WO2016100421A1 - Compositions durcissables de polymère partiellement fluoré - Google Patents

Compositions durcissables de polymère partiellement fluoré Download PDF

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Publication number
WO2016100421A1
WO2016100421A1 PCT/US2015/065933 US2015065933W WO2016100421A1 WO 2016100421 A1 WO2016100421 A1 WO 2016100421A1 US 2015065933 W US2015065933 W US 2015065933W WO 2016100421 A1 WO2016100421 A1 WO 2016100421A1
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partially fluorinated
curable
polymer composition
fluorinated polymer
amorphous fluoropolymer
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PCT/US2015/065933
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English (en)
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Werner M.A. Grootaert
Miguel A. Guerra
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3M Innovative Properties Company
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Priority to MX2017008046A priority Critical patent/MX2017008046A/es
Priority to CA2971219A priority patent/CA2971219A1/fr
Priority to CN201580069383.0A priority patent/CN107109012A/zh
Priority to JP2017532105A priority patent/JP6802164B2/ja
Priority to KR1020177019629A priority patent/KR20170099947A/ko
Priority to EP15870930.3A priority patent/EP3234011A4/fr
Publication of WO2016100421A1 publication Critical patent/WO2016100421A1/fr

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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/244—Stepwise homogeneous crosslinking of one polymer with one crosslinking system, e.g. partial curing
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08K5/00—Use of organic ingredients
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    • C08K5/05—Alcohols; Metal alcoholates
    • 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
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • 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
    • 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
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2323/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
    • 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
    • C08J2327/00—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
    • C08J2327/02—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
    • C08J2327/12—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
    • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
    • 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
    • C08J2327/00—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
    • C08J2327/02—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
    • C08J2327/12—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
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • 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
    • C08J2327/00—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
    • C08J2327/02—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
    • C08J2327/12—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
    • C08J2327/20—Homopolymers or copolymers of hexafluoropropene
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators

Definitions

  • compositions comprising a partially fluorinated amorphous
  • fluoropolymer substantially free of iodine, bromine and nitrile cure sites with a curing agent comprising a terminal olefin with at least one olefinic hydrogen are disclosed.
  • a curable partially fluorinated polymer comprising:
  • a partially fluorinated amorphous fluoropolymer wherein the partially fluorinated amorphous fluoropolymer comprises carbon-carbon double bonds or is capable of forming carbon-carbon double bonds along the partially fluorinated amorphous fluoropolymer, wherein the partially fluorinated amorphous fluoropolymer is substantially free of bromine, iodine, and nitrile;
  • a curing agent comprising a terminal olefin with at least one olefinic hydrogen.
  • a method of making a partially fluorinated elastomer comprising curing the curable partially fluorinated polymer composition disclosed above.
  • crosslinking 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; and "interpolymerized” refers to monomers that are polymerized together to form a polymer backbone; and
  • polymer refers to macromolecules made up of large numbers (e.g., hundreds or more) of interpolymerized monomer units and have high molecular weight (e.g., more than 10,000, 20,000, 50,000 or even 100,000 grams/mole).
  • 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.).
  • a partially fluorinated amorphous fluoropolymer substantially free of bromine, iodine, and nitrile groups can be cured with a compound comprising a terminal olefin with at least one olefinic hydrogen.
  • the amorphous fluoropolymers of the present disclosure are partially fluorinated polymers.
  • an amorphous partially fluorinated polymer is a polymer comprising at least one carbon-hydrogen bond and at least one carbon-fluorine bond on the backbone of the polymer.
  • the amorphous partially fluorinated polymer is highly fluorinated, wherein at least 60, 70, 80, or even 90% of the polymer backbone comprises C-F bonds.
  • the amorphous fluoropolymer of the present disclosure also comprises carbon- carbon double bonds and/or is capable of forming carbon-carbon double bonds along the polymer chain.
  • the partially fluorinated amorphous fluoropolymer comprises carbon-carbon double bonds along the backbone of the partially fluorinated amorphous fluoropolymer or is capable of forming carbon-carbon double bonds along the backbone of the partially fluorinated amorphous fluoropolymer.
  • the partially fluorinated amorphous fluoropolymer comprises carbon-carbon double bonds or is capable of forming carbon-carbon double bonds in a pendent group off of the backbone of the partially fluorinated amorphous fluoropolymer.
  • the fluoropolymer capable of forming carbon-carbon double bonds means that the fluoropolymer contains units capable of forming double bonds. Such units include, for example, two adjacent carbons, along the polymer backbone or pendent side chain, wherein a hydrogen is attached to the first carbon and a leaving group is attached to the second carbon. During an elimination reaction (e.g., thermal reaction, and/or use of acids or bases), the leaving group and the hydrogen leave forming a double bond between the two carbon atoms.
  • an elimination reaction e.g., thermal reaction, and/or use of acids or bases
  • An exemplary leaving group includes: a fluoride, an alkoxide, a hydroxide, a tosylate, a mesylate, an amine, an ammonium, a sulfide, a sulfonium, a sulfoxide, a sulfone, and combinations thereof.
  • the amorphous fluoropolymer comprises a plurality of these groups (carbon- carbon double bonds or groups capable of forming double bonds) to result in a sufficient cure. Generally, this means at least 0.1, 0.5, 1, 2, or even 5 mol%; at most 7, 10, 15, or even 20 mol % (i.e., moles of these carbon-carbon double bonds or precursors thereof per mole of polymer).
  • the amorphous partially fluorinated polymer is derived from at least one hydrogen containing monomer such as vinylidene fluoride.
  • the amorphous fluoropolymer comprises adjacent
  • VDF vinylidene fluoride
  • hexafluoropropylene ⁇ I IFF hexafluoropropylene
  • VDF or tetrafiuoroethylene
  • a fluorinated comonomer capable of delivering an acidic hydrogen atom to the polymer backbone, such as trifluoroethylene; vinyl fluoride; 3,3,3-trifluoropropene-l ; pentafluoropropene (e.g., 2- hydropentafluoropropylene and I-hydropentafluoropropylene); 2,3,3,3-tetrafluoropropene; and combinations thereof
  • small amounts e.g., less than 10, 5, 2, or even 1 wt%) of additional monomers may be added so long as the amorphous fluoropolymer is able to be cured using the curing agent disclosed herein.
  • the amorphous fluoropolymer is additionally derived from a hydrogen containing monomer including: pentafluoropropylene (e.g., 2- hydropentafluropropylene), propylene, ethylene, isobutylene, and combinations thereof.
  • the amorphous fluoropolymer is additionally derived from a perfluorinated monomer.
  • Exemplary perfluorinated monomers include:
  • CF2 CFOCF 2 OCF2CF 2 CF3
  • perfluoro(alkylallyl ether) such as perfluoromethyl allyl ether, perfluoro(alkyloxyallyl ether) such as perfluoro-4,8-dioxa-l-nonene (i.e.,
  • CF2 CFCF 2 OCF 2 )30CF3], and combinations thereof.
  • Exemplary types of polymers include those comprising interpolymerized units derived from (i) vinylidene fluoride, tetrafluoroethylene, and propylene; (ii) vinylidene fluoride, tetrafluoroethylene, ethylene, and perfluoroalkyl vinyl ether, such as
  • the amorphous fluoropolymers of the present disclosure can be cured without the need for pendent bromine, iodine, or nitrile cure sites along the polymer backbone. Often, the iodine and bromine-containing cure site monomers, which are polymerized into the fluoropolymer and/or the chain ends, can be expensive among other things.
  • the amorphous fluoropolymer of the present disclosure is substantially free of I, Br, and nitrile groups, wherein the amorphous fluoropolymer comprises less than 0.1, 0.05, 0.01, or even 0.005 mole percent relative to the total polymer.
  • the amorphous fluoropolymers of the present disclosure are non-grafted, meaning that they do not comprise pendant groups including vinyl, allyl, acrylate, amido, sulfonic acid salt, pyridine, carboxylic ester, carboxylic salt, hindered silanes that are aliphatic or aromatic tri-ethers or tri-esters.
  • the amorphous fluoropolymer does not comprise a monophenol graft.
  • the curing agent of the present disclosure is a compound containing at least one terminal olefin with at least one olefinic hydrogen.
  • the curing agent comprises a terminal carbon-carbon double bond with at least one of the carbons comprising at least one hydrogen.
  • the curing agent of the present disclosure is represented by Formula I:
  • Xi, X 2 , and X 3 are independently selected from H, CI, and F and at least one of Xi, X 2 , and X 3 is H; R is a monovalent group.
  • R is a monovalent group comprising 1 to 20 carbon atoms, which can be linear, branched or cyclic.
  • R may be aromatic, aliphatic, or comprise both an aromatic and an aliphatic portion.
  • R may be non-fluorinated (comprising no fluorine atoms), partially fluorinated (comprising at least one C-H bond and at least one C-F bond, or perfluorinated (comprising no C-H bonds and at least one C-F bond).
  • R comprises at least one catenated heteroatom such as O, S or N (e.g., an ether linkage).
  • R comprises a terminal group selected from an alcohol (-OH), an amine (- H 2 , - HR, and - RR' where R and R' are an organic group), a thiol (-SH), a carboxylic acid (-COOH), an olefin.
  • R' comprises an alkylene group, a cylcoalkylene, an arylene group, or combination thereof (e.g., alkarylene) comprising at least 1, 2, 4, or even 6 carbon atoms and at most 30, 25, 20, or even 15 carbon atoms.
  • the curing agent is a non-polymeric, small molecule, having a molecular weight of less than 2000, 1500, 1000, 500, 250, or even 175 g/mol.
  • the curing agent is selected from at least one of a divinyl and a diallyl compound.
  • a compound comprising at least two vinyl moieties or at least two allyl moieties.
  • the curing agent comprises a vinyl moiety and an allyl moiety.
  • the curing agent comprises at least one nonfluorinated terminal olefin group. In one embodiment, the curing agent comprises a non-aromatic terminal olefin and/or non-aromatic alcohol. In one embodiment, the curing agent comprises at least one phenolic group.
  • Exemplary curing agent include:
  • Rf is a fluorinated alkyl group.
  • Rf may be partially or fully fluorinated.
  • Rf may comprise catenated heteroatoms such as O, S, or N.
  • Rf may be linear or branched, saturated or unsaturated.
  • Rf is a CI to C12 fluorinated alkyl group (optionally, perfluorinated).
  • the curing agent should be used in quantities substantial enough to cause the amorphous fluoropolymer to cure, as indicated by a rise in torque on a moving die rheometer. For example, at least 1, 1.5, 2, 2.5, 3, or even 4 or more millimoles per 100 parts of the amorphous fluoropolymer is used. If too little curing agent is used, the amorphous fluoropolymer will not cure. For example, no more than 20, 15, 10, or even 8 millimoles of the curing agent per 100 parts of the amorphous fluoropolymer is used. If too much curing agent is used, the amorphous fluoropolymer can become brittle.
  • the curable partially fluorinated polymer composition is substantially free of a monophenol, meaning that the composition comprising the amorphous fluoropolymer comprises less than 0.1, 0.01, or even 0.001 % moles of monophenol versus the moles of amorphous fluoropolymer.
  • an acid acceptor is used in the present disclosure, such acid acceptors include organic, inorganic, or blends of thereof.
  • inorganic acceptors include magnesium oxide, lead oxide, calcium oxide, calcium hydroxide, dibasic lead phosphate, zinc oxide, barium carbonate, strontium hydroxide, calcium carbonate, hydrotalcite, etc.
  • Organic acceptors include amines, epoxies, sodium stearate, and magnesium oxalate.
  • Particularly suitable acid acceptors include calcium hydroxide, magnesium oxide and zinc oxide. Blends of acid acceptors may be used as well. The amount of acid acceptor will generally depend on the nature of the acid acceptor used.
  • At least 0.5, 1, 2, 3, or even 4 parts of the acid acceptor per 100 parts of the amorphous fluoropolymer are used. In one embodiment, no more than 10, 7, or even 5 parts of the acid acceptor per 100 parts of the amorphous fluoropolymer are used.
  • an organo onium compound is added to the composition as a phase transfer catalyst to assist with the crosslinking of the amorphous fluoropolymer and/or may be used to generate the double bonds on the fluoropolymer through
  • organo onium compounds include quaternary ammonium hydroxides or salts, quaternary phosphonium hydroxides or salts, and ternary su!fonium hydroxides or salts.
  • a phosphonium and ammonium salts or compounds comprise a central atom of phosphorous or nitrogen, respectively, covalently bonded to four organic moieties by means of a carbon-phosphorous (or carbon-nitrogen) covalent bonds and i s ionical iy associated with an anion.
  • the organic moieties can be the same or different.
  • a sulfonium compound i a sulfur-containing organic compound in which at least one sulfur atom is covalently bonded to three organic moieties having from 1 to 20 carbon atoms by means of carbon-sulfur covalent bonds and i s ionicaliy associated with an anion.
  • the organic moieties can be the same or different.
  • the sulfonium compounds may have more than one relatively positive sulfur atom, e.g.
  • organo onium compounds suitable for use in this disclosure are known and are described in the an. See, for example, U. S. Pat. Nos. 5,262,490 (Ko!b et al.) and
  • Exemplary organo onium compounds include: Cs-Ce symmetrical
  • tetraalkylammonium salts unsymmetrtcal letraaikyiammomum salts wherein the sum of alkyl carbons is between 8 and 24 and benzyltrialkylammonium salts wherein the sum of alkyl carbons is between 7 and 19 (for example tetrabutylammonium bromide,
  • tetrapentyiammonium chloride tetrapropyl ammonium bromide, tetrahexy!ammonim chloride, and tetraheptylammonium bromidetetramethylammonium chloride); quaternary phosphonium salts, such as tetrabutylphosphonium salts, tetraphenylphosphonium chloride, benzyitriphenylphosphonium chloride, tributylallylphosphonium chloride, tributylbenzyl phosphonium chloride, tributyl-2-methoxypropylphospbonium chloride, benzyldiphenyl(dimethylamino)phosphonium chloride, 8-benzyl-l,8-diazobicyclo[5.4.0]7- undecenium chloride, benzyltris(dimethyl.amino)phosph.onium chloride, and
  • organ o onium compounds include I,8 ⁇ diazabieydo[5 A0]undec-7-ene and l ,5-diazabicyclo[4.3.0]non-5-ene.
  • Phenolate is a preferred anion for the quaternary ammonium and phosphonium salts.
  • the organo onium compound is used between 1 and 5 millimoles per 100 parts of the amorphous fluoropolymer (mmhr).
  • the curable composition comprises a peroxide, used to initiate the cure.
  • peroxides include organic peroxides.
  • Exemplary peroxides include: 2,5-dimethyl-2,5-di(t-butylperoxy)hexane; dicumyl peroxide; di(2-t-butylperoxyisopropyl)benzene; dialkyl peroxide; bis (dialkyl peroxide); 2,5-dimethyl-2,5-di(tertiarybutylperoxy)3-hexyne; dibenzoyl peroxide; 2,4- dichlorobenzoyl peroxide; tertiarybutyl perbenzoate; a,a'-bis(t-butylperoxy- diisopropylbenzene); t-butyl peroxy isopropyl carbonate, t-butyl peroxy 2-ethylhexyl carbonate, t-amyl peroxy 2-ethylhexyl carbonate, t-hexylperoxy isopropyl carbonate, di[l,3-d
  • the amount of free radical source 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.
  • a typical coagent is a compound that comprises a terminal unsaturation site, which is incorporated into the polymer during curing to assist with curing, typically peroxide curing.
  • exemplary coagents include: tri(methyl)allyl isocyanurate (TMAIC), triallyl isocyanurate (TAIC), tri(methyl)allyl cyanurate, poly-triallyl isocyanurate (poly-TAIC), triallyl cyanurate (TAC), xylylene-bis(diallyl isocyanurate) (XBD), N,N'-m-phenylene bismaleimide, diallyl phthalate, tris(diallylamine)-s-triazine, triallyl phosphite, 1,2- polybutadiene, ethyleneglycol diacrylate, diethyleneglycol diacrylate, and combinations thereof.
  • the amorphous fluoropolymers of the present disclosure can be cured without the use of these coagents or can be cured using these coagents, without the need of a bromine, iodine, or nitrile end group.
  • the curable composition is substantially free (less than 1, 0.5, or even 0.1 wt % or even below detection) of a typical coagent. This can be advantageous because of the coagents expense, incompatibility with fluorinated polymers, and impact on processing (e.g., bleeding out of compositions, mold fouling).
  • the curable composition can also contain a wide variety of additives of the type normally used in the preparation of elastomeric compositions, such as pigments, fillers (such as carbon black), pore-forming agents, and those known in the art.
  • additives of the type normally used in the preparation of elastomeric compositions, such as pigments, fillers (such as carbon black), pore-forming agents, and those known in the art.
  • the curable amorphous fluoropolymer compositions may be prepared by mixing the amorphous fluoropolymer, the curing agent, along with the other components (e.g., the acid acceptor, the onium compound, peroxide, and/or additional additives) in conventional rubber processing equipment to provide a solid mixture, i.e. a solid polymer containing the additional ingredients, also referred to in the art as a "compound".
  • This process of mixing the ingredients to produce such a solid polymer composition containing other ingredients is typically called “compounding”.
  • Such equipment includes rubber mills, internal mixers, such as Banbury mixers, and mixing extruders. The temperature of the mixture during mixing typically will not rise above about 120°C.
  • the components and additives are distributed uniformly throughout the resulting fluorinated polymer
  • the “compound” can then be extruded or pressed in a mold, e.g., a cavity or a transfer mold and subsequently be oven-cured. In an alternative embodiment curing can be done in an autoclave.
  • Curing is typically achieved by heat-treating the curable amorphous fluoropolymer composition.
  • the heat-treatment is carried out at an effective temperature and effective time to create a cured fluoroelastomer.
  • Optimum conditions can be tested by examining the cured fluoroelastomer for its mechanical and physical properties.
  • curing is carried out at temperatures greater than 120°C or greater than 150°C.
  • Typical curing conditions include curing at temperatures between 160°C and 210°C or between 160°C and 190°C.
  • Typical curing periods include from 3 to 90 minutes.
  • Curing is preferably carried out under pressure. For example pressures from 10 to 100 bar may be applied.
  • a post curing cycle may be applied to ensure the curing process is fully completed.
  • Post curing may be carried out at a temperature between 170°C and 250°C for a period of 1 to 24 hours.
  • the partially fluorinated amorphous fluoropolymer in the curable composition has a Mooney viscosity in accordance with ASTM D 1646-06 TYPE A by a MV 2000 instrument (available from Alpha Technologies, Ohio, USA) using large rotor (ML 1+10) at 121 °C.
  • the amorphous fluoropolymer becomes an elastomer, becoming a non-flowing fluoropolymer, and having an infinite viscosity (and therefore no measurable Mooney viscosity).
  • the cure system comprising the curing agent and amorphous fluoropolymer disclosed herein, may exhibit both the chemical resistance of a typical iodine/bromine and coagent containing peroxide cure system, while at the same time elevating the poor heat resistance of these conventional iodine or bromine containing fluoroelastomers, due to their lack of bromine or iodine and therefore resulting in a cured fluoropolymer having simultaneously sufficient heat and chemical resistance.
  • the cured fluoroelastomers are particularly useful as seals, gaskets, and molded parts in automotive, chemical processing, semiconductor, aerospace, and petroleum industry applications, among others.
  • Exemplary embodiments include the following:
  • Embodiment 1 A curable partially fluorinated polymer composition comprising:
  • a partially fluorinated amorphous fluoropolymer wherein the partially fluorinated amorphous fluoropolymer comprises carbon-carbon double bonds or is capable of forming carbon-carbon double bonds along the partially fluorinated amorphous fluoropolymer, wherein the partially fluorinated amorphous fluoropolymer is substantially free of bromine, iodine, and nitrile;
  • Embodiment 2 a curing agent comprising a terminal olefin with at least one olefinic hydrogen; [0059] Embodiment 2.
  • the curable partially fluonnated polymer composition of embodiment 1 further comprising a peroxide.
  • Embodiment 3 The curable partially fluorinated polymer composition of any one of the previous embodiments, wherein the curing agent comprises a phenolic group.
  • Embodiment 4 The curable partially fluorinated polymer composition of any one of embodiments 1-2, wherein the curing agent comprises a non-aromatic olefinic alcohol.
  • Embodiment 5 The curable partially fluorinated polymer composition of any one of the previous embodiments, wherein the curing agent is selected from at least one of a di-vinyl and a di-allyl compound.
  • Embodiment 7 The curable partially fluorinated polymer composition of any one of the previous embodiments, wherein the curing agent is selected from at least one of:
  • Embodiment 8 The curable partially fluorinated polymer composition of any one of the previous embodiments, wherein the partially fluorinated amorphous fluoropolymer comprises carbon-carbon double bonds along the backbone of the partially fluorinated amorphous fluoropolymer or is capable of forming carbon-carbon double bonds along the backbone of the partially fluorinated amorphous fluoropolymer.
  • Embodiment 9 The curable partially fluorinated polymer composition of any one of the previous embodiments, wherein the partially fluorinated amorphous fluoropolymer comprises (i) adjacent copoiymerized units of VDF and HFP, (ii) copolymers zed units of VDF and a fluorinated comonomer having an acidic hydrogen atom; (iii) copoiymerized units of TFE and a fluorinated comonomer having an acidic hydrogen atom; and (iv) combinations thereof
  • Embodiment 10 The curable partially fluorinated polymer composition of embodiment 8, wherein the fluorinated comonomer having an acidic hydrogen atom is selected from: trifluoroethylene; vinyl fluoride; 3,3,3-trifluoropropene-l;
  • Embodiment 11 The curable partially fluorinated polymer composition of any one of the previous embodiments, wherein the partially fluorinated amorphous fluoropolymer is derived from (i) vinylidene fluoride, tetrafluoroethylene, and propylene; (ii) vinylidene fluoride, tetrafluoroethylene, ethylene, and perfluoroalkyl vinyl ether, such as
  • Embodiment 12 The curable partially fluorinated polymer composition of any one of the previous embodiments, wherein the curable composition is substantially free of a coagent.
  • Embodiment 13 The curable partially fluorinated polymer composition of any one of the previous embodiments, further comprising an organo onium compound.
  • Embodiment 14 The curable partially fluorinated polymer composition of embodiment 13, wherein the organo onium compound is selected from at least one of a phosphonium or a sulfonium.
  • Embodiment 15 The curable partially fluorinated polymer composition of any one of the previous embodiments, further comprising an acid acceptor.
  • Embodiment 16 The curable partially fluorinated polymer composition of embodiment 15, wherein the acid acceptor is selected from at least one of magnesium oxide, lead oxide, calcium oxide, calcium hydroxide, dibasic lead phosphate, zinc oxide, barium carbonate, strontium hydroxide, calcium carbonate, and hydrotalcite.
  • the acid acceptor is selected from at least one of magnesium oxide, lead oxide, calcium oxide, calcium hydroxide, dibasic lead phosphate, zinc oxide, barium carbonate, strontium hydroxide, calcium carbonate, and hydrotalcite.
  • Embodiment 17 The curable partially fluorinated polymer composition of any one of embodiments 2-16, wherein the peroxide is selected from at least one of 2,5-dimethyl- 2,5-di(t-butylperoxy)-hexane, dicumyl peroxide, di(2-t-butylperoxyisopropyl)benzene, and combinations thereof.
  • the peroxide is selected from at least one of 2,5-dimethyl- 2,5-di(t-butylperoxy)-hexane, dicumyl peroxide, di(2-t-butylperoxyisopropyl)benzene, and combinations thereof.
  • Embodiment 18 The curable partially fluorinated polymer composition of any one of the previous embodiments, comprising 1 to 10 millimoles of the curing agent per 100 parts of the partially fluorinated amorphous fluoropolymer.
  • Embodiment 19 An article comprising the cured composition of any one of embodiments 1-18.
  • Embodiment 20 The method of making a partially fluorinated elastomer comprising:
  • VDF/TFE/P #1 Base resistant amorphous fluoropolymer 35 mole % VDF/40 mole % TFE/ 25 mole % P made according to "Preparation VDF/TFE/P#1"
  • VDF/TFE/P #2 Amorphous copolymer of VDF/TFE/P commercially available from Asahi Glass, Tokyo, Japan under the trade designation AFLAS 200P.
  • VDF/TFE/HFP Amorphous copolymer VDF/TFE/HFP terpolymer made
  • Carbon black N990 carbon black commercially available from Cabot, Boston,
  • Silica filler Commercially available from US Silica, Frederick, MA under the trade designation "MIN-U-SIL 5"
  • Triphenylbenzylphosphonium chloride cure accelerator commercially available from Sigma-Aldrich, St.Louis, MO
  • Onium 2 Organophosphonium cure accelearator commercially available from 3M, St.Paul, MN under the trade designation "Dynamar FX 5166".
  • VAROX DBPH-50 from R.T. Vanderbilt Company, Inc., Norwalk, CT
  • MgO An acid acceptor. Magnesium oxide powder commercially available from Akrochem Corp., Akron, Ohio under the trade designation "ELASTOMAG 170"
  • Ca(OH) 2 An acid acceptor.
  • Calcium hydroxide commercially available under the trade designation "Rhenofit CF” from RheinChemie, Mannheim, Germany
  • the reaction was initiated with addition of l,4g ammonium peroxodisulphate (APS) dissolved in 280mL deionized water by continuously feeding.
  • APS ammonium peroxodisulphate
  • 280mL deionized water deionized water
  • the composition of the resulted polymer was 13.5 mole % MV31, 69.7 mole% VDF, 16.1mole% TFE, and 0.7mole% BTFE.
  • the top glyme solution phase was removed and placed in a round bottom flask and rotary evaporated at 50°C/2 torn This was followed by heating to 50°C at 0.13 kPa (1 torr) using a vacuum pump for one hour followed by the addition of 400g of chloroform and stirred slurry for 20 hrs. The slurry was filtered and the solution was rotary evaporated at 50°C/20 torr isolated 50g viscous oily product. A second chloroform extraction done to the solids gave 21g of additional oily product for a 76% yield.
  • hexafluorofluoroisopropylidene phenol was done by flash chromatography (available under the trade designation "INTELLIFLASH 280", Analogix Co., Santa Clara, CA) with a silica gel column eluding first with heptane as the nonpolar solvent and ending with ethyl acetate as the polar solvent. LC/UV analysis gave 99.23 mole percent of
  • CH 2 CHCH2-OC6H4C(CF3)2C 6 H4-OH.
  • the material as synthesized was diluted in methanol to a 50% solids concentration in order to better facilitate the incorporation into the polymer.
  • the top methyl-t-butyl ether solution phase was removed and placed in a round bottom flask and evaporated at 50°C/1.33 kPa (10 torr), using a rotary evaporator. A charge of 55g of hexane to the product mixture and stirred to give two phases. The bottom phase was extracted with an additional 50g of hexane. The bottom phase was washed twice with chloroform to extract the desired product and filtered to remove insoluble starting diol. The chloroform solution was removed and placed in a round bottom flask and evaporated at 55°C/10torr using a rotary evaporator to isolate 19g product mixture.
  • the reaction temperature of 160°F (71 °C) was maintained.
  • the latex was free of coagulum and had a solids content of approximately 27%.
  • the polymer was isolated by coagulation with magnesium chloride, washing with DI water, and drying at 280°F (138°C) until a moisture content of ⁇ 0.5 weight per cent was reached.
  • Cure rheology tests were carried out using uncured, compounded samples using a rheometer marketed under the trade designation Monsanto Moving Die Rheometer (MDR) Model 2000 by Monsanto Company, Saint Louis, Missouri, in accordance with ASTM D 5289-93a at 177 °C, no pre-heat, 30 min elapsed time, and a 0.5 degree arc. Both the minimum torque (ML) and highest torque attained during a specified period of time when no plateau or maximum torque (MH) was obtained were measured.
  • MDR Monsanto Moving Die Rheometer
  • Tan(delta) is equal to the ratio of the tensile loss modulus to the tensile storage modulus (lower tan(delta) means more elastic).
  • O-rings having a cross-section thickness of 0.139 inch (3.5 mm) were molded (15 min cure at 177 °C) followed by a postcure in air for 16 hrs at 232°C.
  • the O- rings were subjected to compression set testing following a similar method as described in
  • ASTM 395-89 method B (analyzed in triplicate), with 25 % initial deflection at variable time and temperature as per Tables 2 and 3.
  • VDF/TFE/P #2 (AFLAS 200P) contains an onium.
  • the combined ID and 2D 3 ⁇ 4-NMR spectral data were used to positively confirm the presence of a small amount of a component with a tetrabutylammonium cationic specie (0.36 wt.% of (CH 3 CH 2 CH 2 CH 2 ) 4 -N (+) .

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Abstract

L'invention concerne une composition durcissable de polymère partiellement fluoré et un procédé correspondant. La composition comprend : (i) un fluoropolymère amorphe partiellement fluoré, le fluoropolymère amorphe partiellement fluoré comprenant des doubles liaisons carbone-carbone ou pouvant former des doubles liaisons carbone-carbone le long du fluoropolymère amorphe partiellement fluoré, le fluoropolymère amorphe partiellement fluoré étant pratiquement exempt de brome, d'iode et de nitrile ; et (ii) un agent de durcissement comprenant une oléfine terminale présentant au moins un hydrogène oléfinique.
PCT/US2015/065933 2014-12-19 2015-12-16 Compositions durcissables de polymère partiellement fluoré WO2016100421A1 (fr)

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MX2017008046A MX2017008046A (es) 2014-12-19 2015-12-16 Composiciones de polímero parcialmente fluorado curables.
CA2971219A CA2971219A1 (fr) 2014-12-19 2015-12-16 Compositions durcissables de polymere partiellement fluore
CN201580069383.0A CN107109012A (zh) 2014-12-19 2015-12-16 可固化的部分氟化的聚合物组合物
JP2017532105A JP6802164B2 (ja) 2014-12-19 2015-12-16 硬化性部分フッ素化ポリマー組成物
KR1020177019629A KR20170099947A (ko) 2014-12-19 2015-12-16 경화성 부분 플루오르화 중합체 조성물
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WO2019126298A1 (fr) 2017-12-22 2019-06-27 3M Innovative Properties Company Élastomères halogénés durcis à l'aide de peroxyde possédant une couche superficielle contenant du silicium
WO2019239288A1 (fr) 2018-06-12 2019-12-19 3M Innovative Properties Company Compositions de revêtement contenant un polymère fluoré et articles obtenus à partir de celles-ci
US11292763B2 (en) 2017-05-19 2022-04-05 3M Innovative Properties Company Methods of making a polyfluorinated allyl ether and compounds relating to the methods

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WO2021038384A1 (fr) * 2019-08-23 2021-03-04 3M Innovative Properties Company Compositions de fluoropolymère durcissables comprenant un composé contenant un phtalonitrile et une liaison oléfinique et articles durcis à partir de ces compositions
JP2024064171A (ja) * 2022-10-27 2024-05-14 ダイキン工業株式会社 フッ素ゴム架橋用組成物および成形品
WO2024090559A1 (fr) * 2022-10-27 2024-05-02 ダイキン工業株式会社 Composition pour réticulation de caoutchouc fluoré, et article moulé

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WO2019126298A1 (fr) 2017-12-22 2019-06-27 3M Innovative Properties Company Élastomères halogénés durcis à l'aide de peroxyde possédant une couche superficielle contenant du silicium
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WO2019239288A1 (fr) 2018-06-12 2019-12-19 3M Innovative Properties Company Compositions de revêtement contenant un polymère fluoré et articles obtenus à partir de celles-ci

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JP2017538023A (ja) 2017-12-21
CN107109012A (zh) 2017-08-29
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