CN102010636B - Anti-pollution flashover normal-temperature cured fluorocarbon resin coating and preparation method thereof - Google Patents
Anti-pollution flashover normal-temperature cured fluorocarbon resin coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a normal-temperature cured fluorocarbon resin coating, which consists of the following components in percentage by weight: 35 to 70 percent of tetrafluorochloroethylene-vinyl ester polymer, 5.5 to 12 percent of curing agent, 2 to 10 percent of coupling agent, 1 to 10 percent of pigment, 1 to 30 percent of hydrophobic particles, 0.03 to 3 percent of aid, 20 to 40 percent of solvent and 0.001 to 1 percent of catalyst, wherein the coupling agent is fluorosilane with a -CF3 group and a -CF2 group; the aid is a flatting agent, an antifoaming agent and a dispersing agent; the solvent is butyl acetate and methyl isobutyl ketone; the catalyst is dibutyltin dilaurate; and the curing agent is aliphatic diisocyanate. By adopting a specific coating formula, due to the combined action of the fluorosilane coupling agent and the hydrophobic particles, the anti-pollution flashover fluorocarbon resin coating has a static contact angle theta of 120 degrees, is excellent in hydrophobic performance and hydrophobic migration property, high in anti-pollution flashover performance, high in coating leveling property, smooth in surface, and high in self-cleanliness, chemicals resistance and hot-water resistance, and has an adhesive force reaching a zero level.
Description
Technical field
The invention belongs to coatings industry, specifically, the present invention relates to a kind of anti-pollution flashover normal-temperature cured fluorocarbon resin coating and preparation method thereof.
Background technology
Porcelain insulator is the important accessory in the high-tension power transmission and transformation equipment, along with the high speed development of industry, the sharp increase of transmitting capacity, and the improving constantly of power transmission and transforming equipment voltage range, the sub-pollution flashover accident of power system insulation becomes increasingly conspicuous.Wherein, pollution flashover is because porcelain vase glaze surface energy is fine, has good wetting ability, build up easily some and have the filthy material of conductivity, after wet weather makes moist, these dirts can form conducting film on its surface, thereby the dielectric level of insulator is reduced greatly, under normal operation flashover fault occur.The pollution flashover accident generating plane is larger, and the reclosing success ratio reduces, and tends to cause long-time power failure, and its loss that causes is equivalent to 10 times of damage to crops caused by thunder accident, brings great harm to national economy.Pollution flashover accident how to avoid insulator is one of current power system problem anxious to be resolved.
The Flash Decontamination Measurements that present domestic power system generally adopts comprises regular hand sweeping, reinforced insulation configuration, charged mechanical dry cleaning etc., wherein, applies one deck hydrophobic coating at insulator surface, is to improve the effective measure that the insulator resistant is dodged ability.Traditional antifouling flush paint comprises organic silicone oil, organic silicone grease, ceresine etc., wherein, the work-ing life of organic silicone oil is shorter, and organic silicone grease is grease-like for a long time, form the greasy filth layer after particularly adhering to filthy material, be not easy to daily maintenence test and service work, ceresine is not suitable for the dust pollution district, and, the price of silicone oil and silicone grease is high, work-ing life is short, and only the 3-6 month, cleaning was difficult after losing efficacy.The middle and later periods eighties, a kind of novel antifouling occurs and dodged coating-RTV coating, it is a kind of room temperature vulcanized silicone rubber, it has good hydrophobic nature, migration of hydrophobicity, resistant is dodged characteristic, and long-acting, weather-proof, anti-ozone, the advantage such as non-maintaining, but, this product has following shortcoming: the material of coating itself is softer, easily is infected with filthy material, and is difficult to clean, after operation for some time, the dust that is attached to the RTV coating surface increases, and pollution layer thickens, and the speed of the small molecules migration of coating self is also along with slowing down, so that the hydrophobic effect worse and worse, cause at last the obvious reduction of anti-fouling flashover performance.Therefore normal temperature solidifying fluorine carbon resin (FEVE) coating of inventing a kind of anti-pollution flashover is necessary.
Summary of the invention
The object of the invention is to overcome the defective of prior art, a kind of normal temperature curing fluorocarbon resin coating for the anti-pollution flashover of high-tension power transmission and transformation equipment porcelain insulator is provided.
For achieving the above object, the present invention has taked following technical scheme:
A kind of anti-pollution flashover normal-temperature cured fluorocarbon resin coating, described coating are without priming paint coating, percentage composition meter by weight, and this coating is composed of the following components:
Tetrafluoroethylene-vinyl ester polymer 35%～70%
Solidifying agent 5.5%～12%
Coupling agent 2%～10%
Pigment 1%～10%
Hydrophobic particles 1%～30%
Auxiliary agent 0.03%～3%
Solvent 20%～40%
Siccative 0.001%～1%;
Wherein, described coupling agent is for having-CF
3Group and-CF
2The silicon fluoride of group; Described auxiliary agent is flow agent, defoamer and dispersion agent; Described solvent is methyl iso-butyl ketone (MIBK) (MIBK) and butylacetate; Described siccative is dibutyl tin laurate; Described solidifying agent is aliphatic diisocyanate.
Described tetrafluoroethylene-vinyl ester polymer, its tetrafluoroethylene content reaches 76%.Described coupling agent is for having-CF
3Group and-CF
2The silicon fluoride coupling agent of group, it has bifunctional, the existing group-OCH that can be hydrolyzed
2CH
3, organic group-CF is arranged again
3Molecular end-CF
3Group, surface energy are very low, and it can towards the air close-packed arrays, improve the hydrophobicity on surface greatly.Preferably, described coupling agent is 17 fluorine certain herbaceous plants with big flowers base Trimethoxy silane or ten difluoro heptyl propyl trimethoxy silicanes.
Preferably, described pigment is rutile TiO
2Or rutile TiO
2Mixture with other pigment.TiO
2Have very high chemical stability, good thermotolerance, higher surfactivity and unique photocatalytic activity etc., add TiO
2Can greatly improve coating anti-ly stain, washability, antiseptic property and anti-ultraviolet property.The color that adds other pigment (such as phthalocyanine green) adjusting coating can not affect the character of coating.
Preferably, described hydrophobic particles is gas phase SiO
2Or ptfe micropowder.Add gas phase SiO
2, obviously improving the hardness of filming, the weathering resistance of coating, wear resistance, clean surfaces ability improve.Add ptfe micropowder coating is carried out modification, the hydrophobicity migration performance of filming is good.
Preferably, the mass ratio of described methyl iso-butyl ketone (MIBK) and butylacetate is 1: 2.
Preferably, described solidifying agent is HDI tripolymer N3390 (hexamethylene diisocyanate), and NCO content is 16.3 ± 0.3%.HDI tripolymer N3390 gloss retention is good, and hardness is high, and intermolecularly can not form hydrogen bond, and viscosity is low, is conducive to reduce the consumption of solvent, is easy to make high solid coating.
Preferably, described flow agent is BYK310, and described defoamer is organosilicon 100# or organosilicon 014A, and described dispersion agent is FC-4430 or organosilicon C1208.Percentage composition meter by weight, the content of described flow agent is 0.01～1%, and the content of described defoamer is 0.01～0.5%, and the content of described dispersion agent is rutile TiO
21～3% of content.
The present invention also provides the method for preparing above-mentioned anti-pollution flashover normal-temperature cured fluorocarbon resin coating, may further comprise the steps:
(1) in solidifying agent, adds partial solvent, stir, obtain curative systems;
(2) tetrafluoroethylene-vinyl ester polymer, hydrophobic particles, dispersion agent, defoamer, partial solvent are mixed the ultrasonic grinding that stirs 0.5～1h or grind 0.5～1h;
(3) add again the pigment that is dissolved in residual solvent, ultrasonic grinding 0.5～1h, or grind 0.5～2h, or ultrasonic wave is disperseed 0.5～1h;
(4) add again flow agent, coupling agent, mix, obtain coating system;
(5) curative systems of step (1) and the coating system of step (4) are mixed, add siccative, namely can be used for spraying.
The present invention also provides a kind of anti-pollution flashover normal-temperature cured fluorocarbon resin coating, described coating comprises finish paint and priming paint, described finish paint is above-mentioned anti-pollution flashover normal-temperature cured fluorocarbon resin coating, described priming paint is the epoxy primer that organobentonite is strengthened the priming paint surfaceness, specifically, described priming paint is the percentage composition meter by weight, and is composed of the following components:
Resins, epoxy 25%～50%
Solidifying agent 15%～40%
Acetone 15%～30%
Coupling agent 0.1%～1%
Organobentonite 2%～15%.
Compared with prior art, anti-pollution flashover fluorocarbon resin coating of the present invention has following performance:
1, the present invention adopts specific formulation for coating material, and by the acting in conjunction of silicon fluoride coupling agent and hydrophobic particles, the static contact angle θ of anti-pollution flashover fluorocarbon resin coating can reach 110 °, and hydrophobicity performance and hydrophobicity migration performance are good, and anti-fouling flashover performance is high;
2, the coating of the present invention good leveling property of filming, smooth surface, self-cleaning is good; Chemical resistance is good, and hot water resistance can be good;
3, of the present invention have a primer base, and the sticking power of its priming paint can reach 0 grade, and the sticking power between priming paint and the finish paint also can reach 0 grade;
4, do not contain the oiliness small molecules such as silicone oil or fluorocarbon oil in the coating of the present invention, film coated surface has good recoatability; Coating weatherability can be good, and outdoor use efflorescence or obscission can not occur more than 20 years; Ambient cure, constructability can adopt the multiple forms of construction work such as spraying, brushing simultaneously.
Embodiment
Below by embodiment embodiment of the present invention are described in further detail, but embodiments of the present invention are not limited to this.The raw material of following examples 1-3 is respectively available from following manufacturer:
Tetrafluoroethylene-vinyl ester polymer: Da Jin fluorine chemical (Guangzhou) branch office; Coupling agent: the Harbin good chemistry of silicones of snow fluorine company limited, Ninghua, road, Nanjing worker company limited; Pigment: South Sea Bai Chen polymer novel material; Hydrophobic particles: day Bender mountain, Beijing Hua Tongrui technology-industry-trade company of speeding; Defoamer (auxiliary agent): gather into million industry organosilicon raw material company limiteds; Tensio-active agent (auxiliary agent): Shanghai is to the haze chemical industry; Flow agent (auxiliary agent): German BYK; Solidifying agent: Huizhou City's thunder is won chemical industry; Dibutyl tin laurate: avenge good fluorine silication worker company limited; Butylacetate: commercially available; MIBK: commercially available.Resins, epoxy: Ba Ling petrochemical industry; Polyamide 6 50: Ba Ling petrochemical industry; T31 modified fatty amine: Changsha chemical research institute; Organobentonite: sky, Huangpu, the Guangzhou light company limited of Thailandization; Coupling agent: sunlight Xinghua, Guangzhou worker; Acetone: commercially available;
Embodiment 1 anti-pollution flashover fluorocarbon resin coating (priming paint is arranged)
Finish paint
Tetrafluoroethylene-vinyl ester polymer 70kg
HDI tripolymer N3390 (solidifying agent) 9kg
Coupling agent 4kg
Rutile TiO
2(pigment) 4.5kg
Gas phase SiO
2(hydrophobic particles) 7kg
Flow agent BYK310 (auxiliary agent) 1kg
Defoamer 100# (auxiliary agent) 0.7kg
Dispersion agent FC-4430 (auxiliary agent) 0.1kg
Butylacetate: MIBK=2: 1 (solvent) 51kg
Dibutyl tin laurate (siccative) 1kg
Priming paint
E-44 (Resins, epoxy) 100kg
Modified amine: polyamide 6 50=3: 4 (solidifying agent) 70kg
KH550 (coupling agent) 1kg
BK-886 (wilkinite) 20kg
Acetone 60kg
The preparation method of the coating of embodiment 1 is:
(1) acetone is added among the E-44, add polyamide 6 50 and stir;
(2) wilkinite BK-886 is added in the system of step (1), stir, and then add Silane coupling agent KH550, modified fatty amine, mixing, application;
(3) with tetrafluoroethylene-vinyl ester polymer, gas phase SiO
2, the 30kg butylacetate, 15kg MIBK mixing, defoamer 100#, dispersion agent FC-4430 stir, basket-type grinder grinds 0.5h;
(4) in the system of step (3), add the 2kg acid butyl ester, the rutile TiO that 1kg MIBK mixed solvent disperses
2, use basket-type grinder to grind 1h, then filter;
(5) in the filtrate of step (4), add flow agent BYK 310, coupling agent, dibutyl tin laurate, mix;
(6) add the 2kg butylacetate in HDI tripolymer N3390,1kg MIBK mixed solvent stirs, and then mixes in 1: 1 ratio with step (5) system, sprays after the priming paint of step (2) is solidifying 12h.
The coating adhesion of preparation reaches 0 grade, smooth surface is smooth, the contact angle of hydrophobic nature reaches 112 °, hydrophobicity migration performance, chemical resistance reaches more than the 7d and does not come off, variable color, wrinkling iso-metamorphism phenomenon, does not come off behind the salt water resistance performance 200d, variable color, wrinkling iso-metamorphism phenomenon.The volume specific resistance of coating＞1.0 * 10
14Ω m, relative permittivity＜3.0, loss of value angle tangent value tg δ＜0.3%, dielectric strength＞18kV/mm.Anti creepage trace and galvanic corrosion damage＞TMA2.5 level.
Embodiment 2 anti-pollution flashover fluorocarbon resin coatings (priming paint is arranged)
Finish paint:
Tetrafluoroethylene-vinyl ester polymer 250kg
HDI tripolymer N3390 (solidifying agent) 30kg
Coupling agent 30kg
Rutile TiO
2(pigment) 15kg
Ptfe micropowder (hydrophobic particles) 70kg
Gas phase SiO
2(hydrophobic particles) 7kg
Flow agent BYK310 (auxiliary agent) 2.5kg
Defoamer 100# (auxiliary agent) 1.5kg
Dispersion agent FC-4430 (auxiliary agent) 0.4kg
Butylacetate: MIBK=2: 1 (solvent) 120kg
Dibutyl tin laurate (siccative) 2kg
Priming paint:
E-44 (Resins, epoxy) 150kg
Modified amine: polyamide 6 50=3: 7 (solidifying agent) 100kg
KH550 (coupling agent) 2kg
BK-886 (wilkinite) 35kg
Acetone 100kg
The preparation method of the coating of embodiment 2 is:
(1) acetone is added among the E-44, add polyamide 6 50 and stir;
(2) wilkinite BK-886 is added in the system of step (1), stir, and then add Silane coupling agent KH550, modified fatty amine, mixing, application;
(3) with tetrafluoroethylene-vinyl ester polymer, gas phase SiO
2, the 66kg butylacetate, 33kg MIBK mixing, defoamer 100#, dispersion agent FC-4430 stir, basket-type grinder grinds 0.5h;
(4) in the system of step (3), add ptfe micropowder, use basket-type grinder to grind 0.5h;
(5) in the system of step (4), add the 10kg butylacetate, the rutile TiO that 5kg MIBK mixed solvent disperses
2, use basket-type grinder to grind 1h, then filter;
(6) in the filtrate of step (5), add flow agent BYK 310, coupling agent, dibutyl tin laurate, mix;
(7) add the 4kg butylacetate in HDI tripolymer N3390,2kg MIBK mixed solvent stirs, and then mixes in 1: 1 ratio with step (6) system, sprays after the priming paint of step (2) is solidifying 12h.
The coating adhesion of preparation reaches 0 grade, smooth surface is smooth, the contact angle of hydrophobic nature reaches 121 °, hydrophobicity migration performance, chemical resistance reaches more than the 7d and does not come off, variable color, wrinkling iso-metamorphism phenomenon, does not come off behind the salt water resistance performance 200d, variable color, wrinkling iso-metamorphism phenomenon.The volume specific resistance of coating＞1.0 * 10
14Ω m, relative permittivity＜3.0, loss of value angle tangent value tg δ＜0.3%, dielectric strength＞18kV/mm.Anti creepage trace and galvanic corrosion are decreased greater than the TMA2.5 level.
More than be for the specifying of possible embodiments of the present invention, but this embodiment limits claim of the present invention, allly do not break away from equivalence of the present invention and implement or change, all should be contained in the claim of the present invention.
Claims (9)
1. anti-pollution flashover normal-temperature cured fluorocarbon resin coating is characterized in that: described coating is for without priming paint coating, percentage composition meter by weight, and this coating comprises following component:
Wherein, described coupling agent is for having-CF
3Group and-CF
2The silicon fluoride of group; Described auxiliary agent is flow agent, defoamer and dispersion agent; Described solvent is methyl iso-butyl ketone (MIBK) and butylacetate; Described siccative is dibutyl tin laurate; Described solidifying agent is aliphatic diisocyanate, and described hydrophobic particles is gas phase SiO
2Mixture with ptfe micropowder.
2. anti-pollution flashover normal-temperature cured fluorocarbon resin coating according to claim 1 is characterized in that, described coupling agent is 17 fluorine decyl Trimethoxy silanes or ten difluoro heptyl propyl trimethoxy silicanes.
3. anti-pollution flashover normal-temperature cured fluorocarbon resin coating according to claim 1 is characterized in that, described pigment is rutile TiO
2Or rutile TiO
2Mixture with other pigment.
4. anti-pollution flashover normal-temperature cured fluorocarbon resin coating according to claim 1 is characterized in that, the mass ratio of described methyl iso-butyl ketone (MIBK) and butylacetate is 1: 2.
5. anti-pollution flashover normal-temperature cured fluorocarbon resin coating according to claim 1 is characterized in that, described solidifying agent is HDI tripolymer N3390.
6. anti-pollution flashover normal-temperature cured fluorocarbon resin coating according to claim 1 is characterized in that, described flow agent is BYK310, and described defoamer is organosilicon 100# or organosilicon 014A, and described dispersion agent is FC-4430 or organosilicon C1208.
7. a method for preparing anti-pollution flashover normal-temperature cured fluorocarbon resin coating claimed in claim 1 is characterized in that, may further comprise the steps:
(1) in solidifying agent, adds partial solvent, stir, obtain curative systems;
(2) tetrafluoroethylene-vinyl ester polymer, hydrophobic particles, dispersion agent, defoamer, partial solvent are mixed, stir, ultrasonic grinding 0.5～1h, or grind 0.5～2h;
(3) add again the pigment that is dissolved in residual solvent, ultrasonic grinding 0.5～1h, or grind 0.5～2h, or ultrasonic wave is disperseed 0.5～1h;
(4) add again flow agent, coupling agent, mix, obtain coating system;
(5) curative systems of step (1) and the coating system of step (4) are mixed, add siccative, and get final product.
8. anti-pollution flashover normal-temperature cured fluorocarbon resin coating, it is characterized in that: described coating comprises finish paint and priming paint, described finish paint is each described anti-pollution flashover normal-temperature cured fluorocarbon resin coating of claim 1-5, and described priming paint is the percentage composition meter by weight, and is composed of the following components:
9. anti-pollution flashover normal-temperature cured fluorocarbon resin coating according to claim 8, it is characterized in that: described Resins, epoxy is E-44; Described solidifying agent is comprised of T31 modified fatty amine and polyamide 6 50, and the mass ratio of described T31 modified fatty amine and polyamide 6 50 is 1: 2～3; Described organobentonite is BK-886.
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