CN102220063A - Low surface energy icing-resistant coating and preparation method thereof - Google Patents
Low surface energy icing-resistant coating and preparation method thereof Download PDFInfo
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- CN102220063A CN102220063A CN2011101234686A CN201110123468A CN102220063A CN 102220063 A CN102220063 A CN 102220063A CN 2011101234686 A CN2011101234686 A CN 2011101234686A CN 201110123468 A CN201110123468 A CN 201110123468A CN 102220063 A CN102220063 A CN 102220063A
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- 239000011248 coating agent Substances 0.000 title claims abstract description 29
- 238000000576 coating method Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000839 emulsion Substances 0.000 claims abstract description 40
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- -1 acrylic ester Chemical class 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 239000003063 flame retardant Substances 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 7
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 238000004945 emulsification Methods 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- BIFQHCGLXZWNLN-UHFFFAOYSA-N 2,2,6-trifluoro-4-methyl-4-propyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound CCC[Si]1(C)O[SiH](F)O[Si](F)(F)O1 BIFQHCGLXZWNLN-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- SHDFBWXJPBODKK-UHFFFAOYSA-N butyl-dichloro-(trifluoromethyl)silane Chemical compound FC([Si](Cl)(Cl)CCCC)(F)F SHDFBWXJPBODKK-UHFFFAOYSA-N 0.000 claims description 4
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000376 reactant Substances 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
- MWKJTNBSKNUMFN-UHFFFAOYSA-N trifluoromethyltrimethylsilane Chemical compound C[Si](C)(C)C(F)(F)F MWKJTNBSKNUMFN-UHFFFAOYSA-N 0.000 claims description 4
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000013530 defoamer Substances 0.000 claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 238000004581 coalescence Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- HCOKJWUULRTBRS-UHFFFAOYSA-N propan-2-yloxysilane Chemical compound CC(C)O[SiH3] HCOKJWUULRTBRS-UHFFFAOYSA-N 0.000 claims description 2
- 239000008279 sol Substances 0.000 claims description 2
- MJINPUKGRATQAC-UHFFFAOYSA-N triethoxy(prop-1-enyl)silane Chemical compound CCO[Si](OCC)(OCC)C=CC MJINPUKGRATQAC-UHFFFAOYSA-N 0.000 claims description 2
- OWUTVCVPEOXXHD-UHFFFAOYSA-N trimethoxy(prop-1-enyl)silane Chemical compound CO[Si](OC)(OC)C=CC OWUTVCVPEOXXHD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims 1
- 235000019395 ammonium persulphate Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract 2
- 239000002518 antifoaming agent Substances 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 239000011258 core-shell material Substances 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 239000003755 preservative agent Substances 0.000 abstract 2
- 230000002335 preservative effect Effects 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 238000010556 emulsion polymerization method Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000003973 paint Substances 0.000 description 7
- 230000002209 hydrophobic effect Effects 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000010425 asbestos Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052895 riebeckite Inorganic materials 0.000 description 3
- 238000004781 supercooling Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical group CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
The invention relates to a low surface energy icing-resistant coating and a preparation method thereof. The icing-resistant coating comprises a core-shell type SiO2@ fluorine-containing acrylic ester emulsion, a flame retardant, a flatting agent, a preservative, a defoaming agent and deionzed water. The preparation method of the icing-resistant coating comprises the following steps of: compositing the core-shell type SiO2@ fluorine-containing acrylic ester emulsion step by step by adopting a semi-continuous free radical emulsion polymerization method, uniformly stirring the deionized water and the flame retardant which are weighted according to a proportion, adding into the emulsion, then adding the preservative and the defoaming agent for uniform grinding, and finally filtering to obtain the product. The icing-resistant coating has the advantages of low surface energy, high water repellency and ice repellency, capability of reducing the adhesive force of water and ice to the greatest extent and causing the ice to easily fall off, non-toxicity and harmlessness, accordance with the environment-friendly requirements in terms of all performance indexes, simplicity and practicability in projects, convenience in control, lower cost and good using effect.
Description
Technical field
The present invention relates to a kind of low surface energy anti-ice cover coating and preparation method thereof, belong to the material technology field.
Background technology
Icing and accumulated snow are a kind of spontaneous phenomenons, but can cause significant damage to industry, cause the accident of all kinds of big power systems as meeting, and extreme case may cause the paralysis fully of power system down, brings great inconvenience to productive life.Machinery and electrical accidents such as the harm that powerline ice-covering causes power system comprises conductor galloping, breaks, collapses, insulator arc-over, safe and reliable operations such as serious threat electric power, communication and aviation.
In general, the icing phenomenon of lead wherein mainly comprises factors such as temperature, humidity, cold and heat air convection current, circulation and wind speed owing to various meteorological reasons form.Contain supercooled water droplets winter in the rain, this water droplet is extremely unstable, because of the existence that does not have the nuclei of crystallization exists with liquid form, in case drop on the lead, lead will make super-cooling waterdrop freeze rapidly and cover on the lead as the effect of the nuclei of crystallization, form so-called icing.From forming mechanism, icing can be divided into following several: the steam in (1) atmosphere adheres to when supersaturation and distillation is condensed, and the radial crystallization of formation is called rime.In general, water droplet freezed in advance than the needed time of combining closely mutually when rime formed, and had formed the exsiccant ice that comprises many spaces or bubble.Therefore, such ice concentration is less, and is also more open.(2) super-cooling waterdrop in the atmosphere forms limpid smooth transparent icing and is called glaze in the windward side of lead.The time of the time ratio collision of this class droplets freeze will be grown.Therefore, the icing of formation is smooth, and density is bigger and tight, and with the strong adhesion of lead.(3) super-cooling waterdrop forms the transparent and opaque ice sheet that replaces overlapping or similar obscure glass in the windward side.The sticking power of this class icing is also bigger, generally is difficult to remove.
The harm of icing is that people are obvious to all, and that people also strive to find is economic and practical, the method for environmental protection, workable control icing.Up to the present, the method for control icing mainly contains following several:
(1) mechanical deicing: in the serious area of icing with primary instrument such as waddy, bamboo pole to icing beat, bump etc. removes icing.This method effect is obvious, spend smaller, with strong points, yet its operability is not strong, is merely able to be difficult to promote the use of on a large scale in the emergent use among a small circle of icing serious area.And needing lot of manpower and material resources in its operating process, use range is very restricted.
(2) electro-thermal deicing method: so-called electro-thermal deicing method, promptly use heat with ice-out.As: in part icing serious area, on lead, feed big galvanic current, icing is melted by the joule heating that produces on the lead; Similar substantially with DC ice melting, what only be to use is alternating-current; Thereby the heat that the discharge by the electric wire surface produces keeps the temperature of lead to prevent the generation of icing.Electro-thermal deicing method effect is apparent in view, and is simple to operate, workable, but energy consumption is very big, and in the icing serious area, power system is generally collapsed, and electro-thermal deicing this moment is just unrealistic.Therefore electro-thermal deicing only limits to the icing serious area and uses among a small circle, can not promote on a large scale.
(3) photo-thermal deicing method: use the technology of the energy of light wave with the icing thawing, the light of use mainly contains infrared and UV-light, also has laser deicing.Because at icing weather, light is generally not strong.Therefore, be difficult to obtain due effect.Adopt laser to the aerial high-voltage power transmission line deicing as CN101325321A, CN101478136A adopts the microwave deicing, though deicing at a distance, the problems such as potential safety hazard that required outage of mechanical deicing and close contact exist have been solved, but the energy consumption of laser and microwave deicing is bigger, and technology imperfection also, also be difficult to the effect that obtains.
(4) anti-icing paint: mainly comprise photo-thermal type anti-icing paint, electroheating type anti-icing paint and hydrophobic type coating three classes.Photo-thermal type anti-icing paint improves the temperature of lead by absorbing sunlight, thereby makes conductor temperature above freezing at water, thereby reaches the requirement of anti-icing.This class coating is owing to limited by the weather reason, and at the weather of ice and snow, general light is not strong, is difficult to play due effect, so study lessly, application prospect is less.The electroheating type anti-icing paint keeps the temperature of lead by the electric heating on the lead, thereby makes lead above freezing at water.This class coating generally is to mix a small amount of conducting material in coating, thereby makes coating form semi-conductor layer, produces electric heating thereby lead forms small stray current.This type of coating is because bigger to the loss of electric energy, and application prospect has certain restriction.Hydrophobic type coating passes through to reduce the bonding force between water or ice and the lead, thereby prevents to freeze.Because the general hydrophobic ice of also relatively hating, even if ice is not strong in its surface attachment bonding force yet, subsequent disposal is also many easily.
In aforesaid method, the anti-icing paint development is one of main direction of anti-icing.Prepare anti-icing paint as employing organic fluorinated silicone macromolecular materials such as CN1010358106A, CN101230224A, US20020139956A1 and CN101514270A, because hydrophobic performance is limited, and to plain conductor, pottery, glass and shaft tower etc. base material sticking power less, be difficult to be applied to production practice.
Low surface energy anti-ice cover coating of the present invention can effectively increase and base material sticking power, has higher contact angle and less roll angle again.Therefore, anti-ice cover coating of the present invention has anti-ice cover practical function preferably.
Summary of the invention
Technical problem to be solved by this invention provides anti-ice cover coating of the good and base material strong adhesion of a kind of hydrophobic performance and preparation method thereof.
Low surface energy anti-ice cover coating of the present invention, wherein each component and quality percentage composition thereof are as follows:
Its preparation method divided for three steps carried out:
The surface modification of the first step silicon sol
Under magnetic agitation, silicon sol, silane coupling agent, ethanol and ammoniacal liquor are added in the reaction vessel, temperature of reaction 25-60 ℃, reaction times 1-12 hour, promptly get the silicon sol of surface modification, the quality percentage composition of each component of reactant is as follows:
Hud typed SiO of second step
2The preparation of @ fluorinated acrylate emulsion
In reaction vessel, add deionized water, emulsifying agent, modified silicasol, acrylate, Ethylene glycol dimethacrylate and fluorochemical monomer, stir 0.5h and obtain pre-emulsification emulsion; Get 40% pre-emulsion, add the part ammonium persulfate solution, heated and stirred 1h obtains seed emulsion; With remaining pre-emulsion and initiator solution, within 3h, dropwise then, temperature of reaction 55-85 ℃, get hud typed SiO after polymerization finishes
2The @ fluorinated acrylate emulsion, the quality percentage composition of each component of reactant is as follows:
The preparation of the 3rd step low surface energy anti-ice cover coating
Under the room temperature, in reaction vessel, add hud typed SiO
2@ fluorinated acrylate emulsion, dispersion agent, pigment, film coalescence aid, wetting agent, flow agent, sanitas, defoamer and deionized water stir.
Scheme is more specifically:
Silicon sol in the above-mentioned reaction is of a size of 5nm-500 μ m, and pattern is spherical or the chain pearl.
Silane coupling agent in the above-mentioned reaction is a vinyltrimethoxy silane, vinyltriethoxysilane, the propenyl Trimethoxy silane, the propenyl triethoxyl silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane or methacryloxypropyl three (isopropoxy) silane, the trifluoro propyl Trimethoxy silane, the trifluoro propyl dimethyl dichlorosilane (DMCS), trifluoro propyl methyl cyclotrisiloxane, ten trifluoro octyl group Trimethoxy silanes, the trifluoromethyl trimethyl silane, 1H, 1H, 2H, the mixture of one or more in 2H-perfluoro capryl front three (second) TMOS.
In the above-mentioned reaction acrylate have the following formula structure:
R wherein
1, R
2, R
3, R
4Be H, CH independently
3, C
2H
5, C
3H
7
Fluorochemical monomer in the above-mentioned reaction is selected from trifluoro propyl Trimethoxy silane, trifluoro propyl dimethyl dichlorosilane (DMCS), trifluoro propyl methyl cyclotrisiloxane, ten trifluoro octyl group Trimethoxy silanes, trifluoromethyl trimethyl silane, 1H, 1H, 2H, 2H-perfluoro capryl front three (second) TMOS and have one or more mixture in the fluorine monomer of following array structure:
Wherein, R
1For-C
xH
2x+1, 0≤x≤4; C
nF
mH
2n-m-1In 1≤n≤10,1≤m≤18, x, n, m are integer.
During low surface energy anti-ice cover coating film forming provided by the invention, organo-siloxane stretches to the inside of coating, adheres to base material, increases the sticking power of coating and base material; Hud typed SiO
2The @ fluorinated acrylate emulsion, by from delamination, the silicon sol original position of stratum nucleare structure uneven surface, fluorine stretches to coatingsurface in the fluorinated acrylate of shell, effectively reduce surface energy, increase and the contact angle of water and reduce and water between roll angle, reach good anti-ice cover effect.
Anti-ice cover coating of the present invention has following beneficial effect:
(1), and there is not corrosion with the good sticking power of lead;
(2) the bionical super hydrophobic film of Xing Chenging has high hydrophobic and hates ice, can effectively prevent sleet in the adhering to of conductive line surfaces, and prevents that conductive line surfaces from freezing, and can reduce the transmission pressure ice cover;
(3) middle layer can go out adhering to of ion delay ice in severe environment ionization, thereby reaches the purpose that prevents to coagulate ice and deicing.
Simple on engineering, convenient control of coating of the present invention and cost are lower, and result of use is good.Can be widely used in icing controls such as high-tension cable, iron tower, communication link and aircraft surface.
Embodiment
The present invention further is illustrated by the following example, but non-in order to limit the scope of the invention.
Embodiment 1
Under magnetic agitation, with 50g be of a size of the spherical colloidal silica of 20nm, gamma-methyl allyl acyloxypropyl trimethoxysilane and the 49.5mL deionized water of 1.0g joins in the there-necked flask of 250mL, be warming up to 45 ℃ after stirring 30min, drip 1.0g ammoniacal liquor, in 6 hours reaction times, promptly get the silicon sol of surface modification.
In the four-hole boiling flask of churned mechanically 250mL is housed, 5g modified silicasol, 60g methyl methacrylate, 1g methacrylic acid ten difluoro heptyl esters, 0.1g Ethylene glycol dimethacrylate, 3g OP-10,1.5g SDS and 80g deionized water stir 0.5h and obtain pre-emulsification emulsion successively.Get 40% pre-emulsion, add the ammonium persulfate solution of 40wt%, heated and stirred 1h obtains seed emulsion.With remaining pre-emulsion and initiator solution, within 3h, dropwise then, temperature of reaction 55-85 ℃, get hud typed SiO after polymerization finishes
2The @ fluorinated acrylate emulsion.
Under the room temperature, 20g deionized water and 1g asbestos powder are stirred, join the hud typed SiO of 100g
2In the @ fluorinated acrylate emulsion, add 0.5g3-propylene glycol and 0.1g silicone emulsion mill again and spare, filter and obtain product.
The performance of products obtained therefrom such as following table 1.
Table 1
Embodiment 2
Under magnetic agitation, the gamma-methyl allyl acyloxypropyl trimethoxysilane and the 49.5mL deionized water that are of a size of each 5g of spherical colloidal silica, the 1.0g of 500nm, 10nm, 50nm and 100nm are joined in the there-necked flask of 250mL, be warming up to 45 ℃ after stirring 30min, drip 1.0g ammoniacal liquor, in 6 hours reaction times, promptly get the silicon sol of surface modification.
In the four-hole boiling flask of churned mechanically 250mL is housed, 5g modified silicasol, 60g methyl methacrylate, 1g methacrylic acid ten difluoro heptyl esters, 0.1g Ethylene glycol dimethacrylate, 3g OP-10,1.5g SDS and 80g deionized water stir 0.5h and obtain pre-emulsification emulsion successively.Get 40% pre-emulsion, add the ammonium persulfate solution of 40wt%, heated and stirred 1h obtains seed emulsion.With remaining pre-emulsion and initiator solution, within 3h, dropwise then, temperature of reaction 55-85 ℃, get hud typed SiO after polymerization finishes
2The @ fluorinated acrylate emulsion.
Under the room temperature, 20g deionized water and 1g asbestos powder are stirred, join the hud typed SiO of 100g
2In the @ fluorinated acrylate emulsion, add 0.5g ammediol and 0.1g silicone emulsion mill again and spare, filter and obtain product.The performance of products obtained therefrom such as following table 2.
Table 2
Embodiment 2
Keep embodiment 1 other conditions constant, methyl methacrylate is replaced with methyl acrylate, butyl methacrylate, butyl acrylate and Jia Jibingxisuanyizhi successively.Prepared low surface energy anti-ice cover coating has good mechanical performance and anti-ice performance, and performance data and embodiment 1 are very approaching.
Embodiment 3
Keep embodiment 1 other conditions constant, methacrylic acid ten difluoro heptyl esters are replaced with vinylformic acid hexafluoro butyl ester, dodecafluorhe-ptylacrylate, methacrylic acid hexafluoro butyl ester, trifluoroethyl methacrylate and methacrylic acid ten trifluoro monooctyl esters successively.Prepared low surface energy anti-ice cover coating has good mechanical performance and anti-ice performance, and performance data and embodiment 1 are very approaching.
Embodiment 4
Under magnetic agitation, the gamma-methyl allyl acyloxypropyl trimethoxysilane and the 49.5mL deionized water that are of a size of chain pearl silicon sol 10g, the 1.0g of 80nm are joined in the there-necked flask of 250mL, be warming up to 45 ℃ after stirring 30min, drip 1.0g ammoniacal liquor, in 6 hours reaction times, promptly get the silicon sol of surface modification.
In the four-hole boiling flask of churned mechanically 250mL is housed, 5g modified silicasol, 60g methyl methacrylate, 1g methacrylic acid ten difluoro heptyl esters, 0.1g Ethylene glycol dimethacrylate, 3g OP-10,1.5g SDS and 80g deionized water stir 0.5h and obtain pre-emulsification emulsion successively.Get 40% pre-emulsion, add the ammonium persulfate solution of 40wt%, heated and stirred 1h obtains seed emulsion.With remaining pre-emulsion and initiator solution, within 3h, dropwise then, temperature of reaction 55-85 ℃, get hud typed SiO after polymerization finishes
2The @ fluorinated acrylate emulsion.
Under the room temperature, 20g deionized water and 1g asbestos powder are stirred, join the hud typed SiO of 100g
2In the @ fluorinated acrylate emulsion, add 0.5g ammediol and 0.1g silicone emulsion mill again and spare, filter and obtain product.The performance of products obtained therefrom such as following table 3.
Table 2
Claims (6)
1. low surface energy anti-ice cover coating, it is characterized in that: wherein each component and quality percentage composition thereof are as follows:
Hud typed SiO
2@ fluorinated acrylate emulsion 80～90
Fire retardant 0～5%
Flow agent 0～5%
Sanitas 0～0.8%
Defoamer 0～9%
Deionized water 10～20%.
2. the preparation method of the described coating of claim 1 is characterized in that:
The surface modification of the first step silicon sol
Under magnetic agitation, silicon sol, silane coupling agent, ethanol and ammoniacal liquor are added in the reaction vessel, temperature of reaction 25-60 ℃, reaction times 1-12 hour, promptly get the silicon sol of surface modification, the quality percentage composition of each component of reactant is as follows:
Component quality percentage composition %
Silicon sol 50
Silane coupling agent 0.5
Ethanol 45
Ammoniacal liquor 0.01
Water 4.99
Hud typed SiO of second step
2The preparation of @ fluorinated acrylate emulsion
In reaction vessel, add deionized water, emulsifying agent, modified silicasol, acrylate, Ethylene glycol dimethacrylate and fluorochemical monomer, stir 0.5h and obtain pre-emulsification emulsion; Get 40% pre-emulsion, add the part ammonium persulfate solution, heated and stirred 1h obtains seed emulsion; With remaining pre-emulsion and initiator solution, within 3h, dropwise then, temperature of reaction 55-85 ℃, get hud typed SiO after polymerization finishes
2The @ fluorinated acrylate emulsion, the quality percentage composition of each component of reactant is as follows:
Component quality percentage composition %
Modified silicasol 0.1～30
Acrylate 20～60
Fluorochemical monomer 0.1～20
Ethylene glycol dimethacrylate 0～1.5
Emulsifying agent 1～5
Ammonium persulphate 0.2～1
Deionized water 40～75
The preparation of the 3rd step low surface energy anti-ice cover coating
Under the room temperature, in reaction vessel, add hud typed SiO
2@ fluorinated acrylate emulsion, dispersion agent, pigment, film coalescence aid, wetting agent, flow agent, sanitas, defoamer and deionized water stir.
3. preparation method according to claim 2 is characterized in that: described silicon sol is of a size of 5nm-500 μ m, and pattern is spherical or the chain pearl.
4. according to claim 2 or 3 described preparation methods, it is characterized in that: described silane coupling agent is a vinyltrimethoxy silane, vinyltriethoxysilane, the propenyl Trimethoxy silane, the propenyl triethoxyl silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane or methacryloxypropyl three (isopropoxy) silane, the trifluoro propyl Trimethoxy silane, the trifluoro propyl dimethyl dichlorosilane (DMCS), trifluoro propyl methyl cyclotrisiloxane, ten trifluoro octyl group Trimethoxy silanes, the trifluoromethyl trimethyl silane, 1H, 1H, 2H, the mixture of one or more in 2H-perfluoro capryl front three (second) TMOS.
5. according to claim 2 or 3 described preparation methods, it is characterized in that: described acrylate has the following formula structure:
R wherein
1, R
2, R
3, R
5Be H, CH independently
3, C
2H
5, C
3H
7
6. according to claim 2 or 3 described preparation methods, it is characterized in that: described fluorochemical monomer is selected from trifluoro propyl Trimethoxy silane, trifluoro propyl dimethyl dichlorosilane (DMCS), trifluoro propyl methyl cyclotrisiloxane, ten trifluoro octyl group Trimethoxy silanes, trifluoromethyl trimethyl silane, 1H, 1H, 2H, 2H-perfluoro capryl front three (second) TMOS and have one or more mixture in the fluorine monomer of following array structure:
Wherein, R
1For-C
xH
2x+1, 0≤x≤4; C
nF
mH
2n-m-1In 1≤n≤10,1≤m≤18, x, n, m are integer.
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