WO2016037403A1 - 一种氟化poss复合有机硅涂层及制备方法与防覆冰应用 - Google Patents

一种氟化poss复合有机硅涂层及制备方法与防覆冰应用 Download PDF

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WO2016037403A1
WO2016037403A1 PCT/CN2014/089720 CN2014089720W WO2016037403A1 WO 2016037403 A1 WO2016037403 A1 WO 2016037403A1 CN 2014089720 W CN2014089720 W CN 2014089720W WO 2016037403 A1 WO2016037403 A1 WO 2016037403A1
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fluorinated
coating
poss
polyhedral oligomeric
oligomeric silsesquioxane
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French (fr)
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袁晓燕
陶超
朱孔营
罗程皞
赵蕴慧
李晓晖
张凯强
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Tianjin University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens

Definitions

  • the invention relates to a method for preparing an anti-icing coating by fluorinating polyhedral oligomeric silsesquioxane (fluorinated POSS) and silicone.
  • anti-icing coating anti-icing coating, etc.
  • deicing direct deicing by external force, spraying deicer, heating, etc.
  • anti-icing coating is an important and effective anti-icing method.
  • the anti-icing coating mainly adopts low surface energy materials, super-hydrophobic surfaces and lubricating layers to prevent ice.
  • Silicone materials are a common class of low surface energy anti-icing materials.
  • US patent US 20070254170 has been proposed R2180 is a corrosion resistant anti-icing coating material (Hoover KL, Watson CR, Putnam JW, Dolan RC, Bonarrigo BB, Kurz PL, Weisse MA. Erosion resistant anti-icing coatings. US 20070254170, 2007).
  • U.S. Patent No. 7,514,017 discloses an anti-icing coating comprising a hydrophobic material such as silicone as a matrix resin and comprising a silicone phase change material (Bhamidipati MV. Methods and compositions for inhibiting surface icing. US 7514017, 2009). In US Pat. No.
  • a sol-gel preparation process for an anti-icing coating is proposed, which is an "interpenetrating network structure" formed by crosslinking of a silicone, and the system contains an ice suppressant such as a polyol ( Simendinger WH, Miller, SD. Anti-icing composition. US 6702953, 2004).
  • Dow Corning 184 silicone resin can be used as a matrix resin as an anti-icing coating material, which is composed of a hydrogen-containing polysiloxane (component A) and polymethylvinylsiloxane (component B).
  • a silicone product that is crosslinked and cured based on a hydrosilylation reaction (Alizadeh A, Bahadur V, Shang W, Zhu Y, Buckley D, Dhinojwala A, Sohal M. Influence of substrate elasticity on droplet impact dynamics. Langmuir, 2013, 29 :4520-4524).
  • SLIPS lubricating liquid filled porous surface
  • U.S. Patent No. 20140147627 discloses a method for preparing a SLIPS surface using perfluoro
  • the organic matter or organosilicon compound is wetted as a lubricating fluid and adheres to the surface of the rough substrate to form a stable lubricating layer.
  • the substrate has a certain topological structure or is composed of a porous material. The selection of the substrate material is very wide, including poly four.
  • Polymer materials such as vinyl fluoride, epoxy resin, and polyester, metal materials such as aluminum, and inorganic ceramic materials (Aizenberg J, Aizenberg M, Kang SH, Kim P, Tang KY, Wong TS. Clippery surfaces with high pressure stability, optical transparency , and self-healing characteristics.US 20140147627, 2014).
  • Fluoropolymers are a class of low surface energy materials that are commonly used for hydrophobic and oleophobic modification and are also useful in ice protection.
  • Chinese patent CN 102205680 B discloses an anti-icing composite coating comprising three layers, the inner layer is a silicone modified epoxy layer, the middle layer is a polyelectrolyte salt layer, and the outer layer is modified by fluorosilicone.
  • Acrylate layer Huang Chi, Li Yan, Hu Mingjie, Zhao Yuming, Liu Xinghai, Li Xiaolin, Huang Ronghua, Luo Yunbai. An anti-icing coating and its preparation method. CN 102205680 B, 2014).
  • Polyhedral oligomeric silsesquioxane is a class of organic-inorganic hybrid molecules with an inorganic core at the center and eight organic groups at the apex.
  • the POSS molecules with different functional groups can be synthesized by molecular design.
  • the POSS molecules with eight vertices of organic fluorine groups are low surface energy, functional, nanoscale organic-inorganic hybrid molecules.
  • Cia patent CN 101029137 A discloses a fluorinated POSS acrylate block copolymer resin and a synthetic method thereof, the polymer film has certain hydrophobic properties and has a certain hardness (Dai Lizong, Chen Jiangfeng, Xu Yiting, Deng Yuanming, Peng Xiaoliang. A fluorine-containing POSS acrylate block copolymer resin and its synthesis method. CN 101029137 A, 2007).
  • Chinese patent CN 101875707 A discloses a fluorinated POSS acrylate copolymer and a preparation method comprising the same, and the obtained coating has low surface energy and high antifouling ability (Cold Shiwei, Hu Wen, Wu Ping) A fluorine-containing POSS acrylate copolymer and a process for the preparation thereof and a coating.
  • CN 101875707 A, 2010 Mabry et al.
  • fluorinated POSS is one of the most hydrophobic crystalline materials (Mabry JM, Vij A, Iacono ST, Viers BD. Fluorinated polyhedral oligomeric silsesquioxanes (F-POSS). Angewandte Chemie International Edition, 2008, 47: 4137-4140). Golovin et al.
  • the different cross-linking modes of the layers give the surface a controllable wrinkle morphology (Gan Y,Jiang X,Yin J.Self-wrinkling patterned surface of photocuring coating induced by the fluorinated POSS containing thiol groups (F-POSS-SH) as The reactive nanoadditive.Macromolecules, 2012, 45:7520-7526).
  • Yagüe et al. deposited a hard coating on the biaxially pre-stretched PDMS surface by chemical vapor deposition (iCVD) to form regular pleat patterns (Yagüe JL, Yin J, Boyce MC, Gleason KK. Design of Ordered wrinkled patterns with dynamically tuned properties.Physics Procedia, 2013, 46: 40-45).
  • the low surface energy fluorinated POSS as a co-crosslinking agent has little application in the anti-icing coating, and it is not seen to be low.
  • the surface energy fluorinated POSS is combined with the lubrication and anti-icing mechanism.
  • the invention introduces low surface energy fluorinated POSS as a co-crosslinking agent into the organosilicon matrix, and realizes micro-nano-scale wrinkling of the coating surface by adjusting the degree of cross-linking; in addition, the low-molecular-weight hydrogen present in the system Polysiloxane realizes the three-layer contact surface of the ice-lubricating layer-solid coating surface, relatively reduces the contact surface of the ice body with the solid surface of the coating, and the combination of surface pleats and the lubricating layer makes the ice adhesion strength of the coating Greatly reduced, significantly improved anti-icing effect.
  • the object of the present invention is to prepare a fluorinated polyhedral oligomeric silsesquioxane (fluorinated POSS) composite silicone anti-icing coating.
  • the material in the invention is easy to obtain, the preparation method is simple, and the reaction conditions are controllable.
  • the invention discloses a fluorinated polyhedral oligomeric silsesquioxane (fluorinated POSS) composite silicone coating, which is obtained by oligomerizing a fluorinated polyhedron containing eight silicon hydrides and a fluorine-containing alkyl chain respectively.
  • the silsesquioxane (fluorinated POSS) is compounded with silicone and cured by a hydrosilylation reaction to form a film.
  • fluorinated polyhedral oligomeric silsesquioxane (fluorinated POSS) composite silicone anti-icing coating using vinyl polysiloxane as a matrix material, hydrogen-containing polysiloxane participates in crosslinking reaction and simultaneously lubricates The effect is to lubricate the water/ice and solid coating on the surface of the coating.
  • the surface micro-nano-scale topology can reduce the contact area of water or ice with the surface, which is beneficial to the improvement of anti-icing performance.
  • the object of the present invention is achieved by the following technical solution, which combines a fluorinated POSS with a silicone material to form an anti-icing coating.
  • the composition and percentage of each component are (the sum of the mass percentages of each component is 100%):
  • Fluorinated POSS 1 to 25%
  • Hydrogen-containing polysiloxane 5 to 30%;
  • Vinyl polysiloxane 10 to 50%
  • the balance is solvent.
  • x represents the number of remaining silicon hydrogen bonds in the fluorinated POSS, and 2 ⁇ x ⁇ 6, which is obtained by 1 H-NMR analysis.
  • x is obtained by 1 H-NMR analysis, ie, the integral area of two H-signal peaks on the methylene group in H--i(CH 3 ) 2 CH 2 - in -SiH in the 1 H-NMR spectrum of fluorinated POSS Calculated to give an average of the results of several fluorinated POSS molecules.
  • the hydrogen-containing polysiloxane has a molecular weight of from 2,000 to 3,000 g/mol.
  • m/n 5 to 10.
  • the vinyl polysiloxane has a molecular weight of 25,000 to 30,000 g/mol.
  • the above fluorinated POSS composite silicone anti-icing coating, the catalyst used is one of a Karstedts catalyst or a chloroplatinic acid catalyst.
  • the above fluorinated POSS composite silicone anti-icing coating is used in one of toluene, xylene, trifluorotoluene, dichloromethane, chloroform and tetrahydrofuran.
  • the fluorinated POSS is mixed with the hydrogen-containing polysiloxane, the vinyl polysiloxane, the catalyst and the solvent according to the above mass percentage, and the solution is uniformly stirred by ultrasonic stirring for 1 to 2 hours; a certain amount of the solution is coated on the substrate.
  • the surface was dried at room temperature, and then placed in a blast oven at 80-120 ° C for 2 to 4 hours to form a film, and a fluorinated POSS composite silicone anti-icing coating was obtained.
  • the coating method may be by dripping, spin coating, spin coating, dip coating, or the like.
  • fluorinated polyhedral oligomeric silsesquioxane (fluorinated POSS) starting materials containing silicon hydrogen bonds and fluorine-containing alkyl chains Dutkiewicz M, Maciejewski H, Marciniec B, Karasiewicz J. New fluorocarbofunctional spherosilicates: synthesis and characterization can be used. .Organometallics, 2011, 30: 2149-2153 prepared as follows:
  • the hydrophobic, anti-icing performance test and the wrinkle morphology observation method are as follows:
  • the contact angle tester was used to test the wettability values of the advancing angle and receding angle of the coating, and the contact angle hysteresis value was calculated.
  • the contact angle tester model was Shanghai Zhongchen Instrument Equipment Co., Ltd. JC2000D, and the contact angle calculation utilized the five-point fitting method. .
  • the advancing/retracting angle test method is as follows: 5 ⁇ L of water droplets are fixed on the surface of the coating, and the liquid is continuously dropped/absorbed at a rate of 0.1 ⁇ L/s until the droplet moves to the contact line on either side of the coating surface, at which time the side
  • the contact angle value is the advancing/retracting angle value, and the difference between the two is the contact angle hysteresis value.
  • the coating was subjected to an ice shear strength test using a side push method, a push-pull force meter, and a cold stage.
  • the cold stage was cooled to -15 ° C at 2 ° C / min and kept for 2 h, so that ultrapure water was frozen into a column on the surface of the coating.
  • the push-pull force gauge is fixed on the electric moving platform, and the distance between the push-pull force gauge probe and the coating surface is not more than 2 mm, and is pushed forward at a speed of 0.5 mm/s, and the recording is pushed away from the coating surface from the beginning of contact with the glass cylinder to the icicle.
  • the maximum shear force F, and calculate the ice shear strength ⁇ F / S.
  • the push-pull gauge model is Japan ImadaZP-500N, and 10 samples are averaged.
  • the surface of the coating was measured by the Hitachi S-4800 Field Emission Scanning Electron Microscope (SEM) and the CSPM5500 Low Temperature Atomic Force Microscope (AFM) of Guangzhou Prima Nano Instrument Co., Ltd., where the SEM magnification was 400 ⁇ . 5000, AFM operation mode is tap mode.
  • fluorinated POSS The effect of fluorinated POSS and the formation of pleats in the coatings prepared in the present invention are as follows:
  • the introduction of fluorinated POSS provides the coating with low surface energy and micro-nano scale roughness.
  • the fluorinated POSS is reactive and can participate in the crosslinking reaction as a crosslinking agent.
  • the fluorine-containing alkyl chain in the fluorinated POSS draws the POSS molecules to the surface due to the low surface energy and is concentrated on the surface, so that it is less distributed inside the coating, and gradually forms a double-layer crosslinked structure, and the surface layer is composed of
  • the fluorinated POSS is composed of a vinyl polysiloxane
  • the base layer is composed of a hydrogen-containing polysiloxane and a vinyl polysiloxane. Since the formation of the double-layer crosslinked structure is completely dependent on the self-aggregation of the fluorinated POSS, the boundary line is not obvious, and there is also a trace amount of fluorinated POSS along the depth gradient distribution in the base layer.
  • the degree of cross-linking of the two layers is different, and the POSS molecules themselves have a certain rigidity, and the degree of hardness and hardness between the two layers is also different, resulting in different stresses between the two layers and internal stresses which are inwardly contracted, and finally the micro-nano-level wrinkles appear on the surface.
  • the pleats together with the POSS molecules provide a nano-scale roughness of the coating, resulting in a reduced contact area between the ice and the solid surface and a decrease in the adhesion of the ice to the surface of the coating.
  • the lubricating effect in the present invention is as follows: the internal crosslinking of the coating is incomplete, and the low molecular weight polysiloxane having fluidity is still blocked inside the coating or stored in a surface layer having micro-nano structure wrinkles for lubrication.
  • the water/ice and solid coatings are lubricated on the surface of the coating to achieve minimal water contact angle hysteresis and ice shear strength.
  • the fluorinated POSS in the surface layer is rapidly cross-linked and cured with the vinyl polysiloxane during the heating process, and the hydrogen-containing polysiloxane of the base layer is heated due to the heat transfer process.
  • Meuler et al. tested the water advancing angle, receding angle and ice shear strength of a series of low surface energy polymer coatings and polymer/POSS composite coatings. The results showed that the ice shear strength of most coatings was Between 165 and 510 kPa, the water contact angle lag is 5.6 to 44.6 ° (Meuler AJ, Smith JD, Varanasi KK, Mabry JM, McKinley GH, Cohen RE. Relationships between water wettability and ice adhesion. ACS Applied Materials & Interfaces, 2010, 2: 3100-3110).
  • SLIPS surface ice shear strength can be as low as 40 kPa (Mishchenko L, Hatton B, Bahadur V, Ashley Taylor J, Krupenkin T, Aizenberg J. Design of ice-free nanostructured surfaces based on repulsion of impacting water droplets. ACS Nano, 2010, 4:7699-7707).
  • the fluorinated POSS cooperates with the silicone material and the liquid lubricant to impart a very small contact angle hysteresis and ice shear strength to the fluorinated POSS and silicone composite coating of the present invention.
  • the water contact angle hysteresis can be as low as 2°
  • the ice shear strength can be as low as 20 kPa, which can be effectively applied to hydrophobic and anti-icing coatings.
  • Figure 1 SEM photograph of the coating of Example 1.
  • a fluorinated POSS that is, four ( ⁇ 3, 3, 4, 4, 5, 5,6,6,7,7,8,8,8-tridecafluorooctyloxycarbonyl-methylethyl ⁇ dimethylsilyl)tetrakis(dimethylsilyl) cage polysilses Alkane, its structural formula is
  • the resulting coating had a water contact angle hysteresis of 2°, an ice shear strength of 25 kPa, and a water contact angle of 105°.
  • a pleat pattern having a width of about 1.2 ⁇ m and a pleat pitch of about 1.1 ⁇ m was observed by SEM and AFM.
  • Figure 1 shows a SEM photograph of the coating.
  • a fluorinated POSS that is, four ( ⁇ 2, 2, 3, 4, 4, 4-hexafluorobutoxycarbonyl-methylethyl ⁇ dimethylsilyl)tetrakis(dimethylsilyl) cage polysilsesquioxane, the structural formula is
  • the resulting coating had a water contact angle hysteresis of 5°, an ice shear strength of 49 kPa, and a water contact angle of 103°. It was observed by SEM and AFM that wrinkles having a width of about 600 nm and a wrinkle pitch of about 600 nm were observed.
  • a fluorinated POSS that is, four ( ⁇ 2, 2, 3, 3, 4, 4,5,5,6,6,7,7-dodecylheptyloxycarbonyl-methylethyl ⁇ dimethylsilyl)tetrakis(dimethylsilyl) cage polysilsesquioxane, Its structural formula is
  • the resulting coating had a water contact angle hysteresis of 4.5°, an ice shear strength of 40 kPa, and a water contact angle of 104°. It was observed by SEM and AFM that wrinkles having a width of about 900 nm and a wrinkle pitch of about 950 nm were observed.
  • the ratio of the peak area of the characteristic peak at a chemical shift of 0.83 or 1.06 to the peak area of the characteristic peak of H in the SiH at a chemical shift of 4.72 is the ratio of the two H numbers, that is, the fluorine-containing group and SiH in the eight vertices.
  • the ratio of the number of groups, the total number of two groups is 8, and the average number of fluorine-containing groups per apex of each fluorinated POSS molecule is calculated to be 3, and the calculation method in the other embodiments is the same as above.
  • a 13 mL solution was dispensed onto the surface of a 20 cm x 20 cm aluminum plate and allowed to dry for 1 h at room temperature. Subsequently, the substrate was placed in an oven for cross-linking, the set temperature was 100 ° C, and the crosslinking time was 3 h, and finally a composite coating of fluorinated POSS and a silicone material was obtained.
  • the resulting coating had a water contact angle hysteresis of 3°, an ice shear strength of 20 kPa, and a water contact angle of 105°. It was observed by SEM and AFM that wrinkles having a width of about 1.1 ⁇ m and a wrinkle pitch of about 1.1 ⁇ m were observed.
  • a fluorinated POSS that is, four ( ⁇ 3, 3, 4, 4, 5, 5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorocarbonylcarbonyl-methylethyl ⁇ dimethylsilyl)tetrakis(dimethylsilyl) Cage polysilsesquioxane, the structural formula is
  • the resulting coating had a water contact angle hysteresis of 7°, an ice shear strength of 50 kPa, and a water contact angle of 105°. It was observed by SEM and AFM that wrinkles having a width of about 1.3 ⁇ m and a wrinkle pitch of about 1.6 ⁇ m were observed.
  • a fluorinated POSS that is, four ( ⁇ 3, 3, 4, 4, 5, 5,6,6,6-nonafluorohexyl ⁇ dimethylsilyl)tetrakis(dimethylsilyl) cage polysilsesquioxane, the structural formula is
  • the resulting coating had a water contact angle hysteresis of 5.2°, an ice shear strength of 46 kPa, and a water contact angle of 104°.
  • a pleat pattern having a width of about 760 nm and a pleat pitch of about 750 nm was observed by SEM and AFM.
  • a fluorinated POSS that is, four ( ⁇ 3, 3, 4, 4, 5, 5,6,6,7,7,8,8,8-tridecafluorooctyl ⁇ dimethylsilyl)tetrakis(dimethylsilyl) cage polysilsesquioxane, the structural formula is
  • the resulting coating had a water contact angle hysteresis of 4°, an ice shear strength of 27 kPa, and a water contact angle of 105°.
  • a pleat pattern having a width of about 1.0 ⁇ m and a pleat pitch of about 1.0 ⁇ m was observed by SEM and AFM.
  • a fluorinated POSS that is, four ( ⁇ 3, 3, 4, 4, 5, 5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoroalkyl ⁇ dimethylsilyl)tetrakis(dimethylsilyl) cage polyp Siloxane, its structural formula is
  • the resulting coating had a water contact angle hysteresis of 8°, an ice shear strength of 52 kPa, and a water contact angle of 105°.
  • a pleat pattern having a width of about 1.4 ⁇ m and a pleat pitch of about 1.7 ⁇ m can be observed by SEM and AFM.
  • the resulting coating had a water contact angle hysteresis of 3.5°, an ice shear strength of 35.7 kPa, and a water contact angle of 104°.
  • a pleat pattern having a width of about 800 nm and a pleat pitch of about 850 nm can be observed by SEM and AFM.
  • a fluorinated POSS that is, six ( ⁇ 2, 2, 3, 4, 4, 4-hexafluorobutoxycarbonyl-methylethyl ⁇ dimethylsilyl) bis(dimethylsilyl) cage polysilsesquioxane, the structural formula is
  • the resulting coating had a water contact angle hysteresis of 6°, an ice shear strength of 50 kPa, and a water contact angle of 103°.
  • a pleat pattern having a width of about 550 nm and a pleat pitch of about 580 nm can be observed by SEM and AFM.
  • the resulting coating had a water contact angle hysteresis of 7.2°, an ice shear strength of 55 kPa, and a water contact angle of 105°.
  • a pleat pattern having a width of about 1.2 ⁇ m and a pleat pitch of about 1.6 ⁇ m can be observed by SEM and AFM.
  • the film was coated on the surface of a 20 cm ⁇ 20 cm aluminum plate by dip coating, and dried at room temperature for 1 h. Subsequently, the substrate was placed in an oven for cross-linking, the set temperature was 80 ° C, and the crosslinking time was 3 h, and finally a composite coating of fluorinated POSS and a silicone material was obtained.
  • the resulting coating had a water contact angle hysteresis of 12.5°, an ice shear strength of 60 kPa, and a water contact angle of 106°.
  • a pleat pattern having a width of about 1.6 ⁇ m and a pleat pitch of about 1.9 ⁇ m was observed by SEM and AFM.
  • a fluorinated POSS that is, five ( ⁇ 3, 3, 4, 4, 5, 5,6,6,6-nonafluorohexyl ⁇ dimethylsilyl)tris(dimethylsilyl) cage polysilsesquioxane, the structural formula is
  • the coating was first spread by 600 rpm for 6 s to spread the droplets evenly, and then dried at 3000 rpm for 10 s at room temperature for 1 h. Subsequently, the substrate was placed in an oven for crosslinking, the temperature was set to 100 ° C, and the crosslinking time was 3 h, and finally a composite coating of the fluorinated POSS and the silicone material was obtained.
  • the resulting coating had a water contact angle hysteresis of 5°, an ice shear strength of 44 kPa, and a water contact angle of 104°.
  • a pleat pattern having a width of about 790 nm and a wrinkle pitch of about 800 nm can be observed by SEM and AFM.

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Abstract

本发明公开了一种氟化POSS复合有机硅涂层及制备方法与防覆冰应用；该涂层是通过将八个顶点分别含有硅氢键和含氟烷基链的氟化POSS与有机硅复合，并通过硅氢加成反应固化成膜来实现的。将上述氟化POSS引入双组分有机硅体系中，使之与含氢聚硅氧烷和乙烯基聚硅氧烷一起形成涂层，由于低表面能含氟烷基链的牵引，使得氟化POSS在涂层表面富集，并使得涂层表面产生微纳米尺度的规则褶皱，其与含氢聚硅氧烷在涂层表面起到的润滑作用协同，从而减小涂层表面的水接触角滞后和冰剪切强度。本发明材料易得，方法简便，条件可控，所制备的涂层水接触角滞后可低至2°，冰剪切强度可低至20kPa，作为防覆冰涂层可有效减少覆冰。

Description

一种氟化POSS复合有机硅涂层及制备方法与防覆冰应用 技术领域
本发明涉及一种氟化多面体低聚倍半硅氧烷(氟化POSS)与有机硅复合制备防覆冰涂层的方法。
背景技术
结冰、凝霜现象会给人类的日常生活造成极大不便和危害，如供电线路故障和飞机结冰造成的灾难等。解决这一问题有防冰(涂覆防覆冰涂层等)和除冰(通过外力、喷洒除冰剂、加热等方法直接除冰)两类方式。其中，防覆冰涂层是一类重要且有效的防冰方法。目前防覆冰涂层主要采取低表面能材料、超疏水表面以及润滑层防冰等手段。
有机硅材料是一类常用的低表面能防冰材料。美国专利US 20070254170曾提出
Figure PCTCN2014089720-appb-000001
R2180是一种耐腐蚀的防覆冰涂层材料(Hoover KL,Watson CR,Putnam JW,Dolan RC,Bonarrigo BB,Kurz PL,Weisse MA.Erosion resistant anti-icing coatings.US 20070254170,2007)。美国专利US7514017公开了一种以有机硅等疏水材料为基体树脂，并含有有机硅相变材料的防覆冰涂层(Bhamidipati MV.Methods and compositions for inhibiting surface icing.US 7514017,2009)。美国专利US 6702953中提出了一种防覆冰涂层的溶胶-凝胶制备过程，该涂层基体是有机硅交联形成的“互穿网络结构”，体系中含有多元醇等抑冰剂(Simendinger WH,Miller,SD.Anti-icing composition.US 6702953,2004)。Dow Corning公司的
Figure PCTCN2014089720-appb-000002
184有机硅树脂可作为基体树脂用作防覆冰涂层材料，它是由含氢聚硅氧烷(A组分)和聚甲基乙烯基硅氧烷(B组分)为主要组分，基于硅氢加成反应进行交联固化的有机硅产品(Alizadeh A,Bahadur V,Shang W,Zhu Y,Buckley D,Dhinojwala A,Sohal M.Influence of substrate elasticity on droplet impact dynamics.Langmuir,2013,29:4520-4524)。
除了低表面能材料防冰，润滑防冰机理由于其能够有效减小冰剪切强度而引起研究人员的广泛关注，例如Aizenberg等人提出的润滑液体填充多孔表面(SLIPS)的概念。SLIPS的原理是利用毛细作用，将一种与水不互溶的低表面能含氟有机液体封锁在表面拓扑结构中，得到分子水平的光滑表面，以减小表面的接触角滞后和冰剪切强度(Mishchenko L,Hatton B,Bahadur V,Ashley Taylor J,Krupenkin T,Aizenberg J.Design of ice-free nanostructured surfaces based on repulsion of impacting water droplets.ACS Nano,2010,4:7699-7707)。美国专利US 20140147627中公布了一种制备SLIPS表面的方法，利用全氟有 机物或有机硅化合物作为润滑液润湿并附着在粗糙基材表面，形成一层稳定的润滑层，基材有一定拓扑结构或由多孔材料构成，基材材料的选择非常广泛，包括聚四氟乙烯、环氧树脂、聚酯等高分子材料，铝等金属材料以及无机陶瓷材料(Aizenberg J,Aizenberg M,Kang SH,Kim P,Tang KY,Wong TS.Slippery surfaces with high pressure stability,optical transparency,and self-healing characteristics.US 20140147627,2014)。
含氟聚合物是一类低表面能材料，常用于疏水、疏油改性，在防冰方面也有应用。例如，中国专利CN 102205680 B公布了一种防覆冰复合涂层，共包含三层，内层为有机硅改性环氧树脂层，中间层为聚电解质盐层，外层为氟硅改性的丙烯酸酯层(黄驰，李岩，胡铭杰，赵宇明，刘兴海，黎小林，黄荣华，罗运柏.一种防覆冰涂层及其制备方法.CN 102205680 B,2014)。
多面体低聚倍半硅氧烷(POSS)是一类有机-无机杂化分子，其中央是无机内核，八个顶点为有机基团，通过分子设计可以合成含有不同官能团的POSS分子。八个顶点为有机含氟基团的POSS分子为低表面能的、功能性的、纳米尺度的有机-无机杂化分子。
氟化POSS近年来引起了研究人员的广泛关注。中国专利CN 101029137 A中公布了一种氟化POSS丙烯酸酯嵌段共聚物树脂及其合成方法，该聚合物膜有一定的疏水性能，并具有一定的硬度(戴李宗，陈江枫，许一婷，邓远名，彭小亮.一种含氟POSS丙烯酸酯嵌段共聚物树脂及其合成方法.CN 101029137 A,2007)。中国专利CN 101875707 A公布了一种氟化POSS丙烯酸酯共聚物以及含有该共聚物涂层的制备方法，所得到的涂层具有低表面能和高防污能力(冷世伟，胡文，吴平.一种含氟POSS丙烯酸酯共聚物及其制备方法与一种涂料.CN 101875707 A,2010)。Mabry等人成功合成了八个顶点均为九氟己基或十三氟辛基或十七氟癸基的氟化POSS，并通过研究发现氟化POSS是一类最疏水的晶体材料(Mabry JM,Vij A,Iacono ST,Viers BD.Fluorinated polyhedral oligomeric silsesquioxanes(F-POSS).Angewandte Chemie International Edition,2008,47:4137-4140)。Golovin等人将十七氟癸烷基POSS喷涂至具有微米级柱状规则排列拓扑结构的聚二甲基硅氧烷表面，得到了超疏水且超疏油的表面(Golovin K,Lee DH,Mabry JM,Tuteja A.Transparent,flexible,superomniphobic surfaces with ultra-low contact angle hysteresis.Angewandte Chemie International Edition,2013,52:13007-13011)。Meuler等人将十七氟癸烷基POSS分别与Tecnoflon氟橡胶或聚甲基丙烯酸乙酯在Asahiklin溶剂中共混后旋涂至钢板表面，结果显示冰粘附强度分别较Tecnoflon氟橡胶表面或聚甲基丙烯酸乙酯表面明显下降，当共混组成为80wt％聚甲基丙烯酸乙酯和20wt％十七氟癸烷基POSS时，冰粘附强度和接触角滞后 达到最小值，分别为165kPa和5.6°，表明氟化POSS有利于提高涂层的防覆冰性能，在防覆冰领域有应用前景(Meuler AJ,Smith JD,Varanasi KK,Mabry JM,McKinley GH,Cohen RE.Relationships between water wettability and ice adhesion.ACS Applied Materials & Interfaces,2010,2:3100-3110)。
表面褶皱在薄膜表面微纳结构的引入方面有广泛应用，因此，对褶皱的研究受到越来越多的关注。比如，蒋雪松课题组以含有2个十七氟癸基丙烯酸酯基团和6个巯基的POSS(F-POSS-SH)为交联剂，以环氧树脂为基材，利用光固化制备薄膜。该体系中由于低表面能的F-POSS-SH的迁移作用产生了双层交联体系，其表面层通过点击化学反应交联固化，基层通过光引发C＝C之间反应交联固化，两层不同的交联方式使得表面产生了可控的褶皱形貌(Gan Y,Jiang X,Yin J.Self-wrinkling patterned surface of photocuring coating induced by the fluorinated POSS containing thiol groups (F-POSS-SH) as the reactive nanoadditive.Macromolecules,2012,45:7520-7526)。Yagüe等人通过化学气相沉积(iCVD)的方法在双轴预拉伸的PDMS表面沉积一层硬质涂层来形成表面有规律的褶皱图案(YagüeJL,Yin J,Boyce MC,Gleason KK.Design of ordered wrinkled patterns with dynamically tuned properties.Physics Procedia,2013,46:40-45)。
虽然对氟化POSS的合成以及应用的研究越来越多，但低表面能的氟化POSS作为共交联剂，在防覆冰涂层方面的应用却鲜有涉及，并且，未见将低表面能的氟化POSS与润滑防冰机理相结合的案例。本发明将低表面能的氟化POSS作为共交联剂引入到有机硅基体中，通过交联程度的调控实现涂层表面的微纳米尺度褶皱化；此外，通过体系中存在的低分子量含氢聚硅氧烷实现冰层-润滑层-固体涂层表面的三相接触面，相对减少冰体与涂层固体表面的接触面，表面褶皱化和润滑层的结合使得涂层的冰粘附强度大大降低，显著提高防覆冰效果。
发明内容
本发明的目的在于制备一种氟化多面体低聚倍半硅氧烷(氟化POSS)复合有机硅防覆冰涂层，本发明中材料易得，制备方法简便，反应条件可控。
本发明公开的一种氟化多面体低聚倍半硅氧烷(氟化POSS)复合有机硅涂层，是通过将八个顶点分别含有硅氢键和含氟烷基链的氟化多面体低聚倍半硅氧烷(氟化POSS)与有机硅复合，并通过硅氢加成反应固化成膜来实现的。将氟化多面体低聚倍半硅氧烷引入双组分有机硅体系中，使之与含氢聚硅氧烷和乙烯基聚硅氧烷一起形成涂层，由于低表面能含 氟烷基链的牵引，使得氟化POSS在涂层表面富集，并使得涂层表面产生微纳米尺度的规则褶皱，从而减小涂层表面的接触角滞后和冰剪切强度。
上述氟化多面体低聚倍半硅氧烷(氟化POSS)复合有机硅防覆冰涂层，以乙烯基聚硅氧烷为基体材料，含氢聚硅氧烷参与交联反应并同时起润滑作用，使水/冰与固体涂层在涂层表面发生润滑。表面微纳尺度的拓扑结构能够减小水或冰与表面的接触面积，从而有利于防冰性能的提高。
本发明的目的通过以下技术方案实现，将氟化POSS与有机硅材料复合形成防覆冰涂层。其组成及各组成质量百分比为(各组分质量百分比之和为100％)：
氟化POSS：1～25％；
含氢聚硅氧烷：5～30％；
乙烯基聚硅氧烷：10～50％；
催化剂：0.0001％；
余量为溶剂。
上述氟化POSS的结构式为：
Figure PCTCN2014089720-appb-000003
式中，x表示氟化POSS中剩余硅氢键的个数，2≤x≤6，由1H-NMR分析得到。R为-CH2CH2(CF2)yCF3或-CH2CH(CH3)COORf，其中y＝3、5、7或9，Rf为-CH2CF2CHFCF3，-CH2CH2(CF2)4CHFCF3，-CH2CH2(CF2)5CF3或-CH2CH2(CF2)7CF3中的一种。x由1H-NMR分析得到，即通过氟化POSS的1H-NMR谱图中-SiH中H与-OSi(CH3)2CH2-中亚甲基上两个H特征峰的积分面积进行计算而得，为若干氟化POSS分子结果的平均值。
上述含氢聚硅氧烷的结构式为：
Figure PCTCN2014089720-appb-000004
式中，p/q＝1～5。含氢聚硅氧烷的分子量为2000～3000g/mol。
上述乙烯基聚硅氧烷的结构式为：
Figure PCTCN2014089720-appb-000005
式中，m/n＝5～10。乙烯基聚硅氧烷的分子量为25000～30000g/mol。
上述氟化POSS复合有机硅防覆冰涂层，所用催化剂为Karstedts催化剂或氯铂酸催化剂中的一种。
上述氟化POSS复合有机硅防覆冰涂层，所用溶剂为甲苯、二甲苯、三氟甲苯、二氯甲烷、三氯甲烷和四氢呋喃中的一种。
上述氟化POSS复合有机硅防覆冰涂层的制备方法如下：
将氟化POSS与含氢聚硅氧烷、乙烯基聚硅氧烷、催化剂和溶剂按上述质量百分比配成溶液，超声搅拌1～2h使溶液呈均匀透明状；取一定量溶液涂覆在基板表面，室温下表干，随后放入80～120℃鼓风烘箱中交联2～4h成膜，得到氟化POSS复合有机硅防覆冰涂层。
涂覆方法可以采用滴涂、利用旋涂仪旋涂、喷涂或者浸涂等。
对于含有硅氢键和含氟烷基链的氟化多面体低聚倍半硅氧烷(氟化POSS)原料，可以采用Dutkiewicz M,Maciejewski H,Marciniec B,Karasiewicz J.New fluorocarbofunctional spherosilicates:synthesis and characterization.Organometallics,2011,30:2149-2153的如下方法制备：
称量一定质量的二甲基硅烷基笼形聚倍半硅氧烷与全氟正烯烃或氟烷基甲基丙烯酸酯，加入反应器中，利用甲苯、二甲苯、三氟甲苯、二氯甲烷、三氯甲烷或四氢呋喃中的一种作为溶剂溶解，配成10～50wt％的溶液，加入磁子，打开磁力搅拌，通N2气30min除去体系中的空气。接着加入Karstedts催化剂或氯铂酸催化剂在20～100℃下反应36～72h，产率98％。待反应结束，利用减压旋蒸的方法除去残留溶剂，得到氟化多面体低聚倍半硅氧烷，即氟化POSS。
疏水、防冰性能测试以及褶皱形貌观察方法如下：
利用接触角测试仪测试涂层的前进角、后退角等润湿性数值，并计算接触角滞后数值，接触角测试仪型号为上海中晨仪器设备有限公司JC2000D，接触角计算利用五点拟合法。前进角/后退角测试方法如下：将5μL水滴固着在涂层表面，以0.1μL/s的速度连续滴加/吸出液体，直到液滴与涂层表面任一侧接触线移动，此时该侧接触角数值即为前进角/后退角数值，两者之差即接触角滞后数值。
利用侧推法、使用推拉力计以及冷台对涂层进行冰剪切强度测试。测试过程如下：每 组样品取10个，放置于冷台上，将用1H,1H,2H,2H-全氟辛基三氯硅烷进行疏水处理过的底面直径为1cm的玻璃圆柱放置于涂层表面，滴入450μL超纯水，水与样品接触面积为S＝78.5mm2。在冷台上面放置有机玻璃罩,并通入N2气防止结霜。将冷台以2℃/min速度降温至-15℃并保温2h，使得超纯水在涂层表面结冰成柱。将推拉力计固定在电移动台上，推拉力计探头与涂层表面距离不大于2mm，以0.5mm/s的速度向前推动，记录从开始接触玻璃圆柱到冰柱被推离涂层表面的最大剪切力F，并计算冰剪切强度σ＝F/S。推拉力计型号为日本ImadaZP-500N，10个样品取平均值。
利用日本日立公司的S-4800场发射扫描电子显微镜(SEM)和广州本原纳米仪器有限公司的CSPM5500低温型原子力显微镜(AFM)检测涂层表面的褶皱形貌，其中，SEM放大倍数为400～5000，AFM运行模式为轻敲模式。
本发明中所制备涂层中氟化POSS的作用以及褶皱形成的原因如下：氟化POSS的引入为涂层提供了低表面能和微纳米尺度的粗糙度。而且，本发明中氟化POSS具有反应活性，可以作为交联剂参与交联反应。另外，氟化POSS中含氟烷基链由于表面能低的缘故牵引POSS分子迁移至表面并在表面富集，使得其在涂层内部分布较少，逐渐形成双层交联结构，表面层由氟化POSS与乙烯基聚硅氧烷组成，基层由含氢聚硅氧烷和乙烯基聚硅氧烷组成。由于双层交联结构的形成完全依赖氟化POSS的自聚集，其分界线并不明显，在基层也有痕量氟化POSS随深度变化梯度分布。两层交联程度不同，加之POSS分子本身具有一定刚性，两层之间软硬程度也不同，导致两层间应力不同而产生向内收缩的内应力，最终致使表面出现微纳级别的褶皱。褶皱形貌与POSS分子共同为涂层提供了微纳米尺度的粗糙度，使得冰与固体表面接触面积减小，且冰与涂层表面的结合力下降。
本发明中润滑作用如下：涂层内部交联不完全，其中仍含有具有流动性的低分子量聚硅氧烷被封锁在涂层内部或者储存在具有微纳结构褶皱的表面层中起润滑作用，使水/冰与固体涂层在涂层表面发生润滑，从而获得极小的水接触角滞后和冰剪切强度。其中，由于所形成的双层交联结构中，表面层中的氟化POSS在加热过程中迅速与乙烯基聚硅氧烷交联固化，而基层的含氢聚硅氧烷由于传热过程的延迟与剩余的有机硅氧烷交联，但由于双键含量的限制会有一部分小分子含氢硅油未交联完全，其含量通过氟化POSS、含氢聚硅氧烷和乙烯基聚硅氧烷的投料量以及官能配比进行控制。
Meuler等人对一系列低表面能的聚合物涂层以及聚合物/POSS复合涂层的水前进角、后退角以及冰剪切强度进行了测试，结果显示大多数涂层的冰剪切强度在165～510kPa之间，水接触角滞后为5.6～44.6°(Meuler AJ,Smith JD,Varanasi KK,Mabry JM,McKinley GH, Cohen RE.Relationships between water wettability and ice adhesion.ACS Applied Materials & Interfaces,2010,2:3100-3110)。SLIPS表面冰剪切强度可低至40kPa(Mishchenko L,Hatton B,Bahadur V,Ashley Taylor J,Krupenkin T,Aizenberg J.Design of ice-free nanostructured surfaces based on repulsion of impacting water droplets.ACS Nano,2010,4:7699-7707)。在本发明中氟化POSS与有机硅材料和液体润滑剂协同作用，使得本发明的氟化POSS与有机硅复合涂层拥有极小的接触角滞后和冰剪切强度。其中，水接触角滞后可低至2°，冰剪切强度可低至20kPa，可以有效应用于疏水、防冰涂层方面。
附图说明
图1：实施例1的涂层SEM照片。
具体实施方式
下面结合具体实例进一步说明本发明的技术方案。
实施例1：
(1)氟化POSS的制备：
将20g二甲基硅烷基笼形聚倍半硅氧烷与34g甲基丙烯酸十三氟辛酯加入三口瓶中，加入54g甲苯配成50wt％的溶液，加入磁子，打开磁力搅拌，通N2气30min除去体系中的空气。接着加入50μgKarstedts催化剂在60℃下反应48h。待反应结束，利用减压蒸馏的方法除去残留溶剂，得到粗产物，再将粗产物在真空干燥箱中真空干燥24h，得到氟化POSS，即四({3,3,4,4,5,5,6,6,7,7,8,8,8-十三氟辛氧基羰基-甲基乙基}二甲基硅烷基)四(二甲基硅烷基)笼形聚倍半硅氧烷，其结构式为
Figure PCTCN2014089720-appb-000006
(2)氟化POSS复合有机硅防覆冰涂层的制备：
将10g上述得到的氟化POSS与10g聚甲基氢硅氧烷(分子量为2000～2500g/mol,p/q＝1)、10g聚甲基乙烯基硅氧烷(分子量为25000～28000g/mol,m/n＝5)加入烧杯中，溶于70g三氟甲苯配成浓度为30wt％的溶液，加入100μgKarstedts催化剂。超声搅拌1h，溶液呈均匀透明状。取26mL溶液滴涂至20cm×20cm铝板表面。室温下表干1h。随后，将基板放入烘箱中交联，设定温度为80℃，交联时间为3h，最终获得氟化POSS与有机硅材料复合涂层。
所得涂层水接触角滞后为2°，冰剪切强度为25kPa，水接触角为105°。利用SEM和AFM能够观察到宽度在1.2μm左右，褶皱间距在1.1μm左右的褶皱图案。图1所示为该涂层的SEM照片。
实施例2：
(1)氟化POSS的制备：
将20g二甲基硅烷基笼形聚倍半硅氧烷与19.6g甲基丙烯酸六氟丁酯加入三口瓶中，加入356.4g甲苯配成10wt％的溶液，加入磁子，打开磁力搅拌，通N2气30min除去体系中的空气。接着加入50μgKarstedts催化剂在20℃下反应72h。待反应结束，利用减压蒸馏的方法除去残留溶剂，得到粗产物，再将粗产物在真空干燥箱中真空干燥24h，得到氟化POSS，即四({2,2,3,4,4,4-六氟丁氧基羰基-甲基乙基}二甲基硅烷基)四(二甲基硅烷基)笼形聚倍半硅氧烷，其结构式为
Figure PCTCN2014089720-appb-000007
(2)氟化POSS复合有机硅防覆冰涂层的制备：
将25g上述得到的氟化POSS与25g聚甲基氢硅氧烷(分子量为2000～2500g/mol,p/q＝1)、25g聚甲基乙烯基硅氧烷(分子量为25000～28000g/mol,m/n＝5)加入烧杯中，溶于25g三氟甲苯配成浓度为75wt％的溶液，加入100μg氯铂酸催化剂。超声搅拌1h，溶液呈均匀透明状。取11mL溶液滴涂至20cm×20cm铝板表面，室温下表干1h。随后，将基板放入烘箱中交联，设定温度为80℃，交联时间为4h，最终获得氟化POSS与有机硅材料复合涂层。
所得涂层水接触角滞后为5°，冰剪切强度为49kPa，水接触角为103°。利用SEM和AFM能够观察到宽度在600nm左右，褶皱间距在600nm左右的褶皱。
实施例3：
(1)氟化POSS的制备：
将20g二甲基硅烷基笼形聚倍半硅氧烷与31.4g甲基丙烯酸十二氟庚酯加入三口瓶中，加入205.6g甲苯配成20wt％的溶液，加入磁子，打开磁力搅拌，通N2气30min除去体系中的空气。接着加入50μgKarstedts催化剂在30℃下反应72h。待反应结束，利用减压蒸馏的方法除去残留溶剂，得到粗产物，再将粗产物在真空干燥箱中真空干燥24h，得到氟化POSS，即四({2,2,3,3,4,4,5,5,6,6,7,7-十二氟庚氧基羰基-甲基乙基}二甲基硅烷基)四(二甲基硅烷基)笼形聚倍半硅氧烷，其结构式为
Figure PCTCN2014089720-appb-000008
(2)氟化POSS复合有机硅防覆冰涂层的制备：
将20g上述得到的氟化POSS与10g聚甲基氢硅氧烷(分子量为2000～2500g/mol,p/q＝1)、40g聚甲基乙烯基硅氧烷(分子量为25000～28000g/mol,m/n＝5)加入烧杯中，溶于30g三氟甲苯配成浓度为70wt％的溶液，加入100μgKarstedts催化剂。超声搅拌2h，溶 液呈均匀透明状。取15mL溶液滴涂至20cm×20cm铝板表面，室温下表干1h。随后，将基板放入烘箱中交联，设定温度为90℃，交联时间为3h，最终获得氟化POSS与有机硅材料复合涂层。
所得涂层水接触角滞后为4.5°，冰剪切强度为40kPa，水接触角为104°。利用SEM和AFM能够观察到宽度在900nm左右，褶皱间距在950nm左右的褶皱。
实施例4：
(1)氟化POSS的制备：
将20g二甲基硅烷基笼形聚倍半硅氧烷与25.5g甲基丙烯酸十三氟辛酯加入三口瓶中，加入166g甲苯配成30wt％的溶液，加入磁子，打开磁力搅拌，通N2气30min除去体系中的空气。接着加入50μgKarstedts催化剂在40℃下反应72h。待反应结束，利用减压蒸馏的方法除去残留溶剂，得到粗产物，再将粗产物在真空干燥箱中真空干燥24h，得到氟化POSS，即三({3,3,4,4,5,5,6,6,7,7,8,8,8-十三氟辛氧基羰基-甲基乙基}二甲基硅烷基)五(二甲基硅烷基)笼形聚倍半硅氧烷，接上含氟基团个数计算方法如下：如表1所示：
表1
Figure PCTCN2014089720-appb-000009
化学位移在0.83或1.06处特征峰的峰面积与化学位移在4.72处的SiH中H的特征峰的峰面积之比为两种H个数之比，即八个顶点中含氟基团与SiH基团个数之比，两种基团总数为8，经计算可得平均每个氟化POSS分子八个顶点所含含氟基团的个数为3，其他实施例中计算方法同上。
其结构式为
Figure PCTCN2014089720-appb-000010
(2)氟化POSS复合有机硅防覆冰涂层的制备：
将9g上述得到的氟化POSS与21g聚甲基氢硅氧烷(分子量为2000～2500g/mol,p/q＝1)、30g聚甲基乙烯基硅氧烷(分子量为25000～28000g/mol,m/n＝5)加入烧杯中，溶于40g二甲苯配成浓度为60wt％的溶液，加入100μg氯铂酸催化剂。超声搅拌1h，溶液呈均匀透明状，。取13mL溶液滴涂至20cm×20cm铝板表面，室温下表干1h。随后，将基板放入烘箱中交联，设定温度为100℃，交联时间为3h，最终获得氟化POSS与有机硅材料复合涂层。
所得涂层水接触角滞后为3°，冰剪切强度为20kPa，水接触角为105°。利用SEM和AFM能够观察到宽度在1.1μm左右，褶皱间距在1.1μm左右的褶皱。
实施例5：
(1)氟化POSS的制备：
将20g二甲基硅烷基笼形聚倍半硅氧烷与41.8g甲基丙烯酸十七氟癸酯加入三口瓶中，加入92.7g甲苯配成40wt％的溶液，加入磁子，打开磁力搅拌，通N2气30min除去体系中的空气。接着加入50μgKarstedts催化剂在50℃下反应72h。待反应结束，利用减压蒸馏的方法除去残留溶剂，得到粗产物，再将粗产物在真空干燥箱中真空干燥24h，得到氟化POSS，即四({3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-十七氟癸氧基羰基-甲基乙基}二甲基硅烷基)四(二甲基硅烷基)笼形聚倍半硅氧烷，其结构式为
Figure PCTCN2014089720-appb-000011
(2)氟化POSS复合有机硅防覆冰涂层的制备：
将5g上述得到的氟化POSS与20g聚甲基氢硅氧烷(分子量为2000～2500g/mol,p/q＝1)、25g聚甲基乙烯基硅氧烷(分子量为25000～28000g/mol,m/n＝5)加入烧杯中，溶于50g二氯甲烷配成浓度为50wt％的溶液，加入100μgKarstedts催化剂。超声搅拌1h，溶液呈均匀透明状。取19mL溶液滴涂至20cm×20cm铝板表面，室温下表干1h。随后，将基板放入烘箱中交联，设定温度为110℃，交联时间为2h，最终获得氟化POSS与有机硅材料复合涂层。
所得涂层水接触角滞后为7°，冰剪切强度为50kPa，水接触角为105°。利用SEM和AFM能够观察到宽度在1.3μm左右，褶皱间距在1.6μm左右的褶皱。
实施例6：
(1)氟化POSS的制备：
将20g二甲基硅烷基笼形聚倍半硅氧烷与19.3g全氟丁基乙烯加入三口瓶中，加入39g二甲苯配成50wt％的溶液，加入磁子，打开磁力搅拌，通N2气30min除去体系中的空气。接着加入50μgKarstedts催化剂在60℃下反应48h。待反应结束，利用减压蒸馏的方法除去残留溶剂，得到粗产物，再将粗产物在真空干燥箱中真空干燥24h，得到氟化POSS，即四({3,3,4,4,5,5,6,6,6-九氟己烷基}二甲基硅烷基)四(二甲基硅烷基)笼形聚倍半硅氧烷，其结构式为
Figure PCTCN2014089720-appb-000012
(2)氟化POSS复合有机硅防覆冰涂层的制备：
将9g上述得到的氟化POSS与9g聚甲基氢硅氧烷(分子量为2000～2500g/mol,p/q＝1)、36g聚甲基乙烯基硅氧烷(分子量为25000～28000g/mol,m/n＝5)加入烧杯中，溶于50g三氯甲烷配成浓度为56wt％的溶液，加入100μgKastedts催化剂。超声搅拌2h，溶液呈均匀透明状。取15mL溶液滴涂至20cm×20cm铝板表面，室温下表干1h。随后，将基材放入烘箱中交联，设定温度为120℃，交联时间为2h，最终获得氟化POSS与有机硅材料复合涂层。
所得涂层水接触角滞后为5.2°，冰剪切强度为46kPa，水接触角为104°。利用SEM和AFM能够观察到宽度在760nm左右，褶皱间距在750nm左右微米的褶皱图案。
实施例7：
(1)氟化POSS的制备：
将20g二甲基硅烷基笼形聚倍半硅氧烷与27.2g全氟己基乙烯加入三口瓶中，加入188.8g三氟甲苯配成20wt％的溶液，加入磁子，打开磁力搅拌，通N2气30min除去体系中的空气。接着加入50μgKarstedts催化剂在70℃下反应48h。待反应结束，利用减压蒸馏的方法除去残留溶剂，得到粗产物，再将粗产物在真空干燥箱中真空干燥一昼夜，得到氟化POSS，即四({3,3,4,4,5,5,6,6,7,7,8,8,8-十三氟辛烷基}二甲基硅烷基)四(二甲基硅烷基)笼形聚倍半硅氧烷，其结构式为
Figure PCTCN2014089720-appb-000013
(2)氟化POSS复合有机硅防覆冰涂层的制备：
将5g上述得到的氟化POSS与20g聚甲基氢硅氧烷(分子量为2000～2500g/mol,p/q＝1)、50g聚甲基乙烯基硅氧烷(分子量为25000～28000g/mol,m/n＝5)加入烧杯中，溶于25g四氢呋喃配成浓度为75wt％的溶液，加入100μg氯铂酸催化剂。超声搅拌1h，溶液呈均匀透明状。取15mL溶液滴涂至20cm×20cm铝板表面，室温下表干1h。随后，将基材放入烘箱中交联，设定温度为80℃，交联时间为4h，最终获得氟化POSS与有机硅材料复合涂层。
所得涂层水接触角滞后为4°，冰剪切强度为27kPa，水接触角为105°。利用SEM和AFM能够观察到宽度在1.0μm左右，褶皱间距在1.0μm左右的褶皱图案。
实施例8：
(1)氟化POSS的制备：
将20g二甲基硅烷基笼形聚倍半硅氧烷与35.1g全氟辛基乙烯加入三口瓶中，加入56.3g二氯甲烷配成40wt％的溶液，加入磁子，打开磁力搅拌，通N2气30min除去体系中的空气。接着加入50μgKarstedts催化剂在80℃下反应36h。待反应结束，利用减压蒸馏的方法除去残留溶剂，得到粗产物，再将粗产物在真空干燥箱中真空干燥一昼夜，得到氟化POSS，即四({3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-十七氟癸烷基}二甲基硅烷基)四(二甲基硅烷基)笼形聚倍半硅氧烷，其结构式为
Figure PCTCN2014089720-appb-000014
(2)氟化POSS复合有机硅防覆冰涂层的制备：
将8g上述得到的氟化POSS与12g聚甲基氢硅氧烷(分子量为2500～3000g/mol,p/q＝1)、20g聚甲基乙烯基硅氧烷(分子量为28000～30000g/mol,m/n＝5)加入烧杯中，溶于60g二甲苯配成浓度为40wt％的溶液，加入100μgKarstedts催化剂。超声搅拌1h，溶液呈均匀透明状。取19mL溶液滴涂至20cm×20cm铝板表面，室温下表干1h。随后，将基材放入烘箱中交联，设定温度为90℃，交联时间为3h，最终获得氟化POSS与有机硅材料复合涂层。
所得涂层水接触角滞后为8°，冰剪切强度为52kPa，水接触角为105°。利用SEM和AFM能够观察到宽度在1.4μm左右，褶皱间距在1.7μm左右的褶皱图案。
实施例9：
(1)氟化POSS的制备：
将20g二甲基硅烷基笼形聚倍半硅氧烷与23.6g甲基丙烯酸十二氟庚酯加入三口瓶中，加入65.4g二氯甲烷配成40wt％的溶液，加入磁子，打开磁力搅拌，通N2气30min除去体系中的空气。接着加入50μgKarstedts催化剂在80℃下反应36h。待反应结束，利用减压蒸馏的方法除去残留溶剂，得到粗产物，再将粗产物在真空干燥箱中真空干燥一昼夜，得到氟化POSS，即三({2,2,3,3,4,4,5,5,6,6,7,7-十二氟庚氧基羰基-甲基乙基}二甲基硅烷基)五(二甲基硅烷基)笼形聚倍半硅氧烷，其结构式为
Figure PCTCN2014089720-appb-000015
(2)氟化POSS复合有机硅防覆冰涂层的制备：
将5g上述得到的氟化POSS与5g聚甲基氢硅氧烷(分子量为2000～2500g/mol,p/q＝1)、10g聚甲基乙烯基硅氧烷(分子量为28000～30000g/mol,m/n＝5)加入烧杯中，溶于80g三氟甲苯配成浓度为20wt％的溶液，加入100μgKarstedts催化剂。超声搅拌1h，溶液呈均匀透明状。取40mL溶液喷涂至20cm×20cm铝板表面，室温下表干1h。随后，将基材放入烘箱中交联，设定温度为110℃，交联时间为2h，最终获得氟化POSS与有机硅材料复合涂层。
所得涂层水接触角滞后为3.5°，冰剪切强度为35.7kPa，水接触角为104°。利用SEM和AFM能够观察到宽度在800nm左右，褶皱间距在850nm左右的褶皱图案。
实施例10：
(1)氟化POSS的制备：
将20g二甲基硅烷基笼形聚倍半硅氧烷与29.5g甲基丙烯酸六氟丁酯加入反应器中，加入115.5g甲苯配成30wt％的溶液，加入磁子，打开磁力搅拌，通N2气30min除去体系中的空气。接着加入50μL氯铂酸催化剂在80℃下反应12h。待反应结束，利用减压蒸馏的方法除去残留溶剂，得到粗产物，再将粗产物在真空干燥箱中真空干燥一昼夜，得到氟化POSS，即六({2,2,3,4,4,4-六氟丁氧基羰基-甲基乙基}二甲基硅烷基)二(二甲基硅烷基)笼形聚倍半硅氧烷，其结构式为
Figure PCTCN2014089720-appb-000016
(2)氟化POSS复合有机硅防覆冰涂层的制备：
将2g上述得到的氟化POSS与13g聚甲基氢硅氧烷(分子量为2500～3000g/mol,p/q＝1)、15g聚甲基乙烯基硅氧烷(分子量为28000～30000g/mol,m/n＝5)加入烧杯中，溶于70g三氟甲苯配成浓度为30wt％的溶液，加入100μg氯铂酸催化剂。超声搅拌1h，溶液呈均匀透明状。采用浸涂的方法在20cm×20cm铝板表面涂膜，室温下表干1h。随后，将基板放入烘箱中交联，设定温度为80℃，交联时间为3h，最终获得氟化POSS与有机硅材料复合涂层。
所得涂层水接触角滞后为6°，冰剪切强度为50kPa，水接触角为103°。利用SEM和AFM可以观察到宽度在550nm左右，褶皱间距在580nm左右的褶皱图案。
实施例11：
(1)氟化POSS的制备：
将20g二甲基硅烷基笼形聚倍半硅氧烷与20.9g甲基丙烯酸十七氟癸酯加入反应器中，加入95.4g甲苯配成30wt％的溶液，加入磁子，打开磁力搅拌，通N2气30min除去体系中的空气。接着加入50μL氯铂酸催化剂在80℃下反应12h。待反应结束，利用减压蒸馏的方法除去残留溶剂，得到粗产物，再将粗产物在真空干燥箱中真空干燥一昼夜，得到氟化POSS，即二({3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-十七氟癸氧基羰基-甲基乙基}二甲基硅烷基)六(二甲基硅烷基)笼形聚倍半硅氧烷，其结构式为
Figure PCTCN2014089720-appb-000017
(2)氟化POSS复合有机硅防覆冰涂层的制备：
将5g上述得到的氟化POSS与30g聚甲基氢硅氧烷(分子量为2000～2500g/mol,p/q＝3)、35g聚甲基乙烯基硅氧烷(分子量为25000～28000g/mol,m/n＝8)加入烧杯中，溶于30g三氟甲苯配成浓度为70wt％的溶液，加入100μg氯铂酸催化剂。超声搅拌1h，溶液呈均匀透明状。采用浸涂的方法在20cm×20cm铝板表面涂膜，室温下表干1h。随后，将基板放入烘箱中交联，设定温度为80℃，交联时间为3h，最终获得氟化POSS与有机硅材料复合涂层。
所得涂层水接触角滞后为7.2°，冰剪切强度为55kPa，水接触角为105°。利用SEM和AFM可以观察到宽度在1.2μm左右，褶皱间距在1.6μm左右的褶皱图案。
实施例12：
(1)氟化POSS的制备：
将20g二甲基硅烷基笼形聚倍半硅氧烷与21.5g全氟癸基乙烯加入反应器中，加入96.8g甲苯配成30wt％的溶液，加入磁子，打开磁力搅拌，通N2气30min除去体系中的空气。接着加入50μL氯铂酸催化剂在80℃下反应12h。待反应结束，利用减压蒸馏的方法除去残留溶剂，得到粗产物，再将粗产物在真空干燥箱中真空干燥一昼夜，得到氟化POSS，即二({3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-二十一氟十二烷基}二甲基硅烷基)六(二甲基硅烷基)笼形聚倍半硅氧烷，其结构式为
Figure PCTCN2014089720-appb-000018
(2)氟化POSS复合有机硅防覆冰涂层的制备：
将1g上述得到的氟化POSS与6g聚甲基氢硅氧烷(分子量为2500～3000g/mol,p/q＝5)、10g聚甲基乙烯基硅氧烷(分子量为28000～30000g/mol,m/n＝10)加入烧杯中，溶于83g三氟甲苯配成浓度为17wt％的溶液，加入100μg氯铂酸催化剂。超声搅拌1h，溶液呈均匀透明状。采用浸涂的方法在20cm×20cm铝板表面涂膜，室温下表干1h。随后，将基板放入烘箱中交联，设定温度为80℃，交联时间为3h，最终获得氟化POSS与有机硅材料复合涂层。
所得涂层水接触角滞后为12.5°，冰剪切强度为60kPa，水接触角为106°。利用SEM和AFM可以观察到宽度在1.6μm左右，褶皱间距在1.9μm左右的褶皱图案。
实施例13：
(1)氟化POSS的制备：
将20g二甲基硅烷基笼形聚倍半硅氧烷与24.2g全氟丁基乙烯加入三口瓶中，加入71.6g三氯甲烷配成30wt％的溶液，加入磁子，打开磁力搅拌，通N2气30min除去体系中的空气。接着加入50μgKarstedts催化剂在90℃下反应36h。待反应结束，利用减压蒸馏的方法除去残留溶剂，得到粗产物，再将粗产物在真空干燥箱中真空干燥一昼夜，得到氟化POSS，即五({3,3,4,4,5,5,6,6,6-九氟己烷基}二甲基硅烷基)三(二甲基硅烷基)笼形聚倍半硅氧烷，其结构式为
Figure PCTCN2014089720-appb-000019
(2)氟化POSS复合有机硅防覆冰涂层的制备：
将6g上述得到的氟化POSS与12g聚甲基氢硅氧烷(分子量为2500～3000g/mol,p/q＝1)、11g聚甲基乙烯基硅氧烷(分子量为25000～28000g/mol,m/n＝5)加入烧杯中，溶于71g二氯甲烷配成浓度为29wt％的溶液，加入167μg氯铂酸催化剂。超声搅拌1h，溶液呈均匀透明状。取10mL溶液旋涂至20cm×20cm铝板表面，旋涂时，先利用600转/分旋涂6s，使液滴铺展均匀，再利用3000转/分旋涂10s室温下表干1h。随后，将基材放入烘箱中交联，设定温度为100℃，交联时间为3h，最终获得氟化POSS与有机硅材料复合涂层。
所得涂层水接触角滞后为5°，冰剪切强度为44kPa，水接触角为104°。利用SEM和AFM能够观察到宽度在790nm左右，褶皱间距在800nm左右的褶皱图案。
以上对本发明做了示例性的描述，应该说明的是，在不脱离本发明的核心的情况下，任何简单的变形、修改或者其他本领域技术人员能够不花费创造性劳动的等同替换均落入本发明的保护范围。

Claims (9)

  1. 氟化多面体低聚倍半硅氧烷复合有机硅防覆冰涂层，其特征在于，组成及各组成质量百分比为：
    氟化多面体低聚倍半硅氧烷：1～25％；
    含氢聚硅氧烷：5～30％；
    乙烯基聚硅氧烷：10～50％；
    催化剂：0.0001％；
    余量为溶剂。
  2. 根据权利要求1所述的氟化多面体低聚倍半硅氧烷复合有机硅防覆冰涂层，其特征在于，氟化多面体低聚倍半硅氧烷的结构式为
    Figure PCTCN2014089720-appb-100001
    式中，2≤x≤6，R为-CH2CH2(CF2)yCF3或-CH2CH(CH3)COORf，其中y＝3、5、7或9，Rf为-CH2CF2CHFCF3，-CH2CH2(CF2)4CHFCF3，-CH2CH2(CF2)5CF3或-CH2CH2(CF2)7CF3中的一种；x由1H-NMR分析得到，即通过氟化POSS的1H-NMR谱图中-SiH中H与-OSi(CH3)2CH 2-中亚甲基上两个H特征峰的积分面积进行计算而得，为若干氟化POSS分子结果的平均值。
  3. 根据权利要求1所述的氟化多面体低聚倍半硅氧烷复合有机硅防覆冰涂层，其特征在于，含氢聚硅氧烷的结构式为：
    Figure PCTCN2014089720-appb-100002
    式中，p/q＝1～5。
  4. 根据权利要求1所述的氟化多面体低聚倍半硅氧烷复合有机硅防覆冰涂层，其特征在于，含氢聚硅氧烷的分子量为2000～3000g/mol。
  5. 根据权利要求1所述的氟化多面体低聚倍半硅氧烷复合有机硅防覆冰涂层，其特征在于，乙烯基聚硅氧烷的结构式为：
    Figure PCTCN2014089720-appb-100003
    式中，m/n＝5～10。
  6. 根据权利要求1所述的氟化多面体低聚倍半硅氧烷复合有机硅防覆冰涂层，其特征在于，乙烯基聚硅氧烷的分子量为25000～30000g/mol。
  7. 根据权利要求1所述的氟化多面体低聚倍半硅氧烷复合有机硅防覆冰涂层，其特征在于，所用催化剂为Karstedts催化剂或氯铂酸催化剂中的一种。
  8. 根据权利要求1所述的氟化多面体低聚倍半硅氧烷复合有机硅防覆冰涂层，其特征在于，所用溶剂为甲苯、二甲苯、三氟甲苯、二氯甲烷、三氯甲烷或四氢呋喃中的一种。
  9. 根据权利要求1所述的氟化多面体低聚倍半硅氧烷复合有机硅防覆冰涂层的制备方法如下：
    将氟化多面体低聚倍半硅氧烷与含氢聚硅氧烷、乙烯基聚硅氧烷、催化剂和溶剂按一定质量百分比配成溶液，超声搅拌1～2h使溶液呈透明状；取一定量溶液涂覆在基板表面，室温下表干，随后放入80～120℃鼓风烘箱中交联2～4h成膜，得到氟化多面体低聚倍半硅氧烷复合有机硅防覆冰涂层。
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