CN112851880A - Water-soluble acrylic acid modified epoxy ester resin and preparation method thereof - Google Patents
Water-soluble acrylic acid modified epoxy ester resin and preparation method thereof Download PDFInfo
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Abstract
The invention is applicable to the field of material preparation, and provides a water-soluble acrylic acid modified epoxy ester resin and a preparation method thereof, wherein the water-soluble acrylic acid modified epoxy ester resin comprises the following raw materials: styrene, acrylic acid, polyethylene glycol acrylate, methyl methacrylate, glycidyl acrylate, modified shell filler, an antioxidant, a nonionic emulsifier and an initiator; the modified shell filler is obtained by modifying a shell filler by a coupling agent; the shell filler is obtained by coating the surface of a shell powder filler with the shell powder filler as a capsule core and a polycyanularamine formaldehyde resin as a capsule wall material; the water-soluble acrylic acid modified epoxy ester resin provided by the embodiment of the invention has the advantages of stable storage, low viscosity, flat and glossy surface of a paint film formed by drying, 0-grade adhesion, no bubbling and peeling in a water resistance test (at 23 ℃ for 168h), excellent water resistance, no bubbling and rustiness in a salt spray resistance test for 168h, and excellent salt spray resistance.
Description
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a water-soluble acrylic acid modified epoxy ester resin and a preparation method thereof.
Background
At present, the domestic steel structure anticorrosive paint is mainly solvent type paint, 37 percent of steel structure paint in developed countries of Europe and America is water-based paint, and the water-based paint comprises water emulsion type paint and water-soluble paint. The water-emulsion paint has poor water resistance and poor adhesive force due to the addition of the emulsifier, so the application of the water-emulsion paint is limited. The water-soluble paint replaces the organic solvent with water, so that the emission of the organic solvent is less, and the coating performance can be compared favorably with that of a solvent-based paint, and therefore, the research of the water-soluble paint becomes a research hotspot in the field.
The existing water-soluble paint mainly comprises a water-soluble acrylic paint and a water-soluble acrylic polyurethane two-component paint, and although the water-soluble acrylic paint has good weather resistance, the indexes of adhesion, hardness, wear resistance and the like of the water-soluble acrylic paint are poorer than those of a solvent-based two-component paint; the aqueous acrylic polyurethane two-component coating has excellent performances, but is expensive, so that the application of the aqueous acrylic polyurethane two-component coating is limited.
Therefore, how to develop a high-performance and low-price water-soluble coating is a technical problem which needs to be solved urgently in the field.
Disclosure of Invention
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a water-soluble acrylic acid modified epoxy ester resin, aiming at solving the problems of poor adhesive force, hardness and wear resistance of the existing water-soluble acrylic acid coating.
The embodiment of the invention is realized in such a way that the water-soluble acrylic acid modified epoxy ester resin comprises the following raw materials in parts by weight: 30-42 parts of styrene, 26-34 parts of acrylic acid, 32-38 parts of acrylic acid polyethylene glycol ester, 76-85 parts of methyl methacrylate, 28-36 parts of glycidyl acrylate, 12-24 parts of modified shell filler, 1-5 parts of antioxidant, 0.5-1.3 parts of non-ionic emulsifier and 2-6 parts of initiator;
the modified shell filler is obtained by modifying a shell filler by a coupling agent; the shell filler is obtained by coating the surface of the shell powder filler with shell powder filler as a capsule core and polycyanularamine formaldehyde resin as a capsule wall material.
As a further scheme of the invention: the antioxidant is one or more of antioxidant CA, antioxidant 1010 and antioxidant 1076 in any mass ratio.
As a further scheme of the invention: the feed comprises the following raw materials in parts by weight: the nonionic emulsifier is alkylphenol polyoxyethylene.
As a further scheme of the invention: the feed comprises the following raw materials in parts by weight: the initiator is ammonium persulfate or potassium persulfate.
As a further scheme of the invention: the preparation method of the modified coated shell filler specifically comprises the following steps:
mixing melamine, 15-25% by mass of formaldehyde solution and distilled water according to the weight ratio of 1: (1-3): (2-4), adjusting the pH value to 8-9, and reacting at 50-75 ℃ for 0.5-1 h to obtain a melamine formaldehyde resin prepolymer;
mixing the melamine formaldehyde resin prepolymer with a surfactant aqueous solution with the mass fraction of 25-35% according to the weight ratio of 1: (10-15), stirring for 0.5-1 h, adding shell powder and gelatin, wherein the weight ratio of the melamine-formaldehyde resin prepolymer to the shell powder to the gelatin is (0.5-1): 1 (0.3-0.5), adjusting the pH value of the system to 2-4, reacting at 45-75 ℃ for 2-4 h, filtering, washing and drying to obtain a shell powder filler;
adding the coated shell powder filler into a high-speed dispersion machine, uniformly spraying a coupling agent accounting for 0.5-1.5% of the mass of the shell powder filler at the temperature of 90-110 ℃, keeping stirring for 30-40 min, and discharging to obtain the modified shell filler.
As a further scheme of the invention: the surfactant is cetyl trimethyl ammonium bromide.
As a further scheme of the invention: the coupling agent is one or more of vinyl trimethoxy silane, vinyl triethoxy silane and gamma-aminopropyl triethoxy silane in any mass ratio.
As a further scheme of the invention: the feed comprises the following raw materials in parts by weight: 32-40 parts of styrene, 28-32 parts of acrylic acid, 33-37 parts of acrylic acid polyethylene glycol ester, 78-84 parts of methyl methacrylate, 29-35 parts of glycidyl acrylate, 14-22 parts of modified shell filler, 2-5 parts of antioxidant, 0.8-1.3 parts of non-ionic emulsifier and 3-6 parts of initiator.
As a further scheme of the invention: the feed comprises the following raw materials in parts by weight: 35 parts of styrene, 30 parts of acrylic acid, 35 parts of acrylic acid polyethylene glycol ester, 81 parts of methyl methacrylate, 32 parts of glycidyl acrylate, 21 parts of modified shell filler, 2 parts of antioxidant, 1.2 parts of nonionic emulsifier and 3 parts of initiator.
A preparation method of water-soluble acrylic acid modified epoxy ester resin comprises the following steps:
1) taking the following raw materials in parts by weight: 30-42 parts of styrene, 26-34 parts of acrylic acid, 32-38 parts of acrylic acid polyethylene glycol ester, 76-85 parts of methyl methacrylate, 28-36 parts of glycidyl acrylate, 12-24 parts of modified shell filler, 1-5 parts of antioxidant, 0.5-1.3 parts of non-ionic emulsifier and 2-6 parts of initiator;
2) adding styrene, acrylic acid, polyethylene glycol acrylate, methyl methacrylate, glycidyl acrylate, modified shell filler and an antioxidant into a reaction kettle, and fully mixing to obtain a mixture A;
3) dissolving an initiator in water to prepare an initiator solution B;
4) adding the nonionic emulsifier and water into another reaction kettle, and heating to 78-82 ℃; and dropwise adding the mixture A into a reaction kettle at a constant speed for 3-4h, adding the initiator solution A into the reaction kettle every 30min in the dropwise adding process, preserving the temperature for 2-3h after the dropwise adding is finished, and cooling to room temperature to obtain the water-soluble acrylic acid modified epoxy ester resin.
The water-soluble acrylic acid modified epoxy ester resin provided by the embodiment of the invention has the advantages of stable storage, low viscosity, smooth and glossy surface of a paint film formed by drying, 0-grade adhesion, no bubbling or peeling in a water resistance test (23 ℃, 168h), excellent water resistance, no bubbling or rusting in a salt spray resistance test for 168h, and excellent salt spray resistance; the added modified shell filler is obtained by coating the shell powder filler as a capsule core and the melamine formaldehyde resin as a capsule wall material on the surface of the shell powder filler, so that the surface of the modified coated shell filler is compact and uniform in particle size, the modified coated shell filler is good in compatibility and uniform in dispersion in a system, a stable system is formed, and no additional dispersing agent is needed; on the other hand, by adding the modified shell filler, the surface hardness can be obviously improved, and high impact resistance and high toughness can be maintained.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The technical effects of the water-soluble acrylic modified epoxy ester resin of the present invention will be further described with reference to the following examples, but the specific implementation methods mentioned in these examples are only illustrative and explanatory of the technical scheme of the present invention, and do not limit the scope of the present invention, and all modifications and substitutions based on the above principles should be within the scope of the present invention.
Example 1
Mixing melamine, 20% by mass of formaldehyde solution and distilled water according to the weight ratio of 1: 2: 3, regulating the pH value to 8-9, and reacting for 1h at the temperature of 60 ℃ to obtain a melamine formaldehyde resin prepolymer; mixing the melamine formaldehyde resin prepolymer with a hexadecyl trimethyl ammonium bromide aqueous solution with the mass fraction of 30% according to the proportion of 1: 15, adding shell powder and gelatin after stirring for 1h, wherein the weight ratio of the melamine-formaldehyde resin prepolymer to the shell powder to the gelatin is 0.7:1:0.4, adjusting the pH value of the system to 2-4, reacting for 4h at 50 ℃, filtering, washing and drying to obtain a shell powder filler; adding the coated shell powder filler into a high-speed dispersion machine, uniformly spraying 1% of vinyltrimethoxysilane based on the mass of the shell powder filler into the high-speed dispersion machine at the temperature of 100 ℃, keeping stirring for 35min, and discharging to obtain a modified shell filler for later use; taking the following raw materials in parts by weight: 30 parts of styrene, 26 parts of acrylic acid, 32 parts of acrylic acid polyethylene glycol ester, 76 parts of methyl methacrylate, 28 parts of glycidyl acrylate, 12 parts of modified shell filler, 1 parts of antioxidant CA, 0.5 part of alkylphenol polyoxyethylene and 2 parts of ammonium persulfate; adding styrene, acrylic acid, polyethylene glycol acrylate, methyl methacrylate, glycidyl acrylate, modified shell filler and antioxidant CA into a reaction kettle, and fully mixing to obtain a mixture A; dissolving ammonium persulfate in water to prepare an initiator solution B; adding alkylphenol polyoxyethylene and water into another reaction kettle, and heating to 80 ℃; and dropwise adding the mixture A into a reaction kettle at a constant speed for 4h, adding the initiator solution A into the reaction kettle every 30min in the dropwise adding process, preserving the heat for 3h after the dropwise adding is finished, and cooling to room temperature to obtain the water-soluble acrylic acid modified epoxy ester resin.
Example 2
Mixing melamine, 20% by mass of formaldehyde solution and distilled water according to the weight ratio of 1: 2: 3, regulating the pH value to 8-9, and reacting for 1h at the temperature of 60 ℃ to obtain a melamine formaldehyde resin prepolymer; mixing the melamine formaldehyde resin prepolymer with a hexadecyl trimethyl ammonium bromide aqueous solution with the mass fraction of 30% according to the proportion of 1: 15, adding shell powder and gelatin after stirring for 1h, wherein the weight ratio of the melamine-formaldehyde resin prepolymer to the shell powder to the gelatin is 0.7:1:0.4, adjusting the pH value of the system to 2-4, reacting for 4h at 50 ℃, filtering, washing and drying to obtain a shell powder filler; adding the coated shell powder filler into a high-speed dispersion machine, uniformly spraying 1% of vinyltrimethoxysilane based on the mass of the shell powder filler into the high-speed dispersion machine at the temperature of 100 ℃, keeping stirring for 35min, and discharging to obtain a modified shell filler for later use; taking the following raw materials in parts by weight: 42 parts of styrene, 34 parts of acrylic acid, 38 parts of acrylic acid polyethylene glycol ester, 85 parts of methyl methacrylate, 36 parts of glycidyl acrylate, 24 parts of modified shell filler, 5 parts of antioxidant CA, 1.3 parts of alkylphenol polyoxyethylene and 6 parts of ammonium persulfate; adding styrene, acrylic acid, polyethylene glycol acrylate, methyl methacrylate, glycidyl acrylate, modified shell filler and antioxidant CA into a reaction kettle, and fully mixing to obtain a mixture A; dissolving ammonium persulfate in water to prepare an initiator solution B; adding alkylphenol polyoxyethylene and water into another reaction kettle, and heating to 80 ℃; and dropwise adding the mixture A into a reaction kettle at a constant speed for 4h, adding the initiator solution A into the reaction kettle every 30min in the dropwise adding process, preserving the heat for 3h after the dropwise adding is finished, and cooling to room temperature to obtain the water-soluble acrylic acid modified epoxy ester resin.
Example 3
Mixing melamine, 20% by mass of formaldehyde solution and distilled water according to the weight ratio of 1: 2: 3, regulating the pH value to 8-9, and reacting for 1h at the temperature of 60 ℃ to obtain a melamine formaldehyde resin prepolymer; mixing the melamine formaldehyde resin prepolymer with a hexadecyl trimethyl ammonium bromide aqueous solution with the mass fraction of 30% according to the proportion of 1: 15, adding shell powder and gelatin after stirring for 1h, wherein the weight ratio of the melamine-formaldehyde resin prepolymer to the shell powder to the gelatin is 0.7:1:0.4, adjusting the pH value of the system to 2-4, reacting for 4h at 50 ℃, filtering, washing and drying to obtain a shell powder filler; adding the coated shell powder filler into a high-speed dispersion machine, uniformly spraying 1% of vinyltrimethoxysilane based on the mass of the shell powder filler into the high-speed dispersion machine at the temperature of 100 ℃, keeping stirring for 35min, and discharging to obtain a modified shell filler for later use; taking the following raw materials in parts by weight: 32 parts of styrene, 28 parts of acrylic acid, 33 parts of acrylic acid polyethylene glycol ester, 78 parts of methyl methacrylate, 29 parts of glycidyl acrylate, 14 parts of modified shell filler, 2 parts of antioxidant CA, 0.8 part of alkylphenol polyoxyethylene and 3 parts of ammonium persulfate; adding styrene, acrylic acid, polyethylene glycol acrylate, methyl methacrylate, glycidyl acrylate, modified shell filler and antioxidant CA into a reaction kettle, and fully mixing to obtain a mixture A; dissolving ammonium persulfate in water to prepare an initiator solution B; adding alkylphenol polyoxyethylene and water into another reaction kettle, and heating to 80 ℃; and dropwise adding the mixture A into a reaction kettle at a constant speed for 4h, adding the initiator solution A into the reaction kettle every 30min in the dropwise adding process, preserving the heat for 3h after the dropwise adding is finished, and cooling to room temperature to obtain the water-soluble acrylic acid modified epoxy ester resin.
Example 4
Mixing melamine, 20% by mass of formaldehyde solution and distilled water according to the weight ratio of 1: 2: 3, regulating the pH value to 8-9, and reacting for 1h at the temperature of 60 ℃ to obtain a melamine formaldehyde resin prepolymer; mixing the melamine formaldehyde resin prepolymer with a hexadecyl trimethyl ammonium bromide aqueous solution with the mass fraction of 30% according to the proportion of 1: 15, adding shell powder and gelatin after stirring for 1h, wherein the weight ratio of the melamine-formaldehyde resin prepolymer to the shell powder to the gelatin is 0.7:1:0.4, adjusting the pH value of the system to 2-4, reacting for 4h at 50 ℃, filtering, washing and drying to obtain a shell powder filler; adding the coated shell powder filler into a high-speed dispersion machine, uniformly spraying a mixture of 1% of vinyltrimethoxysilane and gamma-aminopropyltriethoxysilane based on the mass of the shell powder filler at the temperature of 100 ℃, keeping stirring for 35min, and discharging to obtain a modified shell filler for later use; taking the following raw materials in parts by weight: 40 parts of styrene, 32 parts of acrylic acid, 37 parts of acrylic acid polyethylene glycol ester, 84 parts of methyl methacrylate, 35 parts of glycidyl acrylate, 22 parts of modified shell filler, 5 parts of a mixture of an antioxidant CA, an antioxidant 1010 and an antioxidant 1076, 1.3 parts of alkylphenol polyoxyethylene ether and 6 parts of ammonium persulfate; adding a mixture of styrene, acrylic acid, polyethylene glycol acrylate, methyl methacrylate, glycidyl acrylate, modified shell filler, antioxidant CA, antioxidant 1010 and antioxidant 1076 into a reaction kettle, and fully mixing to obtain a mixture A; dissolving ammonium persulfate in water to prepare an initiator solution B; adding alkylphenol polyoxyethylene and water into another reaction kettle, and heating to 80 ℃; and dropwise adding the mixture A into a reaction kettle at a constant speed for 4h, adding the initiator solution A into the reaction kettle every 30min in the dropwise adding process, preserving the heat for 3h after the dropwise adding is finished, and cooling to room temperature to obtain the water-soluble acrylic acid modified epoxy ester resin.
Example 5
Mixing melamine, 20% by mass of formaldehyde solution and distilled water according to the weight ratio of 1: 2: 3, regulating the pH value to 8-9, and reacting for 1h at the temperature of 60 ℃ to obtain a melamine formaldehyde resin prepolymer; mixing the melamine formaldehyde resin prepolymer with a hexadecyl trimethyl ammonium bromide aqueous solution with the mass fraction of 30% according to the proportion of 1: 15, adding shell powder and gelatin after stirring for 1h, wherein the weight ratio of the melamine-formaldehyde resin prepolymer to the shell powder to the gelatin is 0.7:1:0.4, adjusting the pH value of the system to 2-4, reacting for 4h at 50 ℃, filtering, washing and drying to obtain a shell powder filler; adding the coated shell powder filler into a high-speed dispersion machine, uniformly spraying gamma-aminopropyltriethoxysilane with the mass of 1% of the shell powder filler under the condition that the temperature is 100 ℃, keeping stirring for 35min, and discharging to obtain a modified shell filler for later use; taking the following raw materials in parts by weight: 34 parts of styrene, 30 parts of acrylic acid, 34 parts of acrylic acid polyethylene glycol ester, 79 parts of methyl methacrylate, 29 parts of glycidyl acrylate, 18 parts of modified shell filler, 10762 parts of antioxidant, 1 part of alkylphenol polyoxyethylene ether and 3 parts of potassium persulfate; adding styrene, acrylic acid, polyethylene glycol acrylate, methyl methacrylate, glycidyl acrylate, modified shell filler and an antioxidant 1076 into a reaction kettle, and fully mixing to obtain a mixture A; dissolving potassium persulfate in water to prepare an initiator solution B; adding alkylphenol polyoxyethylene and water into another reaction kettle, and heating to 80 ℃; and dropwise adding the mixture A into a reaction kettle at a constant speed for 4h, adding the initiator solution A into the reaction kettle every 30min in the dropwise adding process, preserving the heat for 3h after the dropwise adding is finished, and cooling to room temperature to obtain the water-soluble acrylic acid modified epoxy ester resin.
Example 6
Mixing melamine, 20% by mass of formaldehyde solution and distilled water according to the weight ratio of 1: 2: 3, regulating the pH value to 8-9, and reacting for 1h at the temperature of 60 ℃ to obtain a melamine formaldehyde resin prepolymer; mixing the melamine formaldehyde resin prepolymer with a hexadecyl trimethyl ammonium bromide aqueous solution with the mass fraction of 30% according to the proportion of 1: 15, adding shell powder and gelatin after stirring for 1h, wherein the weight ratio of the melamine-formaldehyde resin prepolymer to the shell powder to the gelatin is 0.7:1:0.4, adjusting the pH value of the system to 2-4, reacting for 4h at 50 ℃, filtering, washing and drying to obtain a shell powder filler; adding the coated shell powder filler into a high-speed dispersion machine, uniformly spraying 1% of vinyltriethoxysilane based on the mass of the shell powder filler at the temperature of 100 ℃, keeping stirring for 35min, and discharging to obtain a modified shell filler for later use; taking the following raw materials in parts by weight: 38 parts of styrene, 32 parts of acrylic acid, 36 parts of acrylic acid polyethylene glycol ester, 82 parts of methyl methacrylate, 33 parts of glycidyl acrylate, 22 parts of modified shell filler, 10103 parts of antioxidant, 1.2 parts of alkylphenol polyoxyethylene ether and 4 parts of potassium persulfate; adding styrene, acrylic acid, polyethylene glycol acrylate, methyl methacrylate, glycidyl acrylate, modified shell filler and antioxidant 1010 into a reaction kettle, and fully mixing to obtain a mixture A; dissolving potassium persulfate in water to prepare an initiator solution B; adding alkylphenol polyoxyethylene and water into another reaction kettle, and heating to 80 ℃; and dropwise adding the mixture A into a reaction kettle at a constant speed for 4h, adding the initiator solution A into the reaction kettle every 30min in the dropwise adding process, preserving the heat for 3h after the dropwise adding is finished, and cooling to room temperature to obtain the water-soluble acrylic acid modified epoxy ester resin.
Example 7
Mixing melamine, 20% by mass of formaldehyde solution and distilled water according to the weight ratio of 1: 2: 3, regulating the pH value to 8-9, and reacting for 1h at the temperature of 60 ℃ to obtain a melamine formaldehyde resin prepolymer; mixing the melamine formaldehyde resin prepolymer with a hexadecyl trimethyl ammonium bromide aqueous solution with the mass fraction of 30% according to the proportion of 1: 15, adding shell powder and gelatin after stirring for 1h, wherein the weight ratio of the melamine-formaldehyde resin prepolymer to the shell powder to the gelatin is 0.7:1:0.4, adjusting the pH value of the system to 2-4, reacting for 4h at 50 ℃, filtering, washing and drying to obtain a shell powder filler; adding the coated shell powder filler into a high-speed dispersion machine, uniformly spraying 1% of vinyltrimethoxysilane based on the mass of the shell powder filler into the high-speed dispersion machine at the temperature of 100 ℃, keeping stirring for 35min, and discharging to obtain a modified shell filler for later use; taking the following raw materials in parts by weight: 35 parts of styrene, 30 parts of acrylic acid, 35 parts of acrylic acid polyethylene glycol ester, 81 parts of methyl methacrylate, 32 parts of glycidyl acrylate, 21 parts of modified shell filler, 2 parts of antioxidant CA, 1.2 parts of alkylphenol polyoxyethylene and 3 parts of ammonium persulfate; adding styrene, acrylic acid, polyethylene glycol acrylate, methyl methacrylate, glycidyl acrylate, modified shell filler and antioxidant CA into a reaction kettle, and fully mixing to obtain a mixture A; dissolving ammonium persulfate in water to prepare an initiator solution B; adding alkylphenol polyoxyethylene and water into another reaction kettle, and heating to 80 ℃; and dropwise adding the mixture A into a reaction kettle at a constant speed for 4h, adding the initiator solution A into the reaction kettle every 30min in the dropwise adding process, preserving the heat for 3h after the dropwise adding is finished, and cooling to room temperature to obtain the water-soluble acrylic acid modified epoxy ester resin.
Comparative example 1
Taking the following raw materials in parts by weight: 35 parts of styrene, 30 parts of acrylic acid, 35 parts of acrylic acid polyethylene glycol ester, 81 parts of methyl methacrylate, 32 parts of glycidyl acrylate, 2 parts of antioxidant CA, 1.2 parts of alkylphenol polyoxyethylene and 3 parts of ammonium persulfate; adding styrene, acrylic acid, polyethylene glycol acrylate, methyl methacrylate, glycidyl acrylate and an antioxidant CA into a reaction kettle, and fully mixing to obtain a mixture A; dissolving ammonium persulfate in water to prepare an initiator solution B; adding alkylphenol polyoxyethylene and water into another reaction kettle, and heating to 80 ℃; and dropwise adding the mixture A into a reaction kettle at a constant speed for 4h, adding the initiator solution A into the reaction kettle every 30min in the dropwise adding process, preserving the heat for 3h after the dropwise adding is finished, and cooling to room temperature to obtain the water-soluble acrylic acid modified epoxy ester resin.
Comparative example 2
Mixing melamine, 20% by mass of formaldehyde solution and distilled water according to the weight ratio of 1: 2: 3, regulating the pH value to 8-9, and reacting for 1h at the temperature of 60 ℃ to obtain a melamine formaldehyde resin prepolymer; mixing the melamine formaldehyde resin prepolymer with a hexadecyl trimethyl ammonium bromide aqueous solution with the mass fraction of 30% according to the proportion of 1: 15, adding shell powder and gelatin after stirring for 1h, wherein the weight ratio of the melamine-formaldehyde resin prepolymer to the shell powder to the gelatin is 0.7:1:0.4, adjusting the pH value of the system to 2-4, reacting for 4h at 50 ℃, filtering, washing and drying to obtain a shell powder filler for later use; taking the following raw materials in parts by weight: 35 parts of styrene, 30 parts of acrylic acid, 35 parts of acrylic acid polyethylene glycol ester, 81 parts of methyl methacrylate, 32 parts of glycidyl acrylate, 21 parts of shell filler, 2 parts of antioxidant CA, 1.2 parts of alkylphenol polyoxyethylene and 3 parts of ammonium persulfate; adding styrene, acrylic acid, polyethylene glycol acrylate, methyl methacrylate, glycidyl acrylate, shell filler and antioxidant CA into a reaction kettle, and fully mixing to obtain a mixture A; dissolving ammonium persulfate in water to prepare an initiator solution B; adding alkylphenol polyoxyethylene and water into another reaction kettle, and heating to 80 ℃; and dropwise adding the mixture A into a reaction kettle at a constant speed for 4h, adding the initiator solution A into the reaction kettle every 30min in the dropwise adding process, preserving the heat for 3h after the dropwise adding is finished, and cooling to room temperature to obtain the water-soluble acrylic acid modified epoxy ester resin.
Experimental example 1
The water-soluble acrylic acid modified epoxy ester resins prepared in examples 1 to 7 and comparative examples 1 to 2 were coated and air-dried at room temperature to form films, and the obtained paint films were subjected to the following performance tests, the test results of which are shown in Table 1.
TABLE 1
| Item | Hardness of pencil | Adhesion/grade | Water resistance (23 ℃, 168h) | Salt spray resistance (168h) |
| Example 1 | 2H | 0 | Does not foam or fall off | No bubbling and corrosion |
| Example 2 | 1H | 0 | Does not foam or fall off | No bubbling and corrosion |
| Example 3 | 2H | 0 | Does not foam or fall off | No bubbling and corrosion |
| Example 4 | 1H | 0 | Does not foam or fall off | No bubbling and corrosion |
| Example 5 | 2H | 0 | Does not foam or fall off | No bubbling and corrosion |
| Example 6 | 1H | 0 | Does not foam or fall off | No bubbling and corrosion |
| Example 7 | 3H | 0 | Does not foam or fall off | No bubbling and corrosion |
| Comparative example 1 | B | 1 | Blistering and falling off | Bubbling, corrosion-free |
| Comparative example 2 | HB | 1 | Foaming and slight detachment | Blistering, slight corrosion |
The result shows that compared with the water-soluble acrylic acid modified epoxy ester resin prepared by the comparative examples 1-2, the water-soluble acrylic acid modified epoxy ester resin prepared by the comparative examples 1-7 has the advantages of stable storage, low viscosity, flat surface of a paint film formed by drying, gloss, 0-grade adhesion, no foaming and no peeling in a water resistance test (23 ℃, 168h), excellent water resistance, no foaming and corrosion in a salt spray resistance test for 168h, and excellent salt spray resistance, particularly the whole performance is influenced by the loss of the modified shell filler, the modified shell filler added in the invention takes the shell powder filler as a capsule core, and the melamine formaldehyde resin as a capsule material to coat the surface of the shell powder filler to obtain the modified coated shell filler which has compact surface and uniform particle size, good compatibility, uniform dispersion in a system and stable system formation, no additional dispersant is needed; on the other hand, by adding the modified shell filler, the surface hardness can be obviously improved, and high impact resistance and high toughness can be maintained.
In conclusion, the water-soluble acrylic acid modified epoxy ester resin provided by the embodiment of the invention has the advantages of stable storage, low viscosity, smooth surface of a paint film formed by drying, luster, 0-grade adhesion, no bubbling and peeling in a water resistance test (23 ℃ for 168h), excellent water resistance, no bubbling and corrosion in a salt spray resistance test for 168h, and excellent salt spray resistance; the added modified shell filler is obtained by coating the shell powder filler as a capsule core and the melamine formaldehyde resin as a capsule wall material on the surface of the shell powder filler, so that the surface of the modified coated shell filler is compact and uniform in particle size, the modified coated shell filler is good in compatibility and uniform in dispersion in a system, a stable system is formed, and no additional dispersing agent is needed; on the other hand, by adding the modified shell filler, the surface hardness can be obviously improved, and high impact resistance and high toughness can be maintained.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The water-soluble acrylic acid modified epoxy ester resin is characterized by comprising the following raw materials in parts by weight: 30-42 parts of styrene, 26-34 parts of acrylic acid, 32-38 parts of acrylic acid polyethylene glycol ester, 76-85 parts of methyl methacrylate, 28-36 parts of glycidyl acrylate, 12-24 parts of modified shell filler, 1-5 parts of antioxidant, 0.5-1.3 parts of non-ionic emulsifier and 2-6 parts of initiator;
the modified shell filler is obtained by modifying a shell filler by a coupling agent; the shell filler is obtained by coating the surface of the shell powder filler with shell powder filler as a capsule core and polycyanularamine formaldehyde resin as a capsule wall material.
2. The water-soluble acrylic acid modified epoxy ester resin as claimed in claim 1, wherein the antioxidant is one or more of antioxidant CA, antioxidant 1010 and antioxidant 1076 in any mass ratio.
3. The water-soluble acrylic-modified epoxy ester resin according to claim 1, wherein the nonionic emulsifier is alkylphenol ethoxylates.
4. The water-soluble acrylic-modified epoxy ester resin of claim 1, wherein the initiator is ammonium persulfate or potassium persulfate.
5. The water-soluble acrylic acid modified epoxy ester resin according to claim 1, wherein the preparation method of the modified coated shell filler specifically comprises:
mixing melamine, 15-25% by mass of formaldehyde solution and distilled water according to the weight ratio of 1: (1-3): (2-4), adjusting the pH value to 8-9, and reacting at 50-75 ℃ for 0.5-1 h to obtain a melamine formaldehyde resin prepolymer;
mixing the melamine formaldehyde resin prepolymer with a surfactant aqueous solution with the mass fraction of 25-35% according to the weight ratio of 1: (10-15), stirring for 0.5-1 h, adding shell powder and gelatin, wherein the weight ratio of the melamine-formaldehyde resin prepolymer to the shell powder to the gelatin is (0.5-1): 1 (0.3-0.5), adjusting the pH value of the system to 2-4, reacting at 45-75 ℃ for 2-4 h, filtering, washing and drying to obtain a shell powder filler;
adding the coated shell powder filler into a high-speed dispersion machine, uniformly spraying a coupling agent with the mass of 0.5-1.5% of the shell powder filler under the condition that the temperature is 90-110 ℃, keeping stirring for 30-40 min, and discharging to obtain the modified shell filler.
6. The water-soluble acrylic-modified epoxy ester resin of claim 5, wherein the surfactant is cetyltrimethylammonium bromide.
7. The water-soluble acrylic acid modified epoxy ester resin as claimed in claim 5, wherein the coupling agent is one or more of vinyltrimethoxysilane, vinyltriethoxysilane and gamma-aminopropyltriethoxysilane in any mass ratio.
8. The water-soluble acrylic modified epoxy ester resin of claim 1, comprising the following raw materials in parts by weight: 32-40 parts of styrene, 28-32 parts of acrylic acid, 33-37 parts of acrylic acid polyethylene glycol ester, 78-84 parts of methyl methacrylate, 29-35 parts of glycidyl acrylate, 14-22 parts of modified shell filler, 2-5 parts of antioxidant, 0.8-1.3 parts of non-ionic emulsifier and 3-6 parts of initiator.
9. The water-soluble acrylic modified epoxy ester resin of claim 1, comprising the following raw materials in parts by weight: 35 parts of styrene, 30 parts of acrylic acid, 35 parts of acrylic acid polyethylene glycol ester, 81 parts of methyl methacrylate, 32 parts of glycidyl acrylate, 21 parts of modified shell filler, 2 parts of antioxidant, 1.2 parts of nonionic emulsifier and 3 parts of initiator.
10. The method for producing a water-soluble acrylic-modified epoxy ester resin according to any one of claims 1 to 9, comprising the steps of:
1) taking the following raw materials in parts by weight: 30-42 parts of styrene, 26-34 parts of acrylic acid, 32-38 parts of acrylic acid polyethylene glycol ester, 76-85 parts of methyl methacrylate, 28-36 parts of glycidyl acrylate, 12-24 parts of modified shell filler, 1-5 parts of antioxidant, 0.5-1.3 parts of non-ionic emulsifier and 2-6 parts of initiator;
2) adding styrene, acrylic acid, polyethylene glycol acrylate, methyl methacrylate, glycidyl acrylate, modified shell filler and an antioxidant into a reaction kettle, and fully mixing to obtain a mixture A;
3) dissolving an initiator in water to prepare an initiator solution B;
4) adding the nonionic emulsifier and water into another reaction kettle, and heating to 78-82 ℃; and dropwise adding the mixture A into a reaction kettle at a constant speed for 3-4h, adding the initiator solution A into the reaction kettle every 30min in the dropwise adding process, preserving the temperature for 2-3h after the dropwise adding is finished, and cooling to room temperature to obtain the water-soluble acrylic acid modified epoxy ester resin.
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| CN106589211A (en) * | 2016-12-05 | 2017-04-26 | 刘立超 | Aqueous epoxy-modified acrylic resin and paint and preparation method thereof |
| CN107056996A (en) * | 2017-01-13 | 2017-08-18 | 佛山市顺德区地缘电子科技有限公司 | A kind of water-soluble acrylic modified epoxy organosilicon resin and preparation method and application |
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| CN111793319A (en) * | 2020-08-12 | 2020-10-20 | 汕头市邦腾科技有限公司 | High-toughness modified plastic and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106589211A (en) * | 2016-12-05 | 2017-04-26 | 刘立超 | Aqueous epoxy-modified acrylic resin and paint and preparation method thereof |
| CN107056996A (en) * | 2017-01-13 | 2017-08-18 | 佛山市顺德区地缘电子科技有限公司 | A kind of water-soluble acrylic modified epoxy organosilicon resin and preparation method and application |
| CN111253527A (en) * | 2020-01-15 | 2020-06-09 | 深圳市瑞成科讯实业有限公司 | Water-resistant moisture-proof sizing agent, preparation method and water-resistant moisture-proof paper |
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