CN108864882B - Self-lubricating anti-icing coating and preparation method thereof - Google Patents
Self-lubricating anti-icing coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a self-lubricating anti-icing coating which comprises a component A and a component B, wherein the component A comprises the following components in percentage by mass in the component A: 20-70% of modified acrylic resin, 5-50% of anti-icing lubricant, 1-5% of auxiliary agent and 20-50% of organic solvent; the B component is polyisocyanate curing agent produced by Wanhua company, and the mass ratio of the A component to the B component is 5: 1-10: 1; the structural formula of the modified acrylic resin is as follows:
wherein R1 is alkyl with 1-12 carbon atoms, R2 is a low surface energy functional group, and m, p, q, and z are integers of 1-15. The invention also discloses a preparation method of the coating. After the coating disclosed by the invention is formed into a film, the coating has good bonding capability with a substrate, excellent mechanical property, smooth surface and good self-lubricating effect, the adhesion strength of ice coating on the surface is low, and the effect of easy deicing is realized under the condition of mechanical vibration or the self weight of the ice coating.
Description
Technical Field
The invention belongs to the field of anti-icing materials, and relates to a self-lubricating anti-icing coating and a preparation method thereof. The coating formed by the coating disclosed by the invention has the advantages of low friction coefficient, low ice coating adhesion, excellent mechanical property and the like.
Background
The phenomenon of adhesion and icing of rain and snow on the surface of a material is a common natural phenomenon, but ice coating not only brings inconvenience to daily production and life of people, but also brings serious influence on the operation of mechanical equipment. The ice and snow are condensed and attached on the surfaces of airplanes, radars, electric power systems, ship decks, offshore oil development platforms and the like, so that the working efficiency and the service life of mechanical parts are seriously influenced, and even great economic loss and casualty accidents are caused. In early 2008, one ice and snow disaster attacks dozens of provinces and cities in the south of China. In the peak of the spring transportation, the sections of the south-north traffic aorta Jingzhu expressway in the Guangdong and Hunan areas are covered by ice and snow and are disconnected. Not only traffic is interrupted and spring transportation is blocked, electric power and water supply facilities are seriously damaged in most areas in south, ice accumulation of power transmission line facilities is serious, a large number of power transmission towers and lines are broken, and daily life of the masses is seriously influenced, so that direct economic loss caused by the next ice and snow disaster exceeds one trillion yuan. Therefore, the research significance of the anti-icing and quick deicing technologies is great, wherein the quick deicing technology is particularly important. Currently, there are mainly 4 deicing methods: mechanical deicing is carried out, deicing is carried out through manual operation and proper deicing machinery is adopted, and the deicing device is low in cost, strong in passivity and low in efficiency. Secondly, spreading an anti-icing agent, and reducing the freezing point by spreading the anti-icing agent on the surface of the base material, wherein the method has pollution to soil and corrosion to the road surface, and can only be temporarily spread, and the time efficiency is short. Heating to deice, heating to deice the surface of the base material, for example, hot air or hot oil is used to deice the surface of an airplane. And fourthly, the anti-icing coating reduces the adhesive force of ice to the surface of the base material and the ice coating amount on the surface by changing the wetting characteristic of the surface of the base material, and makes the ice easily separate from the surface of the base material by utilizing the action of wind and natural force. The method is simple and convenient, has low cost, and can greatly reduce the working difficulty due to small adhesion of ice to the surface of the base material even if manual deicing is needed under extreme conditions. At present, the anti-icing coating is commercialized, but most of the anti-icing coating is made of organic silicon materials, such as R-2180 produced by Nusil corporation, Mega Guard Liqui Cote coating produced by Kiss-Cote corporation, RIP-4004 produced by S & A Fernandina corporation, and the like, and the anti-icing of the coating surface is realized by means of high elasticity and low modulus of the coating. Although such coatings have good anti-icing effects, they have low modulus, poor strength, poor adhesion to the substrate, and limited use in most anti-icing applications.
Disclosure of Invention
The invention aims to provide a self-lubricating anti-icing coating and a preparation method thereof.
Aiming at the problems of poor mechanical property, unobvious anti-icing and deicing properties and the like of most of the current anti-icing coatings, the invention introduces the interface lubrication concept into the anti-icing and deicing coatings, develops an anti-icing and deicing coating integrating self-lubricating property and anti-icing and deicing property, and the coating has excellent mechanical property, self-lubricating property and low ice adhesion.
A self-lubricating anti-icing coating is characterized by comprising an A-type component and a B-type component, wherein the A-type component comprises the following components in percentage by mass in the A-type component: 20-70% of modified acrylic resin, 5-50% of anti-icing lubricant, 1-5% of auxiliary agent and 20-50% of organic solvent; the B component is polyisocyanate curing agent produced by Wanhua company, and the mass ratio of the A component to the B component is 5: 1-10: 1; the structural formula of the modified acrylic resin is as follows:
wherein R1 is alkyl with 1-12 carbon atoms, R2 is a low surface energy functional group, and m, p, q, and z are integers of 1-15.
And the R2 is a polydimethylsiloxane chain or a fluorocarbon alkyl chain.
The anti-icing lubricant is one or more of molybdenum disulfide, crystalline flake graphite, graphite fluoride, paraffin fluoride, polyethylene wax, polyamide wax, liquid paraffin, polyolefin, polyethylene oxide, polydimethylsiloxane, long-chain alkane and perfluoroalcohol.
The polyisocyanate curing agent is one or two of Wanhua PM200/100, polymerization modified MDI-50, MDI-100 and N75B.
The auxiliary agent is a mixture of a wetting dispersant, a flatting agent, a defoaming agent and an anti-settling agent, and the mass ratio of the wetting dispersant, the flatting agent, the defoaming agent and the anti-settling agent is 2:1:1: 4.
The wetting dispersant is one or two of 103, 104, 161 and 163 of Germany BYK series; the defoaming agent is one or two of Germany BYK051, 052 and 066; the leveling agent is one or two of Germany BYK300 and Germany 354; the anti-settling agent is one or two of BYK410 and BYK 405.
The organic solvent is a mixture of toluene and N, N-dimethylformamide in a mass ratio of 1: 1.
The preparation method of the self-lubricating ice-covering-proof coating is characterized by comprising the following steps:
1) preparation of modified acrylic resin
Carrying out free radical copolymerization on a low surface energy monomer, a methacrylate soft and hard monomer and styrene in the presence of an initiator by taking toluene and N, N-dimethylformamide as a mixed solvent to obtain modified acrylic resin;
2) preparation of class A Components
Mixing modified acrylic resin, anti-icing lubricant and an organic solvent, dispersing for 10-20 minutes, then sequentially adding various auxiliaries, stirring, dispersing for 10-20 minutes at a high speed, and then ball-milling for 4-10 hours until the fineness of the coating is less than 50 mu m to obtain a component A;
3) preparation of the coating
And (3) uniformly mixing the A-type component and the B-type component according to the ratio of 5: 1-10: 1 to obtain the self-lubricating ice-covering-resistant coating.
The low surface energy monomer is one or two of vinyl silsesquioxane, vinyl polydimethylsiloxane, polydimethylsiloxane methacrylate, tridecafluorooctyl methacrylate, dodecafluoroheptyl acrylate, hexafluoroisopropyl methacrylate and hexafluorobutyl acrylate.
The methacrylate soft and hard monomer is one or a mixture of more of beta hydroxyethyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate, isobornyl methacrylate and lauryl methacrylate.
The initiator is azobisisobutyronitrile, and the dosage of the initiator is 2-3% of the total mass of the low surface energy monomer, the methacrylate soft and hard monomer and the styrene.
The mass ratio of the toluene to the N, N-dimethylformamide is 1: 1.
The low surface energy monomer, the methacrylate soft and hard monomers and the styrene have the following molar ratio: 1-2: 8-13: 4-6.
The self-lubricating ice-coating-preventing coating disclosed by the invention is formed after being cured, has strong binding force with a substrate, smooth surface and low friction coefficient, has an excellent self-lubricating effect, and is an ice-coating-preventing coating material easy to remove ice. The film-forming resin used in the invention is acrylate resin modified by low surface energy groups, and the polarity of the acrylate resin is changed, so that the resin and the lubricant have better miscibility, and simultaneously have low surface energy characteristics, and the adhesion strength of ice coating on the surface of the coating is reduced.
The conventional performance of the coating sprayed on the tin plate is as follows:
1) adhesion force: GB1720-79 (circle drawing), level 1;
2) impact resistance: GB1732-79, 50 cm & Kg;
3) hardness: GB6379-86, grade H;
4) flexibility: GB1731-79, 1 mm;
5) coating surface energy: less than 25 mJ.m-2；
6) Drying time of a paint film: GB1728-79, room temperature 16-25 ℃, surface drying for 1 hour, and actual drying time for 6 hours.
The self-lubricating ice-covering-preventing coating can be coated on a low-carbon steel plate (150 multiplied by 250 multiplied by 1.5 mm) with an anti-corrosion primer in a spraying or brushing mode, the thickness of a dry film of the anti-corrosion primer is 100-300 mu m, and the thickness of the coating is controlled to be 100-200 mu m, so that a satisfactory ice-preventing and removing effect can be obtained. According to the surface friction coefficient characterization of the coating, the friction coefficient of the self-lubricating ice-coating-proof coating on the ice surface is only 0.05, and the self-lubricating ice-coating-proof coating is only a common coating 1/4. The ice adhesion test proves that the ice adhesion strength of the self-lubricating ice-coating-preventing coating is only 50KPa, the self-lubricating ice-coating-preventing coating is only 1/30 of a bare low-carbon steel plate, the deicing efficiency is improved by 97%, and the ice adhesion test result is shown in table 1.
Table 1 ice adhesion test statistical table
Drawings
FIG. 1 is a comparison graph of the friction coefficient of the self-lubricating ice-coating-proof coating on the ice surface and the friction coefficient of a common epoxy coating.
FIG. 2 is a comparison graph of ice adhesion of the self-lubricating ice-coating-preventing coating according to the present invention.
FIG. 3 is a graph of deicing efficiency of a large-scale cryogenic box and the self-lubricating anti-icing coating of the present invention.
Detailed Description
The modified acrylic polymer resin of the present invention is prepared as follows:
70 g of a toluene and N, N-dimethylformamide mixed organic solvent with the mass ratio of 1:1 is added into a reaction bottle, 34 g of methyl methacrylate, 3.5 g of ethyl acrylate, 4 g of butyl acrylate, 22 g of styrene, 4.5 g of beta-hydroxyethyl methacrylate, 23 g of vinyl polysiloxane monomer and 1.5 g of azobisisobutyronitrile are dropwise added at 90 ℃ under the nitrogen purging, the dropwise addition is controlled within 1.5 hours, and the temperature is kept for 2 hours. Then 14.5 g of mixed solvent in which 0.5 g of azobisisobutyronitrile is dissolved is added within 0.5 hour, and the temperature is kept for 1 hour, thus obtaining the modified acrylic resin I.
70 g of a toluene and N, N-dimethylformamide mixed organic solvent with the mass ratio of 1:1 is added into a reaction bottle, 26 g of methyl methacrylate, 4 g of ethyl acrylate, 4 g of butyl acrylate, 21 g of styrene, 4.5 g of beta-hydroxyethyl methacrylate, 48 g of tridecafluorooctyl methacrylate and 1.5 g of azobisisobutyronitrile are dropwise added at 90 ℃ under the nitrogen purging, the dropping is finished within 1.5 hours, and the temperature is kept for 2 hours. Then 15 g of mixed solvent in which 0.5 g of azobisisobutyronitrile is dissolved is replenished within 0.5 hour, and the temperature is kept for 1 hour to obtain the fluoroalkyl modified acrylic acid low surface energy resin II.
Adding 60 g of a toluene and N, N-dimethylformamide mixed organic solvent with the mass ratio of 1:1 into a reaction bottle, dropwise adding 18 g of methyl methacrylate, 3.5 g of ethyl acrylate, 5 g of butyl acrylate, 15 g of styrene, 4.5 g of beta-hydroxyethyl methacrylate, 48 g of vinyl silsesquioxane monomer and 1.5 g of azobisisobutyronitrile at 90 ℃ under the nitrogen purging, controlling the dropping within 1.5 hours, and keeping the temperature for 2 hours. Then 15 g of mixed solvent in which 0.5 g of azobisisobutyronitrile is dissolved is added within 0.5 hour, and the temperature is kept for 1 hour, thus obtaining the modified acrylic resin III.
Example 1
Adding the modified acrylic resin I and the organic solvent into a dispersion cylinder, sequentially adding the auxiliary agent and the anti-icing lubricant, stirring and dispersing for 10 minutes, then ball-milling for 6 hours, and checking viscosity and fineness to obtain the A-type component.
The group A is distributed as follows:
fluoroalkyl group-modified acrylic resin i: 40 g
Anti-icing lubricant: silicone oil 20 g
Coating auxiliary agent: BYK 1630.8 g, BYK 0520.4 g, BYK 3000.4 g, BYK 4101.6 g
Mixing solvent: toluene 8 g, N, N-dimethylformamide 8 g
And (3) fully and uniformly mixing the component A and the Wanhua 75B curing agent according to the mass ratio of 6:1, and then carrying out spraying construction.
Example 2
The preparation process of the self-lubricating ice-covering-proof coating of the embodiment is the same as that of the embodiment 1.
The group A is distributed as follows:
40 g of modified acrylic resin II
Anti-icing lubricant: polyethylene wax 20 g
Coating auxiliary agent: BYK 1630.8 g, BYK 0520.4 g, BYK 3000.4 g, BYK 4101.6 g
Mixing solvent: toluene 8 g, N, N-dimethylformamide 8 g
And (3) fully and uniformly mixing the component A and the Wanhua PM200 curing agent according to the mass ratio of 8:1, and then carrying out spraying construction.
Example 3
The preparation process of the self-lubricating ice-covering-proof coating of the embodiment is the same as that of the embodiment 1.
Modified acrylic resin III: 40 g
Anti-icing lubricant: graphite fluoride 20 g
Coating auxiliary agent: BYK 1630.8 g, BYK 0520.4 g, BYK 3000.4 g, BYK 4101.6 g
Mixing solvent: toluene 8 g, N, N-dimethylformamide 8 g
And (3) fully and uniformly mixing the component A and the Wanhua PM200 curing agent according to the mass ratio of 6:1, and then carrying out spraying construction.
Example 4
The preparation process of the self-lubricating ice-covering-proof coating of the embodiment is the same as that of the embodiment 1.
Modified acrylic resin III: 40 g
Anti-icing lubricant: graphite fluoride 10 g, polyethylene wax 10 g
Coating auxiliary agent: BYK 1630.8 g, BYK 0520.4 g, BYK 3000.4 g, BYK 4101.6 g
Mixing solvent: toluene 8 g, N, N-dimethylformamide 8 g
And (3) fully and uniformly mixing the component A and the Wanhua PM200 curing agent according to the mass ratio of 8:1, and then carrying out spraying construction.
Example 5
The preparation process of the self-lubricating ice-covering-proof coating of the embodiment is the same as that of the embodiment 1.
Modified acrylic resin III: 40 g
Anti-icing lubricant: 6 g of molybdenum disulfide, 6 g of graphite fluoride and 8 g of silicone oil
Coating auxiliary agent: BYK 1630.8 g, BYK 0520.4 g, BYK 3000.4 g, BYK 4101.6 g
Mixing solvent: toluene 8 g, N, N-dimethylformamide 8 g
And (3) fully and uniformly mixing the component A and the Wanhua PM200 curing agent according to the mass ratio of 8:1, and then carrying out spraying construction.
Claims (9)
1. A self-lubricating anti-icing coating is characterized by comprising an A-type component and a B-type component, wherein the A-type component comprises the following components in percentage by mass in the A-type component: 20-70% of modified acrylic resin, 5-50% of anti-icing lubricant, 1-5% of auxiliary agent and 20-50% of organic solvent; the B component is polyisocyanate curing agent produced by Wanhua company, and the mass ratio of the A component to the B component is 5: 1-10: 1; the structural formula of the modified acrylic resin is as follows:
wherein R1 is alkyl with carbon number of 1-12, R2 is a low surface energy functional group, and m, p, q and z are integers of 1-15;
the R2 is a polydimethylsiloxane chain;
the preparation method of the modified acrylic resin comprises the following steps: carrying out free radical copolymerization on a low surface energy monomer, a methacrylate soft and hard monomer and styrene in the presence of an initiator by taking toluene and N, N-dimethylformamide as a mixed solvent to obtain modified acrylic resin;
the anti-icing lubricant is one or more of molybdenum disulfide, crystalline flake graphite, graphite fluoride, paraffin fluoride, polyethylene wax, polyamide wax, liquid paraffin, polyethylene oxide, polydimethylsiloxane, long-chain alkane and perfluoroalcohol; the auxiliary agent is a mixture of a wetting dispersant, a flatting agent, a defoaming agent and an anti-settling agent, and the mass ratio of the wetting dispersant, the flatting agent, the defoaming agent and the anti-settling agent is 2:1:1: 4; the organic solvent is a mixture of toluene and N, N-dimethylformamide in a mass ratio of 1: 1.
2. The paint according to claim 1, wherein the polyisocyanate curing agent is one or two of Wanhua PM200/100, polymerization modified MDI-50 and MDI-100.
3. The coating of claim 1 wherein the wetting dispersant is one or two of 103, 104, 161, 163 of the german BYK series; the defoaming agent is one or two of Germany BYK051, 052 and 066; the leveling agent is one or two of Germany BYK300 and Germany 354; the anti-settling agent is one or two of BYK410 and BYK 405.
4. The coating according to any one of claims 1 to 3, characterized in that the self-lubricating anti-icing coating is applied to the substrate with the anti-corrosion primer by means of spraying or brushing, the thickness of the anti-corrosion primer dry film is 100-300 μm, and the thickness of the self-lubricating anti-icing coating is 100-200 μm.
5. The method for preparing the self-lubricating ice-covering-preventing coating according to any one of claims 1 to 4, characterized by comprising the steps of:
1) preparation of modified acrylic resin
Carrying out free radical copolymerization on a low surface energy monomer, a methacrylate soft and hard monomer and styrene in the presence of an initiator by taking toluene and N, N-dimethylformamide as a mixed solvent to obtain modified acrylic resin;
2) preparation of class A Components
Mixing modified acrylic resin, an anti-icing lubricant and an organic solvent, dispersing for 10-20 minutes, then sequentially adding various auxiliaries, stirring, dispersing for 10-20 minutes at a high speed, and then ball-milling for 4-10 hours until the fineness of the coating is less than 50 mu m to obtain a component A;
3) preparation of the coating
And (3) uniformly mixing the A-type component and the B-type component according to the ratio of 5: 1-10: 1 to obtain the self-lubricating ice-covering-resistant coating.
6. The method according to claim 5, wherein the methacrylate soft and hard monomers are one or more of beta hydroxyethyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate, isobornyl methacrylate and lauryl methacrylate.
7. The method according to claim 5, wherein the initiator is azobisisobutyronitrile, and the amount of the initiator is 2-3% of the total mass of the low surface energy monomer, the methacrylate soft and hard monomers and the styrene.
8. The method according to claim 5, wherein the mass ratio of toluene to N, N-dimethylformamide is 1: 1.
9. The method according to claim 5, wherein the low surface energy monomer, the methacrylate soft and hard monomers and the styrene are present in a molar ratio of: 1-2: 8-13: 4-6.
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| CN114025474B (en) * | 2021-11-22 | 2022-07-19 | 百强电子（深圳）有限公司 | Printed circuit board and method for manufacturing the same |
| CN117720896B (en) * | 2023-12-22 | 2024-05-17 | 湖北亮绿环保技术有限公司 | Ultra-low temperature high-efficiency paraffin removal and prevention agent for petroleum and natural gas as well as preparation method and application thereof |
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