CN101798366A - Water-borne perfluoroalkyl fluorocarbon emulsion, water-borne cable anti-icing paint containing same and preparation method thereof - Google Patents
Water-borne perfluoroalkyl fluorocarbon emulsion, water-borne cable anti-icing paint containing same and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a water-borne cable anti-icing paint containing water-borne perfluoroalkyl fluorocarbon emulsion, which comprises the following raw materials in percentage by weight: 58 to 62 percent of aqueous perfluoroalkyl fluorocarbon emulsion, 1.5 to 2.5 percent of water-borne polytetrafluoroethylene emulsifying wax, 15 to 20 percent of water-borne color paste, 0.1 to 0.5 percent of pH regulator, 1 to 2 percent of amino resin cross-linking agent or water-borne polyurethane cross-linking agent, 0.1 to 0.2 percent of antiseptic preservative, 1 to 1.2 percent of cellulose and the balance of deionized water, wherein the water-borne color paste is the mixture of the water-borne color paste with one color or the water-borne color paste with more than two colors. The water-borne cable anti-icing paint of the invention is big in water repellent angle, low in surface energy, excellent in water repellent and oil repellent properties, safe and environment-friendly, can firmly adhere to the surface of a cable in a low temperature and cold environment and is obvious in anti-icing function.
Description
Technical field
The present invention relates to a kind of water-borne perfluoroalkyl fluorocarbon emulsion, the water-borne cable anti-icing paint that contains this emulsion and preparation method, belong to the emulsion polymerization technology field.
Background technology
The power transmission and transformation cable is under outdoor cold environment, especially freezing weather snows, the icing phenomenon in ubiquity surface, cause that outstanding pulling force is multiplied under the cable, cable often takes place cause the line fault of fracture too much owing to freezing, when bringing considerable influence for normal production of people and life, also cause bigger financial loss to power department.It is reported that the fund that China is used for power transmission facility repair and maintenance every year has more than ten hundred million yuans, to cause line fault be one of recurrent overhauling project and cable freezes.Therefore, cable anti-icing more and more is subjected to people's attention.Relevant icephobic coating mainly contains CN101307208A disclosed " high-hydrophobicity anti-icing and anti-frosting coatings and preparation method thereof " at present, this coating mainly adopts polyoxyethylene, organosilane or fluorine containing silane resin, receive micron-scale aluminum oxide or silicon oxide, silane coupling agent promotor and mixed organic solvents etc. makes high-hydrophobicity anti-icing and anti-frosting coatings, by surfaceness in the raising system and low surface, suppress just to send out the formation of beginning hoar crystal, have the frosting of the delaying time, reduce the characteristic of frosting degree.CN100491482C disclosed " water-based dope of restraining frost " adopts and contains water-absorbent crosslinked resin, can absorb moisture content in a large number, the freezing point that sodium-chlor that adds or potassium chloride particle can effectively reduce water makes the moisture that absorbs in the coating can keep not freezing state for a long time, thereby reaches the effect that presses down frost.Though this coating has the high hydrophobicity energy, play the effect of anti-freeze and anti-frosting, can only metal base, and be not suitable for outdoor power transmission and transformation cable.CN1556161A disclosed " wind-power electricity generation blade icephobic coating " utilizes the not wetting property of graphite to water, is base-material with Resins, epoxy, adds thinner, properties-correcting agent, and solidifying agent is formed.Have the particle water that steam is formed and can't condense in the surface and icing characteristic, but in the problem that has wet poor adhesive force.
Summary of the invention
The purpose of this invention is to provide a kind of hydrophobic oleophobic performance good be the perfluoroalkyl fluorocarbon emulsion and the preparation method of medium with water.
Another object of the present invention provides a kind of safety, environmental protection, energy firm attachment at cable surface, makes it have the water-borne cable anti-icing paint and the preparation method of the aquosity perfluoroalkyl fluorocarbon emulsion of obvious icing protection.
The present invention is that the technical scheme that achieves the above object is: a kind of water-borne perfluoroalkyl fluorocarbon emulsion is characterized in that: its raw material is made up of following component by mass percent: comprise
Tetrafluoroethylene 18.6～21.4%,
Hydroxyethyl allyl ether 2.5～2.8%,
Methacrylic acid hexafluoro butyl ester 4.5～5.0%,
Octadecyl acrylate 1.0～1.5%,
Butyl acrylate 3.0～4.5%,
Vinyl acetate 2.0～2.4%,
N-BUTYL ACETATE solvent 26.0～30.0%,
Initiator 0.06～0.09%,
Perfluor caproic acid sulfonate sodium emulsifying agent 3.0～4.0%,
PH conditioning agent 0.07～0.1%,
The deionized water surplus.
Described initiator is the wherein a kind of of azo-bis-isobutyl cyanide, benzoyl peroxide, dicumyl peroxide; Described PH conditioning agent selects for use 2-amino-2-methyl-1-propanol, ammoniacal liquor, yellow soda ash, sodium bicarbonate, sodium-acetate, Sodium phosphate dibasic or citric acid wherein a kind of.
The preparation method of a kind of water-borne perfluoroalkyl fluorocarbon emulsion of the present invention, it is characterized in that: earlier with 2.5～2.8% hydroxyethyl allyl ether and 4.5～5.0% methacrylic acid hexafluoro butyl ester, 1.0～1.5% octadecyl acrylate, 3.0～4.5% butyl acrylate, 2.0～2.4% vinyl acetate, 26.0～30.0% N-BUTYL ACETATE solvent and 0.06～0.09% initiator drop in the reactor, decompression deflates, the tetrafluoroethylene of adding 18.6～21.4%, react 18～22h down at 65～75 ℃, make the solvent-borne type fluoro-resin, the solid content of solvent-borne type fluoro-resin is 53.0～55.0% by percentage to the quality, be coated with-4 glasss of viscosity 180～250 seconds, in solid hydroxyl value 40～45mgKOH/g, in solid acid number 25～30mgKOH/g;
With the solvent-borne type fluoro-resin that makes heat temperature raising to 80～90 ℃ under whipped state, steaming desolventizes 90～95% of N-BUTYL ACETATE solvent total amount in the type fluoro-resin, the perfluor caproic acid sulfonate sodium emulsifying agent of adding 3.0～4.0% and 31.0～35.0% deionized water, be stirred to translucent white liquid, add 0.07～0.1% PH conditioning agent again the pH value of liquid is adjusted in 7.5～9.0, make the water-borne perfluoroalkyl fluorocarbon emulsion, by percentage to the quality the solid content 48.0～52.0% of emulsion.
The water-borne cable anti-icing paint of a kind of aquosity perfluoroalkyl fluorocarbon of the present invention emulsion, it is characterized in that: its raw material is made up of following component by mass percent: comprise
Water-borne perfluoroalkyl fluorocarbon emulsion 58.0～62.0%,
Water-based tetrafluoroethylene emulsifying wax 1.5～2.5%,
Aqueous color paste 15.0～20.0%,
PH conditioning agent 0.1～0.5%,
Amino resin crosslinking agent or aqueous polyurethane linking agent 1.0～2.0%,
Fungicidal preservative 0.1～0.2%,
Mierocrystalline cellulose 1.0～1.2%,
The deionized water surplus.
Wherein, aqueous color paste is by a kind of aqueous color paste of color wherein, or the mixture of the aqueous color paste of any two or more colors wherein.
Wherein said aqueous polyurethane linking agent is selected the wetting ability aliphatic polymeric isocyanate for use; Described amino resin crosslinking agent select for use height methyl-etherified melamine resin, methyl etherified high imino-melamine resin, glycoluril resin or methyl etherified high imino-melamine resin one of them; Described PH conditioning agent is selected amino 2 methyl isophthalic acid propyl alcohol or the ammoniacal liquor of 2-for use.
The preparation method of the single-component water-based cable anti-icing paint of aquosity perfluoroalkyl fluorocarbon emulsion of the present invention is characterized in that:
(1), get 50%～55% the dropping in the paint cylinder of 10% and deionized water total amount of 1.0～1.2% Mierocrystalline celluloses and PH conditioning agent total amount, open homogenizer and be stirred to transparent liquid, make cellulose solution;
(2), 58.0～62.0% water-borne perfluoroalkyl fluorocarbon emulsion input is joined in the lacquer cylinder, opening stirrer stirs, with the PH conditioning agent pH value of water-borne perfluoroalkyl fluorocarbon emulsion is controlled at 7.5～9.0, after stirring 10～15min, the aqueous color paste of adding 15.0～20.0% is mixed colours, toning finishes, add 1.5～2.5% water-based tetrafluoroethylene emulsifying wax and 1.0～2.0% amino resin crosslinking agent again, 0.1～0.2% fungicidal preservative and remaining deionized water, the feed liquid dispersed with stirring is even, regulate the pH value of feed liquid 7.5～9.0 with remaining PH conditioning agent again, add the cellulose solution that makes and regulate and control viscosity, make finished product coating in 3～4.0Pa.S scope.
The preparation method of the bi-component waterborne cable anti-icing paint of aquosity perfluoroalkyl fluorocarbon emulsion of the present invention is characterized in that:
(1), 55% the dropping in the reactor of 10% and deionized water total amount of the whole and PH conditioning agent total amount of extracting cellulose, homogenizer is stirred to transparent liquid, makes cellulose solution;
(2), 58.0～62.0% water-borne perfluoroalkyl fluorocarbon emulsion input is joined in the lacquer cylinder, the unlatching stirrer stirs, with the PH conditioning agent pH value of water-borne perfluoroalkyl fluorocarbon emulsion is controlled at 7.5～9.0, after stirring 10～15min, the aqueous color paste of adding 15.0～20.0%, 1.5～2.5% water-based tetrafluoroethylene emulsifying wax, 0.1～0.2% fungicidal preservative and remaining deionized water, the feed liquid dispersed with stirring is even, regulate the pH value of feed liquid in 7.5～9.0 scopes with remaining PH conditioning agent again, add the cellulose solution that makes and regulate and control viscosity, make the A component at 3～4.0Pa.S; 1.0～2.0% aqueous polyurethane linking agent put into fast encloses container is airtight to be deposited, make the B component, add the A component during use and the B component mixes, make finished product coating.
The present invention adopts tetrafluoroethylene, hydroxyethyl allyl ether, methacrylic acid hexafluoro butyl ester, octadecyl acrylate, vinyl acetate and butyl acrylate are raw material, with perfluor caproic acid sulfonate sodium is emulsifying agent, so can adopt fluorochemical monomer and fluorine-containing emulsifier etc. to prepare to have good stability, the water-based emulsion of utmost point low surface energy; Because this water-borne perfluoroalkyl fluorocarbon emulsion is a kind of hydroxyl reactive emulsion with multifunctional monomer, in the emulsion film forming process, fluoro-containing group is closely arranged and orientation at polymer surfaces, solidify and film forming through further reacting, form the coating that cross-linking density height, the strict orientation of fluoro-containing group are fixed on film coated surface, this coating has ultralow surface free energy, extraordinary weathering resistance and excellent anti-freeze property; Behind film-forming, its hydrophobic angle of filming is greater than 114 °, and surface energy is lower than 23.0mJ/m
2Therefore has good hydrophobic oleophobic anti-stain characteristic energy, behind this coating of cable insulation surface-coated, because surface energy is little, and be difficult for being adhered to, so frozen water is difficult in the surface of insulating layer accumulation and solidifies by other material, even there is a small amount of tiny ice slag to remain in above the cable, very poor because of its adhesive power, along with growing up gradually of small ice pearl will come off under deadweight of ice pearl and convection of air oscillating action automatically, cable has obvious anti-freeze effect under the low-temperature cold environment.The present invention adopts homemade low surface energy water-based emulsion, in conjunction with water-based tetrafluoroethylene emulsifying wax, effectively reduces the surface energy of filming, further improved the anti-stain characteristic of filming, chemical property is stable, makes frozen water be difficult to wetting sticking in film coated surface more, plays anti-freeze preferably effect.Behind the water-borne cable anti-icing paint film-forming of the present invention, perfluoroalkyl stretches in air, make the electronics in a large amount of fluorine carbon bonds be strapped in all of atom tightly, and the fluorine carbon bond be at present known to organic chemistry bond energy maximum (485.8kJ/mol), the best structure of uvioresistant form, making films has good ageing resistance and extraordinary weather resisteant.The present invention has excellent De Integrated such as heat-resisting, weather-proof, water-fast, oil resistant, resistant to chemical media by the water-borne cable anti-icing paint that contains the perfluoroalkyl fluorocarbon emulsion and make and closes performance and Safety and Environmental Protection.
Embodiment
Water-borne perfluoroalkyl fluorocarbon emulsion of the present invention, its raw material is formed by having following component by mass percent:
Tetrafluoroethylene 18.6～21.4%,
Hydroxyethyl allyl ether 2.5～2.8%,
Methacrylic acid hexafluoro butyl ester 4.5～5.0%,
Octadecyl acrylate 1.0～1.5%,
Butyl acrylate 3.0～4.5%,
Vinyl acetate 2.0～2.4%,
N-BUTYL ACETATE solvent 26.0～30.0%,
Initiator 0.06～0.09%,
Perfluor caproic acid sulfonate sodium emulsifying agent 3.0～4.0%,
PH conditioning agent 0.07～0.1%,
The deionized water surplus.
The present invention adopts this fluorine-containing emulsifier of perfluor caproic acid sulfonate sodium, has improved the stability of emulsion system greatly.Above-mentioned PH conditioning agent selects for use 2-amino-2-methyl-1-propanol, ammoniacal liquor, yellow soda ash, sodium bicarbonate, sodium-acetate, Sodium phosphate dibasic or citric acid wherein a kind of, its initiator is selected the wherein a kind of of azo-bis-isobutyl cyanide, benzoyl peroxide, dicumyl peroxide for use, and above-mentioned component is the commercially available prod.Concrete component of water-borne perfluoroalkyl fluorocarbon emulsion of the present invention and mass percent are shown in Table 1,
Table 1
| Concrete component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Tetrafluoroethylene | ??18.6 | ??19.00 | ??20.6 | ??19.6 | ??20.35 | ??20.0 | ??21.4 |
| Hydroxyethyl allyl ether | ??2.5 | ??2.5 | ??2.6 | ??2.7 | ??2.5 | ??2.8 | ??2.5 |
| Methacrylic acid hexafluoro butyl ester | ??5.0 | ??4.9 | ??4.7 | ??4.8 | ??4.6 | ??4.8 | ??4.5 |
| Octadecyl acrylate | ??1.24 | ??1.0 | ??1.16 | ??1.0 | ??1.5 | ??1.0 | ??1.21 |
| Butyl acrylate | ??4.5 | ??4.0 | ??3.9 | ??4.2 | ??3.5 | ??4.1 | ??3.0 |
| Vinyl acetate | ??2.0 | ??2.3 | ??2.4 | ??2.1 | ??2.3 | ??2.1 | ??2.2 |
| The N-BUTYL ACETATE solvent | ??28.00 | ??29.00 | ??28.00 | ??27.00 | ??29.00 | ??29.00 | ??30.00 |
| Initiator | ??0.06 | ??0.08 | ??0.07 | ??0.072 | ??0.06 | ??0.08 | ??0.09 |
| Perfluor caproic acid sulfonate sodium emulsifying agent | ??3.0 | ??3.4 | ??3.5 | ??3.6 | ??3.12 | ??3.9 | ??4.0 |
| The PH conditioning agent | ??0.1 | ??0.08 | ??0.07 | ??0.07 | ??0.07 | ??0.09 | ??0.1 |
| Deionized water | ??35.0 | ??33.74 | ??33.0 | ??34.858 | ??33.0 | ??32.13 | ??31.0 |
Water-borne perfluoroalkyl fluorocarbon emulsion of the present invention prepares by the following method, press table 1 respectively with hydroxyethyl allyl ether and methacrylic acid hexafluoro butyl ester and octadecyl acrylate, butyl acrylate, vinyl acetate, N-BUTYL ACETATE solvent and initiator drop in the reactor, decompression extracts air, add tetrafluoroethylene, react 18～22h down at 65～75 ℃, make the solvent-borne type fluoro-resin, be fluoro-resin liquid, by mass percentage, the solid content 53.0～55.0% of this solvent-borne type fluoro-resin, be coated with-4 glasss of viscosity 180～250 seconds, in solid hydroxyl value 40～45mgKOH/g, in solid acid number 25～30mgKOH/g with the solvent-borne type fluoro-resin that makes heat temperature raising to 80～90 ℃ under whipped state, steaming desolventizes 90～95% of N-BUTYL ACETATE solvent total amount in the type fluoro-resin, it is the N-BUTYL ACETATE solvent of 23.4.0～28.5%, add perfluor caproic acid sulfonate sodium emulsifying agent and deionized water respectively by table 1, be stirred to translucent white liquid, and again ammoniacal liquor is added this liquid by table 1, regulate pH value 7.5～9.0, promptly make water-borne perfluoroalkyl fluorocarbon emulsion of the present invention, the solid content 48.0～52.0% of emulsion by mass percentage, the present invention prepares the water-based emulsion of utmost point low surface energy by fluorochemical monomer and fluorine-containing emulsifier etc., and this emulsion is the reactive emulsion of multifunctional monomer.The data that the water-borne perfluoroalkyl fluorocarbon emulsion that table 2 couple the present invention makes is tested,
Table 2
| Test event | Index | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Outward appearance | Band blue light, white emulsion | Band blue light, white emulsion | Band blue light, white emulsion | Band blue light, white emulsion | Band blue light, white emulsion | Band blue light, white emulsion | Band blue light, white emulsion | Band blue light, white emulsion |
| PH value | ??7.5～9.0 | ??8.2 | ??8.0 | ??8.1 | ??8.2 | ??8.0 | ??8.0 | ??8.2 |
| Mechanical stability (30min) | By | By | By | By | By | By | By | By |
| Calcium ion stability | By | By | By | By | By | By | By | By |
| Freeze-thaw stability | By | By | By | By | By | By | By | By |
| Sticking power (drawing the circle method) level | ??1～2 | ??1 | ??1 | ??1 | ??1 | ??2 | ??2 | ??1 |
| Fluorine content % (quality) | ??≥36 | ??37.0 | ??36.5 | ??36.8 | ??36.4 | ??37.1 | ??36.9 | ??36.3 |
| Solids content % (quality) | ??48.0～??52.0 | ??51.2 | ??49.0 | ??49.8 | ??49.7 | ??49.5 | ??50.3 | ??50.5 |
| Solid hydroxyl value mgkoh/g | ??40.0～??45.0 | ??43.2 | ??42.0 | ??43.5 | ??44.0 | ??43.8 | ??44.6 | ??44.3 |
The water-borne cable anti-icing paint of aquosity perfluoroalkyl fluorocarbon emulsion of the present invention, its raw material is formed by having following component by mass percent:
Water-borne perfluoroalkyl fluorocarbon emulsion 58.0～62.0%,
Water-based tetrafluoroethylene emulsifying wax 1.5～2.5%,
Aqueous color paste 15.0～20.0%,
PH conditioning agent 0.1～0.5%,
Amino resin crosslinking agent/aqueous polyurethane linking agent 1.0～2.0%,
Fungicidal preservative 0.1～0.2%,
Mierocrystalline cellulose 1.0～1.2%,
The deionized water surplus.
Wherein, aqueous color paste is by a kind of aqueous color paste of color wherein, or the mixture of the aqueous color paste of any two or more colors wherein, can select for use the aqueous color paste of different colours to put according to the color of setting, and the color of filming is provided.And the PH conditioning agent is amino 2 methyl isophthalic acid propyl alcohol (AMP-95) or ammoniacal liquor, to adjust the potential of hydrogen of coating, improves execution of coating and storage stability.Amino resin crosslinking agent of the present invention is a kind of drying-type linking agent, can select height methyl-etherified melamine resin for use, as the CYMEL-350 of U.S. CYTEC company; Or methyl etherified high imino-melamine resin, as CYMEL-327; Or glycoluril resin, as CYMEL-1171; Or methyl etherified high imino-melamine resin, as the Resimene of U.S. SOLUTIA company
-717 aminoresin because aminoresin contains polybasic imino-high reactivity functional group, have the hydroxyl that contains with water-based emulsion 130 ℃ of quick crosslinked film forming.Aqueous polyurethane linking agent of the present invention is the water-based aliphatic polymeric isocyanate, is a kind of normal temperature type linking agent, the BAYHYDROL that can select for use German Bayer company to produce
-3100, VPLS2319, VPLS2336, XP248, XP2547 or XP2570 etc., because this class aqueous polyurethane linking agent is the prepolymer that has polynary NCO group, with other water-base resin compatibility is preferably arranged, the hydroxyl that can be at normal temperatures contains with water-based emulsion reacts and crosslinked film forming, it is tough and tensile firm to film, and has good physical and chemical performance.Fungicidal preservative is selected the D7LT of Wuxi, Jiangsu Province LanXess company of foreign capital affiliate for use, can prevent coating storage and film process to produce bacterium, guarantees the stability of quality product.Mierocrystalline cellulose of the present invention is selected the CMCAB Mierocrystalline cellulose for use, is carboxylated celluosic resin, and acid number is about about 60, can be prefabricated into water dispersion or solution, in order to regulate outside the dope viscosity, also produces crosslinking reaction with linking agent, improves the sticking power and the physical strength of filming.
The concrete component of water-borne cable anti-icing paint and the mass percent of aquosity perfluoroalkyl fluorocarbon emulsion of the present invention are shown in Table 3,
Table 3
The single-component water-based cable anti-icing paint of aquosity perfluoroalkyl fluorocarbon emulsion of the present invention, its preparation method is as follows:
(1), respectively press 50～55% the dropping in the paint cylinders of 10% and deionized water total amount of the whole of table 3 extracting cellulose and PH conditioning agent total amount, homogenizer is stirred to transparent liquid, makes cellulose solution;
(2), by table 2 water-borne perfluoroalkyl fluorocarbon emulsion input is joined in the lacquer cylinder respectively, opening stirrer stirs, with the PH conditioning agent pH value of water-borne perfluoroalkyl fluorocarbon emulsion is controlled at 7.5～9.0, after stirring 10～15min, adding aqueous color paste by table 3 mixes colours, toning finishes, press table 3 and add water-based tetrafluoroethylene emulsifying wax, amino resin crosslinking agent and fungicidal preservative and remaining deionized water, the feed liquid dispersed with stirring is even, regulate the pH value of feed liquid 7.5～9.0 with remaining PH conditioning agent again, add the cellulose solution that makes and regulate and control viscosity at 3～4.0Pa.S (No. 4 rotors, 60 rev/mins) scope, make single-component water-based cable anti-icing paint, this single-component water-based cable anti-icing paint is a baking-type.During construction, after the water-borne cable anti-icing paint that makes is adjusted to the required viscosity of construction with deionized water, the making sheet of on the ABS plate, spraying paint then, after drying under the 130 ℃/2-3min condition, surveying dried film thickness is 10 ± 2 μ m, then this model is put into temperature and for-25 ℃, humidity be in 25% the refrigerator, get a blank ABS plate simultaneously and do contrast and observe, take out after 8 hours and can find: blank ABS plate surface has the very thin frost of one deck successive; And the model surface only has a small amount of discontinuous small ice pearl.
The double-component aqueous cable anti-icing paint of aquosity perfluoroalkyl fluorocarbon emulsion of the present invention, its preparation method is as follows:
Press 50～55% the dropping in the paint cylinders of 10% and deionized water total amount of whole % of extracting cellulose in the table 3 and PH conditioning agent total amount, open homogenizer and be stirred to transparent liquid, make cellulose solution (1), respectively;
(2), respectively by in the table 3 water-borne perfluoroalkyl fluorocarbon emulsion input being joined in the lacquer cylinder, the unlatching stirrer stirs, with the PH conditioning agent pH value of water-borne perfluoroalkyl fluorocarbon emulsion is controlled at 7.5～9.0, after stirring 10～15min, adding aqueous color paste by table 3 mixes colours, toning finishes, press water-based tetrafluoroethylene emulsifying wax and fungicidal preservative and remaining deionized water that table 3 adds, the feed liquid dispersed with stirring is even, regulate the pH value of feed liquid in 7.5～9.0 scopes with remaining PH conditioning agent again, add the cellulose solution that makes and regulate and control viscosity at 3～4.0Pa.S (No. 4 rotors, 60 rev/mins), make the A component, get final product by putting into airtight the depositing of encloses container fast behind the table 3 water intaking based polyurethane linking agent, i.e. the B component, be two components, adding A component and B component mix during use, make double-component aqueous cable anti-icing paint, and this double-component aqueous cable anti-icing paint is the normal temperature self-drying type.During construction, A component and B component mixed and add after deionized water is adjusted to the required viscosity of construction, making sheet after the ABS plate is through dip-coating or spraying, surveying dried film thickness after doing 48 hours is 10 ± 2 μ m, then this model is put into temperature and be in 25% the refrigerator for-25 ℃, humidity, get a blank ABS plate simultaneously and do the contrast observation, take out after 8 hours and can find: blank ABS plate surface has the very thin frost of one deck successive; And the model surface only has a small amount of discontinuous small ice pearl.
Table 4 is the ABS board test data that are coated with the water-borne cable anti-icing paint of aquosity perfluoroalkyl fluorocarbon emulsion of the present invention.
Table 4
As can be seen, icephobic coating of the present invention to film through the hydrophobic angle of measuring be 114 °, surface energy is 23.0mJ/m
2Make the material of high surface energies such as frozen water be difficult in film coated surface wetting, sprawl, condense; demonstrate good hydrophobic oleophobic and anti-stain characteristic energy; cable is behind anti-freeze coating protective; in temperature is that 0～-25 ℃, humidity are under 25% condition; the cable surface amount of freezing reduces more than 60%, and institute a small amount of small ice pearl of tying extremely should come off under vibrating.
Claims (10)
1. water-borne perfluoroalkyl fluorocarbon emulsion, it is characterized in that: its raw material is made up of following component by mass percent: comprise
Tetrafluoroethylene 18.6～21.4%,
Hydroxyethyl allyl ether 2.5～2.8%,
Methacrylic acid hexafluoro butyl ester 4.5～5.0%,
Octadecyl acrylate 1.0～1.5%,
Butyl acrylate 3.0～4.5%,
Vinyl acetate 2.0～2.4%,
N-BUTYL ACETATE solvent 26.0～30.0%,
Initiator 0.06～0.09%,
Perfluor caproic acid sulfonate sodium emulsifying agent 3.0～4.0%,
PH conditioning agent 0.07～0.1%,
The deionized water surplus.
2. 1 described water-borne perfluoroalkyl fluorocarbon emulsion as requested is characterized in that: described initiator is the wherein a kind of of azo-bis-isobutyl cyanide, benzoyl peroxide, dicumyl peroxide.
3. 1 described water-borne perfluoroalkyl fluorocarbon emulsion as requested, it is characterized in that: described PH conditioning agent selects for use 2-amino-2-methyl-1-propanol, ammoniacal liquor, yellow soda ash, sodium bicarbonate, sodium-acetate, Sodium phosphate dibasic or citric acid wherein a kind of.
4. the preparation method of a water-borne perfluoroalkyl fluorocarbon emulsion as claimed in claim 1, it is characterized in that: earlier with 2.5～2.8% hydroxyethyl allyl ether and 4.5～5.0% methacrylic acid hexafluoro butyl ester, 1.0～1.5% octadecyl acrylate, 3.0～4.5% butyl acrylate, 2.0～2.4% vinyl acetate, 26.0～30.0% N-BUTYL ACETATE solvent and 0.06～0.09% initiator drop in the reactor, decompression deflates, the tetrafluoroethylene of adding 18.6～21.4%, react 18～22h down at 65～75 ℃, make the solvent-borne type fluoro-resin, the solid content of solvent-borne type fluoro-resin is 53.0～55.0% by percentage to the quality, be coated with-4 glasss of viscosity 180～250 seconds, in solid hydroxyl value 40～45mgKOH/g, in solid acid number 25～30mgKOH/g;
With the solvent-borne type fluoro-resin that makes heat temperature raising to 80～90 ℃ under whipped state, steaming desolventizes 90～95% of N-BUTYL ACETATE solvent total amount in the type fluoro-resin, the perfluor caproic acid sulfonate sodium emulsifying agent of adding 3.0～4.0% and 31.0～35.0% deionized water, be stirred to translucent white liquid, add 0.07～0.1% PH conditioning agent again the pH value of liquid is adjusted in 7.5～9.0, make the water-borne perfluoroalkyl fluorocarbon emulsion, by percentage to the quality the solid content 48.0～52.0% of emulsion.
5. the water-borne cable anti-icing paint of an aquosity perfluoroalkyl fluorocarbon emulsion as claimed in claim 1, it is characterized in that: its raw material is made up of following component by mass percent: comprise
Water-borne perfluoroalkyl fluorocarbon emulsion 58.0～62.0%,
Water-based tetrafluoroethylene emulsifying wax 1.5～2.5%,
Aqueous color paste 15.0～20.0%,
PH conditioning agent 0.1～0.5%,
Amino resin crosslinking agent or aqueous polyurethane linking agent 1.0～2.0%,
Fungicidal preservative 0.1～0.2%,
Mierocrystalline cellulose 1.0～1.2%,
The deionized water surplus.
Wherein, aqueous color paste is by a kind of aqueous color paste of color wherein, or the mixture of the aqueous color paste of any two or more colors wherein.
6. the water-borne cable anti-icing paint of aquosity perfluoroalkyl fluorocarbon emulsion according to claim 5 is characterized in that: described aqueous polyurethane linking agent is selected the wetting ability aliphatic polymeric isocyanate for use.
7. the water-borne cable anti-icing paint of aquosity perfluoroalkyl fluorocarbon emulsion according to claim 5 is characterized in that: described amino resin crosslinking agent select for use height methyl-etherified melamine resin, methyl etherified high imino-melamine resin, glycoluril resin or methyl etherified high imino-melamine resin one of them.
8. the water-borne cable anti-icing paint of aquosity perfluoroalkyl fluorocarbon emulsion according to claim 5 is characterized in that: described PH conditioning agent is selected amino 2 methyl isophthalic acid propyl alcohol or the ammoniacal liquor of 2-for use.
9. preparation method as the single-component water-based cable anti-icing paint of aquosity perfluoroalkyl fluorocarbon emulsion as described in the claim 5 is characterized in that:
(1), get 50%～55% the dropping in the paint cylinder of 10% and deionized water total amount of 1.0～1.2% Mierocrystalline celluloses and PH conditioning agent total amount, open homogenizer and be stirred to transparent liquid, make cellulose solution;
(2), 58.0～62.0% water-borne perfluoroalkyl fluorocarbon emulsion input is joined in the lacquer cylinder, opening stirrer stirs, with the PH conditioning agent pH value of water-borne perfluoroalkyl fluorocarbon emulsion is controlled at 7.5～9.0, after stirring 10～15min, the aqueous color paste of adding 15.0～20.0% is mixed colours, toning finishes, add 1.5～2.5% water-based tetrafluoroethylene emulsifying wax and 1.0～2.0% amino resin crosslinking agent again, 0.1～0.2% fungicidal preservative and remaining deionized water, the feed liquid dispersed with stirring is even, regulate the pH value of feed liquid 7.5～9.0 with remaining PH conditioning agent again, add the cellulose solution that makes and regulate and control viscosity, make finished product coating in 3～4.0Pa.S scope.
10. preparation method as the bi-component waterborne cable anti-icing paint of aquosity perfluoroalkyl fluorocarbon emulsion as described in the claim 5 is characterized in that:
(1), 55% the dropping in the reactor of 10% and deionized water total amount of the whole and PH conditioning agent total amount of extracting cellulose, homogenizer is stirred to transparent liquid, makes cellulose solution;
(2), 58.0～62.0% water-borne perfluoroalkyl fluorocarbon emulsion input is joined in the lacquer cylinder, the unlatching stirrer stirs, with the PH conditioning agent pH value of water-borne perfluoroalkyl fluorocarbon emulsion is controlled at 7.5～9.0, after stirring 10～15min, the aqueous color paste of adding 15.0～20.0%, 1.5～2.5% water-based tetrafluoroethylene emulsifying wax, 0.1～0.2% fungicidal preservative and remaining deionized water, the feed liquid dispersed with stirring is even, regulate the pH value of feed liquid in 7.5～9.0 scopes with remaining PH conditioning agent again, add the cellulose solution that makes and regulate and control viscosity, make the A component at 3～4.0Pa.S; 1.0～2.0% aqueous polyurethane linking agent put into fast encloses container is airtight to be deposited, make the B component, add the A component during use and the B component mixes, make finished product coating.
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