CN104987803A - Anti-icing ionic liquid gel film and preparation method therefor - Google Patents
Anti-icing ionic liquid gel film and preparation method therefor Download PDFInfo
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- CN104987803A CN104987803A CN201510465167.XA CN201510465167A CN104987803A CN 104987803 A CN104987803 A CN 104987803A CN 201510465167 A CN201510465167 A CN 201510465167A CN 104987803 A CN104987803 A CN 104987803A
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Abstract
The invention relates to an anti-icing ionic liquid gel film and a preparation method therefor. The ionic liquid gel disclosed by the invention consists of a polymer three-dimensional network and free ionic liquid, or consists of a poly ionic liquid three-dimensional network and free ionic liquid. The ionic liquid gel film provided by the invention overcomes the defects of high production cost, poor long residual action, low deicing efficiency, poor stability, poor mechanical strength and difficult extensive preparation existing in a conventional anti-icing material, has the characteristics that the stability is good, the preparation method is simple, the ionic liquid gel film is suitable for extensive preparation, and the mechanical property is excellent, and is a novel long-acting anti-icing material which can be extensively prepared.
Description
Technical field
The invention belongs to icing protection coating preparation and application field, relate to the method utilizing ionic liquid gel film preparation anti-icing coatings.
Background technology
Icing phenomenon be extensively present in road surface, cold district, aerospace, cryogenic refrigeration, cryogenic liquid accumulating and etc. on the cold surface in field.Anti-icing coatings for reduce freeze cause traffic accident, prevention communication line and electrical network tower damage, improve refrigerator and heat transfer equipment heat transfer efficiency etc. all significant.The method that tradition prepares anti-icing coatings comprises electrochemical method, sol-gel method, mechanical deicing's method, and because production cost is high, long-lasting difference, deicing efficiency be low, there is potential safety hazard, strongly limit practical application.In recent years, by infiltrating inspiration special in nature life system, investigators design and have prepared a series of bionical anti-icing coatings (D. Qu é r é et al. Langmuir, 25,7214-7216 (2009); J. Aizenberg et al. ACS Nano, 4,7699-7707 (2010); J. Aizenberg et al. Nature, 477,443-447 (2011); J. Wang et al. ACS Nano, 8,3152-3169 (2014)).Super-hydrophobic coat as inspired by lotus leaf relies on the gas cloud in its microstructure, greatly can limit the formation of ice; And significantly reduce the adhesive power between ice and interface by the liquid lubrication layer on the easy sliding surface of Herba nepenthis inspiration, thus the ice that can be easy to be formed under small External Force Acting removes.However, also there is deadly defect in above-mentioned anti-freeze material.As super hydrophobic surface needs to construct complicated micro nano structure, make its stability and bad mechanical strength, can not actual needs be met.Although easy sliding surface has satisfactory stability, in prepared by simple and easy to do big area, also face huge challenge.Therefore be badly in need of a kind of novel anti-freeze material of development, the requirement of life-time service can be met, the bottleneck of big area preparation difficulty can be solved again.
Summary of the invention
The object of the present invention is to provide a kind of method utilizing ionic liquid gel film preparation anti-icing coatings.It is characterized in that: the method is without the need to constructing micro-nano Multi-scale model, good stability; Preparation method is simple, adopts the free-radical polymerized crosslinking reaction of light or thermofixation, is applicable to big area preparation; By designing the chemical structure of ionic liquid, its zero pour can near-80
oc, ensures the stable existence of liquid lubrication layer in condition of ultralow temperature; The physical strength of ionic liquid gel regulates by proportioning raw materials, reaches excellent mechanical property.
The present invention is achieved through the following technical solutions.
A kind of anti-freeze film, is ionic liquid gel film, it is characterized in that: described ionic liquid gel film is with hydrophobic polymer or poly ion liquid for three-dimensional network skeleton, and non-polymeric hydrophobic ionic liquid is external phase.
The preparation method of anti-freeze film of the present invention comprises following three kinds:
(1) polymer monomer free-radical polymerized being cross-linked in non-polymeric ion liquid prepares ionic liquid gel
Hydrophobic polymer monomer, hydrophobicity non-polymeric ion liquid, initiator, linking agent are dissolved in solvent, mixing and stirring, nitrogen bubble deoxygenation.Be coated in substrate, react under the condition of UV-light or heat, prepare ionic liquid gel film.
(2) polymkeric substance directly and non-polymeric ion liquid physics be cross-linked to form ionic liquid gel
By hydrophobic polymer, solvent, hydrophobicity non-polymeric ion liquid mixing, be stirred to even colloidal sol, be coated in substrate, after solvent evaporates is complete, obtain ionic liquid gel film.
(3) ionic liquid monomer free-radical polymerized being cross-linked in non-polymeric ion liquid prepares ionic liquid gel
Ionic liquid monomer, hydrophobicity non-polymeric ion liquid, initiator, linking agent are dissolved in solvent, mixing and stirring, nitrogen bubble deoxygenation.Be coated in substrate, react under the condition of UV-light or heat, prepare ionic liquid gel film.
In preparation method (1) described in the present invention, hydrophobic polymer monomer is one or more in methyl acrylate, methyl methacrylate, butyl methacrylate, 4-vinylpridine, vinylbenzene.
In preparation method (2) described in the present invention, hydrophobic polymer is one or more in polymethylmethacrylate, polyvinylidene difluoride (PVDF)-R 1216, polydimethylsiloxane.
In preparation method (3) described in the present invention, ionic liquid monomer is one or more in two (trifluoromethane sulphonyl) inferior amine salt of 1-vinyl-3-butyl imidazole, 1-vinyl-3-butyl imidazole hexafluorophosphate, 1-vinyl-3-butyl imidazole a tetrafluoro borate, two (trifluoromethane sulphonyl) inferior amine salt of 1-vinyl-3-ethyl imidazol(e), 1-vinyl-3-ethyl imidazol(e) hexafluorophosphate, 1-vinyl-3-ethyl imidazol(e) a tetrafluoro borate, 1-vinyl-3-ethyl imidazol(e) dintrile amine salt.
In preparation method (1) (2) (3) described in the present invention, hydrophobicity non-polymeric ion liquid is two (trifluoromethane sulphonyl) inferior amine salt of 1-second class-3-Methylimidazole, two (trifluoromethane sulphonyl) inferior amine salt of 1-propyl group-3-Methylimidazole, 1-hexyl-3-methyl imidazolium tetrafluoroborate, 1-octyl group-3-methyl imidazolium tetrafluoroborate, 1-octyl group-3-Methylimidazole hexafluorophosphate, two (trifluoromethane sulphonyl) inferior amine salt of 1-octyl group-3-Methylimidazole, 1-butyl-2, two (trifluoromethane sulphonyl) inferior amine salt of 3-methylimidazole, two (trifluoromethane sulphonyl) inferior amine salt of N-butyl-N-methylpyrrole, two (trifluoromethane sulphonyl) inferior amine salt of 1-nitrile third class-3-Methylimidazole, one or more in two (trifluoromethane sulphonyl) inferior amine salt of 1-benzyl-3-Methylimidazole.
In preparation method (1) (2) (3) described in the present invention, solvent is one or more in acetone, methylene dichloride, toluene.
In described preparation method (1) (3) in the present invention, monomer initiator is one or more in benzophenone, benzoyl peroxide, Diisopropyl azodicarboxylate.
In preparation method (1) (3) described in the present invention, linking agent is polyethylene glycol dimethacrylate.
In preparation method (1) (2) (3) described in the present invention, substrate is aluminium flake, copper sheet, iron plate, plastics, glass, silicon-dioxide, pottery.
In described preparation method (1) (2) (3) in the present invention, the mass ratio of hydrophobicity non-polymeric ion liquid/solvent is 1000/1000-1000/0.
In preparation method of the present invention (2), the mass ratio of hydrophobic polymer/solvent is 10/1000-100/1000.In preparation method (3) described in the present invention, the mass ratio of ionic liquid monomer/hydrophobicity non-polymeric ion liquid is 100/1000-1000/0.
In preparation method (1) (3) described in the present invention, the mass ratio of initiator/polymer monomer is 1/1000-20/1000.
In preparation method (1) (3) described in the present invention, the mass ratio of linking agent/polymer monomer is 1/1000-50/1000.
In preparation method (1) described in the present invention, the mass ratio of hydrophobic polymer monomer/hydrophobicity non-polymeric ion liquid is 100/1000-1000/1000.
In described preparation method (1) (3) in the present invention, light-initiated wavelength is 250 nm-420 nm.
In described preparation method (1) (3) in the present invention, Heating temperature is 70-90 oC.
Anti-freeze ionic liquid gel film provided by the invention, overcome existing anti-icing coatings production cost high, long-lasting difference, deicing efficiency be low, bad mechanical strength, can not the defect prepared of big area.The ionic liquid gel property of thin film that the present invention obtains is stablized, through reaching 1 year placement or through ultraviolet lighting after an hour on its deicing properties without impact.The zero pour of ionic liquid lowly can reach-80
oc, makes prepared ionic liquid gel film still keep deicing properties under very low temperature.Method of the present invention is easy and simple to handle, be easy to control, required equipment is simple, can scale operation.
Accompanying drawing explanation
Fig. 1 be anti-freeze ionic liquid gel film of the present invention prepare schematic diagram
Embodiment
Following examples are only be further described technical scheme of the present invention, instead of limit technical scheme of the present invention.
Embodiment 1
Hydrophobic monomer methyl acrylate, hydrophobicity non-polymeric ion liquid 1-octyl group-3-methyl imidazolium tetrafluoroborate, initiator Diisopropyl azodicarboxylate, linking agent polyethylene glycol dimethacrylate are with weight ratio 1000/1000/10/10 mixing and stirring, nitrogen bubble deoxygenation in 30 minutes, even application is on aluminium flake, and then under 80 oC heated conditions, reaction forms anti-freeze ionic liquid gel film.
Embodiment 2
Hydrophobic monomer methyl methacrylate, hydrophobicity non-polymeric ion liquid 1-octyl group-3-methyl imidazolium tetrafluoroborate, initiator benzoyl peroxide, linking agent polyethylene glycol dimethacrylate are with weight ratio 1000/1000/10/10 mixing and stirring, nitrogen bubble deoxygenation in 30 minutes, even application is on iron plate, and then under 80 oC heated conditions, reaction forms anti-freeze ionic liquid gel film.
Embodiment 3
Hydrophobic monomer butyl methacrylate, hydrophobicity non-polymeric ion liquid 1-octyl group-3-methyl imidazolium tetrafluoroborate, initiator benzoyl peroxide, linking agent polyethylene glycol dimethacrylate are with weight ratio 1000/1000/10/10 mixing and stirring, nitrogen bubble deoxygenation in 30 minutes, even application is on copper sheet, and then under 80 oC heated conditions, reaction forms anti-freeze ionic liquid gel film.
Embodiment 4
Two (trifluoromethane sulphonyl) inferior amine salt of hydrophobic monomer 4-vinylpridine, hydrophobicity non-polymeric ion liquid 1-octyl group-3-Methylimidazole, initiator benzophenone, linking agent polyethylene glycol dimethacrylate are with weight ratio 1000/2000/10/20 mixing and stirring, nitrogen bubble deoxygenation in 30 minutes, on the glass sheet, then under 265 nm UV-irradiation, polymerization crosslinking obtains anti-freeze ionic liquid gel film to even application.
Embodiment 5
Hydrophobic monomer vinylbenzene, hydrophobicity non-polymeric ion liquid 1-octyl group-3-Methylimidazole hexafluorophosphate, initiator benzoyl peroxide, linking agent polyethylene glycol dimethacrylate are with weight ratio 1000/2000/10/20 mixing and stirring, nitrogen bubble deoxygenation in 30 minutes, on silica, then under 265 nm UV-irradiation, polymerization crosslinking obtains anti-freeze ionic liquid gel film to even application.
Embodiment 6
Hydrophobic polymer polymethylmethacrylate, methylene dichloride mix with mass ratio 50/1000, and magnetic agitation is to becoming transparent uniform solution.Then in above-mentioned solution, add two (trifluoromethane sulphonyl) inferior amine salt of hydrophobicity non-polymeric ion liquid 1-second class-3-Methylimidazole (mass ratio of two (trifluoromethane sulphonyl) inferior amine salt of polymethylmethacrylate/1-second class-3-Methylimidazole is 100/1000), continue to be stirred to uniform solution.Then gained dissolution homogeneity is coated to ceramic surface, after methylene dichloride volatilization, obtains anti-freeze ionic liquid gel film.
Embodiment 7
Hydrophobic polymer polyvinylidene difluoride (PVDF)-R 1216, acetone mix with mass ratio 50/1000, and magnetic agitation is to becoming transparent uniform solution.Then in above-mentioned solution, add hydrophobicity non-polymeric ion liquid 1-hexyl-3-methyl imidazolium tetrafluoroborate (mass ratio of polyvinylidene difluoride (PVDF)-R 1216/1-hexyl-3-methyl imidazolium tetrafluoroborate is 100/1000), continue to be stirred to uniform solution.Then gained dissolution homogeneity is coated to aluminium flake surface, after acetone volatilization, obtains anti-freeze ionic liquid gel film.
Embodiment 8
Hydrophobic polymer polydimethylsiloxane prepolymer body, solidifying agent, mix with mass ratio 1000/100, magnetic agitation is to becoming transparent uniform solution.Then in above-mentioned solution, add two (trifluoromethane sulphonyl) inferior amine salt of hydrophobicity non-polymeric ion liquid N-butyl-N-methylpyrrole (mass ratio of two (trifluoromethane sulphonyl) inferior amine salt of polydimethylsiloxane/N-butyl-N-methylpyrrole is 1000/1000), continue to be stirred to uniform solution.Then gained dissolution homogeneity is coated to glass sheet surface, 80
oc heats 2 h and obtains anti-freeze ionic liquid gel film.
Embodiment 9
Two (trifluoromethane sulphonyl) inferior amine salt of ionic liquid monomer 1-vinyl-3-butyl imidazole, hydrophobicity non-polymeric ion liquid 1-octyl group-3-methyl imidazolium tetrafluoroborate, initiator benzoyl peroxide, linking agent polyethylene glycol dimethacrylate are with weight ratio 1000/1000/10/10 mixing and stirring, nitrogen bubble deoxygenation in 30 minutes, even application is on iron plate, and then under 80 oC heated conditions, reaction forms anti-freeze ionic liquid gel film.
Embodiment 10
Two (trifluoromethane sulphonyl) inferior amine salt of ionic liquid monomer 1-vinyl-3-butyl imidazole hexafluorophosphate, hydrophobicity non-polymeric ion liquid 1-nitrile third class-3-Methylimidazole, initiator benzophenone, linking agent polyethylene glycol dimethacrylate are with weight ratio 1000/1000/10/10 mixing and stirring, nitrogen bubble deoxygenation in 30 minutes, even application is on iron plate, and then under 265 nm UV-irradiation, polymerization crosslinking obtains anti-freeze ionic liquid gel film.
Embodiment 11
Two (trifluoromethane sulphonyl) inferior amine salt of ionic liquid monomer 1-vinyl-3-butyl imidazole a tetrafluoro borate, hydrophobicity non-polymeric ion liquid 1-benzyl-3-Methylimidazole, initiator benzophenone, linking agent polyethylene glycol dimethacrylate are with weight ratio 1000/1000/10/10 mixing and stirring, nitrogen bubble deoxygenation in 30 minutes, even application is on copper sheet, and then under 265 nm UV-irradiation, polymerization crosslinking obtains anti-freeze ionic liquid gel film.
Embodiment 12
Two (trifluoromethane sulphonyl) inferior amine salt of ionic liquid monomer 1-vinyl-3-ethyl imidazol(e), hydrophobicity non-polymeric ion liquid 1-octyl group-3-Methylimidazole hexafluorophosphate, initiator Diisopropyl azodicarboxylate, linking agent polyethylene glycol dimethacrylate are with weight ratio 1000/1000/20/50 mixing and stirring, nitrogen bubble deoxygenation in 30 minutes, even application on the glass sheet, then 80
ounder C heated condition, polymerization crosslinking obtains anti-freeze ionic liquid gel film.
Embodiment 13
Two (trifluoromethane sulphonyl) inferior amine salt of ionic liquid monomer 1-vinyl-3-ethyl imidazol(e) hexafluorophosphate, hydrophobicity non-polymeric ion liquid 1-octyl group-3-Methylimidazole, initiator Diisopropyl azodicarboxylate, linking agent polyethylene glycol dimethacrylate are with weight ratio 1000/1000/20/50 mixing and stirring, nitrogen bubble deoxygenation in 30 minutes, even application on the glass sheet, then 80
ounder C heated condition, polymerization crosslinking obtains anti-freeze ionic liquid gel film.
Embodiment 14
Ionic liquid monomer 1-vinyl-3-ethyl imidazol(e) a tetrafluoro borate, hydrophobicity non-polymeric ion liquid 1-butyl-2, two (trifluoromethane sulphonyl) inferior amine salt of 3-methylimidazole, initiator benzoyl peroxide, linking agent polyethylene glycol dimethacrylate are with weight ratio 1000/1000/20/50 mixing and stirring, nitrogen bubble deoxygenation in 30 minutes, even application on silica, then 80
ounder C heated condition, polymerization crosslinking obtains anti-freeze ionic liquid gel film.
Embodiment 15
Two (trifluoromethane sulphonyl) inferior amine salt of ionic liquid monomer 1-vinyl-3-ethyl imidazol(e) dintrile amine salt, hydrophobicity non-polymeric ion liquid N-butyl-N-methylpyrrole, initiator benzophenone, linking agent polyethylene glycol dimethacrylate are with weight ratio 1000/1000/20/50 mixing and stirring, nitrogen bubble deoxygenation in 30 minutes, on silica, then under 265 nm UV-irradiation, polymerization crosslinking obtains anti-freeze ionic liquid gel film to even application.
Claims (10)
1. an anti-freeze film, is ionic liquid gel film, it is characterized in that: described ionic liquid gel film is with hydrophobic polymer or poly ion liquid for three-dimensional network skeleton, and non-polymeric hydrophobic ionic liquid is external phase.
2. the preparation method of anti-freeze film according to claim 1, it is characterized in that, polymer monomer free-radical polymerized being cross-linked in non-polymeric ion liquid prepares ionic liquid gel, and wherein polymkeric substance is as three-dimensional network, and non-polymeric hydrophobic ionic liquid is as external phase; Said method comprising the steps of:
Hydrophobic polymer monomer, hydrophobicity non-polymeric ion liquid, initiator, linking agent are dissolved in solvent;
Mixing and stirring;
React under the condition of UV-light or heat, prepare anti-freeze ionic liquid gel film.
3. the preparation method of anti-freeze film according to claim 1, is characterized in that, polymkeric substance directly and non-polymeric ion liquid physics be cross-linked to form ionic liquid gel, said method comprising the steps of:
By hydrophobic polymer, solvent, hydrophobicity non-polymeric ion liquid mixing;
Be stirred to even colloidal sol;
Make solvent evaporates complete, obtain anti-freeze ionic liquid gel film.
4. the preparation method of anti-freeze film according to claim 1, it is characterized in that, ionic liquid monomer free-radical polymerized being cross-linked in non-polymeric ion liquid prepares ionic liquid gel, and wherein poly ion liquid is as three-dimensional network, and non-polymeric hydrophobic ionic liquid is as external phase; Said method comprising the steps of:
Ionic liquid monomer, hydrophobicity non-polymeric ion liquid, initiator, linking agent are dissolved in solvent;
Mixing and stirring;
React under the condition of UV-light or heat, prepare anti-freeze ionic liquid gel film.
5. method according to claim 2, is characterized in that being, described polymer monomer is one or more in methyl acrylate, methyl methacrylate, butyl methacrylate, 4-vinylpridine, vinylbenzene.
6. method according to claim 3, is characterized in that, described hydrophobic polymer is one or more in polymethylmethacrylate, polyvinylidene difluoride (PVDF)-R 1216, polydimethylsiloxane.
7. the method according to claim 2 or 4, is characterized in that, described initiator is one or more in benzophenone, benzoyl peroxide, Diisopropyl azodicarboxylate;
Described linking agent is polyethylene glycol dimethacrylate.
8. according to the method one of claim 2-4 Suo Shu, it is characterized in that, described solvent is one or more in acetone, methylene dichloride, toluene.
9. according to the method one of claim 2-4 Suo Shu, it is characterized in that, described hydrophobicity non-polymeric ion liquid is two (trifluoromethane sulphonyl) inferior amine salt of 1-second class-3-Methylimidazole, two (trifluoromethane sulphonyl) inferior amine salt of 1-propyl group-3-Methylimidazole, 1-hexyl-3-methyl imidazolium tetrafluoroborate, 1-octyl group-3-methyl imidazolium tetrafluoroborate, 1-octyl group-3-Methylimidazole hexafluorophosphate, two (trifluoromethane sulphonyl) inferior amine salt of 1-octyl group-3-Methylimidazole, 1-butyl-2, two (trifluoromethane sulphonyl) inferior amine salt of 3-methylimidazole, two (trifluoromethane sulphonyl) inferior amine salt of N-butyl-N-methylpyrrole, two (trifluoromethane sulphonyl) inferior amine salt of 1-nitrile third class-3-Methylimidazole, one or more in two (trifluoromethane sulphonyl) inferior amine salt of 1-benzyl-3-Methylimidazole.
10. method according to claim 4, it is characterized in that, described ionic liquid monomer is one or more in two (trifluoromethane sulphonyl) inferior amine salt of 1-vinyl-3-butyl imidazole, 1-vinyl-3-butyl imidazole hexafluorophosphate, 1-vinyl-3-butyl imidazole a tetrafluoro borate, two (trifluoromethane sulphonyl) inferior amine salt of 1-vinyl-3-ethyl imidazol(e), 1-vinyl-3-ethyl imidazol(e) hexafluorophosphate, 1-vinyl-3-ethyl imidazol(e) a tetrafluoro borate, 1-vinyl-3-ethyl imidazol(e) dintrile amine salt.
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| CN105385256A (en) * | 2015-11-11 | 2016-03-09 | 中国人民解放军国防科学技术大学 | Super-hydrophobic coating and preparation method thereof |
| CN107142728A (en) * | 2017-05-18 | 2017-09-08 | 广东柏堡龙股份有限公司 | A kind of preparation method of the Thermochromic fabric of surface hydrophobicity |
| CN110444807A (en) * | 2018-05-03 | 2019-11-12 | 华中科技大学 | A kind of composite gel polymer electrolyte, preparation method and application |
| CN111533847A (en) * | 2020-06-01 | 2020-08-14 | 中国科学院长春应用化学研究所 | High-strength ionic liquid gel and preparation method thereof |
| CN111600033A (en) * | 2020-05-28 | 2020-08-28 | 珠海冠宇电池股份有限公司 | Negative electrode binder and application thereof |
| CN112375494A (en) * | 2020-11-16 | 2021-02-19 | 张建峰 | Silicon-based coating material and preparation method thereof |
| CN113956773A (en) * | 2021-11-29 | 2022-01-21 | 厦门双瑞船舶涂料有限公司 | Anti-icing coating for wind power blade and preparation method thereof |
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| CN112375494A (en) * | 2020-11-16 | 2021-02-19 | 张建峰 | Silicon-based coating material and preparation method thereof |
| CN113956773A (en) * | 2021-11-29 | 2022-01-21 | 厦门双瑞船舶涂料有限公司 | Anti-icing coating for wind power blade and preparation method thereof |
| CN113956773B (en) * | 2021-11-29 | 2022-06-14 | 厦门双瑞船舶涂料有限公司 | Anti-icing coating for wind power blade and preparation method thereof |
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