WO2021030670A1 - Article comprenant un noyau élastomère et un revêtement fluoroélastomère déposé en phase vapeur - Google Patents

Article comprenant un noyau élastomère et un revêtement fluoroélastomère déposé en phase vapeur Download PDF

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WO2021030670A1
WO2021030670A1 PCT/US2020/046325 US2020046325W WO2021030670A1 WO 2021030670 A1 WO2021030670 A1 WO 2021030670A1 US 2020046325 W US2020046325 W US 2020046325W WO 2021030670 A1 WO2021030670 A1 WO 2021030670A1
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formula
monomer
integer
chamber
linear
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PCT/US2020/046325
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Logan P. SANOW
Timothy J. RESKI
Lindsey Peplinski
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Quadion Llc
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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
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—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
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1408—Monomers containing halogen
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating

Definitions

  • Fluoroelastomeric materials can be used to provide improved chemical resistance against a wide variety of chemicals and solvents, radiation, and flammability. Unfortunately, the cost of many fluoroelastomeric materials make it cost-prohibitive to utilize articles made entirely thereof. There is therefore an ongoing need for methods of providing protective barrier coatings on underlying structures.
  • Some illustrative articles include an elastomeric part with a vapor deposited fluropolymer, for example fluoroelastomeric coating thereon.
  • the coating functions to provide select properties of the fluoroelastomer to the underlying elastomeric part at a reduced cost. These properties can include, for example chemical resistance, gas impermeability, low coefficient of friction, biocompatibility, low fouling, high dielectric constant, and others.
  • the fluoroelastomeric coating is formed by introducing one or more fluorinated monomers in the vapor phase, then initiating a chemical reaction on or near the surface of the elastomeric part that results in the polymerization of the monomers to produce fluorinated copolymers.
  • a difunctional monomer may also be introduced in order to promote cross-linking between the chains of the fluoroelastomeric coating or between the polymer chains of the coating and the underlying elastomeric substrate.
  • FIG. 1 depicts an illustration of the iCVD process.
  • FIG. 2 shows a FTIR spectra obtained in Example 1.
  • Disclosed articles and methods utilize some form of chemical vapor deposition (CVD) to form one or more polymers on a substrate from at least one monomer Because of the limited solubility of highly fluorinated polymers, CVD is preferable from a processing standpoint, which limits the processing options for applying as a coating. Virtually any type of CVD can be utilized. Examples of specific types of CVD that can be utilized can include, for example initiated chemical vapor deposition (iCVD), plasma enhanced chemical vapor deposition (peCVD), initiated peCVD (ipeCVD), hot wire chemical vapor deposition (hwCVD), oxidative chemical vapor deposition (oCVD), and photo-initiated chemical vapor deposition (photo-iCVD). It is noted that the process that forms the polymer coating is a solvent free process, thereby it may offer the advantage of being environmentally conscious.
  • iCVD initiated chemical vapor deposition
  • peCVD plasma enhanced chemical vapor deposition
  • ipeCVD initiated peCVD
  • hwCVD hot
  • iCVD can be utilized. iCVD involves introducing gas phase monomers into a vacuum chamber along with one or more radical initiators.
  • FIG. 1 provides a schematic illustration of the process and reaction involved in iCVD.
  • a heating source e.g., a heating element
  • R the initiator
  • M monomers
  • P polymer
  • the substrate can also optionally be cooled or heated to regulate adsorption of monomers and oligomers on the surface of the substrate as well as regulation of the polymerization rate.
  • the polymerization reaction takes place primarily in the liquid phase on the surface of the substrate, but may occur partially in the gas phase.
  • the pressure of the system can optionally be controlled. For example, the pressure can be kept between 0.05-5 Torr during the reaction.
  • the temperature of the heating element is dependent on the initiator used, such that the temperature of the heating element must be high enough to result in bond cleavage of the initiator. If the heating element temperature is too high, undesirable side reactions may occur (gas phase powder formation, degradation of monomers, etc).
  • the temperature of the chamber, monomer vessel, initiator vessel and processing lines may be controlled to discourage adsorption of process gases and to allow for bake-out of the vacuum system.
  • the temperature of the substrate is controlled to allow for optimized deposition rates.
  • the temperature of the substrate may be between -196 and 200 °C. In some embodiments, the temperature range is between -79 and 70 °C.
  • the pressure of the system could range from 0.001 Torr to 1500 Torr, the pressure of the system is determined by the volatility of the monomers and initiators such that they are introduced in the gas phase, the required conformity of the thin film, and the sensitivity of the polymerization reaction to the presence of non-process gases (e.g. Air, oxygen, water vapor).
  • non-process gases e.g. Air, oxygen, water vapor
  • the flow rate of monomers to the deposition chamber can be controlled by mass flow controllers, flow control orifices, manual needle valves, carrier gas flow, and/or monomer temperature; in order to influence deposition rate, polymer composition, and conformality.
  • Initiators can include peroxide species that can be volatilized in the process, Azo compounds, or any compound that creates radicals upon heating.
  • Some examples of initiators that may be used are; perfluorobutane sulfonyl fluoride, perfluorooctane sulfonyl fluoride, tert- butyl peroxy benzoate, /cvV-butyl peroxide, and tert- amyl peroxide, azobisisobutyronitrile, perfluorononanes.
  • the polymer coatings may be a homopolymer of a bulky fluorinated monomer such as PMVE.
  • the polymer is a copolymer or terpolymer where at least two monomers are utilized to form disclosed polymer coatings.
  • At least one monomer is a source of difluorocarbene in a final polymer and at least one monomer is a source of perfluororalkylvinyl ether in the final polymer.
  • Illustrative monomers that can provide difluorocarbene to the final polymer can include, for example difluorocarbene (CF2), fluorinated ethylenes, fluorinated alkenes (which can also be referred to as fluorinated olefins), or combinations thereof.
  • Difluorocarbene can be produced in- situ from, for example hexafluoropropylene oxide (HFPO).
  • difluorocarbene maybe produced from sodium chlorodifluoroacetate, HCF2CI, HCF2Br, IVfeSnCFs, sodium chlorodifluoroacetate, methyl chlorodifluoroacetate, tetrafluoroethane b-sultone, difluoro(fluorosulfonyl)acetic acid, methyl difluoro(fluorosulfonyl)acetate, trimethylsilyl difluoro(fluorosulfonyl)acetate.
  • fluorinated ethylenes can include, for example tetrafluoroethylene, trifluoroethylene, vinylidene fluoride (1,1-difluoroethylene), and 1,2-difluoroethylene.
  • Chemical structures of some of the specific above noted illustrative monomers can be seen below:
  • a general structure of fluorinated olefins can be seen below in Formula F (Formula I) where Ri is a linear or branched saturated radical having a formula of -C a F(2a+i), where a is an integer from 1 to 5.
  • a specific illustrative fluorinated olefin can include, for example hexafluoropropylene (HFPO).
  • Illustrative monomers that can provide perfluororalkylvinyl ether to the final polymer can include, for example fluorinated vinyl ethers, which can have a general structure as seen in Formula II or III below: where Ri is a linear or branched saturated radical having a formula of -C a F(2a+i), where a is an integer from 1 to 5; and (Formula III)
  • Ri is H, or a linear or branched saturated radical having a formula of -C a HbF[(2a+i)-b] where a is an integer from 1 to 5 and b is an integer from zero (0) to (2a+l).
  • Illustrative monomers that can provide perfluororalkylvinyl ether to the final polymer can also include, for example fluorinated dioxolanes, which can have a general structure as seen in Formula IV or V below: (Formula IV) where x is 1 or 2, and Ri and R2 are independently selected from fluorine, or linear or branched perfluoroalkyl radicals having a formula of -C a F(2a+i), where a is an integer from 1 to 5; and (Formula V) where Ri is selected from fluorine, or linear or branched perfluoroalkyl radicals having a formula of -C a F(2a+i), where a is an integer from 1 to 5.
  • Illustrative monomers that can provide perfluororalkylvinyl ether to the final polymer can also include, for example perfluorodivinyl ethers , which can have a general structure as seen in Formulas VI, VII, VIII, or IX below:
  • (Formula VIII) where x is an integer from 1 to 3 and Ri is selected from -CH20(0 )P(0H)0H, -CN, -CH2
  • Specific illustrative monomers that can provide perfluororalkylvinyl ether to the final polymer can include, for example perfluoromethylvinyl ether (PMVE), perfluoroethylvinyl ether (PEVE), perfluoropropylvinyl ether (PPVE), methyl perfluoro(5-methyl-4,7-dioxanon-8-enoate), 2,2- bis(trifluoromethyl)-4,5-difluoro-l,3-dioxole, 2,2-bis(trifluoromethyl)-4-fluoro-5- trifluoromethoxy-l,3-dioxole, perfluoro-2-methylene-4-methyl-l,3-dioxolane, and l,l,2,4,4,5,5,6,7,7-decafluoro-3-oxa-l,6-heptadiene.
  • PMVE perfluoromethylvinyl ether
  • PEVE perfluoroeth
  • an optional cross-linking monomer can also be introduced into the chamber during the CVD process.
  • the optional monomer (or monomers) can include difunctional monomers that can be introduced to promote cross linking between polymer chains in the coating or between polymer chains of the coating and the substrate itself.
  • the optional monomer may introduce functional groups into the polymer chain which can be crosslinked through an additional step, such as thermal, irradiation, chemical or plasma treatment. This additional step may be done during deposition or after deposition.
  • Introduction of an optional monomer(s) to introduce crosslinking may serve to increase the durability of the coating, increase the chemical resistance of the coating, increase adhesion of the coating to the underlying substrate, or any combination thereof, for example.
  • Non-limiting examples of cross- linking monomers include; divinylbenzene, l,4-Bis(4-vinylphenoxy)butane, Bis(2- methacryloyl)oxyethyl disulfide, polyethylene glycol) diacrylate, triallyl isocyanurate, triallyl Cyanurate, hydrocarbon olefins such as (ethylene and propylene), bromo-substituted fluorinated compounds (e.g.
  • the vapor deposited thin film may be cross-linked during or after deposition using heat, e-beam irradiation, gamma irradiation, plasma treatment.
  • Polymerization of the one or more monomers forms a polymer.
  • the polymer can be described as a copolymer of a straight chained fluoroalkyl monomer (such as difluorocarbene or tetrafluoroethylene and a perfluoro monomer containing bulky side groups (such are perfluoroalkyl vinyl ethers).
  • the preferred polymer can be described as a copolymer of difluorocarbene and a perfluoroalkylvinyl ether.
  • a representative example of this polymer, which would be produced from the polymerization of the decomposition product of HFPO e.g.
  • Formula (X) (Formula X) where m and n are both integers m and n can independently range from 0 to 1000 such that m+n is between 5 and 1000.
  • the ratio of m to n can be 100:1, 50:1, 10:1, 3:1, 1:1, 1:5, 1:10, 1:50, 1:100, or 0:1.
  • the preferable ratio of m to n is 3:1.
  • Polymers formed herein are amorphous in nature due to the introduction of the perfluoroalkyl vinyl ether copolymer into the perfluoro polymeric backbone, which reduces the crystallinity of the perfluoro polymeric backbone.
  • the presence of a bulky co-monomer into a typically straight chain polymer prevents interchain packing which leads to reduced crystallinity.
  • the coating is intended to be used above the glassing transition (T ) of the polymer that comprises the coating.
  • T g of the coating will range from -196 to 230°C, the preferred range being -100 to 25°C, the most preferred range being -100 to -15°C.
  • the substrate upon which the coating is deposited or formed can include virtually any underlying structure or material.
  • the substrate can be an elastomeric material.
  • the elastomeric material can include thermoset elastomers.
  • useful thermoset elastomers can be compounded.
  • Thermoset elastomers are commercially available in a wide range of compositions and properties.
  • Illustrative other types of substrates can include, for example, thermoplastic elastomers (TPEs), thermoplastic vulcinates (TP Vs), thermoplastics, woven fibers, non-woven fibers, and cellulose.
  • Thermoset elastomer materials include both natural rubber (NR) and synthetic rubbers.
  • Illustrative, non-limited examples include, polyurethane, epoxy, polyester, polyisoprene (IR), styrene-butadiene rubbers (SBR), carboxylated styrene-butadiene (XSBR), polybutadiene (BR), polychloroprene (CR), polysulfide (T), epichlorohydrin (CO), epichlorohydrin-ethyleneoxide, polyacrylate (ACM), chlorinated polyethylene, chlorosulfonated polyethylene (CSM), polyester- polyurethanes (AU), polyether-polyurethanes (EU), isobutylene (methylpropene), ethylene- propylene (EP), ethylene propylene diene monomer (EPDM), butyl (HR), bromobutyl, chlorobutyl, nitrile (NBR), silicone (MQ), hydrogenated nitrile (HNBR), carboxylated NBR (XNBR), fluorocarbon (F
  • a useful surface can include rubber.
  • the rubber can be thermoset elastomer in finished part form.
  • a raw dry rubbery material is mixed with various compounding ingredients.
  • Compounding is a term of art that refers to a process of sequentially adding ingredients into the raw rubber to make a final homogeneous mix that is typically referred to as a rubber compound. Rubber that has not been compounded can be referred to as raw rubber.
  • Common compounding ingredients added into the rubber can include, for example one or more of vulcanizing agents, vulcanization accelerators, activators for the accelerators, fillers, processing aids, antidegradants and other miscellaneous ingredients for specific purposes.
  • the compounding ingredients are used to make the rubber compound have the desired final properties in its final form.
  • thermoset elastomer is not a raw rubbery material and may include one or more of: a vulcanizing agent, a vulcanization accelerator, an activator for an accelerator, a filler, a processing aid, a softener, an antidegradant, as well as other chemical moieties that result from the inclusion of such materials and the compounding process.
  • Vulcanization is a chemical process for converting uncured natural rubber or synthetic elastomer or other polymers into more durable materials via a process that can include heat or radiation or pressure with the addition of vulcanization agents, curatives and optionally with accelerators.. These additives modify the polymer by forming cross-links (bridges) between individual polymer chains.
  • vulcanization agents are crosslinkers, sulfur, peroxide, metallic oxides (e.g., MgO, ZnO, PbO), acetoxysilane, multiarmed vinylic compounds (e.g., diacrylates, triacrylates, dimethacrylates, ethylene glycol dimethacrylate, trimethacrylates, acrylamides, phenols, methlyenebisacrylamide, hydroxydimethoxyethylacrylamide).
  • a vulcanization accelerator is a chemical substance that causes vulcanization of rubber to take place more rapidly or at lower temperatures.
  • Activators support vulcanization, e.g., zinc oxide, stearic acid, palmitic acid, lauric acid, fatty acids, and salts thereof.
  • Many fillers are known and used to enhance color or physical properties, for example, carbon black, white clay, mineral fillers, silica, and calcium carbonate.
  • Processing aids are available in great variety and are used to improve processability of a rubber compound or to alter its physical properties, for example, as a lubricant, dispersing agent, wetting agent, plasticizer, blowing agent, factice, softener, or tackifying agent.
  • An anti degradant deters the aging of a compounded rubber, for example, an antioxidant, antiozonants, amine type anti-degradant, and phenolic type anti-degradant.
  • Illustrative forms of surfaces can include virtually any form of surfaces, including two dimensional, e.g., substantially flat, surfaces; and three dimensional surfaces, e.g., regular or irregular particles, formed (using any process(es)) articles having virtually any shape whatsoever.
  • Illustrative three dimensional surfaces can be formed into final articles and then coated with a disclosed coating and then formed into final articles; or a combination thereof.
  • Illustrative substrates can also include complex geometries, such as blind holes, undercuts, structures with significant roughness, recessed or protruding gating structures, overmolded inserts, printed surfaces, extruded parts, expanded articles, and highly extended materials.
  • Preferred substrates include low-cost materials that lack chemical resistance or have undesirable surface characteristics in certain applications. These substrates may include polyurethane, epoxy, polyester, polyisoprene (IR), styrene-butadiene rubbers (SBR), carboxylated styrene-butadiene (XSBR), polybutadiene (BR), ethylene-propylene (EP), ethylene propylene diene monomer (EPDM), butyl (HR), butyl (HR), bromobutyl, chlorobutyl, nitrile (NBR), silicone (MQ), hydrogenated nitrile (HNBR), carboxylated NBR (XNBR), fluorocarbon (FKM). More preferred embodiments include a fluorocarbon coating on ethylene propylene diene monomer (EPDM), hydrogenated nitrile (HNBR), silicone (MQ), fluorocarbon (FKM) rubber substrates.
  • IR polyisoprene
  • SBR sty
  • the substrate surface prior to deposition of the thin film it is necessary to clean and prepare the substrate surface prior to deposition of the thin film.
  • This cleaning and preparation may be done outside of the deposition process or inside the deposition chamber.
  • Cleaning may be necessary to promote adhesion of the coating by removing particulate contamination, residual processing aids, and mold release. Cleaning may be done in a variety of ways including but not limited to; detergent washing, clean air blowing, ozone treatment, solvent washing, plasma etching, CO2 abrasive cleaning, and wiping.
  • Surface preparation may be necessary to promote adhesion of the coating to the substrate, this preparation may include activation of the surface through attachment of unsaturated moieties, changing the surface energy, or application of a primer.
  • the coating can function as a barrier between the underlying substrate and the surrounding environment.
  • the coating can function as a barrier to fluids, for example, gases, liquids, or both.
  • the coating can have a thickness ranging from 1 nm to 1000 pm. More preferred coating thickness is 5 nm to 200 pm. The most preferred coating thickness is between l m to 100 pm.
  • various properties, improvement on various properties, or a combination thereof can be imparted to the overall article by the addition of the coating as compared to the article without the coating (e.g., the elastomeric substrate).
  • These properties can include, for example chemical resistance, gas impermeability, low coefficient of friction, biocompatibility, low fouling, high dielectric constant, and others.
  • An article comprising: an elastomeric substrate; and an amorphous fluoropolymer coating disposed on the elastomeric substrate.
  • a method of forming an article comprising: providing an elastomeric substrate in a chamber; introducing a first monomer into the chamber, wherein the first monomer comprises a source of difluorocarbene; introducing a second monomer into the chamber, wherein the second monomer comprises a source of perfluororalkylvinyl ether; and initiating polymerization of at least the first and the second monomer to form a polymer coating on the elastomeric substrate.
  • the first monomer comprises hexafluoropropylene oxide, tetrafluoroethylene, trifluoroethylene, vinylidene fluoride (1,1- difluoroethylene), 1,2-difluoroethylene, or combinations thereof.
  • the first monomer comprises a monomer of formula I (Formula I) where Ri is a linear or branched saturated radical having a formula of -C a F ( 2a+i ) , where a is an integer from 1 to 5.
  • Ri is a linear or branched saturated radical having a formula of -C a F ( 2a+i ) , where a is an integer from 1 to 5.
  • a is an integer from 1 to 5.
  • the first monomer comprises hexafluoropropylene oxide (HFPO).
  • the second monomer comprises a monomer of formula II or III (Formula II) where Ri is a linear or branched saturated radical having a formula of -CaF(2a+i), where a is an integer from 1 to 5; and (Formula III) where Ri is H, or a linear or branched saturated radical having a formula of -C a HbF[(2a+i)-b] where a is an integer from 1 to 5 and b is an integer from zero (0) to (2a+l).
  • the second monomer comprises a monomer of formula IV or V: (Formula IV) where x is 1 or 2, and Ri and R2 are independently selected from fluorine, or linear or branched perfluoroalkyl radicals having a formula of -CaF(2a+i), where a is an integer from 1 to 5; and (Formula V) where Ri is selected from fluorine, or linear or branched perfluoroalkyl radicals having a formula of -C a F(2a+i), where a is an integer from 1 to 5.
  • the second monomer comprises a monomer of formula VI, VII, VIII, or IX below:
  • the second monomer is selected from the group consisting of: perfluoromethylvinyl ether (PMVE), perfluoroethylvinyl ether (PEVE), perfluoropropylvinyl ether (PPVE), methyl perfluoro(5-methyl-4,7-dioxanon-8-enoate), 2,2- bis(trifluoromethyl)-4,5-difluoro-l,3-dioxole, 2,2-bis(trifluoromethyl)-4-fluoro-5- trifluoromethoxy-l,3-dioxole, perfluoro-2-methylene-4-methyl-l,3-dioxolane, and l,l,2,4,4,5,5,6,7,7-decafluoro-3-oxa-l,6-heptadiene.
  • PMVE perfluoromethylvinyl ether
  • PEVE perfluoroethylvinyl ether
  • PPVE perfluoropropyl
  • iCVD initiated chemical vapor deposition
  • peCVD plasma enhanced chemical vapor deposition
  • ipeCVD initiated peCVD
  • hwCVD hot wire chemical vapor deposition
  • oCVD oxidative chemical vapor deposition
  • photo-iCVD photo-initiated chemical vapor deposition
  • a conductive trace that “comprises” silver may be a conductive trace that “consists of’ silver or that “consists essentially of’ silver.
  • compositions, apparatus, system, method or the like means that the components of the composition, apparatus, system, method or the like are limited to the enumerated components and any other components that do not materially affect the basic and novel characteristic(s) of the composition, apparatus, system, method or the like.
  • a 60 Shore A, peroxide cured FKM Terpolymer was used as the substrate.
  • a 1.5x1x0.2 mm coupon was cut and washed ultrasonically with IPA followed by rinses with Type 1 reverse osmosis water.
  • the coupon was placed on aluminum foil and transferred to a custom built iCVD chamber. Air was evacuated from the reaction chamber to a base pressure of 13 mTorr.
  • Perfluoropropyl vinyl ether, Hexafluoropropene oxide, perfluorobutane sulfonyl fluoride and triallylisocyanurate was fed into the reaction chamber at 14.5 seem, 7 seem, 4.5 seem and 0.2 seem respectively.
  • Chamber pressure was maintained at 75 mTorr through the use of a downstream throttle valve.
  • Nichrome C 26 AWG was resistively heated to 500°C.
  • Deposition was monitored by a quartz crystal microbalance (QCM), a 1 micrometer thick coating was deposited over a 30 minute reaction time. The filament was allowed to cool then the gas flow was stopped. The reaction chamber was repressurized with room air.

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Abstract

L'invention concerne des articles qui comprennent un substrat élastomère; et un revêtement fluoropolymère amorphe disposé sur le substrat élastomère. L'invention concerne également des procédés de fabrication de tels articles.
PCT/US2020/046325 2019-08-15 2020-08-14 Article comprenant un noyau élastomère et un revêtement fluoroélastomère déposé en phase vapeur WO2021030670A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2024037567A1 (fr) * 2022-08-16 2024-02-22 江苏菲沃泰纳米科技股份有限公司 Revêtement hydrophile, procédé de préparation, et dispositif

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