Curable fluoroelastomer composition

Abstract

The present invention relates to a specific fluoroelastomer composition comprising: (i) a fluoroelastomer (fluoroelastomer A) obtained from an emulsion polymerization process without a fluorinated surfactant, having a main chain comprising iodine atoms and / or bromine atoms, and containing 40 to 80 mol% repeating units derived from vinylidene fluoride (VDF) and 20 to 60 mol% repeating units derived from one or more additional fluorinated monomers different from VDF; (ii) one or more organic peroxides; (iii) one or more curing aids; and (iv) one or more fatty acid salts. This composition yields a cured part having improved c-set performance compared to the same composition without the addition of fatty acid salts.

Description

[Technical Field]

[0001] The present invention relates to a novel peroxide-curable fluoroelastomer composition based on a fluoroelastomer produced without the use of a fluorinated surfactant, and to a method for producing a fluoroelastomer molded article using the same. [Background technology]

[0002] This application claims priority under European Patent Application Publication No. 23164295.0, filed on 27 March 2023, and the entire contents of this application are incorporated herein by reference for all purposes.

[0003] Fluoroelastomers based on vinylidene fluoride (also known as 1,1-difluoroethylene or VDF) are a group of high-performance materials with diverse applications in the chemical process industry (CPI), including O-rings, valve stem seals, shaft seals, gaskets, and hoses.

[0004] Typically, VDF-based fluoroelastomers are amorphous copolymers of VDF, produced by emulsion polymerization, which involves reacting a water-soluble polymerization initiator in the presence of a fluorinated monomer and, in many cases, at least one surfactant (also called an emulsifier). In the past, fluorinated surfactants were used as emulsifiers, but emulsion polymerization processes using non-fluorinated surfactants have been developed to improve the environmental impact of the process. More recently, methods for producing VDF-based fluoroelastomers by emulsion polymerization without the use of surfactants are also described, for example, in International Publication No. 2019 / 002180.

[0005] The resulting fluoroelastomer is typically molded into the shape of the desired object and then cured to produce the final cured part (this process is also called "vulcanization").

[0006] The properties of the final vulcanized parts manufactured from such fluoroelastomers are greatly influenced by the curing system used, and it is understood that peroxide-based curing yields higher performance than bisphenol-based ionic curing.

[0007] In peroxide-based curing, the peroxide is added to a fluoroelastomer containing specific curing sites that are reactive under radical conditions, either as pendant groups or terminal groups in the repeating units of the main chain, and to a polyfunctional unsaturated compound. Under the influence of heat, the peroxide generates radicals that facilitate the reaction between the fluoroelastomer chains activated by the curing sites and the polyfunctional unsaturated compound to form a cured mass with chemically interconnected polymer chains.

[0008] Curing of VDF-based fluoroelastomers produced without the use of fluorinated surfactants has been observed to be less efficient in some cases than curing of fluoroelastomers produced by conventional processes using fluorinated surfactants, even though the monomer and curing site composition is the same. In particular, as detailed in the experimental section of this literature, the compression set (c-set) values ​​of certain VDF-based fluoroelastomers having iodine / bromine curing sites and undergoing peroxide-based curing were observed to be inferior to those obtained from VDF-based fluoroelastomers produced from emulsification processes without fluorinated surfactants.

[0009] At present, the reason for this effect is unknown and not bound by theory, but it is speculated that this effect may be due to differences in the distribution and types of chain-end groups in fluoroelastomers obtained from processes that do not use fluorinated surfactants.

[0010] Therefore, there is a need to improve the curing performance of fluoroelastomer compositions that are manufactured by emulsion polymerization without the use of fluorinated surfactants.

[0011] Therefore, an object of the present invention is to provide a fluoroelastomer composition in which the fluoroelastomer is obtained from an emulsion polymerization process without the use of a fluorinated surfactant, and which has performance in terms of c-set value equivalent to a similar composition of a fluoroelastomer obtained from a conventional emulsion process using a fluorinated surfactant after peroxide-based curing. [Overview of the project]

[0012] The present invention (i) Fluoroelastomer (Fluoroelastomer A), • Obtained from an emulsion polymerization process carried out without fluorinated surfactants, • Containing iodine atoms and / or bromine atoms, The main chain comprises 40-80 mol% repeating units derived from vinylidene fluoride (VDF) and 20-60 mol% repeating units derived from one or more additional fluorinated monomers different from VDF. Fluoroelastomer A and (ii) One or more organic peroxides, (iii) One or more curing agents, (iv) One or more fatty acid salts, This relates to a fluoroelastomer composition containing [a specific compound / component].

[0013] The applicant surprisingly found that the addition of fatty acid salts to the composition improved the c-set performance of the cured material, resulting in a composition containing a fluoroelastomer produced without a fluorinated surfactant having substantially the same c-set performance as a composition containing a fluoroelastomer produced using a fluorinated surfactant. [Modes for carrying out the invention]

[0014] For the purposes of this specification and the following claims, For example, the use of parentheses around symbols or numbers that identify a formula, such as "fluoroelastomer (A)," is solely for the purpose of making the symbols or numbers more easily distinguishable from the rest of the text, and therefore the parentheses can be omitted. Unless otherwise specified, terms such as "fluorinated surfactant" and "fluorinated monomer" are intended to include partially and completely fluorinated compounds. The term "phr," commonly used in the elastomer industry, means "parts per 100 parts of rubber," or parts by weight per 100 parts by weight of elastomer. • The term "fluoroelastomer" refers to a polymer that serves as a base component for obtaining a true elastomer. • Such polymers are amorphous polymers, or have a low degree of crystallinity (having a heat of fusion of less than 5 J / g, preferably less than 3 J / g, more preferably less than 1 J / g, as measured by ASTM D-3418) and a glass transition temperature (T) below room temperature. g ) is a polymer having ). In most cases, fluoroelastomer (A) is advantageously below 10°C, preferably below 5°C, more preferably 0°C. g It holds.

[0015] A true elastomer is defined by ASTM, Special Technical Bulletin, Standard 184 as a material that can be stretched to twice its intrinsic length at room temperature and, when released after being held under tension for 5 minutes, simultaneously returns to within 10% of its initial length.

[0016] The composition of the present invention comprises a fluoroelastomer A comprising 40 to 80 mol% of repeating units derived from vinylidene fluoride (VDF) and 20 to 60 mol% of repeating units derived from one or more additional fluorinated monomers different from VDF. Optionally, fluoroelastomer A may also contain repeating units derived from one or more ethylenically unsaturated monomers (hereinafter referred to as hydrogenated monomers) that do not contain fluorine atoms.

[0017] Non-limiting examples of suitable fluorinated monomers different from VDF that can be used in the fluoroelastomer A of the present invention include, in particular (a) C2-C8 perfluoroolefins such as tetrafluoroethylene (TFE) and hexafluoropropylene (HFP); (b) Hydrogen-containing C2-C8 olefins such as vinyl fluoride (VF), trifluoroethylene (TrFE), hexafluoroisobutene (HFIB), and perfluoroalkyl ethylene of the formula CH2=CH-R f (wherein R f is a C1-C6 perfluoroalkyl group); (c) C2-C8 fluoroolefins containing at least one of iodine, chlorine, and bromine such as chlorotrifluoroethylene (CTFE); (d) (Per)fluoroalkyl vinyl ethers (PAVE) of the formula CF2=CFOR f (wherein R f is a C1-C6 (per)fluoroalkyl group, preferably CF3, C2F5, C3F7); (e) (Per)fluoro-oxy-alkyl vinyl ethers of the formula CF2=CFOX (wherein X is a C1-C 12 ((per)fluoro)-oxyalkyl, such as a perfluoro-2-propoxypropyl group); (f) A compound of the formula:

Chemical formula

[0018] Examples of optional hydrogenated monomers include C2-C8 nonfluorinated olefins (Ol), such as ethylene, propylene, 1-butene, diene monomers, and styrene monomers. When present, such optional hydrogenated monomers preferably account for less than 20 mol%, preferably less than 10 mol%, and more preferably less than 5 mol%, based on the total repeating units of fluoroelastomer A.

[0019] Optionally, fluoroelastomer (A) has the general formula: [ka] (In the formula, R1, R2, R3, R4, R5, and R6 are H or C1-C5 alkyl groups, which are equal to or different from each other; Z is preferably a linear or branched C1-C5 alkyl group, which optionally contains an oxygen atom and is at least partially fluorinated.) 18 Hydrocarbon radicals (including alkylene or cycloalkylene radicals), or (per)fluoropolyoxyalkylene radicals, such as those described in European Patent Application Publication No. 661304A (AUSIMONT SPA) dated July 5, 1995. This also includes repeating units derived from one or more bis-olefins [bis-olefins (OF)] having the characteristic [of the same element].

[0020] If present, one or more bis-olefins (OF) are preferably of the formulas (OF-1), (OF-2), and (OF-3): (OF-1) [ka] (In the formula, j is an integer between 2 and 10, preferably between 4 and 8, and R1, R2, R3, R4 are equal to or different from each other, and H, F, or C 1~5 (It is an alkyl or (per)fluoroalkyl group.) (OF-2) [ka] (In the formula, each of A, which is equal to or different from each other and each instance is different, is independently selected from F, Cl, and H; each of B, which is equal to or different from each other and each instance is different from F, Cl, H, and OR B (Here, R B (is a branched or linear alkyl radical that can be partially, substantially, or completely fluorinated or chlorinated) independently selected from; E is a divalent group having 2 to 10 carbon atoms, optionally fluorinated, and may have an ether bond inserted; preferably, E is m an integer from 3 to 5 - (CF2) m - is the base; the preferred bis-olefin of the (OF-2) type is F2C=CF-O-(CF2)5-O-CF=CF2); (OF-3) [ka] (In the formula, E, A and B have the same meanings as defined above, R5, R6 and R7 are equal to or different from each other, and H, F or C 1~5 (It is an alkyl or (per)fluoroalkyl group.) Selected from a group consisting of those that follow the rule.

[0021] When one or more bis-olefins are used, the resulting fluoroelastomer A typically contains 0.01 mol% to 5 mol% of units derived from one or more bis-olefins, relative to the total amount of units of fluoroelastomer A.

[0022] An exemplary fluoroelastomer (A) that may be used in the composition of the present invention has the following monomer composition (mol %) relative to the total number of moles of repeating units: (i) 40-80% vinylidene fluoride (VDF), 10-45% hexafluoropropene (HFP), 0-30% tetrafluoroethylene (TFE), 0-15% (per)fluoroalkyl vinyl ether (PAVE), 0-5% bis-olefin (OF); (ii) 50-80% vinylidene fluoride (VDF), 5-50% (per)fluoroalkyl vinyl ether (PAVE), 0-20% tetrafluoroethylene (TFE), 0-5% bis-olefin (OF); (viii) Vinylidene fluoride (VDF) 40-85%, (per)fluoro-methoxy-vinyl ether (MOVE) 5-40%, (per)fluoroalkyl vinyl ether (PAVE) 0-30%, tetrafluoroethylene (TFE) 0-40%, hexafluoropropene (HFP) 0-30%, bis-olefin (OF): 0-5% It possesses the following characteristics.

[0023] Fluoroelastomer (A) contains iodine and / or bromine atoms; the choice between iodine and bromine is not particularly critical, provided that they ensure sufficient reactivity in curing. Nevertheless, iodine is generally preferred.

[0024] These iodine or bromine atoms may be included in fluoroelastomer (A) as pending groups bonded to the backbone of the fluoroelastomer (A) polymer chain (by the incorporation of repeating units derived from monomers having iodine and / or bromine atoms (referred to as curing site-containing repeating units) into the fluoroelastomer (A) chain, and / or as terminal groups of the polymer chain.

[0025] Among the repeating units containing the hardened area, the following are particularly important: (CSM-1) formula: [ka] (In the formula, A Hf Each of them is either the same as or different from each other and in each existence, and is independently selected from F, Cl, and H; B Hf F, Cl, H and OR Hf B (Here, R Hf B (is a branched-chain or linear alkyl radical that can be partially, substantially, or completely fluorinated or chlorinated); W Hf Each of them is the same or different from each other and in each existence, independently bonded to a covalent or oxygen atom; E Hf R is a divalent group having 2 to 10 carbon atoms that is optionally fluorinated; Hf R is a branched or linear alkyl radical that can be partially, substantially, or completely fluorinated; Hf is a halogen atom selected from the group consisting of iodine and bromine, which may have an ether bond inserted; preferably E is -(CF2) m -Base (m is an integer between 3 and 5) Iodine or bromine-containing monomers, (CSM-2) Cyanide-containing ethylenically unsaturated compounds, sometimes fluorinated. We can list some examples.

[0026] Among the type (CSM1) monomers containing curing sites, preferred monomers are selected from the following group: (CSM1-A) formula: [ka] Iodine-containing perfluorovinyl ethers (wherein m is an integer between 0 and 5, n is an integer between 0 and 3, but at least one of m and n is non-zero, and Rfi is F or CF3 (especially those described in U.S. Patent No. 4,745,165 (AUSIMONT SPA), U.S. Patent No. 4,564,662 (MINNESOTA MINING), and European Patent Application Publication No. 199138A (DAIKIN IND., LTD.))); (CSM-1B) formula: CX1X2 = CX3 - (CF2CF2) p -I Iodine-containing ethylenically unsaturated compounds of the form (wherein X1, X2, and X3 are either the same or different from each other, independently H or F, and p is an integer from 1 to 5) (among these compounds, CH2=CHCF2CF2I, I(CF2CF2)2CH=CH2, ICF2CF2CF=CH2, and I(CF2CF2)2CF=CH2 can be cited); (CSM-1C) formula: CHR=CH-Z-CH2CHR-I (In the formula, R is H or CH3, and Z is a linear or branched C1-C18 (per)fluoroalkylene radical or (per)fluoropolyoxyalkylene radical that optionally contains one or more ether oxygen atoms.) Iodine-containing ethylenically unsaturated compounds (among these compounds, CH2=CH-(CF2)4CH2CH2I, CH2=CH-(CF2)6CH2CH2I, CH2=CH-(CF2)8CH2CH2I, and CH2=CH-(CF2)2CH2CH2I can be cited); (CSM-1D) Bromo and / or iodoalpha-olefins containing 2 to 10 carbon atoms, for example, bromotrifluoroethylene or bromotetrafluorobutene as described in U.S. Patent No. 4035565 (DU PONT) or other compounds disclosed in U.S. Patent No. 4694045 (DU PONT), bromine and / or iodoalpha-olefins.

[0027] According to the first embodiment, iodine atoms and / or bromine atoms are included as pending groups bonded to the backbone of the fluoroelastomer polymer chain. The fluoroelastomer according to this embodiment contains repeating units derived from an iodine or bromine monomer (CSM-1) in an amount of 0.05 to 5 moles per 100 moles of all other repeating units of the fluoroelastomer (A) to advantageously ensure an iodine and / or bromine weight content to satisfy the requirements for achieving a sufficient curing rate and crosslinking density.

[0028] According to a second preferred embodiment, iodine atoms and / or bromine atoms are included as terminal groups of fluoroelastomer (A); the perfluoroelastomer according to this embodiment is generally, - Iodinating and / or brominating chain transfer agents, where preferred chain transfer agents are typically of formula R f (I) x (Br) y (In the formula, R f A chain transfer agent is a (per)fluoroalkyl or (per)fluorochloroalkyl containing 1 to 8 carbon atoms, while x and y are integers from 0 to 2 such that 1 ≤ x + y ≤ 2 (see, for example, U.S. Patent No. 4,243,770 (Daikin Industries, Ltd.) January 6, 1981 and U.S. Patent No. 4,943,622 (Nippon Mectron Co., Ltd.) July 24, 1990); and - Alkali metal or alkaline earth metal iodides and / or bromides, particularly those described in U.S. Patent No. 5,173,553 (AUSIMONT SRL) dated December 22, 1992 It is obtained by adding at least one of the following.

[0029] This means that the preferred reagent (CTA-X) is an iodinating and / or brominating organic chain transfer agent, more preferably of formula R f (I) x (Br) y (In the formula, R f However, it is a (per)fluoroalkyl or a (per)fluorochloroalkyl containing 1 to 8 carbon atoms, while x and y are integers from 0 to 2 such that 1 ≤ x + y ≤ 2. Most preferably, it is of formula R' f (I) x’ (Br) y’ (In the formula, R' f However, it is a perfluoroalkyl group containing 1 to 8 carbon atoms, while x' and y' are integers between 0 and 2 such that 1 ≤ x' + y' ≤ 2, and most preferably x' = 2 and y' = 0.

[0030] In the method of the present invention, an iodized reagent (CTA-X), particularly formula R f (I)2 or R' f (I)2 reagent is preferred, where R f and R' f The above is true.

[0031] When using chain transfer agents, the typical amounts used are 1 to 100 mmol of I and / or Br per kg of fluoroelastomer.

[0032] The fluoroelastomer (A) of the present invention advantageously contains iodine atoms and / or bromine atoms in an amount of 0.001 to 10% by weight, preferably 0.05 to 5% by weight, more preferably 0.1 to 2% by weight, and even more preferably 0.1 to 1% by weight, based on the total weight of the fluoroelastomer (A).

[0033] As described above, the fluoroelastomer A of the present invention is obtained from an emulsion polymerization process carried out without fluorinated surfactants. Preferably, the process is carried out without surfactants, including fluorinated and non-fluorinated surfactants.

[0034] A method for preparing fluoroelastomer A typically involves forming an aqueous reaction medium in a sealable reactor, the reaction medium being free of fluorinated surfactants, containing a free radical initiator, and optionally including a chain transfer agent, preferably an iodine-containing chain transfer agent. The reactor is typically sealed and pressurized with a monomer gas containing VDF, while other monomers are added as gases or liquids depending on the type of monomer. Typically, polymerization is carried out at a temperature of 40°C to 120°C, more preferably 50°C to 100°C, and at a pressure of 10 to 60 bar, more preferably 20 to 55 bar.

[0035] While the selection of radical initiators is not particularly limited, it is understood that those suitable for the method according to the present invention are selected from compounds that can initiate and / or accelerate the polymerization process.

[0036] Inorganic radical initiators may be used, and these include, but are not limited to, persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate, and permanganates such as potassium permanganate.

[0037] Furthermore, organic radical initiators may be used, and these include, but are not limited to, acetylcyclohexanesulfonyl peroxide, diacetyl peroxydicarbonate, dialkyl peroxydicarbonate, such as diethyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, tert-butyl perneodecanoate, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), tert-butyl perpivalate, dioctanoyl peroxide, dilauroyl peroxide, 2,2'-azobis(2,4-dimethylvaleronitrile), tert-butyl azo Examples include -2-cyanobutane, dibenzoyl peroxide, tert-butyl-per-2-ethylhexanoate, tert-butyl permaleate, 2,2'-azobis(isobutyronitrile), bis(tert-butylperoxy)cyclohexane, tert-butyl-peroxyisopropyl carbonate, tert-butyl peracetate, 2,2'-bis(tert-butylperoxy)butane, dicumyl peroxide, di-tert-amyl peroxide, di-tert-butyl peroxide (DTBP), p-methane hydroperoxide, pinan hydroperoxide, cumene hydroperoxide, and tert-butyl hydroperoxide.

[0038] Other suitable radical initiators include halogenated radical initiators, such as chlorocarbon and fluorocarbon acyl peroxides, such as trichloroacetyl peroxide, bis(perfluoro2-propoxypropionyl) peroxide, [CF3CF2CF2OCF(CF3)COO]2, perfluoropropionyl peroxide, (CF3CF2CF2COO)2, (CF3CF2COO)2, {(CF3CF2CF2)-[CF(CF3)CF2O] m -CF(CF3)-COO}2 (in the formula, m=0~8), [ClCF2(CF2)] n COO]2 and [HCF2(CF2)] n COO]2 (in the formula, n=0~8), Perfluoroalkylazo compounds, such as perfluoroazoisopropane, [(CF3)2CFN=]2, RN=NR 〇 (R 〇 Examples include a linear or branched perfluorocarbon group having 1 to 8 carbon atoms, stable or sterically hindered perfluoroalkane radicals, such as the hexafluoropropylene trimer radical, [(CF3)2CF]2(CF2CF2)C· radical, and perfluoroalkanes.

[0039] A redox system comprising at least two components that form a redox pair, such as dimethylaniline-benzoyl peroxide, diethylaniline-benzoyl peroxide, and diphenylamine-benzoyl peroxide, may be used as a radical initiator to initiate the polymerization process.

[0040] A particularly suitable method for preparing fluoroelastomer A by emulsion polymerization without using surfactants, especially fluorinated surfactants, is the method described in International Publication No. 2019 / 002180 (Solvay Specialty Polymers Italy SpA), in which the polymerization process is carried out in the presence of a redox initiation system comprising at least one organic radical initiator and at least one compound having at least one sulfinic acid group.

[0041] Examples of fluorinated surfactants not used in this invention include fluorinated surfactants that conform to the following formula: R * -X B- (T + ) (In the formula, R * This is a C5-C16 (per)fluoroalkyl chain or (per)fluoropolyoxyalkylene chain containing one or more etheric oxygen atoms. X B- -COO - or -SO3 - And, T + H+ NH4 + (and selected from alkali metal ions).

[0042] Specific fluorinated surfactants not used in this invention correspond to the following general formulas: [ka] (In the formula, X1, X2, and X3 are the same or different from each other and are independently selected from C1-6 (per)fluoroalkyl groups containing H, F and optionally one or more catenary oxygen atoms or non-catenary oxygen atoms; L represents a bond or divalent group; RF is a divalent fluorinated C1-3 crosslinking group; and Y is a hydrophilic functional group selected from anionic, cationic, and nonionic functional groups.)

[0043] Exemplary embodiments of fluorinated surfactants not added in the method of the present invention include, among others, ammonium perfluoroctanate, (per)fluoropolyoxyalkylenes and partially fluorinated alkyl sulfonates terminated with one or more carboxylic acid groups, optionally in the form of salts with sodium, ammonium and alkali metals, and formula: [ka] (In the formula, Xa is an alkali metal or ammonium moiety.) It is a compound of [the compound].

[0044] The composition of the present invention comprises one or more organic peroxides (O) and one or more curing aids (U) that together form a crosslinking system capable of promoting the curing of fluoroelastomer A.

[0045] The selection of one or more organic peroxides (O) is not particularly critical, provided that they can generate radicals with the help of a transition metal catalyst. Among the most commonly used peroxides, - Di(alkyl / aryl) peroxides such as di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, di(t-butylperoxyisopropyl)benzene, and dicumyl peroxide; - Diacyl peroxides such as dibenzoyl peroxide, disuccinate peroxide, di(4-methylbenzoyl) peroxide, di(2,4-dichlorobenzoyl) peroxide, dilauroyl peroxide, decanoyl peroxide, etc. - Percarboxylic acids and esters such as di-tert-butylperbenzoate, t-butylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylethylbutylperoxy-2-ethylhexanoate, and 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane. - Peroxy carbonates, especially di(4-t-butylcyclohexyl)peroxydicarbonate, di(2-phenoxyethyl)peroxydicarbonate, bis[1,3-dimethyl-3-(tert-butylperoxy)butyl]carbonate, t-hexylperoxyisopropyl carbonate, t-butylperoxyisopropyl carbonate, etc. - Perketals, e.g., 1,1-bis(tert-butylperoxy)cyclohexane and 2,2-bis(tert-butylperoxy)butane, - Ketone peroxides, for example, cyclohexanone peroxide and acetylacetone peroxide, - Organic hydroperoxides, for example, cumene hydroperoxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide (also known as 2-[(2-hydroperoxybutan-2-yl)peroxy]butan-2-peroxol) and pinan hydroperoxide, - Oil-soluble azo initiators, e.g., 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-cyano-2-butane), dimethyl-2,2'-azobisdimethylisobutyrate, dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-Azobis(cyclohexane-l-carbonitride), 2,2'-Azobis[N-(2-propenyl)-2-methylpropionamide], 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'-Azobis(N-cyclohexyl-2-methylpropionamide), 2,2'-Azobis(isobutyronitrile), 2,2'-Azobis(2-cyano-2-butane), Dimethyl-2,2'-Azobisdimethylisobutylene 1,1'-Azobis(cyclohexanecarbonitride), 2-(t-butylazo)-2-cyanopropane, 2,2'-Azobis[2-methyl-N-(1,1)-bis(hydroxymethyl)-2-hydroxyethyl]propionamide, 2,2'-Azobis[2-methyl-N-hydroxyethyl]-propionamide, 2,2'-Azobis(N,N'-dimethyleneisobutylamine), 2,2'-Azobis(2-methyl-N-[1, 1-Bis(hydroxymethyl)-2-hydroxyethyl]propionamide), 2,2'-Azobis(2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide), 2,2'-Azobis[2-5-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-Azobis(isobutylamide) dihydrate, 2,2'-Azobis(2,2,4-trimethylpentane), 2,2'-Azobis(2-methylpropane) We can list some examples.

[0046] Other suitable peroxide systems are, in particular, those described in European Patent Application Publication No. 136596A (MONTEDISON SPA) of April 10, 1985, and European Patent Application Publication No. 410351A (AUSIMONT SRL) of January 30, 1991, the contents of which are incorporated herein by reference.

[0047] The selection of the most appropriate peroxide according to the curing conditions (time, temperature) will be made by those skilled in the art.

[0048] The amount of peroxide (O) in the composition of this embodiment is typically 0.1 to 15 phr, preferably 0.2 to 12 phr, and more preferably 1.0 to 7.0 phr (wherein "phr" generally means "parts by weight of peroxide per 100 parts by weight of fluoroelastomer A" in the art).

[0049] One or more curing aids U are selected from polyunsaturated compounds. In this specification, the term "polyunsaturated compound" refers to a compound containing two or more carbon-carbon unsaturated compounds.

[0050] Compound (U) may be selected from compounds containing two carbon-carbon unsaturated atoms, compounds containing three carbon-carbon unsaturated atoms, and compounds containing four or more carbon-carbon unsaturated atoms.

[0051] Among the compounds (U) containing two carbon-carbon unsaturated atoms, examples of bis-olefins [bis-olefins (OF)], as detailed above, are preferably selected from those following any of the formulas (OF-1), (OF-2), and (OF-3).

[0052] Among compounds (U) containing three carbon-carbon unsaturated compounds, the following can be listed: (i) Trisubstituted cyanurate compounds of the following general formula: [ka] (In the formula, R is equal to or different from each other and each instance is different.) cy Each of these is H or base-R rcy OR rcy Selected independently from, R rcy These are C1-C5 alkyl groups, which may contain halogens, and are equal to or different from each other in each occurrence, Jcy Each of these is independently selected from bonds or divalent hydrocarbon groups, optionally containing a heteroatom; Among this group, preferred compounds are triallyl cyanurate and trivinyl cyanurate. (ii) Trisubstituted isocyanurate compounds of the following general formula: [ka] (In the formula, R is equal to or different from each other and each instance is different.) isocy Each of these is H or base-R risocy OR risocy Selected independently from, R risocy These are C1-C5 alkyl groups, which may contain halogens, and are equal to or different from each other in each occurrence, J isocy Each of these is independently selected from bonds or divalent hydrocarbon groups, optionally containing a heteroatom; Among this group, preferred compounds are triallyl isocyanurate (also known as "TAIC") and trivinyl isocyanurate, with TAIC being the most preferred. (iii) Trisubstituted triazine compounds of the following general formula: [ka] (In the formula, R az Each of them is either equal to or different from the others, and each instance is independent of H or base-R. raz OR raz Selected from, R raz It is a C1-C5 alkyl group, and may contain a halogen, J az Each of them is either equal to or different from one another, and each instance independently, selected from bonded or divalent hydrocarbon groups, optionally containing a heteroatom; Trisubstituted triazine compounds include, in particular, the compounds disclosed in European Patent Application Publication No. 0860436A (AUSIMONT SPA) dated August 26, 1998, and International Publication No. 97 / 05122 (DU PONT) dated February 13, 1997. (iv) - A trisubstituted phosphite compound of the following general formula: [Chemical formula] (In the formula, each of R ph is the same as or different from each other, and each time it appears, independently, is H or a group - R rph or -OR rph , R rph is C1-C5 alkyl, optionally containing halogen, and each of J ph is the same as or different from each other, and each time it appears, independently, is selected from a bond or a divalent hydrocarbon group, optionally containing heteroatoms; Among the preferred compounds of these groups is triallyl phosphite.) (v) - A trisubstituted alkyltrisiloxane of the following general formula: [Chemical formula] (In the formula, each of R si is the same as or different from each other, and each time it appears, independently, is H or a group - R rsi or -OR rsi , R rsi is C1-C5 alkyl, optionally containing halogen, each of R’ si is the same as or different from each other, and each time it appears, independently, is selected from a C1-C5 alkyl group, optionally containing halogen, and each of J si is the same as or different from each other, and each time it appears, independently, is selected from a bond or a divalent hydrocarbon group, optionally containing heteroatoms; Among the preferred compounds of this group are 2,4,6-trivinylmethyltrisiloxane and 2,4,6-trivinylethyltrisiloxane.); (vi) - An N,N-disubstituted acrylamide compound of the following general formula: [Chemical formula] (In the formula, each of R an is the same as or different from each other, and each time it appears, independently, is H or a group - Rran OR ran Selected from, R ran It is a C1-C5 alkyl group, and may contain a halogen, J an Each of them is either equal to or different from one another, and each instance is independently selected from the group consisting of a bond or a divalent hydrocarbon group (and optionally including a heteroatom), A preferred compound in this group is N,N-diallylcrylamide.

[0053] Among compounds (U) containing four or more carbon-carbon unsaturated compounds, formula: [ka] Tris(diallylamine)-s-triazine, Examples include hexa-allylphosphoramide, N,N,N',N'-tetra-allylterephthalamide, and N,N,N',N'-tetra-allylmalonamide.

[0054] Generally, it is preferable that compound (U) is selected from the group consisting of bisolefins (OF) as detailed above, particularly (OF-1) type olefins, and trisubstituted isocyanurate compounds as detailed above, particularly TAIC.

[0055] The amount of compound (U) is usually in the range of 0.1 to 20 phr, preferably 1 to 15 phr, and more preferably 1 to 10 phr (wherein "phr" in the art generally means "parts by weight of polyunsaturated compound U per 100 parts by weight of fluoroelastomer A").

[0056] Another component of the composition of the present invention is one or more fatty acid salts.

[0057] Preferably, one or more fatty acid salts are selected from metal salts of fatty acids. Metals for the metal salts of fatty acids include, for example, alkali metals, alkaline earth metals, and transition metals. Preferred metals are sodium, potassium, calcium, magnesium, barium, zinc, and aluminum. Suitable carbon chains for fatty acid salts are preferably C12-C28, more preferably C14-C26, even more preferably C16-C24, and most preferably C16-C22.

[0058] The fatty acid metal salt may be, for example, a salt of behenic acid (C22), eicosenoic acid (C20), stearic acid (C18), palmitic acid (C16), myristic acid (C14), or lauric acid (C12). Among these, salts of stearic acid and palmitic acid are preferred, and metal salts of stearic acid are more preferred.

[0059] The most preferred fatty acid metal salts for use herein are sodium stearate, potassium stearate, barium stearate, calcium stearate, zinc stearate, magnesium stearate, or aluminum stearate.

[0060] The amount of fatty acid salt usable in the composition of the present invention is typically 0.05 to 5 phr, preferably 0.1 to 2 phr, more preferably 0.1 to 1.5 phr, and most preferably 0.2 to 1 phr.

[0061] Composition (C) of the present invention may further contain additional components that are generally usable for peroxide curing of fluoroelastomers, and more specifically, the composition usually further includes (a) Generally, one or more basic metal compounds in an amount of 0.5 to 15.0 phr, preferably 1 to 10 phr, more preferably 1 to 5 phr, per 100 parts by weight of fluoroelastomer (A) (basic metal compounds are generally selected from the group consisting of (j) oxides or hydroxides of divalent metals, for example, oxides or hydroxides of Mg, Zn, Ca, or Pb, and (jj) metal salts of weak acids, for example, stearic acid, benzoic acid, carbonic acid, oxide, or phosphate salts of Ba, Na, K, Pb, and Ca). (b) One or more acid acceptors that are not basic metal compounds, generally in an amount of 0.5 to 15.0 phr, preferably 1 to 10.0 phr, and more preferably 1 to 5 phr, per 100 parts by weight of fluoroelastomer (A) (These acid acceptors are generally selected from nitrogen-containing organic compounds, for example, 1,8-bis(dimethylamino)naphthalene, octadecylamine, etc., as described in European Patent Application Publication No. 708797A (DU PONT) (May 1, 1996)). It may include.

[0062] In general, the presence of basic metal oxides is undesirable because, under certain conditions, it has been found to potentially reduce the chemical resistance, particularly to acids, of hardened fluoroelastomer components.

[0063] The compositions of the present invention may contain other conventional additives such as fillers, thickeners, pigments, antioxidants, stabilizers, and processing aids / plasticizers. Carbon black is often used as a favorable reinforcing agent.

[0064] In another embodiment, the present invention relates to a method for producing the above-described composition, the method comprising producing the fluoroelastomer A using an emulsion polymerization process carried out without a fluorinated surfactant, the fluoroelastomer A having a main chain comprising iodine atoms and / or bromine atoms and comprising 40 to 80 mol% repeating units derived from vinylidene fluoride (VDF) and 20 to 60 mol% repeating units derived from one or more additional fluorinated monomers different from VDF. The method also comprises mixing the fluoroelastomer A with one or more organic peroxides, one or more curing aids, and one or more fatty acid salts.

[0065] In another aspect, the present invention also relates to a method for manufacturing a molded article, which includes curing the composition of the present invention described above.

[0066] The composition can be secondarily processed into desired molded products by, for example, molding (injection molding, extrusion molding), calendering, coating, screen printing, or on-site molding, and the molded products are advantageously vulcanized (cured) during the processing itself and / or in subsequent processes (post-treatment or post-curing), and advantageously, the relatively soft, weak, uncured fluoroelastomer composition is converted into a finished product made of a non-sticky, strong, insoluble, chemical-resistant, and heat-resistant cured fluoroelastomer material.

[0067] The present invention also relates to cured articles obtained from the compositions detailed above. These cured articles are typically obtained by molding and curing fluoroelastomer compositions, as detailed above. These cured articles may be sealing articles such as O(square) rings, packings, gaskets, diaphragms, shaft seals, valve shaft seals, piston rings, crankshaft seals, camshaft seals, and oil seals, or they may be piping and tube materials, particularly flexible hoses or other items such as conduits for the delivery of hydrocarbon fluids and fuels.

[0068] The present invention further relates to an assembly comprising a substrate and at least one cured product, as detailed above.

[0069] The choice of substrate is not particularly limited. The compositions of the present invention ensure adhesion to various metals and, in particular, to non-metallic substrates such as plastics and rubber substrates (among these, polyamide substrates and silicone substrates are particularly noteworthy).

[0070] The assembly of the present invention is generally manufactured by the steps of bringing a composition (C) as detailed above into contact with a substrate, subjecting the composition (C) to vulcanization (curing) while it is in contact with the substrate, and optionally subjecting the assembly to a subsequent heat treatment step (post-treatment or post-curing).

[0071] To our surprise, the applicant found that cured products obtained from the composition of the present invention had lower c-set values ​​compared to cured products obtained from the same composition without fatty acid salts (which reflects a more effective and improved curing process).

[0072] Therefore, a further aspect of the present invention is: (i) Fluoroelastomer (Fluoroelastomer A), • Obtained from an emulsion polymerization process carried out without fluorinated surfactants, • Containing iodine atoms and / or bromine atoms, The main chain comprises 40-80 mol% repeating units derived from vinylidene fluoride (VDF) and 20-60 mol% repeating units derived from one or more additional fluorinated monomers different from VDF. Fluoroelastomer A and (ii) One or more organic peroxides, (iii) One or more curing agents, This involves the use of fatty acids to reduce the c-set value of cured materials obtained from curable compositions containing [specific fatty acids].

[0073] If any disclosure in a patent, patent application, or publication incorporated herein by reference is found to be in conflict with this statement to an extent that would obscure the terminology, this statement shall prevail.

[0074] The present invention will be described in more detail below in relation to the following embodiments, but the purpose is merely illustrative and not to limit the scope of the invention. [Examples]

[0075] Materials used: Fluoroelastomer 1 (having a molar composition of VDF 70% - HFP 19% - TFE 16% and an iodine content of 0.4% by weight) was prepared as follows: 11.5 L of demineralized water, after exhaustion, was introduced into a 22 L vertical autoclave equipped with a stirrer operating at 450 rpm. The autoclave was then heated to 80°C and maintained at that temperature for the entire duration of the reaction. The autoclave pressure was increased to 13.7 bar by supplying HFP monomer. A gaseous mixture of monomers consisting of 70.5 mol% VDF, 19 mol% HFP, and 11 mol% TFE was supplied to the autoclave to bring the pressure to 26 bar. Then, 10.61 g of C4F8I2 and 0.90 g of formula H2C=CH-(CF2)6-CH=CH2 Bisolefins were introduced. An 8.22 g / l solution of t-butyl hydroperoxide in desalted water was pumped into the autoclave at a constant feed rate. Simultaneously, but separately, a 23.5 g / l solution of Bruggolite type E28 in desalted water was pumped into the autoclave at essentially the same feed rate. After the start, the VDF / HFP / TFE mixture was continuously fed to maintain a constant pressure, and a total of 16.49 g of bisolefins were added in 19 steps. After the instantaneous monomer conversion rate exceeded 2000 g / h, the feed rates of TBHP and Bruggolite E28 decreased by approximately 25% and were maintained constant for the remainder of the reaction. At the point of 1056 g of monomer conversion, 16.3 g of C4F8I2 was added. A final aliquot of 8.98 g of C4F8I2 was introduced at the point of 4224 g of monomer conversion.

[0076] Polymerization was continued until the total monomer consumption reached 5280 g after 212 minutes, and then the autoclave was depressurized, degassed, and cooled. The resulting latex had a solids content of 26.6 wt%. It was coagulated with an Al2(SO4)3 solution and dried, and then for the obtained fluoroelastomer crumb, the Mooney viscosity (ML)(1+10) was measured at 121 °C.

[0077] Fluoroelastomer 2 has the same molar composition and iodine content as Fluoroelastomer 1, but is prepared by emulsion polymerization in the presence of a fluoro surfactant. The same procedure as for Fluoroelastomer 1 was followed, but 2.5 g of ammonium persulfate (instead of the E28 / TBHP redox initiator) was used as the initiator, and the formula: CF2ClO(CF2-CF(CF3)O) n (CF2O) m 8.8 ml of perfluoropolyoxyalkylene having acidic end groups of CF2COOH (n / m = 10, average molecular weight 600), 5.6 ml of 30 vol% aqueous NNH4OH solution, 20.0 ml of deionized water, and the formula: CF3O(CF2CF(CF3)O) n (CF2O) m 105 ml of the microemulsion previously obtained by mixing 5.5 ml of GALDEN D02 perfluoropolyether of CF3 (n / m = 20, average molecular weight 450) was used. Fluoroelastomers 1 to 2 were obtained from Solvay Specialty Polymers Italy S.p.A. Bruggolite E28: Obtained from Bruggermann. Organic peroxide: 2,5-Dimethyl-2,5-di(tert-butylperoxy)hexane from Arkema. Curing aid: Triallyl cyanurate (TAIC) from Degussa. Carbon black N-990: From Cancarb. Stearic acid and all stearates: Obtained from Faci Group. Sodium dodecyl sulfate: Obtained from Sigma Aldrich.

[0078] In all examples, the fluoroelastomer was mixed with the additives detailed in the following table using an open mill. The O-rings (size class = 214) were cured in a press die at 180°C for 10 minutes, and then treated in an air-circulating oven at 230°C for 4 hours. The curing process was monitored by monitoring the torque curve with a moving dirometer until a plateau was reached at the maximum torque value.

[0079] For each composition, the compression set (c-set) value was determined according to ASTM D395, Method B, for the standard AS568A (Type 214) of cured O-ring spaceman (200°C, after 70 hours).

[0080] The following compositions Ex.1 to 6 were prepared as examples of the present invention: Ex.1: Fluoroelastomer 1:100 parts by weight, Carbon Black N-990: 30% Heavy Duty Organic peroxide: 1.35 parts by weight Taic: 3 parts by weight Calcium stearate: 1 part by weight Ex.2-6: Example: Same composition as Ex.1 except that the following was added instead of calcium stearate: Ex.2-Magnesium stearate: 1 part by weight Ex. 3-Magnesium stearate 0.25 parts by weight Ex. 0.25 parts by weight of zinc stearate (e.g., 4-zinc stearate) Ex. 0.25 parts by weight of sodium 5-stearate Ex. 0.25 parts by weight of potassium zinc stearate

[0081] The following compositions CEx.1-3 were prepared as comparative examples: CEx.1: The composition is the same as Ex.1, except that fatty acids are not added. CEx.2: Same composition as CEX. Same composition as CEx.1 except that fluoroelastomer 2 is used instead of fluoroelastomer 1. CEx.3: The composition is the same as Ex.3, except that fluoroelastomer 2 was used instead of fluoroelastomer 1 in Example. CEx.4: The composition is the same as Ex.4, except that fluoroelastomer 2 was used instead of fluoroelastomer 1 in Example. CEx.5 The composition is the same as Ex.5, except that fluoroelastomer 2 was used instead of fluoroelastomer 1 in Example. CEx.6 The composition is the same as Ex.6, except that fluoroelastomer 2 was used instead of fluoroelastomer 1 in Example. CEx.7 The same composition as Ex.1, except that the same amount of stearic acid was used instead of calcium stearate in this example. CEx.8 The same composition as Ex.1, except that the same amount of sodium dodecyl sulfate was used instead of calcium stearate in this example.

[0082] The table below shows the c-set values ​​obtained for the spaceman O-rings from the cured compositions, as measured as described above. It is clear that, in the absence of fatty acid salts, the c-set value of the composition containing fluoroelastomer 1 (prepared without the use of fluorinated surfactants) is higher (i.e., less desirable) than that of the composition containing fluoroelastomer 2 (prepared with fluorinated surfactants). The data demonstrate that adding either of the tested fatty acid salts (both the tested levels of 1 part by weight and 0.25 parts by weight) brings the c-set value of the fluoroelastomer 1-based composition to a level equivalent to that obtained from the fluoroelastomer 2-based composition, thus allowing the use of a more environmentally friendly fluoroelastomer for the same application.

[0083] The data also shows that adding the same fatty acid salt to a composition based on fluoroelastomer 2 does not affect the c-set value of the O-ring obtained by the composition. Comparative Example 6 also shows that adding a fatty acid (as an acid, not as a salt) to a composition based on fluoroelastomer 1 instead of the fatty acid salt of the present invention does not have a significant effect on the c-set value. Comparative Example 7 shows the effect of using sodium dodecyl sulfate instead of the fatty acid salt. The composition could not be cured under normal curing conditions.

[0084] [Table 1]

Claims

1. (i) Fluoroelastomer (Fluoroelastomer A), - Obtained from an emulsion polymerization process carried out without fluorinated surfactants, - Contains iodine atoms and / or bromine atoms, - Having a main chain comprising 40-80 mol% repeating units derived from vinylidene fluoride (VDF) and 20-60 mol% repeating units derived from one or more additional fluorinated monomers different from VDF, Fluoroelastomer A and (ii) One or more organic peroxides, (iii) One or more curing aids, (iv) One or more fatty acid salts, A fluoroelastomer composition containing the following:

2. The fluoroelastomer composition according to claim 1, wherein the fluoroelastomer contains iodine atoms and / or bromine atoms in an amount of 0.1 to 10.0% by weight relative to the total weight of the fluoroelastomer (A).

3. The fluoroelastomer composition according to claim 1 or 2, wherein one or more fatty acid salts are present in an amount of 0.05 to 5 phr.

4. The fluoroelastomer composition according to any one of claims 1 to 3, wherein the one or more fatty acid salts are selected from metal salts of fatty acids, preferably having a C12-C28 carbon chain, more preferably a C14-C26 carbon chain, even more preferably a C16-C24 carbon chain, and most preferably a C16-C22 carbon chain.

5. The one or more organic peroxides mentioned above - For example, di(alkyl / aryl) peroxides such as di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, di(t-butylperoxyisopropyl)benzene, and dicumyl peroxide; - Diacyl peroxides such as dibenzoyl peroxide, disuccinate peroxide, di(4-methylbenzoyl) peroxide, di(2,4-dichlorobenzoyl) peroxide, dilauroyl peroxide, decanoyl peroxide, etc. - Percarboxylic acids and esters such as di-tert-butylperbenzoate, t-butylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylethylbutylperoxy-2-ethylhexanoate, and 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, - In particular, peroxycarbonates such as di(4-t-butylcyclohexyl)peroxydicarbonate, di(2-phenoxyethyl)peroxydicarbonate, bis[1,3-dimethyl-3-(tert-butylperoxy)butyl]carbonate, t-hexylperoxyisopropyl carbonate, and t-butylperoxyisopropyl carbonate. - Perketals, for example, 1,1-bis(tert-butylperoxy)cyclohexane and 2,2-bis(tert-butylperoxy)butane, - Ketone peroxides, for example, cyclohexanone peroxide and acetylacetone peroxide, - Organic hydroperoxides, for example, cumene hydroperoxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide (also known as 2-[(2-hydroperoxybutan-2-yl)peroxy]butan-2-peroxol) and pinan hydroperoxide, - Oil-soluble azo initiators, e.g., 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-cyano-2-butane), dimethyl-2,2'-azobisdimethylisobutyrate, dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-Azobis(cyclohexane-l-carbonitride), 2,2'-Azobis[N-(2-propenyl)-2-methylpropionamide], 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'-Azobis(N-cyclohexyl-2-methylpropionamide), 2,2'-Azobis(isobutyronitrile), 2,2'-Azobis(2-cyano-2-butane), dimethyl-2,2'-Azobisdimethylisobutyrate t,1'-azobis(cyclohexanecarbonitride), 2-(t-butylazo)-2-cyanopropane, 2,2'-azobis[2-methyl-N-(1,1)-bis(hydroxymethyl)-2-hydroxyethyl]propionamide, 2,2'-azobis[2-methyl-N-hydroxyethyl]propionamide, 2,2'-azobis(N,N'-dimethyleneisobutylamine), 2,2'-azobis(2-methyl-N-[1,1 2,2'-Azobis(2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide), 2,2'-Azobis[2-5methyl-N-(2-hydroxyethyl)propionamide], 2,2'-Azobis(isobutylamide) dihydrate, 2,2'-Azobis(2,2,4-trimethylpentane), 2,2'-Azobis(2-methylpropane), A fluoroelastomer composition according to any one of claims 1 to 4, selected from the group consisting of the following.

6. The fluoroelastomer composition according to any one of claims 1 to 5, wherein the one or more organic peroxides are contained in an amount of 0.1 to 15 phr, preferably 0.2 to 12 phr, and more preferably 1 to 7 phr.

7. The one or more additional fluorinated monomers described above (a) C such as tetrafluoroethylene (TFE) and hexafluoropropylene (HFP) ２ ~C ８ Perfluorolefin; (b) Vinyl fluoride (VF), trifluoroethylene (TrFE), hexafluoroisobutene (HFIB), a formula CH ２ =CH-R ｆ (wherein, R ｆ is a C １ -C ６ perfluoroalkyl group), perfluoroalkyl ethylene, etc., hydrogen-containing C ２ -C ８ olefin hydrogen-containing C ２ -C ８ olefin; (c) C containing at least one of iodine, chlorine, and bromine, such as chlorotrifluoroethylene (CTFE) ２ ~C ８ Fluoroolefin; (d) Formula CF ２ = CFOR ｆ (In the formula, R ｆ C １ ~C ６ (Per)fluoroalkyl groups, preferably CF ３ , C ２ F ５ , C ３ F ７ (Per)fluoroalkyl vinyl ether (PAVE); (e) Formula CF ２ =CFOX (where X is C containing a catenary oxygen atom) １ ~C １２ (Per)fluoro-oxy-alkyl vinyl ethers of ((per)fluoro)-oxyalkyl groups, such as perfluoro-2-propoxypropyl groups; (f) Formula: 【Chemistry 1】 (In the formula, R is either equal to or different from each other) ｆ３ , R ｆ４ , R ｆ５ , R ｆ６ Each of these is a fluorine atom and C １ ~C ６ (Per)fluoroalkyl groups (containing one or more oxygen atoms optionally), for example, in particular -CF ３ , -C ２ F ５ , -C ３ F ７ , -OCF ３ , -OCF ２ CF ２ OCF ３ (Selected independently from the group consisting of) (Per)fluorodioxole having; preferably perfluorodioxole; (g) Formula: CF ２ =CFOCF ２ OR ｆ２ (In the formula, R ｆ２ C １ ~C ６ (Per)fluoroalkyl; C ５ ~C ６ A cyclic (per)fluoroalkyl group; and a C group comprising at least one catenary oxygen atom. ２ ~C ６ Selected from the group consisting of (per)fluorooxyalkyl groups; R ｆ２ -CF ２ CF ３ (MOVE1);-CF ２ CF ２ OCF ３ (MOVE2); or -CF ３ (MOVE3) (Per)fluoro-methoxy-vinyl ether having (MOVE, as used herein); A fluoroelastomer composition according to any one of claims 1 to 6, selected from the group consisting of the following.

8. The one or more curing aids mentioned above A: Compounds containing two carbon-carbon unsaturated compounds, preferably selected from bis-olefins having the following general formula: 【Chemistry 2】 (In the formula, R is either equal to or different from each other) １ , R ２ , R ３ , R ４ , R ５ and R ６ is H or C １ ~C ５ It is an alkyl group; Z is preferably a linear or branched C group optionally containing at least partially fluorinated oxygen atoms. １ ~C １８ (Hydro)carbon radicals (including alkylene or cycloalkylene radicals), or (per)fluoro(poly)oxyalkylene radicals containing one or more catenary ether bonds); B: Compounds containing three carbon-carbon unsaturated groups, preferably compounds selected from the following group: (i) - Trisubstituted cyanurate compounds of the following general formula: 【Transformation 3】 (In the formula, R is equal to or different from each other and each instance thereof) ｃｙ Each of these is H or base-R ｒｃｙ OR ｒｃｙ Selected independently from, R ｒｃｙ C may contain halogens. １ ~C ５ Alkyl, equal to or different from each other and each occurrence, J ｃｙ Each of these may optionally contain a heteroatom (selected independently from bonds or divalent hydrocarbon groups); (ii) - Trisubstituted isocyanurate compounds of the following general formula: 【Chemistry 4】 (In the formula, R is equal to or different from each other and each instance thereof) ｉｓｏｃｙ Each of these is H or base-R ｒｉｓｏｃｙ OR ｒｉｓｏｃｙ Selected independently from, R ｒｉｓｏｃｙ C may contain halogens. １ ~C ５ Alkyl, equal to or different from each other and each occurrence, J ｉｓｏｃｙ Each of these may optionally contain a heteroatom (selected independently from bonds or divalent hydrocarbon groups); (iii) - Trisubstituted triazine compounds of the following general formula: 【Transformation 5】 (In the formula, R ａｚ Each of them is either equal to or different from the others, and each instance is independent of H or base-R. ｒａｚ OR ｒａｚ Selected from, R ｒａｚ C １ ~C ５ It is alkyl, and may contain halogens, J ａｚ Each of them is either equal to or different from one another, and each instance is independently selected from bonded or divalent hydrocarbon groups, and optionally contains a heteroatom; (iv) - Trisubstituted phosphite compounds of the following general formula: 【Transformation 6】 (wherein each of R ｐｈ is the same as or different from each other and, each time it appears, independently is H or a group - R ｒｐｈ or - OR ｒｐｈ selected from, R ｒｐｈ is C １ ~C ５ alkyl, optionally containing halogen, and each of J ｐｈ is the same as or different from each other and, each time it appears, independently is selected from a bond or a divalent hydrocarbon group, optionally containing heteroatoms); (v) - Trisubstituted alkyltrisiloxanes of the following general formula: 【Transformation 7】 (wherein each of R ｓｉ is the same as or different from each other and, each time it appears, independently is H or a group - R ｒｓｉ or -OR ｒｓｉ selected from, R ｒｓｉ is C １ - C ５ alkyl, optionally containing halogen, each of R' ｓｉ is the same as or different from each other and, each time it appears, independently is selected from C １ - C ５ alkyl groups, optionally containing halogen, each of J ｓｉ is the same as or different from each other and, each time it appears, independently is selected from a bond or a divalent hydrocarbon group, optionally containing heteroatoms); (vi) - N,N-disubstituted acrylamide compounds of the following general formula: 【Transformation 8】 (In the formula, R ａｎ Each of them is either equal to or different from the others, and each instance is independent of H or base-R. ｒａｎ OR ｒａｎ Selected from, R ｒａｎ C １ ~C ５ It is alkyl, and may contain halogens, J ａｎ Each of them is either equal to or different from one another, and each instance is independently selected from bonded or divalent hydrocarbon groups, and optionally contains a heteroatom; C: A compound (U) containing four or more carbon-carbon unsaturated compounds, preferably of the following formula: 【Chemistry 9】 Tris(diallylamine)-s-triazine, A compound (U) selected from hexa-allylphosphoramide, N,N,N',N'-tetra-allylterephthalamide, and N,N,N',N'-tetra-allylmalonamide; A fluoroelastomer composition according to any one of claims 1 to 7, selected from the group consisting of the following.

9. The fluoroelastomer composition according to any one of claims 1 to 8, wherein the one or more curing aids are present in an amount of 0.1 to 20 phr, preferably 1 to 15 phr, and more preferably 1 to 10 phr.

10. The fluoroelastomer composition according to any one of claims 1 to 9, wherein the fluoroelastomer A is obtained from an emulsion polymerization process carried out without a surfactant.

11. The fluoroelastomer composition according to claim 10, wherein the emulsion polymerization process is carried out in the presence of a redox initiation system comprising at least one organic radical initiator and at least one compound having at least one sulfinic acid group.

12. A method for producing the composition according to any one of claims 1 to 11, (i) To produce the fluoroelastomer A described in claim 1 by an emulsion polymerization process carried out without a fluorinated surfactant, Using the (per)fluoroelastomer composition described in any one of claims 1 to 11 for the purpose of manufacturing molded products, (ii) The fluoroelastomer A is - One or more organic peroxides, - One or more curing aids, and - One or more fatty acid salts Mixing with A method that includes this.

13. A method for producing a molded article, comprising curing a fluoroelastomer composition according to any one of claims 1 to 11.

14. A cured article obtained from any one of the compositions described in claims 1 to 11, wherein the cured article is selected from the group consisting of sealing articles such as O (square) rings, packings, gaskets, diaphragms, shaft seals, valve stem seals, piston rings, crankshaft seals, camshaft seals, and oil seals, or optionally piping and tubing, in particular flexible hoses or other items such as conduits for the delivery of hydrocarbon fluids and fuels.

15. The use of one or more fatty acid salts in the composition, (i) Fluoroelastomer (Fluoroelastomer A), - Obtained from an emulsion polymerization process carried out without fluorinated surfactants, - Contains iodine atoms and / or bromine atoms, - Having a main chain comprising 40-80 mol% repeating units derived from vinylidene fluoride (VDF) and 20-60 mol% repeating units derived from one or more additional fluorinated monomers different from VDF, Fluoroelastomer A and (ii) One or more organic peroxides, (iii) One or more curing aids, Use for reducing the c-set value of a cured material obtained from the curing of the composition containing the above.

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