CN116179041B - Preparation method of hydrophilic coating with high firmness - Google Patents
Preparation method of hydrophilic coating with high firmness Download PDFInfo
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- CN116179041B CN116179041B CN202310158457.4A CN202310158457A CN116179041B CN 116179041 B CN116179041 B CN 116179041B CN 202310158457 A CN202310158457 A CN 202310158457A CN 116179041 B CN116179041 B CN 116179041B
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- 239000011248 coating agent Substances 0.000 title claims abstract description 60
- 238000000576 coating method Methods 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 79
- 238000005507 spraying Methods 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- ZUIXFZJBOJTTET-OWOJBTEDSA-N 5-[(e)-2-(3,4,5-trihydroxyphenyl)ethenyl]benzene-1,2,3-triol Chemical compound OC1=C(O)C(O)=CC(\C=C\C=2C=C(O)C(O)=C(O)C=2)=C1 ZUIXFZJBOJTTET-OWOJBTEDSA-N 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 15
- 230000032683 aging Effects 0.000 claims abstract description 13
- XQLXSGCTOLBFAK-UHFFFAOYSA-N 1-prop-2-enoyloxypentyl prop-2-enoate Chemical compound CCCCC(OC(=O)C=C)OC(=O)C=C XQLXSGCTOLBFAK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 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 abstract description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 239000000839 emulsion Substances 0.000 claims abstract description 9
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 5
- 239000004005 microsphere Substances 0.000 claims description 27
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 16
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 239000011268 mixed slurry Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000000052 comparative effect Effects 0.000 description 15
- 239000010935 stainless steel Substances 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 238000012360 testing method Methods 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical group C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
Classifications
-
- 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
- C09D135/00—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 a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D135/02—Homopolymers or copolymers of esters
-
- 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
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention belongs to the technical field of hydrophilic coating preparation, and particularly relates to a preparation method of a high-firmness hydrophilic coating. The preparation method of the hydrophilic coating provided by the invention comprises the following steps: mixing sodium silicate, graphene oxide, a solvent, urea and styrene-acrylic emulsion, aging and roasting to obtain hollow silica microspheres; mixing and reacting the hollow silica microspheres, vinyl trimethoxy silane, ethyl orthosilicate and a solvent to obtain modified hollow silica microspheres; mixing modified hollow silica microspheres, 4,3',5' -trihydroxy resveratrol, butyl acrylate and a solvent, and adding azodiisobutyronitrile for reaction to obtain a block polymer; and mixing the block polymer, the pentanediol diacrylate, the initiator and the solvent to obtain a spraying liquid, spraying the spraying liquid onto the surface of the substrate, and curing to obtain the hydrophilic coating. The method can effectively improve the hydrophilic property of the coating and the firmness of the coating and the base material.
Description
Technical Field
The invention belongs to the technical field of hydrophilic coating preparation, and particularly relates to a preparation method of a high-firmness hydrophilic coating.
Background
In practical life, in order to increase the wettability of a substrate (such as glass and alloy), a layer of hydrophilic material is often coated on the surface of the substrate to form a hydrophilic layer, and the method has wide application in the fields of building materials, liquid transportation, medical materials and the like.
The existing hydrophilic layer preparation method mainly comprises an electrostatic spinning method, a sol-gel method, a layer-by-layer self-assembly method and the like, the process is complex, the obtained hydrophilic coating is poor in hydrophilic performance and limited in firmness with a base material, for example, the existing hydrophilic coating preparation method generally comprises the steps of depositing a silicon oxide nano particle layer on the surface of the base material, and then forming a silicate material on the surface of the silicon oxide nano particle layer, wherein the formed hydrophilic coating has good hydrophilicity, but the adhesive force between the hydrophilic coating and the base material is not high, the firmness is limited, and the service life of the hydrophilic coating is seriously influenced.
Therefore, developing a method for preparing a hydrophilic coating that is excellent in hydrophilic properties and has high firmness to a substrate is of great significance.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect that the hydrophilic coating obtained by the existing preparation method of the hydrophilic coating cannot achieve both good hydrophilic performance and high firmness with a base material, and further provide a preparation method of the hydrophilic coating with high firmness.
Therefore, the invention adopts the technical proposal that,
a preparation method of a hydrophilic coating with high firmness comprises the following steps:
1) Mixing sodium silicate, graphene oxide, a solvent, urea and styrene-acrylic emulsion, aging, centrifuging after aging, filtering, drying and roasting to obtain hollow silica microspheres;
2) Mixing and reacting hollow silica microspheres, vinyl trimethoxy silane, ethyl orthosilicate and a solvent, filtering, washing and drying after the reaction is finished to obtain modified hollow silica microspheres with carbon-carbon double bonds on the surfaces;
3) Mixing modified hollow silica microspheres with carbon-carbon double bonds on the surfaces, 4,3',5' -trihydroxy resveratrol (CAS number: 637776-83-1), butyl acrylate and a solvent, then adding azodiisobutyronitrile for reaction, adding water after the reaction is finished, filtering and drying to obtain a silica microsphere grafted block polymer;
4) Mixing the silicon dioxide microsphere grafted block polymer, pentanediol diacrylate, an initiator and a solvent to obtain a spraying liquid, spraying the spraying liquid on the surface of a substrate, and curing to obtain the hydrophilic coating formed on the surface of the substrate.
Preferably, the sodium silicate in the step 1) is sodium silicate nonahydrate, and the mass ratio of the sodium silicate nonahydrate to the graphene oxide to the solvent to the urea to the styrene-acrylic emulsion is 100: (8-15): (15-25): (2-8): (200-400).
Preferably, the aging temperature in the step 1) is 80-98 ℃ and the aging time is 2-6h;
the drying temperature is 70-85 ℃ and the drying time is 1-5h;
the roasting temperature is 450-480 ℃, the roasting time is 1-5h, and the roasting process is carried out in an air atmosphere.
Preferably, in the step 2), the mass ratio of the hollow silica microspheres to the vinyl trimethoxy silane to the ethyl orthosilicate to the solvent is 10: (1-5): (8-20): (10-30).
Preferably, step 2) further comprises the step of adjusting the pH of the mixed slurry to 4-6.
Preferably, the reaction temperature in step 2) is 70-90 ℃ and the reaction time is 2-8h.
Preferably, the mass ratio of the modified hollow silica microspheres with carbon-carbon double bonds on the surface in the step 3) to the 4,3',5' -trihydroxy resveratrol, butyl acrylate, solvent and azodiisobutyronitrile is (3-7): (15-25): (5-15): (20-60): (2-8);
the addition amount of the water is 3-6 times of the mass of the solvent;
the reaction temperature is 70-90 ℃ and the reaction time is 2-8h.
Preferably, the mass ratio of the silica microsphere grafted block polymer, the pentanediol diacrylate, the initiator and the solvent in the step 4) is (3-7): (3-8): (1-3): (10-50);
the curing temperature is 50-70 ℃ and the curing time is 20-60min;
the initiator is dibenzoyl peroxide.
Preferably, the solvent is at least one selected from ethanol, propanol and isopropanol.
Preferably, the substrate is an alloy; the hydrophilic coating has a thickness of 10-30 microns.
The technical scheme of the invention has the following advantages:
according to the preparation method of the high-firmness hydrophilic coating, firstly, graphene oxide is added in the preparation process of microspheres for doping, the formed microspheres take latex as a core, the latex disappears after roasting to form graphene oxide doped hollow silica microspheres, then the microspheres are modified and introduced with carbon-carbon double bonds, the modified microspheres are used for copolymerization grafting with 4,3',5' -trihydroxy resveratrol and acrylic ester to obtain a silica microsphere grafted block polymer, finally, the silica microsphere grafted block polymer, pentanediol diacrylate, an initiator and a solvent are mixed to prepare a spraying liquid, the spraying liquid is sprayed on the surface of a substrate, and the spraying liquid is solidified to form a hydrophilic coating on the surface of the substrate. According to the invention, the hollow silica microspheres doped with graphene oxide are skillfully copolymerized and grafted into the polymer, so that the hollow silica microspheres are not only beneficial to dispersing, but also the doping of graphene oxide is beneficial to improving the hydrophilic performance of the coating, and active groups of the graphene oxide can be better combined with the base material, so that the firmness between the coating and the base material is improved. In addition, in the process of preparing the silicon dioxide microsphere grafted block polymer, 4,3',5' -trihydroxy resveratrol is adopted as a comonomer, the structure of a plurality of phenolic hydroxyl groups is beneficial to improving the hydrophilic performance of the coating, and meanwhile, the structure of the double benzene ring linkage is beneficial to dispersing active groups, so that the hydrophilic performance of the coating can be effectively improved, the firmness of the coating and a base material can be improved, and the service life of the coating can be prolonged.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a preparation method of a hydrophilic coating with high firmness, which comprises the following steps:
(1) 100g of sodium silicate nonahydrate (Na 2 SiO 3 ·9H 2 O), 10g of graphene oxide, 20g of propanol, 5g of urea and 300g of styrene-acrylic emulsion are mixed, and aged at 90 DEG CAfter aging for 4 hours, centrifuging, filtering, drying the precipitate at 80 ℃ for 3 hours, and roasting the precipitate at 450 ℃ for 3 hours in an air atmosphere to obtain hollow silica microspheres;
(2) Uniformly mixing 10g of hollow silica microspheres, 3g of vinyl trimethoxy silane, 10g of ethyl orthosilicate and 20g of propanol, regulating the pH of slurry to 4.5, reacting at 80 ℃ for 6 hours, filtering after the reaction, washing with propanol, and drying to obtain modified hollow silica microspheres with carbon-carbon double bonds on the surfaces;
(3) Mixing 5g of modified hollow silica microspheres with carbon-carbon double bonds on the surfaces, 20g of 4,3',5' -trihydroxy resveratrol, 10g of butyl acrylate and 50g of isopropanol, then adding 5g of azodiisobutyronitrile, reacting for 6 hours at 80 ℃, adding 200g of water after the reaction is finished, precipitating, filtering, and drying a filter cake to obtain a silica microsphere grafted block polymer;
(4) Mixing 5g of silicon dioxide microsphere grafted block polymer, 6g of pentanediol diacrylate, 2g of dibenzoyl peroxide and 20g of ethanol to obtain spraying liquid, spraying the spraying liquid onto the surface of a medical stainless steel material, and curing at 60 ℃ for 30min after the spraying is finished to form a hydrophilic coating on the surface of the stainless steel, wherein the thickness of the coating is 20 microns.
Example 2
The embodiment provides a preparation method of a hydrophilic coating with high firmness, which comprises the following steps:
(1) 100g of sodium silicate nonahydrate (Na 2 SiO 3 ·9H 2 O), 12g of graphene oxide, 20g of propanol, 5g of urea and 300g of styrene-acrylic emulsion are mixed, aged for 4 hours at 90 ℃, centrifuged after the aging is finished, filtered, and the precipitate is dried at 80 ℃ for 3 hours and then baked at 460 ℃ for 3 hours in an air atmosphere to obtain hollow silica microspheres;
(2) Uniformly mixing 10g of hollow silica microspheres, 3g of vinyl trimethoxy silane, 10g of ethyl orthosilicate and 20g of propanol, regulating the pH of slurry to 4.5, reacting at 80 ℃ for 6 hours, filtering after the reaction, washing with propanol, and drying to obtain modified hollow silica microspheres with carbon-carbon double bonds on the surfaces;
(3) Mixing 5g of modified hollow silica microspheres with carbon-carbon double bonds on the surfaces, 22g of 4,3',5' -trihydroxy resveratrol, 11g of butyl acrylate and 50g of isopropanol, then adding 6g of azodiisobutyronitrile, reacting for 6 hours at 80 ℃, adding 200g of water after the reaction is finished, precipitating, filtering, and drying a filter cake to obtain a silica microsphere grafted block polymer;
(4) Mixing 5g of silicon dioxide microsphere grafted block polymer, 6g of pentanediol diacrylate, 2g of dibenzoyl peroxide and 20g of ethanol to obtain spraying liquid, spraying the spraying liquid onto the surface of a medical stainless steel material, and curing at 70 ℃ for 40min after the spraying is finished to form a hydrophilic coating on the surface of the stainless steel, wherein the thickness of the coating is 20 microns.
Example 3
The embodiment provides a preparation method of a hydrophilic coating with high firmness, which comprises the following steps:
(1) 100g of sodium silicate nonahydrate (Na 2 SiO 3 ·9H 2 O), 13g of graphene oxide, 20g of propanol, 5g of urea and 300g of styrene-acrylic emulsion are mixed, aged for 4 hours at 90 ℃, centrifuged after the aging is finished, filtered, and the precipitate is dried at 80 ℃ for 3 hours and then baked at 460 ℃ for 3 hours in an air atmosphere to obtain hollow silica microspheres;
(2) Uniformly mixing 10g of hollow silica microspheres, 3g of vinyl trimethoxy silane, 10g of ethyl orthosilicate and 20g of propanol, regulating the pH of slurry to 4.5, reacting at 80 ℃ for 6 hours, filtering after the reaction, washing with propanol, and drying to obtain modified hollow silica microspheres with carbon-carbon double bonds on the surfaces;
(3) Mixing 6g of modified hollow silica microspheres with carbon-carbon double bonds on the surfaces, 24g of 4,3',5' -trihydroxy resveratrol, 11g of butyl acrylate and 50g of isopropanol, then adding 6g of azodiisobutyronitrile, reacting for 6 hours at 80 ℃, adding 200g of water after the reaction is finished, precipitating, filtering, and drying a filter cake to obtain a silica microsphere grafted block polymer;
(4) Mixing 5g of silicon dioxide microsphere grafted block polymer, 6g of pentanediol diacrylate, 2g of dibenzoyl peroxide and 20g of ethanol to obtain spraying liquid, spraying the spraying liquid onto the surface of a medical stainless steel material, and curing at 70 ℃ for 60min after the spraying is finished to form a hydrophilic coating on the surface of the stainless steel, wherein the thickness of the coating is 20 microns.
Comparative example 1
The comparative example provides a method for preparing a hydrophilic coating with high firmness, which comprises the following steps:
(1) Uniformly mixing 10g of nano silicon dioxide, 3g of vinyl trimethoxy silane, 10g of ethyl orthosilicate and 20g of propanol, regulating the pH of slurry to 4.5, reacting for 6 hours at 80 ℃, filtering after the reaction is finished, washing with propanol, and drying to obtain modified silicon dioxide microspheres with carbon-carbon double bonds on the surfaces;
(2) Mixing 5g of modified silicon dioxide microspheres with carbon-carbon double bonds on the surfaces, 20g of 4,3',5' -trihydroxy resveratrol, 10g of butyl acrylate and 50g of isopropanol, then adding 5g of azodiisobutyronitrile, reacting for 6 hours at 80 ℃, adding 200g of water after the reaction is finished, precipitating and separating out, filtering, and drying a filter cake to obtain a silicon dioxide microsphere grafted block polymer;
(3) Mixing 5g of silicon dioxide microsphere grafted block polymer, 6g of pentanediol diacrylate, 2g of dibenzoyl peroxide and 20g of ethanol to obtain spraying liquid, spraying the spraying liquid onto the surface of a medical stainless steel material, and curing at 60 ℃ for 30min after the spraying is finished to form a hydrophilic coating on the surface of the stainless steel, wherein the thickness of the coating is 20 microns.
Comparative example 2
This comparative example provides a method for preparing a hydrophilic coating with high firmness, which is different from example 1 in that graphene oxide is not added in step (1).
Comparative example 3
The comparative example provides a method for preparing a hydrophilic coating with high firmness, which comprises the following steps:
(1) 100g of sodium silicate nonahydrate (Na 2 SiO 3 ·9H 2 O), 10g of graphene oxide, 20g of propanol, 5g of urea and 300g of styrene-acrylic emulsion are mixed, aged for 4 hours at 90 ℃, centrifuged after the aging is finished, filtered, and the precipitate is dried at 80 ℃ for 3 hours and then baked at 450 ℃ for 3 hours in an air atmosphere to obtain hollow silica microspheres;
(2) Mixing 5g of hollow silica microspheres, 20g of 4,3',5' -trihydroxy resveratrol, 10g of butyl acrylate and 50g of isopropanol, then adding 5g of azodiisobutyronitrile, reacting for 6 hours at 80 ℃, adding 200g of water after the reaction is finished, precipitating and separating out, filtering, and drying a filter cake to obtain a silica microsphere doped polymer;
(3) Mixing 5g of silicon dioxide microsphere doped polymer, 6g of pentanediol diacrylate, 2g of dibenzoyl peroxide and 20g of ethanol to obtain spraying liquid, spraying the spraying liquid on the surface of a medical stainless steel material, and curing for 30min at 60 ℃ after the spraying is finished to form a hydrophilic coating on the surface of the stainless steel, wherein the thickness of the coating is 20 microns.
Comparative example 4
This comparative example provides a method for preparing a hydrophilic coating with high firmness, which is different from example 1 in that 4,3',5' -trihydroxy resveratrol is replaced by 1, 2-stilbene in step (3).
Comparative example 5
This comparative example provides a method for preparing a hydrophilic coating with high firmness, which is different from example 1 in that 4,3',5' -trihydroxy resveratrol is replaced with vinylcyclohexane in step (3).
Test case
Water contact angle test: testing the wettability of the coating by adopting a contact angle measuring instrument; the coating is placed in an air environment, water drops are dripped on the surface of the coating, and water contact is tested after the water drops are stabilized.
Fastness testing: according to GB/T2791-1995 Standard of flexible Material vs. flexible Material of adhesive T peel Strength test method, a 100mm long aluminum alloy tensile test piece is selected, a spray coating solution is uniformly coated on a test surface of the tensile test piece, the coating length is 80mm, and the tensile test is carried out on a tester for testing the peel strength of the tensile test piece after curing for 30min at 60 ℃.
The test results are shown in Table 1.
TABLE 1
| Sample of | Contact angle of water/degree | Peel strength/(kN/m) |
| Example 1 | 7.45 | 0.27 |
| Example 2 | 7.01 | 0.29 |
| Example 3 | 6.82 | 0.33 |
| Comparative example 1 | 15.45 | 0.25 |
| Comparative example 2 | 12.07 | 0.24 |
| Comparative example 3 | 18.81 | 0.15 |
| Comparative example 4 | 25.37 | 0.12 |
| Comparative example 5 | 27.01 | 0.10 |
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (6)
1. The preparation method of the hydrophilic coating with high firmness is characterized by comprising the following steps:
1) Mixing sodium silicate, graphene oxide, a solvent, urea and styrene-acrylic emulsion, aging, centrifuging after aging, filtering, drying and roasting to obtain hollow silica microspheres;
2) Mixing and reacting hollow silica microspheres, vinyl trimethoxy silane, ethyl orthosilicate and a solvent, filtering, washing and drying after the reaction is finished to obtain modified hollow silica microspheres with carbon-carbon double bonds on the surfaces;
3) Mixing modified hollow silica microspheres with carbon-carbon double bonds on the surfaces, 4,3',5' -trihydroxy resveratrol, butyl acrylate and a solvent, then adding azodiisobutyronitrile for reaction, adding water after the reaction is finished, filtering and drying to obtain a silica microsphere grafted block polymer;
4) Mixing a silicon dioxide microsphere grafted block polymer, pentanediol diacrylate, an initiator and a solvent to obtain a spraying liquid, spraying the spraying liquid on the surface of a substrate, and curing to obtain a hydrophilic coating formed on the surface of the substrate;
the sodium silicate in the step 1) is sodium silicate nonahydrate, and the mass ratio of the sodium silicate nonahydrate to graphene oxide to the solvent to the urea to the styrene-acrylic emulsion is 100: (8-15): (15-25): (2-8): (200-400);
the mass ratio of the hollow silicon dioxide microspheres to the vinyl trimethoxy silane to the ethyl orthosilicate to the solvent in the step 2) is 10: (1-5): (8-20): (10-30);
the mass ratio of the modified hollow silica microsphere with carbon-carbon double bonds on the surface in the step 3) to the 4,3',5' -trihydroxy resveratrol, butyl acrylate, solvent and azodiisobutyronitrile is (3-7): (15-25): (5-15): (20-60): (2-8); the addition amount of the water is 3-6 times of the mass of the solvent; the reaction temperature is 70-90 ℃ and the reaction time is 2-8h;
the mass ratio of the silicon dioxide microsphere grafted block polymer, the pentanediol diacrylate, the initiator and the solvent in the step 4) is (3-7): (3-8): (1-3): (10-50); the curing temperature is 50-70 ℃ and the curing time is 20-60min; the initiator is dibenzoyl peroxide.
2. The method for preparing a high-firmness hydrophilic coating according to claim 1, wherein the aging temperature in step 1) is 80-98 ℃ and the aging time is 2-6 hours;
the drying temperature is 70-85 ℃ and the drying time is 1-5h;
the roasting temperature is 450-480 ℃, the roasting time is 1-5h, and the roasting process is carried out in an air atmosphere.
3. The method for producing a high-firmness hydrophilic coating according to claim 1, further comprising the step of adjusting the pH of the mixed slurry to 4 to 6 in step 2).
4. The method for preparing a highly robust hydrophilic coating according to claim 1, wherein the reaction temperature in step 2) is 70-90 ℃ and the reaction time is 2-8 hours.
5. The method for producing a highly durable hydrophilic coating according to claim 1, wherein the solvent is at least one selected from the group consisting of ethanol, propanol, and isopropanol.
6. The method for producing a high-firmness hydrophilic coating according to any one of claims 1 to 5, wherein the base material is an alloy; the hydrophilic coating has a thickness of 10-30 microns.
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| CN109913073A (en) * | 2019-03-01 | 2019-06-21 | 浙江大学 | A kind of super-hydrophilic coating and preparation method for medical endoscope camera lens |
| CN113354993A (en) * | 2021-07-15 | 2021-09-07 | 乐普（北京）医疗器械股份有限公司 | Hydrophilic coating, preparation method and coating firmness testing method |
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| CN109913073A (en) * | 2019-03-01 | 2019-06-21 | 浙江大学 | A kind of super-hydrophilic coating and preparation method for medical endoscope camera lens |
| CN113354993A (en) * | 2021-07-15 | 2021-09-07 | 乐普（北京）医疗器械股份有限公司 | Hydrophilic coating, preparation method and coating firmness testing method |
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