Classifications

• • 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
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/43—Compounds containing sulfur bound to nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C08L101/04—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
  • 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
  • C08L27/20—Homopolymers or copolymers of hexafluoropropene

Definitions

• composition comprising a partially fluorinated elastomer gum and an ionic liquid is described along with methods of making and uses thereof.
• Partially fluoroelastomers such as copolymers of vinylidene fluoride (VDF) and hexafluoropropylene (HFP), and terpolymers of tetrafluoroethylene (TFE), vinylidene fluoride (VDF) and hexafluoropropylene (HFP) have been used for a variety of applications.
• Cure systems such as a peroxide cure system, amine cure system, and polyol cure system can be used to crosslink the partially fluorinated elastomer gums.
• Compression set resistance is the ability of the material to retain its original shape/size when deformed by a force and the force is removed.
• the crosslinking density is one factor influencing the compression set of partially fluorinated elastomers.
• Crosslinkers can be used (e.g., bisphenol AF or its complexes with benzyltriphenylphosphonium chloride), however, as the amount of crosslinker is increased, cure speed is decreased.
• Mooney viscosity is another factor influencing the compression set of partially fluorinated elastomers.
• partially fluorinated elastomers having a higher Mooney viscosity have a lower compression set.
• the higher the Mooney viscosity the more difficult it can be to process the partially fluorinated elastomer gum.
• composition comprising curable fluoroelastomers that has good processing properties (such as cure speed, Mooney viscosity, etc.) while balancing the fluoroelastomers final properties (such as compression set).
• processing properties such as cure speed, Mooney viscosity, etc.
• fluoroelastomers final properties such as compression set.
• a composition comprising: (i) a partially fluorinated elastomer gum comprising a partially fluorinated polymer; and (ii) less than 10 wt % of an ionic liquid based on the total weight of the partially fluorinated polymer and the ionic liquid.
• the amount of the ionic liquid is greater than 0.01 wt% and less than 1.0 wt% based on the total weight of the ionic liquid and the partially fluorinated polymer. [0008] In another embodiment, the amount of the ionic liquid is greater than 1.0 wt% and less than 10.0 wt% based on the total weight of the ionic liquid and the partially fluorinated polymer.
• an article comprising a curable composition comprising: (i) a partially fluorinated elastomer gum comprising a partially fluorinated polymer; and (ii) less than 10 wt % of an ionic liquid based on the total weight of the partially fluorinated polymer and the ionic liquid.
• a cured article comprising (i) a partially fluorinated elastomer gum comprising a partially fluorinated polymer; (ii) less than 10 wt % of an ionic liquid based on the total weight of the partially fluorinated polymer and the ionic liquid; and (iii) a curative.
• a and/or B includes, (A and B) and (A or B);
• copolymer means a polymer derived from two or more different monomeric units and includes terpolymers, quadpolymers, etc.
• 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.).
• Ionic liquids which are salts in a liquid state, have been finding increased applications due to their unique properties, which include high ionic conductivity, wide electrochemical stability, good thermal stability, wide temperature liquid ranges, and environmentally-friendly nature.
• Ionic liquids have been added to gel polymer electrolytes or ionically conductive polymers such as PVDF/HFP copolymers or sulfonated tetrafluoroethylene based fluoropolymers available under the trade designation "NAFION" to improve the polymer's ionic conductivity for use as electrolytes in lithium batteries, super capacitors, fuel cells, etc.
• the ionic liquids typically are added in a weight ratio of at least 0.4 to 1 versus the polymer. See, for example, Fuller, J. et ah, J. Electrochem. Soc, vol. 144, no. 4, 2007, p. L67-L-69.
• JP Pat. Publ. No. 2007-281048 discloses a gel composition for heat dissipation comprising an ionic liquid and a gelling agent, wherein the gelling agent is more than 2 weight (wt) % and less than 50 wt %. If the gelling agent is less than 2% by weight, the gelling of the composition is said to be insufficient and if the gelling agent exceeds 50% by weight, the elasticity and flexability of the gel composition is said to be lost and the composition will become hard.
• a composition can be attained having among other things, improved cure speed, lower Mooney viscosity, and/or improved compression set.
• an ionic liquid may be used to solubilize the a component in the cure system, e.g. bisphenol AF
• crosslinker and/or benzyltriphenylphosphonium chloride (crosslinking aid), which in one embodiment, may provide improved dispersion of the curative.
• 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
• cation examples 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-methoxyethylammonium, 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- ⁇ , ⁇ , ⁇ -tributylammonium, N,N,N-trimethyl-N-hexylammonium, N,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. It is advantageous that the group constituting the cation is substituted with fluorine atoms, because good compatibility with a fluoropolymer is expected.
• R- OS0 3 " a sulfate
• R-S0 3 ⁇ a sulfon
• 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 a 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 ((RfSC ⁇ " ), a perfluoroalkylsulfonate (RfSCV) and a tris(perfluoroalkylsulfonyl)methide ((RfSC ⁇ 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. Specific examples of the
• bis(perfluoroalkylsulfonyl)imide include: bis(trifluoromethanesulfonyl)imide,
• perfluoroalkylsulfonate examples include: trifluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate and nonafluorobutanesulfonate.
• tris(perfluoroalkylsulfonyl)methide examples include: tris(trifluoromethanesulfonyl)methide, tris(pentafluoroethanesulfonyl)methide,
• bis(trifluoromethanesulfonyl)imide can be advantageously used, because of excellent heat resistance and good compatibility with the fluoropolymer.
• bis(trifluoromethanesulfonyl)imide and N-methyl-N,N,N-tributylammonium bis(trifluoromethanesulfonylimide, which are free of an aromatic ring, are particularly suitable for non-coloring applications.
• the ionic liquid is blended with a partially fluorinated elastomer gum that comprises a partially fluorinated polymer to form the compositions of the present disclosure.
• a polymer refers to a macromolecule derived from repeated monomeric units, wherein the macromolecule has a molecular weight greater than 20,000 grams/mole.
• the partially fluorinated polymer as disclosed herein comprises hydrogen atoms as well as fluorine atoms along the carbon backbone of the polymer.
• the partially fluorinated polymer should comprise at least 50%, 60%, or even 70% of amount of fluorine atoms by weight along the carbon backbone of the polymer; and at most 75 or 76 of amount of fluorine atoms by weight along the carbon backbone of the polymer.
• the partially fluorinated polymer should also comprise at least 0.1%, but no more than 40%, 25%, 10%, 5%, or even 1% hydrogen atoms by weight along the carbon backbone of the polymer.
• the partially fluorinated polymer may be derived from one or more fluorinated monomer(s) such as tetrafluoroethylene (TFE), vinyl fluoride (VF), vinylidene fluoride (VDF), hexafluoropropylene (HFP), pentafluoropropylene, trifluoroethylene, trifluorochloroethylene (CTFE), perfluorovinyl ethers (including perfluoroallyl vinyl ethers and perfluoroalkoxy vinyl ethers), perfluoroallyl ethers (including perfluoroalkyl allyl ethers and perfluoroalkoxy allyl ethers), perfluoroalkyl vinyl monomers, and combinations thereof.
• fluorinated monomer(s) such as tetrafluoroethylene (TFE), vinyl fluoride (VF), vinylidene fluoride (VDF), hexafluoropropylene (HFP), pentafluoropropylene,
• Suitable perfluoroalkyl vinyl monomers correspond to the general formula:
• CH 2 CH-R d f wherein R d f represents a perfluoroalkyl group of 1-10, or even 1-5 carbon atoms.
• R b fO (R b fO) m R c f
• R a f and R b f are different linear or branched perfluoroalkylene groups of 1 -6 carbon atoms, in particular 2-6 carbon atoms
• m and n are independently 0-10
• R c f is a perfluoroalkyl group of 1-6 carbon atoms.
• R f represents a perfluorinated aliphatic group that may contain no, one or more oxygen atoms and up to 10, 8, 6 or even 4 carbon atoms.
• CF 2 CF 2 -CF 2 -0-(CF 2 ) x -0-(CF 2 ) y -F wherein x is an integer from 2 to 5 and y is an integer from 1 to 5.
• the partially fluorinated polymer is a copolymer.
• Examplary fluoropolymers include for example, those produced by 3M Co., St. Paul, MN;
• the partially fluorinated polymer may be polymerized in the presence of a chain transfer agent and/or cure site monomers to introduce cure sites into the fluoropolymer.
• Exemplary chain transfer agents include: an iodo-chain transfer agent, a bromo-chain transfer agent, or a chloro-chain transfer agent.
• suitable iodo-chain transfer agent in the polymerization include the formula of RI X , where (i) R is a perfluoroalkyl or
• 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-l,2- dichloro-1, 1 ,2-trifluoroethane, 4-iodo- 1 ,2,4-trichloroperfluorobutan, and mixtures thereof.
• the chain transfer agent may be a perfluorinated bromo-compound.
• Cure-site monomers if used, comprise at least one of a bromine, iodine, and/or nitrogen cure moiety.
• non-fluorinated bromo-or iodo-olefms e.g., vinyl iodide and allyl iodide
• CF 2 CFCF 2 C1, and combinations thereof.
• the cure site monomers comprise nitrogen-containing cure moieties.
• CF 2 CFO(CF 2 ) u OCF(CF 3 )CN wherein u is an integer from 2 to 6;
• CF 2 CF[OCF 2 CF(CF 3 )] r O(CF 2 ) t CN wherein r is 1 or 2, and t is an integer from 1 to 4; and derivatives and combinations of the foregoing.
• CF 2 CFOCF 2 CF(CF 3 )OCF 2 CF(CF 3 )CN
• CF 2 CFOCF 2 CF 2 CF 2 OCF(CF 3 )CN
• CF 2 CFOCF 2 CF(CF 3 )OCF 2 CF 2 CN; and combinations thereof.
• the partially fluorinated polymer is a partially fluorinated elastomer gum obtained generally by polymerizing one or more types of monomers.
• the partially fluorinated elastomer gum may or may not be crosslinked. Crosslinking of the partially fluorinated elastomer gum can be performed generally with a peroxide, a polyol, or a polyamine cure system (or curative).
• Peroxide curatives include organic or inorganic peroxides. Organic peroxides are preferred, particularly those that do not decompose during dynamic mixing temperatures.
• the crosslinking using a peroxide can be performed generally by using an organic peroxide as a crosslinking agent and, if desired, a crosslinking aid such as diallyl ether of glycerin, triallylphosphoric acid, diallyl adipate, diallylmelamine and triallyl isocyanurate (TAIC), tri(methyl)allyl isocyanurate (TMAIC), tri(methyl)allyl cyanurate, poly-triallyl isocyanurate (poly- TAIC), xylylene-bis(diallyl isocyanurate) (XBD), and N,N'-m-phenylene bismaleimide.
• TAIC diallyl ether of glycerin, triallylphosphoric acid, diallyl adipate, diallylmelamine and triallyl isocyanurate
• TMAIC tri(methyl)allyl isocyanurate
• poly- TAIC poly-triallyl isocyanurate
• XBD
• organic peroxide examples include benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-di- methyl-2,5-di-tert-butylperoxyhexane, 2,4-dichlorobenzoyl peroxide, 1 , 1 -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, 0,0'- l,3-propanediyl 00,00'-bis(l,l-dimethylethyl) ester, tert- butylperoxy benzoate,
• peroxide curatives are listed in U.S. Pat. No. 5,225,504 (Tatsu et al.).
• the amount of peroxide curing agent used generally will be 0.1 to 5, preferably 1 to 3 parts by weight per 100 parts of fluoropolymer.
• Other conventional radical initiators are suitable for use with the present disclosure.
• the crosslinking using a polyol is performed generally by using a polyol compound as a crosslinking agent, a crosslinking aid such as ammonium salt, phosphonium salt and iminium salt, and a hydroxide or oxide of a divalent metal such as magnesium, calcium, or zinc.
• a polyol compound examples include bisphenol AF, bisphenol A, bisphenol S, dihydroxybenzophenone, hydroquinone, 2,4,6-trimercapto-S-triazine, 4,4'-thiodiphenol, and a metal salt thereof.
• the crosslinking using a polyamine is performed generally by using a polyamine compound as a crosslinking agent, and an oxide of a divalent metal such as magnesium, calcium, or zinc.
• a polyamine compound or the precursor of the polyamine compound include hexamethylenediamine and a carbamate thereof, 4,4'-bis(aminocyclohexyl)methane and a carbamate thereof, and N,N'-dicinnamylidene-l,6-hexamethylenediamine.
• This crosslinking agent, crosslinking aid, and acid-receiving agent composed of a hydroxide, oxide, or the like of a divalent metal each may be used in a conventionally known amount, and the amount used can be appropriately determined by one skilled in the art while taking into consideration the miscibility with the fluoropolymer, mechanical strength of the crosslinked fluoropolymer, profitability and the like.
• the amount used of each of these components participating in the crosslinking may be, for example, about 1 part by mass or more, about 5 parts by mass or more, about 10 parts by mass or more, or about 15 parts by mass or more, and about 60 parts by mass or less, about 40 parts by mass or less, about 30 parts by mass or less, or about 20 parts by mass or less, per 100 parts by mass of the fluoropolymer.
• the total amount of the components participating in the crosslinking may be, for example, about 1 part by mass or more, about 5 parts by mass or more, or about 10 parts by mass or more, and about 60 parts by mass or less, about 40 parts by mass or less, or about 30 parts by mass or less, per 100 parts by mass of the fluoropolymers.
• a low amount of the ionic liquid i.e., less than 10, 8, 6, 5, 3, 2, or even 1 weight % of the ionic liquid based on the total weight of the partially fluorinated polymer and the ionic liquid
• a sufficient amount of ionic liquid e.g., greater than 0.0005 wt % of the ionic liquid based on the total weight of the partially fluorinated polymer and the ionic liquid
• a sufficient amount of ionic liquid must be used, to elicit some improvement (whether it be with respect to processing or final product properties) in the composition of the present disclosure versus when no ionic liquid is present.
• the amount of the ionic liquid is greater than 0.010, 0.020, 0.050, 0.070, 0.10, 0.20, or even 0.50 wt% and less than 1.0, 0.90, 0.80, or even 0.60 wt% based on the total weight of the ionic liquid and the partially fluorinated polymer.
• the amount of the ionic liquid is greater than 1.0, 2.0, or even 4.0 wt% and less than 10.0, 9.0, 8.0, or even 6.0 wt% based on the total weight of the ionic liquid and the partially fluorinated polymer.
• the present disclosure is directed to a composition
• a miscible blend means the blend of the ionic liquid and the partially fluorinated polymer is a molecular level dispersion, which is different from a microphase separation or dispersion, e,g, gel, and the miscible blend will behave as one component. In other words, the miscible blend will have a single glass transition temperature (T g ).
• the single T g of the miscible blend will be substantially the same as the T g of the partially fluorinated polymer. If a blend of ionic liquid and fluoropolymer is immiscible, two T g 's would be observed and at least one of the T g 's would be the same as the T g for the fluoropolymer.
• the glass transition temperature (T g ) is the temperature at which a polymer transitions from an amorphous state to a glassy state.
• DSC differential scanning calorimetry
• G loss modulus
• G' storage modulus
• the T g of the miscible blend according to the present disclosure (comprising the partially fluorinated polymer (either cured or uncured) and the ionic liquid) will be substantially the same as the T g of the partially fluorinated polymer (either cured or uncured).
• the T g of the partially fluorinated polymer blended with the ionic liquid is less than 3, 2, 1, or even 0 °C different than the T g of the partially fluorinated polymer itself.
• a composition comprising the elastomer gum can have among other things, improved cure speed, lower Mooney viscosity, and/or improved compression set.
• Ionic liquids are known as an ion conductive liquid. See, for example, Masayoshi Watanabe and Tomoo, Solid State Ionics, vol. 86-88 (1996) 353-356. Because a low amount (e.g., less than 10 wt %) of the ionic liquid to a partially fluorinated polymer is used, in one
• the ionic liquid does not substantially change the ionic character of the partially fluorinated polymer.
• substantially change means that the addition of the ionic liquid to the partially fluorinated polymer, does not make the partially fluorinated polymer go from a non-conductive material (i.e., less than 10 "8 S/cm) to a semi- conductive (i.e., between 10 "8 S/cm and 10 1 S/cm ) or a conductive material (i.e., greater than 10 1 S/cm), nor make the partially fluorinated polymer go from a semi-conductive material to a conductive material.
• the composition is non-conductive meaning that it has a conductivity of less than about 1 xlO "8 S/cm, 1 x 10 ⁇ 9 S/cm, or even 1 x 10 "10 S/cm.
• the amount of ionic liquid used and its impact on the resulting composition can vary based on the ionic liquid used, the partially fluorinated polymer composition, and the cure system employed. For example, in one embodiment, when a low amount of ionic liquid is used, the compression set increases. In another embodiment, when a low amount of ionic liquid is used, the compression set compression set is unchanged or slightly lower, however, the cure time shortens. In another embodiment, when a low amount of ionic liquid is used, the Mooney viscosity decreases.
• the ionic liquid which may have a solubility for the polymer and the curing agent, can improve the homogeneity of the composition and thus, improve, for example, the cure speed and/or the compression set.
• an ionic liquid may be used to replace the traditional volatile solvents (such as ethanol or methanol), which have been used to dissolve or disperse the solid curative when incorporating it into the polymer.
• the solid curative (or curing agent) is soluble (i.e., colorless and clear or hazy) in the ionic liquid when rolled at 2.4 rpms (revolutions per minute) for lhour at 23°C.
• the solid curative (or curing agent) is soluble (i.e., colorless and clear or hazy) in the ionic liquid when rolled at 2.4 rpms for 16 hrs at 40°C.
• adjuvants such as, for example, acid acceptors, process aids, or colorants may be added to the composition.
• Such fillers include: an organic or inorganic filler such as clay, silica (S1O 2 ), alumina, iron red, talc, diatomaceous earth, barium sulfate, wollastonite (CaSi0 3 ), calcium carbonate (CaC0 3 ), calcium fluoride, titanium oxide, iron oxide and carbon black fillers, a polytetrafluoroethylene powder, PFA (TFE/perfluorovinyl ether copolymer) powder, an electrically conductive filler, a heat-dissipating filler, and the like may be added as an optional component to the composition.
• an organic or inorganic filler such as clay, silica (S1O 2 ), alumina, iron red, talc, diatomaceous earth, barium sulfate, wollastonite (CaSi0 3 ), calcium carbonate (CaC0 3 ), calcium fluoride, titanium oxide, iron oxide and carbon black fillers, a
• 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 composition comprises less than 40, 30, 20, 15, or even 10% by weight of the inorganic filler.
• acid acceptors may be employed to facilitate the cure and thermal stability of the compound.
• Suitable acid acceptors may include magnesium oxide, lead oxide, calcium oxide, calcium hydroxide, dibasic lead phosphite, zinc oxide, barium carbonate, strontium hydroxide, calcium carbonate, hydrotalcite, alkali stearates, magnesium oxalate, or combinations thereof.
• the acid acceptors are preferably used in amounts ranging from about 1 to about 20 parts per 100 parts by weight of the polymer.
• a solution or liquid dispersion containing the partially fluorinated elastomer gum, the ionic liquid and other components described above may be prepared using a solvent such as ketone (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone), ether (e.g., diethyl ether,
• ketone e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone
• ether e.g., diethyl ether
• the solution or liquid dispersion prepared may be coated on the surface of a substrate such as paper, fiber, film, sheet, tape, plate, tube, pipe, tank and vessel, and the solvent may be removed by drying. In this way, an article containing a composition layer and a substrate can be formed.
• a substrate such as paper, fiber, film, sheet, tape, plate, tube, pipe, tank and vessel, and the solvent may be removed by drying. In this way, an article containing a composition layer and a substrate can be formed.
• the method for mixing the partially fluorinated elastomer gum, the ionic liquid and other components described above include, for example, kneading with use of a twin roll for rubber, a pressure kneader or a Banbury mixer.
• the mixture may then be processed and shaped such as by extrusion or molding to form an article of various shapes such as sheet, a hose, a hose lining, an o-ring, a gasket, or a seal composed of the composition of the present disclosure.
• the shaped article may then be heated to cure the gum composition and form a cured elastomer article.
• Pressing of the compounded mixture is typically conducted at a temperature of about 120-220°C, preferably about 140-200°C, for a period of about 1 minute to about 15 hours, usually for about 1-15 minutes.
• the molds first may be coated with a release agent and prebaked.
• the molded vulcanizate can be post cured in an oven at a temperature of about 140-240°C, preferably at a temperature of about 160-230°C, for a period of about 1-24 hours or more, depending on the cross-sectional thickness of the sample.
• the temperature during the post cure is usually raised gradually from the lower limit of the range to the desired maximum temperature.
• the maximum temperature used is preferably about 260°C, and is held at this value for about 1 hour or more.
• compositions of the present disclosure may be used in articles, such as a hose, a gasket, or a seal. These compositions may or may not be cured.
• Exemplary embodiments of the present disclosure include, but are not limited to the following:
• Embodiment 1 A composition comprising:
• Embodiment 2 The composition of embodiment 1, wherein the partially fluorinated polymer has a glass transition temperature and the addition of the ionic liquid does not substantially change the glass transition temperature.
• Embodiment 3 The composition according to any one of the previous embodiments, wherein the amount of the ionic liquid is greater than 0.01 wt% and less than 1.0 wt% based on the total weight of the ionic liquid and the partially fluorinated polymer.
• Embodiment 4 The composition according to any one of embodiments 1-2, wherein the amount of the ionic liquid is greater than 1.0 wt% and less than 10.0 wt% based on the total weight of the ionic liquid and the partially fluorinated polymer.
• Embodiment 5 The composition according to any one of the previous embodiments, wherein the partially fluorinated polymer is a copolymer.
• Embodiment 6 The composition according to any one of the previous embodiments, wherein the ionic liquid has a melting point of about 100°C or less.
• Embodiment 7 The composition according to any one of the previous embodiments, wherein the partially fluorinated polymer is derived from one or more fluorinated monomer(s) selected from at least one of tetrafluoroethylene, vinyl fluoride, vinylidene fluoride,
• hexafluoropropylene pentafluoropropylene, trifluoroethylene, trifluorochloroethylene, a perfluoroalkyl vinyl ether, a perfluoroalkyl allyl ether, a perfluoroalkoxy vinyl ether, and a perfluoroalkoxy allyl ether.
• Embodiment 8 The composition according to any one of the previous embodiments, wherein the partially fluorinated polymer is a vinylidene fluoride/hexafluoropropylene copolymer, a tetrafluoroethylene/vinylidene fluoride/hexafluoropropylene copolymer, a
• tetrafluoroethylene/propylene copolymer a tetrafluoroethylene/vinylidene fluoride/PMVE copolymer, a tetrafluoroethylene/vinylidene fluoride/propylene copolymer, a
• chlorotrifluoroethylene/vinylidene fluoride copolymer or an ethylene/hexafluoropropylene copolymer.
• Embodiment 9 The composition according to any one of embodiment 1 -7, with the proviso that the partially fluorinated polymer is not a vinylidene fluoride/hexafluoropropylene copolymer.
• Embodiment 10 The composition according to any one of the previous embodiments, wherein the anion of the ionic liquid comprises a perfluoroalkyl group.
• Embodiment 11 The composition according to any one of the previous embodiments, wherein the cation portion of the ionic liquid is selected from 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- methoxyethylammonium, N-methyl-N,N,N-tris(methoxyethyl)ammonium, N-methyl-N,N,N- tributylammonium, N,N,N-trimethyl-N-hexylammonium, N,N-diethyl-N-methyl-N-(2- methoxy ethyl) ammonium, 1 -propyl-tetrahydrothiophenium,
• Embodiment 12 The composition according to any one of the previous embodiments, wherein the anion portion of the ionic liquid is selected from bis(trifluoromethanesulfonyl) imide, bis(pentafluoroethanesulfonyl)imide, bis(heptafluoropropanesulfonyl)imide,
• bis(nonafluorobutanesulfonyl)imide bis(nonafluorobutanesulfonyl)imide, trifluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, tris(trifluoromethanesulfonyl)methide, tris(pentafluoroethanesulfonyl)methide, tris(heptafluoropropanesulfonyl)methide,
• Embodiment 13 The composition according to any one of the previous embodiments, wherein the partially fluorinated polymer further comprises a cure site, wherein the cure-site is selected from at least one of a bromine, iodine, and nitrogen cure moiety.
• CF 2 CFOCF 2 CF(CF 3 )OCF 2 CF 2 CN
• CF 2 CFOCF 2 CF(CF 3 )OCF 2 CF(CF 3 )CN
• CF 2 CFOCF 2 CF 2 CF 2 OCF(CF 3 )CN
• CF 2 CFOCF 2 CF(CF 3 )OCF 2 CF 2 CN.
• Embodiment 15 The composition according to any one of embodiments 13-14, wherein the partially fluorinated elastomer gum is peroxide curable.
• Embodiment 16 The composition according to any one of the previous embodiments, further comprising a peroxide, and optionally, a crosslinking aid.
• Embodiment 17 The composition according to embodiment 16, wherein the peroxide is selected from at least one of: benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, 2,5- dimethyl-2,5-di(tbutylperoxy)hexane, di-t-butyl peroxide, t-butylperoxy benzoate, and 2,5- dimethyl-2,5-di(t-butylperoxy)hexane-3, laurel peroxide.
• the peroxide is selected from at least one of: benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, 2,5- dimethyl-2,5-di(tbutylperoxy)hexane, di-t-butyl peroxide, t-butylperoxy benzoate, and 2,5- dimethyl-2,5-di(t-butylperoxy)hexane-3, laurel peroxide
• Embodiment 18 The composition according to any one of embodiments 13-14, wherein the partially fluorinated elastomer gum is bisphenol or amine curable.
• Embodiment 19 The composition according to any one of the previous embodiments, further comprising bisphenol A.
• Embodiment 20 The composition according to any one of the previous embodiments further comprising an inorganic filler.
• Embodiment 21 The composition according to embodiment 20, wherein the inorganic filler is selected from at least one of carbon black, graphite, clay, silica, talc, diatomaceous earth, barium sulfate, wollastonite, calcium carbonate, calcium fluoride, titanium oxide, and iron oxide.
• the inorganic filler is selected from at least one of carbon black, graphite, clay, silica, talc, diatomaceous earth, barium sulfate, wollastonite, calcium carbonate, calcium fluoride, titanium oxide, and iron oxide.
• Embodiment 22 The composition according to any one of the previous embodiments, wherein the composition comprises less than 20% by weight of the inorganic filler.
• Embodiment 23 The composition according to any one of the previous embodiments further comprising a organic filler selected from at least one of a PTFE powder and a PFA powder.
• Embodiment 23 The composition according to any one of the previous embodiments, wherein the composition is non-conductive.
• Embodiment 24 An article comprising the composition according to any one of the previous embodiments.
• Embodiment 25 A cured article comprising the composition according to any one of embodiments 1-23.
• Embodiment 26 The cured article according to embodiment 25, wherein the cured article is a hose, a gasket, or a seal.
• Embodiment 27 A method comprising blending (i) partially fluorinated elastomer gum comprising a partially fluorinated polymer and (ii) less than 10 wt % of an ionic liquid based on the total weight of the partially fluorinated polymer and the ionic liquid.
• Embodiment 28 The method of embodiment 27, wherein the partially fluorinated polymer has a glass transition temperature and the addition of the ionic liquid does not substantially change the glass transition temperature.
• Embodiment 29 The method of any one of embodiments 27-28, wherein the amount of the ionic liquid is greater than 0.01 wt% and less than 1.0 wt% based on the total weight of the ionic liquid and the partially fluorinated polymer.
• Embodiment 30 The method of any one of embodiments 27-28, wherein the amount of the ionic liquid is greater than 1.0 wt% and less than 10.0 wt% based on the total weight of the ionic liquid and the partially fluorinated polymer.
• Embodiment 31 The method of any one of embodiments 27-30, wherein the partially fluorinated polymer is a copolymer.
• Embodiment 32 The method of any one of embodiments 27-31, wherein the ionic liquid has a melting point of about 100°C or less.
• Embodiment 33 The method of any one of embodiments 27-32, with the proviso that the partially fluorinated polymer is not a vinylidene fluoride/hexafluoropropylene copolymer.
• Embodiment 34 The method of any one of embodiments 27-33, wherein the anion of the ionic liquid comprises a perfluoroalkyl group.
• Embodiment 35 The method of any one of embodiments 27-34, further comprising curing the partially fluorinated elastomer gum with a curing system selected from at least one of a peroxide system, a polyol system, and a polyamine system.
• a curing system selected from at least one of a peroxide system, a polyol system, and a polyamine system.
• Embodiment 36 Use of the cured article of embodiment 25 as a hose, gasket or a seal.
• Embodiment 37 A composition comprising:
• Embodiment 38 The composition of embodiment 37, wherein the cured partially fluorinated polymer has a glass transition temperature and the addition of the ionic liquid does not substantially change the glass transition temperature.
• Mooney viscosity of the compounded formulations were tested following a procedure as disclosed in ASTM D- 1646-07 "Standard Test Method for Rubber- Viscosity, Stress Relaxation, and Pre-Vulcanization Characteristics (Mooney Viscometer)".
• the pre heat time was 1 min at 121 °C and the test time was 10 min. at 121°C.
• the glass transition temperature was determined by a peak temperature of tan ⁇ calculated from storage modulus (G') and loss modulus (G") using a dynamic mechanical analyzer, AR 2000EX (manufactured by TA Instruments, New Castle, DE) in accordance with
• Mooney Viscosity Method described above. The Mooney Viscosity for the samples is shown in Tables 5-8 below. Then, if used, Carbon, Cure 4, Coagent, MgO, and Ca(OH) 2 was placed in the center of the polymer band and compounded again on the two roll mill.
• Example 10 A 10% solution was made with 1.0 grams of bisphenol AF (solid) was added to 9.0 grams of IL#1 in a glass jar. The resulting solution was clear and colorless.
• Example 1 1 A 20% solution was made with 2.0 grams of bisphenol AF (solid) was added to 8.0 grams of IL#1 in a glass jar. After 16 hrs at 40°C on the roller, the resulting solution was clear and colorless.
• Example 12 A 1% solution was made with 0.1 grams of benzyltriphenyl phosphonium chloride (solid) was added to 9.9 grams of IL#1 in a glass jar. After 16 hrs at 40°C on the roller, the resulting solution was clear and colorless.
• Example 13 A 10% solution was made with 1.0 grams of benzyltriphenyl phosphonium chloride (solid) was added to 9.0 grams of IL#1 in a glass jar. The resulting solution was white and cloudy indicating that the curative was not completely dissolved.
• Example 14 A 1% solution was made with 0.1 grams of the Cure 2 in IL#1 in a glass jar. After 16 hrs at 40°C on the roller, the resulting solution was clear and colorless.
• Example 15 A 1% solution was made with 0.1 grams of a 1 : 1 complex of triphenylbenzylphosphonium with bisphenol AF (solid) in IL#1 in a glass jar. After 16 hrs at 40°C on the roller, the resulting solution was colorless and hazy, indicating that the curative was almost completely dissolved.
• Example 1 A Compounds were made as Example 1 A. The amounts of materials used in preparing the fluoroelastomer gums of the Examples and Comparative Examples are shown below in Table 9, wherein the amounts are given in parts by weight. The compounded fluoroelastomer gum samples above were then tested for cure properties following the "MDR" Method described above. The results are shown in Table 10 below.

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