WO2022130063A1 - Compositions de fluoropolymères durcissables conductrices et fluoroélastomères en résultant - Google Patents

Compositions de fluoropolymères durcissables conductrices et fluoroélastomères en résultant Download PDF

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WO2022130063A1
WO2022130063A1 PCT/IB2021/060664 IB2021060664W WO2022130063A1 WO 2022130063 A1 WO2022130063 A1 WO 2022130063A1 IB 2021060664 W IB2021060664 W IB 2021060664W WO 2022130063 A1 WO2022130063 A1 WO 2022130063A1
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curable
composition
conductive
previous
fluoropolymer composition
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Yuta Suzuki
Tatsuo Fukushi
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3M Innovative Properties Company
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride

Definitions

  • the present disclosure relates to a conductive composition comprising a partially fluorinated amorphous polymer in an ionic liquid. Methods of making an article using the composition are disclosed herein.
  • fluoropolymeric elastomers Due to their elasticity and inertness to chemical reactivity, heat, or both, fluoropolymeric elastomers are useful in making articles such as seals, gaskets, o-rings, and hoses.
  • fluoroelastomers are used in conductive applications because of the high resistivity and hardness of fluoroelastomers.
  • a curable, conductive fluoropolymer composition comprises:
  • conductive particles having a surface area of less than 500 m 2 /g; wherein if cured to provide a cured composition, the cured composition has a volume resistivity of less than 1 x 10 4 Ohms*cm and a Duro A hardness of less than 80.
  • a method of making a conductive fluoroelastomeric composition comprising
  • conductive particles having a surface area of less than 500 m 2 /g to form a curable composition; and (ii) curing the curable composition to form the conductive fluoroelastomeric composition, wherein the conductive fluoroelastomeric composition has a volume resistivity of less than 1 x 10 4 Ohms*cm and a Duro A hardness of less than 80.
  • a and/or B includes, (A and B) and (A or B);
  • backbone refers to the main continuous chain of the polymer
  • crosslink refers to connecting two pre-formed polymer chains using chemical bonds or chemical groups
  • cure site refers to functional groups, which may participate in crosslinking
  • interpolymerized refers to monomers that are polymerized together to form a polymer backbone
  • “monomer” is a molecule which can undergo polymerization which then form part of the essential structure of a polymer
  • perfluorinated means a group or a compound derived from a hydrocarbon wherein all hydrogen atoms have been replaced by fluorine atoms.
  • a perfluorinated compound may however still contain atoms other than fluorine and carbon atoms, like oxygen atoms, chlorine atoms, bromine atoms and iodine atoms; and
  • polymer refers to a macrostructure having a number average molecular weight (Mn) of at least 10,000, 30,000 dalton, 50,000, 100,000, 200,000, 500,000, or even at least 1,000,000 dalton and not such a high molecular weight as to cause premature gelling of the polymer.
  • Mn number average molecular weight
  • At least one includes all numbers of one and greater (e.g., at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100, etc.).
  • compositions of the present disclosure are conductive (e.g., electroconductive and/or thermalconductive).
  • the curable fluoropolymers of the present disclosure are amorphous, meaning that there is an absence of long-range order (i.e., in long-range order the arrangement and orientation of the macromolecules beyond their nearest neighbors is understood).
  • the amorphous polymer has no detectable crystalline character by DSC (differential scanning calorimetry).
  • the fluoropolymer would have no melting point or melt transitions with an enthalpy more than 0.002, 0.01, 0.1, or even 1 Joule/g from the second heat of a heat/cool/heat cycle, when tested using a DSC thermogram with a first heat cycle starting at -85°C and ramped at 10 °C/min to 350°C, cooling to -85°C at a rate of 10°C/min and a second heat cycle starting from -85°C and ramped at 10 °C/min to 350°C.
  • the amorphous fluoropolymers of the present disclosure are partially fluorinated.
  • a partially fluorinated amorphous polymer comprises both C-F and C-H bonds along the carbon backbone of the polymer chain.
  • the amorphous fluoropolymer of the present disclosure comprises at least 30, 50, 60%, 66, 68, 70, or even 71% by weight of fluorine, and no more than 72, or even 73% by weight of fluorine (based on the total weight of the amorphous fluoropolymer).
  • the amorphous fluoropolymer is derived from at least one hydrogencontaining monomer and at least one fluorine-containing monomer. In one embodiment, the amorphous fluoropolymer is derived from a monomer comprising both an olefinic hydrogen and an olefinic fluorine, such as vinylidene fluoride. Hydrogen containing monomers include those known in the art. The hydrogen-containing monomers may or may not contain fluorine atoms.
  • Exemplary hydrogen-containing monomers include: vinylidene fluoride, pentafluoropropylene (e.g., 2-hydropentafluoropropylene), vinyl fluoride, trifluoroethylene, propylene, ethylene, isobutylene, and combinations thereof.
  • Fluorine-containing monomers include those known in the art.
  • the amorphous fluoropolymer comprises interpolymerized units derived from vinylidene fluoride (VDF). In one embodiment, the amorphous fluoropolymer is derived from 25-75 wt % VDF or even 35-70 wt % VDF.
  • VDF vinylidene fluoride
  • the amorphous fluoropolymer comprises interpolymerized units derived from at least 25, 30, 40, 45, 50, or even 60 wt% and at most 65, 70, or even 75 wt% VDF; and at least 25, 30 or even 35 wt% and at most 50, 60, or even 70 wt% HFP.
  • the amorphous fluoropolymer comprises interpolymerized units derived from at least 45, 50, 55, or even 60 wt% and at most 65, 70, or even 75 wt% VDF; at least 10, 15, or even 20 wt% and at most 30, 35, 40, or even 45 wt% HFP; and at least 3, 5, or even 7 wt% and at most 10 or even 15 wt% TFE.
  • the amorphous fluoropolymer comprises interpolymerized units derived from at least 25, 30, or even 35 wt% and at most 40, 45, 50, 55, or even 65 wt% VDF; at least 15, 20, 25, or even 30 wt% and at most 35, 40, or even 45 wt% HFP; and at least 1, 5, 10 15, 20, or even 25 wt% and at most 30, 35, or even 40 wt% TFE.
  • the amorphous fluoropolymer comprises interpolymerized units derived from at least 30, 35, 40, or even 45 wt% and at most 55, 60, or even 65 wt% VDF; at least 25, 30, or even 35 wt% and at most 40, 45, 50, 55, 60, or even 65 wt% PMVE; and at least 3, 5, or even 7 wt% and at most 10, 15, or even 20 wt% TFE.
  • the amorphous fluoropolymer comprises interpolymerized units derived from at least 30, 35, 40, or even 45 wt% and at most 55, 60, or even 65 wt% VDF; at least 10, 15, 20, 25, or even 35 wt% and at most 40, 45, 50, 55, or even 60 wt% PMVE; and at least 10 15, or even 20 wt% and at most 25, 30, or even 35 wt% TFE.
  • the amorphous fluoropolymer comprises interpolymerized units derived from at least 5, 10, or even 15 wt% and at most 20, 25, or even 30 wt% VDF; at least 5, 10, or even 15 wt% and at most 20, 25, or even 30 wt% propylene; and at least 50, 55, 60, or even 65 wt% and at most 70, 75, 80, or even 85 wt% TFE.
  • perfluorinated ether compounds include for example, perfluorinated alkyl vinyl ether such as perfluorinated methyl vinyl ether (PMVE), perfluorinated alkyl allyl ether such as perfluorinated methyl allyl ether, and perfluorinated alkoxy vinyl ether and perfluorinated alkoxy allyl ether.
  • perfluorinated alkyl vinyl ether such as perfluorinated methyl vinyl ether (PMVE)
  • perfluorinated alkyl allyl ether such as perfluorinated methyl allyl ether
  • perfluorinated alkoxy vinyl ether and perfluorinated alkoxy allyl ether perfluorinated alkoxy vinyl ether.
  • the amorphous fluoropolymer of the present disclosure contains cure sites which facilitate cross-linking of the fluoropolymer. These cure sites comprise at least one of I, Br, and CN.
  • the fluoropolymer may be polymerized in the presence of a chain transfer agent and/or cure site monomers to introduce cure sites into the fluoropolymer.
  • a chain transfer agent and/or cure site monomers are known in the art.
  • Exemplary chain transfer agents include: an iodo-chain transfer agent, a bromo-chain transfer agent, or a chloro-chain transfer agent.
  • the iodo-chain transfer agent may be a perfluorinated iodo-compound.
  • Exemplary iodo-perfluoro- compounds include 1,3-diiodoperfluoropropane, 1,4-diiodoperfluorobutane, 1, 6- diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,10-diiodoperfluorodecane, 1,12- diiodoperfluorododecane, 2-iodo- 1 ,2-dichloro-l, 1 ,2-trifluoroethane, 4-iodo- 1,2,4- trichloroperfluorobutan, and mixtures thereof.
  • the iodo-chain transfer agent is of the formula I(CF2)n-O-Rf-(CF2) m I, wherein n is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, m is is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 and Rf is a partially fluorinated or perfluorinated alkylene segment, which can be linear or branched and optionally comprises at least one catenated ether linkage.
  • Exemplary compounds include: I-CF2-CF2-O-CF2-CF2-I, I-CF(CF 3 )-CF2-O-CF2-CF 2 -I, I-CF 2 -CF 2 -O-CF(CF 3 )- CF2-O-CF2-CF2-I, I-(CF(CF 3 )-CF 2 -O)2-CF2-CF 2 -I, I-CF 2 -CF2-O-(CF2)2-O-CF2-CF 2 -I, I-CF2-CF2- O-(CF 2 ) 3 -O-CF2-CF2-I, and I-CF 2 -CF2-O-(CF2) 4 -O-CF2-CF2-I, I-CF2-CF2-CF2-O-CF2-CF2-I, and I- CF2-CF2-CF2-O-CF(CF 3 )-CF2-O-CF2-CF2-I,
  • the bromine is derived from a brominated chain transfer agent of the formula: RBr x , where (i) R is a perfluor
  • Cure site monomers if used, comprise at least one of a bromine, iodine, and/or nitrile cure moiety.
  • non-fluorinated bromo-or iodo-olefins e.g., vinyl iodide and allyl iodide, can be used.
  • the amorphous fluoropolymer composition of the present disclose comprises iodine, bromine, and/or nitrile cure sites, which are subsequently used to crosslink the amorphous fluoropolymer.
  • the amorphous fluoropolymer composition of the present disclosure comprises at least 0.1, 0.5, 1, 2, or even 2.5 wt% of iodine, bromine, and/or nitrile groups versus the total weight of the amorphous fluoropolymer.
  • the amorphous fluoropolymer of the present disclosure comprises no more than 3, 5, or even 10 wt% of iodine, bromine, and/or nitrile groups versus the total weight of the amorphous fluoropolymer.
  • the amorphous fluoropolymer comprising cure sites is blended with a second amorphous fluoropolymer, which may or may not comprise bromine, iodine, and/or nitrile cure sites.
  • Fluoropolymers generally have higher resistivities. Therefore, conductive particles are added to achieve compositions with lower resistivities.
  • the conductive particles have a surface area of less than 500, 250, 100, 50, 25, 20, 10, or even 1 m 2 /g (meters squared per gram).
  • the surface area of the conductive particles can be determined using techniques known in the art. One common technique is the nitrogen adsorption method and application of BET theory. This method is commonly used to determine surface area and involves adsorbing a monolayer of nitrogen on the surface of the conductive particle under cryogenic conditions. The amount of adsorbed nitrogen is proportional to the surface area.
  • information related to pore size can be obtained by allowing continued adsorption of nitrogen under cryogenic conditions, until the entire pore structure is fdled with liquid nitrogen, and applying BJH theory (or other theory) to calculate average pore diameter.
  • BJH theory or other theory
  • This method will generally measure pores having an average diameter up to about 2000 Angstroms.
  • mercury intrusion porosimetry may be utilized to measure average pore diameters.
  • the conductive particles are carbon particles.
  • the carbon particles disclosed herein are those materials that comprise predominately (e.g., greater than 90, 95, 99% mole) elemental carbon in the bulk.
  • the carbon particles may include amorphous carbons, crystalline carbons, graphitized carbons, and combinations thereof.
  • Exemplary carbons include, elemental carbon, carbon black, acetylene black, graphite, graphene, graphitized carbon, carbon nanotubes, multiwall carbon nanotubes (MWCNT), TKK F-type carbon, P-type carbon, graphitized Vulcan, graphitized carbon, and specialty carbon black.
  • Exemplary conductive carbon particles include carbon fibers available under the trade designation “SG-249” from Osaka Gas Chemical Co., Ltd., Osaka, Japan, and synthetic graphite available as “4546” from Asbury Carbons, Asbury, NJ.
  • useful carbon particles in this disclosure is not intended to be limited to the specific examples indicated hereinabove, but is intended to include all useful physical forms of carbons, such as powders, plates, rods, foams, felts, fibers, branched fibers, cloths, etc.
  • the amount of conductive particles in the conductive composition can vary depending on the type of carbon and/or the surface area of the conductive particles.
  • the conductive composition comprises at least 10, 20, 30, or even 40 wt%; and at most 50, 75, 100, 150, 200, 300, 400, or even 500 wt % of the conductive particles versus the fluoropolymer. If there are not enough conductive particles, the composition will not have the requisite conductivity. If there are too many conductive particles, then the cured composition (or fluoroelastomer) will not have the requisite hardness.
  • the curable compositions of the present disclosure comprise a peroxide.
  • the peroxide is an organic peroxide, preferably, a tertiary butyl peroxide having a tertiary carbon atom attached to peroxy oxygen.
  • Exemplary peroxides include: benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-di-methyl-2,5-di-tert-butylperoxyhexane, 2,4-dichlorobenzoyl peroxide, l,l-bis(tert- butylperoxy)-3,3,5-trimethylchlorohexane, tert-butyl peroxy isopropylcarbonate (TBIC), tert-butyl peroxy 2-ethylhexyl carbonate (TBEC), tert-amyl peroxy 2-ethylhexyl carbonate, tert-hexylperoxy isopropyl carbonate, carbonoperoxoic acid, O,O'-l,3-propanediyl OO, OO'-bis( 1,1 -dimethylethyl) ester, tert-butylperoxy benzo
  • the amount of peroxide used generally will be at least 0.1, 0.2, 0.4, 0.6, 0.8, 1, 1.2, or even 1.5; at most 2, 2.25, 2.5, 2.75, 3, 3.5, 4, 4.5, 5, or even 5.5 parts by weight per 100 parts of the amorphous fluoropolymer.
  • the curable fluoropolymer composition further comprises a crosslinking agent.
  • the crosslinking agent is a multifunctional polyunsaturated compound, which includes allyl-containing cyanurates, isocyanurates, and phthalates, homopolymers of dienes, and co-polymers of dienes and vinyl aromatics.
  • allyl-containing cyanurates include allyl-containing cyanurates, isocyanurates, and phthalates, homopolymers of dienes, and co-polymers of dienes and vinyl aromatics.
  • these crosslinking agents are commercially available including di- and triallyl compounds, divinyl benzene, vinyl toluene, vinyl pyridine, 1,2-cis-poly butadiene and their derivatives.
  • TAIC tri(methyl)allyl is
  • the amount of crosslinking agent used generally will be at least 0.1, 0.5, or even 1 part by weight per 100 parts of amorphous fluoropolymer; and at most 2, 2.5, 3, or even 5 parts by weight per 100 parts of amorphous fluoropolymer.
  • the partially fluorinated amorphous polymers disclosed herein are dissolved and/or dispersed in the ionic liquid to form the curable compositions.
  • An ionic liquid is a unique salt, which is in a liquid state at about 100°C or less, has negligible vapor pressure, and high thermal stability.
  • the ionic liquid is composed of a cation and an anion and has a melting point of generally about 100°C or less (i.e., being a liquid at about 100°C or less), about 95°C or less, or even about 80°C or less.
  • Certain ionic liquids exist in a molten state even at ambient temperature since their melting points are less than room temperature, and therefore they are sometimes referred to as ambient temperature molten salts.
  • the cation and/or anion of the ionic liquid are relatively sterically-bulky, and typically one and/or both of these ions are an organic ion.
  • the ionic liquid can be synthesized by known methods, for example, by a process such as anion exchange or metathesis process, or via an acid-base or neutralization process.
  • the cation of the ionic liquid of the present disclosure may be an ammonium ion, a phosphonium ion, a sulfonium ion or the like, including various delocalized heteroaromatic cations, but is not limited thereto.
  • the ammonium ion includes an ammonium ion selected from the group consisting of alkylammonium, imidazolium, pyridinium, pyrrolidinium, pyrrolinium, pyrazinium, pyrimidinium, triazonium, triazinium, quinolinium, isoquinolinium, indolinium, quinoxalinium, piperidinium, oxazolinium, thiazolinium, morpholinium, piperazinium, and a combination thereof.
  • the phosphonium ion include a phosphonium ion selected from the group consisting of tetraalkylphosphonium, arylphosphonium, alkylarylphosphonium and a combination thereof.
  • sulfonium ion examples include a sulfonium ion selected from the group consisting of alkylsulfonium, arylsulfonium, thiophenium, tetrahydrothiophenium, and a combination thereof.
  • the alkyl group directly bonded to nitrogen atom, phosphorus atom, or sulfur atom may be a linear, branched or cyclic alkyl group having a carbon number of at least 1, 2, or even 4 and not more than 8, 10, 12, 15, or even 20.
  • the alkyl group may optionally contain heteroatoms such as O and N and S in the chain or at the end of the chain (e.g., a terminal -OH group).
  • the aryl group directly bonded to nitrogen atom, phosphorus atom or sulfur atom may be a monocyclic or condensed cyclic aryl group having a carbon number of at least 5, 6, or even 8 and not more than 12, 15, or even 20.
  • An arbitrary site in the structure constituting such a cation may be further substituted by an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, an aralkyl group, an arylalkyl group, an alkoxy group, an aryloxy group, a hydroxyl group, a carbonyl group, a carboxyl group, an ester group, an acyl group, an amino group, a dialkylamino group, an amide group, an imino group, an imide group, a nitro group, a nitrile group, a sulfide group, a sulfoxide group, a sulfone group
  • Specific examples of the cation include N-ethyl-N'-methylimidazolium, N-methyl-N- propylpiperidinium, N,N,N-trimethyl-N-propylammonium, N-methyl-N,N,N-tripropylammonium, N,N,N -trimethyl-N -butylammoniuim, N,N,N -trimethyl -N -methoxy ethylammonium, N -methyl - N,N,N-tris(methoxyethyl)ammonium, N,N-dimethyl-N-butyl-N-methoxyethylammonium, N,N- dimethyl-N,N-dibutylammonium, N-methyl-N,N-dibutyl-N-methoxyethylammonium, N-methyl- N,N,N-tributylammonium, N,N,N-trimethyl-N
  • a cation not containing a functional group or moiety exhibiting reactivity is advantageous in view of heat resistance, and examples of such a cation include N-methyl-N-propyl piperidinium and N,N,N-trimethyl-N- propylammonium .
  • a phosphate represented by the formula: PRf such as hexafluorophosphate (PFg ) and hexaalkylphosphate, an imide (R2N ), a methide (R3C ), nitrate ion (NO3 ), or nitrite ion (NO2 ).
  • each R may be independently a hydrogen atom, a halogen atom (fluorine, chlorine, bromine, iodine), a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, arylalkyl, acyl or sulfonyl group, or the like.
  • a heteroatom such as an oxygen atom, a nitrogen atom and a sulfur atom may be contained in the main chain or ring of the group R, and a part or all of hydrogen atoms on the carbon atom of the group R may be replaced with fluorine atoms.
  • R's may be the same or different. Because of good compatibility with fluoropolymer in general, it is advantageous that a part or all of hydrogen atoms on the carbon atom of the group R in the anion be replaced by fluorine atoms and it is advantageous that the anion contains a perfluoroalkyl group.
  • Examples of the anion containing a perfluoroalkyl group include a bis(perfluoroalkylsulfonyl)imide ((RfSCh N ), a perfluoroalkylsulfonate (RfSO, ) and a tris(perfluoroalkylsulfonyl)methide ((RfSCh C ) (wherein Rf represents a perfluoroalkyl group).
  • the carbon number of the perfluoroalkyl group may be, for example, from at least 1, 2, 3 or even 4 to at most 8, 10, 12, 15, or even 20.
  • bis(perfluoroalkylsulfonyl)imide examples include: bis(trifluoromethanesulfonyl)imide, bis(pentafluoroethanesulfonyl)imide, bis(heptafluoropropanesulfonyl)imide and bis(nonafluorobutanesulfonyl)imide.
  • Specific examples of the perfluoroalkylsulfonate include: trifluoromethane sulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate and nonafluorobutane sulfonate.
  • tris(perfluoroalkylsulfonyl)methide examples include: tris(trifluoromethanesulfonyl)methide, tris(pentafluoroethanesulfonyl)methide, tris(heptafluoropropanesulfonyl)methide, tris(nonafluorobutanesulfonyl)methide, and a combination thereof.
  • N-methyl-N- propylpiperidinium bis(trifluoromethanesulfonyl)imide, N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide, N-ethyl-N'-methylimidazolium bis(trifluoromethanesulfonyl)imide, N,N,N-trimethyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide and N-methyl-N,N,N-tributylammonium bis(trifluoromethanesulfonyl)imide can be advantageously used, because of excellent heat resistance and good compatibility with fluoropolymer.
  • the curable composition comprises at least 10, 20, 30 or even 40 wt % of the ionic liquid. In one embodiment, the curable composition comprises at most 50, 60, 70, 75, or even 80 wt % of the ionic liquid.
  • the ionic liquid has a boiling point greater than 275, 300, 350, or even 400°C.
  • Ionic liquids with higher boiling points can be advantageous in the present disclosure because they can assist with the conductivity of the cured fluoropolymer.
  • the use of the ionic liquid allows the hardness of the fluoroelastomeric composition to be maintained or at least able to form sheets, even upon the addition of larger amounts of conductive particles.
  • compositions of the present disclosure comprise additional components, which facilitate the processing or final properties of the resulting article.
  • additional components which facilitate the processing or final properties of the resulting article.
  • conventional adjuvants such as, for example, fillers, acid acceptors, process aids, or colorants (e.g., pigments or dyes) may be added to the curable composition.
  • Exemplary fillers include: an organic or inorganic filler such as clay, silica (SiC>2), alumina, iron red, talc, diatomaceous earth, barium sulfate, wollastonite (CaSiCh), calcium carbonate (CaCCE), calcium fluoride, magnesium oxide, titanium oxide, iron oxide, aluminum nitride, silicon carbide, boron nitride, molybdenum sulfide, pigment, high temperature plastics, a heat-dissipating filler, and the like may be added as an optional additive to the composition.
  • an organic or inorganic filler such as clay, silica (SiC>2), alumina, iron red, talc, diatomaceous earth, barium sulfate, wollastonite (CaSiCh), calcium carbonate (CaCCE), calcium fluoride, magnesium oxide, titanium oxide, iron oxide, aluminum nitride, silicon carbide, boron nit
  • the filler components may result in a compound that is capable of retaining a preferred elasticity and physical tensile, as indicated by an elongation and tensile strength value, while retaining desired properties such as retraction at lower temperature (TR-10).
  • the filler content is between 0.01 to 10 % or up to 30 % or even up to 50 % by weight based on the total weight of the composition.
  • the curable composition comprising the partially fluorinated amorphous polymer, the peroxide, crosslinking agent, ionic liquid, conductive filler, and optional additives can be combined together, using techniques known in the art, and cured.
  • the curable compositions of the present disclosure are dispensable, meaning the viscosity is low enough such that the curable composition can be delivered onto a substrate.
  • the viscosity of the curable compositions at 25°C is at least 50, 100, 500, 1000, 2000, 4000, 6000 or even 10000 cP (centiPoise).
  • the curable compositions have a viscosity at 25°C of at most 2000, 4000, 6000, 8000, 10000, 15000, 20000, 50000, 100000, 200000, 500000, or even 1000000 cP.
  • the curable compositions disclosed herein can be dispensed and/or compounded and molded using techniques known in the art to form articles. These curable articles can then be exposed to thermal radiation to cure the fluoropolymer, generating the fluoroelastomer.
  • the curable composition is at least partially cured using thermal radiation, whereby the curable composition is exposed to temperatures greater than 120, 140, 160, 180, 200, 220, or even 250°C; and less than the decomposition temperature of the fluoropolymer or its components (e.g., less than 300, or even 275°C), causing the peroxide cure initiator to activate, resulting in the crosslinking (or curing) of the composition.
  • curing is performed in an oven.
  • the cured compositions have a Duro A hardness of at least 10, 20, 30 or even 40; and at most 80, 75, 70, 65, or even 60.
  • the cured compositions have a volume resistivity of less than 1 x 10 4 Ohms*cm, or even 1 x 10 2 Ohms*cm. In one embodiment, the cured compositions have a surface resistivity of less than 1 x 10 4 Ohms per square, or even 1 x 10 2 Ohms per square of material.
  • the cured compositions have a thermal conductivity of greater than 0.1, 0.2, 0.5, 1.0, 2.0, 3.0, 5.0, 10.0 W/m-K, or even 12 W/m-K.
  • the cured compositions have an electrical conductivity of greater than 10,000 1/S, or even 100 1/S.
  • the articles of the present disclosure are shaped and can include gaskets, ring lip seals, washer seals, O-rings, grooved seals, etc.
  • volume resistivity and surface resistance were measured using a picoammeter available under the trade designation R8340A from Advantest, Tokyo, Japan, according to methods described in JIS K6911-1995. These measurements were made on press-cured sheets of compound. Measurements were not made on samples that could not be formed into sheets. The applied voltage for the measurements and the resulting measured volume and surface resistivities are presented in Table 2.
  • Resistance Method 2 Resistance of heat-cured samples were measured using a two contact method, with an applied voltage of 20 mV and a contact spacing of 10 mm. Measurements were not made for samples that could not be formed into sheets. The results of the measurements are presented in Table 2.
  • Durometer A hardness was measured for press-cured sheets of compound according to ASTM D 2240-05 “Standard Test Method for Rubber Property-Durometer Hardness” using an ASKER Durometer Type A from Kobunshi Keiki Co., Ltd., Kyoto, Japan. Hardness was not measured for samples that could not be formed into sheets.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne l'utilisation de liquides ioniques pour améliorer la conductivité et la dureté de compositions fluoroélastomères. L'invention concerne une composition durcissable, conductrice comprenant un polymère amorphe partiellement fluoré ayant un site de durcissement d'iode, de brome et/ou de nitrile; un liquide ionique; un peroxyde; un agent de réticulation; et des particules conductrices ainsi que des articles durcis en résultants. Les articles durcis ont une résistivité volumique inférieure à 1 x 104 Ohms • Cm et une dureté Duro A inférieure à 80.
PCT/IB2021/060664 2020-12-18 2021-11-17 Compositions de fluoropolymères durcissables conductrices et fluoroélastomères en résultant WO2022130063A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5225504A (en) 1992-02-14 1993-07-06 Nok Corporation Process for producing peroxide-vulcanizable, fluorine-containing elastomer
EP2416488A1 (fr) * 2009-03-31 2012-02-08 Daikin Industries, Ltd. Film d'électrode pour élément d'actionnement polymère et élément d'actionnement polymère la comprenant
WO2014179432A1 (fr) * 2013-05-02 2014-11-06 3M Innovative Properties Company Élastomères partiellement fluorés et procédés de fabrication et d'utilisation de ceux-ci
JP2019085475A (ja) * 2017-11-06 2019-06-06 三菱電線工業株式会社 シール材用ゴム材料及びそれを用いたシール材

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5225504A (en) 1992-02-14 1993-07-06 Nok Corporation Process for producing peroxide-vulcanizable, fluorine-containing elastomer
EP2416488A1 (fr) * 2009-03-31 2012-02-08 Daikin Industries, Ltd. Film d'électrode pour élément d'actionnement polymère et élément d'actionnement polymère la comprenant
WO2014179432A1 (fr) * 2013-05-02 2014-11-06 3M Innovative Properties Company Élastomères partiellement fluorés et procédés de fabrication et d'utilisation de ceux-ci
JP2019085475A (ja) * 2017-11-06 2019-06-06 三菱電線工業株式会社 シール材用ゴム材料及びそれを用いたシール材

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