WO2016100420A1 - Compositions durcissables de polymère partiellement fluoré - Google Patents

Compositions durcissables de polymère partiellement fluoré Download PDF

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WO2016100420A1
WO2016100420A1 PCT/US2015/065932 US2015065932W WO2016100420A1 WO 2016100420 A1 WO2016100420 A1 WO 2016100420A1 US 2015065932 W US2015065932 W US 2015065932W WO 2016100420 A1 WO2016100420 A1 WO 2016100420A1
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partially fluorinated
vinylidene fluoride
tetrafluoroethylene
amorphous fluoropolymer
polymer composition
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PCT/US2015/065932
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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 JP2017532135A priority Critical patent/JP2017538025A/ja
Priority to CN201580069377.5A priority patent/CN107318265A/zh
Priority to EP15870929.5A priority patent/EP3233938A4/fr
Priority to MX2017008045A priority patent/MX2017008045A/es
Priority to CA2971217A priority patent/CA2971217A1/fr
Priority to KR1020177019628A priority patent/KR20170099946A/ko
Publication of WO2016100420A1 publication Critical patent/WO2016100420A1/fr

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    • 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
    • C08F214/28—Hexyfluoropropene
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/011—Crosslinking or vulcanising agents, e.g. accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and 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
    • C08F14/18—Monomers containing fluorine
    • 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
    • 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
    • C08F214/22—Vinylidene fluoride
    • C08F214/222—Vinylidene fluoride 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
    • 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
    • C08F214/22—Vinylidene fluoride
    • C08F214/225—Vinylidene fluoride with non-fluorinated comonomers
    • 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
    • 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
    • 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
    • C08K3/28—Nitrogen-containing 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing 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
    • C08K5/04—Oxygen-containing 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
    • C08K5/04—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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C08K5/08—Quinones

Definitions

  • compositions comprising a partially fluorinated amorphous
  • fluoropolymer with a curing agent comprising a terminal olefin with at least one olefinic hydrogen and a nucleophilic group 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 chain;
  • a method of making a partially fluorinated elastomer comprising curing the curable partially fluorinated polymer composition disclosed above.
  • a and/or B includes, (A and B) and (A or B);
  • backbone refers to the main continuous chain of the polymer
  • 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.
  • 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 such as those disclosed herein can be cured with a curing agent comprising a terminal olefin with at least one olefinic hydrogen along with an acid acceptor and an onium compound.
  • 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 halide, an alkoxide, a hydroxide, a tosylate, a mesylate, an amine, an ammonium, a sulfide, a sulfonium, a sulfoxide, a sulfone, and combinations thereof. Also contemplated would be a
  • fluoropolymer comprising adjacent carbons either having both bromine or both iodine atoms attached resulting in the leaving of Br 2 or I 2 .
  • 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
  • HFP hexafluoropropylene
  • VDF or tetrafluoroethylene
  • 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 1 -hydropentafiuoropropylene); 2,3,3, 3-tetrafiuoropropene; and combinations thereof
  • 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 fluoropolymer of the present disclosure can be cured without the need for pendent bromine or iodine cure sites.
  • 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 partially fluorinated amorphous polymer comprises iodine and/or bromine cure sites, which can be used, for example, to enhance the cure of the fluoropolymer.
  • the partially fluorinated amorphous polymer is further derived from a bromine and/or iodine-containing cure site monomer capable of participating in a peroxide curing reaction.
  • Such bromine and/or iodine-containing cure site monomers include:
  • each X may be the same or different and represents H or F
  • Z is Br or I
  • each X independently represents H or F, Z' is Br or I, Rf is a perfluoroalkylene Ci-Ci 2 , optionally containing chlorine atoms and r is 0 or 1 ; for instance: bromotrifluoroethylene, 4-bromo-perfluorobutene-l, and the like; or bromofluoroolefins such as l-bromo-2,2-difluoroethylene and 4-bromo-3,3,4,4-tetrafluorobutene-l ;
  • bromo- olefins such as vinyl bromide and 4-bromo-l-butene.
  • the amorphous fluoropolymer is polymerized in the presence of a bromine and/or iodine-containing chain transfer agent, as is known in the art, such as those having the formula RfPx, wherein P is Br or I, preferably I, Rf is an x-valent alkyl radical having from 1 to 12 carbon atoms, which, optionally may also contain chlorine atoms. Typically, x is 1 or 2.
  • a bromine and/or iodine-containing chain transfer agent as is known in the art, such as those having the formula RfPx, wherein P is Br or I, preferably I, Rf is an x-valent alkyl radical having from 1 to 12 carbon atoms, which, optionally may also contain chlorine atoms. Typically, x is 1 or 2.
  • Useful chain transfer agents include perfluorinated alkyl monoiodide, perfluorinated alkyl diiodide, perfluorinated alkyl monobromide,
  • the amorphous fluoropolymer is substantially free of I, or Br, 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 fluoropolymer of the present disclosure is non- grafted, meaning that it does 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 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; L is a bond or a linking group; and M is a nucleophilic group.
  • L represents a single bond or a linking group.
  • the linking group can be a catenated O, S, or N atom (e.g., an ether linkage), or a divalent organic group, optionally comprising a catenated heteroatom (e.g., O, S or N), and/or optionally substituted.
  • the divalent organic group may be linear, branched, or cyclic.
  • the divalent organic group may be aromatic or aliphatic.
  • the divalent organic group 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).
  • the divalent organic group is -(CH 2 ) n (0)m- P-(Rf) P -(P)q - where n is an integer from 1-10; m is 0 or 1; P is selected from at least one of: an aromatic, a substituted aromatic, and (CH 2 ) n where n is an integer from 1-10; Rf is selected from at least one of: (CF 2 ) n where n is an integer from 1-10, and C(CF 3 ) 2 wherein Rf may be cyclic or aliphatic and/or contain at least one catenated heteroatoms such as O, S and N; p is 0 or 1; and q is 0 or 1.
  • Exemplary divalent organic groups include: -CH 2 -C6H4(OCH 3 )-, -CH 2 -0-CH 2 (CF 2 ) 4 -CH 2 - and -CH 2 -0-C 6 H4-C(CF 3 ) 2 -C 6 H4-, and -CH 2 -0-C 6 H 4 -C(CF 3 ) 2 - C 6 H 4 -0-CH 2 -.
  • M is nucleophilic group, meaning it comprises an unshared electron pair.
  • An exemplary nucleophilic group includes: an alcohol (-OH), an amine (- H2, - HR, and - NRR' where R and R' are an organic group), a thiol (-SH), and carboxylic acid (-COOH).
  • the curing agent comprises at least one nonfluorinated terminal olefin group, in other words, the olefin does not comprise any fluorine atoms.
  • the curing agent comprises a non-aromatic terminal olefin and/or non- aromatic alcohol.
  • 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 sails, and ternary sulf onium 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 is ionicaliy associated with an anion.
  • the organic moieties can be the same or different.
  • a sulfonium compound is 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 is 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 art. See, for example, U.S. Pat. Nos. 5,262,490 (Kolb et al.) and 4,912, 171 (Grootaert et al), herein incorporated by reference.
  • Exemplary organo onium compounds include: C3 symmetrical
  • tetraalkylammonium salts unsymmetrical tetraalkylammonium salts wherein the sum of alky] carbons is between 8 and 24 and benzyltrialkyj ammonium salts wherein the sum of alkyl carbons is between 7 and 19 (for example tetrabutylammonium bromide,
  • tetrapentylammonium chloride tetrapropyl ammonium bromide, tetrahexylammonim chloride, and tetraheptylammonium bromidetetramethy!ammonium chloride); quaternary phosphonium salts, such as tetrabutylphosphonium salts, tetraphenylphosphonium chloride, benzyitriphenylphosphonium chloride, tributylaliylphosphonium chloride, tributylbenzyl phosphonium chloride, tributyl-2-methoxypropyl.phosphonium chloride, benzyldiphenyl(dirnethylamino)phosphonium chloride, 8-benzyl-l ,8-diazobicyc!o[5.4.0]7- undeceniuni chloride, benzyltris(dimethylamino)phosphonium chloride, and
  • organo onium compounds include 1 ,8-diazabicyclo[5. .0]undec-7-ene and l,5-diazabicyclo[4.3.0]non-5-ene.
  • Phenol ate 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 free radical source, used to initiate the cure.
  • free radical sources include peroxides such as organic peroxides.
  • peroxides such as 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.
  • the curable composition is substantially free of a free radical source, in other words, less than 0.05 or even 0.01 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.
  • the curable composition is substantially free (less than 1, 0.5, or even 0.1 part per 100 parts per amorphous fluoropolymer% 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 and the curing agent, along with the other components (e.g., the acid acceptor, the onium compound, the free radical source, and/or the 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.
  • mixing the components and additives are distributed uniformly throughout the resulting fluorinated polymer "compound” or polymer sheets.
  • 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 fluoroelastomer is particularly useful as seals, gaskets, and molded parts in automotive, chemical processing, semiconductor, aerospace, and petroleum industry applications, among others.
  • Exemplary embodiments of the present disclosure include:
  • 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 chain;
  • Embodiment 2 The curable partially fluonnated polymer composition of embodiment 1 wherein the partially fluorinated amorphous fluoropolymer comprises (i) adjacent copolymerized units of VDF and HFP; (ii) copolymerized units of VDF and a fluonnated comonomer having an acidic hydrogen atom; (iii) copolymerized units of TFE and a fluo inated comonomer having an acidic hydrogen atom; and (iv) combinations thereof.
  • Embodiment 3 The curable partially fluorinated polymer composition of a embodiment 2 wherein the fluorinated comonomer having an acidic hydrogen atom is selected from: trifluoroethylene; vinyl fluoride; 3,3,3-trifluoropropene-l;
  • Embodiment 4 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 6 The curable partially fluorinated polymer composition of any one of the previous embodiments, wherein the nucleophilic group is selected from an alcohol, an amine, and a thiol.
  • Embodiment 7 The curable partially fluorinated polymer composition of any one of the previous embodiments, wherein the curing agent comprises a nonfluorinated terminal olefin group.
  • Embodiment 8 The curable partially fluorinated polymer composition of any one of the previous embodiments, wherein the curing agent comprises a non-aromatic alcohol.
  • Embodiment 9 The curable partially fluorinated polymer composition of any one of the previous embodiments, wherein the curable partially fluorinated polymer composition is substantially free of a monophenol.
  • Embodiment 10 The curable partially fluorinated polymer composition of any one of the previous embodiments, wherein the curing agent is selected from at least one of:
  • n is an integer from 1 to 10.
  • Embodiment 11 The curable partially fluorinated polymer composition of any one of the previous embodiments, wherein the organo onium compound is selected from at least one of a phosphonium or a sulfonium.
  • Embodiment 12 The curable partially fluorinated polymer composition of any one of the previous embodiments, wherein the partially fluorinated amorphous fluoropolymer is further derived from a cure site monomer comprising at least one of I and Br.
  • Embodiment 13 The curable partially fluorinated polymer composition of any one of embodiments 1-11, wherein the fluoropolymer is substantially free of I, Br, and CI.
  • Embodiment 14 The curable partially fluorinated polymer composition of any one of the previous embodiments, 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 15 The curable partially fluorinated polymer composition of any one of the previous embodiments, further comprising a free radical source.
  • Embodiment 16 The curable partially fluorinated polymer composition of embodiment 15, wherein the free radical source is selected from at least one of a peroxide.
  • Embodiment 17 The curable partially fluorinated polymer composition of embodiment 16, wherein the composition is substantially free of a cogent.
  • Embodiment 18 An article comprising the cured composition of any one of embodiments 1-17.
  • Embodiment 19 The method of making a partially fluorinated elastomer comprising:
  • VAROX DBPH-50 from R.T. Vanderbilt Company, Inc.
  • MgO An acid acceptor. Magnesium oxide powder commercially available from Akrochem Corp., Akron, Ohio under the trade designation "ELASTOMAG 170"
  • the composition of the resulted polymer was 13.5 mole % MV31, 69.7 mole% VDF, 16.1mole% TFE, and 0.7mole% BTFE.
  • CH 2 CH CH 2 , and 23.7% of HO-C 6 H 4 C(CF3) 2 C6H4-OH.
  • the isolation of allyl ether phenyl 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.
  • 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.
  • HARDNESS [0094] Hardness Shore A (2") was measured on post cured samples according to ASTM D-2240-05 (2010) and as indicated in Table 2 and 3.
  • 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 associé. La composition comprenant : (i) un fluoropolymère amorphe partiellement fluoré, le fluoropolymère amorphe partiellement fluoré comprenant des liaisons doubles carbone-carbone ou étant apte à former des liaisons doubles carbone-carbone le long de la chaîne de fluoropolymère amorphe partiellement fluoré ; (ii) 1 à 10 parties d'un agent de durcissement pour 100 parties du fluoropolymère amorphe partiellement fluoré, l'agent de durcissement étant de la formule CX1X2=CX3-L-M, dans laquelle X1, X2 et X3 sont indépendamment choisis parmi H, Cl et F, et au moins l'un de X1, X2 et X3 est H ; L est une liaison ou un groupe de liaison ; et M est un groupe nucléophile ; (iii) un accepteur d'acide ; et (iv) un composé organo-onium.
PCT/US2015/065932 2014-12-19 2015-12-16 Compositions durcissables de polymère partiellement fluoré WO2016100420A1 (fr)

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JP2017532135A JP2017538025A (ja) 2014-12-19 2015-12-16 硬化性部分フッ素化ポリマー組成物
CN201580069377.5A CN107318265A (zh) 2014-12-19 2015-12-16 可固化的部分氟化的聚合物组合物
EP15870929.5A EP3233938A4 (fr) 2014-12-19 2015-12-16 Compositions durcissables de polymère partiellement fluoré
MX2017008045A MX2017008045A (es) 2014-12-19 2015-12-16 Composiciones de polímero parcialmente fluorado curables.
CA2971217A CA2971217A1 (fr) 2014-12-19 2015-12-16 Compositions durcissables de polymere partiellement fluore
KR1020177019628A KR20170099946A (ko) 2014-12-19 2015-12-16 경화성 부분 플루오르화 중합체 조성물

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WO2018125790A1 (fr) 2016-12-28 2018-07-05 3M Innovative Properties Company Élastomères halogénés contenant du silicium
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

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EP3234011A4 (fr) * 2014-12-19 2018-08-01 3M Innovative Properties Company Compositions durcissables de polymère partiellement fluoré
US20210002456A1 (en) * 2018-02-19 2021-01-07 3M Innovative Properties Company Curable fluoroelastomer composition
CN113939557B (zh) * 2019-06-06 2023-08-18 3M创新有限公司 包含含邻苯二甲腈和亲核官能团的化合物的可固化含氟聚合物组合物及由其制得的固化制品
JP2022544415A (ja) * 2019-08-12 2022-10-18 ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー 接着性非晶質パーフルオロポリマー組成物
CN114805660B (zh) * 2022-05-07 2023-06-06 中国科学院化学研究所 一种官能化三氟乙烯基化合物的合成及其树脂制备方法

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WO2018125790A1 (fr) 2016-12-28 2018-07-05 3M Innovative Properties Company Élastomères halogénés contenant du silicium
US11326040B2 (en) 2016-12-28 2022-05-10 3M Innovative Properties Company Silicon-containing halogenated elastomers
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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JP2017538025A (ja) 2017-12-21
EP3233938A1 (fr) 2017-10-25
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