CN101792633B - Preparation method for antistatic super hydrophobic composite coating - Google Patents
Preparation method for antistatic super hydrophobic composite coating Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 30
- 239000011248 coating agent Substances 0.000 title claims abstract description 29
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- -1 silicate ester Chemical class 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 23
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 17
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims abstract description 16
- 230000032683 aging Effects 0.000 claims abstract description 16
- 238000007669 thermal treatment Methods 0.000 claims abstract description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 229920005603 alternating copolymer Polymers 0.000 claims description 15
- 238000010907 mechanical stirring Methods 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 9
- GZBAUYZREARCNR-UHFFFAOYSA-N C(CCCCCCCCC)[Si](OC)(OC)OC.[F] Chemical class C(CCCCCCCCC)[Si](OC)(OC)OC.[F] GZBAUYZREARCNR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 238000003851 corona treatment Methods 0.000 claims description 7
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000742 Cotton Polymers 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- GLAGNWFONBGYIE-UHFFFAOYSA-N 3-[[difluoro(1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctylsulfonyl)methoxy]-bis(trifluoromethoxy)silyl]-N,N,1,1,2,2,3,3-octafluoropropan-1-amine Chemical compound C(C(C(C(C(F)(F)S(=O)(=O)C(O[Si](C(C(C(N(F)F)(F)F)(F)F)(F)F)(OC(F)(F)F)OC(F)(F)F)(F)F)(F)F)(F)F)(F)F)(C(C(C(F)(F)F)(F)F)(F)F)(F)F GLAGNWFONBGYIE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- UWGJCHRFALXDAR-UHFFFAOYSA-N diethoxy-ethyl-methylsilane Chemical compound CCO[Si](C)(CC)OCC UWGJCHRFALXDAR-UHFFFAOYSA-N 0.000 claims description 4
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 3
- 229960003493 octyltriethoxysilane Drugs 0.000 claims description 3
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 claims description 3
- UVSMIEOWIMUEOU-UHFFFAOYSA-N triethoxy(8-fluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCCCCCF UVSMIEOWIMUEOU-UHFFFAOYSA-N 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims 1
- 238000005507 spraying Methods 0.000 abstract description 13
- 230000003068 static effect Effects 0.000 abstract description 9
- 238000007385 chemical modification Methods 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- 238000005096 rolling process Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- 239000012467 final product Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 4
- 229920004933 Terylene® Polymers 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000008040 ionic compounds Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000002048 multi walled nanotube Substances 0.000 description 1
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Abstract
The invention discloses a preparation method for antistatic super hydrophobic composite coating, comprising the following steps: dissolving 0.2-2 parts of styrene-maleic anhydride alternate copolymer by weight into 20-1000 parts of solvent by weight, adding 1 part of carbon nanotube by weight and then evenly mixing, adding 0-26 parts of ammonia water and 0.2-2 parts of silicate ester or titanate compound by weight, stirring and mixing to enable silicate ester or titanate compound to perform hydrolysis reaction, adding 0.1-2 parts of silicate ester or titanate compound and 0.02-0.5 part of fluorine containing silane coupling agent by weight, evenly mixing and spraying on base materials, carrying out aging and thermal treatment to obtain stable antistatic super hydrophobic composite coating. The invention has simple operation and mild condition, the carbon nanotube can be directly used without the need of any chemical modification, the obtained composite coating has good hydrophobicity, the static contact angle and rolling angle between the composite coating and water are respectively larger than 150 degrees and less than 3 degrees, and the surface resistivity is 106-1011 omega, thus meeting the requirement of antistatic transparent coating and having wide application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of antistatic super hydrophobic composite coating, belong to technical field of nano material.
Background technology
Super hydrophobic surface (spending less than 5 greater than 150 degree, roll angle with the static contact angle of water) with " lotus leaf " effect has been subject to paying close attention to widely in scientific research and practical application area, has broad application prospects in fields such as preparation self-cleaning surface, oily water separations.In recent years, a lot of methods that prepare super hydrophobic surface have been arranged, for example: document [Kang-Shyang Liao, Albert Wan, et al., Superhydrophobic SurfacesFormed Using Layer-by-Layer Self-Assembly with Aminated Multiwall CarbonNanotubes, Langmuir, 2008,24 (8), 4245-4253] method of chemically modified is amination of carbon nano tube, thereby on amino group, obtain having again the coating of super-hydrophobicity by the method access hydrophobic group of layer assembly, however the structure of the method meeting destroying carbon nanometer tube itself, and the operation more complicated, time is long, and range of application is wideless.Document [Erbil HY, Demirel AL, Avci Y, et al., Transformation of asimple plastic into a superhydrophobic surface, Science, 2003,299,5611,1377-1380] the polypropylene solution coatings is carried out vacuum-drying, control spherulite size and form have obtained spongiform porous polypropylene coating with super-hydrophobicity.Yet the method needs a large amount of organic solvents, is of limited application.In addition, also have compression molding, for example with the polymkeric substance heating and be pressed in the alumina templates with nano pore, remove template after the cooling, can form the array of nanofiber on the polymer surfaces, have super-hydrophobicity.Yet the preparation process more complicated of the alumina templates of using in this method also needs to remove template after the moulding.Document [Kenneth K.S.Lau, Jos é Bico, Kenneth B.K.Teo, et al., Nano Letters, 2003,3,12,1071-1075] carbon nano pipe array that utilizes chemical Vapor deposition process to grow at the base material of supported catalyst has super-hydrophobicity and high conductivity.Yet this method steps is more, and the reaction times is longer, and chemical gaseous phase deposition need at high temperature carry out.Document [Vasiliosgeorgakilas, Athanasios B.Bourlinos, Radek Zboril, and Christos Trapalis, Chem.Mater., 2008,20 (9), 2884-2886, Synthesis, Characterization and Aspects of SuperhydrophobicFunctionalized Carbon Nanotubes] utilize carbon nanotube to prepare super-hydrophobic coat, yet, carbon nanotube in this method need to pass through grafting modification, uses the larger DMF of toxicity to be solvent in the more and reaction process of reactions steps.Therefore, aforesaid method respectively has weak point.Simultaneously, static resistance has great importance for the practical application of super hydrophobic material, and still, general static inhibitor is ionic compound, easily suction, and it is disadvantageous therefore keeping super-hydrophobicity for material surface.
Summary of the invention
The objective of the invention is in order to overcome the shortcoming of above method, the preparation that provide a kind of simple, mild condition, is easy to mass-producing has the method for the super hydrophobic composite coating of static resistance.
The objective of the invention is to be achieved through the following technical solutions:
The preparation method of antistatic super hydrophobic composite coating comprises the steps, the following stated part by weight:
1) 0.2～2 part of styrene-maleic anhydride alternating copolymer is dissolved in 20～1000 parts of solvents, add 1 part of carbon nanotube, by mechanical stirring with ultrasonic it is uniformly dispersed, add 0.2～2 part of silicon ester or titanate compound and 0～26 part of ammoniacal liquor, and stirred 5 minutes～48 hours so that silicon ester or titanate compound generation hydrolysis reaction, then replenish 0.1～2 part of silicon ester or titanate compound and 0.02～0.5 part of fluorine containing silane coupling agent, and stir;
2) with step 1) resulting dispersion liquid is sprayed on the base material equably, and ageing is heated to 100-280 ℃ of thermal treatment 5 minutes to 2 hours after 0.5～72 hour, obtain end article.
Among the present invention, said solvent is one or more the mixture in water, ethanol, Virahol, acetone, butanone and the Isosorbide-5-Nitrae-dioxane.
Among the present invention, said silicon ester or titanate compound are one or more the mixtures in tetraethoxy, methyl silicate, aminopropyl triethoxysilane, ethyl trimethoxy silane, γ-methacryloxypropyl trimethoxy silane, vinyltriethoxysilane, glycidyl ether oxygen propyl trimethoxy silicane, octyltri-ethoxysilane, Union carbide A-162, dimethyldiethoxysilane, tetrabutyl titanate, tetraethyl titanate and the titanium isopropylate.
Among the present invention, said fluorine containing silane coupling agent is 17 fluorine decyl Trimethoxy silanes, perfluoro capryl ethyl trimethoxy silane, perfluoro capryl ethyl-methyl diethoxy silane, 13 fluoro octyltri-ethoxysilane, perfluorooctyl sulfonyl-3-aminopropyl trimethoxysilane or two perfluorooctyl sulfonyls-3-aminopropyl trimethoxysilane.
Among the present invention, said base material is a kind of in glass, pottery, cotton, silk, terylene, polycarbonate or the polyester.Wherein, soaked 0.5-2 hour with 1: 1 hydrogen peroxide of weight ratio and vitriol oil mixing solutions for glass and ceramic base material, then with washed with de-ionized water, dry, to improve the bonding force of coating.For cotton, silk, terylene, polycarbonate or polyester base material corona treatment 5-60 second, to improve the bonding force of coating.
Beneficial effect of the present invention is:
1) compare with existing method, the inventive method starting material are simple and easy to, easy and simple to handle, mild condition, easily mass-producing.Particularly carbon nanotube does not need to carry out any chemical modification and just can directly use.
2) carbon nanotube can give coating certain electroconductibility;
3) hydrophobicity of gained antistatic super hydrophobic composite coating is good, with the quiet contact angle of water greater than 150 °, roll angle is less than 3 °, and has satisfactory stability, carries out after the drying in 7 days even soak in water again, its contact angle and roll angle remain unchanged.
Description of drawings
Fig. 1 is the stereoscan photograph on compound coating surface.
Fig. 2 is the stereoscan photograph of compound coating section.
Fig. 3 is the static contact angle optical photograph of compound coating, and its static contact angle is 162 ± 3 degree.
Fig. 4 is the roll angle optical photograph of compound coating, and its roll angle is about 1.2 degree.
Embodiment
The embodiment that below provides further introduces invention, need to prove, the invention is not restricted to following examples.
Embodiment 1
0.6 gram styrene-maleic anhydride alternating copolymer is dissolved in 30 milliliters of ethanol, add 1 gram carbon nanotube and mix 15 minutes and ultrasonic 5 minutes, 1.3 gram aminopropyl triethoxysilanes and 0.7 gram tetraethoxy are joined in the system, add 2.6 gram ammoniacal liquor, stir, reacted 0.5 hour; Then add 0.16 gram tetraethoxy and 0.1 gram, 17 fluorine decyl Trimethoxy silanes, after stirring, solution spraying to glass baseplate, after the ageing 12 hours, is heated to 180 ℃ of thermal treatments and obtained final product in 1 hour.Glass uses first 1: 1 hydrogen peroxide of weight ratio and vitriol oil mixing solutions to soak 0.5 hour, then with washed with de-ionized water, dry.Fig. 1 is the stereoscan photograph on this compound coating surface.Fig. 2 is the stereoscan photograph of this compound coating section.Fig. 3 is the static contact angle optical photograph of this compound coating, and its static contact angle is 162 ± 3 degree.Fig. 4 is the roll angle optical photograph of this compound coating, and its roll angle is about 1.2 degree.In addition, measuring its surface resistivity with megger is 2.4 * 10
7Ω.
Embodiment 2
0.2 gram styrene-maleic anhydride alternating copolymer is dissolved in 50 milliliters of ethanol, added 1.0 gram carbon nanotube mechanical stirring 20 minutes and ultrasonic 10 minutes, 1.0 gram aminopropyl triethoxysilanes and 0.5 gram tetraethoxy are joined in the system, add 26 gram ammoniacal liquor, stir, reacted 1 hour, then add 4.0 the gram tetraethoxys and 0.4 the gram 17 fluorine decyl Trimethoxy silanes mix, with solution spraying to glass baseplate, after the ageing 24 hours, be heated to 150 ℃ of thermal treatments and obtained final product in 3 hours.With the quiet contact angle of water more than 160 °, roll angle is less than 2 °, surface resistivity is 1.3 * 10
6Ω.Glass uses first 1: 1 hydrogen peroxide of weight ratio and vitriol oil mixing solutions to soak 2 hours, then with washed with de-ionized water, dry.
Embodiment 3
1 gram styrene-maleic anhydride alternating copolymer is dissolved in the mixed solvent of 20 milliliters of ethanol and 1 ml water, adds 1 gram carbon nanotube, ultrasonic 10 minutes and mechanical stirring 30 minutes add 2 gram Union carbide A-162s, stir 48 hours.In addition 2 gram tetraethoxys and 0.5 gram, 17 fluorine decyl Trimethoxy silanes are joined in the above-mentioned system, make uniform dispersion liquid; Solution spraying to ceramic base material, after the ageing 12 hours, is heated to 200 ℃ of thermal treatments and obtained final product in 30 minutes.With the quiet contact angle of water more than 150 °, roll angle is less than 2 °, surface resistivity is 4.5 * 10
6Ω.Ceramic base material uses first 1: 1 hydrogen peroxide of weight ratio and vitriol oil mixing solutions to soak 1 hour, then with washed with de-ionized water, dry.
Embodiment 4
2 gram styrene-maleic anhydride alternating copolymers are dissolved in the mixed solvent of 100 milliliters of ethanol and 100 milliliters of Virahols, added 1 gram carbon nanotube mechanical stirring 30 minutes and ultrasonic 10 minutes, add 2 gram dimethyldiethoxysilanes, stir.Add again 26 gram ammoniacal liquor, stirred 5 minutes, in addition 2 gram tetraethoxys and 0.2 gram, 17 fluorine decyl Trimethoxy silanes are joined in the above-mentioned system, make uniform dispersion liquid; Solution spraying to carrying out in advance on 60 seconds the cotton of corona treatment, after the ageing 12 hours, is heated to 200 ℃ of thermal treatments and obtained final product in 30 minutes.With the quiet contact angle of water more than 150 °, roll angle is less than 2 °, surface resistivity is 1.5 * 10
6Ω.
Embodiment 5
0.2 gram styrene-maleic anhydride alternating copolymer is dissolved in 200 milliliters of acetone, added 1 gram carbon nanotube mechanical stirring 30 minutes and ultrasonic 10 minutes, add 0.1 gram aminopropyl triethoxysilane and 0.1 gram tetraethoxy, stir; Add 5.2 gram ammoniacal liquor, stirred 30 minutes; In addition 0.1 gram tetraethoxy and 0.02 gram, 17 fluorine decyl Trimethoxy silanes are joined in the above-mentioned system, make uniform dispersion liquid; Solution spraying to carrying out in advance on 5 seconds the silk of corona treatment, after the ageing 0.5 hour, is heated to 100 ℃ of thermal treatments and obtained final product in 2 hours.With the quiet contact angle of water more than 150 °, roll angle is less than 2 °, surface resistivity is 7.8 * 10
7Ω.
Embodiment 6
2 gram styrene-maleic anhydride alternating copolymers are dissolved in 1000 milliliters of ethanol, added 1 gram carbon nanotube mechanical stirring 30 minutes and ultrasonic 10 minutes, add 1.0 gram aminopropyl triethoxysilanes, stir.Add again 5.2 gram ammoniacal liquor, in addition 2.0 gram tetraethoxys and 0.5 gram, 17 fluorine decyl Trimethoxy silanes are joined in the above-mentioned system, make uniform dispersion liquid; Solution is sprayed onto carries out in advance on 30 seconds the terylene of corona treatment, after the ageing 12 hours, be heated to 200 ℃ of thermal treatments and obtained final product in 30 minutes.With the quiet contact angle of water more than 150 °, roll angle is less than 2 °, surface resistivity is 3.2 * 10
7Ω.
Embodiment 7
2 gram styrene-maleic anhydride alternating copolymers are dissolved in 1000 milliliters of ethanol, added 1 gram carbon nanotube mechanical stirring 30 minutes and ultrasonic 10 minutes, add 1.0 gram glycidyl ether oxygen propyl trimethoxy silicanes, stir.Add again 5.2 gram ammoniacal liquor, in addition 2.0 gram tetrabutyl titanates and 0.5 gram perfluoro capryl ethyl trimethoxy silane are joined in the above-mentioned system, make uniform dispersion liquid; Solution spraying to carrying out in advance on 20 seconds the polycarbonate of corona treatment, after the ageing 12 hours, is heated to 200 ℃ of thermal treatments and obtained final product in 30 minutes.With the quiet contact angle of water more than 150 °, roll angle is less than 3 °, surface resistivity is 6.4 * 10
6Ω.
Embodiment 8
2 gram styrene-maleic anhydride alternating copolymers are dissolved in 1000 milliliters of ethanol, added 1 gram carbon nanotube mechanical stirring 30 minutes and ultrasonic 10 minutes, add 0.5 gram methyl silicate and 0.5 gram ethyl trimethoxy silane, stir.Add again 5.2 gram ammoniacal liquor, in addition 2.0 gram tetrabutyl titanates and 0.5 gram perfluoro capryl ethyl-methyl diethoxy silane are joined in the above-mentioned system, make uniform dispersion liquid; Solution spraying to carrying out in advance on 20 seconds the polyester of corona treatment, after the ageing 12 hours, is heated to 200 ℃ of thermal treatments and obtained final product in 30 minutes.With the quiet contact angle of water more than 150 °, roll angle is less than 2 °, surface resistivity is 3.2 * 10
6Ω.
Embodiment 9
2 gram styrene-maleic anhydride alternating copolymers are dissolved in 1000 milliliters of ethanol, added 1 gram carbon nanotube mechanical stirring 30 minutes and ultrasonic 10 minutes, add 0.5 gram methyl silicate and 0.5 gram ethyl trimethoxy silane, stir.Add again 5.2 gram ammoniacal liquor, in addition 2.0 gram tetrabutyl titanates and 0.5 gram perfluoro capryl ethyl-methyl diethoxy silane are joined in the above-mentioned system, make uniform dispersion liquid; Solution spraying to base material, after the ageing 12 hours, is heated to 200 ℃ of thermal treatments and obtained final product in 30 minutes.With the quiet contact angle of water more than 150 °, roll angle is less than 2 °, surface resistivity is 8.4 * 10
9Ω.
Embodiment 10
2 gram styrene-maleic anhydride alternating copolymers are dissolved in 1000 milliliters of ethanol, added 1 gram carbon nanotube mechanical stirring 30 minutes and ultrasonic 10 minutes, add 0.5 gram γ-methacryloxypropyl trimethoxy silane and 0.5 gram vinyltriethoxysilane, stir.Add again 5.2 gram ammoniacal liquor, in addition 2.0 gram tetraethyl titanates and 0.5 gram, 13 fluoro octyltri-ethoxysilane are joined in the above-mentioned system, make uniform dispersion liquid; Solution spraying to base material, after the ageing 12 hours, is heated to 200 ℃ of thermal treatments and obtained final product in 30 minutes.With the quiet contact angle of water more than 150 °, roll angle is less than 2 °, surface resistivity is 1.8 * 10
8Ω.
Embodiment 10
2 gram styrene-maleic anhydride alternating copolymers are dissolved in 1000 milliliters of ethanol, added 1 gram carbon nanotube mechanical stirring 30 minutes and ultrasonic 10 minutes, add 0.5 gram aminopropyl triethoxysilane and 0.5 gram octyltri-ethoxysilane, stir.Add again 5.2 gram ammoniacal liquor, in addition 2.0 gram titanium isopropylates and 0.5 gram perfluorooctyl sulfonyl-3-aminopropyl trimethoxysilane are joined in the above-mentioned system, make uniform dispersion liquid; Solution spraying to base material, after the ageing 12 hours, is heated to 200 ℃ of thermal treatments and obtained final product in 30 minutes.With the quiet contact angle of water more than 150 °, roll angle is less than 2 °, surface resistivity is 2.9 * 10
10Ω.
Embodiment 11
2 gram styrene-maleic anhydride alternating copolymers are dissolved in 1000 milliliters of ethanol, added 1 gram carbon nanotube mechanical stirring 30 minutes and ultrasonic 10 minutes, add 0.5 gram aminopropyl triethoxysilane and 0.5 gram Union carbide A-162, stir.Add again 5.2 gram ammoniacal liquor, in addition 2.0 gram titanium isopropylates and 0.5 gram perfluorooctyl sulfonyl-3-aminopropyl trimethoxysilane are joined in the above-mentioned system, make uniform dispersion liquid; Solution spraying to base material, after the ageing 12 hours, is heated to 200 ℃ of thermal treatments and obtained final product in 30 minutes.With the quiet contact angle of water more than 150 °, roll angle is less than 2 °, surface resistivity is 3.3 * 10
9Ω.
Embodiment 12
2 gram styrene-maleic anhydride alternating copolymers are dissolved in 1000 milliliters of ethanol, added 1 gram carbon nanotube mechanical stirring 30 minutes and ultrasonic 10 minutes, add 0.5 gram aminopropyl triethoxysilane and 0.5 gram dimethyldiethoxysilane, stir.Add again 5.2 gram ammoniacal liquor, in addition 2.0 gram titanium isopropylates and 0.5 gram two perfluorooctyl sulfonyls-3-aminopropyl trimethoxysilane are joined in the above-mentioned system, make uniform dispersion liquid; Solution spraying to base material, after the ageing 12 hours, is heated to 200 ℃ of thermal treatments and obtained final product in 30 minutes.With the quiet contact angle of water more than 150 °, roll angle is less than 3 °, surface resistivity is 6.2 * 10
11Ω.
Claims (5)
1. the preparation method of an antistatic super hydrophobic composite coating is characterized in that comprising the steps, the following stated part by weight:
1) 0.2～2 part of styrene-maleic anhydride alternating copolymer is dissolved in 20～1000 parts of solvents, add 1 part of carbon nanotube, by mechanical stirring and ultrasonic wave it is uniformly dispersed, add 0.2～2 part of silicon ester or titanate compound and 0～26 part of ammoniacal liquor, and stirred 5 minutes～48 hours so that silicon ester or titanate compound generation hydrolysis reaction, then replenish 0.1～2 part of silicon ester or titanate compound and 0.02～0.5 part of fluorine containing silane coupling agent, and stir;
2) with step 1) resulting dispersion liquid is sprayed on the base material equably, and ageing is heated to 100-280 ℃ of thermal treatment 5 minutes to 2 hours after 0.5～72 hour, obtain end article;
Said solvent is one or more the mixture in water, ethanol, Virahol, acetone, butanone and the Isosorbide-5-Nitrae-dioxane;
Said silicon ester or titanate compound are one or more the mixtures in tetraethoxy, methyl silicate, aminopropyl triethoxysilane, ethyl trimethoxy silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, vinyltriethoxysilane, glycidyl ether oxygen propyl trimethoxy silicane, octyltri-ethoxysilane, Union carbide A-162, dimethyldiethoxysilane, tetrabutyl titanate, tetraethyl titanate and the titanium isopropylate.
2. the preparation method of antistatic super hydrophobic composite coating according to claim 1 is characterized in that said fluorine containing silane coupling agent is 17 fluorine decyl Trimethoxy silanes, perfluoro capryl ethyl trimethoxy silane, perfluoro capryl ethyl-methyl diethoxy silane, 13 fluoro octyltri-ethoxysilane, perfluorooctyl sulfonyl-3-aminopropyl trimethoxysilane or two perfluorooctyl sulfonyls-3-aminopropyl trimethoxysilane.
3. the preparation method of antistatic super hydrophobic composite coating according to claim 1 is characterized in that, said base material is glass, pottery, cotton, silk, polycarbonate or polyester.
4. the preparation method of antistatic super hydrophobic composite coating according to claim 3 is characterized in that, said glass or ceramic base material soaked 0.5-2 hour with hydrogen peroxide and the vitriol oil mixing solutions of weight ratio 1:1, then with washed with de-ionized water, dry.
5. the preparation method of antistatic super hydrophobic composite coating according to claim 3 is characterized in that, said cotton, silk, polycarbonate or polyester base material corona treatment 5-60 second.
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