at least one of sodium chloride, calcium chloride, magnesium chloride, titanium tetrachloride, aluminum trichloride, ferrous chloride, copper chloride, beryllium chloride, strontium chloride, barium chloride, boron chloride, germanium chloride, tin chloride, lead chloride, arsenic chloride, strontium chloride, nickel chloride, vanadium chloride and gallium chloride;
the doping element precursor is selected from at least one of sodium dihydrogen phosphate, tripotassium phosphate, potassium nitrate, sodium sulfate and potassium sulfate;
the lipophilic donor is at least one selected from n-hexyltrichlorosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrichlorosilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, dodecyltrichlorosilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, dodecylcarboxylic acid, hexadecylcarboxylic acid and dodecylsulfonic acid.
2. The nano-modified waterborne acrylic resin of claim 1, wherein the nano-dispersion has a pH of 2 to 5, and/or a solid content of 15% to 25%, and/or a viscosity value of 10 to 25s over-coated in-4 cups at 25 ℃.
3. The nano-modified aqueous acrylic resin according to claim 1, wherein the nano-material in the nano-dispersion has a particle size of 15nm to 200 nm.
4. The nano-modified aqueous acrylic resin according to claim 1, wherein the nano-dispersion is prepared by a method comprising the steps of:
(1) hydrolysis:
sequentially putting 20-30 parts of the deionized water, the alkali neutralizing agent and 4-7 parts of the lower alcohol into a reaction kettle, and starting stirring; adding the rest of the deionized water and the rest of the lower alcohol into an overhead tank, stirring at the speed of 300-800r/min, sequentially and slowly adding the main element precursor, the doped element precursor and the lipophilic donor, and stirring to form a uniform solution; dropwise adding the solution in the elevated tank into the reaction kettle at a constant speed for 2-5h, continuously reacting for 1-5h after dropwise adding, heating to 80-120 ℃, reacting for 2-8h, and cooling to room temperature;
(2) centrifugal separation:
introducing the liquid in the reactor into a centrifuge for centrifugal separation at the speed of 3000-5000r/min for 30-60 min;
(3) and (3) suction filtration:
and carrying out suction filtration on the liquid after centrifugal separation under the vacuum pressure of-0.4 Mpa to-0.9 Mpa, and filtering out solid matters to obtain clear liquid, namely the nano dispersion liquid for emulsion polymerization.
5. The nano-modified aqueous acrylic resin of claim 1, wherein the vinyl monomer is at least one selected from the group consisting of styrene, methyl styrene, vinyl chloride, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, vinyl trimethoxysilane, and vinyl triethoxysilane.
6. The nano-modified aqueous acrylic resin according to claim 1, wherein the acrylate monomer is at least one selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, isobornyl methacrylate, glycidyl acrylate and glycidyl methacrylate.
7. The nano-modified aqueous acrylic resin of claim 1, wherein the alkali neutralizing agent is at least one selected from the group consisting of potassium hydroxide, lithium hydroxide, ammonia, monoethanolamine, diethanolamine, triethanolamine, N-dimethylethanolamine and triethylamine.
8. The nano-modified aqueous acrylic resin as claimed in claim 1, wherein the lower alcohol is at least one selected from methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol
9. The method for preparing nano-modified aqueous acrylic resin according to claim 1, comprising the steps of:
(1) adding a vinyl monomer, an acrylate monomer and a functional monomer into a solvent, and carrying out free radical polymerization reaction at the temperature of 70-80 ℃ to obtain a polymer solution;
(2) transferring the polymer solution prepared in the step (1) to a dispersion kettle, and then dropwise adding the nano dispersion liquid under high-speed dispersion for 30-60 min; then, dropwise adding deionized water for 60-90min until a water continuous phase is formed;
(3) distilling under reduced pressure at vacuum degree of-0.4 Mpa to-0.9 Mpa and 60 deg.C-80 deg.C, and removing solvent.
10. The method for preparing nano-modified aqueous acrylic resin according to claim 9, wherein the radical polymerization process in the step (1) comprises: adding a solvent into a reaction kettle, heating to 70-80 ℃, preparing a vinyl monomer, an acrylate monomer, a functional monomer and an initiator in an overhead tank, stirring to dissolve the initiator uniformly, dropwise adding a mixture of the vinyl monomer, the acrylate monomer, the functional monomer and the initiator into the reaction kettle at a constant speed for 3 hours, and preserving heat for 1 hour after dropwise adding is finished.
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