CN102241939A - Organic-inorganic hybrid super-hydrophilic coating as well as preparation method and application thereof - Google Patents
Organic-inorganic hybrid super-hydrophilic coating as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an organic-inorganic hybrid super-hydrophilic coating as well as a preparation method and an application thereof. The preparation method comprises: firstly carrying out hydrolysis condensation polymerization by a sol-gel method with ethyl orthosilicate used as a precursor, hydrochloric acid used as a catalyst, ethanol used as a solvent, a silane coupling agent used as a modifier and a proper amount of water to obtain a modified silica sol, then carrying out free radical polymerization on the modified silica sol and reactive hydrophilic monomers to obtain an organic-inorganic hybrid material, and carrying out solvent replacement to obtain an aqueous organic-inorganic hybrid super-hydrophilic coating. The coating is coated on plastics, glass or metal substrates through dipping or brushing to form a coating layer, the coating layer has a contact angle with water less than 5 degrees, the adhesion force with the substrates of level-0 and the hardness greater than 6H, and water drops can spread out quickly on the coating layer.
Description
Technical field
The present invention relates to a kind of super hydrophilic coating, particularly relate to a kind of super hydrophilic coating of hybrid inorganic-organic; The invention still further relates to this hybrid inorganic-organic super hydrophilic coating the preparation method and use the application that this hydrophilic coating prepares the super-hydrophilic coating of hybrid inorganic-organic.
Technical background
Under home, material surface all has in various degree repulsion to water.For this reason, need carry out hydrophilic treatment to material surface.Hydrophilic treatment is divided into the processing of inorganic system again, organic system is handled and the organic and inorganic compound syzygy is handled.People call ultra-hydrophilic surface that obtain by surface modification with surfaces water droplet contact angle＜5 °, and for the formation of ultra-hydrophilic surface two kinds of methods are arranged generally, and its mechanism of action has nothing in common with each other.First method is to utilize the photochemical catalysis material, and second method is by the transformation to material surface chemistry and how much microstructures.Super hydrophilic coating has been applied to various commercial fields, relates to aspects such as self-cleaning, antifog, antifouling property and biological medicine.
The glass light penetration coefficient that general ultra-clear glasses surface is subjected to after the oil pollution obviously declines to a great extent to only having an appointment 70%, but the ultra-clear glasses of coating super-hydrophilic coating can promote light transmittance gradually up to about more than 95% as brand-new glass under the irradiation of light, and then can keep the efficiency of conversion of solar-energy photo-voltaic cell; In the application in plastics, hydrophilic coating can improve the compactness of plastics, bright and clean, wetting ability and wear resisting property; Idle call aluminium foil self can form the oxide film of one deck densification in the metal substrate in air; this layer oxide film has the uncorroded effect of protection inner layer metal aluminium; but this oxide film is an intermediate oxide; when in the environment that is in humidity, acid, alkali, oxidisability; oxide film is easy to generate corresponding chemical reaction; rapid oxidation or galvanic corrosion then take place in the internal layer aluminium foil that loses oxide film; shorten its work-ing life; therefore the aluminium to having solidity to corrosion to require or using in the drying and watering cycle condition, need to its carry out surface treatment with
Obtain high moisture-proofArtificial protection.
The Chinese invention patent application of publication number CN 1405252 discloses a kind of air conditioner aluminium foil hydrophilic coating.This coating mixes modified epoxy, aminoresin, sulfonate surfactant and deionized water, makes hydrophilic coating.This invention coating has good hydrophilicity and anti-current water erosion, is applicable to the hydrophilic treatment of air conditioner aluminium foil, reduces air flow resistance, and is energy-saving and cost-reducing, and antifouling easy cleaning.But the hydrophilic coating initial stage wetting ability of this kind method preparation is about 15 °, does not reach super hydrophily.
The Chinese invention patent of publication number CN 1687249A discloses a kind of preparation method of super-hydrophilic coating.This method is coated to carrier surface with the titanium dioxide hydro-colloid, through suitable temperature oven dry and UV-irradiation, forms the powder colloid coating with super water-wet behavior at carrier surface again.The coating of titanium dioxide charge capacity that this invention generates is big, combination is firm, behind ultraviolet source irradiation, produces strong and stable super water-wet behavior.Photocatalytic surfaces is because the existence of bridge location oxygen is arranged, and when being subjected to ultraviolet excitation, generates active oxygen radical (as: OH, O from the teeth outwards
2 -, OOH), can generate oxygen base hole with the hole reaction.Simultaneously, water is adsorbed in the oxygen base hole, becomes chemical absorbed water, forms the hydrophilic microcell of equally distributed nanoscale on the surface, causes the formation of hydrophilic surface.But the hydroxyl group that they produce compares with bridge location oxygen and is unstable, and when stopping illumination, the hydroxyl of chemisorption is replaced by airborne oxygen, gets back to hydrophobic state again.
Publication number is the hydrophilic treatment method that the Chinese invention patent of CN 1400235 discloses a kind of polyolefin micropore material.This method is with surfactant soln or emulsion dip treating polyolefin micropore material, it is characterized in that, elder generation's water, tensio-active agent, stablizer, defoamer wiring solution-forming or emulsion are as hydrophilic processing liquid, use the hydrophilic processing liquid dipping polyolefin micropore material that is disposed then, it is carried out dip treating, be polyolefin micropore material surface keyed jointing or adsorption surface active agent molecule, improve surface energy.This invented technology is simple, and is with low cost, has good hydrophilicity.But the method for this kind hydrophilic treatment requires surface substrate to have certain roughness, and this has very big restriction to this hydrophilic treatment method.
Summary of the invention
The objective of the invention is to solve prior art and adopt the photochemical catalysis material when stopping illumination, easily to get back to the deficiency of hydrophobic state, provide a kind of effectively simple, need not UV-irradiation, use extensively the super hydrophilic coating of the hybrid inorganic-organic that wetting ability is stable.
The preparation method of the super hydrophilic coating of the hybrid inorganic-organic that another object of the present invention is to provide above-mentioned.
The present invention also has a purpose to be to provide the super hydrophilic coating of using hybrid inorganic-organic to prepare the method for super-hydrophilic coating.
Purpose of the present invention is achieved through the following technical solutions:
The preparation method of the super hydrophilic coating of a kind of hybrid inorganic-organic comprises the steps and processing condition:
(1) in mass fraction, 26～52 parts tetraethoxys, 0.39～20 part silane coupling agent be added in 34～52 parts the dehydrated alcohol, after the water that adds 13～21 parts while stirring fully stirs, regulating pH by dilute hydrochloric acid is 3～4, obtains hydrolysate at 40～70 ℃ of following hydrolysis 4～10h; Described silane coupling agent is R ' (CH
2)
nSi (OR)
3, n=0,1,2 or 3 wherein, OR is hydrolyzable alkoxyl group, R ' is for having organic segment of carbon-carbon double bond class;
(2) in mass fraction, the hydrolysate of 10～77 parts of steps (1), 3～27 parts of response type hydrophilic monomers, 0.1～1 part of Diisopropyl azodicarboxylate joined in 18～63 parts the ethanol, under 75～85 ℃ of bath temperatures, carry out Raolical polymerizable 4～8h, prepare hybrid inorganic-organic materials; Described response type hydrophilic monomer for contain-OH ,-CONH
2,-COOH or-SO
3The carbon carbon double bond monomer of H hydrophilic radical;
(3) in described hybrid inorganic-organic materials, adding 70～170 parts of water under the high-speed stirring of 1300～2000 r/min, and stir and carry out solvent exchange 10～40min, under 65 ℃～85 ℃ conditions, ethanol is steamed, obtain the super hydrophilic coating of water-based hybrid inorganic-organic.
Further, described hydrolyzable alkoxyl group is preferably-OC
2H
5Or-OCH
3
Described silane coupling agent is vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three (beta-methoxy-oxyethyl group) silane or γ-(methacryloxy) propyl trimethoxy silicane.
The described organic segment that has a carbon-carbon double bond class for contain vinyl and hydrophilic radical-OH ,-CONH
2,-COOH or-SO
3Organic segment of H.
Described response type hydrophilic monomer is one or more in Hydroxyethyl acrylate, acrylamide, vinylformic acid, methacrylic acid and the 2-acrylamido-2-methyl propane sulfonic acid.
The super hydrophilic coating of a kind of hybrid inorganic-organic is by method for preparing.
Use the method that super hydrophilic coating prepares the hybrid inorganic-organic super-hydrophilic coating: it is standby that ground is carried out pre-treatment, adopt pickling process or squeegee process to be coated on the pretreated ground the super hydrophilic coating of hybrid inorganic-organic, coat-thickness is 20～40 μ m, under 50～80 ℃ of conditions, toast 5～20min, obtain the hybrid inorganic-organic super-hydrophilic coating; Described ground is plastics, glass or metal substrate.
The contact angle of described hybrid inorganic-organic super-hydrophilic coating and water is less than 5 °, and water droplet is sprawled rapidly, with base material sticking power be 0 grade, hardness is greater than 6H.
The present invention is in preparation process, at first adopting sol-gel method will contain carbon-carbon double bond class organo-siloxane and tetraethoxy carries out the cohydrolysis condensation and obtains silicon sol, utilize this silicon sol and response type hydrophilic monomer to carry out Raolical polymerizable again and obtain hybrid inorganic-organic materials, obtain the super hydrophilic coating of water-based hybrid inorganic-organic through solvent exchange at last.Adopt pickling process or squeegee process will surpass hydrophilic coating and be coated on the substrate surface,, on ground, obtain the film of one deck densification through suitable temperature baking.This coatingsurface not only have a large amount of hydrophilic radical-OH ,-CONH
2,-COOH and (or)-SO
3H, silica sphere also has a large amount of not hydroxyls of condensation simultaneously; Coatingsurface is made up of many silica dioxide granule clusters, and this cluster provides higher roughness for the coatingsurface hydrophilic radical, and these 2 is the major cause that forms super hydrophilic effect.
The present invention compared with prior art has following advantage and beneficial effect:
(1) preparation method of the present invention is simple, and the reaction conditions gentleness can adopt the technology of pickling process and squeegee process to film on a large scale, filming is evenly distributed, and contact angle is less than 5 ° on this coating for water droplet, and water droplet is sprawled rapidly, with base material sticking power be 0 grade, the coating pencil hardness is greater than 6H;
(2) and TiO
2Super-hydrophilic coating is compared, and the coating that adopts method preparation of the present invention is to the UV-light no requirement (NR), and coating hydrophilic is stable, is particularly useful for loseing in the air conditioner aluminium foil of light.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is further described, but the scope of protection of the invention is not limited to the scope of embodiment statement.
Embodiment 1:
(1) 15g tetraethoxy, 1.5g γ-(methacryloxy) propyl trimethoxy silicane are added in the 24.15g dehydrated alcohol, adding while stirring after 8.00g water fully stirs, dropwise adding 10% dilute hydrochloric acid more while stirring, to regulate pH be 3.5, obtains hydrolysate at 60 ℃ of following hydrolysis 6h;
(2) hydrolysate, 15g vinylformic acid, 0.495g Diisopropyl azodicarboxylate in the step (1) are joined in the 100g dehydrated alcohol, under 85 ℃ of bath temperatures, carry out Raolical polymerizable 6h, prepare hybrid inorganic-organic materials;
(3) add 115g water in the hybrid inorganic-organic materials that under the high-speed stirring of 1500 r/min, in step (2), obtains, and stir and carry out solvent exchange 25min, under 75 ℃ bath temperature, the ethanol decompression is steamed then, obtain the super hydrophilic coating of water-based hybrid inorganic-organic, this coating is the water white transparency shape;
(4) with acetone, 10%(quality) dilute sulphuric acid, distilled water wash aluminium flake successively, the super hydrophilic coating of the hybrid inorganic-organic that obtains in the step (3) is adopted on the aluminium flake after squeegee process is coated on washing, coat-thickness is about 30 μ m, under 70 ℃ of conditions, toast 10min, obtain the hybrid inorganic-organic super-hydrophilic coating;
(5) the OCA-40 type contact angle instrument of the German Dataphysics of employing company is tested super-hydrophilic coating, record with water contact angle be 5 °, and water droplet is sprawled rapidly on coating (aluminium flake) surface, with base material sticking power be 0 grade, the coating pencil hardness is 8H.
Embodiment 2:
(1) 21g tetraethoxy, 1.5g γ-(methacryloxy) propyl trimethoxy silicane are added in the 34.81g dehydrated alcohol, adding while stirring after 11.13g water fully stirs, dropwise adding 10% dilute hydrochloric acid more while stirring, to regulate pH be 3.5, obtains hydrolysate at 60 ℃ of following hydrolysis 6h;
(2) hydrolysate, 9g vinylformic acid, 0.315g Diisopropyl azodicarboxylate in the step (1) are joined in the 90g dehydrated alcohol, under 85 ℃ of bath temperatures, carry out Raolical polymerizable 6h, prepare hybrid inorganic-organic materials;
(3) add 110g water in the hybrid inorganic-organic materials that under the high-speed stirring of 1400 r/min, in step (2), obtains, and stir and carry out solvent exchange 30min, under 80 ℃ bath temperature, the ethanol decompression is steamed then, obtain the super hydrophilic coating of water-based hybrid inorganic-organic, this coating is the water white transparency shape;
(4) with acetone, 10%(quality) dilute sulphuric acid, distilled water wash aluminium flake successively, adopt squeegee process on the aluminium flake after the washing the super hydrophilic coating of hybrid inorganic-organic that obtains in (3), coat-thickness is about 30 μ m, under 50 ℃ of conditions, toast 20min, obtain the hybrid inorganic-organic super-hydrophilic coating;
(5) the OCA-40 type contact angle instrument of the German Dataphysics of employing company is tested super-hydrophilic coating, record with water contact angle be 5 °, and water droplet is sprawled rapidly on coating (aluminium flake) surface, with base material sticking power be 0 grade, the coating pencil hardness is 8H.
Embodiment 3:
(1) 27g tetraethoxy, 1.5g γ-(methacryloxy) propyl trimethoxy silicane are added in the 43.75g dehydrated alcohol, adding while stirring after 14.39g water fully stirs, dropwise adding 10% dilute hydrochloric acid more while stirring, to regulate pH be 3.5, obtains hydrolysate at 60 ℃ of following hydrolysis 6h;
(2) hydrolysate, 3g vinylformic acid, 0.135g Diisopropyl azodicarboxylate in the step (1) are joined in the 80g dehydrated alcohol, under 85 ℃ of bath temperatures, carry out Raolical polymerizable 6h, prepare hybrid inorganic-organic materials;
(3) add 110g water in the hybrid inorganic-organic materials that under the high-speed stirring of 1500 r/min, in step (2), obtains, and stir and carry out solvent exchange 25min, under 80 ℃ bath temperature, the ethanol decompression is steamed then, obtain the super hydrophilic coating of water-based hybrid inorganic-organic, this coating is the water white transparency shape;
(4) with acetone, 10%(quality) dilute sulphuric acid, distilled water wash aluminium flake successively, the super hydrophilic coating of the hybrid inorganic-organic that obtains in the step (3) is adopted on the aluminium flake after squeegee process is coated on washing, coat-thickness is about 30 μ m, under 50 ℃ of conditions, toast 20min, obtain the hybrid inorganic-organic super-hydrophilic coating;
(5) the OCA-40 type contact angle instrument of the German Dataphysics of employing company is tested super-hydrophilic coating, record with water contact angle be 5 °, and water droplet is sprawled rapidly on coating (aluminium flake) surface, with base material sticking power be 0 grade, the coating pencil hardness is 8H.
Embodiment 4:
(1) 21g tetraethoxy, 1.5g vinyltriethoxysilane are added in the 34.81g dehydrated alcohol, adding while stirring after 11.13g water fully stirs, dropwise adding 10% dilute hydrochloric acid more while stirring, to regulate pH be 3, obtains hydrolysate at 70 ℃ of following hydrolysis 4h;
(2) hydrolysate, 6g vinylformic acid, 3g acrylamide, 0.315g Diisopropyl azodicarboxylate in the step (1) are joined in the 90g dehydrated alcohol, under 85 ℃ of bath temperatures, carry out Raolical polymerizable 6h, the preparation hybrid inorganic-organic materials;
(3) add 110g water in the hybrid inorganic-organic materials that under the high-speed stirring of 1800 r/min, in step (2), obtains, and stir and carry out solvent exchange 15min, under 80 ℃ bath temperature, the ethanol decompression is steamed then, obtain the super hydrophilic coating of water-based hybrid inorganic-organic, this coating is the water white transparency shape;
(4) with acetone, 10%(quality) dilute sulphuric acid, distilled water wash sheet glass successively, the super hydrophilic coating of the hybrid inorganic-organic that obtains in (3) is adopted on the sheet glass after squeegee process is coated on washing, coat-thickness is about 30 μ m, under 50 ℃ of conditions, toast 20min, obtain the hybrid inorganic-organic super-hydrophilic coating;
(5) the OCA-40 type contact angle instrument of the German Dataphysics of employing company is tested super-hydrophilic coating, record with water contact angle be 5 °, and water droplet is sprawled rapidly on coating (sheet glass) surface, with base material sticking power be 0 grade, the coating pencil hardness is 8H.
Embodiment 5:
(1) 21g tetraethoxy, 0.9g γ-(methacryloxy) propyl trimethoxy silicane are added in the 33.86g dehydrated alcohol, adding while stirring after 11.06g water fully stirs, dropwise adding 10% dilute hydrochloric acid more while stirring, to regulate pH be 3.5, obtains hydrolysate at 60 ℃ of following hydrolysis 6h;
(2) hydrolysate, 9g vinylformic acid, 0.30g Diisopropyl azodicarboxylate in the step (1) are joined in the 90g dehydrated alcohol, under 85 ℃ of bath temperatures, carry out Raolical polymerizable 6h, prepare hybrid inorganic-organic materials;
(3) add 110g water in the hybrid inorganic-organic materials that under the high-speed stirring of 1700 r/min, in step (2), obtains, and stir and carry out solvent exchange 30min, under 70 ℃ bath temperature, the ethanol decompression is steamed then, obtain the super hydrophilic coating of water-based hybrid inorganic-organic, this coating is the water white transparency shape;
(4) acetone, 10%(quality) dilute sulphuric acid, distilled water wash sheet glass successively, the super hydrophilic coating of the hybrid inorganic-organic that obtains in the step (3) is adopted on the sheet glass sheet after squeegee process is coated on washing, coat-thickness is about 30 μ m, under 50 ℃ of conditions, toast 20min, obtain the hybrid inorganic-organic super-hydrophilic coating;
(5) the OCA-40 type contact angle instrument of the German Dataphysics of employing company is tested super-hydrophilic coating, record with water contact angle be 3 °, and water droplet is sprawled rapidly at coatingsurface (glass), with base material sticking power be 0 grade, the coating pencil hardness is 7H.
Embodiment 6:
(1) 21g tetraethoxy, 0.9g vinyltriethoxysilane are added in the 33.86g dehydrated alcohol, adding while stirring after 11.06g water fully stirs, dropwise adding 10% dilute hydrochloric acid more while stirring, to regulate pH be 4, obtains hydrolysate at 50 ℃ of following hydrolysis 8h;
(2) hydrolysate, 4.5g vinylformic acid, 3g acrylamide, 1.5g2-acrylamido-2-methyl propane sulfonic acid, 0.30g Diisopropyl azodicarboxylate in the step (1) are joined in the 90g dehydrated alcohol, under 85 ℃ of bath temperatures, carry out Raolical polymerizable 6h, prepare hybrid inorganic-organic materials;
(3) add 110g water in the hybrid inorganic-organic materials that under the high-speed stirring of 1700 r/min, in step (2), obtains, and stir and carry out solvent exchange 20min, under 70 ℃ bath temperature, the ethanol decompression is steamed then, obtain the super hydrophilic coating of water-based hybrid inorganic-organic, this coating is the water white transparency shape;
(4) acetone, 10 %(quality) dilute sulphuric acid, distilled water wash plastics successively, the super hydrophilic coating of the hybrid inorganic-organic that obtains in the step (3) is adopted on the plastics after squeegee process is coated on washing, coat-thickness is about 30 μ m, under 50 ℃ of conditions, toast 20min, obtain the hybrid inorganic-organic super-hydrophilic coating;
(5) the OCA-40 type contact angle instrument of the German Dataphysics of employing company is tested super-hydrophilic coating, record with water contact angle be 3 °, and water droplet is sprawled rapidly at coatingsurface (plastics), with base material sticking power be 0 grade, the coating pencil hardness is 7H.
Claims (8)
1. the preparation method of the super hydrophilic coating of hybrid inorganic-organic is characterized in that comprising the steps and processing condition:
(1) in mass fraction, 26～52 parts tetraethoxys, 0.39～20 part silane coupling agent be added in 34～52 parts the dehydrated alcohol, after the water that adds 13～21 parts while stirring fully stirs, regulating pH by dilute hydrochloric acid is 3～4, obtains hydrolysate at 40～70 ℃ of following hydrolysis 4～10h; Described silane coupling agent is R ' (CH
2)
nSi (OR)
3, n=0,1,2 or 3 wherein, OR is hydrolyzable alkoxyl group, R ' is for having organic segment of carbon-carbon double bond class;
(2) in mass fraction, the hydrolysate of 10～77 parts of steps (1), 3～27 parts of response type hydrophilic monomers, 0.1～1 part of Diisopropyl azodicarboxylate joined in 18～63 parts the ethanol, under 75～85 ℃ of bath temperatures, carry out Raolical polymerizable 4～8h, prepare hybrid inorganic-organic materials; Described response type hydrophilic monomer for contain-OH ,-CONH
2,-COOH or-SO
3The carbon carbon double bond monomer of H hydrophilic radical;
(3) in described hybrid inorganic-organic materials, adding 70～170 parts of water under the high-speed stirring of 1300～2000 r/min, and stir and carry out solvent exchange 10～40min, under 65 ℃～85 ℃ conditions, ethanol is steamed, obtain the super hydrophilic coating of water-based hybrid inorganic-organic.
2. preparation method according to claim 1 is characterized in that: described hydrolyzable alkoxyl group is-OC
2H
5Or-OCH
3
3. preparation method according to claim 1 is characterized in that: the described organic segment that has a carbon-carbon double bond class for contain vinyl and hydrophilic radical-OH ,-CONH
2,-COOH or-SO
3Organic segment of H.
4. preparation method according to claim 1 is characterized in that: described silane coupling agent is vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three (beta-methoxy-oxyethyl group) silane or γ-(methacryloxy) propyl trimethoxy silicane.
5. preparation method according to claim 1 is characterized in that: described response type hydrophilic monomer is one or more in Hydroxyethyl acrylate, acrylamide, vinylformic acid, methacrylic acid and the 2-acrylamido-2-methyl propane sulfonic acid.
6. the super hydrophilic coating of hybrid inorganic-organic is characterized in that by the described method preparation of claim 1.
7. application rights requires 6 described super hydrophilic coatings to prepare the method for hybrid inorganic-organic super-hydrophilic coating: it is standby that ground is carried out pre-treatment, adopt pickling process or squeegee process to be coated on the pretreated ground the super hydrophilic coating of hybrid inorganic-organic, coat-thickness is 20～40 μ m, under 50～80 ℃ of conditions, toast 5～20min, obtain the hybrid inorganic-organic super-hydrophilic coating; Described ground is plastics, glass or metal substrate.
8. according to the described method for preparing the hybrid inorganic-organic super-hydrophilic coating of claim 7, it is characterized in that: the contact angle of described hybrid inorganic-organic super-hydrophilic coating and water is less than 5 °, and water droplet is sprawled rapidly, with base material sticking power be 0 grade, hardness is greater than 6H.
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