CN117210129A - Hydrophobic oleophobic antifouling wear-resistant coating and preparation method thereof - Google Patents
Hydrophobic oleophobic antifouling wear-resistant coating and preparation method thereof Download PDFInfo
- Publication number
- CN117210129A CN117210129A CN202311289800.5A CN202311289800A CN117210129A CN 117210129 A CN117210129 A CN 117210129A CN 202311289800 A CN202311289800 A CN 202311289800A CN 117210129 A CN117210129 A CN 117210129A
- Authority
- CN
- China
- Prior art keywords
- coating
- preparation
- polydimethylsiloxane
- substrate
- drying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 85
- 239000011248 coating agent Substances 0.000 title claims abstract description 75
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 33
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 41
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 41
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 41
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 15
- 238000005507 spraying Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000013067 intermediate product Substances 0.000 claims description 4
- 239000012267 brine Substances 0.000 claims description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 3
- 238000005935 nucleophilic addition reaction Methods 0.000 claims description 2
- 238000006268 reductive amination reaction Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 8
- 239000008199 coating composition Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 230000008439 repair process Effects 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000003075 superhydrophobic effect Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000012650 click reaction Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000006748 scratching Methods 0.000 description 2
- 230000002393 scratching effect Effects 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 1
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 1
- LBZRRXXISSKCHV-UHFFFAOYSA-N [B].[O] Chemical group [B].[O] LBZRRXXISSKCHV-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRTALTYTFFNPAC-UHFFFAOYSA-N boroxin Chemical compound B1OBOBO1 BRTALTYTFFNPAC-UHFFFAOYSA-N 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000013003 healing agent Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920006273 intrinsic self-healing polymer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention mainly relates to the technical field of coating compositions, and particularly discloses a hydrophobic oleophobic antifouling wear-resistant coating and a preparation method thereof. The coating is obtained by mixing modified polydimethylsiloxane and nano silicon dioxide in a solvent and then spraying the mixture on the surface of a substrate. Compared with the prior art, the coating prepared by the method has high transparency, is very suitable for being applied to the surface of glass, and has the advantages of hydrophobic and oleophobic surfaces, good self-repairing effect and high repairing rate.
Description
Technical Field
The invention relates to the technical field of coating compositions, in particular to a hydrophobic oleophobic antifouling wear-resistant coating and a preparation method thereof.
Background
Coatings, i.e. a continuous uniform film (< 60 μm) applied to the surface of an object for protecting or decorating the substrate, tend to be contaminated with various contaminants or damaged by different forces, thus requiring frequent cleaning or re-painting after a period of use. Many instruments and equipment, wall surfaces, object surfaces and the like have great requirements for antifouling and self-cleaning. In addition, many architectural glazings or glass curtain walls also require hydrophobic and oleophobic coatings to reduce the additional cost of cleaning. The adhesion of contaminants to the surface of the coating over time can have an effect on its appearance and other properties and can even lead to its failure to protect. The factors influencing the antifouling properties of the coating are mainly the wettability of the surface of the coating, whereas the wettability of the solid surface is mainly influenced by its surface roughness and composition. Thus, the antifouling coatings are generally prepared by modifying the surface chemistry and distribution to adjust the wettability of the surface to reduce the surface energy of the system, such as by introducing low surface energy species such as silicon, fluorine, etc.; or filling the nanoparticles increases the surface roughness of the coating.
Chinese patent 202010809760.2 discloses a preparation method of a transparent amphiphobic coating: in the form of chain fumed silica and hollow rod-like Mg (OH) 2-x F x As a film material, chain-shaped fumed silica and hollow rod-shaped Mg (OH) are subjected to hydroxyl condensation reaction and mercapto-alkene click reaction 2-x F x And (3) modifying, and depositing sol on a substrate such as glass by adopting a spraying method. The coating prepared by the invention has high transparency, excellent performances such as superhydrophobicity, superoleophobicity, self-cleaning and the like, wide application range, simple, quick and expandable spraying method, and is suitable for various large-area substrates such as ceramics, metals, plastics, wood, fabrics, glass and the like. The sulfhydryl-alkene click reaction adopted by the invention is simple and efficient, can finish amphiphobic modification within 20 minutes, and is a promising method for grafting fluorinated groups to realize super amphiphobicity.
Chinese patent 201310345228.X discloses a stable transparent super-hydrophobic or super-amphiphobic coating, and a preparation method and application thereof. The preparation steps of the coating are as follows: blending the nano particles, epoxy resin and solvent to obtain an epoxy resin hybridization solution; dissolving fluorine-containing substances and catalysts in a solvent to prepare a fluorine-containing solution; spraying the epoxy resin hybridization solution on the surface of a substrate, drying the substrate at the temperature of 80-130 ℃ for 0.5-5 hours, spraying the fluorine-containing solution on the surface of the substrate, drying the substrate at the temperature of 80-130 ℃ for 0.5-5 hours after the solvent volatilizes to dryness, and finally flushing the surface of the substrate with the solvent to obtain the stable and transparent super-hydrophobic or super-amphiphobic coating. The super-hydrophobic or super-amphiphobic coating can be applied to hydrophobic and oleophobic modification of most substrate surfaces.
In the prior art, most of the antifouling coatings on the glass surface use fluorine groups to achieve low surface energy, but the use of fluorine in large quantities is not only not environment-friendly but also has certain toxicity, which is not in accordance with sustainable development strategies. In addition, because the durability of the special coating at the position of the glass coating is critical, the coating needs to have certain wear resistance and self-repairing capability, so that the maintenance cost can be reduced, and the service life of the coating can be prolonged.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention aims to solve the technical problem of a hydrophobic oleophobic antifouling wear-resistant coating and a preparation method thereof.
The self-repairing material is divided into an exogenous self-repairing material and an intrinsic self-repairing material according to a repairing mechanism, wherein the exogenous self-repairing material is obtained by dispersing microcapsules or micro-pipelines wrapped with a repairing agent in bulk phase materials. When the material is damaged by mechanical damage, the microcapsules and the micro-pipelines dispersed in the bulk material are broken, and the repairing agent is released and reacts, so that the damage self-repairing of the material is realized. However, the exogenous self-repairing material has low repairing times and low efficiency, thus limiting practical application. Intrinsic self-healing materials are materials that do not contain any insulating healing agent, and when damaged, can repair themselves automatically or under external stimuli (e.g., photo-thermal, electro-thermal, humidity, etc.). The self-repairing material realizes self-repairing by using reversible intermolecular force, so that the repairing times are not limited, and the repairing efficiency is higher.
In the invention, the intermediate product is obtained by nucleophilic addition of diamino-polydimethylsiloxane and 4-aminopyridine-2, 6-dicarboxaldehyde, and then the intermediate product is subjected to reductive amination with 2-aldehyde-5-methylphenylboronic acid to obtain the modified polydimethylsiloxane, and the solution obtained by mixing the modified polydimethylsiloxane and nano silicon dioxide is sprayed on the surface of a substrate and dried to obtain the hydrophobic and oleophobic antifouling wear-resistant coating. Because the prepared modified polydimethylsiloxane has reversible hydrogen bond, imine bond and nitrogen-boron coordination bond, the modified polydimethylsiloxane can start self-repairing when the surface of the coating is damaged and loses the hydrophobic and oleophobic characteristics, so that the original wettability is recovered, and a good self-repairing effect is achieved under the combined action of multiple mechanisms, and the repairing rate is higher. In addition, the flexible silicon-oxygen chain in the polydimethylsiloxane can endow the polydimethylsiloxane with good molecular chain movement capability, and the molecular chains can mutually diffuse at the interface in the self-repairing process, so that the recombination at the damaged part can be quickened in the self-repairing process.
In order to achieve the aim, the invention provides a preparation method of a hydrophobic oleophobic antifouling wear-resistant coating, which comprises the following steps:
s1, adding 4-12 parts by weight of diamino-polydimethylsiloxane into 10-20 parts by weight of ethanol, adding 0.04-0.1 part by weight of 4-aminopyridine-2, 6-dicarboxaldehyde, heating to 65-85 ℃, stirring for 6-10 hours, cooling to room temperature, diluting with water, precipitating, filtering, washing with alcohol, and drying residues for the next step;
s2, adding the product of the last step into 15-25 parts by weight of methanol, adding 0.5-1.6 parts by weight of 2-aldehyde-5-methylbenzeneboronic acid, 0.01-0.05 part by weight of triethylamine and 0.05-0.1 part by weight of 3A molecular sieve, stirring for 4-8 hours at 35-50 ℃ in an argon atmosphere after the addition is finished, adding 0.2-0.8 part by weight of sodium borohydride, continuously stirring for 12-18 hours, filtering, adding acid into the filtrate, quenching, separating liquid, washing with alkali, washing with brine, drying and concentrating to obtain modified polydimethylsiloxane;
s3, adding 1.5-5 parts by weight of modified polydimethylsiloxane and 1-10 parts by weight of nano silicon dioxide into 50-100 parts by weight of ethanol, uniformly dispersing, spraying the mixture on the surface of a substrate, controlling the thickness of the coating to be less than 500nm, and drying the substrate at 50-60 ℃ to obtain the nano silicon dioxide.
The invention also provides an anti-fouling wear-resistant coating with hydrophobic and oleophobic properties, which is prepared by the method.
The invention has the beneficial effects that:
1. compared with the prior art, the coating prepared by the method has high transparency, is very suitable for being applied to the surface of glass, does not need to be treated at high temperature, and can not only be hydrophobic and oleophobic, but also show good antifouling and self-cleaning effects under various solutions;
2. compared with the prior art, the modified polydimethylsiloxane prepared by the invention has reversible hydrogen bond, imine bond and nitrogen-boron coordination bond, so that the modified polydimethylsiloxane can start self-repairing when the surface of a coating is damaged and loses the hydrophobic and oleophobic characteristics, the original wettability is recovered, and a good self-repairing effect is achieved under the combined action of multiple mechanisms, so that the repairing rate is higher.
Detailed Description
Diamino-polydimethylsiloxane, mw=5000, mikrin.
Polydimethylsiloxane, OFX-193, dow Corning.
4-aminopyridine-2,6-dicarbaldehyde, CAS no: 1221640-00-1.
Nano silicon dioxide with the grain diameter of 5-10 nm.
Comparative example 1
A preparation method of a hydrophobic oleophobic antifouling wear-resistant coating comprises the following steps:
adding 2g of polydimethylsiloxane and 1.5g of nano silicon dioxide into 100mL of ethanol, uniformly dispersing, spraying on the surface of a glass substrate, controlling the thickness of the coating to be less than 500nm, and drying the substrate at 55 ℃ to obtain the hydrophobic oleophobic antifouling wear-resistant coating.
Example 1
A preparation method of a hydrophobic oleophobic antifouling wear-resistant coating comprises the following steps:
s1, adding 5g of diamino-polydimethylsiloxane into 15mL of ethanol, adding 0.065g of 4-aminopyridine-2, 6-dicarboxaldehyde, heating to 80 ℃, stirring for 6 hours, cooling to room temperature, diluting with water, precipitating, filtering, washing with alcohol, and drying the residue at 50 ℃ for 4 hours for the next step;
s2, adding the product of the last step into 20mL of methanol, adding 0.8g of 2-aldehyde-5-methylbenzeneboronic acid, 0.03g of triethylamine and 0.1g of 3A molecular sieve, stirring for 4 hours at 45 ℃ in an argon atmosphere after the addition, adding 0.6g of sodium borohydride, continuously stirring for 12 hours, filtering, adding acid into the filtrate, quenching, separating the filtrate, washing with alkali, washing with salt water, drying, and concentrating at 45 ℃ and minus 0.9MPa to obtain modified polydimethylsiloxane;
s3, adding 2g of modified polydimethylsiloxane and 1.5g of nano silicon dioxide into 100mL of ethanol, uniformly dispersing, spraying on the surface of a glass substrate, controlling the thickness of the coating to be less than 500nm, and drying the substrate at 55 ℃ to obtain the hydrophobic oleophobic antifouling wear-resistant coating.
Example 2
A preparation method of a hydrophobic oleophobic antifouling wear-resistant coating comprises the following steps:
s1, adding 5g of diamino-polydimethylsiloxane into 15mL of ethanol, adding 0.065g of 4-aminopyridine-2, 6-dicarboxaldehyde, heating to 80 ℃, stirring for 6 hours, cooling to room temperature, diluting with water, precipitating, filtering, washing with alcohol, and drying the residue at 50 ℃ for 4 hours for the next step;
s2, adding 2g of the product obtained in the last step and 1.5g of nano silicon dioxide into 100mL of ethanol, uniformly dispersing, spraying on the surface of a glass substrate, controlling the thickness of the coating to be less than 500nm, and drying the substrate at 55 ℃ to obtain the hydrophobic oleophobic antifouling wear-resistant coating.
Example 3
A preparation method of a hydrophobic oleophobic antifouling wear-resistant coating comprises the following steps:
s1, adding 5g of diamino-polydimethylsiloxane into 20mL of methanol, adding 0.8g of 2-aldehyde-5-methylbenzylboric acid, 0.03g of triethylamine and 0.1g of 3A molecular sieve, stirring for 4 hours at 45 ℃ in an argon atmosphere after the addition, adding 0.6g of sodium borohydride, continuously stirring for 12 hours, filtering, adding acid into filtrate, quenching, separating liquid, washing with alkali, washing with brine, drying, and concentrating at 45 ℃ and minus 0.9MPa to obtain modified polydimethylsiloxane;
s2, adding 2g of modified polydimethylsiloxane and 1.5g of nano silicon dioxide into 100mL of ethanol, uniformly dispersing, spraying on the surface of a glass substrate, controlling the thickness of the coating to be less than 500nm, and drying the substrate at 55 ℃ to obtain the hydrophobic oleophobic antifouling wear-resistant coating.
Example 4
A hydrophobic oleophobic antifouling wear-resistant coating and a preparation method thereof comprise the following steps:
s1, adding 5g of diamino-polydimethylsiloxane into 15mL of ethanol, adding 0.065g of 4-aminopyridine-2, 6-dicarboxaldehyde, heating to 80 ℃, stirring for 6 hours, cooling to room temperature, diluting with water, precipitating, filtering, washing with alcohol, and drying the residue at 50 ℃ for 4 hours for the next step;
s2, adding the product of the last step into 20mL of methanol, adding 0.8g of 2-aldehyde-5-methylbenzeneboronic acid, 0.03g of triethylamine and 0.1g of 3A molecular sieve, stirring for 4 hours at 45 ℃ in an argon atmosphere after the addition, adding 0.6g of sodium borohydride, continuously stirring for 12 hours, filtering, adding acid into the filtrate, quenching, separating the filtrate, washing with alkali, washing with salt water, drying, and concentrating at 45 ℃ and minus 0.9MPa to obtain modified polydimethylsiloxane;
s3, adding 2g of modified polydimethylsiloxane and 2g of nano silicon dioxide into 100mL of ethanol, uniformly dispersing, spraying on the surface of a glass substrate, controlling the thickness of the coating to be less than 500nm, and drying the substrate at 55 ℃ to obtain the hydrophobic oleophobic antifouling wear-resistant coating.
Example 5
A preparation method of a hydrophobic oleophobic antifouling wear-resistant coating comprises the following steps:
s1, adding 5g of diamino-polydimethylsiloxane into 15mL of ethanol, adding 0.065g of 4-aminopyridine-2, 6-dicarboxaldehyde, heating to 80 ℃, stirring for 6 hours, cooling to room temperature, diluting with water, precipitating, filtering, washing with alcohol, and drying the residue at 50 ℃ for 4 hours for the next step;
s2, adding the product of the last step into 20mL of methanol, adding 0.8g of 2-aldehyde-5-methylbenzeneboronic acid, 0.03g of triethylamine and 0.1g of 3A molecular sieve, stirring for 4 hours at 45 ℃ in an argon atmosphere after the addition, adding 0.6g of sodium borohydride, continuously stirring for 12 hours, filtering, adding acid into the filtrate, quenching, separating the filtrate, washing with alkali, washing with salt water, drying, and concentrating at 45 ℃ and minus 0.9MPa to obtain modified polydimethylsiloxane;
s3, adding 2.5g of modified polydimethylsiloxane and 1.5g of nano silicon dioxide into 100mL of ethanol, uniformly dispersing, spraying on the surface of a glass substrate, controlling the thickness of the coating to be less than 500nm, and drying the substrate at 55 ℃ to obtain the hydrophobic oleophobic antifouling wear-resistant coating.
Test example 1
The coatings prepared in the comparative examples and examples were subjected to contact angle testing, and the liquids tested included water, edible oil, and ethylene glycol. The obtained coating is subjected to light transmittance test, ultraviolet-visible light transmittance is tested by adopting a spectrophotometer, and specific test methods refer to GB/T2410-2008 'determination of transparent plastic light transmittance and haze'.
Table 1 results of hydrophobic oleophobic and light transmittance test of the coating
The coatings of the comparative examples and examples exhibited good repellency, i.e., a higher contact angle, to a variety of liquids due to the low surface energy characteristics of the polydimethylsiloxane in combination with the roughened surface structure, which imparts good hydrophobic and oleophobic properties to the coating. However, in example 4, when the amount of nano silica increases, the transmittance and the contact angle decrease, and in example 5, the modified polydimethylsiloxane only decreases, probably because the silica nanoparticles are white and the polydimethylsiloxane is transparent, the amount of silica directly affects the transparency of the coating, and the ratio between the polydimethylsiloxane and the silica affects the roughness of the surface of the coating, thus reflecting the change of the contact angle. From the test results, the coating of the embodiment 1 has the best hydrophobic and oleophobic effects and high transparency, is very suitable for being applied to the surfaces of objects such as glass which need high light transmittance, not only can prevent dirt and self-clean, but also can reduce the cost of manual maintenance.
Test example 2
The coatings prepared in the control and examples were subjected to wear resistance and self-repair tests. The abrasion resistance test is to evaluate the abrasion resistance of the super-hydrophobic coating through a sand paper abrasion experiment. The sample was placed on 800 mesh sandpaper, a 200g weight load was applied, and then the sample was moved at a constant speed in a fixed direction for 10cm, causing abrasion to the sample. The contact angle was measured once for each abrasion and the effect of the abrasion length on the wettability was evaluated. The self-repairing test is to test the repairing condition of the coating after being scratched and oxidized, and the blade is adopted to manufacture scratches on the surface of the coating in a mode of scratching the coating but not scratching the substrate, and then the sample is subjected to heat treatment to testThe water contact angle of the surface of the coating after treatment; o for coating surface 2 After plasma etching to change the hydrophobicity into hydrophilicity, the surface was again tested for water contact angle after being left at room temperature for 2 d.
Table 2 coating wear test and self-healing test
From the test results, it can be seen that the coatings prepared in the comparative example and the examples have better wear resistance, the hydrophobicity is not easily lost when the abrasive paper is worn, and in example 4, the silica nanoparticles are not uniformly dispersed in the polydimethylsiloxane after the proportion is increased, so that the coatings are easily fallen off when the abrasive paper is worn, and the surface wettability is affected. It can be seen from the repair test that the surface of the coating is damaged and falls off after the coating is scratched, so that the water contact angle is reduced, but the migration of the molecular chain of the self-repairing polymer at the bottom layer is accelerated after the heat treatment, the originally broken functional group or hydrogen bond moves along with the molecular chain to generate non-directional recombination, so that the scratch is repaired, the self-repairing of the coating is realized, and compared with other coatings, the self-repairing method of the coating in embodiment 1 can repair the broken part faster and better when the coating is heated due to the fact that a plurality of reversible bonds of hydrogen bonds, imine bonds and nitrogen-boron coordination bonds exist in the coating at the same time, and can recover to the previous level after the heat treatment. O (O) 2 The plasma etching can cause serious oxidation of surface substances in a short time, so that the surface of the coating is changed from hydrophobic to hydrophilic, but hydrophilic groups generated by etching disappear from the surface of the coating in the self-repairing process, and new polydimethylsiloxane chain segments can move, so that the surface of the coating is covered again, the surface substance composition is recovered, and the repair of the hydrophobic property is realized. In the indoor environment, hydrophilic groups on the surface of the hydrophilic coating can absorb water from the surrounding environment, water molecules can promote dissociation of nitrogen coordinated boron-oxygen hexacyclic rings, molecular chain movement capacity is increased, molecular chains are enabled to migrate to an oxidized area more quickly, and therefore surface energy of the coating is reduced. When moisture disappears, the boron-nitrogen coordination boron-oxygen ring bondThe surface is re-polymerized and the repair is completed. The key to the excellent self-healing properties of example 1 is not only the reversible nitrogen-boron coordination boroxine described above, but also the fact that the presence of the double dynamic reversible chemical network of hydrogen bonds and imine bonds accelerates the recombination of the interfacial functionalities, thus enabling the best self-healing effect to be demonstrated compared to the control and other examples.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (8)
1. The preparation method of the hydrophobic oleophobic antifouling wear-resistant coating is characterized in that the coating is obtained by mixing modified polydimethylsiloxane and nano silicon dioxide in a solvent and then spraying the mixture on the surface of a substrate.
2. A method of preparing a coating as claimed in claim 1, comprising the steps of:
s1, nucleophilic addition of diamino-polydimethylsiloxane and 4-aminopyridine-2, 6-dicarboxaldehyde to obtain an intermediate product;
s2, carrying out reductive amination on the intermediate product in the S1 and 2-aldehyde-5-methylphenylboronic acid to obtain modified polydimethylsiloxane;
s3, mixing the modified polydimethylsiloxane and the nano silicon dioxide in a solvent, and spraying the mixture on the surface of a substrate.
3. A method of preparing a coating as claimed in claim 1, comprising the steps of:
s1, adding diamino-polydimethylsiloxane into ethanol, adding 4-aminopyridine-2, 6-dicarboxaldehyde, heating and stirring, cooling to room temperature, diluting with water, precipitating, filtering, washing with alcohol, and drying residues for the next step;
s2, adding the product of the last step into methanol, adding 2-aldehyde-5-methylphenylboric acid, triethylamine and 3A molecular sieve, heating and stirring for 4-8 hours in an argon atmosphere after the addition, adding sodium borohydride, continuously stirring for 12-18 hours, filtering, adding acid into the filtrate to quench, separating liquid, and drying and concentrating after alkaline washing and brine washing to obtain modified polydimethylsiloxane;
s3, adding the modified polydimethylsiloxane and the nano silicon dioxide into ethanol, uniformly dispersing, spraying the mixture on the surface of the substrate, and drying the substrate to obtain the nano silicon dioxide.
4. A method of preparation as claimed in claim 3, wherein: the heating temperature in the step S1 is 65-85 ℃.
5. A method of preparation as claimed in claim 3, wherein: and in the step S1, the stirring time is 6-10 h.
6. A method of preparation as claimed in claim 3, wherein: the heating temperature in the step S2 is 35-50 ℃.
7. A method of preparation as claimed in claim 3, wherein: the temperature range of the drying in the step S3 is 50-60 ℃.
8. A hydrophobic oleophobic antifouling wear resistant coating prepared by the method of any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311289800.5A CN117210129A (en) | 2023-10-08 | 2023-10-08 | Hydrophobic oleophobic antifouling wear-resistant coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311289800.5A CN117210129A (en) | 2023-10-08 | 2023-10-08 | Hydrophobic oleophobic antifouling wear-resistant coating and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117210129A true CN117210129A (en) | 2023-12-12 |
Family
ID=89037018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311289800.5A Pending CN117210129A (en) | 2023-10-08 | 2023-10-08 | Hydrophobic oleophobic antifouling wear-resistant coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117210129A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181530A (en) * | 2018-08-31 | 2019-01-11 | 吉林大学 | Bis- compound super-hydrophobic coats of scale silica of dimethyl silicone polymer-and forming method thereof |
| CN110790937A (en) * | 2019-12-05 | 2020-02-14 | 青岛科技大学 | Repairable and easily-soluble organic silicon elastomer containing boron-oxygen bonds and preparation method thereof |
| CN111892846A (en) * | 2020-08-18 | 2020-11-06 | 东北石油大学 | Water-based self-repairing super-hydrophobic coating and preparation method thereof |
| CN113150284A (en) * | 2020-12-24 | 2021-07-23 | 西南科技大学 | Triple-repaired double-cross-linked polysiloxane super-hydrophobic elastomer and preparation method thereof |
| CN113773746A (en) * | 2021-06-30 | 2021-12-10 | 重庆交通大学 | High-wear-resistance repairable self-cleaning coating, coating structure and construction method thereof |
| CN115819776A (en) * | 2023-02-22 | 2023-03-21 | 山东东岳有机硅材料股份有限公司 | Self-repairing polysiloxane elastomer based on strong and weak hydrogen bond effects and preparation method thereof |
-
2023
- 2023-10-08 CN CN202311289800.5A patent/CN117210129A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181530A (en) * | 2018-08-31 | 2019-01-11 | 吉林大学 | Bis- compound super-hydrophobic coats of scale silica of dimethyl silicone polymer-and forming method thereof |
| CN110790937A (en) * | 2019-12-05 | 2020-02-14 | 青岛科技大学 | Repairable and easily-soluble organic silicon elastomer containing boron-oxygen bonds and preparation method thereof |
| CN111892846A (en) * | 2020-08-18 | 2020-11-06 | 东北石油大学 | Water-based self-repairing super-hydrophobic coating and preparation method thereof |
| CN113150284A (en) * | 2020-12-24 | 2021-07-23 | 西南科技大学 | Triple-repaired double-cross-linked polysiloxane super-hydrophobic elastomer and preparation method thereof |
| CN113773746A (en) * | 2021-06-30 | 2021-12-10 | 重庆交通大学 | High-wear-resistance repairable self-cleaning coating, coating structure and construction method thereof |
| CN115819776A (en) * | 2023-02-22 | 2023-03-21 | 山东东岳有机硅材料股份有限公司 | Self-repairing polysiloxane elastomer based on strong and weak hydrogen bond effects and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 郭玉海等: "高新纺织材料研究与应用丛书 聚四氟乙烯过滤材料", 31 August 2022, 中国纺织出版社, pages: 80 - 84 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5415927A (en) | Water-repellant glass products and process for the production thereof | |
| Zeng et al. | Facile fabrication of durable superhydrophobic and oleophobic surface on cellulose substrate via thiol-ene click modification | |
| EP0810186B1 (en) | Water-repellent glass plate | |
| CN107141948B (en) | Compound aqueous solution for preparing self-repairing antifogging and antifrosting coating and application thereof | |
| CN106519971A (en) | Hydrophilic siliceous coating solution and coating method | |
| US3476827A (en) | Coating compositions comprising polysilicic acid,selected organic polymers,and selected silicones | |
| CN113698656B (en) | Antifogging film material and preparation method thereof | |
| CN108559347B (en) | Water-based paint for automobile plastic parts | |
| CN117210129A (en) | Hydrophobic oleophobic antifouling wear-resistant coating and preparation method thereof | |
| US6706906B2 (en) | Water repellent composition, surface-treated substrate, process for its production and article for transport equipment | |
| Chang et al. | Preparation of nanosilica/polyacrylate antifog coatings on polycarbonate substrates | |
| AU2012227320B2 (en) | Non-stick ceramic coating composition and process | |
| TWI734914B (en) | A coating and glass of self-cleaning and anti-reflective properties simultaneously and manufacturing methods thereof | |
| CN108948829B (en) | Water-repellent oil-repellent agent and water-repellent oil-repellent automobile glass | |
| KR102000753B1 (en) | Clear coating composition | |
| CN113083640A (en) | Spraying method of anti-fingerprint nano coating | |
| JPH1059745A (en) | Water repellent glass and its production | |
| US20220064483A1 (en) | Surface coating compositions | |
| CN115418144B (en) | Ultra-low alcoholysis degree polyvinyl alcohol anti-fog coating material and manufacturing method thereof | |
| US11767434B2 (en) | Composition for a stainless coating, stainless member including the stainless coating, and method of manufacturing same | |
| CN115926614B (en) | Bionic super-hydrophilic coating with anti-frost, anti-fog and anti-fouling functions and preparation and application thereof | |
| KR19980048678A (en) | Manufacturing method of water repellent glass or water repellent ceramic | |
| JP7428979B2 (en) | Antifogging agent composition, antifogging article having an antifogging film formed from the composition | |
| AU2022307027A1 (en) | Polysilazane compositions | |
| WO2020116541A1 (en) | Coating agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |