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WO2025001110A1 - 一种具有表面不粘性全氟橡胶制品的制备方法 - Google Patents

一种具有表面不粘性全氟橡胶制品的制备方法 Download PDF

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Publication number
WO2025001110A1
WO2025001110A1 PCT/CN2024/073792 CN2024073792W WO2025001110A1 WO 2025001110 A1 WO2025001110 A1 WO 2025001110A1 CN 2024073792 W CN2024073792 W CN 2024073792W WO 2025001110 A1 WO2025001110 A1 WO 2025001110A1
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Prior art keywords
perfluororubber
product
surface treatment
coating
rubber
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English (en)
French (fr)
Inventor
陈欢
李宏
谢昌杰
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Ic Seal Co Ltd
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Ic Seal Co Ltd
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Publication of WO2025001110A1 publication Critical patent/WO2025001110A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • 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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08J2300/102—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene

Definitions

  • the invention relates to the technical field of layered products, and in particular to a method for preparing a perfluororubber product with non-sticky surface.
  • Perfluororubber products have the characteristics of high cleanliness, heat resistance, chemical resistance, plasma resistance, etc., and are also used in semiconductor and liquid crystal manufacturing equipment. However, perfluororubber products often adhere to the surface of metals, silicon wafers and other materials in contact with them, making them impossible to tear off. This affects the normal operation of semiconductor and liquid crystal manufacturing equipment in positions where switching operations are frequently performed. When mechanical force is used for tearing, it will cause damage to products such as silicon wafers, perfluororubber products, and production equipment, thereby reducing production efficiency and product yield, and further affecting the performance of the equipment.
  • the methods for treating the surface of perfluororubber products to make them non-sticky include: (1) adding additives with low melting point or low molecular weight; (2) plasma treatment of fluororubber products; (3) coating the surface of fluororubber products with silane coupling agents, reactive silicone resins or non-crystalline fluoropolymer resins; (4) blending perfluororesin with perfluororubber raw rubber and using the perfluoroplastic-rich area on the surface of the final product to provide non-stickiness.
  • the above treatment methods have certain problems and need to be further improved, including that the addition of additives may cause the release of gas or the introduction of new pollutants, which has a fatal impact on the application fields with high purity requirements; there is also the problem of adhesion between the different materials of perfluororubber and reactive silicone resin, and the mechanical strength of the silicone resin in the surface treatment layer is not high, and the solvent resistance, oil resistance and chemical resistance are slightly poor, which affects the use of perfluororubber seals; and the price of non-crystalline perfluororesin is very expensive and the output is low, and the method of coating with non-crystalline fluoropolymer cannot be used on a large scale.
  • the method of blending and modifying perfluororubber and perfluororesin is relatively easy to implement for raw material manufacturers of fluororubber/fluororesin, because it is easier to blend the two types of fluoropolymer materials in their original form when they are just polymerized. However, it is difficult to implement for back-end processing manufacturers.
  • the Chinese patent application number CN200810034222.X discloses a water-based polyethersulfone non-stick coating composition and a preparation method thereof that does not contain perfluorooctanoic acid, which is used for non-stick coating of electric rice cookers, but is not intended for surface coating treatment of fluororubber products. Therefore, providing a preparation method for a perfluororubber product with non-stick surface is a technical problem that needs to be solved at present.
  • the present invention provides a method for preparing a perfluororubber product with a non-sticky surface, comprising the following steps: S1. preparing a perfluororubber product: mixing a perfluororubber raw rubber with a vulcanizing agent to obtain a mixed rubber; vulcanizing the mixed rubber at a high temperature to obtain a perfluororubber product;
  • S3 one-step surface treatment The FEP emulsion, the aqueous dispersion of polyethersulfone and SiO 2 are uniformly mixed to obtain a coating a sprayed or dipped on the surface of the perfluororubber product, and the surface is heated to obtain a perfluororubber product pretreated;
  • Two-step surface treatment spraying or dipping the surface of the pretreated perfluororubber product with a non-stick coating a and heating it to obtain a perfluororubber product having a non-stick surface after heating;
  • the surface roughness Ra of the perfluororubber product is greater than 5 ⁇ m
  • the heating temperature in S4 is set to be lower than 360°C.
  • the surface of the perfluororubber product is roughened by sandblasting, coarse grinding, water grinding or the like, residual particles on the surface are brushed off, and degreasing is performed by using an organic solvent.
  • the applicant unexpectedly discovered in the experiment that by roughening and degreasing the surface of the perfluororubber products and then performing a two-step surface treatment, especially when the surface roughness Ra of the perfluororubber products after treatment is greater than 5 ⁇ m, the bonding strength between the surface of the perfluororubber products and the coating can be improved, and the problem of surface coating falling off will not occur under the action of external force, especially when external force is applied in high-temperature water, the surface coating of the perfluororubber products will not fall off, and no particles will fall off.
  • the surface coating has high fastness and improves the permanent service life of the perfluororubber products.
  • the perfluororubber products have good surface non-stickiness during use, especially when they come into contact with the surfaces of materials such as metals and silicon wafers under pressure, they are easy to tear off, and will not cause damage to products such as silicon wafers, perfluororubber products, and production equipment, thereby improving production efficiency and product yield.
  • the high temperature vulcanization in S1 is a vulcanization process using primary compression vulcanization and secondary vulcanization.
  • the mixed rubber is placed at 160-180° C. and heated for 10-20 minutes, while maintaining a pressure of 5 MPa for primary compression vulcanization to obtain vulcanized rubber a; the vulcanized rubber a is placed at 280-300° C. and heated for at least 20 hours for secondary vulcanization to obtain a perfluororubber product.
  • the mixed rubber is heated at 170° C. for 15 minutes, and maintained at a pressure of 5 MPa for primary compression vulcanization to obtain vulcanized rubber a; the vulcanized rubber a is heated at 290° C. for at least 20 hours for secondary vulcanization to obtain a perfluororubber product.
  • the perfluororubber used in S1 may contain 45-80 mol % of tetrafluoroethylene monomer units, 15-55 mol % of perfluoroether monomer units, and 0.1-5 mol % of cross-linking point monomer units of perfluororubber.
  • the cross-linking point monomer unit of the perfluororubber contains one or a combination of functional groups such as C-X (X is iodine or bromine), nitrile, carboxyl or alkoxycarbonyl.
  • the filler includes an organic filler or an inorganic filler.
  • the filler includes one or both of carbon black and silicon dioxide.
  • the vulcanizing agent comprises one or more combinations of organometallic compounds, amino-containing organic compounds or functionalized derivatives thereof.
  • the vulcanizing agent is a bisaminophenol vulcanizing agent.
  • the raw materials for preparing the perfluororubber product in S1 also include a vulcanization accelerator.
  • the vulcanization accelerator includes a combination of one or more of multifunctional maleimide, N,N'-m-phenylene bismaleimide, and triallyl isocyanurate.
  • the raw material for preparing the coating a is selected from at least one of fluororesin, fluororubber raw rubber, tackifying composition and dispersant.
  • the fluororubber raw rubber may be in the form of particles, powder or liquid dispersion.
  • the powder and dispersion forms are preferred.
  • the melting point of the fluororesin is 250-350°C.
  • the fluororesin may be in the form of powder or liquid dispersion.
  • the fluororesin is selected from one or more combinations of polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and ethylene-tetrafluoroethylene copolymer.
  • the adhesion-promoting composition comprises a thermoplastic resin and a vulcanizing agent.
  • the content of the viscosity-increasing component is 0.05wt%-5wt%, preferably 0.1wt%-2wt%.
  • the vulcanizing agent is selected from one or more of organic peroxides, inorganic peroxides, aminobenzene, bisaminophenol compounds, oxazole, imidazole, thiazole, and triazine compounds.
  • the adhesion-promoting composition may further include a vulcanization accelerator; the vulcanization accelerator is selected from the group consisting of multifunctional maleimide PAPI, N,N'-m-phenylene bismaleimide, and triallyl isocyanurate. or more.
  • a vulcanization accelerator is selected from the group consisting of multifunctional maleimide PAPI, N,N'-m-phenylene bismaleimide, and triallyl isocyanurate. or more.
  • the dispersant is selected from at least one of water, an organic solvent, a surfactant, and a modifying additive.
  • the inventors found during the experiment that by using a dispersant, the raw material components can be combined to form a uniformly dispersed liquid composition, and the viscosity, solid content and surface tension of the liquid composition can be further adjusted, and the coating a can be further uniformly dispersed on the surface of the perfluororubber product and can be uniformly adhered to the surface of the perfluororubber product, which is beneficial for the coating a to form a thin film layer with uniform thickness and good adhesion during curing.
  • thermoplastic resin is greater than 200°C.
  • thermoplastic resin includes one or more combinations of amide groups, imide groups, sulfide groups, sulfone groups, ether groups, and phenylene groups.
  • thermoplastic resin is selected from one or more of polyamide-imide, polyphenylene sulfide, polyether sulfone, and liquid crystal polymer.
  • thermoplastic resin is one or both of polyethersulfone and polyamideimide.
  • the fluororesin in the coating a is selected from one or more combinations of polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and ethylene-tetrafluoroethylene copolymer.
  • the fluororubber raw rubber may contain nitrile groups.
  • the raw materials available for the fluororubber raw rubber include FFKM1 and FFKM2.
  • the FFKM1 is a nitrile-containing perfluororubber, which is purchased from 3M Company of the United States and has a model number of PFE-131TZ.
  • the FFKM2 is a heat-resistant perfluororubber, and its manufacturer and model are Solvay of the United States, and its model is PFR 95.
  • the raw material for preparing the non-stick coating a includes a fluororesin having a melting point of 250-350°C.
  • the non-stick coating a is in the form of powder or emulsion.
  • the fluororesin is selected from one or more combinations of polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and ethylene-tetrafluoroethylene copolymer.
  • examples of fluororesins include MJ-102 from Mitsui Chemours, PFA powder with a particle size of about 5-50 ⁇ m, and FEP emulsion of FR463 from Shanghai San Ai Fu.
  • the PFA is a tetrafluoroethylene-perfluoroalkyl ether copolymer.
  • the FEP is a tetrafluoroethylene-hexafluoropropylene copolymer.
  • the heating temperature in S4 is 10-60° C. higher than the melting point of the resin material contained in the non-stick coating a.
  • the heating temperature in S4 is set to be 20-50° C. higher than the melting point of the non-stick coating material, and is controlled to be lower than the temperature at which the fluororubber material begins to degrade.
  • coating a is used for one-step surface treatment
  • the raw materials for preparing coating a include fluororesin, fluororubber raw rubber, tackifying composition, and dispersant
  • the resin content is 30-95wt%
  • the fluororubber content is 0-40wt%
  • the thermoplastic resin is 0-5wt%
  • the dispersant is the remainder
  • polyethersulfone or polyamide-imide with a heat deformation temperature greater than 200°C is used as the thermoplastic resin for perfluororubber.
  • the rubber product is subjected to one-step surface treatment, and after the surface treatment, it is heated again to dry at a temperature higher than the melting point of the fluororesin and the vulcanization temperature of the fluororubber, so that the outer layer of the perfluororubber product forms an intermediate bonding layer, and the powdered or emulsion fluororesin used in the two-step surface treatment is used for two-step surface treatment.
  • the melting point of the fluororesin is 250-350°C, and the heating temperature is set below 360°C. This can improve the bonding strength between the coatings after the two-step surface treatment of the perfluororubber product, so that the coating after the two-step surface treatment will not fall off at high temperatures. It can also improve the problem of yellowing of perfluororubber products during high-temperature treatment.
  • Figure 1 is an O-ring shape diagram.
  • FIG. 2 is a diagram showing the peeling state of the surface treatment layer of the non-sticky perfluororubber product prepared in Example 2.
  • FIG3 is a diagram showing the yellowing state of the surface non-sticky perfluororubber product substrate prepared in Example 5.
  • the surface treatment method defined in the present invention can improve the problem of surface stickiness of perfluororubber products, and the surface coating will not fall off under the action of external force, thereby achieving a permanent sealing effect.
  • the perfluororubber product can be The surface has good non-stick effect, especially when it comes into contact with the surface of metal, silicon wafer and other materials under pressure. It is easy to tear off and will not cause damage to products such as silicon wafers, perfluororubber products, and production equipment, thereby improving production efficiency and product yield.
  • a method for preparing a perfluororubber product with non-sticky surface comprises the following steps:
  • the surface of the perfluororubber product is roughened by sandblasting, rough grinding, water grinding, etc., the residual particles on the surface are brushed off, and acetone is used for degreasing. After the surface treatment in step S2, the surface roughness Ra of the perfluororubber product is greater than 5 ⁇ m;
  • One-step surface treatment 100 g of PFA powder, 20 g of FFKM1 rubber powder, and 0.3 g of bisaminophenol vulcanizing agent were mixed evenly to obtain coating a, and coating a was sprayed on the surface of the perfluororubber product by electrostatic spraying, and the perfluororubber product was heated to 320°C at a heating rate of 2°C/min, and maintained at this temperature for 15 min to obtain a surface pretreated perfluororubber product;
  • the nitrile-based perfluororubber raw rubber in S1 is purchased from FFKM1 of 3M Company of the United States, with model number PFE-131TZ.
  • the bisaminophenol vulcanizing agent in S1 is 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, and its CAS number is 83558-87-6.
  • the spraying amount of coating a is 100 g/m 2 .
  • the PFA is a tetrafluoroethylene-perfluoroalkyl ether copolymer.
  • the PFA powder used in S3 was purchased from Japan Mitsui Chemours, model number MJ-102.
  • the particle size is about 5-50 ⁇ m.
  • the bisaminophenol vulcanizing agent in S3 is 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, and its CAS number is 83558-87-6.
  • the amount of PFA powder sprayed is 100 g/m 2 .
  • the PFA powder used in S4 is purchased from Mitsui Chemours of Japan, model number is MJ-102, and particle size is about 5-50 ⁇ m.
  • a method for preparing a perfluororubber product with non-sticky surface comprises the following steps:
  • perfluororubber products 100 g of perfluororubber raw rubber, 20 g of carbon black, 10 g of silica, and 3 g of a vulcanizing agent are mixed on an open mill to obtain a mixed rubber; the mixed rubber is heated at 170°C for 15 min, and a primary compression vulcanization is performed at a pressure of 5 MPa to obtain a vulcanized rubber a; the vulcanized rubber a is heated at 290°C for 20 h for secondary vulcanization to obtain a perfluororubber product;
  • the surface of the perfluororubber product is roughened by sandblasting, rough grinding, water grinding, etc., the residual particles on the surface are brushed off, and acetone is used for degreasing. After the surface treatment in step S2, the surface roughness Ra of the perfluororubber product is greater than 5 ⁇ m;
  • One-step surface treatment 100 g of FEP latex, 20 g of raw rubber dispersion of perfluororubber, 1 g of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 3 g of triallyl isocyanurate, 10 g of silica and 30 g of organic solvent were mixed uniformly by a homogenizer to obtain a coating a, and the coating a was sprayed on the surface of the perfluororubber product, heated to 280 ° C and maintained for 10 min to obtain a surface pretreated perfluororubber product;
  • Two-step surface treatment spray FEP emulsion on the surface of the pre-treated perfluororubber product, and heat it at 290°C for 10 minutes to obtain a perfluororubber product with a non-sticky surface.
  • the perfluororubber raw rubber used in S1 is heat-resistant perfluororubber, and the heat-resistant perfluororubber is purchased from Solvay in the United States, and the model is PFR 95.
  • the carbon black used in S1 is purchased from Cabot Corporation of the United States, with a model number of N330.
  • the silicon dioxide used in S1 is purchased from Evonik
  • the vulcanizing agent used in S1 is 2,5-dimethyl-2,5-di-tert-butyl peroxyhexane, with a CAS number of 78-63-7.
  • the FEP is a tetrafluoroethylene-hexafluoropropylene copolymer.
  • the FEP emulsion used in S3 was purchased from Shanghai San Ai Fu, with a model number of FR463.
  • the dispersion liquid of the raw rubber of perfluoro rubber used in S3 contains 30 wt % of the raw rubber of perfluoro rubber and 70 wt % of the aqueous solution containing fluorine-containing surfactant.
  • the mass ratio of the fluorinated surfactant to water in the aqueous solution of the fluorinated surfactant is 0.5:100.
  • the fluorinated surfactant can be purchased from Jinan Qifu New Material Technology Co., Ltd., model number is perfluorohexylamine oxide CF386N.
  • the perfluororubber raw rubber was purchased from Solvay in the United States, and the model is PFR 95.
  • the organic solvents used in S3 are butanol and ethyl acetate; the weight of the butanol and ethyl acetate is
  • the ratio is 1:1.
  • the FEP emulsion used in S4 was purchased from Shanghai San Ai Fu, with a model number of FR463.
  • the spraying amount of coating a is 100 g/m 2 .
  • the amount of FEP emulsion sprayed is 100 g/m 2 .
  • a method for preparing a perfluororubber product with non-sticky surface comprises the following steps:
  • the surface of the perfluororubber product is roughened by sandblasting, rough grinding, water grinding, etc., the residual particles on the surface are brushed off, and acetone is used for degreasing. After the surface treatment in step S2, the surface roughness Ra of the perfluororubber product is greater than 5 ⁇ m;
  • One-step surface treatment 100 g of FEP emulsion, 5 g of aqueous dispersion of polyethersulfone and 10 g of SiO 2 were mixed to obtain coating a, and the coating a was sprayed on the surface of the perfluororubber product, heated to 280 ° C and maintained for 10 min to obtain a surface pretreated perfluororubber product;
  • Two-step surface treatment spray FEP emulsion on the surface of the pre-treated perfluororubber product, and heat it at 300°C for 10 minutes to obtain a perfluororubber product with a non-sticky surface.
  • the nitrile-based perfluororubber raw rubber in S1 is purchased from FFKM1 of 3M Company of the United States, with model number PFE-131TZ.
  • the bisaminophenol curing agent in S1 is 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, CAS The number is 83558-87-6.
  • the FEP is a tetrafluoroethylene-hexafluoropropylene copolymer.
  • the FEP emulsion used in S3 was purchased from Shanghai San Ai Fu, with a model number of FR463.
  • the aqueous dispersion of polyethersulfone in S3 was purchased from Quark WP-421.
  • the FEP emulsion used in S4 was purchased from Shanghai San Ai Fu, with a model number of FR463.
  • the spraying amount of coating a is 100 g/m 2 .
  • the amount of FEP emulsion sprayed is 100 g/m 2 .
  • a method for preparing a perfluororubber product with non-sticky surface comprises the following steps:
  • the surface of the perfluororubber product is roughened by sandblasting, rough grinding, water grinding, etc., the residual particles on the surface are brushed off, and acetone is used for degreasing. After the surface treatment in step S2, the surface roughness Ra of the perfluororubber product is greater than 5 ⁇ m;
  • One-step surface treatment 100 g of PTFE emulsion and 1 g of polyamide-imide aqueous dispersion were mixed to obtain coating a, and the coating a was sprayed on the surface of the perfluororubber product and heated in an oven at 340 ° C for 10 min to obtain a surface pretreated perfluororubber product;
  • the surface pretreated perfluororubber product is immersed in PTFE emulsion for 20 seconds, and then placed in an oven at 340°C for 10 minutes to obtain a perfluororubber product with a non-stick surface.
  • the nitrile-based perfluororubber raw rubber in S1 is purchased from FFKM1 of 3M Company of the United States, with model number PFE-131TZ.
  • the bisaminophenol vulcanizing agent in S1 is 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, and its CAS number is 83558-87-6.
  • the PTFE emulsion used in S3 was purchased from San Ai Fu FR303A.
  • the polyamide-imide aqueous dispersion used in S3 was purchased from Quark New Materials SI-308.
  • the PTFE emulsion used in S4 was purchased from San Ai Fu FR303A.
  • the spraying amount of coating a is 100 g/m 2 .
  • a method for preparing a perfluororubber product with non-sticky surface comprises the following steps:
  • the surface of the perfluororubber product is roughened by sandblasting, rough grinding, water grinding, etc., the residual particles on the surface are brushed off, and acetone is used for degreasing. After the surface treatment in step S2, the surface roughness Ra of the perfluororubber product is greater than 5 ⁇ m;
  • One-step surface treatment 100 g of PTFE emulsion and 1 g of polyamide-imide aqueous dispersion were mixed to obtain coating a, and the coating a was sprayed on the surface of the perfluororubber product and heated in an oven at 340 ° C for 10 min to obtain a surface pretreated perfluororubber product;
  • the surface pretreated perfluororubber product is immersed in PTFE emulsion for 20 seconds, and then placed in an oven at 360°C for 10 minutes to obtain a perfluororubber product with a non-stick surface.
  • the nitrile-based perfluororubber raw rubber in S1 is purchased from FFKM1 of 3M Company of the United States, with model number PFE-131TZ.
  • the bisaminophenol vulcanizing agent in S1 is 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, and its CAS number is 83558-87-6.
  • the PTFE emulsion used in S3 was purchased from San Ai Fu FR303A.
  • the polyamide-imide aqueous dispersion used in S3 was purchased from Quark New Materials SI-308.
  • the PTFE emulsion used in S4 was purchased from San Ai Fu FR303A.
  • the spraying amount of coating a is 100 g/m 2 .
  • the perfluororubber product is a perfluororubber seal, and its shape and structure are an O-ring.
  • the shape of the O-ring is shown in FIG1 .
  • the perfluororubber products prepared in the embodiments without falling solid matter were tested. Specifically, 10 perfluorororubber products with non-sticky surface prepared in Embodiment 1, Embodiment 3 and Embodiment 5 were placed in a 304 stainless steel test mold with a roughness of no more than 1.0 ⁇ m, and the fastening nut was tightened to make the deformation of the perfluororubber product (O-ring) 25%. After being placed at 204°C for 24 hours, they were taken out and cooled to room temperature. After 3 hours, the minimum tensile force required to pull the O-ring apart from the stainless steel mold was measured by a tensile testing machine. The tensile speed was 1 mm/s. The measured value was the adhesion value of the O-ring under this condition. The maximum and minimum values were removed and the average value was taken. The test results are shown in Table 1.
  • the vacuum degree set when O 2 and the blend of O 2 and CF 4 in a volume ratio of 1:1 were used as plasma treatment gases for the test was 15 mtorr, and the vacuum degree set when CF 4 was used as the plasma treatment gas for the test was 40 mtorr; the gas flow rate of the plasma treatment gas was set to 80 sccm; 10 perfluororubber products with non-sticky surfaces prepared in Examples 1-5 were tested, the maximum and minimum values were removed, and the average value was taken.
  • the test results are shown in Table 1.

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Abstract

本发明涉及层状产品技术领域，具体涉及一种具有表面不粘性全氟橡胶制品的制备方法，包括以下步骤：S1.制备全氟橡胶制品：将全氟橡胶生胶与填料或硫化剂进行混合后得到混炼胶；将混炼胶进行硫化得到全氟橡胶制品；S2.表面处理：对全氟橡胶制品进行表面粗糙化和去油脂处理；S3.一步表面处理：将涂料a喷涂或浸渍在全氟橡胶制品的表面，进行加热后得到表面预处理的全氟橡胶制品；S4.两步表面处理：在表面预处理的全氟橡胶制品表面进行喷涂或浸渍不粘性涂料a并进行加热得到具有表面不粘性全氟橡胶制品。通过采用本发明中限定的表面处理方法可以改善全氟橡胶制品表面粘性的问题，在外力的作用下也不会出现表面涂层的脱落。

Description

一种具有表面不粘性全氟橡胶制品的制备方法 技术领域
本发明涉及层状产品技术领域，具体涉及一种具有表面不粘性全氟橡胶制品的制备方法。
背景技术
全氟橡胶制品具有高洁净度、耐热性、耐化学性、耐等离子体等特性，并且也被应用到半导体、液晶制造设备中，但全氟橡胶制品常黏附于与之接触的金属、硅片等材质的表面，造成无法撕离，并影响了半导体、液晶制造设备在频繁执行开关操作的位置上无法正常运行，当采用机械力进行撕离时会造成硅片、全氟橡胶制品、生产设备等产品的损坏，从而降低了生产效率和产品的良品率，并进一步影响到设备的性能。
目前对于全氟橡胶制品进行表面不粘性处理的方法包括：(1)加入低熔点或低分子量的添加剂原料；(2)对氟橡胶制品进行等离子处理；(3)采用硅烷偶联剂、反应性硅树脂或用非结晶型氟聚合物树脂制备涂层对氟橡胶制品进行表面涂层；(4)采用全氟树脂与全氟橡胶生胶进行共混，利用最终制品表面的全氟塑料富集区域提供不粘性。采用上述处理方法会存在一定的问题，需进一步改进，包括加入添加剂可能会引起气体的释放或引入新的污染物，对于纯净度要求高的应用领域有致命的影响；并且也存在全氟橡胶与反应性硅树脂不同材质间的粘结问题，且表面处理层硅树脂的力学强度不高，耐溶剂性、耐油性及耐化学品性能稍差，影响全氟橡胶密封件的使用场合；并且非结晶型全氟树脂的价格十分昂贵，产量低，用非结晶系氟聚合物涂覆的方法也无法大规模使用。将全氟橡胶与全氟树脂进行共混改性的方法对氟橡胶/氟树脂的原材料厂家而言时比较容易实现，因为两类氟聚合物材料以刚聚合出时的原始形态进行共混比较容易实现，对于后端的加工厂商而言，难以实施。
专利申请号为CN200810034222.X的中国专利公开一种不含全氟辛酸的水性聚醚砜不粘涂料组成及其制备方法，用于电饭锅的不粘涂层，并不是针对氟橡胶制品进行表面涂层处理。因此，提供一种具有表面不粘性全氟橡胶制品的制备方法是目前需要解决的技术问题。
发明内容
为了解决上面问题，本发明提供了一种具有表面不粘性全氟橡胶制品的制备方法，包括以下步骤：S1.制备全氟橡胶制品：将全氟橡胶生胶与硫化剂进行混合后得到混炼胶；将混炼胶进行高温硫化得到全氟橡胶制品；
S2.表面处理：对全氟橡胶制品进行表面粗糙化和去油脂处理；
S3.一步表面处理：将FEP乳液、聚醚砜的水性分散液以及SiO2混合均匀得到涂料a喷涂或浸渍在全氟橡胶制品的表面，进行加热后得到表面预处理的全氟橡胶制品；
S4.两步表面处理：在表面预处理的全氟橡胶制品表面进行喷涂或浸渍不粘性涂料a并进行加热，加热后得到具有表面不粘性全氟橡胶制品；
所述S2中对全氟橡胶制品进行表面粗处理后全氟橡胶制品的表面粗糙度Ra大于5μm；
所述S4中加热的温度设置低于360℃。
进一步的，所述S2中对全氟橡胶制品的表面采用喷砂、粗磨、水磨等方法进行表面粗糙化处理，刷去表面残留的颗粒物，采用有机溶剂进行脱脂。
进一步地，所述S2中采用丙酮对全氟橡胶制品的表面脱脂。
为了改善全氟橡胶制品表面粘性的问题，申请人在实验中意外发现，通过对全氟橡胶制品进行表面粗糙化和去油脂处理后再进行两步表面处理，特别是处理后全氟橡胶制品的表面粗糙度Ra大于5μm时，可以提高全氟橡胶制品表面与涂层的结合牢度，并且在外力的作用下也不会出现表面涂层脱落的问题，特别是在高温水中进行外力作用时全氟橡胶制品的表面涂层不会出现脱落，不产生颗粒物的掉落，表面涂层的牢度高，并且提高了全氟橡胶制品的永久性使用寿命，并且全氟橡胶制品在使用过程中的表面不粘性效果好，特别是在受压下与金属、硅片等材质的表面进行接触时，易撕离，不会造成硅片、全氟橡胶制品、生产设备等产品的损坏，提升了生产效率和产品的良品率。
优选地，所述S1中高温硫化为采用一次模压硫化和二次硫化的硫化工艺。
进一步地，所述将混炼胶放置到160-180℃下加热10-20min，同时保持在5MPa的压力下进行一次模压硫化得到硫化胶a；将硫化胶a放置到280-300℃下加热至少20h进行二次硫化得到全氟橡胶制品。
进一步地，将混炼胶放置到170℃下加热15min，同时保持在5MPa的压力下进行一次模压硫化得到硫化胶a；将硫化胶a放置到290℃下加热至少20h进行二次硫化得到全氟橡胶制品。
优选地，所述S1中采用的全氟橡胶可包含45-80mol％的四氟乙烯单体单元，15-55mol％的全氟醚单体单元，以及0.1-5mol％的全氟橡胶的交联点单体单元。
优选地，所述全氟橡胶的交联点单体单元含有C-X(X为碘或溴)、腈基、羧基或烷氧基羰基等官能团中的一种或几种的组合。
优选地，所述填料包括有机填料或无机填料。
进一步的，所述填料包括炭黑、二氧化硅中的一种或两种。
优选地，所述硫化剂包括有机金属化合物、含氨基的有机化合物或其官能化的衍生物中的一种或多种的组合。
进一步的，所述硫化剂为双氨基苯酚硫化剂。
优选地，所述S1中全氟橡胶制品的制备原料中还包括硫化促进剂。
优选地，所述硫化促进剂包括多官能团马来酰亚胺、N,N'-间苯撑双马来酰亚胺、三烯丙基异氰脲酸酯中的一种或多种的组合。
优选地，所述涂料a的制备原料选自氟树脂、氟橡胶生胶、增粘组合物、分散剂中的至少一种。
优选地，所述氟橡胶生胶的形态可为颗粒状、粉末或液体分散液，根据涂覆用涂层材料的形态不同，分别优选粉末和分散液形态。
优选地，所述氟树脂的熔点为250-350℃。
优选地，所述氟树脂形态可为粉末或液体分散液。
优选地，所述氟树脂选自聚四氟乙烯、四氟乙烯-全氟烷基醚共聚物、四氟乙烯六氟丙烯共聚物、乙烯-四氟乙烯共聚物中的一种或多种的组合。
优选地，所述增粘组合物包括热塑性树脂、硫化剂。
进一步地，所述增粘组分的含量为0.05wt％-5wt％，优选为0.1wt％-2wt％。
优选地，所述硫化剂选自有机过氧化物、无机过氧化物、氨基苯、双氨基苯酚类化合物、噁唑、咪唑、噻唑、三嗪类化合物中的一种或多种。
优选地，所述增粘组合物还可包括硫化促进剂；所述硫化促进剂选自多官能团马来酰亚胺PAPI、N,N'-间苯撑双马来酰亚胺、三烯丙基异氰脲酸酯中的一种 或多种。
优选地，所述分散剂选自水、有机溶剂、表面活性剂、改性添加剂中的至少一种。
发明人在实验过程中发现，通过采用分散剂可以将采用的原料组分共同形成均匀分散的液体组合物，并能进一步调整液体组合物的粘度、固含量和表面张力，并进一步使涂料a在全氟橡胶制品表面均匀分散，并能均匀地附着在全氟橡胶制品表面，有利涂料a在进行固化时能形成厚度均匀、附着性良好的薄膜层。
进一步地，所述热塑性树脂的热变形温度大于200℃。
进一步地，所述热塑性树脂中包括酰胺基、酰亚胺基、硫醚基、砜基、醚基、次苯基中的一种或多种的组合。
进一步地，所述热塑性树脂选自聚酰胺酰亚胺、聚苯硫醚、聚醚砜、液晶聚合物中的一种或多种。
进一步地，所述热塑性树脂为聚醚砜、聚酰胺酰亚胺中的一种或两种。
进一步地，所述涂料a中的氟树脂选自聚四氟乙烯、四氟乙烯-全氟烷基醚共聚物、四氟乙烯六氟丙烯共聚物、乙烯-四氟乙烯共聚物中的一种或多种的组合。
优选地，所述氟橡胶生胶中可包含腈基。
作为一种优选的实例，所述氟橡胶生胶可选用的原料包括FFKM1、FFKM2。
所述FFKM1为含腈基全氟橡胶，其购买厂家为美国3M公司，型号为PFE-131TZ。
所述FFKM2为耐热型全氟橡胶，其购买厂家和型号为美国苏威(Solvay)，型号为PFR 95。
优选地，所述不粘性涂料a的制备原料包括熔点为250-350℃的氟树脂。
优选地，所述不粘性涂料a的状态为粉末状或乳液状。
优选地，所述氟树脂选自聚四氟乙烯、四氟乙烯-全氟烷基醚共聚物、四氟乙烯六氟丙烯共聚物、乙烯-四氟乙烯共聚物中的一种或多种的组合。
在一种实施方式中作为氟树脂的实例，可列举的有日本三井科慕MJ-102，粒径约5-50μm的PFA粉末、上海三爱富FR463的FEP乳液。
所述PFA为四氟乙烯-全氟烷基醚共聚物。
所述FEP为四氟乙烯六氟丙烯共聚物。
优选地，所述S4中加热的温度为大于不粘性涂料a中包含树脂材料熔点10-60℃。
进一步地，所述S4中加热的温度设置为高于不粘性涂层材料熔点温度20-50℃，并控制在低于氟橡胶材料开始发生降解劣化的温度。
为了提高对全氟橡胶制品进行两步表面处理后涂层间的结合牢度，申请人在实验中创造性的发现，通过进行一步表面处理时，采用涂料a进行一步表面处理，并且涂料a的制备原料中包括氟树脂、氟橡胶生胶、增粘组合物、分散剂时，并且树脂含量为30-95wt％、氟橡胶含量为0-40wt％、热塑性树脂0-5wt％，分散剂余量时，采用热变形温度大于200℃的聚醚砜或聚酰胺酰亚胺作为热塑性树脂对全氟橡胶制品进行一步表面处理，经过表面处理后再加热时高于氟树脂的熔点和氟橡胶的硫化温度下进行干燥，使全氟橡胶制品的外层形成中间粘结层，并通过进行两步表面处理时采用的粉末状或乳液状的氟树脂进行两步表面处理，所述氟树脂的熔点为250-350℃，并且加热的温度设置低于360℃时，可以提高全氟橡胶制品进行两步表面处理后涂层间的结合牢度，使两步表面处理后的涂层在高温下不会出现层脱落的问题。并且可以改善全氟橡胶制品在高温处理时出现黄变的问题。
附图说明
图1为O型圈形状图。
图2为实施例2制备得到的表面不粘性全氟橡胶制品表面处理层脱落状态图。
图3为实施例5制备得到的表面不粘性全氟橡胶制品基材黄变状态图。
有益效果
1.通过采用本发明中限定的表面处理方法可以改善全氟橡胶制品表面粘性的问题，在外力的作用下也不会出现表面涂层的脱落，实现永久性密封的效果。
2.通过采用本发明中限定的表面处理方法，使全氟橡胶制品在高温水中进行外力作用时，全氟橡胶制品的表面涂层不会出现脱落，不产生颗粒物的掉落，表面涂层的牢度高。
3.通过采用本发明中限定的表面处理方法，提高了全氟橡胶制品的使用寿命。
4.通过采用本发明中限定的表面处理方法，使全氟橡胶制品在使用过程中的 表面不粘性效果好，特别是在受压下与金属、硅片等材质的表面进行接触时，易撕离，不会造成硅片、全氟橡胶制品、生产设备等产品的损坏，提升了生产效率和产品的良品率。
5.通过采用本发明中限定的表面处理方法，提高了全氟橡胶制品进行两步表面处理后涂层间的结合牢度。
具体实施方式
实施例1
一种具有表面不粘性全氟橡胶制品的制备方法，包括以下步骤：
S1.制备全氟橡胶制品：将1g双氨基苯酚硫化剂与100g含腈基全氟橡胶生胶在开炼机上进行混炼后得到混炼胶；将混炼胶放置到170℃下加热15min，同时保持5MPa的压力下进行一次模压硫化得到硫化胶a；将硫化胶a放置到290℃下加热20h进行二次硫化得到全氟橡胶制品；
S2.表面处理：对全氟橡胶制品的表面采用喷砂、粗磨、水磨等方法进行表面粗糙化处理，刷去表面残留的颗粒物，采用丙酮进行脱脂，经过S2步骤的表面处理，所述全氟橡胶制品的表面粗糙度Ra大于5μm；
S3.一步表面处理：取100g的PFA粉末、20gFFKM1胶粉微粉、0.3g双氨基苯酚类硫化剂混合均匀得到涂料a，将涂料a通过静电喷涂的方法喷涂在全氟橡胶制品的表面，并以2℃/min的升温速度将全氟橡胶制品加热至320℃，并在此温度下保持15min得到表面预处理的全氟橡胶制品；
S4.两步表面处理：在表面预处理的全氟橡胶制品表面利用静电喷涂方法涂覆PFA粉末，以2℃/min的升温速度升温至330℃，并在330℃下保持10min得到具有表面不粘性全氟橡胶制品。
所述S1中含腈基全氟橡胶生胶的购买厂家为美国3M公司的FFKM1，型号为PFE-131TZ。
所述S1中双氨基苯酚硫化剂为2,2-双(3-氨基-4-羟基苯基)-六氟丙烷，CAS号为83558-87-6。
所述S3中一步表面处理过程中，使用涂料a的喷涂量为100g/m2。
所述PFA为四氟乙烯-全氟烷基醚共聚物。
所述S3中采用的PFA粉末的购买厂家为日本三井科慕，型号为MJ-102， 粒径约5-50μm。
所述S3中双氨基苯酚类硫化剂为2,2-双(3-氨基-4-羟基苯基)-六氟丙烷，CAS号为83558-87-6。
所述S4中两步表面处理过程中，使用PFA粉末喷涂量为100g/m2。
所述S4中采用的PFA粉末的购买厂家为日本三井科慕，型号为MJ-102，粒径约5-50μm。
实施例2
一种具有表面不粘性全氟橡胶制品的制备方法，包括以下步骤：
S1.制备全氟橡胶制品：将100g全氟橡胶生胶、20g炭黑、10g二氧化硅、3g硫化剂在开炼机上进行混炼后得到混炼胶；将混炼胶放置到170℃下加热15min，同时保持5MPa的压力下进行一次模压硫化得到硫化胶a；将硫化胶a放置到290℃下加热20h进行二次硫化得到全氟橡胶制品；
S2.表面处理：对全氟橡胶制品的表面采用喷砂、粗磨、水磨等方法进行表面粗糙化处理，刷去表面残留的颗粒物，采用丙酮进行脱脂，经过S2步骤的表面处理，所述全氟橡胶制品的表面粗糙度Ra大于5μm；
S3.一步表面处理：将FEP乳液100g、全氟橡胶的生胶分散液20g、2,5-二甲基-2,5-双(叔丁基过氧)己烷1g、三烯丙基异氰脲酸酯3g、二氧化硅10g以及30g有机溶剂，利用均质机混合均匀得到涂料a，将涂料a喷涂在全氟橡胶制品的表面，加热至280℃并保持10min得到表面预处理的全氟橡胶制品；
S4.两步表面处理：在表面预处理的全氟橡胶制品表面进行喷涂FEP乳液，并置于290℃下加热10min得到具有表面不粘性全氟橡胶制品。
所述S1中采用全氟橡胶生胶为耐热型全氟橡胶，所述耐热型全氟橡胶的购买厂家为美国苏威(Solvay)，型号为PFR 95。
所述S1中采用炭黑的购买厂家为美国卡博特，型号为N330。
所述S1中采用二氧化硅的购买厂家为赢创
所述S1中采用硫化剂为2,5-二甲基-2,5-双叔丁基过氧化己烷，CAS号为78-63-7。
所述FEP为四氟乙烯六氟丙烯共聚物。
所述S3中采用FEP乳液的购买厂家为上海三爱富，型号为FR463。
所述S3中采用全氟橡胶的生胶的分散液中包含30wt％全氟橡胶生胶和70wt％含有含氟表面活性剂的水溶液。
所述含氟表面活性剂的水溶液中含氟表面活性剂与水的质量比为0.5:100。
所述含氟表面活性剂可购买的厂家为济南齐氟新材料技术有限公司，型号全氟己基氧化胺CF386N。
所述全氟橡胶生胶的购买厂家为美国苏威(Solvay)，型号为PFR 95。
所述S3中采用的有机溶剂为丁醇和乙酸乙酯；所述丁醇与乙酸乙酯的重量
比为1：1。
所述S4中采用FEP乳液的购买厂家为上海三爱富，型号为FR463。
所述S3中一步表面处理过程中，使用涂料a的喷涂量为100g/m2。
所述S4中两步表面处理过程中，使用FEP乳液喷涂量为100g/m2。
实施例3
一种具有表面不粘性全氟橡胶制品的制备方法，包括以下步骤：
S1.制备全氟橡胶制品：将1g双氨基苯酚硫化剂与100g含腈基全氟橡胶生胶在开炼机上进行混炼后得到混炼胶；将混炼胶放置到170℃下加热15min，同时保持5MPa的压力下进行一次模压硫化得到硫化胶a；将硫化胶a放置到290℃下加热20h进行二次硫化得到全氟橡胶制品；
S2.表面处理：对全氟橡胶制品的表面采用喷砂、粗磨、水磨等方法进行表面粗糙化处理，刷去表面残留的颗粒物，采用丙酮进行脱脂，经过S2步骤的表面处理，所述全氟橡胶制品的表面粗糙度Ra大于5μm；
S3.一步表面处理：将100g的FEP乳液、5g聚醚砜的水性分散液以及10gSiO2混合均匀得到涂料a，将涂料a喷涂在全氟橡胶制品的表面，加热至280℃并保持10min得到表面预处理的全氟橡胶制品；
S4.两步表面处理：在表面预处理的全氟橡胶制品表面进行喷涂FEP乳液，并置于300℃下加热10min得到具有表面不粘性全氟橡胶制品。
所述S1中含腈基全氟橡胶生胶的购买厂家为美国3M公司的FFKM1，型号为PFE-131TZ。
所述S1中双氨基苯酚硫化剂为2,2-双(3-氨基-4-羟基苯基)-六氟丙烷，CAS 号为83558-87-6。
所述FEP为四氟乙烯六氟丙烯共聚物。
所述S3中采用FEP乳液的购买厂家为上海三爱富，型号为FR463。
所述S3中聚醚砜的水性分散液的购买厂家为夸克WP-421。
所述S3中SiO2的购买厂家和型号为赢创
所述S4中采用FEP乳液的购买厂家为上海三爱富，型号为FR463。
所述S3中一步表面处理过程中，使用涂料a的喷涂量为100g/m2。
所述S4中两步表面处理过程中，使用FEP乳液喷涂量为100g/m2。
实施例4
一种具有表面不粘性全氟橡胶制品的制备方法，包括以下步骤：
S1.制备全氟橡胶制品：将1g双氨基苯酚硫化剂与100g含腈基全氟橡胶生胶在开炼机上进行混炼后得到混炼胶；将混炼胶放置到170℃下加热15min，同时保持5MPa的压力下进行一次模压硫化得到硫化胶a；将硫化胶a放置到290℃下加热20h进行二次硫化得到全氟橡胶制品；
S2.表面处理：对全氟橡胶制品的表面采用喷砂、粗磨、水磨等方法进行表面粗糙化处理，刷去表面残留的颗粒物，采用丙酮进行脱脂，经过S2步骤的表面处理，所述全氟橡胶制品的表面粗糙度Ra大于5μm；
S3.一步表面处理：将100g的PTFE乳液、1g聚酰胺酰亚胺水性分散液混合均匀得到涂料a，将涂料a喷涂在全氟橡胶制品的表面，放在340℃的烘箱加热10min得到表面预处理的全氟橡胶制品；
S4.两步表面处理：在表面预处理的全氟橡胶制品浸渍到PTFE乳液中浸渍20s，浸渍后放在340℃的烘箱加热10min得到具有表面不粘性全氟橡胶制品。
所述S1中含腈基全氟橡胶生胶的购买厂家为美国3M公司的FFKM1，型号为PFE-131TZ。
所述S1中双氨基苯酚硫化剂为2,2-双(3-氨基-4-羟基苯基)-六氟丙烷，CAS号为83558-87-6。
所述S3中采用的PTFE乳液的购买厂家及型号为三爱富FR303A。
所述S3中采用的聚酰胺酰亚胺水性分散液的购买厂家及型号为夸克新材 SI-308。
所述S4中采用的PTFE乳液的购买厂家及型号为三爱富FR303A。
所述S3中一步表面处理过程中，使用涂料a的喷涂量为100g/m2。
实施例5
一种具有表面不粘性全氟橡胶制品的制备方法，包括以下步骤：
S1.制备全氟橡胶制品：将1g双氨基苯酚硫化剂与100g含腈基全氟橡胶生胶在开炼机上进行混炼后得到混炼胶；将混炼胶放置到170℃下加热15min，同时保持5MPa的压力下进行一次模压硫化得到硫化胶a；将硫化胶a放置到290℃下加热20h进行二次硫化得到全氟橡胶制品；
S2.表面处理：对全氟橡胶制品的表面采用喷砂、粗磨、水磨等方法进行表面粗糙化处理，刷去表面残留的颗粒物，采用丙酮进行脱脂，经过S2步骤的表面处理，所述全氟橡胶制品的表面粗糙度Ra大于5μm；
S3.一步表面处理：将100g的PTFE乳液、1g聚酰胺酰亚胺水性分散液混合均匀得到涂料a，将涂料a喷涂在全氟橡胶制品的表面，放在340℃的烘箱加热10min得到表面预处理的全氟橡胶制品；
S4.两步表面处理：在表面预处理的全氟橡胶制品浸渍到PTFE乳液中浸渍20s，浸渍后放在360℃的烘箱加热10min得到具有表面不粘性全氟橡胶制品。
所述S1中含腈基全氟橡胶生胶的购买厂家为美国3M公司的FFKM1，型号为PFE-131TZ。
所述S1中双氨基苯酚硫化剂为2,2-双(3-氨基-4-羟基苯基)-六氟丙烷，CAS号为83558-87-6。
所述S3中采用的PTFE乳液的购买厂家及型号为三爱富FR303A。
所述S3中采用的聚酰胺酰亚胺水性分散液的购买厂家及型号为夸克新材SI-308。
所述S4中采用的PTFE乳液的购买厂家及型号为三爱富FR303A。
所述S3中一步表面处理过程中，使用涂料a的喷涂量为100g/m2。
性能测试
1.涂层牢度测试：
取实施例1-5制备得到的具有表面不粘性全氟橡胶制品各10件，置于100g的去离子水中，在常压100℃下水煮1小时，再在70℃中超声波处理15分钟，检测去离子水中的颗粒物，粗筛过滤、干燥，测试固体掉落物质的质量及固体掉落情况，去掉最大值和最小值，取平均值，测试结果见表1。
所述全氟橡胶制品为全氟橡胶密封件，形状结构为O型圈，所述O型圈形状见图1。
通过图2可以看出实施例2制备得到的表面不粘性全氟橡胶制品的表面处理层有脱落。
2.粘力测试：
根据涂层牢度测试结果，按照无掉落固体物质的实施例中制备得到的全氟橡胶制品进行测试，具体取实施例1、实施例3、实施例5中制备得到的具有表面不粘性全氟橡胶制品各10件，置于粗糙度不大于1.0μm的304不锈钢测试模具中，拧紧紧固螺母使全氟橡胶制品(O型圈)的变形量为25％，在204℃放置24小时后取出，先冷却至室温，3小时后通过拉伸试验机测量从不锈钢之间模具上拉开O型圈所需要的最小拉伸力，拉伸速度为1mm/s，测得的即为此条件下O型圈的粘力值，去掉最大值和最小值，取平均值，测试结果见表1。
3.耐等离子体测试
使用不同的等离子体处理气体(O2、四氟化碳CF4、O2与CF4的体积比为1:1的共混物(O2/CF4))，在100℃的温度下，800w的功率下测试实施例1-5制备得到的具有表面不粘性全氟橡胶制品在60分钟后的质量损失率，O2、O2与CF4的体积比为1:1的共混物作为等离子体处理气体进行测试时设定的真空度为15mtorr，CF4作为等离子体处理气体进行测试时的真空度为40mtorr；等离子体处理气体的气体流量均设定为80sccm；实施例1-5制备得到的具有表面不粘性全氟橡胶制品各10件，去掉最大值和最小值，取平均值，测试结果见表1。
表1

Claims (4)

  1. 一种具有表面不粘性全氟橡胶制品的制备方法，其特征在于，包括以下步骤：
    S1.制备全氟橡胶制品：将全氟橡胶生胶与硫化剂进行混合后得到混炼胶；将混炼胶进行高温硫化得到全氟橡胶制品；
    S2.表面处理：对全氟橡胶制品进行表面粗糙化和去油脂处理；
    S3.一步表面处理：将FEP乳液、聚醚砜的水性分散液以及SiO2混合均匀得到涂料a喷涂或浸渍在全氟橡胶制品的表面，进行加热后得到表面预处理的全氟橡胶制品；
    S4.两步表面处理：在表面预处理的全氟橡胶制品表面进行喷涂或浸渍不粘性涂料a并进行加热，加热后得到具有表面不粘性全氟橡胶制品；
    所述S2中对全氟橡胶制品进行表面粗处理后全氟橡胶制品的表面粗糙度Ra大于5μm；
    所述S4中加热的温度设置低于360℃；
    所述不粘性涂料a的制备原料为熔点为250-350℃的氟树脂，所述不粘性涂料a的状态为粉末状或乳液状；所述氟树脂为四氟乙烯六氟丙烯共聚物。
  2. 如权利要求1所述的具有表面不粘性全氟橡胶制品的制备方法，其特征在于，所述硫化剂包括有机金属化合物、含氨基的有机化合物中的一种或两种的组合。
  3. 如权利要求1所述的具有表面不粘性全氟橡胶制品的制备方法，其特征在于，所述S4中加热的温度为大于不粘性涂料a中包含树脂材料熔点10-60℃。
  4. 如权利要求3所述的具有表面不粘性全氟橡胶制品的制备方法，其特征在于，所述S4中加热的温度为大于不粘性涂料a中包含树脂材料熔点20-50℃。
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