CN112876936A - Waterborne epoxy ester modified acrylate emulsion for woodware and preparation method thereof - Google Patents

Waterborne epoxy ester modified acrylate emulsion for woodware and preparation method thereof Download PDF

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CN112876936A
CN112876936A CN202110341172.5A CN202110341172A CN112876936A CN 112876936 A CN112876936 A CN 112876936A CN 202110341172 A CN202110341172 A CN 202110341172A CN 112876936 A CN112876936 A CN 112876936A
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epoxy ester
acid
woodware
modified acrylate
waterborne epoxy
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CN112876936B (en
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易承志
程蕾
陈国华
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Guangdong Shizhiyi New Materials Co.,Ltd.
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Haishun Yiqi Fuxin Material Foshan Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • C08F283/105Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20Diluents or solvents

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention discloses a waterborne epoxy ester modified acrylate emulsion for woodware and a preparation method thereof, wherein the waterborne epoxy ester modified acrylate emulsion comprises the following steps: (1) preparing an aqueous epoxy ester dispersion; (2) the aqueous epoxy ester dispersion is copolymerized with an acrylate monomer. The resin of the waterborne epoxy ester modified acrylate emulsion contains both epoxy ester components and acrylate components, and the epoxy ester endows a paint film with excellent water resistance, so that the water in a finish paint can be prevented from permeating into wood to cause rib expansion, and simultaneously yellowing caused by seepage of wood oil ester and tannic acid can be prevented; the acrylic ester improves the drying speed and the sanding property of the paint film. The waterborne epoxy ester modified acrylate emulsion has the characteristic of quick drying, has the advantages of quick drying, easiness in polishing, rib expansion resistance, tannin resistance and the like when being used as a woodware sealing agent, and provides an excellent sealing effect.

Description

Waterborne epoxy ester modified acrylate emulsion for woodware and preparation method thereof
Technical Field
The invention relates to the field of waterborne wood lacquer, and mainly relates to waterborne epoxy ester modified acrylate emulsion for wood and a preparation method thereof.
Background
With the increasing awareness of environmental protection and stricter laws and regulations of environmental protection, the traditional oily woodenware paint containing a large amount of volatile organic compounds and harmful substances is gradually replaced by the environment-friendly and healthy water-based paint. However, when the aqueous paint is applied to woodenware, the problems of slow drying, easy expansion, difficult sanding, easy yellowing and the like still exist, and the wide application of the aqueous woodenware paint is limited.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a waterborne epoxy ester modified acrylate emulsion for woodware and a preparation method thereof, and aims to solve the problem that the conventional waterborne woodware paint is slow to dry.
The technical scheme of the invention is as follows:
a preparation method of waterborne epoxy ester modified acrylate emulsion for woodware comprises the following steps:
adding epoxy resin, hydroxy acid and organic monobasic fatty acid, and heating to form a homogeneous phase;
adding a catalyst, and reacting at 100-180 ℃ until the acid value is less than 1 mgKOH/g;
adding a butyl acrylate monomer, and adjusting the temperature to 75-130 ℃;
adding acid anhydride, and reacting for 1-2 h;
cooling to 60-65 ℃, adding an amine neutralizer and reacting for 20-30 min;
adding water for dispersion, and adjusting the solid content to 30-40% to obtain a water-based epoxy ester dispersion;
adding the aqueous epoxy ester dispersoid, water and an emulsifier, heating, beginning to dropwise add the acrylic acid monomer and the initiator when the temperature reaches 80 ℃, finishing dropwise adding within 3-4 h, preserving the temperature for 1-3 h, cooling to below 50 ℃, and neutralizing.
The preparation method of the waterborne epoxy ester modified acrylate emulsion for woodware comprises the step of adding butyl acrylate monomer in an amount which is 10-20% of the total weight of reactants in the previous step.
The preparation method of the waterborne epoxy ester modified acrylate emulsion for the woodware comprises the following steps of (1) adopting a combination of a nonionic emulsifier and an anionic emulsifier, wherein the mass ratio of the nonionic emulsifier to the anionic emulsifier is 3: 1-1: 3.
the preparation method of the waterborne epoxy ester modified acrylate emulsion for the woodware comprises the following steps of preparing a waterborne epoxy ester modified acrylate emulsion, wherein the anionic emulsifier is sodium dodecyl benzene sulfonate, and the nonionic emulsifier is fatty alcohol-polyoxyethylene ether.
The preparation method of the waterborne epoxy ester modified acrylate emulsion for the woodware comprises the following steps of:
25-45% of methyl methacrylate, 25-45% of styrene, 20-30% of butyl acrylate and 0-15% of butyl methacrylate.
The preparation method of the waterborne epoxy ester modified acrylate emulsion for the woodware comprises the following steps of adding a catalyst in an amount of 0.5-1.5% of the total weight of reactants in the previous step;
the total molar ratio of the epoxy resin to the hydroxy acid and the organic monobasic fatty acid is 1: and 2, the molar ratio of the hydroxy acid to the organic monobasic fatty acid is 1: 4-4: 1, the molar ratio of the epoxy resin to the acid anhydride is 1: 0.6-1: 1.5, wherein the molar ratio of the amine neutralizer to the acid anhydride is (0.8-1.2): 1.
the preparation method of the waterborne epoxy ester modified acrylate emulsion for the woodware comprises the following steps of (1) preparing a waterborne epoxy ester modified acrylate emulsion for the woodware, wherein the epoxy resin is any one or more than two of E-51, E-44, E-20 and E-12;
the organic monobasic fatty acid is any one or more than two of linoleic acid, oleic acid, lauric acid, myristic acid, palmitic acid, stearic acid, abietic acid and derivatives thereof;
the hydroxy acid is any one or more than two of 2-hydroxypropionic acid, ricinoleic acid and dodecahydroxystearic acid;
the catalyst is any one or more than two of N, N-dimethylbenzylamine, tetrabutylammonium bromide and lithium neo-decanoate;
the anhydride is one or more than two of phthalic anhydride, succinic anhydride, maleic anhydride and derivatives thereof;
the amine neutralizer is one or more of triethylamine, N-dimethylethanolamine and triethanolamine.
The preparation method of the waterborne epoxy ester modified acrylate emulsion for the woodware comprises the following steps of (1) preparing a waterborne epoxy ester dispersion and an acrylate monomer according to the solid part mass ratio of 50: 50-20: 80; the dosage of the emulsifier is 2 to 4 percent of the total weight of the acrylate monomer; the dosage of the initiator is 0.3 to 1 percent of the total weight of the acrylate monomer.
The preparation method of the waterborne epoxy ester modified acrylate emulsion for the woodware comprises the following step of preparing a waterborne epoxy ester modified acrylate emulsion, wherein the initiator is any one or more than two of dibenzoyl peroxide, azodiisobutyronitrile and ammonium persulfate.
The waterborne epoxy ester modified acrylate emulsion for the woodware is prepared by the preparation method of the waterborne epoxy ester modified acrylate emulsion for the woodware.
Has the advantages that: according to the preparation method of the waterborne epoxy ester modified acrylate emulsion for the woodware, disclosed by the invention, through optimizing the preparation process and raw materials, the resin of the waterborne epoxy ester modified acrylate emulsion contains both epoxy ester and acrylate, the epoxy ester endows a paint film with excellent water resistance, so that the water in finish paint can be prevented from permeating into wood to cause rib expansion, and meanwhile, the yellowing caused by the seepage of wood oil ester and tannic acid can be prevented; the acrylic ester improves the drying speed and the sanding property of the paint film. In addition, in the preparation process, butyl acrylate replaces an organic solvent to be used as a diluent, so that the viscosity of the system can be reduced in the preparation process of the epoxy ester on one hand, and the butyl acrylate can be copolymerized with other monomers in the subsequent reaction process on the other hand, thereby greatly reducing the VOC of the final emulsion.
Detailed Description
The invention provides a waterborne epoxy ester modified acrylate emulsion for woodware and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. 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 invention provides a preparation method of waterborne epoxy ester modified acrylate emulsion for woodware, which comprises the following steps:
(1) preparation of aqueous epoxy ester dispersions
Adding epoxy resin, hydroxy acid and organic monobasic fatty acid, and heating to form a homogeneous phase;
adding a catalyst accounting for 0.5-1.5 percent of the total weight of the reactants in the previous step, and reacting at 100-180 ℃ until the acid value is less than 1 mgKOH/g;
adding butyl acrylate monomer accounting for 10-20% of the total weight of the reactants in the previous step, and adjusting the temperature to 75-130 ℃;
adding acid anhydride, and reacting for 1-2 h;
cooling to 60-65 ℃, adding an amine neutralizer and reacting for 20-30 min;
adding water for dispersion, and adjusting the solid content to 30-40% to obtain the waterborne epoxy ester dispersoid.
Wherein the total molar ratio of the epoxy resin to the hydroxy acid and the organic monobasic fatty acid is 1: and 2, the molar ratio of the hydroxy acid to the organic monobasic fatty acid is 1: 4-4: 1, the molar ratio of the epoxy resin to the acid anhydride is 1: 0.6-1: 1.5, wherein the molar ratio of the amine neutralizer to the acid anhydride is (0.8-1.2): 1.
in the process of synthesizing the aqueous epoxy ester dispersoid, butyl acrylate replaces an organic solvent to be used as a diluent, so that the viscosity of the system can be reduced in the preparation process of the epoxy ester on one hand, and the butyl acrylate can be copolymerized with other monomers in the subsequent reaction process on the other hand, thereby greatly reducing the VOC of the final emulsion.
The epoxy resin can be any one or more than two of E-51, E-44, E-20 and E-12.
The organic monobasic fatty acid can be any one or more than two of linoleic acid, oleic acid, lauric acid, myristic acid, palmitic acid, stearic acid, abietic acid and derivatives thereof.
The hydroxy acid is any one or more than two of 2-hydroxypropionic acid, ricinoleic acid and dodecahydroxystearic acid.
The catalyst can be any one or more than two of N, N-dimethylbenzylamine, tetrabutylammonium bromide and lithium neo-decanoate.
The acid anhydride may be any one or more of phthalic anhydride, succinic anhydride, maleic anhydride and derivatives thereof. The hydrophilic group is introduced by reacting the added acid anhydride with the hydroxyl group in the epoxy resin, thereby making the epoxy ester water-based.
The amine neutralizer can be one or more than two of triethylamine, N-dimethylethanolamine and triethanolamine.
(2) Copolymerization of aqueous epoxy ester dispersions with acrylate monomers
Adding the aqueous epoxy ester dispersoid, water and an emulsifier, and heating;
when the temperature reaches 80 ℃, starting to dropwise add the acrylic monomer and the initiator, finishing dropwise adding within 3-4 h, preserving the temperature for 1-3 h, and cooling to below 50 ℃;
neutralizing and discharging to obtain the waterborne epoxy ester modified acrylate emulsion.
Wherein the mass ratio of the water-based epoxy ester dispersoid to the solid of the acrylate monomer is 50: 50-20: 80; the dosage of the emulsifier is 2 to 4 percent of the total weight of the acrylate monomer; the dosage of the initiator is 0.3 to 1 percent of the total weight of the acrylate monomer. The solid content of the finally prepared waterborne epoxy ester modified acrylate emulsion can be 30-50%.
Preferably, the emulsifier is a combination of a nonionic emulsifier and an anionic emulsifier, and the mass ratio of the nonionic emulsifier to the anionic emulsifier is 3: 1-1: 3, the anionic emulsifier is sodium dodecyl benzene sulfonate, the nonionic emulsifier is fatty alcohol-polyoxyethylene ether, and the combination can ensure that the waterborne epoxy ester modified acrylate emulsion has good synthesis stability and storage stability.
The acrylate monomer is a mixture of methyl methacrylate, styrene, butyl acrylate and butyl methacrylate; the mass ratio of each acrylate monomer in the mixture is respectively as follows: 25-45% of methyl methacrylate, 25-45% of styrene, 20-30% of butyl acrylate and 0-15% of butyl methacrylate. By adopting the combination of the acrylate monomers, on one hand, the drying performance of the epoxy ester can be improved, so that the drying speed and the polishing performance of a paint film are improved, and on the other hand, the cost of the product can be effectively reduced, and the economic benefit is improved.
The initiator can be any one or more than two of dibenzoyl peroxide (BPO), azobisisobutyronitrile and ammonium persulfate.
The invention also provides a waterborne epoxy ester modified acrylate emulsion which is prepared by the preparation method. The resin of the waterborne epoxy ester modified acrylate emulsion contains both epoxy ester components and acrylate components, and the epoxy ester endows a paint film with excellent water resistance, so that the water in a finish paint can be prevented from permeating into wood to cause rib expansion, and simultaneously yellowing caused by seepage of wood oil ester and tannic acid can be prevented; the acrylic ester improves the drying speed and the sanding property of the paint film. The waterborne epoxy ester modified acrylate emulsion has the characteristic of quick drying, has the advantages of quick drying, easiness in polishing, rib expansion resistance, tannin resistance and the like when being used as a woodware sealing agent, and provides an excellent sealing effect.
The present invention is further illustrated by the following specific examples.
Example 1
A preparation method of waterborne epoxy ester modified acrylate emulsion for woodware comprises the following steps:
(1) preparation of aqueous epoxy ester dispersions
Adding E-20 epoxy resin, ricinoleic acid and stearic acid into a reactor, heating to form a homogeneous phase, adding lithium neodecanoate accounting for 1% of the total amount of reactants in the previous step, reacting at 180 ℃ until the acid value is less than 1mgKOH/g, adding butyl acrylate accounting for 20% of the total amount of the reactants in the previous step, adjusting the temperature to 120 ℃, adding succinic anhydride, reacting for 2 hours, cooling to 60-65 ℃, adding triethylamine for neutralization for 30 minutes, adding water for dispersing for 2 hours, and adjusting the solid content to 40% to obtain the aqueous epoxy ester dispersoid;
the total molar ratio of E-20 to ricinoleic and stearic acid is 1: 2, the molar ratio of ricinoleic acid to stearic acid is 1: 3, the molar ratio of E-20 to succinic anhydride is 1:1.5, the molar ratio of triethylamine to succinic anhydride is 1.1: 1.
(2) copolymerization of aqueous epoxy ester dispersions with acrylate monomers
Adding the aqueous epoxy ester dispersion prepared in the step (1), water and an emulsifier into a four-neck flask provided with a thermometer, a condenser, a stirring paddle and a constant-pressure dropping funnel according to the formula amount, starting to dropwise add an acrylic monomer dissolved with dibenzoyl peroxide when the temperature reaches 80 ℃, completing dropwise adding within 3-4 h, then preserving heat for 3h, cooling to below 50 ℃, neutralizing, and discharging to obtain the aqueous epoxy ester modified acrylate emulsion with the solid content of 35%.
The mass ratio (solid parts) of the aqueous epoxy ester dispersion to the acrylate monomer is 50: 50; the acrylate monomer is methyl methacrylate, styrene and butyl acrylate, wherein the methyl methacrylate accounts for 45%, the styrene accounts for 25% and the butyl acrylate accounts for 30%; the dosage of the emulsifier is 2.5 percent of the total weight of the acrylate monomer, the anionic emulsifier is sodium dodecyl benzene sulfonate, the nonionic emulsifier is fatty alcohol-polyoxyethylene ether, and the mass ratio of the fatty alcohol-polyoxyethylene ether to the sodium dodecyl benzene sulfonate is 3: 1; the amount of the initiator is 0.6 percent of the total weight of the acrylate monomer.
The prepared emulsion was subjected to a performance test: (1) testing the drying time; coating the emulsion on wood, and standing for 20 minutes at normal temperature to dry the surface of a paint film; the paint film can be surface dried after being baked for 3 minutes at 70 ℃; (2) and (3) sanding property test: coating the emulsion on the red oak, standing for 2 hours or baking at 70 ℃ for 5 minutes at normal temperature, and then polishing with 240-mesh abrasive paper, wherein the powder is easy to rise during polishing and the abrasive paper is not stuck; (3) anti-tannic acid test: coating the emulsion on red oak, baking at normal temperature for 2 hours or 70 ℃ for 5 minutes, then spraying a water-based white paint, standing at normal temperature for 7 days, and testing in a high-temperature high-humidity test box for 24 hours, wherein the paint film does not turn yellow. In addition, the emulsion obtained has good thermal stability and no change after being stored for 7 days at 50 ℃.
Example 2
A preparation method of waterborne epoxy ester modified acrylate emulsion for woodware comprises the following steps:
(1) preparation of aqueous epoxy ester dispersions
Adding E-44 epoxy resin, 2-hydroxypropionic acid and stearic acid into a reactor, heating to form a homogeneous phase, adding tetrabutylammonium bromide accounting for 0.8% of the total amount of reactants in the previous step, reacting at 100 ℃ until the acid value is less than 1mgKOH/g, adding butyl acrylate accounting for 10% of the total amount of the reactants in the previous step, adjusting the temperature to 80 ℃, adding maleic anhydride, reacting for 2 hours, cooling to 60-65 ℃, adding N, N-dimethylethanolamine, reacting for 30min, adding water, dispersing for 2 hours, and adjusting the solid content to 40% to obtain an aqueous epoxy ester dispersion;
the total molar ratio of E-44 to 2-hydroxypropionic acid and stearic acid is 1: 2; the molar ratio of stearic acid to 2-hydroxypropionic acid to is 1: 2, the molar ratio of E-44 to maleic anhydride is 1: the molar ratio of 1, N, N-dimethylethanolamine to maleic anhydride is 0.9: 1.
(2) copolymerization of aqueous epoxy ester dispersions with acrylate monomers
Adding the aqueous epoxy ester dispersion obtained in the step (1), water and an emulsifier into a four-neck flask provided with a thermometer, a condenser, a stirring paddle and a constant-pressure dropping funnel according to the formula amount, starting to dropwise add an acrylic monomer and an ammonium persulfate aqueous solution when the temperature reaches 80 ℃, completing dropwise addition within 3-4 h, then preserving heat for 1.5h, cooling to below 50 ℃, neutralizing, discharging and obtaining the aqueous epoxy ester modified acrylate emulsion with the solid content of 40%.
The mass ratio (solid parts) of the aqueous epoxy ester dispersion to the acrylate monomer is 40: 60, adding a solvent to the mixture; the acrylate monomer is methyl methacrylate, styrene and butyl acrylate, wherein the methyl methacrylate accounts for 35%, the styrene accounts for 40% and the butyl acrylate accounts for 25%; the dosage of the emulsifier is 3 percent of the total weight of the acrylate monomer, the anionic emulsifier is sodium dodecyl benzene sulfonate, the nonionic emulsifier is fatty alcohol-polyoxyethylene ether, and the mass ratio of the fatty alcohol-polyoxyethylene ether to the sodium dodecyl benzene sulfonate is 2: 1, the dosage of the initiator is 1 percent of the total weight of the acrylate monomer.
The prepared emulsion was subjected to a performance test: (1) testing of drying time: coating the emulsion on wood, and standing for 20 minutes at normal temperature to dry the surface of a paint film; the paint film can be surface dried after being baked for 3 minutes at 70 ℃; (2) and (3) sanding property test: coating the emulsion on the red oak, standing for 2 hours or baking at 70 ℃ for 5 minutes at normal temperature, and then polishing with 240-mesh abrasive paper, wherein the powder is easy to rise during polishing and the abrasive paper is not stuck; (3) anti-tannic acid test: coating the emulsion on red oak, baking at normal temperature for 2 hours or 70 ℃ for 5 minutes, then spraying a water-based white paint, standing at normal temperature for 7 days, and testing in a high-temperature high-humidity test box for 24 hours, wherein the paint film does not turn yellow. In addition, the emulsion obtained has good thermal stability and no change after being stored for 7 days at 50 ℃.
Example 3
A preparation method of waterborne epoxy ester modified acrylate emulsion for woodware comprises the following steps:
(1) preparation of aqueous epoxy ester dispersions
Adding E-44 epoxy resin, ricinoleic acid and abietic acid into a reactor, heating to form a homogeneous phase, adding lithium neodecanoate accounting for 0.8% of the total amount of reactants in the previous step, reacting at 180 ℃ until the acid value is less than 1mgKOH/g, adding butyl acrylate accounting for 12% of the total amount of the reactants in the previous step, adjusting the temperature to 120 ℃, adding succinic anhydride, reacting for 2 hours, cooling to 60-65 ℃, adding triethylamine, reacting for 30 minutes, adding water, dispersing for 2 hours, and adjusting the solid content to 35% to obtain an aqueous epoxy ester dispersion;
the molar ratio of E-44 to ricinoleic acid and abietic acid is 1: 2; the molar ratio of the abietic acid to the ricinoleic acid is 1:1, E-44 to succinic anhydride in a molar ratio of 1:1, molar ratio of triethylamine to succinic anhydride 1:1.
(2) copolymerization of aqueous epoxy ester dispersions with acrylate monomers
Adding the aqueous epoxy ester dispersion obtained in the step (1), water and an emulsifier into a four-neck flask provided with a thermometer, a condenser, a stirring paddle and a constant-pressure dropping funnel according to the formula amount, starting to dropwise add an acrylic monomer and an ammonium persulfate aqueous solution when the temperature reaches 80 ℃, completing dropwise addition within 3-4 h, then preserving heat for 1.5h, cooling to below 50 ℃, neutralizing, discharging and obtaining the aqueous epoxy ester modified acrylate emulsion with the solid content of 35%.
The mass ratio (solid parts) of the aqueous epoxy ester dispersion to the acrylate monomer is 40: 60, adding a solvent to the mixture; the acrylate monomer is methyl methacrylate, styrene, butyl acrylate and butyl methacrylate, wherein the methyl methacrylate accounts for 30 percent, the styrene accounts for 35 percent, the butyl acrylate accounts for 20 percent and the butyl methacrylate accounts for 15 percent, the dosage of the emulsifier is 4 percent of the total weight of the acrylate monomer, the anionic emulsifier is sodium dodecyl benzene sulfonate, the nonionic emulsifier is fatty alcohol polyoxyethylene ether, and the mass ratio of the fatty alcohol polyoxyethylene ether to the sodium dodecyl benzene sulfonate is 2: 1, the dosage of the initiator is 0.5 percent of the total weight of the acrylate monomer.
The prepared emulsion was subjected to a performance test: (1) testing the drying time; coating the emulsion on wood, and standing for 20 minutes at normal temperature to dry the surface of a paint film; the paint film can be surface dried after being baked for 3 minutes at 70 ℃; (2) testing the grindability; coating the emulsion on the red oak, standing for 2 hours or baking at 70 ℃ for 5 minutes at normal temperature, and then polishing with 240-mesh abrasive paper, wherein the powder is easy to rise during polishing and the abrasive paper is not stuck; (3) testing anti-tannic acid; coating the emulsion on red oak, baking at normal temperature for 2 hours or 70 ℃ for 5 minutes, then spraying a water-based white paint, standing at normal temperature for 7 days, and testing in a high-temperature high-humidity test box for 24 hours, wherein the paint film does not turn yellow. In addition, the emulsion obtained has good thermal stability and no change after being stored for 7 days at 50 ℃.
Example 4
A preparation method of waterborne epoxy ester modified acrylate emulsion for woodware comprises the following steps:
(1) preparation of aqueous epoxy ester dispersions
Adding E-51 epoxy resin, 2-hydroxypropionic acid and abietic acid into a reactor, heating to form a homogeneous phase, adding tetrabutylammonium bromide accounting for 1% of the total amount of reactants in the previous step, reacting at 140 ℃ until the acid value is less than 1mgKOH/g, adding butyl acrylate accounting for 15% of the total amount of the reactants in the previous step, adjusting the temperature to 130 ℃, adding phthalic anhydride, reacting for 1.5h, cooling to 60-65 ℃, adding triethylamine, reacting for 30min, adding water, dispersing for 2h, and adjusting the solid content to 30% to obtain the aqueous epoxy ester dispersion;
the total molar ratio of E-51 to 2-hydroxypropionic acid and abietic acid is 1: 2; the molar ratio of the abietic acid to the 2-hydroxypropionic acid is 4: 1, the molar ratio of E-51 to maleic anhydride is 1: 0.8, the molar ratio of triethylamine to phthalic anhydride is 1.2: 1.
(2) copolymerization of aqueous epoxy ester dispersions with acrylate monomers
Adding the aqueous epoxy ester dispersion obtained in the step (1), water and an emulsifier into a four-neck flask provided with a thermometer, a condenser pipe, a stirring paddle and a constant-pressure dropping funnel according to the formula amount, starting to dropwise add an acrylic monomer and an ammonium persulfate aqueous solution when the temperature reaches 80 ℃, completing dropwise addition within 3-4 h, then preserving heat for 1.5h, cooling to below 50 ℃, neutralizing, discharging and obtaining the aqueous epoxy ester modified acrylate emulsion with the solid content of 45%.
The mass ratio (solid parts) of the aqueous epoxy ester dispersion to the acrylate monomer was 30: 70; the acrylate monomer is methyl methacrylate, styrene and butyl acrylate, wherein the methyl methacrylate accounts for 30%, the styrene accounts for 45% and the butyl acrylate accounts for 25%, the dosage of the emulsifier is 2.5% of the total weight of the acrylate monomer, the anionic emulsifier is sodium dodecyl benzene sulfonate, the nonionic emulsifier is fatty alcohol polyoxyethylene ether, and the mass ratio of the fatty alcohol polyoxyethylene ether to the sodium dodecyl benzene sulfonate is 3: 1, the dosage of the initiator is 0.5 percent of the total weight of the acrylate monomer.
The prepared emulsion was subjected to a performance test: (1) testing the drying time; coating the emulsion on wood, and standing for 20 minutes at normal temperature to dry the surface of a paint film; the paint film can be surface dried after being baked for 3 minutes at 70 ℃; (2) testing the grindability; coating the emulsion on the red oak, standing for 2 hours or baking at 70 ℃ for 5 minutes at normal temperature, and then polishing with 240-mesh abrasive paper, wherein the powder is easy to rise during polishing and the abrasive paper is not stuck; (3) testing anti-tannic acid; coating the emulsion on red oak, baking at normal temperature for 2 hours or 70 ℃ for 5 minutes, then spraying a water-based white paint, standing at normal temperature for 7 days, and testing in a high-temperature high-humidity test box for 24 hours, wherein the paint film does not turn yellow. In addition, the emulsion obtained has good thermal stability and no change after being stored for 7 days at 50 ℃.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (10)

1. A preparation method of waterborne epoxy ester modified acrylate emulsion for woodware is characterized by comprising the following steps:
adding epoxy resin, hydroxy acid and organic monobasic fatty acid, and heating to form a homogeneous phase;
adding a catalyst, and reacting at 100-180 ℃ until the acid value is less than 1 mgKOH/g;
adding a butyl acrylate monomer, and adjusting the temperature to 75-130 ℃;
adding acid anhydride, and reacting for 1-2 h;
cooling to 60-65 ℃, adding an amine neutralizer and reacting for 20-30 min;
adding water for dispersion, and adjusting the solid content to 30-40% to obtain a water-based epoxy ester dispersion;
adding the aqueous epoxy ester dispersoid, water and an emulsifier, heating, beginning to dropwise add the acrylic acid monomer and the initiator when the temperature reaches 80 ℃, finishing dropwise adding within 3-4 h, preserving the temperature for 1-3 h, cooling to below 50 ℃, and neutralizing.
2. The method for preparing the waterborne epoxy ester modified acrylate emulsion for woodware as claimed in claim 1, wherein the addition amount of the butyl acrylate monomer is 10% -20% of the total weight of the reactants in the previous step.
3. The method for preparing the waterborne epoxy ester modified acrylate emulsion for woodware according to claim 1, wherein the emulsifier is a combination of a nonionic emulsifier and an anionic emulsifier, and the mass ratio of the nonionic emulsifier to the anionic emulsifier is 3: 1-1: 3.
4. the method for preparing the waterborne epoxy ester modified acrylate emulsion for woodware as claimed in claim 3, wherein the anionic emulsifier is sodium dodecyl benzene sulfonate and the nonionic emulsifier is fatty alcohol-polyoxyethylene ether.
5. The preparation method of the waterborne epoxy ester modified acrylate emulsion for woodware according to claim 1, wherein the acrylate monomer comprises the following raw materials in percentage by mass:
25-45% of methyl methacrylate, 25-45% of styrene, 20-30% of butyl acrylate and 0-15% of butyl methacrylate.
6. The preparation method of the waterborne epoxy ester modified acrylate emulsion for woodware according to claim 1, wherein the addition amount of the catalyst is 0.5-1.5% of the total weight of the reactants in the previous step;
the total molar ratio of the epoxy resin to the hydroxy acid and the organic monobasic fatty acid is 1: and 2, the molar ratio of the hydroxy acid to the organic monobasic fatty acid is 1: 4-4: 1, the molar ratio of the epoxy resin to the acid anhydride is 1: 0.6-1: 1.5, wherein the molar ratio of the amine neutralizer to the acid anhydride is (0.8-1.2): 1.
7. the preparation method of the waterborne epoxy ester modified acrylate emulsion for woodware according to claim 1, wherein the epoxy resin is any one or more than two of E-51, E-44, E-20 and E-12;
the organic monobasic fatty acid is any one or more than two of linoleic acid, oleic acid, lauric acid, myristic acid, palmitic acid, stearic acid, abietic acid and derivatives thereof;
the hydroxy acid is any one or more than two of 2-hydroxypropionic acid, ricinoleic acid and dodecahydroxystearic acid;
the catalyst is any one or more than two of N, N-dimethylbenzylamine, tetrabutylammonium bromide and lithium neo-decanoate;
the anhydride is one or more than two of phthalic anhydride, succinic anhydride, maleic anhydride and derivatives thereof;
the amine neutralizer is one or more of triethylamine, N-dimethylethanolamine and triethanolamine.
8. The preparation method of the waterborne epoxy ester modified acrylate emulsion for woodware according to claim 1, wherein the mass ratio of the waterborne epoxy ester dispersion to the acrylate monomer is 50: 50-20: 80; the dosage of the emulsifier is 2 to 4 percent of the total weight of the acrylate monomer; the dosage of the initiator is 0.3 to 1 percent of the total weight of the acrylate monomer.
9. The preparation method of the waterborne epoxy ester modified acrylate emulsion for woodware according to claim 1, wherein the initiator is any one or more than two of dibenzoyl peroxide, azobisisobutyronitrile and ammonium persulfate.
10. The waterborne epoxy ester modified acrylate emulsion for woodware is characterized by being prepared by the preparation method of the waterborne epoxy ester modified acrylate emulsion for woodware according to any one of claims 1 to 9.
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