CN113897109A - Diatomite grafted polyurea modified humidity-regulating water-based acrylic coating and preparation method thereof - Google Patents

Diatomite grafted polyurea modified humidity-regulating water-based acrylic coating and preparation method thereof Download PDF

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CN113897109A
CN113897109A CN202111425514.8A CN202111425514A CN113897109A CN 113897109 A CN113897109 A CN 113897109A CN 202111425514 A CN202111425514 A CN 202111425514A CN 113897109 A CN113897109 A CN 113897109A
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diatomite
water
polyurea
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雷小娜
彭鸥
李哲
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Shenzhen Wujing Trading Co ltd
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular

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Abstract

The invention relates to the technical field of coatings, in particular to a diatomite-grafted polyurea modified humidity-regulating water-based acrylic coating, wherein the diatomite subjected to organic modification has very good dispersibility in the water-based acrylic coating, has a good pore structure and abundant pores, is dispersed in a water-based acrylic matrix, can improve the pore structure of water-based acrylic and forms communicated channels and gaps, absorbs water through capillary action, provides a 'channel' for water to enter and exit for the coating film, keeps good water and air permeability, on a macroscopic level, the moisture absorption and release speed of the coating film is improved, a space is provided for the expansion of the water-based acrylic resin, the phenomena of deformation and the like caused by water absorption of the water-based acrylic resin are weakened, and the introduced carbamido is under the action of multiple hydrogen bonds between adjacent molecules, thereby improving the mechanical property of the water-based acrylic resin and obtaining the humidity-controlling water-based acrylic coating with excellent comprehensive performance.

Description

Diatomite grafted polyurea modified humidity-regulating water-based acrylic coating and preparation method thereof
Technical Field
The invention relates to the technical field of coatings, and particularly relates to a diatomite-grafted polyurea modified humidity-regulating water-based acrylic coating and a preparation method thereof.
Background
The acrylic coating is a single-component self-drying coating obtained by adding various additives and auxiliaries on the basis of acrylic resin, has good weather resistance and color retention, is convenient to construct, is a common decorative coating, can be used on the surfaces of substances such as walls, bricks and stones, wood, plastics and the like, and has good adhesive force, and the humidity-regulating acrylic resin coating is a coating with a humidity regulating function, has the characteristics of moisture absorption and release, and can not generate the phenomena of foaming, falling, wall deformation and the like after a coating absorbs water, so that the moisture-absorbing acrylic coating not only needs good moisture absorption and release performance, but also needs good moisture resistance and stability.
Because the diatomite has rich pore structures and has the characteristics of good moisture absorption and desorption, fire prevention, flame retardance and the like, the diatomite is often used as an inorganic filler to enhance the performance of organic coatings, since the humidity-controlling water-based acrylic resin has high water absorption, it is necessary to modify the resin to prevent problems such as foaming and deformation due to water absorption, therefore, the diatomite with excellent performance, rich surface pore channels and good moisture absorption and desorption performance is a very good inorganic filler of the water-based acrylic resin, but the inorganic material is generally poor in compatibility with an organic matrix and poor in modification effect by simple addition, the multiple hydrogen bonds not only do not have great influence on the water absorption of the coating, but also can improve the performance of the coating, therefore, the organic modification of the diatomite through the grafted polyurea can not only enhance the dispersibility of the diatomite in the acrylic resin, but also increase the stability of the coating, thereby achieving a better modification effect.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides the diatomite-grafted polyurea modified humidity-regulating water-based acrylic coating and the preparation method thereof, and solves the problems that the common water-based acrylic resin is easy to foam and deform when absorbing water and the compatibility of diatomite and the water-based acrylic resin is poor.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the diatomite-grafted polyurea modified humidity-regulating water-based acrylic coating comprises the following steps:
(1) adding diatomite and gamma-glycidyl ether oxypropyltrimethoxysilane into a toluene solvent, mixing, and carrying out ultrasonic reaction to obtain epoxy modified diatomite;
(2) soaking epoxy modified diatomite into p-aminobenzaldehyde, adding the p-aminobenzaldehyde into a three-neck flask, heating to perform an epoxy ring-opening reaction, after the reaction is finished, filtering, washing with deionized water, and drying by blasting to obtain aldehyde-based diatomite;
(3) adding aldehyde diatomite and 3-amino-1-adamantanol into a methanol solution, heating and refluxing in a nitrogen atmosphere to perform Schiff base reaction, cooling after the reaction is finished, adding sodium borohydride, stirring for reaction and reduction of the Schiff base, washing with hydrochloric acid and deionized water, and performing vacuum drying to obtain adamantanol modified diatomite;
(4) adding amine-terminated polyether and isophorone diisocyanate into an acetone solution, heating for polymerization reaction, and carrying out isocyanate-terminated polyurea oligomer;
(5) adding adamantane alcohol modified diatomite and a polyurea oligomer into a dimethyl sulfoxide solution, then dropwise adding dibutyltin dilaurate, heating for addition reaction, naturally cooling, carrying out suction filtration, washing with deionized water, and carrying out vacuum drying to obtain an adamantane modified diatomite grafted polyurea oligomer;
(6) deionized water and NaHCO3Adding sodium dodecyl sulfate and tween 20 into a reaction bottle, stirring and emulsifying, heating, adding a mixed solution of adamantane modified diatomite graft polyurea oligomer, acrylic acid, methyl methacrylate, n-butyl acrylate, diketone bisacrylamide and potassium persulfate, preserving heat for polymerization reaction, naturally cooling, filtering and discharging, and adjusting the pH value to 7-8 by using ammonia water to obtain diatomite graft polyurea modified aqueous acrylic emulsion;
(7) adding water, pigment filler, pigment dispersant polyethylene glycol 400, a flatting agent 1, 2-propylene glycol, a defoaming agent tributyl phosphate, a diatomite grafted polyurea modified aqueous acrylic emulsion, a film-forming auxiliary agent alcohol ester twelve, a thickening agent hydroxyethyl cellulose and a pH regulator ammonia water into a dispersing and grinding machine in sequence, and mixing to obtain the diatomite grafted polyurea modified humidity-regulating aqueous acrylic coating.
Preferably, the temperature of the epoxy ring-opening reaction in the step (2) is 120-150 ℃, and the reaction time is 5-7 h.
Preferably, the mass ratio of the aldehyde diatomite to the 3-amino-1-adamantanol in the step (3) is 100: 20-60.
Preferably, the temperature of the Schiff base reaction in the step (3) is 60-80 ℃, and the reaction time is 8-12 h.
Preferably, the mass ratio of the adamantanol-modified diatomaceous earth, the polyurea oligomer and the dibutyltin dilaurate in the step (5) is 100:500-800: 0.5-2.
Preferably, the reaction temperature in the step (5) is 60-90 ℃, and the reaction time is 1-3 h.
Preferably, in the step (6), methyl methacrylate, n-butyl acrylate, acrylic acid, diketone bisacrylamide, adamantane-modified diatomite-grafted polyurea oligomer and NaHCO are adopted3The mass ratio of the sodium dodecyl sulfate to the tween-20 to the potassium persulfate is 100:30-50:1-3:6-10:7-14:0.1-0.2:1.5-2.5:1.5-2.5: 0.3-0.7.
Preferably, the temperature of the polymerization reaction in the step (6) is 70-90 ℃ and the time is 3-6 h.
Preferably, in the step (7), the mass ratio of the diatomite grafted polyurea modified water-based acrylic emulsion to the leveling agent 1, 2-propylene glycol to the defoamer tributyl phosphate to the film forming auxiliary agent alcohol ester twelve to the thickener hydroxyethyl cellulose to the pH regulator ammonia water is 100:0.1-1:0.1-1:3-5: 2-5.
(III) advantageous technical effects
Compared with the prior art, the invention has the following experimental principles and beneficial technical effects:
the diatomite-grafted polyurea modified humidity-regulating water-based acrylic coating is prepared by performing epoxidation modification on diatomite by KH560, performing epoxy ring-opening reaction on the diatomite and amino on p-aminobenzaldehyde, performing Schiff base reaction on aldehyde group at the other end of the diatomite and amino on adamantane, adding sodium borohydride to reduce Schiff base to obtain adamantane alcohol modified diatomite, heating amino-terminated polyether and isophorone diisocyanate to perform polymerization reaction to obtain isocyanate-terminated polyurea oligomer, performing reaction on hydroxyl on the adamantane alcohol modified diatomite and terminal isocyanate group of the polyurea oligomer to obtain adamantane modified diatomite-grafted polyurea oligomer, adding the adamantane modified diatomite-polyurea oligomer and an acrylic monomer into a reaction bottle, emulsifying, performing acrylic polymerization to obtain diatomite-grafted polyurea modified water-based acrylic emulsion, and finally adding an additive to obtain the diatomite-grafted polyurea modified humidity-regulating water-based acrylic coating, the organic modified diatomite has good dispersibility in the water-based acrylic coating, and has a good pore structure and rich pores, so that the diatomite is dispersed in a water-based acrylic matrix as an inorganic filler, the pore structure of the water-based acrylic can be improved, communicated channels and pores are formed, water is adsorbed by capillary action, a channel for water to enter and exit is provided for a coating film, good water permeability and air permeability are maintained, the moisture absorption and moisture release speed of the coating film is improved on a macroscopic level, and meanwhile, due to the existence of the pore structure, a space is provided for the expansion of the water-based acrylic resin, and the phenomena of deformation and the like caused by water absorption of the water-based acrylic resin are reduced.
The diatomite grafted polyurea modified humidity-regulating water-based acrylic coating has the advantages that the humidity resistance of the water-based acrylic coating is improved due to the introduction of adamantane with a stable structure and good moisture resistance, the stability of the water-based acrylic coating is improved, meanwhile, a large number of urea bonds, allophanate bonds and the like exist due to the introduction of polyurea molecular chains, hydrogen bonds can be formed with carbonyl carbon on water-based acrylic, the mechanical property of the water-based acrylic resin is improved under the action of multiple hydrogen bonds between adjacent molecules, the water-based acrylic resin is more stable, the moisture absorption and release properties of the coating are further improved due to the existence of a large number of hydrogen bonds due to the fact that water is mainly transmitted in the moisture absorption coating in a hydrogen bond exchange mode, and the foaming phenomenon caused by the relative deformation of a stable hydrophobic layer and a water-swelling surface layer can not occur due to the fact that the water-based acrylic resin is not hydrophobic, has better water resistance and stability.
Drawings
FIG. 1 is a reaction formula for the synthesis of an aldehydized diatomaceous earth;
FIG. 2 is a reaction formula for the synthesis of adamantanol modified diatomaceous earth;
FIG. 3 is a reaction scheme for the synthesis of adamantane-modified diatomaceous earth-grafted polyurea oligomers.
Detailed Description
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the diatomite-grafted polyurea modified humidity-regulating water-based acrylic coating comprises the following steps:
(1) adding diatomite and gamma-glycidyl ether oxypropyltrimethoxysilane into a toluene solvent, mixing, and carrying out ultrasonic reaction to obtain epoxy modified diatomite;
(2) soaking epoxy modified diatomite into p-aminobenzaldehyde, adding the epoxy modified diatomite into a three-neck flask, heating to 120-150 ℃, reacting for 5-7h, filtering after the reaction is finished, washing with deionized water, and drying by air blasting to obtain aldehyde-based diatomite;
(3) adding aldehyde diatomite and 3-amino-1-adamantanol in a mass ratio of 100:20-60 into a methanol solution, heating and refluxing at 60-80 ℃ in a nitrogen atmosphere, reacting for 8-12h, cooling after the reaction is finished, adding sodium borohydride, stirring to react and reduce Schiff base, washing with hydrochloric acid and deionized water, and drying in vacuum to obtain adamantanol modified diatomite;
(4) adding amine-terminated polyether and isophorone diisocyanate into an acetone solution, heating for polymerization reaction, and carrying out isocyanate-terminated polyurea oligomer;
(5) adding adamantane alcohol modified diatomite and a polyurea oligomer into a dimethyl sulfoxide solution, then dropwise adding dibutyltin dilaurate, wherein the mass ratio of the adamantane alcohol modified diatomite to the polyurea oligomer to the dibutyltin dilaurate is 100:500-800:0.5-2, heating to react for 60-90 ℃, reacting for 1-3h, naturally cooling, performing suction filtration, washing with deionized water, and performing vacuum drying to obtain an adamantane modified diatomite grafted polyurea oligomer;
(6) deionized water and NaHCO3Adding sodium dodecyl sulfate and Tween 20 into a reaction bottle, stirring for emulsification, heating, adding mixed solution of adamantane modified diatomite graft polyurea oligomer, acrylic acid, methyl methacrylate, n-butyl acrylate, diketone bisacrylamide and potassium persulfate, wherein the methyl methacrylate and the n-butyl acrylate are addedEster, acrylic acid, diketone bisacrylamide, adamantane modified diatomite grafted polyurea oligomer and NaHCO3The mass ratio of the sodium dodecyl sulfate to the tween-20 to the potassium persulfate is 100:30-50:1-3:6-10:7-14:0.1-0.2:1.5-2.5:1.5-2.5:0.3-0.7, the temperature is raised to 70-90 ℃, the polymerization reaction is carried out under the condition of heat preservation, the polymerization time is 3-6h, the mixture is naturally cooled, filtered, discharged and the pH value is adjusted to 7-8 by ammonia water, and the diatomite grafted polyurea modified water-based acrylic emulsion is obtained;
(7) sequentially adding water, pigment fillers, a pigment dispersant polyethylene glycol 400, a flatting agent 1, 2-propylene glycol, a defoaming agent tributyl phosphate, a diatomite grafted polyurea modified aqueous acrylic emulsion, a film forming auxiliary agent alcohol ester twelve, a thickening agent hydroxyethyl cellulose and a pH regulator ammonia water into a dispersing and grinding machine, wherein the mass ratio of the diatomite grafted polyurea modified aqueous acrylic emulsion, the flatting agent 1, 2-propylene glycol, the defoaming agent tributyl phosphate, the film forming auxiliary agent alcohol ester twelve, the thickening agent hydroxyethyl cellulose and the pH regulator ammonia water is 100:0.1-1:0.1-1:3-5:2-5, and mixing to obtain the diatomite grafted polyurea modified humidity-regulating aqueous acrylic coating.
Example 1
(1) Adding diatomite and gamma-glycidyl ether oxypropyltrimethoxysilane into a toluene solvent, mixing, and carrying out ultrasonic reaction to obtain epoxy modified diatomite;
(2) soaking epoxy modified diatomite into p-aminobenzaldehyde, adding the epoxy modified diatomite into a three-neck flask, heating to 120 ℃, reacting for 5 hours, filtering after the reaction is finished, washing with deionized water, and drying by air blasting to obtain aldehyde-based diatomite;
(3) adding aldehyde diatomite and 3-amino-1-adamantanol in a mass ratio of 100:20 into a methanol solution, heating and refluxing at 60 ℃ in a nitrogen atmosphere, reacting for 8 hours, cooling after the reaction is finished, adding sodium borohydride, stirring to react and reduce Schiff base, washing with hydrochloric acid and deionized water, and drying in vacuum to obtain adamantanol modified diatomite;
(4) adding amine-terminated polyether and isophorone diisocyanate into an acetone solution, heating for polymerization reaction, and carrying out isocyanate-terminated polyurea oligomer;
(5) adding adamantane alcohol modified diatomite and polyurea oligomer into a dimethyl sulfoxide solution, then dropwise adding dibutyltin dilaurate, wherein the mass ratio of the adamantane alcohol modified diatomite to the polyurea oligomer to the dibutyltin dilaurate is 100:500:0.5, heating to react for 60 ℃, reacting for 1h, naturally cooling, performing suction filtration, washing with deionized water, and performing vacuum drying to obtain an adamantane modified diatomite grafted polyurea oligomer;
(6) deionized water and NaHCO3Adding sodium dodecyl sulfate and Tween 20 into a reaction bottle, stirring and emulsifying, heating, adding mixed solution of adamantane modified diatomite graft polyurea oligomer, acrylic acid, methyl methacrylate, n-butyl acrylate, diketone bisacrylamide and potassium peroxide, wherein the mixed solution of methyl methacrylate, n-butyl acrylate, acrylic acid, diketone bisacrylamide, adamantane modified diatomite graft polyurea oligomer, NaHCO3Heating to 70 ℃, keeping the temperature and carrying out polymerization reaction for 3 hours, naturally cooling, filtering and discharging, and adjusting the pH value to 7 by ammonia water to obtain the diatomite-grafted polyurea modified aqueous acrylic emulsion, wherein the mass ratio of the sodium dodecyl sulfate, the tween-20 and the potassium persulfate is 100:30:1:6:7:0.1:1.5:1.5: 0.3;
(7) sequentially adding water, pigment fillers, a pigment dispersant polyethylene glycol 400, a flatting agent 1, 2-propylene glycol, a defoaming agent tributyl phosphate, a diatomite grafted polyurea modified aqueous acrylic emulsion, a film forming auxiliary agent alcohol ester twelve, a thickening agent hydroxyethyl cellulose and a pH regulator ammonia water into a dispersing and grinding machine, wherein the mass ratio of the diatomite grafted polyurea modified aqueous acrylic emulsion, the flatting agent 1, 2-propylene glycol, the defoaming agent tributyl phosphate, the film forming auxiliary agent alcohol ester twelve, the thickening agent hydroxyethyl cellulose and the pH regulator ammonia water is 100:0.1:0.1:3:2, and mixing to obtain the diatomite grafted polyurea modified humidity-regulating aqueous acrylic coating.
Example 2
(1) Adding diatomite and gamma-glycidyl ether oxypropyltrimethoxysilane into a toluene solvent, mixing, and carrying out ultrasonic reaction to obtain epoxy modified diatomite;
(2) soaking epoxy modified diatomite into p-aminobenzaldehyde, adding the epoxy modified diatomite into a three-neck flask, heating to 130 ℃, reacting for 6 hours, filtering after the reaction is finished, washing with deionized water, and drying by air blasting to obtain aldehyde-based diatomite;
(3) adding aldehyde diatomite and 3-amino-1-adamantanol in a mass ratio of 100:30 into a methanol solution, heating and refluxing at 65 ℃ in a nitrogen atmosphere, reacting for 9 hours, cooling after the reaction is finished, adding sodium borohydride, stirring to react and reduce Schiff base, washing with hydrochloric acid and deionized water, and drying in vacuum to obtain adamantanol modified diatomite;
(4) adding amine-terminated polyether and isophorone diisocyanate into an acetone solution, heating for polymerization reaction, and carrying out isocyanate-terminated polyurea oligomer;
(5) adding adamantane alcohol modified diatomite and polyurea oligomer into a dimethyl sulfoxide solution, then dropwise adding dibutyltin dilaurate, wherein the mass ratio of the adamantane alcohol modified diatomite to the polyurea oligomer to the dibutyltin dilaurate is 100:570:0.8, heating to react at 70 ℃, reacting for 2h, naturally cooling, performing suction filtration, washing with deionized water, and performing vacuum drying to obtain an adamantane modified diatomite grafted polyurea oligomer;
(6) deionized water and NaHCO3Adding sodium dodecyl sulfate and Tween 20 into a reaction bottle, stirring and emulsifying, heating, adding mixed solution of adamantane modified diatomite graft polyurea oligomer, acrylic acid, methyl methacrylate, n-butyl acrylate, diketone bisacrylamide and potassium peroxide, wherein the mixed solution of methyl methacrylate, n-butyl acrylate, acrylic acid, diketone bisacrylamide, adamantane modified diatomite graft polyurea oligomer, NaHCO3Heating to 75 ℃, keeping the temperature and carrying out polymerization reaction for 4 hours, naturally cooling, filtering and discharging, and adjusting the pH value to 7.5 by using ammonia water to obtain the diatomite grafted polyurea modified aqueous acrylic emulsion, wherein the mass ratio of the sodium dodecyl sulfate, the tween-20 and the potassium persulfate is 100:35:1.5:7:9:0.125:1.8:1.8: 0.4;
(7) sequentially adding water, pigment filler, pigment dispersant polyethylene glycol 400, a leveling agent 1, 2-propylene glycol, a defoaming agent tributyl phosphate, a diatomite grafted polyurea modified aqueous acrylic emulsion, a film forming auxiliary agent alcohol ester twelve, a thickening agent hydroxyethyl cellulose and a pH regulator ammonia water into a dispersing and grinding machine, wherein the mass ratio of the diatomite grafted polyurea modified aqueous acrylic emulsion, the leveling agent 1, 2-propylene glycol, the defoaming agent tributyl phosphate, the film forming auxiliary agent alcohol ester twelve, the thickening agent hydroxyethyl cellulose and the pH regulator ammonia water is 100:0.4:0.4:3.5:2.8, and mixing to obtain the diatomite grafted polyurea modified humidity-regulating aqueous acrylic coating.
Example 3
(1) Adding diatomite and gamma-glycidyl ether oxypropyltrimethoxysilane into a toluene solvent, mixing, and carrying out ultrasonic reaction to obtain epoxy modified diatomite;
(2) soaking epoxy modified diatomite into p-aminobenzaldehyde, adding the epoxy modified diatomite into a three-neck flask, heating to 140 ℃, reacting for 6 hours, filtering after the reaction is finished, washing with deionized water, and drying by air blasting to obtain aldehyde-based diatomite;
(3) adding aldehyde diatomite and 3-amino-1-adamantanol in a mass ratio of 100:40 into a methanol solution, heating and refluxing at 70 ℃ in a nitrogen atmosphere, reacting for 10 hours, cooling after the reaction is finished, adding sodium borohydride, stirring to react and reduce Schiff base, washing with hydrochloric acid and deionized water, and drying in vacuum to obtain adamantanol modified diatomite;
(4) adding amine-terminated polyether and isophorone diisocyanate into an acetone solution, heating for polymerization reaction, and carrying out isocyanate-terminated polyurea oligomer;
(5) adding adamantane alcohol modified diatomite and polyurea oligomer into a dimethyl sulfoxide solution, then dropwise adding dibutyltin dilaurate, wherein the mass ratio of the adamantane alcohol modified diatomite to the polyurea oligomer to the dibutyltin dilaurate is 100:650:1.2, heating to react at 80 ℃, reacting for 2h, naturally cooling, performing suction filtration, washing with deionized water, and performing vacuum drying to obtain an adamantane modified diatomite grafted polyurea oligomer;
(6) deionized water and NaHCO3Adding sodium dodecyl sulfate and tween 20 into a reaction bottle, stirring and emulsifying, heating, adding adamantane modified diatomite graft polyurea oligomer, acrylic acid, methyl methacrylate, n-butyl acrylate and diketone diacryloylMixing the amine mixed solution with potassium peroxide, wherein the mixture comprises methyl methacrylate, n-butyl acrylate, acrylic acid, diketone bisacrylamide, adamantane modified diatomite grafted polyurea oligomer and NaHCO3Heating to 80 ℃, keeping the temperature for polymerization for 5 hours, naturally cooling, filtering, discharging, and adjusting the pH value to 8 by ammonia water to obtain the diatomite-grafted polyurea modified aqueous acrylic emulsion;
(7) sequentially adding water, pigment filler, pigment dispersant polyethylene glycol 400, a flatting agent 1, 2-propylene glycol, defoamer tributyl phosphate, diatomite grafted polyurea modified water-based acrylic emulsion, film-forming assistant alcohol ester twelve, thickener hydroxyethyl cellulose and pH regulator ammonia water into a dispersing and grinding machine, wherein the mass ratio of the diatomite grafted polyurea modified water-based acrylic emulsion, the flatting agent 1, 2-propylene glycol, defoamer tributyl phosphate, film-forming assistant alcohol ester twelve, thickener hydroxyethyl cellulose and pH regulator ammonia water is 100:0.6:0.6:4:3.2, and mixing to obtain the diatomite grafted polyurea modified humidity-regulating water-based acrylic coating.
Example 4
(1) Adding diatomite and gamma-glycidyl ether oxypropyltrimethoxysilane into a toluene solvent, mixing, and carrying out ultrasonic reaction to obtain epoxy modified diatomite;
(2) soaking epoxy modified diatomite into p-aminobenzaldehyde, adding the epoxy modified diatomite into a three-neck flask, heating to 140 ℃, reacting for 6 hours, filtering after the reaction is finished, washing with deionized water, and drying by air blasting to obtain aldehyde-based diatomite;
(3) adding aldehyde diatomite and 3-amino-1-adamantanol in a mass ratio of 100:50 into a methanol solution, heating and refluxing at 75 ℃ in a nitrogen atmosphere, reacting for 10 hours, cooling after the reaction is finished, adding sodium borohydride, stirring to react and reduce Schiff base, washing with hydrochloric acid and deionized water, and drying in vacuum to obtain adamantanol modified diatomite;
(4) adding amine-terminated polyether and isophorone diisocyanate into an acetone solution, heating for polymerization reaction, and carrying out isocyanate-terminated polyurea oligomer;
(5) adding adamantane alcohol modified diatomite and polyurea oligomer into a dimethyl sulfoxide solution, then dropwise adding dibutyltin dilaurate, wherein the mass ratio of the adamantane alcohol modified diatomite to the polyurea oligomer to the dibutyltin dilaurate is 100:720:1.4, heating to react at 80 ℃, reacting for 2h, naturally cooling, performing suction filtration, washing with deionized water, and performing vacuum drying to obtain an adamantane modified diatomite grafted polyurea oligomer;
(6) deionized water and NaHCO3Adding sodium dodecyl sulfate and Tween 20 into a reaction bottle, stirring and emulsifying, heating, adding mixed solution of adamantane modified diatomite graft polyurea oligomer, acrylic acid, methyl methacrylate, n-butyl acrylate, diketone bisacrylamide and potassium peroxide, wherein the mixed solution of methyl methacrylate, n-butyl acrylate, acrylic acid, diketone bisacrylamide, adamantane modified diatomite graft polyurea oligomer, NaHCO3Heating to 80 ℃, keeping the temperature and carrying out polymerization reaction for 5 hours, naturally cooling, filtering and discharging, and adjusting the pH value to 8 by ammonia water to obtain the diatomite-grafted polyurea modified aqueous acrylic emulsion, wherein the mass ratio of the sodium dodecyl sulfate, the tween-20 and the potassium persulfate is 100:42:2.2:9:12:0.175:2.2:2.3: 0.6;
(7) sequentially adding water, pigment filler, pigment dispersant polyethylene glycol 400, a leveling agent 1, 2-propylene glycol, a defoaming agent tributyl phosphate, a diatomite grafted polyurea modified aqueous acrylic emulsion, a film forming auxiliary agent alcohol ester twelve, a thickening agent hydroxyethyl cellulose and a pH regulator ammonia water into a dispersing and grinding machine, wherein the mass ratio of the diatomite grafted polyurea modified aqueous acrylic emulsion, the leveling agent 1, 2-propylene glycol, the defoaming agent tributyl phosphate, the film forming auxiliary agent alcohol ester twelve, the thickening agent hydroxyethyl cellulose and the pH regulator ammonia water is 100:0.8:0.8:4.3:4.2, and mixing to obtain the diatomite grafted polyurea modified humidity-regulating aqueous acrylic coating.
Example 5
(1) Adding diatomite and gamma-glycidyl ether oxypropyltrimethoxysilane into a toluene solvent, mixing, and carrying out ultrasonic reaction to obtain epoxy modified diatomite;
(2) soaking epoxy modified diatomite into p-aminobenzaldehyde, adding the epoxy modified diatomite into a three-neck flask, heating to 150 ℃, reacting for 7 hours, filtering after the reaction is finished, washing with deionized water, and drying by air blasting to obtain aldehyde-based diatomite;
(3) adding aldehyde diatomite and 3-amino-1-adamantanol in a mass ratio of 100:60 into a methanol solution, heating and refluxing at 80 ℃ in a nitrogen atmosphere, reacting for 12 hours, cooling after the reaction is finished, adding sodium borohydride, stirring to react and reduce Schiff base, washing with hydrochloric acid and deionized water, and drying in vacuum to obtain adamantanol modified diatomite;
(4) adding amine-terminated polyether and isophorone diisocyanate into an acetone solution, heating for polymerization reaction, and carrying out isocyanate-terminated polyurea oligomer;
(5) adding adamantane alcohol modified diatomite and a polyurea oligomer into a dimethyl sulfoxide solution, then dropwise adding dibutyltin dilaurate, wherein the mass ratio of the adamantane alcohol modified diatomite to the polyurea oligomer to the dibutyltin dilaurate is 100:800:2, heating to react at 90 ℃, reacting for 3h, naturally cooling, performing suction filtration, washing with deionized water, and performing vacuum drying to obtain an adamantane modified diatomite grafted polyurea oligomer;
(6) deionized water and NaHCO3Adding sodium dodecyl sulfate and Tween 20 into a reaction bottle, stirring and emulsifying, heating, adding mixed solution of adamantane modified diatomite graft polyurea oligomer, acrylic acid, methyl methacrylate, n-butyl acrylate, diketone bisacrylamide and potassium peroxide, wherein the mixed solution of methyl methacrylate, n-butyl acrylate, acrylic acid, diketone bisacrylamide, adamantane modified diatomite graft polyurea oligomer, NaHCO3Heating to 90 ℃, keeping the temperature and carrying out polymerization reaction for 6 hours, naturally cooling, filtering and discharging, and adjusting the pH value to 8 by ammonia water to obtain the diatomite-grafted polyurea modified aqueous acrylic emulsion, wherein the mass ratio of the sodium dodecyl sulfate, the tween-20 and the potassium persulfate is 100:50:3:10:14:0.2:2.5:2.5: 0.7;
(7) sequentially adding water, pigment filler, pigment dispersant polyethylene glycol 400, a flatting agent 1, 2-propylene glycol, a defoaming agent tributyl phosphate, a diatomite grafted polyurea modified aqueous acrylic emulsion, a film forming auxiliary agent alcohol ester twelve, a thickening agent hydroxyethyl cellulose and a pH regulator ammonia water into a dispersing and grinding machine, wherein the mass ratio of the diatomite grafted polyurea modified aqueous acrylic emulsion, the flatting agent 1, 2-propylene glycol, the defoaming agent tributyl phosphate, the film forming auxiliary agent alcohol ester twelve, the thickening agent hydroxyethyl cellulose and the pH regulator ammonia water is 100:1:1:5:5, and mixing to obtain the diatomite grafted polyurea modified humidity-regulating aqueous acrylic coating.
Comparative example 1
(1) Adding diatomite and gamma-glycidyl ether oxypropyltrimethoxysilane into a toluene solvent, mixing, and carrying out ultrasonic reaction to obtain epoxy modified diatomite;
(2) soaking epoxy modified diatomite into p-aminobenzaldehyde, adding the epoxy modified diatomite into a three-neck flask, heating to 120 ℃, reacting for 5 hours, filtering after the reaction is finished, washing with deionized water, and drying by air blasting to obtain aldehyde-based diatomite;
(3) adding aldehyde diatomite and 3-amino-1-adamantanol in a mass ratio of 100:15 into a methanol solution, heating and refluxing at 60 ℃ in a nitrogen atmosphere, reacting for 8 hours, cooling after the reaction is finished, adding sodium borohydride, stirring to react and reduce Schiff base, washing with hydrochloric acid and deionized water, and drying in vacuum to obtain adamantanol modified diatomite;
(4) adding amine-terminated polyether and isophorone diisocyanate into an acetone solution, heating for polymerization reaction, and carrying out isocyanate-terminated polyurea oligomer;
(5) adding adamantane alcohol modified diatomite and polyurea oligomer into a dimethyl sulfoxide solution, then dropwise adding dibutyltin dilaurate, wherein the mass ratio of the adamantane alcohol modified diatomite to the polyurea oligomer to the dibutyltin dilaurate is 100:400:0.4, heating to react for 60 ℃, reacting for 1h, naturally cooling, performing suction filtration, washing with deionized water, and performing vacuum drying to obtain an adamantane modified diatomite grafted polyurea oligomer;
(6) deionized water and NaHCO3Adding sodium dodecyl sulfate and tween 20 into a reaction bottle, stirring for emulsification, heating, adding adamantane modified diatomite grafted polyurea oligomer, acrylic acid, methyl methacrylate and propyleneMixed solution of n-butyl acrylate and diketone bisacrylamide and potassium persulfate, wherein the mixed solution comprises methyl methacrylate, n-butyl acrylate, acrylic acid, diketone bisacrylamide, adamantane modified diatomite grafted polyurea oligomer and NaHCO3Heating to 70 ℃, keeping the temperature and carrying out polymerization reaction for 3 hours, naturally cooling, filtering and discharging, and adjusting the pH value to 7 by ammonia water to obtain the diatomite grafted polyurea modified aqueous acrylic emulsion, wherein the mass ratio of the sodium dodecyl sulfate, the tween-20 and the potassium persulfate is 100:24:0.8:4:5:0.05:1: 0.2;
(7) sequentially adding water, pigment fillers, a pigment dispersant polyethylene glycol 400, a flatting agent 1, 2-propylene glycol, a defoaming agent tributyl phosphate, a diatomite grafted polyurea modified aqueous acrylic emulsion, a film forming auxiliary agent alcohol ester twelve, a thickening agent hydroxyethyl cellulose and a pH regulator ammonia water into a dispersing and grinding machine, wherein the mass ratio of the diatomite grafted polyurea modified aqueous acrylic emulsion, the flatting agent 1, 2-propylene glycol, the defoaming agent tributyl phosphate, the film forming auxiliary agent alcohol ester twelve, the thickening agent hydroxyethyl cellulose and the pH regulator ammonia water is 100:0.08:0.08:2.4:1.6, and mixing to obtain the diatomite grafted polyurea modified humidity-regulating aqueous acrylic coating.
The water paint of the embodiment and the comparative example is coated on a glass plate, after being cured and dried, the glass plate is placed in a state adjusting box for 7 days with the temperature adjusted to 23 ℃ and the humidity adjusted to 50 percent, and the test standard is GB 9278-.
Item Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1
Dry film weight (g) 99.9 99.4 100.3 99.6 100.3 99.8
In the wet film (g) 284.3 307.9 339.1 363.8 316.3 211.5
Water absorption (%) 184.6 209.8 238.1 265.3 215.4 111.9
The aqueous acrylic coatings of examples and comparative examples were cured and cut into standard tensile bars and tested for flexural strength and flexural modulus using an SHK-a104 universal tester.
Figure BDA0003378220150000141

Claims (9)

1. The diatomite grafted polyurea modified humidity-regulating water-based acrylic coating is characterized in that: the preparation method of the diatomite-grafted polyurea modified humidity-regulating water-based acrylic coating comprises the following steps:
(1) adding diatomite and gamma-glycidyl ether oxypropyltrimethoxysilane into a toluene solvent, mixing, and carrying out ultrasonic reaction to obtain epoxy modified diatomite;
(2) soaking epoxy modified diatomite into p-aminobenzaldehyde, adding the p-aminobenzaldehyde into a three-neck flask, heating to perform an epoxy ring-opening reaction, after the reaction is finished, filtering, washing with deionized water, and drying by blasting to obtain aldehyde-based diatomite;
(3) adding aldehyde diatomite and 3-amino-1-adamantanol into a methanol solution, heating and refluxing in a nitrogen atmosphere to perform Schiff base reaction, cooling after the reaction is finished, adding sodium borohydride, stirring for reaction and reduction of the Schiff base, washing with hydrochloric acid and deionized water, and performing vacuum drying to obtain adamantanol modified diatomite;
(4) adding amine-terminated polyether and isophorone diisocyanate into an acetone solution, heating for polymerization reaction, and carrying out isocyanate-terminated polyurea oligomer;
(5) adding adamantane alcohol modified diatomite and a polyurea oligomer into a dimethyl sulfoxide solution, then dropwise adding dibutyltin dilaurate, heating for addition reaction, naturally cooling, carrying out suction filtration, washing with deionized water, and carrying out vacuum drying to obtain an adamantane modified diatomite grafted polyurea oligomer;
(6) deionized water and NaHCO3Adding sodium dodecyl sulfate and tween 20 into a reaction bottle, stirring and emulsifying, heating, adding a mixed solution of adamantane modified diatomite graft polyurea oligomer, acrylic acid, methyl methacrylate, n-butyl acrylate, diketone bisacrylamide and potassium persulfate, preserving heat for polymerization reaction, naturally cooling, filtering and discharging, and adjusting the pH value to 7-8 by using ammonia water to obtain diatomite graft polyurea modified aqueous acrylic emulsion;
(7) adding water, pigment filler, pigment dispersant polyethylene glycol 400, a flatting agent 1, 2-propylene glycol, a defoaming agent tributyl phosphate, a diatomite grafted polyurea modified aqueous acrylic emulsion, a film-forming auxiliary agent alcohol ester twelve, a thickening agent hydroxyethyl cellulose and a pH regulator ammonia water into a dispersing and grinding machine in sequence, and mixing to obtain the diatomite grafted polyurea modified humidity-regulating aqueous acrylic coating.
2. The diatomite-grafted polyurea modified humidity-controlling waterborne acrylic coating as claimed in claim 1, wherein: the temperature of the epoxy ring-opening reaction in the step (2) is 120-150 ℃, and the reaction time is 5-7 h.
3. The diatomite-grafted polyurea modified humidity-controlling waterborne acrylic coating as claimed in claim 1, wherein: the mass ratio of the aldehyde diatomite to the 3-amino-1-adamantanol in the step (3) is 100: 20-60.
4. The diatomite-grafted polyurea modified humidity-controlling waterborne acrylic coating as claimed in claim 1, wherein: the temperature of the Schiff base reaction in the step (3) is 60-80 ℃, and the reaction time is 8-12 h.
5. The diatomite-grafted polyurea modified humidity-controlling waterborne acrylic coating as claimed in claim 1, wherein: the mass ratio of the adamantanol modified diatomite, the polyurea oligomer and the dibutyltin dilaurate in the step (5) is 100:500-800: 0.5-2.
6. The diatomite-grafted polyurea modified humidity-controlling waterborne acrylic coating as claimed in claim 1, wherein: the reaction temperature in the step (5) is 60-90 ℃, and the reaction time is 1-3 h.
7. The diatomite-grafted polyurea modified humidity-controlling waterborne acrylic coating as claimed in claim 1, wherein: in the step (6), methyl methacrylate, n-butyl acrylate, acrylic acid and diketone bisAcrylamide, adamantane modified diatomite grafted polyurea oligomer and NaHCO3The mass ratio of the sodium dodecyl sulfate to the tween-20 to the potassium persulfate is 100:30-50:1-3:6-10:7-14:0.1-0.2:1.5-2.5:1.5-2.5: 0.3-0.7.
8. The diatomite-grafted polyurea modified humidity-controlling waterborne acrylic coating as claimed in claim 1, wherein: the temperature of the polymerization reaction in the step (6) is 70-90 ℃, and the time is 3-6 h.
9. The diatomite-grafted polyurea modified humidity-controlling waterborne acrylic coating as claimed in claim 1, wherein: in the step (7), the mass ratio of the diatomite grafted polyurea modified water-based acrylic emulsion to the leveling agent 1, 2-propylene glycol to the defoaming agent tributyl phosphate to the film forming auxiliary alcohol ester twelve to the thickening agent hydroxyethyl cellulose to the pH regulator ammonia water is 100:0.1-1:0.1-1:3-5: 2-5.
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* Cited by examiner, † Cited by third party
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CN116535927A (en) * 2023-06-16 2023-08-04 江西浙今科技有限公司 Coating for building and preparation method thereof
CN117384702A (en) * 2023-12-12 2024-01-12 广东粤首新科技有限公司 Production process and application of diesel antiwear lubricant

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116535927A (en) * 2023-06-16 2023-08-04 江西浙今科技有限公司 Coating for building and preparation method thereof
CN116535927B (en) * 2023-06-16 2024-01-23 阿贝罗尼新材料河北有限公司 Coating for building and preparation method thereof
CN117384702A (en) * 2023-12-12 2024-01-12 广东粤首新科技有限公司 Production process and application of diesel antiwear lubricant
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