Fluoroelastomer Composition

Abstract

FIELD OF THEINVENTION This invention relates to a fluoroelastomer curable composition, a process for curing the same and cured articles obtained therefrom.

Description

[Technical field]

[0001] This application claims priority from European Patent Application Publication No. 21202584.5, filed October 14, 2021, the entire contents of which are incorporated herein by reference for all purposes.

[0002] FIELD OF THEINVENTION This invention relates to a fluoroelastomer curable composition, a process for curing the same and cured articles obtained therefrom. [Background technology]

[0003] Vulcanized fluoroelastomers have been used in a variety of applications, particularly for the manufacture of sealing items such as oil seals, gaskets, shaft seals, O-rings, etc., due to several desirable properties such as heat resistance, chemical resistance, and weather resistance.

[0004] Nevertheless, "as-polymerized" fluoroelastomers need to undergo a curing / crosslinking process (so-called "vulcanization") to ensure the necessary sealing and mechanical properties to be exhibited in the final part.

[0005] Several techniques have been developed to ensure the formation of three-dimensional cured structures capable of delivering the expected performance. The underlying chemistry generally requires a crosslinking agent to link between the fluoroelastomer polymer chains. The nature and reactivity of the crosslinking agent used allows the categorization of the crosslinking systems. The most widely used systems are either based on polyhydroxy aromatic compounds (typically bisphenols) that react by "ionic" chemistry in the presence of basic compounds and onium accelerators by replacing acidic hydrogen atoms in the chain, or on polyunsaturated compounds that react by radical chemistry in the presence of peroxides by replacing labile groups (typically iodine or bromine atoms) in the chain.

[0006] Although it is recognized that the overall performance of fluoroelastomers will depend on the nature, molecular structure and composition of the fluoroelastomer itself, it is nevertheless true that the chemistry of crosslinking can have a large impact on it.Therefore, the art is continuously searching for alternative and improved crosslinking systems based on alternative chemistry that can achieve superior crosslinking ability and therefore sealing performance of cured parts, and thus are safer and cheaper than the above-mentioned ones, and avoid the shortcomings of the prior art ionic or peroxide crosslinking systems.

[0007] In particular, WO 2016 / 180660 (published on November 17, 2016 in the name of Solvay Specialty Polymers Italy SpA) discloses a fluoroelastomer composition comprising at least one fluoroelastomer (A), at least one base (B) and at least one pyridinium-type salt (P) having at least two groups in the ortho or para position relative to the quaternized nitrogen atom bearing a reactive hydrogen. This patent application discloses several pyridinium-type salts containing aromatic ring quaternized nitrogen atoms, in particular in the form of a salt with p-toluenesulfonate.

[0008] More recently, the pyridinium salts (P) have been disclosed in WO 2020 / 188125 (published on September 24, 2020 in the name of Solvay Specialty Polymers Italy SpA) as components of fluoroelastomer compositions for bisphenol cure and useful for imparting excellent molding and demolding performance with high yields, substantially no mold fouling, and significantly reduced blistering and flash. Summary of the Invention

[0009] The Applicant has noted that the curing performance of the (per)fluoroelastomer compositions disclosed in the above mentioned patent applications comprising at least one pyridinium type salt (P) having at least two groups in the ortho or para position relative to the quaternized nitrogen atom bearing a reactive hydrogen is not optimal for the production of cured articles by injection molding.

[0010] Without wishing to be bound by any theory, the Applicant has noted that the elastomeric compositions disclosed in particular in the above-cited WO 2016 / 180660 A1 exhibit too rapid a torque increase at the start of the injection moulding process, which is undesirable for an optimal curing process.

[0011] Therefore, faced with the technical problem of improving the cited process when using a (per)fluoroelastomer composition comprising at least one pyridinium-type salt, the Applicant has surprisingly found that a composition comprising a selected amount of an organic aromatic acid makes it possible to control, and more precisely to slow down, the increase in torque at the start of the injection moulding process, thus improving the curing process and providing a cured elastomeric composition with excellent mechanical properties.

[0012] Thus, in a first embodiment, the present invention relates to a fluoroelastomer composition [composition (C)] comprising: at least one vinylidene fluoride-based fluoroelastomer [fluoroelastomer (A)] comprising repeat units derived from vinylidene fluoride (VDF) and at least one further (per)fluorinated monomer different from VDF, - 0.30 to 2.5 phr, based on 100 phr of the fluoroelastomer (A), of at least one organic aromatic acid [acid (OA)], which is a compound comprising at least one aromatic ring and at least one acid group linked to said aromatic ring via a sigma bond or a linking group, with the proviso that, if the acid group is -COOH, the aromatic ring does not contain an -OH group in the para or meta position relative to said acid group, at least one pyridinium salt [salt (P)] of the formulas (P1) to (P-12): [ka] [ka] (In the formula, - each of J and J' is equal to or different from each other and independently, for each occurrence, * or N and R * is H or C1-C 12 is a hydrocarbon group, - E is N or formula CR ° H Based on Z is a divalent hydrocarbon group containing 1 to 12 carbon atoms, - W is a bond or a bridging group selected from the group consisting of divalent hydrocarbon groups containing 1 to 12 carbon atoms (preferably divalent aliphatic groups containing 1 to 6 carbon atoms) and divalent fluorocarbon groups containing 1 to 12 carbon atoms (preferably divalent perfluoroaliphatic groups containing 1 to 6 carbon atoms), - Symbols in formulas (P-11) and (P-12): [ka] denotes an aromatic mononuclear or polynuclear ring fused to a pyridinium-type aromatic ring which may contain one or more further nitrogen atoms, optionally quaternized nitrogen atoms, in the ring, - R 1 H , R 2 H , R 3 H , R 4 H , R 5 H , R 6 H , R 7 H , R 8 H , R 9 H , R 10 H, R 11 H , R 12 H , R 13 H , R 14 H , R 15 H , R 16 H , R 17 H , R 18 H , R 19 H , R 20 H , R 21 H , R 22 H , R 23 H , R 24 H , R 25 H , R 26 H , R 27 H , R 28 H、 R 29 H , R 30 H , R 31 H , R 32 H , R 33 H , R 34 H , R 35 H , R 36 H and R° H each of which is equal to or different from one another and independently at each occurrence represents -H or a group of the formula: [ka] (In the formula, R a and R b are equal to or different from each other and are independently H or a hydrocarbon C1-C6 group. is a group [group (α-H)], - Y are equal to or different from each other, and independently may contain oxygen or one or more heteroatoms selected from N, O, S and halogens, and may in particular be an aliphatic or aromatic group; 12 is a hydrocarbon group, - A (m-) is an m-valent anion, however, (i) When the salt (P) is of the formula (P-1), R 1 H , R 2 H and R° H at least two of are groups (α-H); (ii) When the salt (P) is of the formula (P-2), R 3 H and R 4 H is the group (α-H), (iii) When the salt (P) is of the formula (P-3), R 5 H , R 6 H , R 7 H and R 8 H at least two of are groups (α-H); (iv) When the salt (P) is of the formula (P-4), R 9 H , R 10 H , R 11 H , R 12 H and R° H at least two of are groups (α-H); (v) When the salt (P) is of the formula (P-5), R 13 H , R 14 H and R° H at least two of are groups (α-H); (vi) When the salt (P) is of the formula (P-6), R 15 H , R 16 H , R 17 Hand R° H at least two of are groups (α-H); (vii) When the salt (P) is of the formula (P-7), R 18 H , R 19 H , R 20 H , R 21 H and R° H at least two of are groups (α-H); (viii) When the salt (P) is of the formula (P-8), R 22 H , R 23 H , R 24 H and R° H at least two of are groups (α-H); (ix) When the salt (P) is of the formula (P-9), R 25 H , R 26 H , R 27 H and R 28 H at least two of are groups (α-H); (x) When the salt (P) is of the formula (P-10), R 29 H , R 30 H , R 31 H , R 32 H and R 28 H at least two of are groups (α-H); (xi) When the salt (P) is of the formula (P-11), R 33 H , R 34 H and R 28 H at least two of are groups (α-H); (xii) When the salt (P) is of the formula (P-12), R 35 H , R 36 H and R° Hprovided that at least two of are groups (α-H). At least one pyridinium salt [salt (P)] according to any one of The present invention relates to a fluoroelastomer composition [composition (C)] comprising the above compound.

[0013] In a second embodiment, the present invention relates to a method for producing a shaped article comprising the use of composition (C) as described above.

[0014] In a third embodiment, the present invention also relates to a cured article obtained from the composition (C) described above. [Brief description of the drawings]

[0015] [Figure 1] 1 is a chart showing the cure behavior at 170° C. of Comparative Example 1C(*) and Examples 4 and 5 according to the invention, as characterized by a Moving Die Rheometer (MDR). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] For the purposes of the present invention, the term "fluoroelastomer" [fluoroelastomer (A)] is intended to denote a fluoropolymer resin that serves as a base building block to obtain true elastomers, said fluoropolymer resin comprising more than 10% by weight, preferably more than 30% by weight, of repeat units derived from at least one ethylenically unsaturated monomer containing at least one fluorine atom (hereinafter (per)fluorinated monomer) and, optionally, repeat units derived from at least one ethylenically unsaturated monomer not containing a fluorine atom (hereinafter hydrogenated monomer).

[0017] True elastomers are defined by ASTM, Special Technical Bulletin, Standard No. 184, as materials which can be stretched to twice their inherent length at room temperature and which, when held under tension for 5 minutes and then released, simultaneously return to within 10% of their original length.

[0018] The first object of the present invention is to provide a fluoroelastomer composition [composition (C)], at least one vinylidene fluoride-based fluoroelastomer [fluoroelastomer (A)] comprising repeat units derived from vinylidene fluoride (VDF) and at least one further (per)fluorinated monomer different from VDF, - 0.30 to 2.50 phr, based on 100 phr of the fluoroelastomer (A), of at least one organic aromatic acid [acid (OA)], which is a compound comprising at least one aromatic ring and at least one acid group linked to said aromatic ring via a sigma bond or a linking group, with the proviso that, if the acid group is -COOH, the aromatic ring does not contain an -OH group in the para or meta position relative to said acid group, - at least one pyridinium salt [salt (P)] according to any of the formulae (P1) to (P-12) detailed above; The fluoroelastomer composition [composition (C)] comprises:

[0019] The composition may be free of any polyhydroxy aromatic compound crosslinking agents. The composition may typically be free of bisphenol crosslinking agents.

[0020] The fluoroelastomer (A) is usually an amorphous product, i.e. with a low degree of crystallinity (less than 20% by volume of crystalline phase) and a glass transition temperature (T g In most cases, the fluoroelastomer (A) is advantageously a product having a T of less than 10° C., preferably less than 5° C., more preferably less than 0° C., even more preferably less than −5° C. g has.

[0021] The fluoroelastomer (A) typically contains at least 15 mol %, preferably at least 20 mol %, more preferably at least 35 mol % of repeat units derived from VDF, based on the total repeat units of the fluoroelastomer.

[0022] Fluoroelastomer (A) typically comprises at most 85 mol %, preferably at most 80 mol %, more preferably at most 78 mol % of repeat units derived from VDF, based on the total repeat units of the fluoroelastomer.

[0023] Non-limiting examples of suitable (per)fluorinated monomers other than VDF are, inter alia: (a) C2-C8 perfluoroolefins such as tetrafluoroethylene (TFE) and hexafluoropropylene (HFP); (b) Vinyl fluoride (VF), trifluoroethylene (TrFE), formula CH2=CH-R f (In the formula, R f perfluoroalkylethylenes having a hydrogen atom of C2 to C8, which are different from VDF; (c) C2-C8 chloro- and / or bromo- and / or iodo-fluoroolefins such as chlorotrifluoroethylene (CTFE); (d) Formula CF2=CFOR f (In the formula, R f is a C1-C6 (per)fluoroalkyl group, for example, CF3, C2F5, C3F7), (per)fluoroalkyl vinyl ether (PAVE); (e) Formula CF2=CFOX (wherein X is a C1-C 12 (per)fluoro-oxy-alkyl vinyl ethers, such as (per)fluoro-oxyalkyl, e.g. perfluoro-2-propoxypropyl; (f) Formula: [ka] (In the formula, R f3 , R f4 , R f5 , R f6 are equal to or different from each other and are independently a C1-C6 fluoro or per(halo)fluoroalkyl containing a fluorine atom, optionally one or more oxygen atoms, e.g., -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3). (Per)fluorodioxole having (g) Formula: CFX2=CX2OCF2OR'' f (In the formula, R'' f is selected from linear or branched C1-C6 (per)fluoroalkyl, C5-C6 cyclic (per)fluoroalkyl and linear or branched C2-C6 (per)fluorooxyalkyl containing 1-3 catenary oxygen atoms, and X2=F, H, preferably X2 is F, and R'' f is -CF2CF3(MOVE1), -CF2CF2OCF3(MOVE2) or -CF3(MOVE3) (Per)fluoro-methoxy-vinyl ether (hereafter MOVE) It is.

[0024] Generally, the fluoroelastomer (A) will contain repeat units derived from VDF and repeat units derived from HFP.

[0025] The fluoroelastomer (A) may optionally further comprise repeat units derived from one or more fluorine-free monomers (hereinafter hydrogenated monomers). Examples of hydrogenated monomers are, inter alia, C2-C8 non-fluorinated olefins (O1), in particular C2-C8 non-fluorinated α-olefins (O1), such as ethylene, propylene, 1-butene, diene monomers, styrene monomers, C2-C8 non-fluorinated α-olefins (O1), more particularly ethylene and propylene, which may be selected to achieve increased resistance to bases.

[0026] Optionally, the fluoroelastomer (A) has the general formula: [ka] (wherein R1, R2, R3, R4, R5 and R6 are equal to or different from each other and are H, halogen or an optionally halogenated group of C1 to C5, optionally containing one or more oxygen groups; Z is a linear or branched C1 to C5 alkyl group, optionally containing an oxygen atom; 18 or (per)fluoropolyoxyalkylene radicals, as described, for example, in EP 661304 A (AUSIMONT SPA), July 5, 1995. The repeat units may be derived from at least one bis-olefin having the formula:

[0027] Bis-olefins (OF) are represented by the formulae (OF-1), (OF-2) and (OF-3): (OF-1) [ka] (In the formula, j is an integer of 2 to 10, preferably 4 to 8; R1, R2, R3, and R4 are equal to or different from each other; and H, F, or C 1~5 alkyl or (per)fluoroalkyl groups, (OF-2) [ka] wherein each A is equal to or different from each other and at each occurrence and is independently selected from F, Cl, and H; each B is equal to or different from each other and at each occurrence and is independently selected from F, Cl, H, and OR B are independently selected from R B is a branched or linear alkyl group which may be partially, substantially or completely fluorinated or chlorinated, E is an optionally fluorinated divalent group having 2 to 10 carbon atoms, into which ether bonds may be inserted, preferably E is -(CF2) where m is an integer from 3 to 5. m - group, a preferred bis-olefin of type (OF-2) is F2C=CF-O-(CF2)5-O-CF=CF2), (OF-3) [ka] (wherein E, A and B have the same meaning as defined above; R5, R6 and R7 are equal to or different from each other; H, F or C 1~5 alkyl or (per)fluoroalkyl groups. It is preferably selected from the group consisting of those conforming to:

[0028] The fluoroelastomers (A) suitable for the composition of the present invention contain, in addition to the repeating units derived from VDF and HFP, - repeat units derived from at least one bis-olefin [bis-olefin (OF)] as detailed above, - repeat units derived from at least one (per)fluorinated monomer different from VDF and HFP, and - repeat units derived from at least one hydrogenated monomer may include one or more of the following:

[0029] Among the specific monomer compositions of fluoroelastomers (A) suitable for the purposes of the present invention are the following monomer compositions (in mol %): (i) Vinylidene fluoride (VDF) 35-85%, hexafluoropropene (HFP) 10-45%, tetrafluoroethylene (TFE) 0-30%, perfluoroalkyl vinyl ether (PAVE) 0-15%, bis-olefin (OF) 0-5%, (ii) vinylidene fluoride (VDF) 50-80%, perfluoroalkyl vinyl ether (PAVE) 5-50%, tetrafluoroethylene (TFE) 0-20%, bis-olefin (OF) 0-5%, (iii) 20-30% vinylidene fluoride (VDF), 10-30% C2-C8 non-fluorinated olefins (Ol), 18-27% hexafluoropropene (HFP) and / or perfluoroalkyl vinyl ethers (PAVE), 10-30% tetrafluoroethylene (TFE), 0-5% bis-olefins (OF), (iv) Tetrafluoroethylene (TFE) 45-65%, C2-C8 non-fluorinated olefins (Ol) 20-55%, vinylidene fluoride 0.1-30%, bis-olefins (OF) 0-5%, (v) Tetrafluoroethylene (TFE) 33-75%, perfluoroalkyl vinyl ether (PAVE) 15-45%, vinylidene fluoride (VDF) 5-30%, hexafluoropropene HFP 0-30%, bis-olefin (OF) 0-5%, (vi) Vinylidene fluoride (VDF) 35-85%, fluorovinyl ether (MOVE) 5-40%, perfluoroalkyl vinyl ether (PAVE) 0-30%, tetrafluoroethylene (TFE) 0-40%, hexafluoropropene (HFP) 0-30%, bis-olefin (OF) 0-5% Examples of the fluoroelastomer include those having the formula:

[0030] An organic aromatic acid [acid (OA)] is a compound containing at least one aromatic ring and at least one acid group linked to said aromatic ring via a sigma bond or a linking group, with the proviso that when the acid group is -COOH, the aromatic ring does not contain an -OH group in the para or meta position relative to said acid group.

[0031] Preferably, the acid group is linked to the aromatic ring via a sigma bond.

[0032] Preferably, the acid group is selected from -COOH or -SO3H. More preferably, the acid group is -SO3H.

[0033] Thus, in certain embodiments, the present invention provides a method for treating a cancer cell comprising: at least one fluoroelastomer (A), - 0.30 to 2.50 phr, based on 100 phr of the fluoroelastomer (A), of at least one organic aromatic acid [acid (OA)], which is a compound comprising at least one aromatic ring and at least one acid -SO3H group linked to said aromatic ring via a sigma bond or a linking group; - at least one salt (P) as detailed above; A fluoroelastomer composition comprising:

[0034] Preferably, the organic aromatic acid [acid (OA)] contains one electron donating group (also called electron releasing group) in the para position relative to the acid group.

[0035] More preferably, the electron donating group is selected from C1 to C5 alkyl, such as -CH3, -CH2CH3 and -OH, and most preferably, the electron donating group is selected from C1 to C5 alkyl, preferably -CH3 and -CH2CH3.

[0036] More preferably, said acid (OA) is selected from p-toluenesulfonic acid.

[0037] Advantageously, composition (C) comprises an acid (OA) in an amount ranging from 0.30 to 2.20 parts by weight (phr) per 100 parts by weight of fluoroelastomer (A), further ranging from 0.30 to 2.10 phr per 100 phr of fluoroelastomer (A), further ranging from 0.30 to 2.00 phr per 100 phr of fluoroelastomer (A).

[0038] Good results have been obtained with p-toluenesulfonic acid in an amount of 0.30 to 1.00 phr, preferably 0.30 to 0.80 phr, per 100 phr of fluoroelastomer (A).

[0039] Preferred salts (P) of formula (P-1) are represented by the formulas (P-1-a) to (P-1-e): [ka] (In the formula, - Ra and R b has the meaning defined above, preferably R a and R b is H, - Y has the meaning defined above, preferably Y is methyl, - R p and R q are equal to or different from each other, and are H or C1 to C 12 is a hydrocarbon group, - A and m have the meanings defined above. This is in accordance with the following.

[0040] More preferably, the salt (P) of the formula (P-1) is represented by the formulas (P-1-g) to (P-1-p): [ka] wherein A and m have the meanings defined above. The present invention relates to a method for manufacturing a semiconductor device, comprising the steps of:

[0041] A preferred salt (P) of the formula (P-2) is represented by the formula (P-2-a): [ka] (In the formula, - R a and R b has the meaning defined above, preferably R a and R b is H, - Y has the meaning defined above, preferably Y is methyl, - R p and R q are equal to or different from each other, and are H or C1 to C 12 is a hydrocarbon group, - A and m have the meanings defined above. This is in accordance with the following.

[0042] More preferably, the salt (P) of the formula (P-2) is represented by the formula (P-2-b): [ka] wherein A and m have the meanings defined above. It has the following.

[0043] A preferred salt (P) of the formula (P-3) is represented by the formula (P-3-a): [ka] (In the formula, - R a and R b has the meaning defined above, preferably R a and R b is H, - Y has the meaning defined above, preferably Y is methyl, - A and m have the meanings defined above. This is in accordance with the following.

[0044] More preferably, the salt (P) of the formula (P-3) is represented by the formula (P-3-b): [ka] wherein A and m have the meanings defined above. It has the following.

[0045] A preferred salt (P) of the formula (P-4) is represented by the formula (P-4-a): [ka] (In the formula, - R a and R b has the meaning defined above, preferably R a and R b is H, - w is an integer from 1 to 12, preferably from 1 to 6, and most preferably equal to 3, - A and m have the meanings defined above. This is in accordance with the following.

[0046] More preferably, the salt (P) of formula (P-4) has the formula (P-4-b) or (P-4-c): [ka] where A and m have the meanings defined above and w=3. It has the following.

[0047] A preferred salt (P) of the formula (P-5) is represented by the formula (P-5-a): [ka] (In the formula, - R a and R b has the meaning defined above, preferably R a and R b is H, - Y has the meaning defined above, preferably Y is methyl, - A and m have the meanings defined above. This is in accordance with the following.

[0048] More preferably, the salt (P) of formula (P-5) has the formula (P-5-b) or (P-5-c): [ka] wherein A and m have the meanings defined above. It has the following.

[0049] A preferred salt (P) of the formula (P-11) is represented by the formula (P-11-a): [ka] (In the formula, - R a and R b has the meaning defined above, preferably R a and R b is H, - Y has the meaning defined above, preferably Y is methyl, - A and m have the meanings defined above. This is in accordance with the following.

[0050] More preferably, the salt (P) of the formula (P-11) is represented by the formula (P-11-b): [ka] wherein A and m have the meanings defined above. It has the following.

[0051] A preferred salt (P) of the formula (P-12) is represented by the formula (P-12-a): [ka] (In the formula, - R a and R b has the meaning defined above, preferably R a and R b is H, - Y has the meaning defined above, preferably Y is methyl, - A and m have the meanings defined above. This is in accordance with the following.

[0052] More preferably, the salt (P) of the formula (P-12) is represented by the formula (P-12-b): [ka] wherein A and m have the meanings defined above. It has the following.

[0053] The choice of the anion A in the formulae (P-1) to (P-12) is not particularly critical, but it is nevertheless understood that anions selected from the group consisting of arylsulfonates, in particular tosylates (p-toluenesulfonates), fluorine-free alkylsulfonates such as mesylates (methanesulfonates) and fluorine-containing (especially perfluorinated) alkylsulfonates such as triflates (trifluoromethanesulfonates), (fluoroalkylsulfonates having a C1-C6 (fluoro)alkyl chain, halides (iodides, bromides, chlorides) are particularly preferred due to their ready availability from a synthetic point of view.

[0054] In summary, exemplary compounds found to be particularly useful in the compositions of the present invention are those having formulas (Ex-1) through (Ex-9) listed below. [ka]

[0055] The compositions of the invention usually contain salt (P) in an amount of at least 0.1, preferably at least 0.5, more preferably at least 1 phr per 100 phr of fluoroelastomer (A).

[0056] The composition of the invention usually contains salt (P) in an amount of at most 20, preferably at most 15, more preferably at most 10 phr per 100 phr of fluoroelastomer (A).

[0057] Optionally, the composition (C) of the present invention comprises at least one basic compound [base (B)].

[0058] The base (B) suitable for use in the composition (C) of the present invention is not particularly limited.

[0059] The base (B) may be selected from an organic base, an inorganic base or a mixture of at least one organic base and at least one inorganic base.

[0060] Among inorganic bases [bases (IB)], in particular: (i) Divalent metal oxides, in particular oxides of alkaline earth metals or oxides of Zn, Mg, Pb, Ca, such as MgO, PbO and ZnO; (ii) hydroxides of metals, in particular hydroxides of monovalent and divalent metals, in particular hydroxides of alkali and alkaline earth metals, in particular hydroxides selected from the group consisting of Ca(OH)2, Sr(OH)2 and Ba(OH)2; (iii) pK greater than 3 a Metal salts of weak acids having the formula: Examples include:

[0061] Among inorganic bases, Ca(OH)2 has been found to be particularly effective.

[0062] Among organic bases [bases (OB)], in particular: (j) non-aromatic amines or amides according to the general formula (B1m) or (B1d): R bm -[C(O)] t -NR H 2(B1m) R H 2N-[C(O)] t’ -R dm -[C(O)] t’’ -NR H 2(B1d) (In the formula, - each of t, t' and t'' is equal to or different from one another and for each occurrence, and is zero or one; - R H Each of the groups is independently H or C1-C 12 is a hydrocarbon group, - R bm is a monovalent hydrocarbon non-aromatic radical having 1 to 30 carbon atoms, - R bmis a divalent hydrocarbon non-aromatic radical having 1 to 30 carbon atoms, and (jj) Alicyclic secondary or tertiary amines according to the general formula (B2m) or (B2d): [ka] (In the formula, Cy represents a divalent aliphatic group containing at least 4 carbon atoms, optionally containing one or more ethylenically unsaturated double bonds, and optionally containing one or more catenary nitrogen atoms, which form a ring with the nitrogen atom to which it is bonded, - Cy' represents a trivalent aliphatic group containing at least 5 carbon atoms, optionally containing one or more ethylenically unsaturated double bonds, and optionally containing one or more catenary nitrogen atoms, which forms a ring with the nitrogen atom to which it is bonded; (jjj) Aromatic amines or amides according to general formula (B3): Ar b -{[C(O)] t -NR H 2} w (B3) (In the formula, - the t's are equal or different to each other and for each occurrence, and are zero or one; - w is an integer from 1 to 4, - R H Each of the groups is independently H or C1-C 12 is a hydrocarbon group, - Ar b is a mononuclear or polynuclear aromatic radical optionally containing one or more catenary heteroatoms selected from the group consisting of S and O; (jv) heteroaromatic amines containing at least one nitrogen atom contained in a heteroaromatic ring, in particular pyridine derivatives, preferably trimethylpyridine isomers; (v) Guanidine derivatives of formula (B4) or (B5): [ka] (In the formula, - R1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are equal to or different from each other, and are independently H or C1 to C 12 (It is a hydrocarbon group) as well as the corresponding salts of said guanidines (B4) and (B5), in particular the corresponding N-quaternized hydrohalide salts (preferably the hydrochloride salts), (vj) metal alkoxylates, preferably alkoxylates of aliphatic alcohols, more preferably potassium tert-butylate, sodium ethoxide and sodium methoxide Examples include:

[0063] Among the bases of the formulae (B1m) and (B1d), - R bm is a monovalent aliphatic linear radical having 6 to 30 carbon atoms, optionally containing one or more ethylenically unsaturated double bonds; - R dm is a divalent aliphatic straight-chain radical having 6 to 30 carbon atoms, optionally containing one or more ethylenically unsaturated double bonds The above are particularly preferred.

[0064] Among said non-aromatic amines or amides according to general formula (B3): - Formula CH3(CH2) 17 -NH2 octadecylamine, - Formula H2N-C(O)-(CH2) 11 Erucamide, -CH=CH-(CH2)7CH3 oleamide of formula H2N-C(O)-(CH2)7-CH=CH-(CH2)7CH3, hexamethylenediamine of formula H2N-(CH2)6-NH2, - N,N-dimethyloctylamine, - N,N-dimethyldodecylamine, - trioctylamine, - Trihexylamine can be mentioned in particular.

[0065] Among the above-mentioned alicyclic secondary or tertiary amines according to the general formula (B2m) or (B2d), those having the following formula: [ka] Examples of such compounds include 1,8-diazabicycloundec-7-ene (DBU).

[0066] Exemplary embodiments of the aforementioned guanidine derivatives of formula (B-4) are, inter alia, guanidine hydrochloride and di-o-tolylguanidine.

[0067] The amount of base (B) will be adjusted by the person skilled in the art taking into account the nature and basicity of the base (B) used.

[0068] It is nevertheless understood that composition (C) generally comprises from 0.2 to 20, preferably from 6 to 16 parts by weight of the aforementioned base (B) (organic and / or inorganic, as detailed above) per 100 parts by weight of fluoroelastomer (A).

[0069] According to a particularly preferred embodiment, composition (C) comprises at least one organic base and at least one inorganic base.

[0070] In these circumstances, composition (C) usually comprises from 0.1 to 10 parts by weight, preferably from 6 to 16 parts by weight, of said inorganic base and / or usually comprises from 0.1 to 10 parts by weight, preferably from 6 to 16 parts by weight, of said organic base, these parts by weight being referred to relative to 100 parts by weight of fluoroelastomer (A).

[0071] Composition (C) may further comprise one or more organic solvents [solvent (S)].

[0072] The organic solvents are preferably chosen from those in which the salt (P) used has a solubility at room temperature of more than 1 g / l, more preferably more than 10 g / l.

[0073] Non-limiting examples of solvents (S) that can be used are, inter alia: a polar aprotic organic solvent, preferably selected from the group consisting of sulfolane, 4,4'-dichlorodiphenylsulfone, - methylpyrrolidinium bis(trifluoromethanesulfonylimides) of the formula PY1,4-Tf2N and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonylimides) of the formula BMIm-Tf2N: [ka] An ionic liquid preferably selected from the group consisting of It is.

[0074] Other conventional additives such as reinforcing fillers (eg, carbon black), thickeners, pigments, antioxidants, stabilizers, etc. may also be added to composition (C).

[0075] The present invention also relates to the use of the composition (C) described above for producing shaped articles.

[0076] Composition (C) can be processed, for example by molding (injection molding, extrusion), calendering or extrusion, into the desired shaped article, which advantageously undergoes vulcanization (curing) during its own processing and / or in a subsequent step (post-treatment or post-curing) that advantageously converts the relatively soft and weak fluoroelastomer (A) into a non-tacky, strong, insoluble, chemically and heat-resistant cured fluoroelastomer finished article.

[0077] Finally, the present invention relates to the cured articles obtained from the composition (C) detailed above.

[0078] The cured article can be a pipe, a fitting, an O-ring, a hose, among others.

[0079] The invention will now be described with reference to the following examples, the purposes of which are merely illustrative and are not intended to limit the scope of the invention. EXAMPLES

[0080] material A VDF-HFP copolymer sold under the trade name TECNOFLON® 90HS by Solvay Specialty Polymers Italy SpA (hereinafter FKM-1) was used as the base fluoroelastomer.

[0081] MAGLITE® DE high surface area, highly active magnesium oxide (hereafter MgO) was obtained from Merck.

[0082] RHENOFIT® CF (GE 1890) calcium hydroxide (hereafter Ca(OH)2) was obtained from Rhein Chemie.

[0083] The reinforcing filler, Carbon black N990MT (hereafter NT990), was obtained from Cancarb.

[0084] Guanidine, p-toluenesulfonic acid and 4-hydroxybenzoic acid were obtained from Merck Sigma Aldrich.

[0085] method Characterization of the curing behavior The cure behavior was characterized by determining the following properties with a moving die rheometer (MDR) at 170°C or 180°C: M L = minimum torque (lb × in) M H = Maximum torque (lb×in) ΔM=M H -M L (lb×in) ts2 = viscosity is M L 2 units more time than

[0086] The plaques and O-rings (size class=214) were cured in a pressure mold and then post-processed in an air circulating oven under the following conditions: - Molding: 170℃ for 90 minutes - Post cure = 230℃ (8+16 hours)

[0087] Mooney scorch times were determined at 135°C according to ASTM D1646 using an Alpha Technologies Mooney MV200.

[0088] Mechanical properties Tensile properties were determined on specimens punched from the plaques according to ASTM D412C standard at 23°C. TS=tensile strength in MPa M50 = tensile strength in MPa at 50% elongation M100 = tensile strength in MPa at 100% elongation EB = Elongation at break in %

[0089] Shore A hardness (3″) (HDS) was determined on three stacked plaques according to the ASTM D 2240 method.

[0090] Compression set (C-SET) was determined according to ASTM D395, Method B, at 200° C. for 70 hours, on O-ring specimens standard AS568A (Type 214) or on 6 mm buttons (Type 2).

[0091] Preparation Example A - 1,2,4,6-Tetramethyl-pyridinium p-toluenesulfonate [same as Preparation Example 1 in WO 2016 / 180660] A three-necked round-bottom flask equipped with a thermometer, a condenser, and a stirring means was charged with CH2Cl2 (85 ml) and methyl-p-toluenesulfonate (25.50 g). 2,4,6 trimethylpyridine (16.59 g) was then added dropwise at room temperature. The reaction was stirred at 50°C and was complete after 22 hours. The liquid phase was removed by evaporation under vacuum to give a white powder, which was dispersed in diethyl ether (50 ml) under stirring. The liquid phase was filtered off and 39.13 g of pure product was recovered as a white powder in 93% yield (mp 161°C, 1% weight loss: 266°C). 1 H NMR (solvent DO, TMS standard): +7.70 ppm (d; 2H; ortho-H; p-toluenesulfonate); +7.55 (s; 2H; meta-H; 1,2,4,6-tetramethylpyridinium); +7.39 (d; 2 H; meta-H; p-toluenesulfonate; +4.0 (s; 3H; NCH3; 1,2,4,6-tetramethyl-pyridinium); +2.74 (s; 6H; ortho-CH3; 1,2,4,6-tetramethyl-pyridinium); 2.53 (s; 3H; para-CH3; 1,2,4,6-tetramethyl-pyridinium); +2.44 ppm (s; 3H; para-CH3; p-toluenesulfonate).

[0092] Preparation Example B - Mixing Procedure The salt (P) of Preparation Example A above was mixed with the other ingredients in the amounts (phr) set forth in Table 1 below and milled between rolls to prepare a curable compound.

[0093] [Table 1]

[0094] The mechanical properties, viscosity and scorch results of the above compositions are summarized in Table 2 below.

[0095] [Table 2]

[0096] The data in Table 2 (Example 3 vs. Example 5C) show that although more p-hydroxybenzoic acid is required to increase the scorch time, the C-SET of the resulting composition is adversely affected.

[0097] For further comparison, two compositions were prepared containing the salt (P) of Preparative Example A above and an aliphatic acid.

[0098] The ingredients were roll mixed and combined with other ingredients in the amounts (phr) set forth in Table 3 below to prepare curable compounds.

[0099] [Table 3]

[0100] The results in Table 3 indicate that the use of stearic acid does not positively affect the MS scorch time of the compositions.

Claims

1. A fluoroelastomer composition [composition (C)] comprising: at least one vinylidene fluoride-based fluoroelastomer [fluoroelastomer (A)] comprising repeat units derived from vinylidene fluoride (VDF) and at least one further (per)fluorinated monomer different from VDF, - 0.30 to 2.50 phr, based on 100 phr of fluoroelastomer (A), of at least one organic aromatic acid [acid (OA)], a compound comprising at least one aromatic ring and at least one acid group linked to said aromatic ring via a sigma bond or a linking group, with the proviso that if said acid group is -COOH, said aromatic ring does not contain an -OH group in the para or meta position relative to said acid group; at least one pyridinium salt [salt (P)] of the formulae (P1) to (P-12): 【Chemical 1】 【Chemistry 2】 (In the formula, each of J and J' is equal to or different from each other and independently, for each occurrence, represents a C-R ＊ or N, and R ＊ is H or C １ ~C １２ is a hydrocarbon group, E is N or of the formula C-R° Ｈ is the basis of Z is a divalent hydrocarbon group containing 1 to 12 carbon atoms, W is a bond or a bridging group selected from the group consisting of divalent hydrocarbon groups containing 1 to 12 carbon atoms (preferably divalent aliphatic groups containing 1 to 6 carbon atoms) and divalent fluorocarbon groups containing 1 to 12 carbon atoms (preferably divalent perfluoroaliphatic groups containing 1 to 6 carbon atoms), Symbols in formulas (P-11) and (P-12): 【Chemistry 3】 denotes an aromatic mononuclear or polynuclear ring fused to a pyridinium-type aromatic ring which may contain one or more further nitrogen atoms, optionally quaternized nitrogen atoms, in the ring, - R １ Ｈ 、R ２ Ｈ 、R ３ Ｈ 、R ４ Ｈ 、R ５ Ｈ 、R ６ Ｈ 、R ７ Ｈ 、R ８ Ｈ 、R ９ Ｈ 、R １０ Ｈ 、R １１ Ｈ 、R １２ Ｈ 、R １３ Ｈ 、R １４ Ｈ 、R １５ Ｈ 、R １６ Ｈ 、R １７ Ｈ 、R １８ Ｈ 、R １９ Ｈ 、R ２０ Ｈ 、R ２１ Ｈ 、R ２２ Ｈ 、R ２３ Ｈ 、R ２４ Ｈ 、R ２５ Ｈ 、R ２６ Ｈ 、R ２７ Ｈ 、R ２８ Ｈ、 R ２９ Ｈ 、R ３０ Ｈ 、R ３１ Ｈ 、R ３２ Ｈ 、R ３３ Ｈ 、R ３４ Ｈ 、R ３５ Ｈ , R ３６ Ｈ and R° Ｈ are equal to or different from one another and independently at each occurrence represent -H or a group of the formula: 【Chemistry 4】 (In the formula, R ａ and R ｂ are equal to or different from each other and independently represent H or a hydrocarbon C １ ~C ６ (based on a group [group (α-H)] of Y are equal to or different from each other and may in particular be an aliphatic or aromatic group, which may contain oxygen or one or more heteroatoms independently selected from N, O, S and halogens; １ ~C １２ is a hydrocarbon group, - A （ｍ－） is an m-valent anion, however, (i) When the salt (P) is of the formula (P-1), R １ Ｈ , R ２ Ｈ and R° Ｈ at least two of are groups (α-H); (ii) When the salt (P) is of the formula (P-2), R ３ Ｈ and R ４ Ｈ is the group (α-H), (iii) When the salt (P) is of the formula (P-3), R ５ Ｈ , R ６ Ｈ , R ７ Ｈ and R ８ Ｈ at least two of are groups (α-H); (iv) When the salt (P) is of the formula (P-4), R ９ Ｈ , R １０ Ｈ , R １１ Ｈ , R １２ Ｈ and R° Ｈ at least two of are groups (α-H); (v) When the salt (P) is of the formula (P-5), R １３ Ｈ , R １４ Ｈ and R° Ｈ at least two of are groups (α-H); (vi) When the salt (P) is of the formula (P-6), R １５ Ｈ , R １６ Ｈ , R １７ Ｈ and R° Ｈ at least two of are groups (α-H); (vii) When the salt (P) is of the formula (P-7), R １８ Ｈ , R １９ Ｈ , R ２０ Ｈ , R ２１ Ｈ and R° Ｈ at least two of are groups (α-H); (viii) When the salt (P) is of the formula (P-8), R ２２ Ｈ , R ２３ Ｈ , R ２４ Ｈ and R° Ｈ at least two of are groups (α-H); (ix) When the salt (P) is of the formula (P-9), R ２５ Ｈ , R ２６ Ｈ , R ２７ Ｈ and R ２８ Ｈ at least two of are groups (α-H); (x) When the salt (P) is of the formula (P-10), R ２９ Ｈ , R ３０ Ｈ , R ３１ Ｈ , R ３２ Ｈ and R ２８ Ｈ at least two of are groups (α-H); (xi) When the salt (P) is of the formula (P-11), R ３３ Ｈ , R ３４ Ｈ and R ２８ Ｈ at least two of are groups (α-H); (xii) When the salt (P) is of the formula (P-12), R ３５ Ｈ , R ３６ Ｈ and R° Ｈ provided that at least two of are groups (α-H). and at least one pyridinium salt [salt (P)] according to any of the following: A fluoroelastomer composition comprising [composition (C)].

2. Fluoroelastomer (A) comprises at least 15 mol%, preferably at least 20 mol%, more preferably at least 35 mol% of repeating units derived from VDF, based on the total repeating units of said fluoroelastomer; and / or at most 5 mol%, preferably at most 80 mol%, more preferably at most 78 mol% of repeating units derived from VDF, based on the total repeating units of said fluoroelastomer (C).

3. The at least one (per)fluorinated monomer different from VDF is (a) C such as tetrafluoroethylene (TFE) and hexafluoropropylene (HFP) ２ ~C ８ perfluoroolefins, (b) vinyl fluoride (VF), trifluoroethylene (TrFE), and fluorocarbons of formula CH ２ =CH-R ｆ (In the formula, R ｆ is C １ ~C ６ perfluoroalkylethylenes (perfluoroalkyl groups) containing hydrogen atoms different from VDF ２ ~C ８ olefins, (c) C such as chlorotrifluoroethylene (CTFE) ２ ~C ８ chloro-, and / or bromo-, and / or iodo-fluoroolefins; (d) Formula CF ２ =CFOR ｆ (In the formula, R ｆ is C １ ~C ６ (Per)fluoroalkyl groups, such as CF ３ , C ２ F ５ , C ３ F ７ (per)fluoroalkyl vinyl ether (PAVE) of the formula (e) Formula CF ２ =CFOX (wherein X is a C group containing a catenary oxygen atom) １ ~C １２ (per)fluoro-oxy-alkyl vinyl ethers ((per)fluoro)-oxyalkyl, for example perfluoro-2-propoxypropyl groups); (f) Formula: 【Chemistry 5】 (In the formula, R ｆ３ , R ｆ４ , R ｆ５ , R ｆ６ are equal to or different from each other and independently comprise a C containing a fluorine atom, optionally one or more oxygen atoms. １ ~C ６ Fluoro or per(halo)fluoroalkyl, such as —CF ３ , -C ２ F ５ , -C ３ F ７ , -OCF ３ , -OCF ２ CF ２ OCF ３ is) (Per)fluorodioxole having (g) Formula: CFX ２ =CX ２ OCF ２ OR’’ ｆ (In the formula, R'' ｆ is a straight or branched chain C １ ~C ６ (Per)fluoroalkyl, C ５ ~C ６ Cyclic (per)fluoroalkyl and linear or branched C containing 1 to 3 catenary oxygen atoms ２ ~C ６ (per)fluorooxyalkyl, and X ２ = F, H, preferably X ２ is F, and R'' ｆ is -CF ２ CF ３ (MOVE1), -CF ２ CF ２ OCF ３ (MOVE2) or -CF ３ (MOVE 3) (per)fluoro-methoxy-vinyl ether (hereinafter MOVE) having The composition (C) according to claim 1, which comprises, preferably is selected from the group consisting of:

4. 4. Composition (C) according to claim 3, wherein said at least one (per)fluorinated monomer different from VDF is HFP.

5. The fluoroelastomer (A) is repeat units derived from one or more fluorine-free monomers, - General formula: 【Chemistry 6】 (In the formula, R １ , R ２ , R ３ , R ４ , R ５ and R ６ are equal to or different from each other and optionally contain H, halogen or one or more oxygen groups; １ ~C ５ and Z is a linear or branched C １ ~C １８ an optionally halogenated alkylene or cycloalkylene group or a (per)fluoropolyoxyalkylene group of the formula repeat units derived from at least one bis-olefin [bis-olefin (OF)] having the formula: repeat units derived from at least one (per)fluorinated monomer different from VDF and HFP The composition (C) according to claim 1, comprising one or more of:

6. The fluoroelastomer (A) has the following monomer composition (in mol %): (i) vinylidene fluoride (VDF) 35-85%, hexafluoropropene (HFP) 10-45%, tetrafluoroethylene (TFE) 0-30%, perfluoroalkyl vinyl ether (PAVE) 0-15%, bis-olefin (OF) 0-5%, (ii) vinylidene fluoride (VDF) 50-80%, perfluoroalkyl vinyl ether (PAVE) 5-50%, tetrafluoroethylene (TFE) 0-20%, bis-olefin (OF) 0-5%, (iii) vinylidene fluoride (VDF) 20-30%, C ２ ~C ８ non-fluorinated olefin (O1) 10-30%, hexafluoropropene (HFP) and / or perfluoroalkyl vinyl ether (PAVE) 18-27%, tetrafluoroethylene (TFE) 10-30%, bis-olefin (OF) 0-5%, (iv) tetrafluoroethylene (TFE) 45-65%, C ２ ~C ８ Non-fluorinated olefin (O1) 20-55%, vinylidene fluoride 0.1-30%, bis-olefin (OF) 0-5%, (v) tetrafluoroethylene (TFE) 33-75%, perfluoroalkyl vinyl ether (PAVE) 15-45%, vinylidene fluoride (VDF) 5-30%, hexafluoropropene HFP 0-30%, bis-olefin (OF) 0-5%, (vi) vinylidene fluoride (VDF) 35-85%, fluorovinyl ether (MOVE) 5-40%, perfluoroalkyl vinyl ether (PAVE) 0-30%, tetrafluoroethylene (TFE) 0-40%, hexafluoropropene (HFP) 0-30%, bis-olefin (OF) 0-5% The composition (C) according to claim 1, wherein

7. The at least one acid (OA) is at least one aromatic ring and at least one acid group linked to said aromatic ring via a sigma bond, and / or one electron donating group in the para position relative to the acid group The composition (C) of claim 1, comprising:

8. The acid group is —COOH or —SO ３ H, more preferably —SO ３ The composition (C) according to claim 7, wherein the compound (C) is selected from H.

9. The electron donating group is preferably —CH ３ and -CH ２ CH ３ The composition (C) according to claim 7, wherein the C1 to C5 alkyl group is selected from the group consisting of:

10. The at least one acid (OA) comprises at least one aromatic ring and at least one acid -SO bond linked to the aromatic ring via a sigma bond. ３ H group and a —CH ３ and -CH ２ CH ３ The composition (C) according to claim 1, comprising one electron donating group selected from:

11. The composition (C) of claim 1, wherein said at least one acid (OA) is p-toluenesulfonic acid.

12. The composition (C) of claim 1, wherein said at least one acid (OA) is present in an amount of 0.30 to 2.10 phr based on 100 phr of fluoroelastomer (A).

13. The composition (C) according to claim 1, wherein the anion A in the formulas (P-1) to (P-12) is selected from the group consisting of aryl sulfonates and halides (iodide, bromide, chloride).

14. at least one basic compound [base (B)], preferably selected from the group comprising an organic base, an inorganic base or a mixture of at least one organic base and at least one inorganic base, and / or one or more organic solvents [solvent (S)], preferably chosen from the group comprising polar aprotic organic solvents and ionic liquids, one or more conventional additives, preferably selected from the group comprising reinforcing fillers, thickeners, pigments, antioxidants, stabilizers The composition (C) of claim 1 further comprising:

15. A method for producing a molded article comprising the use of the composition (C) according to claim 1.

16. A cured article obtained from the composition (C) of claim 1.

17. 17. The cured article of claim 16, selected from a pipe, a fitting, an O-ring, and a hose.

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