CN102205680A - Anti-icing composite coating and manufacturing method thereof - Google Patents
Anti-icing composite coating and manufacturing method thereof Download PDFInfo
- Publication number
- CN102205680A CN102205680A CN2011100610992A CN201110061099A CN102205680A CN 102205680 A CN102205680 A CN 102205680A CN 2011100610992 A CN2011100610992 A CN 2011100610992A CN 201110061099 A CN201110061099 A CN 201110061099A CN 102205680 A CN102205680 A CN 102205680A
- Authority
- CN
- China
- Prior art keywords
- icing
- composite coating
- layer
- ice
- icing composite
- 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.)
- Granted
Links
Landscapes
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
The invention discloses an anti-icing composite coating and a manufacturing method thereof. The anti-icing composite coating comprises three layers, wherein an inner layer is an organic silicon modified epoxy resin layer, a middle layer is a polyelectrolyte salt layer and an outer layer is a fluorine-silicon modified acrylic ester layer. The anti-icing composite coating is coated on the surfaces of components, such as high-voltage cables, iron towers, communication lines, aircrafts and the like, the adhesive force between the inner layer and a substrate can be increased due to the inner layer, icing can be slowed down due to ions ionized by the middle layer, and the adhesive force of ice on the surface and the icing quantity of the surface can be reduced due to the super hydrophobicity of the outer layer. The anti-icing composite coating has excellent bonding force on the substrate and higher heat conductivity, the surface of the outer layer has low surface tension, high hydrophobicity and high icing resistance, and the adhesive force of water and ice can be reduced to the maximum, thus the water and the ice can be easily removed; meanwhile, the middle layer can ionize ions to delay the adhesion of the ice under severe environment, thus the purposes of icing prevention and ice removal are realized. The manufacturing method disclosed by the invention has the advantages of easiness, feasibility, convenience for control, lower cost, and excellent use effect during engineering.
Description
Technical field
The present invention relates to anti-icing composite coating of a class and preparation method.The invention belongs to chemical, material technology field.
Background technology
Icing and accumulated snow are a kind of natural phenomenas, 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 electric faults 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 ice of the drying 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 frosted glass in the windward side.The adhesive force 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 the most original 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, the scope of application 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 DC current, icing is melted by the Joule heat 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 ultraviolet 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 sunshine, 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 conductive materials in coating, thereby makes coating form semi-conductor layer, produces electric heating thereby lead forms small leakage 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 adhesion between water or ice and the lead, thereby prevents to freeze.Since general hydrophobic also relatively hate ice, even if ice is not strong in its surface attachment adhesion yet, subsequent treatment is also many easily.
In said 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, this coating can effectively reduce water and the adhesive force of ice in conductive line surfaces, but the anti-icing effect of practice explanation is relatively poor, is difficult to be applied to production practices.
Summary of the invention
The present invention is directed to China's power system icing incidence height, the characteristics that harmfulness is big provide a kind of anti-icing composite coating and preparation method thereof.As internal layer, polyelectrolyte is as the middle level with modifying epoxy resin by organosilicon, fluorinated silicone modified acrylate and Ludox compound as skin, thereby the anti-icing composite coating of preparation high-performance.This class composite coating has: (1) and the good adhesive force of lead, and do not have corrosion; (2) in sleety weather, polyelectrolyte can effectively delay to freeze; (3) the outer bionical super-hydrophobic film that forms 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; (4) middle level and outer field synergy make it have deicing property by force, can accelerate the ice-melt time, reduce the adhesive force of ice sheet and lead, improve the icing ability of lead.
Technical scheme provided by the invention is: a kind of anti-icing composite coating, comprise three layers, and internal layer is the modifying epoxy resin by organosilicon layer, and the intermediate layer is the polyelectrolyte salt deposit, and skin is fluorinated silicone modified acrylate layer.
Wherein: the modifying epoxy resin by organosilicon layer, be that reaction temperature is 0～120 ℃ by organosiloxane and epoxy alcohol compound prepared in reaction, the reaction time is 0.5～12 h, the mol ratio of two kinds of monomers is 1:1～1:8, and the organic solvent that reacts used is polarity or non-polar solven.Organo-silicon compound are selected from Si (OR)
4, HSi (OR)
3, RSi (OR ')
3, R
2Si (OR ')
2And R
3The mixture of one or more of Si (OR ') (wherein R and R ' are the alkyl of 1～5 carbon atom); The epoxy alcohol compound is selected from one or more mixture of epoxy prapanol, epoxy butanols; Used polar solvent is selected from ether, oxolane, 1 during described reaction, 4-dioxane, 1-Methoxy-2-propyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, carrene or chloroform, non-polar solven are selected from toluene, dimethylbenzene or n-hexane.
The polyelectrolyte salt deposit mainly comprises one or more the mixture in anionic polyelectrolyte, the cationic polyelectrolyte.Anionic polyelectrolyte is selected from one or more the mixture in polyacrylate, poly-sulfonic acid (ester) salt, polyphenyl sulfonic acid (ester) salt, poly-sulfuric acid (ester) salt, lignosulfonates or the alginate; Cationic polyelectrolyte is selected from one or more the mixture in PDDA, polymethyl acyl-oxygen ethyl-trimethyl salmiac, polyene oxypropyl trimethyl ammonium chloride or the polymethyl acyloxy ethyl-trimethyl salmiac.
Fluorinated silicone modified acrylate is by the organic silicon monomer that contains unsaturated double-bond and Organic fluoride monomer and acrylate monomer copolymerization gained resin.Its organic silicon monomer is selected from a kind of in vinyltrimethoxy silane, VTES, allyltrimethoxysilanis, allyltriethoxysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane or methacryloxypropyl three (isopropoxy) silane; It is a kind of in trifluoro monooctyl ester or the acrylic acid ten trifluoro monooctyl esters that the Organic fluoride monomer is selected from methacrylic acid hexafluoro butyl ester, trifluoroethyl methacrylate, methacrylic acid ten difluoro heptyl esters, acrylic acid hexafluoro butyl ester, dodecafluorhe-ptylacrylate, methacrylic acid; Acrylate monomer is selected from one or more mixtures in methyl methacrylate, EMA, propyl methacrylate, butyl methacrylate, methyl acrylate, the butyl acrylate.
Anti-icing composite coating of the present invention, its coating process can be modes such as spraying, brushing or dip-coating, its be in proper order earlier in-again in-back outside.
The present invention is by three layers of compound use, and internal layer is the modifying epoxy resin by organosilicon layer, and the intermediate layer is the polyelectrolyte salt deposit, and skin is fluorinated silicone modified acrylate.Make composite coating not only good adhesion, higher heat conductivity be arranged to base material, its superficies have low surface tension, high hydrophobic, hate ice, can reduce the adhesive force of water and ice to greatest extent, it is very easily come off, the more important thing is that the intermediate layer can go out ion in adverse circumstances ionization and postpone adhering to of ice, thereby reach the purpose that prevents to coagulate ice and deicing.This method is simple on engineering, convenience is controlled, cost is lower, and result of use is good.Can be widely used in icing controls such as high-tension cable, iron tower, communication line and aircraft surface.
The specific embodiment
The present invention further is illustrated by following unrestriced embodiment, but needs to understand described embodiment only in order to the present invention, but not in order to limit the scope of the invention.
Embodiment 1
The preparation of internal layer-modifying epoxy resin by organosilicon: in 250 mL flasks, add 100 mL ether, 13.2 g HSi (OCH
3)
3, stir, in the time of 0 ℃, add 20.3 g epoxy prapanols and 30.3 g triethylamines, be warming up to 30 ℃ of reactions 8 hours.Stop to stir, filter, separate obtaining colourless modifying epoxy resin by organosilicon liquid.
The preparation of outer-fluorinated silicone modified acrylate: in 250 mL there-necked flasks, add 60 g water successively, 0.2 g lauryl sodium sulfate stirs.Then with 0.5 g VTES, 10.0 g methacrylic acid hexafluoro butyl esters, 5.0 g methyl methacrylates, 0.15 g benzoyl peroxide mixes, and ultrasonic 10 min join in the there-necked flask N then
2Protection is warming up to 75 ℃, reacts 6 h, obtains the water white transparency granulated polymer.Get resulting polymers 15.0 g, 120 mL ethanol add in the single port flask of the 250mL that has return duct successively, are warming up to 70 ℃, stir 3h, promptly get outermost resin.
At first be coated with organic silicon modified epoxy resin in steel-cored aluminium strand, then polyacrylic acid coating sodium applies outermost resin at last.Result such as following table 1.
Table 1
| Project | Requirement | The result |
| Acidproof | 10%H 2SO 4 | No change |
| Alkaline-resisting | 10%NaOH | No change |
| Adhesive force | GB | 0 grade |
| Anti-ice performance | Under the rime condition, keep 12h | No icing |
Embodiment 2
The preparation of internal layer-modifying epoxy resin by organosilicon: in 250 mL flasks, add 150 mL oxolanes, 13.2 g HSi (OCH
3)
3, stir, in the time of 0 ℃, add 21.6 g epoxy butanols and 30.3 g triethylamines, be warming up to 60 ℃ of reaction 5 h.Stop to stir, filter, separate obtaining colourless modifying epoxy resin by organosilicon liquid.
The preparation of outer-fluorinated silicone modified acrylate: in the 250mL there-necked flask, add 60 g water successively, 0.2 g lauryl sodium sulfate stirs.Then with 0.5 g VTES, 10.0 g methacrylic acid hexafluoro butyl esters, 5.0 g methyl methacrylates, 0.15 g benzoyl peroxide mixes, and ultrasonic 10 min join in the there-necked flask N then
2Protection is warming up to 75 ℃, reacts 6 h, obtains the water white transparency granulated polymer.Get resulting polymers 15.0g, 120 mL ethanol add in the single port flask of 250 mL that have return duct successively, are warming up to 70 ℃, stir 3 h, promptly get outermost resin.
In steel-cored aluminium strand, at first be coated with organic silicon modified epoxy resin, then apply the polyphenyl sodium sulfonate, apply outermost resin at last.Result such as following table 2.
Table 1
| Project | Requirement | The result |
| Acidproof | 10%H 2SO 4 | No change |
| Alkaline-resisting | 10%NaOH | No change |
| Adhesive force | GB | 0 grade |
| Anti-ice performance | Under the rime condition, keep 12h | No icing |
Embodiment 3
The preparation of internal layer-modifying epoxy resin by organosilicon: in 300 mL flasks, add 200 mL oxolanes, 15.7g Si (OCH
2CH
3)
4, stir, in the time of 0 ℃, add 23.2 g epoxy prapanols and 30.3 g triethylamines, be warming up to 50 ℃ of reaction 3 h.Stop to stir, filter, separate obtaining colourless modifying epoxy resin by organosilicon liquid.
The preparation of outer-fluorinated silicone modified acrylate: in the 250mL there-necked flask, add 60g water successively, the 0.2g lauryl sodium sulfate stirs.Then with the 0.5g vinyltrimethoxy silane; 10.0g trifluoroethyl methacrylate; 5.0g methyl methacrylate; 0.15g benzoyl peroxide mixes, ultrasonic 10min joins in the there-necked flask then; the N2 protection; be warming up to 75 ℃, reaction 6h obtains the water white transparency granulated polymer.Get resulting polymers 15.0g, 120mL ethanol adds in the single port flask of the 250mL that has return duct successively, is warming up to 70 ℃, stirs 3h, promptly gets outermost resin.
At first be coated with organic silicon modified epoxy resin in steel-cored aluminium strand, then polyacrylic acid coating sodium applies outermost resin at last.Result such as following table 3.
Table 3
| Project | Requirement | The result |
| Acidproof | 10%H 2SO 4 | No change |
| Alkaline-resisting | 10%NaOH | No change |
| Adhesive force | GB | 0 grade |
| Anti-ice performance | Under the rime condition, keep 12h | No icing |
Embodiment 4
The preparation of internal layer-modifying epoxy resin by organosilicon: in 250 mL flasks, add 150 mL oxolanes, 18.8 g C
4H
9Si (OCH
3)
3, stir, in the time of 0 ℃, add 21.6g epoxy butanols and 30.3 g triethylamines, be warming up to 120 ℃ of reactions 5 hours.Stop to stir, filter, separate obtaining colourless modifying epoxy resin by organosilicon liquid.
The preparation of outer-fluorinated silicone modified acrylate: in the 250mL there-necked flask, add 60g water successively, the 0.2g lauryl sodium sulfate stirs.Then with 0.5g methacryloxypropyl triethoxysilane, 10.0 g dodecafluorhe-ptylacrylates, the 5.0g methyl methacrylate, the 0.15g benzoyl peroxide mixes, and ultrasonic 10min joins in the there-necked flask N then
2Protection is warming up to 75 ℃, and reaction 6h obtains the water white transparency granulated polymer.Get resulting polymers 15.0g, 120mL ethanol adds in the single port flask of the 250mL that has return duct successively, is warming up to 70 ℃, stirs 3h, promptly gets outermost resin.
At first be coated with organic silicon modified epoxy resin in steel-cored aluminium strand, then polyacrylic acid coating sodium applies outermost resin at last.Result such as following table 4.
Table 4
| Project | Requirement | The result |
| Acidproof | 10%H 2SO 4 | No change |
| Alkaline-resisting | 10%NaOH | No change |
| Adhesive force | GB | 0 grade |
| Anti-ice performance | Under the rime condition, keep 12h | No icing |
Embodiment 5
The preparation of internal layer-modifying epoxy resin by organosilicon: in 250 mL flasks, add 150 mL oxolanes, 13.2 g glycidoxy-propyltrimethoxy silane, stir, in the time of 0 ℃, add 21.6g epoxy butanols and 30.3g triethylamine, be warming up to 80 ℃ of reactions 2 hours.Stop to stir, filter, separate obtaining colourless modifying epoxy resin by organosilicon liquid.
The preparation of outer-fluorinated silicone modified acrylate: in 250 mL there-necked flasks, add 60 g water successively, 0.2 g lauryl sodium sulfate stirs.Then with 0.5 g VTES, 10.0 g methacrylic acids, ten difluoro heptyl esters, 5.0 g methyl methacrylates, 0.12 g azodiisobutyronitrile mixes, and ultrasonic 10min joins in the there-necked flask N then
2Protection is warming up to 75 ℃, reacts 6 h, obtains the water white transparency granulated polymer.Get resulting polymers 15.0g, 120mL ethanol adds in the single port flask of 250 mL that have return duct successively, is warming up to 70 ℃, stirs 3 h, promptly gets outermost resin.
At first be coated with organic silicon modified epoxy resin in steel-cored aluminium strand, then polyacrylic acid coating sodium applies outermost resin at last.Result such as following table 5.
Table 5
| Project | Requirement | The result |
| Acidproof | 10%H 2SO 4 | No change |
| Alkaline-resisting | 10%NaOH | No change |
| Adhesive force | GB | 0 grade |
| Anti-ice performance | Under the rime condition, keep 12h | No icing |
Embodiment 6
The preparation of internal layer-modifying epoxy resin by organosilicon: in the 250mL flask, add 150mL oxolane, 13.2g (CH
3)
2Si (OC
2H
5)
2, stir, in the time of 0 ℃, add 21.6g epoxy butanols and 30.3g triethylamine, be warming up to 80 ℃ of reactions 2 hours.Stop to stir, filter, separate obtaining colourless modifying epoxy resin by organosilicon liquid.
The preparation of outer-fluorinated silicone modified acrylate: in the 250mL there-necked flask, add 60g water successively, the 0.2g lauryl sodium sulfate stirs.Then with 1.0 g gamma-methyl allyl acyloxypropyl trimethoxysilanes, 15.0g acrylic acid ten trifluoro monooctyl esters, the 3.0g methyl methacrylate, the 2.0g butyl acrylate, the 0.15g benzoyl peroxide mixes, and ultrasonic 10min joins in the there-necked flask N then
2Protection is warming up to 75 ℃, and reaction 10h obtains the water white transparency granulated polymer.Get resulting polymers 15.0g, 120mL ethanol adds in the single port flask of the 250mL that has return duct successively, is warming up to 70 ℃, stirs 3h, promptly gets outermost resin.
In steel-cored aluminium strand, at first be coated with organic silicon modified epoxy resin, then apply sodium lignin sulfonate, apply outermost resin at last.Result such as following table 6.
Table 6
| Project | Requirement | The result |
| Acidproof | 10%H 2SO 4 | No change |
| Alkaline-resisting | 10%NaOH | No change |
| Adhesive force | GB | 0 grade |
| Anti-ice performance | Under the rime condition, keep 12h | No icing |
Embodiment 7
The preparation of internal layer-modifying epoxy resin by organosilicon: in the 250mL flask, add 150mL oxolane, 11.2g HSi (OCH
3)
3With 2 g HMDOs, stir, in the time of 0 ℃, add 21.6g epoxy butanols and 30.3g triethylamine, be warming up to 80 ℃ of reactions 2 hours.Stop to stir, filter, separate obtaining colourless modifying epoxy resin by organosilicon liquid.
The preparation of outer-fluorinated silicone modified acrylate: in the 250mL there-necked flask, add 60g water successively, the 0.2g lauryl sodium sulfate stirs.Then with 0.1g methacryloxypropyl three (isopropoxy) silane; 10.0g trifluoroethyl methacrylate; 3.0g methyl methacrylate; 2.0g butyl methacrylate; 1.0g methyl acrylate, the 0.15g benzoyl peroxide mixes, ultrasonic 10min; join in the there-necked flask N then
2Protection is warming up to 75 ℃, and reaction 8h obtains the water white transparency granulated polymer.Get resulting polymers 30.0g, 100mL ethanol adds in the single port flask of the 250mL that has return duct successively, is warming up to 70 ℃, stirs 3h, promptly gets outermost resin.
In steel-cored aluminium strand, at first be coated with organic silicon modified epoxy resin, then apply polyene oxypropyl trimethyl ammonium chloride, apply outermost resin at last.Result such as following table 7.
Table 7
| Project | Requirement | The result |
| Acidproof | 10%H 2SO 4 | No change |
| Alkaline-resisting | 10%NaOH | No change |
| Adhesive force | GB | 0 grade |
| Anti-ice performance | Under the rime condition, keep 12h | No icing |
Embodiment 8
The preparation of internal layer-modifying epoxy resin by organosilicon: in the 250mL flask, add 150mL oxolane, 13.2g HSi (OCH
3)
3, stir, in the time of 0 ℃, add 21.6g epoxy butanols and 30.3g triethylamine, be warming up to 80 ℃ of reactions 2 hours.Stop to stir, filter, separate obtaining colourless modifying epoxy resin by organosilicon liquid.
The preparation of outer-fluorinated silicone modified acrylate: in the 250mL there-necked flask, add 80g water successively, the 0.15g lauryl sodium sulfate stirs.Then with 5.0g methacryloxypropyl three (isopropoxy) silane, the 5.0g dodecafluorhe-ptylacrylate, the 5.0g methyl methacrylate, the 0.15g ABVN mixes, and ultrasonic 10min joins in the there-necked flask N then
2Protection is warming up to 75 ℃, and reaction 8h obtains the water white transparency granulated polymer.Get resulting polymers 25.0g, 80mL ethanol adds in the single port flask of the 250mL that has return duct successively, is warming up to 70 ℃, stirs 3h, promptly gets outermost resin.
In steel-cored aluminium strand, at first be coated with organic silicon modified epoxy resin, then apply PDDA, apply outermost resin at last.Result such as following table 8.
Table 8
| Project | Requirement | The result |
| Acidproof | 10%H 2SO 4 | No change |
| Alkaline-resisting | 10%NaOH | No change |
| Adhesive force | GB | 0 grade |
| Anti-ice performance | Under the rime condition, keep 12h | No icing |
Embodiment 9
The preparation of internal layer-modifying epoxy resin by organosilicon: in the 250mL flask, add 150 mL 1-Methoxy-2-propyl acetates, 5.2g HSi (OCH
3)
3With 5 g glycidoxy-propyltrimethoxy silanes, stir, in the time of 0 ℃, add 21.6g epoxy butanols and 30.3g triethylamine, be warming up to 80 ℃ of reactions 2 hours.Stop to stir, filter, separate obtaining colourless modifying epoxy resin by organosilicon liquid.
The preparation of outer-fluorinated silicone modified acrylate: in the 250mL there-necked flask, add 80g water successively, 0.15g alkylphenol-polyethenoxy (10) ether sulfosuccinic acid monoester disodium salt stirs.Then with the 1.0g allyltrimethoxysilanis, 15.0g acrylic acid hexafluoro butyl ester, the 2.0g methyl methacrylate, the 0.15g ABVN mixes, and ultrasonic 10min joins in the there-necked flask N then
2Protection is warming up to 75 ℃, and reaction 8h obtains the water white transparency granulated polymer.Get resulting polymers 20.0g, 60mL ethanol adds in the single port flask of the 250mL that has return duct successively, is warming up to 70 ℃, stirs 3h, promptly gets outermost resin.
In steel-cored aluminium strand, at first be coated with organic silicon modified epoxy resin, then apply polymethyl acyl-oxygen ethyl-trimethyl salmiac, apply outermost resin at last.Result such as following table 9.
Table 9
| Project | Requirement | The result |
| Acidproof | 10%H 2SO 4 | No change |
| Alkaline-resisting | 10%NaOH | No change |
| Adhesive force | GB | 0 grade |
| Anti-ice performance | Under the rime condition, keep 12h | No icing |
Embodiment 10
The preparation of internal layer-modifying epoxy resin by organosilicon: in the 250mL flask, add 150mL oxolane, 13.2g HSi (OCH
3)
3, stir, in the time of 0 ℃, add 21.6g epoxy butanols and 30.3g triethylamine, be warming up to 80 ℃ of reactions 2 hours.Stop to stir, filter, separate obtaining colourless modifying epoxy resin by organosilicon liquid.
The preparation of outer-fluorinated silicone modified acrylate: in the 250mL there-necked flask, add 80g water successively, the 0.15g lauryl sodium sulfate stirs.Then with 5.0g methacryloxypropyl three (isopropoxy) silane, the 5.0g dodecafluorhe-ptylacrylate, the 5.0g methyl methacrylate, the 0.15g ABVN mixes, and ultrasonic 10min joins in the there-necked flask N then
2Protection is warming up to 75 ℃, and reaction 8h obtains the water white transparency granulated polymer.Get resulting polymers 25.0g, 80mL ethanol adds in the single port flask of the 250mL that has return duct successively, is warming up to 70 ℃, stirs 3h, promptly gets outermost resin.
In steel-cored aluminium strand, at first be coated with organic silicon modified epoxy resin, then apply PDDA, apply outermost resin at last.Result such as following table 10.
Table 10
| Project | Requirement | The result |
| Acidproof | 10%H 2SO 4 | No change |
| Alkaline-resisting | 10%NaOH | No change |
| Adhesive force | GB | 0 grade |
| Anti-ice performance | Under the rime condition, keep 12h | No icing |
Embodiment 11
The preparation of internal layer-modifying epoxy resin by organosilicon: in the 250mL flask, add 150mL oxolane, 13.2g HSi (OCH
3)
3, stir, in the time of 0 ℃, add 21.6g epoxy butanols and 30.3g triethylamine, be warming up to 80 ℃ of reactions 2 hours.Stop to stir, filter, separate obtaining colourless modifying epoxy resin by organosilicon liquid.
The preparation of outer-fluorinated silicone modified acrylate: in the 250mL there-necked flask, add 80g water successively, the 0.15g neopelex stirs.Then with 5.0g methacryloxypropyl three (isopropoxy) silane, the 6.0g dodecafluorhe-ptylacrylate, the 5.0g methyl methacrylate, the 0.1g benzoyl peroxide mixes, and ultrasonic 10min joins in the there-necked flask N then
2Protection is warming up to 55 ℃, and reaction 12h obtains the water white transparency granulated polymer.Get resulting polymers 18.0g, 90mL ethanol adds in the single port flask of the 250mL that has return duct successively, is warming up to 70 ℃, stirs 3h, promptly gets outermost resin.
In steel-cored aluminium strand, at first be coated with organic silicon modified epoxy resin, then apply PDDA, apply outermost resin at last.Result such as following table 11.
Table 11
| Project | Requirement | The result |
| Acidproof | 10%H 2SO 4 | No change |
| Alkaline-resisting | 10%NaOH | No change |
| Adhesive force | GB | 0 grade |
| Anti-ice performance | Under the rime condition, keep 12h | No icing |
Embodiment 12
The preparation of internal layer-modifying epoxy resin by organosilicon: in 250 mL flasks, add 150 mL oxolanes, 13.2g HSi (OCH
3)
3, stir, in the time of 0 ℃, add 21.6g epoxy butanols and 30.3g triethylamine, be warming up to 80 ℃ of reactions 2 hours.Stop to stir, filter, separate obtaining colourless modifying epoxy resin by organosilicon liquid.
The preparation of outer-fluorinated silicone modified acrylate: in the 250mL there-necked flask, add 100 g water successively, 0.15 g lauryl sodium sulfate stirs.Then with the 0.3g vinyltrimethoxy silane, 15.0g acrylic acid ten trifluoro monooctyl esters, the 1.0g methyl methacrylate, the 0.18g ABVN mixes, and ultrasonic 10min joins in the there-necked flask N then
2Protection is warming up to 85 ℃, and reaction 1h obtains the water white transparency granulated polymer.Get resulting polymers 30.0g, 100mL ethanol adds in the single port flask of the 250mL that has return duct successively, is warming up to 70 ℃, stirs 3 h, promptly gets outermost resin.
At first be coated with organic silicon modified epoxy resin in steel-cored aluminium strand, the sodium of polyacrylic acid coating sodium and alginic acid acid then applies outermost resin at last.Result such as following table 12.
Table 12
| Project | Requirement | The result |
| Acidproof | 10%H 2SO 4 | No change |
| Alkaline-resisting | 10%NaOH | No change |
| Adhesive force | GB | 0 grade |
| Anti-ice performance | Under the glaze condition, keep 12h | The minute quantity icing |
Claims (8)
1. anti-icing composite coating, it is characterized in that: comprise three layers, internal layer is the modifying epoxy resin by organosilicon layer, and the intermediate layer is the polyelectrolyte salt deposit, skin is fluorinated silicone modified acrylate.
2. anti-icing composite coating according to claim 1, it is characterized in that: described modifying epoxy resin by organosilicon layer, be by organosiloxane and epoxy alcohol compound prepared in reaction, reaction temperature is 0～120 ℃, reaction time is 0.5～12 h, the mol ratio of two kinds of monomers is 1:1～1:8, and the organic solvent that reacts used is polarity or non-polar solven.
3. anti-icing composite coating according to claim 2 is characterized in that: described organosiloxane is selected from Si (OR)
4, HSi (OR)
3, RSi (OR ')
3, R
2Si (OR ')
2And R
3The mixture of one or more among the Si (OR '), wherein R and R ' they are the alkyl of 1～5 carbon atom; The epoxy alcohol compound is selected from one or more mixture of epoxy prapanol, epoxy butanols; Used polar solvent is selected from ether, oxolane, 1 during described reaction, 4-dioxane, 1-Methoxy-2-propyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, carrene or chloroform, non-polar solven are selected from toluene, dimethylbenzene or n-hexane.
4. anti-icing composite coating according to claim 1 is characterized in that: described polyelectrolyte salt deposit comprises one or more the mixture in anionic polyelectrolyte, the cationic polyelectrolyte.
5. anti-icing composite coating according to claim 4 is characterized in that: described anionic polyelectrolyte is selected from one or more the mixture in polyacrylate, poly-sulfonic acid (ester) salt, polyphenyl sulfonic acid (ester) salt, poly-sulfuric acid (ester) salt, lignosulfonates or the alginate; Cationic polyelectrolyte is selected from one or more the mixture in PDDA, polymethyl acyl-oxygen ethyl-trimethyl salmiac, polyene oxypropyl trimethyl ammonium chloride or the polymethyl acyloxy ethyl-trimethyl salmiac.
6. anti-icing composite coating according to claim 1 is characterized in that: described fluorinated silicone modified acrylate is by the organic silicon monomer that contains unsaturated double-bond, Organic fluoride monomer and acrylate monomer copolymerization gained resin.
7. anti-icing composite coating according to claim 6 is characterized in that: described organic silicon monomer is selected from a kind of in vinyltrimethoxy silane, VTES, allyltrimethoxysilanis, allyltriethoxysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane, gamma-methyl allyl acyloxypropyl triethoxysilane or methacryloxypropyl three (isopropoxy) silane; The Organic fluoride monomer is selected from a kind of in methacrylic acid hexafluoro butyl ester, trifluoroethyl methacrylate, methacrylic acid ten difluoro heptyl esters, acrylic acid hexafluoro butyl ester, dodecafluorhe-ptylacrylate, methacrylic acid ten trifluoro monooctyl esters or the acrylic acid ten trifluoro monooctyl esters; Acrylate monomer is selected from one or more mixtures in methyl methacrylate, EMA, propyl methacrylate, butyl methacrylate, methyl acrylate, the butyl acrylate.
8. the coating process of the described anti-icing composite coating of claim 1 is spraying, brushing or dip-coating, its be in proper order earlier in-again in-back outside.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110061099.2A CN102205680B (en) | 2011-03-15 | 2011-03-15 | Anti-icing composite coating and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110061099.2A CN102205680B (en) | 2011-03-15 | 2011-03-15 | Anti-icing composite coating and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102205680A true CN102205680A (en) | 2011-10-05 |
| CN102205680B CN102205680B (en) | 2014-07-16 |
Family
ID=44694881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110061099.2A Active CN102205680B (en) | 2011-03-15 | 2011-03-15 | Anti-icing composite coating and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102205680B (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103244820A (en) * | 2013-04-24 | 2013-08-14 | 兰州空间技术物理研究所 | Antifrost heat-insulation device and method for filling liquid nitrogen to low-temperature cover on ground |
| CN103587203A (en) * | 2013-10-30 | 2014-02-19 | 溧阳市哈大成果转化中心有限公司 | Ice protection tailplane leading-edge assembly |
| CN103587209A (en) * | 2013-10-30 | 2014-02-19 | 溧阳市哈大成果转化中心有限公司 | Anti-icing aircraft fairing leading edge |
| CN103589263A (en) * | 2013-10-30 | 2014-02-19 | 溧阳市哈大成果转化中心有限公司 | Coating-containing anti-icing propeller blade leading-edge assembly |
| CN103587192A (en) * | 2013-10-30 | 2014-02-19 | 溧阳市哈大成果转化中心有限公司 | Fairing leading-edge assembly with anti-icing coating |
| CN103587188A (en) * | 2013-10-26 | 2014-02-19 | 溧阳市哈大成果转化中心有限公司 | Ice-proof vertical tail leading edge assembly |
| CN103587199A (en) * | 2013-10-30 | 2014-02-19 | 溧阳市哈大成果转化中心有限公司 | Wingtip's winglet leading edge |
| CN103587190A (en) * | 2013-10-30 | 2014-02-19 | 溧阳市哈大成果转化中心有限公司 | Anti-icing wingtip's winglet leading-edge assembly |
| CN103600541A (en) * | 2013-10-26 | 2014-02-26 | 溧阳市哈大成果转化中心有限公司 | Aircraft engine inlet duct leading edge assembly |
| CN103700450A (en) * | 2012-09-27 | 2014-04-02 | 中国石油化工股份有限公司 | Method and equipment for manufacturing anti-icing metal high-voltage power line |
| CN103587191B (en) * | 2013-10-30 | 2015-07-15 | 溧阳市哈大成果转化中心有限公司 | Anti-icing vertical tail leading-edge assembly |
| CN105154879A (en) * | 2015-09-23 | 2015-12-16 | 北京机械工业自动化研究所 | Composite coating for pitot tube, preparation method of composite coating, and pitot tube with composite coating |
| CN106356164A (en) * | 2016-11-14 | 2017-01-25 | 广东电网有限责任公司电力科学研究院 | Surface treatment technology for anti-icing composite insulator |
| CN106402489A (en) * | 2016-10-09 | 2017-02-15 | 安顺集团建设有限公司 | Pipe jacking construction method of municipal gas pipelines |
| CN108008471A (en) * | 2017-12-01 | 2018-05-08 | 中国化工株洲橡胶研究设计院有限公司 | A kind of water proofing property meteorological balloon and its production method |
| CN110373069A (en) * | 2018-04-12 | 2019-10-25 | 中国科学院化学研究所 | A kind of hydrogel coating and the preparation method and application thereof |
| CN112961544A (en) * | 2021-03-09 | 2021-06-15 | 西北大学 | Oil gel coating for water delivery drag reduction and pollution resistance and preparation method thereof |
| CN115785804A (en) * | 2022-11-29 | 2023-03-14 | 东北农业大学 | Super-hydrophobic photo-thermal anti-icing coating material, preparation method and application |
| CN115975463A (en) * | 2023-02-27 | 2023-04-18 | 国网河南省电力公司方城县供电公司 | Wind power blade protective coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020139956A1 (en) * | 2000-12-14 | 2002-10-03 | Simendinger William H. | Anti-icing composition |
| CN101514270A (en) * | 2009-02-27 | 2009-08-26 | 哈尔滨金士源科技有限公司 | Ice coating resistance paint composition |
| CN102146249A (en) * | 2011-01-14 | 2011-08-10 | 甘肃省电力公司天水超高压输变电公司 | High-voltage power transmission line ice-covering-proof paint and preparation method thereof |
-
2011
- 2011-03-15 CN CN201110061099.2A patent/CN102205680B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020139956A1 (en) * | 2000-12-14 | 2002-10-03 | Simendinger William H. | Anti-icing composition |
| CN101514270A (en) * | 2009-02-27 | 2009-08-26 | 哈尔滨金士源科技有限公司 | Ice coating resistance paint composition |
| CN102146249A (en) * | 2011-01-14 | 2011-08-10 | 甘肃省电力公司天水超高压输变电公司 | High-voltage power transmission line ice-covering-proof paint and preparation method thereof |
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103700450A (en) * | 2012-09-27 | 2014-04-02 | 中国石油化工股份有限公司 | Method and equipment for manufacturing anti-icing metal high-voltage power line |
| CN103244820A (en) * | 2013-04-24 | 2013-08-14 | 兰州空间技术物理研究所 | Antifrost heat-insulation device and method for filling liquid nitrogen to low-temperature cover on ground |
| CN103244820B (en) * | 2013-04-24 | 2015-03-25 | 兰州空间技术物理研究所 | Antifrost heat-insulation device and method for filling liquid nitrogen to low-temperature cover on ground |
| CN103600541A (en) * | 2013-10-26 | 2014-02-26 | 溧阳市哈大成果转化中心有限公司 | Aircraft engine inlet duct leading edge assembly |
| CN103600541B (en) * | 2013-10-26 | 2015-09-23 | 溧阳市哈大成果转化中心有限公司 | A kind of front edge of engine air inlet duct of aircraft assembly |
| CN103587188B (en) * | 2013-10-26 | 2015-06-10 | 溧阳市哈大成果转化中心有限公司 | Ice-proof vertical tail leading edge assembly |
| CN103587188A (en) * | 2013-10-26 | 2014-02-19 | 溧阳市哈大成果转化中心有限公司 | Ice-proof vertical tail leading edge assembly |
| CN103589263B (en) * | 2013-10-30 | 2015-08-05 | 溧阳市哈大成果转化中心有限公司 | A kind of containing the anti-icing propeller blade leading edge assemblies of coating |
| CN103587192B (en) * | 2013-10-30 | 2015-12-09 | 溧阳市哈大成果转化中心有限公司 | A kind of cowl lip assembly with ice-phobic coating |
| CN103587199A (en) * | 2013-10-30 | 2014-02-19 | 溧阳市哈大成果转化中心有限公司 | Wingtip's winglet leading edge |
| CN103587192A (en) * | 2013-10-30 | 2014-02-19 | 溧阳市哈大成果转化中心有限公司 | Fairing leading-edge assembly with anti-icing coating |
| CN103589263A (en) * | 2013-10-30 | 2014-02-19 | 溧阳市哈大成果转化中心有限公司 | Coating-containing anti-icing propeller blade leading-edge assembly |
| CN103587191B (en) * | 2013-10-30 | 2015-07-15 | 溧阳市哈大成果转化中心有限公司 | Anti-icing vertical tail leading-edge assembly |
| CN103587199B (en) * | 2013-10-30 | 2015-07-15 | 溧阳市哈大成果转化中心有限公司 | Wingtip's winglet leading edge |
| CN103587209A (en) * | 2013-10-30 | 2014-02-19 | 溧阳市哈大成果转化中心有限公司 | Anti-icing aircraft fairing leading edge |
| CN103587190B (en) * | 2013-10-30 | 2015-09-23 | 溧阳市哈大成果转化中心有限公司 | A kind of anti-icing winglet leading edge assemblies |
| CN103587203A (en) * | 2013-10-30 | 2014-02-19 | 溧阳市哈大成果转化中心有限公司 | Ice protection tailplane leading-edge assembly |
| CN103587203B (en) * | 2013-10-30 | 2015-12-02 | 溧阳市哈大成果转化中心有限公司 | A kind of ice protection level empennage leading edge assemblies |
| CN103587190A (en) * | 2013-10-30 | 2014-02-19 | 溧阳市哈大成果转化中心有限公司 | Anti-icing wingtip's winglet leading-edge assembly |
| CN105154879A (en) * | 2015-09-23 | 2015-12-16 | 北京机械工业自动化研究所 | Composite coating for pitot tube, preparation method of composite coating, and pitot tube with composite coating |
| CN105154879B (en) * | 2015-09-23 | 2018-08-31 | 北京机械工业自动化研究所 | Pitot-static tube composite coating, preparation method and the Pitot-static tube with the composite coating |
| CN106402489A (en) * | 2016-10-09 | 2017-02-15 | 安顺集团建设有限公司 | Pipe jacking construction method of municipal gas pipelines |
| CN106356164A (en) * | 2016-11-14 | 2017-01-25 | 广东电网有限责任公司电力科学研究院 | Surface treatment technology for anti-icing composite insulator |
| CN108008471A (en) * | 2017-12-01 | 2018-05-08 | 中国化工株洲橡胶研究设计院有限公司 | A kind of water proofing property meteorological balloon and its production method |
| CN108008471B (en) * | 2017-12-01 | 2020-08-07 | 中国化工株洲橡胶研究设计院有限公司 | Waterproof meteorological balloon and production method thereof |
| CN110373069A (en) * | 2018-04-12 | 2019-10-25 | 中国科学院化学研究所 | A kind of hydrogel coating and the preparation method and application thereof |
| CN112961544A (en) * | 2021-03-09 | 2021-06-15 | 西北大学 | Oil gel coating for water delivery drag reduction and pollution resistance and preparation method thereof |
| CN115785804A (en) * | 2022-11-29 | 2023-03-14 | 东北农业大学 | Super-hydrophobic photo-thermal anti-icing coating material, preparation method and application |
| CN115975463A (en) * | 2023-02-27 | 2023-04-18 | 国网河南省电力公司方城县供电公司 | Wind power blade protective coating and preparation method thereof |
| CN115975463B (en) * | 2023-02-27 | 2024-02-06 | 国网河南省电力公司方城县供电公司 | Wind power blade protective coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102205680B (en) | 2014-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102205680B (en) | Anti-icing composite coating and manufacturing method thereof | |
| CN102220063B (en) | Low surface energy icing-resistant coating and preparation method thereof | |
| CN112852289B (en) | Super-hydrophobic anti-icing and deicing coating with photo-thermal effect and preparation method thereof | |
| CN105219263B (en) | Extra high voltage line surface anti-icing paint | |
| CN101307208B (en) | High-hydrophobicity anti-icing and anti-frosting coatings and method for preparing same | |
| CN105032731A (en) | Preparation method for energy-saving anti-icing/deicing coating combining super-hydrophobic coating and heating coating | |
| CN103059650B (en) | Nanometer coating used for preventing icing of high tension transmission line and application thereof | |
| CN102660182A (en) | Nanocomposite ice-coating-proof paint having properties of superhydrophobicity and low adhesive strength | |
| CN101514270A (en) | Ice coating resistance paint composition | |
| CN108587455B (en) | Anti-icing material and preparation method and application thereof | |
| CN103194130B (en) | Icing-proof coating with low ice adhesion, and preparation method and application thereof | |
| CN102558993B (en) | Nano-silica/silicone-acrylate composite icing-resistant coating, and preparation method and application thereof | |
| CN104396646A (en) | Method for eliminating haze through artificially inducing rainfall with charged water mist | |
| CN114231071B (en) | Ice-snow-covering-preventing normal-temperature curing light energy coating easy to remove ice and snow and preparation method thereof | |
| CN111716776B (en) | Photoelectric-thermal super-hydrophobic film, preparation method and anti-icing and deicing application | |
| CN103203938A (en) | Spontaneous heating coating for substrate surface and preparation method of spontaneous heating coating | |
| CN107061193B (en) | Multi-layer structure composite anti-icing and deicing system and assembly method thereof | |
| CN102190935A (en) | Anti-icing coating and use thereof | |
| CN104212413A (en) | Liquid-filled porous silicon resin anti-icing material and preparation method thereof | |
| CN105062168B (en) | Anti-icing paint for power transmission cable | |
| Heyun et al. | Icing and anti-icing of railway contact wires | |
| CN114181614B (en) | MOF-based photo-thermal deicing coating and preparation method thereof | |
| CN205789218U (en) | A kind of anti-ice-snow type optical power grounded waveguide | |
| CN214267966U (en) | Wind-powered electricity generation field scrubbing, defroster based on unmanned aerial vehicle | |
| CN114806389B (en) | Fluorine-containing polyphosphazene visible light-cured aircraft anti-icing coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: RESEARCH INSTITUTE OF SOUTHERN POWER GRID CO., LTD Free format text: FORMER OWNER: SOUTHERN POWER GRID TECHNOLOGY RESEARCH CENTER Effective date: 20111206 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20111206 Address after: 430072 Hubei Province, Wuhan city Wuchang District of Wuhan University Luojiashan Applicant after: Wuhan University Co-applicant after: Research Institute of Southern Power Grid Co., Ltd. Address before: 430072 Hubei Province, Wuhan city Wuchang District of Wuhan University Luojiashan Applicant before: Wuhan University Co-applicant before: Southern Power Grid Technology Research Center |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |