CN114806369B - High-solid-content water-based acrylic baking varnish and preparation method thereof - Google Patents
High-solid-content water-based acrylic baking varnish and preparation method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
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Abstract
The invention discloses a high-solid water-based acrylic baking varnish and a preparation method thereof, wherein the high-solid water-based acrylic baking varnish comprises water-based hydroxyl acrylic dispersion and N, N-dimethylethanolamine which are uniformly stirred and mixed; sequentially adding a dispersing agent, a defoaming agent, a rheological additive, rutile type titanium dioxide and deionized water, stirring, grinding the mixture, and stirring for the second time; adding the closed polyisocyanate dispersoid, the substrate wetting agent, the leveling agent, the anti-explosion auxiliary agent, the thickening agent and deionized water, stirring to control the viscosity, and filtering to obtain the high-solid-content water-based acrylic baking paint. The invention can effectively reduce the VOC content of the water-based acrylic baking varnish system, improve the solid content of the coating system, simultaneously avoid the problems of formaldehyde residue and poor compounding stability, and obtain the protective coating with excellent performance after solidification.
Description
Technical Field
The invention belongs to the technical field of paint, and particularly relates to high-solid-content water-based acrylic baking paint and a preparation method thereof.
Background
The global environmental problem is increasingly serious at present, the environment-friendly requirement of people is hardly met by the solvent type coating, and the water type coating is more and more focused and researched by the industry due to the advantages of low VOC, low odor, green environment protection and the like. The environment-friendly water-based acrylic baking paint has the advantages of high gloss, high hardness, excellent dielectric resistance, good gloss and color retention and the like, is widely applied and favored industrial baking paint, and plays a role in metal decoration and protection in industries such as household appliances, automobiles, motorcycles, medical equipment and the like.
The common water-based acrylic baking varnish on the market at present is mostly prepared from water-soluble acrylic resin and methylated amino resin, wherein the water-soluble acrylic resin is required to be added with hydrophilic cosolvent to obtain good hydrophilicity, so that the resin always contains about 20-25% of alcohol ether solvent, VOC is generally higher than 200g/L, and the resin is still not environment-friendly and has more pungent smell; meanwhile, in order to ensure the water solubility of the resin, an amine neutralizer is required to be added into a water-soluble resin system to neutralize carboxyl groups in a molecular structure into salt, most of the system is slightly alkaline, and the stability of the coating is poor after long-time storage; the hydroxyl acrylic emulsion prepared by emulsion polymerization does not contain solvent, but has poor stability when being compounded with amino resin, and is easy to break and separate out; in addition, formaldehyde is required to be added in the synthesis process of the amino resin, formaldehyde is difficult to thoroughly remove in industrial products, free formaldehyde residues are difficult to avoid, and the long-term use of the amino resin can influence the health of people.
Disclosure of Invention
The invention aims to provide a high-solid-content water-based acrylic baking paint and a preparation method thereof, which can effectively reduce the VOC content of a water-based acrylic baking paint system, avoid the problems of formaldehyde residue and poor compounding stability, improve the solid content of the coating system and obtain a protective coating with excellent performance.
The invention is realized by the following technical scheme.
In one aspect of the invention, a preparation method of a high-solid-content water-based acrylic baking varnish is provided, which comprises the following steps:
uniformly stirring and mixing 40-60 parts of aqueous hydroxy acrylic acid dispersoid and 0.2-0.5 part of N, N-dimethylethanolamine;
sequentially adding 2-4 parts of dispersing agent, 0.2-0.6 part of defoaming agent, 0.2-0.6 part of rheological additive, 15-25 parts of rutile titanium dioxide and 3-5 parts of deionized water into the mixture, continuously stirring and uniformly mixing, grinding the mixture, and then stirring for the second time;
then adding 13-21 parts of closed polyisocyanate dispersoid, 0.5-1.0 parts of substrate wetting agent, 0.2-0.6 parts of flatting agent, 0.5-0.8 parts of anti-bubbling auxiliary agent, 0.3-0.6 parts of thickening agent and 4-9 parts of deionized water, stirring the mixture to 80-90KU, and filtering the mixture to obtain the high-solid-content water-based acrylic baking paint.
Preferably, the stirring speed is 500-600r/min, and the dispersing is carried out for 5-10min; grinding the mixture until the fineness is less than or equal to 20 mu m; the secondary stirring speed is 700-800r/min.
Preferably, the aqueous hydroxyacrylic acid dispersion is prepared according to the following method:
adding 5-6 parts by mass of mixed solvent into a reaction kettle, and heating to obtain mixed solution A;
dropwise adding 24.8-30.2 parts of acrylic ester mixed monomer I into the mixed solution A, and preserving heat to obtain mixed solution B;
dropwise adding 10.4-14.3 parts of acrylic ester mixed monomer II into the mixed solution B, and preserving heat to obtain mixed solution C;
cooling the mixed solution C, adding 0.2-0.6 part of plasticizer, and preserving heat to obtain a mixed solution D;
slowly adding 1.2-2.6 parts of amine neutralizer into the mixed solution D, and preserving heat to obtain a mixed solution E;
and (3) dropwise adding 35-45 parts of deionized water into the mixed solution E at a rotating speed, preserving heat after the dropwise adding is finished, and cooling to obtain the aqueous hydroxy acrylic acid dispersoid.
Preferably, the mixed solvent is heated to 125-135 ℃ and the stirring speed is 150-220 rpm; the dripping time of the acrylate mixed monomer I is 3-4h, and the heat preservation time is 1-2h.
Preferably, the dripping time of the acrylate mixed monomer II is 1-1.5h, and the heat preservation time is 1-2h.
Preferably, the temperature of the mixed solution C is reduced to 75-83 ℃, and the plasticizer is added for heat preservation for 20-30min; adding amine neutralizer into the mixed solution D, keeping the temperature for 35-45min to obtain mixed solution E, dropwise adding deionized water into the mixed solution E at the rotating speed of 800-1200rpm for 0.5-1h, and keeping the temperature for 10-15min.
Preferably, the mixed solvent is one or a mixture of a plurality of propylene glycol butyl ether, dipropylene glycol butyl ether and dipropylene glycol dimethyl ether in any proportion.
Preferably, the plasticizer is one of dioctyl phthalate or epoxidized soybean oil.
Preferably, the amine neutralizer is one of N, N-dimethylethanolamine or triethanolamine.
Preferably, the acrylic ester mixed monomer I is methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate, N-methylene bisacrylamide, an initiator and a chain transfer agent according to the mass ratio of (9.4-15.4): (3.8-7.6): (4.4-7.2): (0.8-1.6): (0.3-0.6): (0.6-1.1): (0.4-0.6) and mixing.
Preferably, the initiator is one of tert-butyl peroxybenzoate or benzoyl peroxide;
preferably, the chain transfer agent is one of propylene glycol butyl ether, dipropylene glycol butyl ether or dipropylene glycol dimethyl ether.
Preferably, the acrylic ester mixed monomer II is methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate, N-methylene bisacrylamide, acrylic acid, an initiator and a chain transfer agent according to the mass ratio of (3.4-5.7): (1.6-3.7): (1.1-2.8): (0.2-0.7): (0.1-0.2): (0.9-1.5): (0.2-0.5): (0.2-0.3) and mixing.
Preferably, the initiator is one of tert-butyl peroxybenzoate or benzoyl peroxide.
Preferably, the chain transfer agent is one of propylene glycol butyl ether, dipropylene glycol butyl ether or dipropylene glycol dimethyl ether.
Preferably, the blocked polyisocyanate dispersion is prepared as follows:
adding 40-50 parts of isocyanate and 0.1-0.2 part of polyurethane catalyst into a reaction kettle according to the mass ratio, heating to 50 ℃, adding 17.5-25.6 parts of 3, 5-dimethylpyrazole in batches, preserving heat for 1h at 50 ℃, then dropwise adding 12.4-21.7 parts of polyether polyol within 1-2h, heating to 80-90 ℃, preserving heat for 3-4h, and cooling to obtain the closed polyisocyanate dispersoid.
Preferably, the isocyanate is one of hexamethylene diisocyanate or isophorone diisocyanate.
Preferably, the polyurethane catalyst is one of DY-12 or DY-20.
Preferably, the polyether polyol is one of YNW-4110 or 330N.
Preferably, the dispersant is one or more of di-high TEGO 750W, TEGO755W or TEGO 760W.
Preferably, the defoamer is one or more of digao TEGO810, TEGO 902W, or Pick BYK 024.
As a preferred alternative to this, the rheological aid is one or more of Pick Optigel WX or sea name humus BENTONE 38;
preferably, the substrate wetting agent is one of the digao TEGO Twain 4100 or TEGO 270.
Preferably, the leveling agent is one of Pick BYK 333 or Di high TEGO Glide 410.
Preferably, the anti-bubbling additive is one of Pick BYKETOL-WS or BYKETOL-AQ.
Preferably, the thickener is one of the sea name of the humus RHEOTLATE 299 or the DeuRheo WT-105A.
In another aspect, the invention provides the high-solid water-diversion acrylic baking varnish prepared by the method.
Due to the adoption of the technical scheme, the invention has the following characteristics and beneficial effects:
compared with the traditional water-soluble hydroxy acrylic resin, the method can effectively reduce the VOC content of the water-based acrylic baking varnish system, and the paint film has the characteristics of high hardness, high glossiness, excellent water resistance and the like by adjusting different proportions of core-shell soft and hard monomers in acrylic molecules. Meanwhile, the problems of formaldehyde residue and poor compounding stability caused by using amino resin are avoided by matching the blocked polyisocyanate dispersoid, the solid content of a coating system can reach more than 63%, and the blocked polyisocyanate dispersoid can be deblocked to release isocyanate groups at a baking temperature of 120 ℃ and react with hydroxyl groups in an acrylic component, so that the protective coating with excellent performance can be obtained.
Detailed Description
The present invention will be described in detail with reference to specific examples, wherein the exemplary embodiments and descriptions of the present invention are provided for the purpose of illustration and are not intended to be limiting.
The embodiment of the invention provides a preparation method of high-solid water-based acrylic baking varnish, which comprises the following steps:
mixing 40-60 parts of aqueous hydroxy acrylic acid dispersoid, 0.2-0.5 part of N, N-dimethylethanolamine, stirring uniformly, adding 2-4 parts of dispersing agent (one or more of Digao TEGO 750W, TEGO W or TEGO 760W), 0.2-0.6 part of defoamer (one or more of Digao TEGO810, TEGO 902W or Pick BYK 024), 0.2-0.6 part of rheological additive (one or more of Pick Optigel WX or Haimao Stokes BENTONE 38), 15-25 parts of rutile titanium dioxide and 3-5 parts of deionized water into the mixture, continuing stirring at 500-600r/min for 5-10min, uniformly mixing, grinding the mixture to fineness of less than or equal to 20 mu m, and carrying out secondary stirring at 700-800r/min. 13-21 parts of a closed polyisocyanate dispersion, 0.5-1.0 parts of a substrate wetting agent (one of Di-high TEGO Twain 4100 or TEGO 270), 0.2-0.6 parts of a leveling agent (one of Pick BYK 333 or Di-high TEGO Glide 410), 0.5-0.8 parts of an anti-bubbling aid (one of Pick BYKETOL-WS or BYKETOL-AQ), 0.3-0.6 parts of a thickener (one or more of Hai-Min-S-D RHEOTE 299 or DeuRheo WT-105A), 4-9 parts of deionized water, stirring to a viscosity of 80-90KU, and filtering to obtain the high-solid water-content acrylic baking paint.
Wherein the aqueous hydroxyacrylic acid dispersion is prepared according to the following method:
adding 5-6 parts by mass of mixed solvent (one or more of propylene glycol butyl ether, dipropylene glycol butyl ether and dipropylene glycol dimethyl ether) into a reaction kettle, heating to 125-135 ℃, and stirring at 150-220 rpm; obtaining a mixed solution A;
dropwise adding 24.8-30.2 parts of acrylic ester mixed monomer I into the mixed solution A for 3-4h, and keeping the temperature for 1-2h; obtaining a mixed solution B; the acrylic ester mixed monomer I (methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate, N-methylene bisacrylamide), an initiator (one of tert-butyl peroxybenzoate or benzoyl peroxide), a chain transfer agent (one of propylene glycol butyl ether, dipropylene glycol butyl ether or dipropylene glycol dimethyl ether) and the mass ratio (9.4-15.4): (3.8-7.6): (4.4-7.2): (0.8-1.6): (0.3-0.6): (0.6-1.1): (0.4-0.6) and mixing.
Dropwise adding 10.4-14.3 parts of acrylic ester mixed monomer II into the mixed solution B for 1-1.5h, and keeping the temperature for 1-2h to obtain mixed solution C; the acrylic ester mixed monomer II is methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate, N-methylene bisacrylamide, acrylic acid, an initiator (one of tert-butyl peroxybenzoate or benzoyl peroxide), a chain transfer agent (one of propylene glycol butyl ether, dipropylene glycol butyl ether or dipropylene glycol dimethyl ether) according to the mass ratio of (3.4-5.7): (1.6-3.7): (1.1-2.8): (0.2-0.7): (0.1-0.2): (0.9-1.5): (0.2-0.5): (0.2-0.3) and mixing.
Cooling the mixed solution C to 75-83 ℃, adding 0.2-0.6 part of plasticizer (dioctyl phthalate or epoxidized soybean oil), and preserving heat for 20-30min to obtain a mixed solution D;
slowly adding 1.2-2.6 parts of amine neutralizer (one of N, N-dimethylethanolamine or triethanolamine) into the mixed solution D, and preserving heat for 35-45min to obtain a mixed solution E;
and (3) dropwise adding 35-45 parts of deionized water into the mixed solution E at the rotating speed of 800-1200rpm for 0.5-1h, preserving heat for 10-15min, preserving heat after the dropwise adding is finished, and cooling to obtain the aqueous hydroxy acrylic acid dispersoid.
Wherein the blocked polyisocyanate dispersion is prepared according to the following method:
adding 40-50 parts by mass of isocyanate (one of hexamethylene diisocyanate or isophorone diisocyanate) and 0.1-0.2 part by mass of polyurethane catalyst (one of DY-12 or DY-20) into a reaction kettle, heating to 50 ℃, adding 17.5-25.6 parts by mass of 3, 5-dimethylpyrazole, preserving heat for 1h at 50 ℃, then dropwise adding 12.4-21.7 parts by mass of polyether polyol (one of YNW-4110 or 330N) within 1-2h, heating to 80-90 ℃, preserving heat for 3-4h, and cooling to obtain the closed polyisocyanate dispersoid.
The invention is further illustrated by the following specific examples.
Example 1
1) Preparation of aqueous hydroxyacrylic acid dispersion:
adding 5 parts by mass of propylene glycol butyl ether into a reaction kettle, heating to 130 ℃, and stirring and dispersing at 200rpm; obtaining a mixed solution A;
28.7 parts of acrylic ester mixed monomer I is dropwise added into the mixed solution A, the dropwise adding time is 4 hours, and the heat preservation time is 1.5 hours; obtaining a mixed solution B; the acrylic ester mixed monomer I is prepared by mixing methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate, N-methylene bisacrylamide, benzoyl peroxide and propylene glycol butyl ether according to the mass ratio (12.6:5.8:6.9:1.6:0.3:1.0:0.5).
11.3 parts of acrylic ester mixed monomer II is dropwise added into the mixed solution B for 1h, and the heat preservation time is 1.5h, so as to obtain mixed solution C; the acrylic ester mixed monomer II is prepared by mixing methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate, N-methylene bisacrylamide, acrylic acid, benzoyl peroxide and propylene glycol butyl ether according to the mass ratio of (4.6:2.6:1.7:0.2:0.1:1.5:0.4:0.2).
Cooling the mixed solution C to 80 ℃, adding 0.6 part of epoxidized soybean oil, and preserving heat for 25min to obtain a mixed solution D;
slowly adding 2.6 parts of triethanolamine into the mixed solution D, and preserving heat for 40min to obtain a mixed solution E;
and (3) dropwise adding 42 parts of deionized water into the mixed solution E at the rotating speed of 1000rpm for 0.5h, preserving heat for 12min, preserving heat after the dropwise adding is finished, and cooling to obtain the aqueous hydroxy acrylic acid dispersoid.
2) Preparing a blocked polyisocyanate dispersion:
adding 43 parts of hexamethylene diisocyanate and 0.1 part of DY-12 in mass ratio into a reaction kettle, heating to 50 ℃, adding 20.5 parts of 3, 5-dimethylpyrazole in batches, preserving heat for 1h at 50 ℃, then dropwise adding 16.7 parts of polyether polyol YNW-4110 in 2h, heating to 80 ℃, preserving heat for 4h, and cooling to obtain the closed polyisocyanate dispersoid.
3) Preparing high-solid water-based acrylic baking paint:
mixing 48 parts of aqueous hydroxy acrylic acid dispersoid and 0.3 part of N, N-dimethylethanolamine in a mass ratio, stirring uniformly, sequentially adding 3 parts of Di-high TEGO 750W, 0.2 part of Di-high TEGO810, 0.4 part of Pick-Optigel WX, 20 parts of rutile type titanium dioxide and 3 parts of deionized water into the mixture, continuously stirring at a speed of 500r/min, dispersing for 8min, uniformly mixing, grinding the mixture until the fineness is less than or equal to 20 mu m, and carrying out secondary stirring at a secondary stirring speed of 700r/min. Then 17 parts of closed polyisocyanate dispersoid, 0.7 part of Di-high TEGO Twain 4100, 0.4 part of Pick BYK 333, 0.5 part of Pick BYKETOL-WS, 0.5 part of Hai Min Style RHEOTAE 299 and 6 parts of deionized water are added, the mixture is stirred to have the viscosity of 90KU, and the mixture is filtered to obtain the high-solid water-based acrylic baking paint.
Example 2
1) Preparation of aqueous hydroxyacrylic acid dispersion:
adding a mixture of 3 parts of dipropylene glycol butyl ether and 3 parts of dipropylene glycol dimethyl ether in a mass ratio into a reaction kettle, heating to 125 ℃, and stirring and dispersing at 180rpm; obtaining a mixed solution A;
29.6 parts of acrylic ester mixed monomer I is dropwise added into the mixed solution A, the dropwise adding time is 3 hours, and the heat preservation time is 1 hour; obtaining a mixed solution B; the acrylic ester mixed monomer I is prepared by mixing methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate, N-methylene bisacrylamide, tert-butyl peroxybenzoate and dipropylene glycol butyl ether according to the mass ratio (14.7:7.0:4.4:1.3:0.6:1.1:0.5).
Dropwise adding 14.1 parts of acrylic ester mixed monomer II into the mixed solution B for 1h, and keeping the temperature for 1h to obtain mixed solution C; the acrylic ester mixed monomer II is prepared by mixing methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate, N-methylene bisacrylamide, acrylic acid, tert-butyl peroxybenzoate and dipropylene glycol butyl ether according to the mass ratio of (5.7:3.7:2.2:0.7:0.2:0.9:0.5:0.2).
Cooling the mixed solution C to 83 ℃, adding 0.2 part of dioctyl phthalate, and preserving the heat for 30min to obtain a mixed solution D;
slowly adding 2.6 parts of N, N-dimethylethanolamine into the mixed solution D, and preserving the heat for 35min to obtain a mixed solution E;
and (3) dropwise adding 45 parts of deionized water into the mixed solution E at the speed of 1200rpm for 1h, preserving heat for 15min, preserving heat after the dropwise adding is finished, and cooling to obtain the aqueous hydroxy acrylic acid dispersoid.
2) Preparing a blocked polyisocyanate dispersion:
50 parts of isophorone diisocyanate and 0.2 part of DY-20 in mass ratio are added into a reaction kettle, the temperature is raised to 50 ℃, 23.6 parts of 3, 5-dimethylpyrazole is added in batches, the temperature is kept at 50 ℃ for 1h, 17.4 parts of polyether polyol 330N is dropwise added in 1h, the temperature is raised to 80 ℃, the temperature is kept for 4h, and the temperature is reduced, so that the closed polyisocyanate dispersoid is obtained.
3) Preparing high-solid water-based acrylic baking paint:
the preparation method comprises the steps of uniformly stirring and mixing 40 parts of aqueous hydroxyl acrylic acid dispersoid and 0.2 part of N, N-dimethylethanolamine in a mass ratio, sequentially adding 2 parts of diGao TEGO 750W, 2 parts of diGao TEGO755W, 0.1 part of diGao TEGO810, 0.2 part of diGao TEGO 902W, 0.3 part of Pick Optigel WX, 0.3 part of Hai-Ming Style BENTONE 38, 25 parts of rutile type titanium dioxide and 5 parts of deionized water, dispersing for 10min, uniformly mixing, grinding the mixture until the fineness is less than or equal to 20 mu m, and carrying out secondary stirring at a secondary stirring speed of 800r/min. Then adding 13 parts of closed polyisocyanate dispersoid, 0.5 part of Di-high TEGO Twain 4100, 0.5 part of Di-high TEGO 270, 0.5 part of Pick BYK 333, 0.8 part of Pick BYKETOL-AQ, 0.3 part of Hai-Min Style RHEOTAE 299, 0.3 part of Hai-Min Style DeuRheo WT-105A and 9 parts of deionized water, stirring the mixture to have the viscosity of 80KU, and filtering to obtain the high-solid water-based acrylic baking paint.
Example 3
1) Preparation of aqueous hydroxyacrylic acid dispersion:
adding 5 parts by mass of dipropylene glycol dimethyl ether serving as a mixed solvent into a reaction kettle, heating to 135 ℃, and stirring and dispersing at 150rpm; obtaining a mixed solution A;
dropwise adding 30.2 parts of acrylic ester mixed monomer I into the mixed solution A for 3.5 hours, and keeping the temperature for 2 hours; obtaining a mixed solution B; the acrylic ester mixed monomer I is prepared by mixing methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate, N-methylene bisacrylamide, benzoyl peroxide and dipropylene glycol dimethyl ether according to the mass ratio (13.2:7.6:6.6:0.8:0.5:0.9:0.6).
11.2 parts of acrylic ester mixed monomer II is dropwise added into the mixed solution B for 1.5 hours and the heat preservation time is 2 hours, so as to obtain mixed solution C; the acrylic ester mixed monomer II is prepared by mixing methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate, N-methylene bisacrylamide, acrylic acid, benzoyl peroxide and dipropylene glycol dimethyl ether according to the mass ratio of (3.4:2.9:2.7:0.2:0.2:1.2:0.3:0.3).
Cooling the mixed solution C to 83 ℃, adding 0.5 part of epoxidized soybean oil, and preserving heat for 20min to obtain a mixed solution D;
slowly adding 1.2 parts of N, N-dimethylethanolamine into the mixed solution D, and preserving the heat for 45min to obtain a mixed solution E;
and (3) dropwise adding 38 parts of deionized water into the mixed solution E at the speed of 800rpm for 1h, preserving heat for 15min, preserving heat after the dropwise adding is finished, and cooling to obtain the aqueous hydroxy acrylic acid dispersoid.
2) Preparing a blocked polyisocyanate dispersion:
adding 45 parts of hexamethylene diisocyanate and 0.2 part of DY-12 into a reaction kettle according to the mass ratio, heating to 50 ℃, adding 25.6 parts of 3, 5-dimethylpyrazole in batches, preserving heat for 1h at 50 ℃, then dropwise adding 21.7 parts of polyether polyol 330N within 1.5h, heating to 85 ℃, preserving heat for 3.5h, and cooling to obtain the closed polyisocyanate dispersoid.
3) Preparing high-solid water-based acrylic baking paint:
50 parts of aqueous hydroxy acrylic acid dispersoid and 0.4 part of N, N-dimethylethanolamine are stirred and mixed uniformly, 2 parts of Di-Gao TEGO755W, 0.2 part of Di-Gao TEGO810, 0.2 part of Pick BYK 024, 0.3 part of rheological additive Pick Optigel WX, 15 parts of rutile type titanium dioxide and 3 parts of deionized water are added into the mixture in sequence, the stirring speed is 600r/min, the dispersion is 7min, the mixture is uniformly mixed, the mixture is ground until the fineness is less than or equal to 20 mu m, secondary stirring is carried out, and the secondary stirring speed is 750r/min. Then 21 parts of closed polyisocyanate dispersoid, 0.5 part of Di-high TEGO Twain 4100, 0.3 part of Di-high TEGO Glide 410, 0.6 part of Pick BYKETOL-AQ, 0.5 part of Hai-Ming Style RHEOTATE 299 and 6 parts of deionized water are added, the mixture is stirred to a viscosity of 85KU, and the mixture is filtered to obtain the high-solid water-based acrylic baking paint.
Example 4
1) Preparation of aqueous hydroxyacrylic acid dispersion:
adding a mixture of 3 parts of propylene glycol butyl ether and 2 parts of dipropylene glycol butyl ether in a mass ratio into a reaction kettle, heating to 125 ℃, and stirring and dispersing at 170rpm; obtaining a mixed solution A;
34.3 parts of acrylic ester mixed monomer I is dropwise added into the mixed solution A, the dropwise adding time is 4 hours, and the heat preservation time is 1 hour; obtaining a mixed solution B; the acrylic ester mixed monomer I is prepared by mixing methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate, N-methylene bisacrylamide, tert-butyl peroxybenzoate and propylene glycol butyl ether according to the mass ratio of (15.4:3.8:7.2:1.2:0.6:0.6:0.5).
Dropwise adding 10.4 parts of acrylic ester mixed monomer II into the mixed solution B for 1h and keeping the temperature for 2h to obtain mixed solution C; the acrylic ester mixed monomer II is prepared by mixing methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate, N-methylene bisacrylamide, acrylic acid, tert-butyl peroxybenzoate and propylene glycol butyl ether according to the mass ratio of (5.5:1.6:1.1:0.3:0.2:1.3:0.2:0.2).
Cooling the mixed solution C to 78 ℃, adding 0.3 part of dioctyl phthalate, and preserving the heat for 30min to obtain a mixed solution D;
slowly adding 2.4 parts of triethanolamine into the mixed solution D, and preserving heat for 45min to obtain a mixed solution E;
and (3) dropwise adding 35 parts of deionized water into the mixed solution E at the speed of 900rpm for 0.5h, preserving heat for 15min, preserving heat after the dropwise adding is finished, and cooling to obtain the aqueous hydroxy acrylic acid dispersoid.
2) Preparing a blocked polyisocyanate dispersion:
adding 42 parts of hexamethylene diisocyanate and 0.1 part of DY-20 in mass ratio into a reaction kettle, heating to 50 ℃, adding 17.5 parts of 3, 5-dimethylpyrazole in batches, preserving heat for 1h at 50 ℃, then dropwise adding 12.4 parts of polyether polyol YNW-4110 in 2h, heating to 80 ℃, preserving heat for 3.5h, and cooling to obtain the closed polyisocyanate dispersoid.
3) Preparing high-solid water-based acrylic baking paint:
60 parts of aqueous hydroxy acrylic acid dispersoid and 0.5 part of N, N-dimethylethanolamine are stirred and mixed uniformly, 1 part of Di-high TEGO 750W, 1 part of Di-high TEGO760W, 0.3 part of Di-high TEGO 902W, 0.2 part of Pick Optigel WX, 15 parts of rutile type titanium dioxide and 3 parts of deionized water are added into the mixture in sequence, the stirring speed is 500r/min continuously, the dispersion is 5min, the mixture is uniformly mixed, the mixture is ground until the fineness is less than or equal to 20 mu m, secondary stirring is carried out, and the secondary stirring speed is 800r/min. 13 parts of closed polyisocyanate dispersoid, 0.8 part of DigaTEGO 270, 0.2 part of Pick BYK 333, 0.7 part of Pick BYKETOL-AQ, 0.3 part of sea name Qingdan RHEOTAE 299 and 4 parts of deionized water are added, the mixture is stirred to have the viscosity of 85KU, and the mixture is filtered to obtain the high-solid water-based acrylic baking paint.
Example 5
1) Preparation of aqueous hydroxyacrylic acid dispersion:
adding 5 parts of dipropylene glycol butyl ether into a reaction kettle according to the mass ratio, heating to 130 ℃, and stirring and dispersing at 220rpm; obtaining a mixed solution A;
29.8 parts of acrylic ester mixed monomer I is dropwise added into the mixed solution A, the dropwise adding time is 3 hours, and the heat preservation time is 1.5 hours; obtaining a mixed solution B; the acrylic ester mixed monomer I is prepared by mixing methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate, N-methylene bisacrylamide, benzoyl peroxide and dipropylene glycol butyl ether according to the mass ratio (9.4:6.4:5.8:1.4:0.5:0.9:0.4).
Dropwise adding 14.3 parts of acrylic ester mixed monomer II into the mixed solution B for 1.5h and keeping the temperature for 2h to obtain mixed solution C; the acrylic ester mixed monomer II is prepared by mixing methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate, N-methylene bisacrylamide, acrylic acid, benzoyl peroxide and dipropylene glycol butyl ether according to the mass ratio of (5.7:3.2:2.8:0.7:0.2:1.1:0.4:0.2).
Cooling the mixed solution C to 77 ℃, adding 0.4 part of epoxidized soybean oil, and preserving heat for 20min to obtain a mixed solution D;
slowly adding 2.1 parts of triethanolamine into the mixed solution D, and preserving heat for 35min to obtain a mixed solution E;
and (3) dropwise adding 40 parts of deionized water into the mixed solution E at the rotating speed of 1100rpm for 1h, preserving heat for 12min, preserving heat after the dropwise adding is finished, and cooling to obtain the aqueous hydroxy acrylic acid dispersoid.
2) Preparing a blocked polyisocyanate dispersion:
adding 44 parts of isophorone diisocyanate and 0.1 part of DY-12 in mass ratio into a reaction kettle, heating to 50 ℃, adding 19.8 parts of 3, 5-dimethylpyrazole in batches, preserving heat for 1h at 50 ℃, then dropwise adding 19.2 parts of polyether polyol 330N in 1h, heating to 90 ℃, preserving heat for 4h, and cooling to obtain the closed polyisocyanate dispersoid.
3) Preparing high-solid water-based acrylic baking paint:
52 parts of aqueous hydroxy acrylic acid dispersoid and 0.4 part of N, N-dimethylethanolamine in mass ratio are stirred and mixed uniformly, 3 parts of Digao TEGO760W, 0.3 part of Digao TEGO810, 0.3 part of Pick BYK 024, 0.5 part of Hai Minder BENTONE 38, 17 parts of rutile type titanium pigment and 4 parts of deionized water are added into the mixture in sequence, the stirring speed is 600r/min, the dispersion is 9min, the mixture is uniformly mixed, the fineness is less than or equal to 20 mu m, the mixture is ground, and secondary stirring is carried out, wherein the secondary stirring speed is 700r/min. Then adding 15 parts of closed polyisocyanate dispersoid, 0.8 part of Di-high TEGO Twain 4100, 0.6 part of Pick BYK 333, 0.6 part of Pick BYKETOL-AQ, 0.3 part of Hai-Min Style RHEOTAE 299, 0.2 part of Hai-Min Style DeuRheo WT-105A and 5 parts of deionized water, stirring the mixture to have the viscosity of 90KU, and filtering the mixture to obtain the high-solid water-based acrylic baking paint.
High solids aqueous acrylic stoving enamels were prepared according to examples 1 to 5, and the solid content, voc content and heat storage stability at 50 ℃ of the paints, and gloss, hardness, flexibility, adhesion, intercoat adhesion, salt spray resistance and xenon lamp artificial aging resistance of the coating films were each tested, and the test results are shown in table 1.
Table 15 group of detection results of high-solid-content water-based acrylic baking varnish
As can be seen from the detection results, the high-solid-content water-based acrylic baking varnish prepared by the embodiment of the invention has higher solid content, and the mass solid content can be up to not lower than 63%; and the storage stability is excellent, the VOC content of the aqueous acrylic baking varnish system can be effectively reduced, and the VOC content is not higher than 80g/L. The prepared paint film has excellent performances, avoids the problems of formaldehyde residue and poor compounding stability, and obtains the protective coating with excellent performances. Therefore, the invention has great economic value and environmental protection value, and is more suitable for popularization and application.
Finally, it should be noted that the foregoing description is only a preferred embodiment of the present invention, and not intended to limit the invention, but while the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of the technical features thereof. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. The preparation method of the high-solid water-based acrylic baking paint is characterized by comprising the following steps of:
uniformly stirring and mixing 40-60 parts of aqueous hydroxy acrylic acid dispersoid and 0.2-0.5 part of N, N-dimethylethanolamine;
sequentially adding 2-4 parts of dispersing agent, 0.2-0.6 part of defoaming agent, 0.2-0.6 part of rheological additive, 15-25 parts of rutile titanium dioxide and 3-5 parts of deionized water into the mixture, continuously stirring and uniformly mixing, grinding the mixture, and then stirring for the second time;
then adding 13-21 parts of closed polyisocyanate dispersoid, 0.5-1.0 part of substrate wetting agent, 0.2-0.6 part of flatting agent, 0.5-0.8 part of anti-bubbling auxiliary agent, 0.3-0.6 part of thickening agent and 4-9 parts of deionized water, stirring the mixture to 80-90KU, and filtering the mixture to obtain the high-solid-content water-based acrylic baking paint;
the aqueous hydroxyacrylic acid dispersion is prepared according to the following method:
adding 5-6 parts by mass of mixed solvent into a reaction kettle, and heating to obtain mixed solution A;
the mixed solvent is one or a mixture of a plurality of propylene glycol butyl ether, dipropylene glycol butyl ether and dipropylene glycol dimethyl ether in any proportion;
dropwise adding 24.8-30.2 parts of acrylic ester mixed monomer I into the mixed solution A, and preserving heat to obtain mixed solution B;
the acrylic ester mixed monomer I is methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate, N-methylene bisacrylamide, an initiator and a chain transfer agent according to the mass ratio of (9.4-15.4): (3.8-7.6): (4.4-7.2): (0.8-1.6): (0.3-0.6): (0.6-1.1): (0.4-0.6) and mixing;
the initiator is one of tert-butyl peroxybenzoate or benzoyl peroxide;
the chain transfer agent is one of propylene glycol butyl ether, dipropylene glycol butyl ether or dipropylene glycol dimethyl ether;
dropwise adding 10.4-14.3 parts of acrylic ester mixed monomer II into the mixed solution B, and preserving heat to obtain mixed solution C;
the acrylic ester mixed monomer II is methyl methacrylate, butyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate, N-methylene bisacrylamide, acrylic acid, an initiator and a chain transfer agent according to the mass ratio of (3.4-5.7): (1.6-3.7): (1.1-2.8): (0.2-0.7): (0.1-0.2): (0.9-1.5): (0.2-0.5): (0.2-0.3) and mixing;
the initiator is one of tert-butyl peroxybenzoate or benzoyl peroxide;
the chain transfer agent is one of propylene glycol butyl ether, dipropylene glycol butyl ether or dipropylene glycol dimethyl ether;
cooling the mixed solution C, adding 0.2-0.6 part of plasticizer, and preserving heat to obtain a mixed solution D;
the plasticizer is one of dioctyl phthalate or epoxidized soybean oil;
slowly adding 1.2-2.6 parts of amine neutralizer into the mixed solution D, and preserving heat to obtain a mixed solution E;
the amine neutralizer is one of N, N-dimethylethanolamine or triethanolamine;
dropwise adding 35-45 parts of deionized water into the mixed solution E at a rotating speed, preserving heat after the dropwise adding is finished, and cooling to obtain a water-based hydroxy acrylic acid dispersion;
the blocked polyisocyanate dispersion was prepared as follows:
adding 40-50 parts of isocyanate and 0.1-0.2 part of polyurethane catalyst into a reaction kettle according to the mass ratio, heating to 50 ℃, adding 17.5-25.6 parts of 3, 5-dimethylpyrazole in batches, preserving heat for 1h at 50 ℃, then dropwise adding 12.4-21.7 parts of polyether polyol within 1-2h, heating to 80-90 ℃, preserving heat for 3-4h, and cooling to obtain a closed polyisocyanate dispersion;
the isocyanate is one of hexamethylene diisocyanate or isophorone diisocyanate;
the polyurethane catalyst is one of DY-12 or DY-20;
the polyether polyol is one of YNW-4110 or 330N;
the VOC content of the aqueous acrylic baking varnish system is reduced by adopting a process combining core-shell emulsion polymerization and soap-free emulsion polymerization to synthesize aqueous hydroxy acrylic dispersion, wherein the VOC content is not higher than 80g/L; the mass solids of the aqueous acrylic baking varnish reaches more than 63%.
2. The method for preparing the high-solid aqueous acrylic baking varnish according to claim 1, wherein the stirring speed is 500-600r/min, and the dispersing is 5-10min; grinding the mixture until the fineness is less than or equal to 20 mu m; the secondary stirring speed is 700-800r/min.
3. The method for preparing a high-solid aqueous acrylic baking varnish according to claim 1, wherein the mixed solvent is heated to 125-135 ℃ and the stirring speed is 150-220 rpm; the dripping time of the acrylic ester mixed monomer I is 3-4h, and the heat preservation time is 1-2h;
the dripping time of the acrylic ester mixed monomer II is 1-1.5h, and the heat preservation time is 1-2h;
cooling the mixed solution C to 75-83 ℃, adding a plasticizer, and preserving heat for 20-30min; adding amine neutralizer into the mixed solution D, keeping the temperature for 35-45min to obtain mixed solution E, dropwise adding deionized water into the mixed solution E at the rotating speed of 800-1200rpm for 0.5-1h, and keeping the temperature for 10-15min.
4. The method for preparing a high solids aqueous acrylic baking varnish according to claim 1, wherein the dispersant is one or more of di-high TEGO 750W, TEGO755W or TEGO 760W;
the defoamer is one or more of digao TEGO810, TEGO 902W or Pick BYK 024;
the rheological aid is one or more of Pick Optigel WX or sea name humus BENTONE 38;
the substrate wetting agent is one of Digao TEGO Twain 4100 or TEGO 270;
the leveling agent is one of Pick BYK 333 or Di-high TEGO Glide 410;
the anti-explosion auxiliary agent is one of Pick BYKETOL-WS or BYKETOL-AQ;
the thickener is one of the sea name of RHEOLATE299 or DeuRheo WT-105A.
5. A high solids, water-borne acrylic baking finish prepared by the method of any one of claims 1-4.
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| CN116023642A (en) * | 2022-12-07 | 2023-04-28 | 清远高新华园科技协同创新研究院有限公司 | A kind of non-ionic double bond monomer and its prepared waterborne acrylic acid polymer and application |
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