CN115477881B - Water-based wear-resistant transparent antifogging resin polymer and preparation method thereof - Google Patents
Water-based wear-resistant transparent antifogging resin polymer and preparation method thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000011347 resin Substances 0.000 title claims abstract description 31
- 229920005989 resin Polymers 0.000 title claims abstract description 31
- 229920000642 polymer Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 23
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 239000000839 emulsion Substances 0.000 claims abstract description 17
- -1 acrylic ester Chemical class 0.000 claims abstract description 16
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims abstract description 9
- CDOUZKKFHVEKRI-UHFFFAOYSA-N 3-bromo-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound BrCCC(=O)NCNC(=O)C=C CDOUZKKFHVEKRI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000004821 distillation Methods 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000004806 packaging method and process Methods 0.000 claims description 7
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 238000005299 abrasion Methods 0.000 claims description 4
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 238000006136 alcoholysis reaction Methods 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 19
- 239000011248 coating agent Substances 0.000 abstract description 17
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- SUDVBWMNUVBMHV-UHFFFAOYSA-N 2-pyridin-4-ylethanol;hydrochloride Chemical compound Cl.OCCC1=CC=NC=C1 SUDVBWMNUVBMHV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N ethyl butylhexanol Natural products CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- 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
- 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
- C09D133/24—Homopolymers or copolymers of amides or imides
- C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Abstract
The invention discloses a water-based wear-resistant transparent antifogging resin polymer and a preparation method thereof, and relates to the technical field of antifogging coatings. The antifog resin polymer is prepared from modified cage-shaped silsesquioxane, aqueous acrylic ester emulsion, polyvinyl alcohol, dioctyl sodium sulfosuccinate and deionized water. The antifogging resin polymer is pure water, low in cost, environment-friendly and pollution-free; the coating prepared by the resin has higher adhesive force, and the formed coating has higher antifogging property, wear resistance and high transparency.
Description
Technical Field
The invention belongs to the technical field of anti-fog coating, and particularly relates to a water-based wear-resistant transparent anti-fog resin polymer and a preparation method thereof.
Background
The core of the antifogging coating is resin, and the biggest problem of the conventional water-based antifogging coating is that the antifogging effect cannot last long; the reason is that the anti-fog coating is often subjected to wiping, the essence is that the resin is not wear-resistant, the anti-fog coating falls off in the wiping process, and the anti-fog effect is lost. To solve this problem, the current solutions are: 3M patent CN 104053731B and patent CN 104080861B, fine magnetic patent CN 104130607B, sandisk patent CN 105017883B, pine patent CN 109666119B. These techniques allow for the preparation of aqueous anti-fog resins and aqueous anti-fog coatings by different methods. These techniques have solved the problem of abrasion resistance by adding silica sol, but affect the transparency of the resin; some achieve wear resistance at the expense of anti-fog effects; all problems are solved, but the preparation is complex, the cost is high, and the mass production popularization is not facilitated. Therefore, the water-based anti-fog resin polymer with excellent anti-fog performance and high wear resistance and transparency is a research hot spot in the current industry.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a water-based wear-resistant transparent antifogging resin polymer and a preparation method thereof. The invention is realized by adopting the following technical scheme:
the water-based wear-resistant transparent antifogging resin polymer disclosed by the invention comprises the following raw materials in parts by mass:
the structural formula of the modified cage-shaped silsesquioxane is as follows:
wherein ,
/>
the modified cage-shaped silsesquioxane is prepared by the following method:
under the protection of inert gas, 100 parts by mass of octavinyl cage-shaped silsesquioxane, 280-320 parts by mass of 4-pyridine ethyl alcohol hydrochloride and 0.3-0.8 part by mass of 2, 2-dimethoxy-2-phenyl acetophenone are added into 1000 parts by mass of solvent, and the mixture is stirred uniformly in a reaction kettle for 20-30 min. The solvent is a mixed solvent of two or more of ethyl acetate, butyl acetate, toluene, acetone, butanone and tetrahydrofuran;
then heating to 50-80 ℃, starting a condensing reflux device, and stirring and reacting for 2-4 hours to obtain the modified cage-shaped silsesquioxane.
The preparation method of the aqueous acrylic ester emulsion comprises the following steps:
(1) 100 parts by mass of butyl acrylate, 250-280 parts by mass of isooctyl acrylate, 3-8 parts by mass of acrylamide), 1-2 parts by mass of acrylic acid, 3-10 parts by mass of hydroxybutyl acrylate and 2-5 parts by mass of 2-acrylamide-2-methylpropanesulfonic acid are added into a reaction kettle, and the temperature is raised to 75-82 ℃;
(2) Starting a condensing reflux device, dropwise adding 200 parts by mass of initiator solution while stirring, wherein the initiator solution contains 3.5-5 parts by mass of initiator, and the balance of acetone solvent, and carrying out heat preservation reaction for 3 hours after the completion of dropwise adding for 2-3 hours;
(3) Cooling to 60-70 ℃, adding 10-20 parts by mass of emulsifier into a reaction kettle, adding 400-600 parts by mass of deionized water, and vigorously stirring for 1h;
(4) And (3) distilling under reduced pressure, and removing the acetone solvent to obtain the aqueous acrylic ester emulsion.
Preferably, the initiator in the step (2) is one of dibenzoyl peroxide or azobisisobutyronitrile.
Preferably, the emulsifier in the step (3) is one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and dodecylphenol polyoxyethylene ether.
Preferably, the polymerization degree of the polyvinyl alcohol is 2000-3000, the alcoholysis degree is 88%, and the marks are PVA2088, PVA2488 or PVA2688.
The preparation method of the water-based wear-resistant transparent antifogging resin polymer comprises the following steps:
s1, adding 1000 parts by mass of deionized water into a reaction kettle, starting a condensation reflux device, heating to 75-80 ℃, adding 50 parts by mass of polyvinyl alcohol into the reaction kettle, stirring for 30-60 min to completely dissolve PVA, respectively adding 300-400 parts by mass of aqueous acrylic ester emulsion and 30-45 parts by mass of dioctyl sodium sulfosuccinate, and uniformly stirring within 20 min;
s2, heating to 85-90 ℃, adding 35-80 parts by mass of modified cage-shaped silsesquioxane, adding the rest deionized water, and stirring for 1h;
s3, distilling under reduced pressure, filtering, discharging and packaging.
Preferably, the reduced pressure distillation parameters of step S3 are as follows:
vacuum degree: -0.4MPa to-0.9 MPa
Distillation temperature: 90-120 DEG C
Distillation time: 40-60 min.
Compared with the prior art, the invention has the following beneficial effects:
the antifog resin polymer is prepared from modified cage-shaped silsesquioxane, aqueous acrylic ester emulsion, polyvinyl alcohol, dioctyl sodium sulfosuccinate and deionized water. The antifogging resin polymer is pure water, low in cost, environment-friendly and pollution-free; the coating prepared by the resin has higher adhesive force, and the formed coating has higher antifogging property, wear resistance and high transparency.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1
An aqueous wear-resistant transparent antifogging resin polymer is prepared by the following steps:
s1, adding 1000 parts by mass of deionized water into a reaction kettle, starting a condensing reflux device, heating to 80 ℃, adding 50 parts by mass of polyvinyl alcohol (PVA 2088) into the reaction kettle, stirring for 50min to completely dissolve the PVA, respectively adding 300 parts by mass of aqueous acrylic ester emulsion and 30 parts by mass of sodium dioctyl sulfosuccinate, and uniformly stirring within 20 min;
s2, heating to 85 ℃, adding 50 parts by mass of modified cage-shaped silsesquioxane, adding 500 parts by mass of deionized water, and stirring for 1h;
s3, distilling under reduced pressure (vacuum degree: minus 0.5MPa; distillation temperature: 100 ℃ and distillation time: 50 min), filtering, discharging and packaging.
Wherein the modified cage silsesquioxane has the following structural formula:
wherein ,
the modified cage-shaped silsesquioxane is prepared by the following method:
under the protection of inert gas, adding 100 parts by mass of octavinyl cage-shaped silsesquioxane, 300 parts by mass of 4-pyridine ethanol hydrochloride and 0.5 part by mass of 2, 2-dimethoxy-2-phenyl acetophenone into 1000 parts by mass of solvent, uniformly stirring in a reaction kettle for 25min, wherein the solvent is formed by mixing ethyl acetate and butyl acetate according to a mass ratio of 1:1;
then heating to 70 ℃, starting a condensing reflux device, and stirring for 3 hours to obtain the modified cage-shaped silsesquioxane.
The preparation method of the aqueous acrylic ester emulsion comprises the following steps:
(1) 100 parts by mass of butyl acrylate, 280 parts by mass of isooctyl acrylate, 3 parts by mass of acrylamide), 1 part by mass of acrylic acid, 3 parts by mass of hydroxybutyl acrylate and 5 parts by mass of 2-acrylamide-2-methylpropanesulfonic acid are added into a reaction kettle, and the temperature is raised to 80 ℃;
(2) Starting a condensing reflux device, dropwise adding 200 parts by mass of initiator solution while stirring, wherein the initiator solution contains 4 parts by mass of initiator, and the balance of acetone solvent, and carrying out heat preservation reaction for 3 hours after 3 hours of dropwise adding;
(3) Cooling to 60 ℃, adding 10 parts by mass of emulsifier into a reaction kettle, adding 400 parts by mass of deionized water, and vigorously stirring for 1h;
(4) And (3) distilling under reduced pressure to remove the acetone solvent, so as to obtain the aqueous acrylic ester emulsion.
Wherein the initiator in the step (2) is dibenzoyl peroxide.
Wherein the emulsifier in the step (3) is sodium dodecyl benzene sulfonate.
Example 2
An aqueous wear-resistant transparent antifogging resin polymer is prepared by the following steps:
s1, adding 1000 parts by mass of deionized water into a reaction kettle, starting a condensing reflux device, heating to 80 ℃, adding 50 parts by mass of polyvinyl alcohol (PVA 2488) into the reaction kettle, stirring for 30min to completely dissolve the PVA, respectively adding 400 parts by mass of aqueous acrylic ester emulsion and 45 parts by mass of sodium dioctyl sulfosuccinate, and uniformly stirring within 20 min;
s2, heating to 90 ℃, adding 80 parts by mass of modified cage-shaped silsesquioxane, adding 1000 parts by mass of deionized water, and stirring for 1h;
s3, distilling under reduced pressure (vacuum degree: minus 0.5MPa; distillation temperature: 100 ℃ and distillation time: 50 min), filtering, discharging and packaging.
Wherein the modified cage silsesquioxane has the following structural formula:
wherein ,
the preparation of the modified cage silsesquioxane is described in example 1.
Under the protection of inert gas, adding 100 parts by mass of octavinyl cage-shaped silsesquioxane, 320 parts by mass of 4-pyridine ethanol hydrochloride and 0.5 part by mass of 2, 2-dimethoxy-2-phenyl acetophenone into 1000 parts by mass of solvent, uniformly stirring in a reaction kettle for 25min, wherein the solvent is formed by mixing ethyl acetate and butyl acetate according to a mass ratio of 1:1;
then heating to 70 ℃, starting a condensing reflux device, and stirring for 3 hours to obtain the modified cage-shaped silsesquioxane.
The preparation method of the aqueous acrylic ester emulsion is described in example 1.
Comparative example 1
An aqueous wear-resistant transparent antifogging resin polymer is prepared by the following steps:
s1, adding 1000 parts by mass of deionized water into a reaction kettle, starting a condensing reflux device, heating to 80 ℃, adding 50 parts by mass of polyvinyl alcohol (PVA 2088) into the reaction kettle, stirring for 50min to completely dissolve the PVA, respectively adding 300 parts by mass of aqueous acrylic ester emulsion and 30 parts by mass of sodium dioctyl sulfosuccinate, and uniformly stirring within 20 min;
s2, heating to 85 ℃, adding 500 parts by mass of deionized water, and stirring for 1h;
s3, distilling under reduced pressure (vacuum degree: minus 0.5MPa; distillation temperature: 100 ℃ and distillation time: 50 min), filtering, discharging and packaging. The preparation method of the aqueous acrylic ester emulsion is referred to in example 1.
Comparative example 2
An aqueous wear-resistant transparent antifogging resin polymer is prepared by the following steps:
s1, adding 1000 parts by mass of deionized water into a reaction kettle, starting a condensing reflux device, heating to 80 ℃, adding 50 parts by mass of polyvinyl alcohol (PVA 2088) into the reaction kettle, stirring for 50min to completely dissolve the PVA, adding 30 parts by mass of dioctyl sodium sulfosuccinate, and stirring uniformly within 20 min;
s2, heating to 85 ℃, adding 50 parts by mass of modified cage-shaped silsesquioxane, adding 500 parts by mass of deionized water, and stirring for 1h;
s3, distilling under reduced pressure (vacuum degree: minus 0.5MPa; distillation temperature: 100 ℃ and distillation time: 50 min), filtering, discharging and packaging. Wherein the preparation method of the modified cage silsesquioxane is referred to in example 1.
Comparative example 3
An aqueous wear-resistant transparent antifogging resin polymer is prepared by the following steps:
s1, adding 1000 parts by mass of deionized water into a reaction kettle, starting a condensing reflux device, heating to 80 ℃, adding 50 parts by mass of polyvinyl alcohol (PVA 2088) into the reaction kettle, stirring for 50min to completely dissolve the PVA, adding 30 parts by mass of dioctyl sodium sulfosuccinate, and stirring uniformly within 20 min;
s2, heating to 85 ℃, adding 500 parts by mass of deionized water, and stirring for 1h;
s3, distilling under reduced pressure (vacuum degree: minus 0.5MPa; distillation temperature: 100 ℃ and distillation time: 50 min), filtering, discharging and packaging.
To the antifog resin polymers prepared in examples 1 to 2 and comparative examples 1 to 3, 3% by mass of a film-forming auxiliary agent (dodecanol ester), 1% by mass of an aqueous curing agent (Colorgea Bayhydur-3100), 2% by mass of a leveling agent (BYK-333), and 2% by mass of a defoaming agent (Tego-825) were added, and diluted with deionized water to prepare an aqueous antifog coating material.
The coating is coated on a PET film with the thickness of 50 mu m by using a wire rod, the dry weight thickness is controlled to be 5 mu m, and the coating is dried for 2min under the condition of a baking oven at 120 ℃ to volatilize the solvent, so that the coating is completely solidified, and the functional film is prepared. The functional films were tested and the specific test results are shown in table 1.
TABLE 1
The anti-fog effect test method is that the film is horizontally placed above the boiled kettle for 10cm, the coating surface is contacted with water vapor, and the water vapor can not be condensed into water fog on the film within 10 seconds.
The anti-fog durability test method comprises the following steps: the film was wiped dry with a paper towel, and the above operation was repeated, and when the repetition was observed for a few times, the film did not have an antifogging effect.
The method for detecting the wear resistance comprises the following steps: the medical alcohol is dipped by paper towel and rubbed back and forth on the coating with 500g force, when the brightness of the film changes obviously, the coating is wiped off, and the wiping times are recorded.
From the test results, it can be seen that when the modified cage silsesquioxane (comparative example 1), the aqueous acrylate emulsion (comparative example 2) and the modified cage silsesquioxane and the aqueous acrylic emulsion (comparative example 3) were not contained in the antifog resin polymer, the adhesion, abrasion resistance, and the antifog durability of the resulting coating were significantly reduced.
It should be noted that the above-mentioned embodiments are only a few specific embodiments of the present invention, and it is obvious that the present invention is not limited to the above embodiments, but other modifications are possible. All modifications directly or indirectly derived from the disclosure of the present invention will be considered to be within the scope of the present invention.
Claims (6)
1. The water-based wear-resistant transparent antifogging resin polymer is characterized by comprising the following raw materials in parts by mass:
the structural formula of the modified cage-shaped silsesquioxane is as follows:
wherein ,
the preparation method of the aqueous acrylic ester emulsion comprises the following steps:
(1) 100 parts by mass of butyl acrylate, 250-280 parts by mass of isooctyl acrylate, 3-8 parts by mass of acrylamide, 1-2 parts by mass of acrylic acid, 3-10 parts by mass of hydroxybutyl acrylate and 2-5 parts by mass of 2-acrylamide-2-methylpropanesulfonic acid are added into a reaction kettle, and the temperature is raised to 75-82 ℃;
(2) Starting a condensing reflux device, dropwise adding 200 parts by mass of initiator solution while stirring, wherein the initiator solution contains 3.5-5 parts by mass of initiator, and the balance of acetone solvent, and carrying out heat preservation reaction for 3 hours after the completion of dropwise adding for 2-3 hours;
(3) Cooling to 60-70 ℃, adding 10-20 parts by mass of emulsifier into a reaction kettle, adding 400-600 parts by mass of deionized water, and vigorously stirring for 1h;
(4) And (3) distilling under reduced pressure, and removing the acetone solvent to obtain the aqueous acrylic ester emulsion.
2. The aqueous abrasion resistant transparent antifogging resin polymer of claim 1, wherein said initiator of step (2) is one of dibenzoyl peroxide or azobisisobutyronitrile.
3. The aqueous wear-resistant transparent antifogging resin polymer of claim 1, wherein the emulsifier in step (3) is one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, and dodecylphenol polyoxyethylene ether.
4. The aqueous wear-resistant transparent antifogging resin polymer according to claim 1, wherein the polyvinyl alcohol has a degree of polymerization of 2000 to 3000 and an alcoholysis degree of 88%.
5. The method for preparing an aqueous wear-resistant transparent antifogging resin polymer according to any one of claims 1 to 4, comprising the steps of:
s1, adding 1000 parts by mass of deionized water into a reaction kettle, starting a condensation reflux device, heating to 75-80 ℃, adding 50 parts by mass of polyvinyl alcohol into the reaction kettle, stirring for 30-60 min to completely dissolve PVA, respectively adding 300-400 parts by mass of aqueous acrylic ester emulsion and 30-45 parts by mass of dioctyl sodium sulfosuccinate, and uniformly stirring within 20 min;
s2, heating to 85-90 ℃, adding 35-80 parts by mass of modified cage-shaped silsesquioxane, adding the rest deionized water, and stirring for 1h;
s3, distilling under reduced pressure, filtering, discharging and packaging.
6. The method for producing an aqueous abrasion-resistant transparent antifogging resin polymer according to claim 5, wherein the reduced pressure distillation parameters of step S3 are as follows:
vacuum degree: -0.4MPa to-0.9 MPa
Distillation temperature: 90-120 DEG C
Distillation time: 40-60 min.
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| JP2002173633A (en) * | 2000-12-06 | 2002-06-21 | Hitachi Chem Co Ltd | Anti-fogging coating, method for producing the same, method for forming anti-fogging coating film and formed product having anti-fogging coating film |
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| JP2002173633A (en) * | 2000-12-06 | 2002-06-21 | Hitachi Chem Co Ltd | Anti-fogging coating, method for producing the same, method for forming anti-fogging coating film and formed product having anti-fogging coating film |
| WO2018019519A1 (en) * | 2016-07-26 | 2018-02-01 | Unilever N.V. | Surface treatment composition capable of imparting underwater superoleophobicity |
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