Non-fluorinated resorcinol and hydroquinone analogues as curing agents for fluoroelastomers

Abstract

The composition comprises a curing agent of Formula 1. R1 and R5 are independently H, Cl, Br, C which may contain chlorine or bromine substitution. 1~18 R2-R4 are independently OH, H, Cl, Br, C which may contain chlorine or bromine substitutions. 1~18 At least one of R2, R3 and R4 is OH. At most three of R1 to R5 are Cl or Br. X is Formula 2 or Formula 3. R6 to R 10 C may independently contain H, Cl, Br, chlorine or bromine substitutions 1~18 R is alkyl or alkoxy, acetyl or methylsulfonyl, nitro, nitrile, keto, aceto, or sulfone, which may be alkyl or aryl substituted or may contain chlorine or bromine substitutions. 11 ~R 18 C may independently contain H, Cl, Br, chlorine or bromine substitutions 1~18 alkyl or alkoxy, nitro, or nitrile; R 11 ~R 18 One of R1 to R5 is a single bond to -(Y)n-. Y is -SO2- or -O-, and n is 0 or 1. At least one of R1 to R5 is a C group which may contain Cl, Br, chlorine or bromine substitution. 1~18 alkyl or alkoxy, or X. When X is present, R6 to R 18 At least one of the C groups may contain Cl, Br, chlorine or bromine substitutions. 1~18 It is alkyl or alkoxy, nitro, nitrile, keto, aceto, or sulfone. [Formula 1] TIFF2025532134000032.tif54128

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to and the benefit of U.S. Provisional Application No. 63 / 408,361, filed September 20, 2022, the entire contents of which are incorporated herein by reference.

[0002] FIELD OF THE INVENTION FIELD OF THE DISCLOSURE This disclosure relates to curatives for fluoroelastomers, and more particularly to non-fluorinated resorcinol and hydroquinone analogs useful as curatives for fluoroelastomers. [Background technology]

[0003] Fluoroelastomers have excellent heat, oil and chemical resistance and are widely used in sealing materials, containers and hoses. Examples of fluoroelastomers include copolymers having monomer units of vinylidene fluoride (VF2) and at least one other copolymerizable fluorine-containing monomer, such as hexafluoropropylene (HFP), tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), or a fluorovinyl ether, such as perfluoro(alkyl vinyl ether) (PAVE). Specific examples of PAVE include perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), and perfluoro(propyl vinyl ether). Other fluoroelastomers include copolymers of TFE and hydrocarbon olefins, such as ethylene or propylene. Perfluoroelastomers that are copolymers of TFE and PAVE are known.

[0004] To fully develop the physical properties of an elastomer for use in molded elastomeric articles, the polymer must be cured, i.e., vulcanized or crosslinked. This is generally accomplished in connection with a molding process by mixing the uncured polymer with a multifunctional curative, heating and molding the mixture into the shape of the desired article, and then further heating the resulting molding mixture, thereby promoting the crosslinking reaction between the curative and the polymer to produce a cured fluoroelastomer article.

[0005] Certain grades of fluoroelastomers, such as certain copolymers of VF2 / HFP or VF2 / HFP / TFE that do not contain cure site monomers, can be cured using polyhydroxy compounds as curing agents. 2,2-bis(4-hydroxyphenyl)hexafluoropropane, also known as bisphenol AF (BPAF), is a widely used curing agent for polyhydroxy-curable grades of fluoroelastomers. As a curing agent for polyhydroxy-curable grades of fluoroelastomers, BPAF provides good processability for the fluoroelastomer during molding into articles and imparts good properties to the cured fluoroelastomer articles. Regarding processing during molding, BPAF does not cause excessive "scorch," i.e., it does not cure rapidly while the article is being molded, but it provides a desirable short cure time once the molded article begins to cure. In the cured fluoroelastomer article, BPAF imparts desirable low "compression set" properties to the fluoroelastomer. Compression set is a commonly used measure of an elastomer's ability to return to nearly its original thickness after being compressed at elevated temperatures.

[0006] Currently, there is a proposed regulation in the European Union that would include BPAF in the group of compounds with endocrine disrupting properties. Therefore, the use of curing agents other than BPAF is desirable. U.S. Patent No. 6,610,790 lists a number of compounds, including resorcinol, hydroquinone, and certain alkyl-substituted resorcinols and hydroquinones, in addition to BPAF, as curing agents for fluoroelastomers. However, the other curing agents listed in U.S. Patent No. 6,610,790 do not provide the good processability and compression set properties that can be provided by BPAF. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] U.S. Patent No. 6,610,790 Summary of the Invention [Means for solving the problem]

[0008] The non-fluorinated resorcinol and hydroquinone analogs disclosed herein offer a good balance of processability and compression set properties as alternative curatives to BPAF in the curing of fluoroelastomers.

[0009] In one embodiment, the curable fluoroelastomer composition comprises a polyhydroxy curable fluoroelastomer, a curative of Formula 1, and an acid acceptor.

[0010] [ka]

[0011] R1 and R5 are C groups which may contain H, Cl, Br, chlorine or bromine substitutions. 1~18 and X are independently selected from the group consisting of alkyl or alkoxy, and R2, R3, and R4 may contain OH, H, Cl, Br, chlorine or bromine substitutions. 1~18and X are independently selected from the group consisting of alkyl or alkoxy, with the proviso that at least one of R2, R3, and R4 is OH, and with the proviso that no more than three of R1, R2, R3, R4, and R5 are Cl or Br.

[0012] X is selected from the group consisting of Formula 2 and Formula 3.

[0013] [ka]

[0014] R6, R7, R8, R9 and R 10 may contain H, Cl, Br, chlorine or bromine substitutions 1~18 independently selected from the group consisting of alkyl or alkoxy, acetyl or methylsulfonyl, nitro, nitrile, keto, aceto, and sulfone, which may be alkyl or aryl substituted or may contain chlorine or bromine substitutions; R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 may contain H, Cl, Br, chlorine or bromine substitutions 1~18 independently selected from the group consisting of alkyl or alkoxy, nitro, and nitrile, and with the proviso that R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 One of them is -(Y) n - is a single bond to -; Y is selected from the group consisting of -SO2- and -O-; n is 0 or 1; provided that at least one of R1, R2, R3, R4, and R5 may contain Cl, Br, chlorine or bromine substitutions. 1~18 alkyl or alkoxy, or X, with the proviso that when X is present, R6, R7, R8, R9, R 10 , R11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 At least one of the C groups may contain Cl, Br, chlorine or bromine substitutions. 1~18 It is alkyl or alkoxy, nitro, nitrile, keto, aceto or sulfone.

[0015] In one embodiment of the composition, at least one of R1 and R5 is H.

[0016] In another embodiment of the composition, at least one of R1, R2, R3, R4, and R5 is H when it is a substituent adjacent to OH.

[0017] In another embodiment of the composition, not more than one of R1, R2, R3, R4, and R5 is X.

[0018] In another embodiment of the composition, no more than two of R1, R2, R3, R4, and R5 are Cl or br.

[0019] In another embodiment of the composition, only one of R2, R3, and R4 is OH.

[0020] In another embodiment of the composition, either R2 or R4 is OH.

[0021] In another embodiment of the composition, R and R are C groups which may contain H, Cl, Br, chlorine or bromine substitutions. 1~18 R2, R3, and R4 are selected from the group consisting of alkyl or alkoxy, and X; R2, R3, and R4 are selected from the group consisting of OH, H, Cl, Br, C which may contain chlorine or bromine substitutions. 1~18 and X is independently selected from the group consisting of alkyl or alkoxy.

[0022] In another embodiment of the composition, one of R1, R2, R3, R4, and R5 is X, and X is Formula 2.

[0023] In another embodiment of the composition, R6, R7, R8, R9, and R 10 may contain H, Cl, Br, chlorine or bromine substitutions 1~6 alkyl or alkoxy; R6, R7, R8, R9, and R 10 At least one of the C groups may contain Cl, Br, or chlorine or bromine substitutions. 1~6 It is alkyl or alkoxy.

[0024] In another embodiment of the composition, R6, R7, R8, R9, and R 10 are independently selected from the group consisting of H, Cl, Br, and tertiary butyl; R6, R7, R8, R9, and R 10 At least one of is Cl, Br, or tertiary butyl.

[0025] In another embodiment of the composition, n is 0.

[0026] In another embodiment of the composition, -Y- is -O-.

[0027] In another embodiment of the composition, the curing agent is

[0028] [ka] is selected from the group consisting of:

[0029] In another embodiment of the composition, the composition contains from about 0.1 to about 10 parts by weight of the curative per 100 parts by weight of the fluoroelastomer.

[0030] In another embodiment of the composition, the polyhydroxy curable fluoroelastomer is a dipolymer of hexafluoropropylene and vinylidene fluoride.

[0031] In another embodiment of the composition, the acid acceptor is selected from the group consisting of powdered magnesium oxide, calcium hydroxide, and combinations thereof.

[0032] In another embodiment of the composition, the curable fluoroelastomer composition does not contain 2,2-bis(4-hydroxyphenyl)hexafluoropropane.

[0033] In another embodiment, the fluoroelastomer masterbatch comprises a polyhydroxy curable fluoropolymer and a curative of Formula 1. The curative is present in a concentration of about 1% to about 50% by weight.

[0034] In one embodiment of the fluoroelastomer masterbatch, the concentration of the curing agent is from about 20% to about 40% by weight.

[0035] In another embodiment, the mixture of curing agent and cure accelerator comprises a curing agent of Formula 1 and a cure accelerator selected from the group consisting of quaternary phosphonium salts, quaternary ammonium salts, and tertiary sulfonium salts.

[0036] In one embodiment of the mixture of curing agent and curing accelerator, the curing accelerator is a tertiary sulfonium salt.

[0037] In another embodiment of the mixture of curing agent and curing accelerator, the curing accelerator is a quaternary ammonium salt.

[0038] In another embodiment of the mixture of curing agent and cure accelerator, the quaternary ammonium salt is tetrabutylammonium hydrogen sulfate.

[0039] In another embodiment of the mixture of curing agent and curing accelerator, the curing accelerator is a quaternary phosphonium salt.

[0040] In another embodiment of the mixture of curing agent and curing accelerator, the quaternary phosphonium salt is benzyltriphenylphosphonium chloride.

[0041] In yet another embodiment, salts for use as fluoroelastomer curatives and cure accelerators include quaternary phosphonium or ammonium salts derived from compounds of Formula 1.

[0042] In one salt embodiment, the set accelerator is a quaternary ammonium salt.

[0043] In another embodiment of the salt, the quaternary ammonium salt is tetrabutylammonium hydrogen sulfate.

[0044] In another salt embodiment, the cure accelerator is a quaternary phosphonium salt.

[0045] In another embodiment of the salt, the salt is a benzyltriphenylphosphonium salt.

[0046] In another embodiment, a method for curing a polyhydroxy curable fluoroelastomer includes forming a curable fluoroelastomer composition comprising a polyhydroxy curable fluoroelastomer, a curing agent of Formula 1, and an acid acceptor, and heating the curable fluoroelastomer composition to cure the polyhydroxy curable fluoroelastomer.

[0047] In one embodiment of the method, the curable fluoroelastomer composition does not contain 2,2-bis(4-hydroxyphenyl)hexafluoropropane.

[0048] In another embodiment, the article is cured by the method.

[0049] In one embodiment of the article, the article is free or substantially free of 2,2-bis(4-hydroxyphenyl)hexafluoropropane.

[0050] In another embodiment, the compound is of formula 1A:

[0051] [ka]

[0052] One of R1 and R2 is H and the other is OH. One of R3 and R4 is H and the other is Formula 2A.

[0053] [ka]

[0054] R5, R6, R7, R8, and R9 are independently selected from the group consisting of H, Cl, Br, OCH3, C(CH3)3, CH3, nitro, nitrile, keto, aceto, and sulfone, with the proviso that when R1 is OH and R3 is of formula 2A: exactly one of R5, R6, R7, R8, and R9 is selected from the group consisting of C(CH3)3, nitrile, aceto, and sulfone, and the rest are H; or exactly one of R5, R6, R8, and R9 is selected from the group consisting of nitro and keto, and the rest of R5, R6, R7, R8, and R9 are H. or exactly one of R5 and R9 is CH3 and the remainder of R5, R6, R7, R8 and R9 are H; or exactly one of R6 and R8 is Br and the remainder of R5, R6, R7, R8 and R9 are H; or at least two of R5, R6, R7, R8 and R9 are independently selected from the group consisting of Cl, OCH3, C(CH3)3, nitro, nitrile, keto, aceto and sulfone; and with the proviso that when R1 is OH and R4 is formula 2A: exactly one of R5, R6, R7, R8 and R9 is C( or R5, R6, R8, and R9 are selected from the group consisting of Cl, Br, OCH3, and CH3, and the remainder of R5, R6, R7, R8, and R9 are H; or R5, R6, R7, R8, and R9 are selected from the group consisting of Cl, Br, OCH3, C(CH3)3, CH3, keto, aceto, and sulfone, and the remainder are H; or R5, R6, R7, R8, and R9 are selected from the group consisting of Cl, Br, OCH3, C(CH3)3, CH3, keto, aceto, and sulfone, and the remainder are H. and with the proviso that when R2 is OH: exactly one of R5, R6, R7, R8, and R9 is selected from the group consisting of keto and sulfone, and the remainder are H; exactly one of R5, R6, R8, and R9 is selected from the group consisting of C(CH3)3 and aceto, and the remainder of R5, R6, R7, R8, and R9 are H; or at least two of R5, R6, R7, R8, and R9 are independently selected from the group consisting of Cl, C(CH3)3, nitrile, keto, aceto, and sulfone.

[0055] In one embodiment of the compound, R 1 is OH and R 2 is H.

[0056] In another embodiment of the compound, R1 is H and R2 is OH.

[0057] Other features and advantages of the present invention will be apparent from the following more detailed description of the preferred embodiment, taken in conjunction with the accompanying drawings which illustrate, by way of example, the principles of the invention. DETAILED DESCRIPTION OF THE INVENTION

[0058] Exemplary non-fluorinated resorcinol and hydroquinone analogs are provided as alternative curatives to BPAF in the curing of fluoroelastomers, offering a good balance of processability and compression set properties.

[0059] In an exemplary embodiment, the curative provides cure and cured fluoroelastomer properties similar to BPAF as a curative. Such cure properties can be measured by a moving die rheometer (MDR) and are expressed as the minimum S' torque (M L ), the maximum S' torque achieved within a specified period (M H ), M L S' (scorch) time from one unit increase in torque (ts1), M L Time (ts2) from S' to 2 unit increase in torque (scorch), M L From M H Time (t) to increase torque by 50% 50 ), and / or M L From M H Time (t) to increase torque by 90% 90Such cured fluoroelastomer properties may include, but are not limited to, compression set resistance, tensile strength (TS), elongation at break (EB), and elastic modulus at 100% (M100), and / or fluid aging properties.

[0060] In an exemplary embodiment, the curing agent is of Formula 1:

[0061] [ka] where R1 and R5 are C groups which may contain H, Cl, Br, chlorine or bromine substitutions. 1~18 and X are independently selected from the group consisting of alkyl or alkoxy, and R2, R3, and R4 may contain OH, H, Cl, Br, chlorine or bromine substitutions. 1~18 independently selected from the group consisting of alkyl or alkoxy, and X, with the proviso that at least one of R, R, and R is OH, and with the proviso that no more than three of R, R, R, R, and R are Cl or Br; X is selected from the group consisting of Formula 2 and Formula 3;

[0062] [ka] In the formula, R6, R7, R8, R9 and R 10 may contain H, Cl, Br, chlorine or bromine substitutions 1~18 independently selected from the group consisting of alkyl or alkoxy, acetyl or methylsulfonyl, nitro, nitrile, keto, aceto, and sulfone, which may be alkyl or aryl substituted or may contain chlorine or bromine substitutions; R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , and R 18may contain H, Cl, Br, chlorine or bromine substitutions 1~18 independently selected from the group consisting of alkyl or alkoxy, nitro, nitrile, keto, aceto, and sulfone, with the proviso that R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 One of them is -(Y) n - is a single bond to -; Y is selected from the group consisting of -SO2- and -O-; n is 0 or 1; provided that at least one of R1, R2, R3, R4, and R5 may contain Cl, Br, chlorine or bromine substitutions. 1~18 alkyl or alkoxy, or X, with the proviso that when X is present, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 At least one of the C groups may contain Cl, Br, chlorine or bromine substitutions. 1~18 It is alkyl or alkoxy, nitro, nitrile, keto, aceto or sulfone.

[0063] In some embodiments, at least one of R1 and R5 is H.

[0064] In some embodiments, at least one of R1, R2, R3, R4, and R5 is H when it is a substituent adjacent to OH.

[0065] In some embodiments, no more than one of R1, R2, R3, R4, and R5 is X.

[0066] In some embodiments, no more than two of R1, R2, R3, R4, and R5 are Cl or Br.

[0067] In some embodiments, only one of R2, R3, and R4 is OH.

[0068] In some embodiments, either R2 or R4 is OH.

[0069] In some embodiments, one of R1, R2, R3, R4, and R5 is X, and X is Formula 2.

[0070] In some embodiments, R, R, R, R, and R 10 may contain H, Cl, Br, chlorine or bromine substitutions 1~6 C, which may contain alkyl, chlorine or bromine substitutions 1~6 alkoxy; R, R, R, R, and R 10 At least one of the C groups may contain Cl, Br, chlorine or bromine substitutions. 1~6 C which may contain alkyl, chlorine or bromine substitutions 1~6 It is an alkoxy.

[0071] In some embodiments, R, R, R, R, and R 10 are independently selected from the group consisting of H, Cl, Br, and tertiary butyl; R6, R7, R8, R9, and R 10 At least one of is fluorine or tertiary butyl.

[0072] In some embodiments, n is 0.

[0073] In some embodiments, -Y- is -O-.

[0074] In some embodiments, the curing agent is a non-fluorinated resorcinol analog. Exemplary non-fluorinated resorcinol analogs include those having the following structure:

[0075] [ka] These may include, but are not limited to:

[0076] In some embodiments, the curing agent is a non-fluorinated hydroquinone analog. Exemplary non-fluorinated hydroquinone analogs include those having the following structure:

[0077] [ka] These may include, but are not limited to:

[0078] In some embodiments, the curing agent has the following structure:

[0079] [ka] is selected from.

[0080] In some embodiments, the curative is part of a curable fluoroelastomer composition that further comprises a polyhydroxy curable fluoroelastomer and an acid acceptor.

[0081] In some embodiments, the curable fluoroelastomer composition comprises from about 0.1 to about 10 parts by weight, alternatively from about 0.2 to about 5 parts by weight, alternatively from about 0.5 to about 5 parts by weight, alternatively from about 1 to about 2.4 parts by weight, of curative per 100 parts by weight of fluoroelastomer, or any value, range, or subrange therebetween.

[0082] The fluoroelastomer can be any polyhydroxy-curable fluoroelastomer. As used herein, "polyhydroxy-curable" refers to a fluoroelastomer known to crosslink with a polyhydroxy curative, such as BPAF. Such fluoroelastomers include, but are not limited to, those with multiple carbon-carbon double bonds along the main elastomeric polymer chain, as well as those containing sites that can be readily dehydrofluorinated. Examples of the latter fluoroelastomers include, but are not limited to, those containing adjacent copolymerized units of vinylidene fluoride (VF2) and hexafluoropropylene (HFP), and those containing adjacent copolymerized units of VF2 (or tetrafluoroethylene) and a fluorinated comonomer having an acidic hydrogen atom (e.g., 2-hydropentafluoropropylene; 1-hydropentafluoropropylene; trifluoroethylene; 2,3,3,3-tetrafluoropropene; or 3,3,3-trifluoropropene). Preferred fluoroelastomers include i) copolymers of vinylidene fluoride with hexafluoropropylene and optionally tetrafluoroethylene (TFE), ii) copolymers of vinylidene fluoride with perfluoro(alkyl vinyl ether), such as perfluoro(methyl vinyl ether), 2-hydropentafluoropropylene, and optionally tetrafluoroethylene, iii) copolymers of tetrafluoroethylene with propylene and 3,3,3-trifluoropropene, iv) copolymers of tetrafluoroethylene, perfluoro(methyl vinyl ether) and hexafluoro-2-(pentafluorophenoxy)-1-(trifluorovinyloxy)propane, and v) copolymers of ethylene with tetrafluoroethylene, perfluoro(methyl vinyl ether) and 3,3,3-trifluoropropylene. In some embodiments, the polyhydroxy-curable fluoroelastomer is a dipolymer of hexafluoropropylene and vinylidene fluoride. The polyhydroxy curable fluoroelastomer may also include iodine or bromine containing elastomers.For example, small amounts (0.01-1 wt%) of chlorine, bromine, or iodine can be introduced with a telogen such as, for example, CH2I2 or I(CF2)4I, or a monomer such as, for example, CH2=CHCF2CF2X (X=Br, I) or chlorotrifluoroethylene. In some embodiments, the polyhydroxy curable fluoroelastomer is, for example, CH2=CH(CF2). n CH=CH2 [wherein n=2 to 8] or CF2=CFO(CF2) n It contains a bisolefin such as OCF=CF2 (wherein n=2 to 8).

[0083] Suitable acid acceptors can include, but are not limited to, powdered magnesium oxide, calcium hydroxide, zinc oxide, bismuth oxide, lead oxide, calcium oxide, hydrotalcite, barium carbonate, calcium carbonate, alkyl stearate, or combinations thereof. In some embodiments, the curable fluoroelastomer composition comprises from about 3 to about 15 parts by weight, alternatively from about 5 to about 15 parts by weight, alternatively from about 6 to about 12 parts by weight, alternatively from about 8 to about 10 parts by weight, of an acid acceptor per 100 parts by weight of fluoroelastomer, or any value, range, or subrange therebetween. In some embodiments, the composition comprises two or more acid acceptors.

[0084] In some embodiments, the curable composition includes an organic base. Suitable organic bases may include, but are not limited to, 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) or a salt thereof, 1,5-diazabicyclo(4.3.0)-non-5-ene (DBN) or a salt thereof, or a combination thereof.

[0085] In some embodiments, the curable composition comprises one or more additives. Suitable additives may include, but are not limited to, processing aids and / or colorants.

[0086] In some embodiments, the fluoroelastomer masterbatch comprises a curative and a polyhydroxy curable fluoropolymer.

[0087] In some embodiments, the mixture of curing agent and cure accelerator comprises a curing agent and a cure accelerator.

[0088] Suitable accelerators include [(C6H5)2S + (C6H 13 )][Cl] - , and [(CH 13 )2S(C6H5)] + [CH3CO2] - and tertiary sulfonium salts such as those of the formula R5R6R7R8Y + X - wherein Y is phosphorus, nitrogen, arsenic, or antimony; R5, R6, R7, and R8 are each independently C1-C 20 alkyl, aryl, aralkyl, alkenyl, and their chlorine, fluorine, bromine, cyano, -OR, and -COOR substituted analogs, where R is C1-C 20 alkyl, aryl, aralkyl, alkenyl, and X is halide, hydroxide, sulfate, sulfite, carbonate, pentachlorothiophenolate, tetrafluoroborate, hexafluorosilicate, hexafluorophosphate, dimethylphosphate, and C1-C 20These may include, but are not limited to, quaternary ammonium, phosphonium, arsonium, and stibonium salts of alkyl, aryl, aralkyl, and alkenyl carboxylates and dicarboxylates. Particularly preferred are benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, tetrabutylammonium hydrogen sulfate, tetrabutylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium bromide, tributylallylphosphonium chloride, tributyl-2-methoxypropylphosphonium chloride, 1,8-diazabicyclo[5.4.0]undec-7-ene, and benzyldiphenyl(dimethylamino)phosphonium chloride. Other suitable cure accelerators include methyltrioctylammonium chloride, methyltributylammonium chloride, tetrapropylammonium chloride, benzyltrioctylphosphonium bromide, benzyltrioctylphosphonium chloride, methyltrioctylphosphonium acetate, tetraoctylphosphonium bromide, methyltriphenylarsonium tetrafluoroborate, tetraphenylstibonium bromide, 4-chlorobenzyltriphenylphosphonium chloride, 8-benzyl-1,8 -diazabicyclo(5.4.0)-7-undecenonium chloride, diphenylmethyltriphenylphosphonium chloride, allyltriphenylphosphonium chloride, tetrabutylphosphonium bromide, m-trifluoromethyl-benzyltrioctylphosphonium chloride, and other quaternary compounds disclosed in U.S. Pat. Nos. 5,591,804, 4,912,171, 4,882,390, 4,259,463, 4,250,278, and 3,876,654.

[0089] In some embodiments, the cure accelerator comprises a quaternary phosphonium salt, a quaternary ammonium salt, or a tertiary sulfonium salt.

[0090] In some embodiments, the cure accelerator comprises benzyltriphenylphosphonium chloride or tetrabutylammonium hydrogen sulfate.

[0091] In some embodiments, the weight ratio of the curing agent to the curing accelerator in the curing agent and curing accelerator mixture ranges from about 1:1 to about 12:1, alternatively from about 1.5:1 to about 10:1, alternatively from about 2:1 to about 8:1, or any value, range, or subrange therebetween.

[0092] In some embodiments, the phenoxides derived from the curing agents of Formula 1 are in the form of quaternary phosphonium salts or quaternary ammonium salts for use as fluoroelastomer curatives and cure accelerators.

[0093] In some embodiments, the process cures a polyhydroxy curable fluoropolymer with a curing agent.

[0094] In some embodiments, the process includes forming a mixture of a polyhydroxy curable fluoropolymer, a curing agent, at least one acid acceptor, and a cure accelerator.

[0095] In some embodiments, the mixture comprises from about 0.05 to about 1.5 parts by weight, alternatively from about 0.1 to about 1 part by weight, alternatively from about 0.2 to about 0.8 parts by weight, alternatively from about 0.25 to about 0.65 parts by weight, of the cure accelerator per 100 parts by weight of fluoroelastomer, or any value, range, or subrange therebetween.

[0096] In some embodiments, the mixture further comprises a filler. The filler can be one or more inorganic fillers, one or more polymeric fillers, or a combination thereof. In some embodiments, the filler is medium heat carbon black. Other suitable inorganic fillers can include, but are not limited to, silica, talc, titanium dioxide (TiO), barium sulfate (BaSO), calcium carbonate (CaCO), or combinations thereof. Suitable polymeric fillers can include, but are not limited to, polytetrafluoroethylene (PTFE). In some embodiments, the mixture comprises from about 10 to about 40 parts by weight, alternatively from about 20 to about 40 parts by weight, alternatively from about 25 to about 35 parts by weight, alternatively about 30 parts by weight, of the filler per 100 parts by weight of fluoroelastomer, or any value, range, or subrange therebetween.

[0097] In some embodiments, the curing temperature ranges from about 150°C to about 200°C, alternatively from about 160°C to about 190°C, alternatively from about 170°C to about 180°C, or any value, range, or subrange therebetween.

[0098] In some embodiments, the cure time is in the range of about 5 to about 60 minutes, alternatively about 5 to about 20 minutes, alternatively about 10 to about 30 minutes, alternatively about 20 to about 30 minutes, or any value, range, or subrange therebetween.

[0099] In some embodiments, the curing agent provides curing properties similar to those of BPAF. L , M H , ts1, ts2, t 50 , and t 90 In some embodiments, the value is within 50%, alternatively within 40%, alternatively within 30%, alternatively within 20%, alternatively within 10%, alternatively within 5%, or any value, range, or subrange therebetween of the value of BPAF as the sclerosing agent.

[0100] In some embodiments, the curing agent provides a cured fluoroelastomer with properties similar to those of a cured fluoroelastomer formed using BPAF as the curing agent. Such properties may include, but are not limited to, compression set resistance, tensile strength, elongation at break, and 100% modulus. In some embodiments, these values ​​are within 50%, alternatively within 40%, alternatively within 30%, alternatively within 20%, alternatively within 10%, alternatively within 5%, or any value, range, or subrange therebetween, of the values ​​of BPAF as the curing agent.

[0101] In some embodiments, a method of curing a polyhydroxy curable fluoroelastomer includes forming a curable fluoroelastomer composition comprising a polyhydroxy curable fluoroelastomer, a curing agent of Formula 1, and an acid acceptor, and heating the curable fluoroelastomer composition to cure the polyhydroxy curable fluoroelastomer.

[0102] In some embodiments, the curable fluoroelastomer composition is free or substantially free of 2,2-bis(4-hydroxyphenyl)hexafluoropropane.

[0103] In some embodiments, the article is cured by a curing method.

[0104] In some embodiments, the article is free or substantially free of 2,2-bis(4-hydroxyphenyl)hexafluoropropane.

[0105] In another embodiment, the compound is of formula 1A:

[0106] [ka] wherein one of R1 and R2 is H and the other is OH; one of R3 and R4 is H and the other is Formula 2A;

[0107]

change

[0108] R5, R6, R7, R8, and R9 are independently selected from the group consisting of H, Cl, Br, OCH3, C(CH3)3, CH3, nitro, nitrile, keto, aceto, and sulfone, with the proviso that when R1 is OH and R3 is of formula 2A: exactly one of R5, R6, R7, R8, and R9 is selected from the group consisting of C(CH3)3, nitrile, aceto, and sulfone, and the rest are H; or exactly one of R5, R6, R8, and R9 is selected from the group consisting of nitro and keto, and the rest of R5, R6, R7, R8, and R9 are H. or exactly one of R5 and R9 is CH3 and the remainder of R5, R6, R7, R8 and R9 are H; or exactly one of R6 and R8 is Br and the remainder of R5, R6, R7, R8 and R9 are H; or at least two of R5, R6, R7, R8 and R9 are independently selected from the group consisting of Cl, OCH3, C(CH3)3, nitro, nitrile, keto, aceto and sulfone; and with the proviso that when R1 is OH and R4 is formula 2A: exactly one of R5, R6, R7, R8 and R9 is C or R5, R6, R7, R8, and R9 are selected from the group consisting of Cl, Br, OCH3, and CH3, and the remainder of R5, R6, R7, R8, and R9 are H; or R5, R6, R7, R8, and R9 are selected from the group consisting of Cl, Br, OCH3, C(CH3)3, CH3, keto, aceto, and and when R2 is OH: exactly one of R5, R6, R7, R8 and R9 is selected from the group consisting of keto and sulfone, and the remainder are H; exactly one of R5, R6, R8 and R9 is selected from the group consisting of C(CH3)3 and aceto, and the remainder of R5, R6, R7, R8 and R9 are H; or at least two of R5, R6, R7, R8 and R9 are independently selected from the group consisting of Cl, C(CH3)3, nitrile, keto, aceto and sulfone.

[0109] Applications for the cured fluoropolymers described herein may include, but are not limited to, sealants, shaft seals, O-rings, containers, hoses, or wearable applications such as, for example, watch bands.

[0110] In some embodiments, the described fluoroelastomers are blended with one or more other fluoroelastomers or polymers to form a polymer blend. Suitable blend polymers include, but are not limited to, nylon or other polyamides.

[0111] Although curing agents have been described herein for curing curable fluoroelastomers, the curing agents may also be used for other purposes. In some embodiments, the curing agent reacts with a polyisocyanate to form a polyurethane.

[0112] In other embodiments, a curing agent is included in the polyester. In some such embodiments, the curing agent is condensed with an aliphatic or aromatic dicarboxylic acid (e.g., terephthalic acid, isophthalic acid, or mixtures thereof, or esters thereof) to form an aliphatic-aromatic polyester or an aromatic-aromatic polyester, respectively. The resulting polymer has an amorphous high T g The introduction of fluorinated aromatic side groups can result in good polymer processability, good thermal stability, and / or good oxidative stability.

[0113] In other embodiments, the curing agent is included in the polyimide, polyamide, polycarbonate, and / or epoxy resin.

[0114] Test Method Moving die rheometer (MDR) measurements Cure properties were measured on approximately 8 grams of the fluoroelastomer cured composition in an MDR-2000 rheometer (Alpha Technologies, Bellingham, WA) according to ASTM D5289. The cure temperature was 177°C and the cure time was 24 minutes. The frequency of the moving die was 1.66 Hz and the oscillation amplitude was 0.5°.

[0115] Reported cure characteristics include M L (unit: dN·m), M H (unit: dN m), ts1 (unit: min), ts2 (unit: min), t 50 (unit: min), t 90 (unit: minutes) is included.

[0116] Measurement of fluoroelastomer properties Compression set resistance was determined for fluoroelastomers according to ASTM D395, Test Method B, using a compression apparatus that compresses fluoroelastomer samples to a deflection of 25%. Prior to compression set testing, the fluoroelastomers were post-cured at 232°C for 16 hours. Compression set resistance is reported as the percent change in thickness after a given time at a given temperature. Three values ​​are reported herein: 200°C for 70 hours (CS1), 200°C for 168 hours (CS2), and 250°C for 70 hours (CS3).

[0117] Tensile properties were measured for the fluoroelastomers before aging at 23°C according to ISO 37:2005 C or 1 2008 test protocols. Measured tensile properties included tensile strength (in MPa), elongation at break (in %), and 100% modulus (in MPa). [Example]

[0118] Synthesis Example Four non-fluorinated resorcinol or hydroquinone analogs were prepared for evaluation as curing agents. The chemical structures of these inventive examples are shown in Table 1.

[0119] [Table 1]

[0120] The non-fluorinated resorcinol analogs of Examples 1, 3, and 4 of the present invention were prepared by a commonly used palladium-catalyzed synthetic approach for coupling arylboronic acids and aryl bromides as building blocks.

[0121] In the synthesis of Example 1 of the present invention, 4-chlorophenylboronic acid (13.5 g, 86.4 mmol), 1-bromo-3,5-dimethoxy-benzene (15 g, 69 mmol), potassium carbonate (17.2 g), Pd(PPh3)4 (0.4 g, 0.35 mmol), water (60 g), and toluene (180 g) were stirred at reflux under nitrogen for 4 hours. The resulting toluene solution was separated, washed with water, and dried over MgSO4. The toluene was removed by distillation, and the resulting (MeO)2C6H3-C6H4-4-Cl was distilled under vacuum (145-150 °C / 1-1.3 Torr). The resulting (MeO)CH-CH-4-Cl intermediate (13.33 g, 78% yield, 53.6 mmol) was hydrolyzed with 48% hydrobromic acid (40.4 g) and acetic acid (45 g) at 114 °C for 5 h to achieve complete conversion. Most of the acid was removed by vacuum distillation, and the distillation residue was neutralized with 9 g of 25% aqueous NaOH, extracted with ethyl acetate, washed with NaHCO solution, and dried over MgSO. The ethyl acetate was removed by distillation to obtain the final pure 3,5-(HO)CH-CH-4-Cl (11.4 g, 96% yield, melting point = 141-144 °C) of Example 1 of the present invention as a pale yellow solid.

[0122] The material for Example 2 of the present invention was obtained from Ambeed, Inc. (Arlington, IL, USA) and used without further purification.

[0123] In the synthesis of Example 3 of the present invention, 15 g (55.7 mmol) of 3,5-di-tert-butyl-bromobenzene and 10 g (55.0 mmol) of 3,5-dimethoxyphenylboronic acid were added to a mixture of 150 mL of dioxane and 50 mL of deionized water under nitrogen, followed by the addition of 15.2 g (110.1 mmol) of potassium carbonate and 0.64 g (0.55 mmol) of Pd(PPh3)4. The reaction mixture was stirred at gentle reflux for 24 hours, and completion of the reaction was confirmed by TLC. All solvent was then evaporated, 300 mL of deionized water was added, and the crude material was washed with water and dried. The crude material was redissolved in diethyl ether, filtered to remove the catalyst, the solvent was evaporated, and the remaining material was recrystallized from hexane. 13.1 g (73.2%) of product was obtained. The resulting material (13 g, 40.0 mmol) was dissolved in 100 mL of DCM cooled in an ice bath, and 10 mL (105.4 mmol) of boron tribromide was added dropwise with vigorous stirring. The reaction mixture was slowly warmed to room temperature and stirred overnight. The solvent was removed, and the reaction mixture was quenched with cold water. The crude product was extracted with dichloromethane. The solution was dried over magnesium sulfate, filtered, and the solvent was evaporated. The residue was recrystallized from hexane / ethyl acetate to give 10.3 g of inventive Example 3 in 86.7% yield.

[0124] In the synthesis of Example 4 of the present invention, 3-nitrophenylboronic acid (24.5 g, 146.7 mmol), 1-bromo-3,5-dimethoxy-benzene (24.5 g, 113 mmol), potassium carbonate (28 g), Pd(PPh3)4 (0.65 g, 0.56 mmol), water (98 g), and toluene (220 g) were stirred at reflux under nitrogen for 4 hours. The resulting toluene solution was separated, washed with water, and dried over MgSO4. The toluene was removed by distillation, and the resulting (MeO)2C6H3-C6H4-3-NO2 (20.8 g, 71.5% yield) was obtained as a distillation residue after removal of more volatile components under vacuum (maximum 190 °C / 0.6-0.9 Torr). The (MeO)CH-CH-4-Cl intermediate (19.5 g, 75.2 mmol) was hydrolyzed with 48% hydrobromic acid (97 g) and acetic acid (93 g) at 114 °C for 5 hours and 116 °C for 3 hours. Most of the acid was removed by vacuum distillation, and the distillation residue was neutralized with 23 g of 20% aqueous NaOH, extracted with ethyl acetate, washed with NaHCO solution, and dried over MgSO. The ethyl acetate was removed by distillation, and the crude 3,5-(HO)CH-CH-3-NO was purified by silica gel chromatography and recrystallized to give Example 4 of the present invention as a yellow solid (4.0 g, 23% yield, melting point = 176-178 °C).

[0125] The melting points of the examples of the present invention were measured and are shown in Table 2.

[0126] [Table 2]

[0127] Comparative Fluoroelastomer Curing Examples Because the conditions for each set of cure runs were slightly different, 2,2-bis(4-hydroxyphenyl)hexafluoropropane (BPAF) (Comparative Examples A-D) was used as the curing agent for comparison of the cure runs for each set of inventive examples of curing agents.

[0128] The comparative fluoroelastomer curable composition contained 100 parts by weight of Viton™ A-500 (The Chemours Company FC LLC, Wilmington, Del.) as a polyhydroxy-curable fluoroelastomer, 30 parts by weight of medium heat carbon black (MT Black) as a filler, 3 parts by weight of powdered MgO (Elastomag® 170, Akrochem Corporation, Akron, Ohio) as an acid acceptor, 6 parts by weight of calcium hydroxide (Hallstar International, Chicago, Ill.) as an acid acceptor, 2 parts by weight of BPAF, and 0.55 parts by weight of benzyltriphenol phosphonium chlorit (BTPPC) as a cure accelerator.

[0129] Fluoroelastomer Curing Examples of the Invention The prepared non-fluorinated resorcinol and hydroquinone analogs were evaluated as curing agents in curable compositions (Inventive Examples 1-4).

[0130] The fluoroelastomer curing compositions of the present invention contained 100 parts by weight of Viton™ A-500 as the polyhydroxy curable fluoroelastomer, 30 parts by weight of MT Black as a filler, 3 parts by weight of powdered MgO as an acid acceptor, 6 parts by weight of calcium hydroxide as an acid acceptor, 1.24 to 2.01 parts by weight of a curing agent, and 0.30 to 0.60 parts by weight of BTPPC as a cure accelerator. The amounts of curing agent and BTPPC in each cure composition are shown in Table 3. The fluoroelastomer curing composition of Example 4 of the present invention also contained 1 part by weight of a processing aid.

[0131] [Table 3]

[0132] In some cases, multiple runs were performed using the same curative, and the amounts of curative and BTPPC were adjusted based on previous results to obtain cure and / or fluoroelastomer properties more similar to those obtained when BPAF was used as the curative.

[0133] Fluoroelastomer cure results The cure properties of the inventive examples from Table 1 and each comparative example for the cured composition of Table 3 are shown in Table 4. Each comparative example is listed immediately before an inventive example from the same MDR run set. When multiple runs were run using the same curative, only the run with the best combination of cure and fluoroelastomer properties was selected and listed in the table.

[0134] [Table 4]

[0135] Table 4 shows that the examples of the present invention provided hardening properties similar to those of BPAF. L The value is in the range of 0.71 to 1.32 dN m, and M H The values ​​ranged from 22.92 to 25.46 dN m, the ts1 values ​​ranged from 0.77 to 1.38 min, the ts2 values ​​ranged from 0.89 to 1.65 min, and the t 50 The values ​​range from 1.41 to 2.34 min, and t 90 The values ​​ranged from 2.36 to 3.84 min.

[0136] Fluoroelastomer Properties The fluoroelastomer properties of the fluoroelastomers formed from the inventive examples in Table 1 and the respective comparative examples in the cured compositions in Table 3 are shown in Table 5. When multiple runs were run using the same curative, only the run with the best combination of cure and fluoroelastomer properties was selected and listed in the table.

[0137] [Table 5]

[0138] Table 5 shows that the inventive examples provided cured fluoroelastomers with similar properties to those formed using BPAF as the curing agent. Table 5 shows that for the inventive examples, TS values ​​ranged from 9.0 to 15.5 MPa, EB values ​​ranged from 150 to 199%, M100 values ​​ranged from 5.5 to 7.3 MPa, CS1 values ​​ranged from 23.3 to 25.6%, CS2 values ​​ranged from 35.6 to 37.2%, and CS3 values ​​ranged from 64.7 to 81.4%.

[0139] All of the above references are incorporated herein by reference.

[0140] While the present invention has been described with reference to preferred embodiments, those skilled in the art will recognize that various changes can be made and equivalents can be substituted for elements thereof without departing from the scope of the invention. It should be understood that many modifications can be made to adapt a particular situation or material to the teachings of the invention without departing from essential scope thereof. Therefore, it is not intended that the invention be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but rather, the invention is intended to include all embodiments falling within the scope of the appended claims.

Claims

1. 1. A curable fluoroelastomer composition comprising: a polyhydroxy curable fluoroelastomer; Formula 1: 【Chemical 1】 [In the formula, R １ and R ５ is C, which may contain H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ X is independently selected from the group consisting of alkoxy, R ２ , R ３ and R ４ is C, which may contain OH, H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ X is independently selected from the group consisting of alkoxy, However, R ２ , R ３ and R ４ at least one of is OH; However, R １ , R ２ , R ３ , R ４ and R ５ no more than three of are Cl or Br; X is a group represented by Formula 2 and Formula 3: 【Chemistry 2】 (In the formula, R ６ , R ７ , R ８ , R ９ and R １０ is C, which may contain H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ independently selected from the group consisting of alkoxy, acetyl or methylsulfonyl, nitro, nitrile, keto, aceto, and sulfone, which may be alkyl- or aryl-substituted or may contain chlorine or bromine substitutions; R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ is C, which may contain H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ independently selected from the group consisting of alkoxy, nitro, nitrile, keto, aceto, and sulfone, with the proviso that R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ One of the groups is -(Y) ｎ - is a single bond to Y is -SO ２ - and -O-, and n is 0 or 1; However, R １ , R ２ , R ３ , R ４ and R ５ At least one of Cl, Br, chlorine-containing C １～１８ Alkyl or alkoxy, bromine-containing C １～１８ alkyl or alkoxy, or X; However, when X is present, R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ At least one of C may contain Cl, Br, chlorine substitution, or bromine substitution. １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ a curing agent selected from the group consisting of alkoxy, nitro, nitrile, keto, aceto, or sulfone; an acid acceptor; 1. A curable fluoroelastomer composition comprising:

2. R １ and R ５ 10. The curable fluoroelastomer composition of claim 1, wherein at least one of: is H.

3. R １ , R ２ , R ３ , R ４ , and R ５ 3. A curable fluoroelastomer composition according to claim 1 or 2, wherein at least one of is H when it is the substituent adjacent to OH.

4. R １ , R ２ , R ３ , R ４ , and R ５ A curable fluoroelastomer composition according to any one of claims 1 to 3, wherein not more than one of: is X.

5. R １ , R ２ , R ３ , R ４ , and R ５ A curable fluoroelastomer composition according to any one of claims 1 to 4, wherein no more than two of are Cl or Br.

6. R ２ , R ３ , and R ４ A curable fluoroelastomer composition according to any one of claims 1 to 5, wherein only one of is OH.

7. R ２ or R ４ 7. The curable fluoroelastomer composition of claim 6, wherein any of: is OH.

8. R １ and R ５ may contain H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ alkoxy, and X; R ２ , R ３ and R ４ may contain OH, H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ The curable fluoroelastomer composition of any one of claims 1 to 7, wherein X is independently selected from the group consisting of alkoxy, and X.

9. R １ , R ２ , R ３ , R ４ , and R ５ A curable fluoroelastomer composition according to any one of claims 1 to 8, wherein one of: is X, and X is of formula 2.

10. R ６ , R ７ , R ８ , R ９ , and R １０ may contain H, Cl, Br, chlorine or bromine substitutions １～６ Alkyl, and C which may contain chlorine or bromine substitution １～６ alkoxy; R ６ , R ７ , R ８ , R ９ , and R １０ at least one of which may contain Cl, Br, chlorine or bromine substitutions; １～６ C which may contain alkyl, chlorine or bromine substitutions １～６ 10. The curable fluoroelastomer composition of claim 9 which is alkoxy.

11. R ６ , R ７ , R ８ , R ９ , and R １０ is independently selected from the group consisting of H, Cl, Br, and tert-butyl; R ６ , R ７ , R ８ , R ９ , and R １０ 10. The curable fluoroelastomer composition of claim 9, wherein at least one of is Cl, Br, or tertiary butyl.

12. A curable fluoroelastomer composition according to any one of claims 1 to 11, wherein n is 0.

13. A curable fluoroelastomer composition according to any one of claims 1 to 12, wherein -Y- is -O-.

14. The curing agent is 【Chemistry 3】 2. The curable fluoroelastomer composition of claim 1, selected from the group consisting of:

15. A curable fluoroelastomer composition according to any one of claims 1 to 14, containing from about 0.1 to about 10 parts by weight of said curative per 100 parts by weight of fluoroelastomer.

16. A curable fluoroelastomer composition according to any one of claims 1 to 15, wherein said polyhydroxy curable fluoroelastomer is a dipolymer of hexafluoropropylene and vinylidene fluoride.

17. A curable fluoroelastomer composition according to any one of claims 1 to 16, wherein said acid acceptor is selected from the group consisting of powdered magnesium oxide, calcium hydroxide, and combinations thereof.

18. A curable fluoroelastomer composition according to any one of claims 1 to 17, wherein said curable fluoroelastomer composition does not comprise 2,2-bis(4-hydroxyphenyl)hexafluoropropane.

19. 1. A fluoroelastomer masterbatch comprising a polyhydroxy curable fluoropolymer and a fluoroelastomer of Formula 1: 【Chemistry 4】 [In the formula, R １ and R ５ is C, which may contain H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ X is independently selected from the group consisting of alkoxy, R ２ , R ３ and R ４ is C, which may contain OH, H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ X is independently selected from the group consisting of alkoxy, However, R ２ , R ３ and R ４ at least one of is OH; However, R １ , R ２ , R ３ , R ４ and R ５ no more than three of are Cl or Br; X is a group represented by Formula 2 and Formula 3: 【Chemistry 5】 (In the formula, R ６ , R ７ , R ８ , R ９ and R １０ is C, which may contain H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ independently selected from the group consisting of alkoxy, acetyl or methylsulfonyl, nitro, nitrile, keto, aceto, and sulfone, which may be alkyl- or aryl-substituted or may contain chlorine or bromine substitutions; R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ is C, which may contain H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ independently selected from the group consisting of alkoxy, nitro, nitrile, keto, aceto, and sulfone, with the proviso that R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ One of the groups is -(Y) ｎ - is a single bond to Y is -SO ２ - and -O-, and n is 0 or 1; However, R １ , R ２ , R ３ , R ４ and R ５ At least one of Cl, Br, chlorine-containing C １～１８ Alkyl or alkoxy, bromine-containing C １～１８ alkyl or alkoxy, or X; However, when X is present, R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ , and R １８ at least one of which may contain Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ a curing agent selected from the group consisting of alkoxy, nitro, nitrile, keto, aceto, or sulfone; Including, The fluoroelastomer masterbatch wherein the curative is present in a concentration of from about 1% to about 50% by weight.

20. 20. The fluoroelastomer masterbatch of claim 19, wherein the concentration of the curative is from about 20% to about 40% by weight.

21. A mixture of a curing agent and a curing accelerator, the mixture comprising a compound of Formula 1: 【Chemistry 6】 [In the formula, R １ and R ５ is C, which may contain H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ X is independently selected from the group consisting of alkoxy, R ２ , R ３ and R ４ is C, which may contain OH, H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ X is independently selected from the group consisting of alkoxy, However, R ２ , R ３ and R ４ at least one of is OH; However, R １ , R ２ , R ３ , R ４ and R ５ no more than three of are Cl or Br; X is a group represented by Formula 2 and Formula 3: 【Chemistry 7】 (In the formula, R ６ , R ７ , R ８ , R ９ and R １０ is C, which may contain H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ independently selected from the group consisting of alkoxy, acetyl or methylsulfonyl, nitro, nitrile, keto, aceto, and sulfone, which may be alkyl- or aryl-substituted or may contain chlorine or bromine substitutions; R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ is C, which may contain H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ independently selected from the group consisting of alkoxy, nitro, nitrile, keto, aceto, and sulfone, with the proviso that R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ One of the groups is -(Y) ｎ - is a single bond to Y is -SO ２ - and -O-, and n is 0 or 1; However, R １ , R ２ , R ３ , R ４ and R ５ At least one of Cl, Br, chlorine-containing C １～１８ Alkyl or alkoxy, bromine-containing C １～１８ alkyl or alkoxy, or X; However, when X is present, R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ At least one of C may contain Cl, Br, chlorine substitution, or bromine substitution. １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ a curing agent selected from the group consisting of alkoxy, nitro, nitrile, keto, aceto, or sulfone; a curing accelerator selected from the group consisting of quaternary phosphonium salts, quaternary ammonium salts, and tertiary sulfonium salts; A mixture comprising:

22. 22. The mixture of curing agent and curing accelerator according to claim 21, wherein the curing accelerator is a tertiary sulfonium salt.

23. 22. The mixture of curing agent and curing accelerator according to claim 21, wherein the curing accelerator is a quaternary ammonium salt.

24. 24. The mixture of curing agent and cure accelerator of claim 23, wherein the quaternary ammonium salt is tetrabutylammonium hydrogen sulfate.

25. 22. The mixture of curing agent and curing accelerator according to claim 21, wherein the curing accelerator is a quaternary phosphonium salt.

26. 26. The mixture of curing agent and curing accelerator of claim 25, wherein the quaternary phosphonium salt is benzyltriphenylphosphonium chloride.

27. 1. A salt for use as a fluoroelastomer curative and cure accelerator, comprising the formula 1: 【Chemistry 8】 [In the formula, R １ and R ５ is C, which may contain H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ X is independently selected from the group consisting of alkoxy, R ２ , R ３ and R ４ is C, which may contain OH, H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ X is independently selected from the group consisting of alkoxy, However, R ２ , R ３ and R ４ at least one of is OH; However, R １ , R ２ , R ３ , R ４ and R ５ no more than three of are Cl or Br; X is a group represented by Formula 2 and Formula 3: 【Chemistry 9】 (In the formula, R ６ , R ７ , R ８ , R ９ and R １０ is C, which may contain H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ independently selected from the group consisting of alkoxy, acetyl or methylsulfonyl, nitro, nitrile, keto, aceto, and sulfone, which may be alkyl- or aryl-substituted or may contain chlorine or bromine substitutions; R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ is C, which may contain H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ independently selected from the group consisting of alkoxy, nitro, nitrile, keto, aceto, and sulfone, with the proviso that R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ One of the groups is -(Y) ｎ - is a single bond to Y is -SO ２ - and -O-, and n is 0 or 1; However, R １ , R ２ , R ３ , R ４ and R ５ At least one of Cl, Br, chlorine-containing C １～１８ Alkyl or alkoxy, bromine-containing C １～１８ alkyl or alkoxy, or X; However, when X is present, R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ At least one of C may contain Cl, Br, chlorine substitution, or bromine substitution. １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ alkoxy, nitro, nitrile, keto, aceto, or sulfone).

28. 28. The salt of claim 27, wherein the cure accelerator is a quaternary ammonium salt.

29. 29. The salt of claim 28, wherein the quaternary ammonium salt is tetrabutylammonium hydrogen sulfate.

30. 28. The salt of claim 27, wherein the cure accelerator is a quaternary phosphonium salt.

31. 31. The salt of claim 30, wherein the salt is a benzyltriphenylphosphonium salt.

32. 1. A method for curing a polyhydroxy curable fluoroelastomer, comprising: the polyhydroxy curable fluoroelastomer; Formula 1: 【Chemistry 10】 [In the formula, R １ and R ５ is C, which may contain H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ X is independently selected from the group consisting of alkoxy, R ２ , R ３ and R ４ is C, which may contain OH, H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ X is independently selected from the group consisting of alkoxy, However, R ２ , R ３ and R ４ at least one of is OH; However, R １ , R ２ , R ３ , R ４ and R ５ no more than three of are Cl or Br; X is a group represented by Formula 2 and Formula 3: 【Chemistry 11】 (In the formula, R ６ , R ７ , R ８ , R ９ and R １０ is C, which may contain H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ independently selected from the group consisting of alkoxy, acetyl or methylsulfonyl, nitro, nitrile, keto, aceto, and sulfone, which may be alkyl- or aryl-substituted or may contain chlorine or bromine substitutions; R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ is C, which may contain H, Cl, Br, chlorine or bromine substitutions １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ independently selected from the group consisting of alkoxy, nitro, nitrile, keto, aceto, and sulfone, with the proviso that R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ One of the groups is -(Y) ｎ - is a single bond to Y is -SO ２ - and -O-, and n is 0 or 1; However, R １ , R ２ , R ３ , R ４ and R ５ At least one of Cl, Br, chlorine-containing C １～１８ Alkyl or alkoxy, bromine-containing C １～１８ alkyl or alkoxy, or X; However, when X is present, R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ At least one of C may contain Cl, Br, chlorine substitution, or bromine substitution. １～１８ C, which may contain alkyl, chlorine or bromine substitutions １～１８ a curing agent selected from the group consisting of alkoxy, nitro, nitrile, keto, aceto, or sulfone; an acid acceptor; forming a curable fluoroelastomer composition comprising: heating the curable fluoroelastomer composition to cure the polyhydroxy curable fluoroelastomer; A method comprising:

33. The method of claim 32, wherein the curable fluoroelastomer composition does not contain 2,2-bis(4-hydroxyphenyl)hexafluoropropane.

34. 33. An article cured by the method of claim 32.

35. 35. The article of claim 34, which is free or substantially free of 2,2-bis(4-hydroxyphenyl)hexafluoropropane.

36. Formula 1A: 【Chemistry 12】 [In the formula, R １ and R ２ one of which is H and the other is OH, R ３ and R ４ is H and the other is a compound of formula 2A: 【Chemistry 13】 (In the formula, R ５ , R ６ , R ７ , R ８ and R ９ is H, Cl, Br, OCH ３ , C(CH ３ ) ３ , C.H. ３ independently selected from the group consisting of nitro, nitrile, keto, aceto, and sulfone; However, R １ is OH and R ３ is formula 2A, R ５ , R ６ , R ７ , R ８ , and R ９ Exactly one of the ３ ) ３ , nitrile, aceto, and sulfone, the remainder being H; or R ５ , R ６ , R ８ , and R ９ and exactly one of R is selected from the group consisting of nitro and keto. ５ , R ６ , R ７ , R ８ , and R ９ The rest of the R ５ and R ９ Exactly one of the ３ and R ５ , R ６ , R ７ , R ８ and R ９ The rest of the R ６ and R ８ Exactly one of R is Br, ５ , R ６ , R ７ , R ８ and R ９ the remainder are H, or R ５ , R ６ , R ７ , R ８ and R ９ At least two of ３ , C(CH ３ ) ３ independently selected from the group consisting of nitro, nitrile, keto, aceto, and sulfone; and However, R １ is OH and R ４ is formula 2A, R ５ , R ６ , R ７ , R ８ , and R ９ Exactly one of the ３ ) ３ , nitrile, keto, aceto, and sulfone, the remainder being H; or R ５ , R ６ , R ８ , and R ９ Exactly one of ３ , and C.H. ３ and R ５ , R ６ , R ７ , R ８ , and R ９ The rest of the R ５ , R ７ and R ９ Exactly one of R is nitro; ５ , R ６ , R ７ , R ８ and R ９ the remainder are H, or R ５ , R ６ , R ７ , R ８ , and R ９ At least two of the ３ , C(CH ３ ) ３ , C.H. ３ independently selected from the group consisting of keto, aceto, and sulfone; and However, R ２ When is OH, R ５ , R ６ , R ７ , R ８ and R ９ wherein exactly one of is selected from the group consisting of keto and sulfone, and the rest are H; or R ５ , R ６ , R ８ and R ９ Exactly one of the ３ ) ３ and aceto; R ５ , R ６ , R ７ , R ８ and R ９ the remainder are H, or R ５ , R ６ , R ７ , R ８ and R ９ At least two of the ３ ) ３ , nitrile, keto, aceto, and sulfone).

37. R １ is OH and R ２ 37. The compound of claim 36, wherein is H.

38. R １ is H and R ２ 37. The compound of claim 36, wherein is OH.

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