Fluorinated resorcinol and hydroquinone analogues as curing agents for fluoroelastomers

Abstract

The composition includes a fluorinated resorcinol or hydroquinone curing agent of Formula 1, [Formula 1] JPEG2025532133000043.jpg50128R1 and R5 are independently H, halogen, optionally partially or fully halogenated C 1~18 Alkyl, optionally partially or fully halogenated C 1~18 R2-R4 are independently OH, H, halogen, optionally partially or fully halogenated C 1~18 wherein R is an alkyl, an optionally partially or fully halogenated C1-18 alkoxy, or X. At least one of R2, R3, and R4 is OH. Not more than three of R1-R5 are halogen. X is Formula 2 or Formula 3 disclosed herein. Also disclosed herein are curable fluoroelastomer compositions, fluoroelastomer masterbatches, mixtures of curatives and cure accelerators, salts, and methods for curing polyhydroxy curable fluoroelastomers comprising the fluorinated resorcinol or hydroquinone curative of Formula 1.

Description

[Technical Field]

[0001] (Reference to Related Application) This application claims priority to and claims the benefit of U.S. Provisional Patent Application No. 63 / 408,349, filed September 20, 2022, the contents of which are incorporated herein by reference in their entirety.

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

[0003] Fluoroelastomers have excellent heat, oil, and chemical resistance and have been widely used in sealing materials, containers, and hoses. Examples of fluoroelastomers include copolymers containing 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 curing agent, 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 of the curing agent with the polymer to produce the cured fluoroelastomer article.

[0005] Certain grades of fluoroelastomers, such as certain copolymers of VF2 / HFP or VF2 / HFP / TFE that do not contain a cure site monomer, can be cured using polyhydroxy compounds as curing agents. 2,2-bis(4-hydroxyphenyl)hexafluoropropane, often referred to 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 too rapidly while the article is being molded, yet 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, the European Union is proposing to restrict the inclusion of BPAF in the class of compounds with endocrine disrupting properties. Therefore, it is desirable to use curing agents other than BPAF. In addition to BPAF, U.S. Patent No. 6,610,790 lists a number of compounds, including resorcinol, hydroquinone, and certain alkyl-substituted resorcinols and hydroquinones, 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 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 curing agent of Formula 1, and an acid acceptor.

[0010] [ka]

[0011] R1 and R5 are independently H, halogen, or optionally partially or fully halogenated C 1~18 Alkyl, optionally partially or fully halogenated C 1~18alkoxy, and X, wherein R2, R3, and R4 are independently selected from the group consisting of OH, H, halogen, and optionally partially or fully halogenated C 1~18 Alkyl, optionally partially or fully halogenated C 1~18 alkoxy, and X, provided that at least one of R2, R3, and R4 is OH, and provided that no more than three of R1, R2, R3, R4, and R5 are halogen.

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

[0013] [ka]

[0014] R6, R7, R8, R9, and R 10 are independently H, C which may be partially or fully halogenated 1~18 Alkyl, optionally partially or fully halogenated C 1~18 alkoxy, partially or fully fluorinated phenyl, optionally alkyl- or aryl-substituted or partially or fully halogenated acetyl or methylsulfonyl, nitro, nitrile, and halogen, provided that N is optionally substituted at exactly one of C2, C3, or C4, in which case the respective R6, R7, or R8 is absent and R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 are independently H, C which may be partially or fully halogenated 1~18 Alkyl, optionally partially or fully halogenated C 1~18 is selected from the group consisting of alkoxy, nitro, nitrile, and halogen, with the proviso that R 11 , R 12 , R 13 , R14 , R 15 , R 16 , R 17 , and R 18 One of them is -(Y) n -, Y is selected from the group consisting of -SO2-, -C(O)-, -C(CF3)2-, and -O-, and n is 0 or 1, provided that at least one of R1, R2, R3, R4, and R5 is fluorine, fluorine-containing C(CF3)2-, or 1~18 Alkyl, Fluorine-containing C 1~18 Alkoxy, or X, provided that X is present and R1, R2, R3, R4, and R5 are all fluorine, fluorine-containing C 1~18 Alkyl or fluorine-containing C 1~18 If not alkoxy, 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 groups is fluorine or fluorine-containing C 1~18 Alkyl or fluorine-containing C 1~18 It is an alkoxy.

[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 halogen.

[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 H, fluorine, or optionally partially or fully fluorinated C 1~18 Alkyl, optionally partially or fully fluorinated C 1~18 alkoxy, and X, wherein R2, R3, and R4 are independently selected from the group consisting of OH, H, fluorine, and optionally partially or fully fluorinated C 1~18 Alkyl, optionally partially or fully fluorinated C 1~18 alkoxy, and X.

[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 are independently H, fluorine, or C, which may be partially or fully fluorinated. 1~6 Alkyl and optionally partially or fully fluorinated C 1~6 alkoxy; R, R, R, R, and R 10 At least one of the C groups may be fluorine, partially or completely fluorinated. 1~6 alkyl, or optionally partially or fully fluorinated C 1~6 It is an alkoxy.

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

[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 above-described curative per 100 parts by weight of fluoroelastomer.

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

[0031] In another embodiment of the composition, the polyhydroxy curable fluoroelastomer is a terpolymer of hexafluoropropylene, vinylidene fluoride, and tetrafluoroethylene.

[0032] In another embodiment of the composition, the acid acceptor is selected from the group consisting of powdered magnesium oxide, calcium hydroxide, and combinations thereof.

[0033] In another embodiment of the composition, the curable fluoroelastomer composition is free of 2,2-bis(4 hydroxyphenyl)hexafluoropropane.

[0034] 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.

[0035] In one embodiment of the fluoroelastomer masterbatch, the concentration of the curing agent is from about 20% to about 40% by weight.

[0036] 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.

[0037] In one embodiment of the mixture of curing agent and curing accelerator, the curing accelerator is a tertiary sulfonium salt.

[0038] In another embodiment of the mixture of curing agent and curing accelerator, the curing accelerator is a quaternary ammonium salt.

[0039] In another embodiment of the mixture of curing agent and curing accelerator, the quaternary ammonium salt is tetrabutylammonium hydrogen sulfate.

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

[0041] In another embodiment of the mixture of curing agent and curing accelerator, the quaternary phosphonium salt is benzyltriphenylphosphonium chloride.

[0042] In yet another embodiment, salts for use as fluoroelastomer curatives and cure accelerators include quaternary phosphonium or quaternary ammonium salts derived from compounds of Formula 1.

[0043] In one salt embodiment, the set accelerator is a quaternary ammonium salt.

[0044] In another embodiment of the salt, the quaternary ammonium salt is tetrabutylammonium hydrogen sulfate.

[0045] In another salt embodiment, the cure accelerator is a quaternary phosphonium salt.

[0046] In another embodiment of the salt, the salt is a benzyltriphenylphosphonium salt.

[0047] In another embodiment, a method for curing a polyhydroxy curable fluoroelastomer comprises 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.

[0048] In one embodiment of the method, the curable fluoroelastomer composition does not include 2,2-bis(4 hydroxyphenyl)hexafluoropropane.

[0049] In another embodiment, the article is cured by the method.

[0050] In one embodiment of the article, the article is free or substantially free of 2,2-bis(4 hydroxyphenyl)hexafluoropropane.

[0051] In another embodiment, the compound is a compound of formula 1A.

[0052] [ka]

[0053] One of R1 and R2 is H and the other is OH. One of R3 and R4 is H and the other is selected from the group consisting of Formula 2A and Formula 3A.

[0054] [ka]

[0055] R5, R6, R7, R8, and R9 are independently selected from the group consisting of H, F, CF3, partially or fully fluorinated phenyl, OCF3, CH3, nitro, and nitrile, with the proviso that at least one of R5, R6, R7, R8, and R9 is selected from the group consisting of F, CF3, partially or fully fluorinated phenyl, and OCF3, with the proviso that when R5, R6, R7, R8, and R9 are independently selected from the group consisting of H and F, at least two are H and at least two are F, with the proviso that when R1 is OH, R3 is of formula 2A, and R5, R6, R7, R8, and R9 are independently selected from the group consisting of H and CF3, at least one of R6 and R8 is H, with the proviso that N may be substituted at exactly one of C2, C3, or C4, in which case the respective R5, R6, or R7 is absent.

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

[0057] In some embodiments, the ring in formula 2A is a benzyl ring.

[0058] In some embodiments, N is substituted at exactly one of C2, C3, or C4, and the ring in formula 2A is a pyridinyl ring.

[0059] 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

[0060] Exemplary fluorinated resorcinol and hydroquinone analogs are provided as curatives to replace BPAF in the curing of fluoroelastomers, offering a good balance of processability and compression set properties.

[0061] In an exemplary embodiment, the curative provides similar cure and cured fluoroelastomer properties to BPAF as the curative. Such cure properties may be measured by a moving die rheometer (MDR) and include, but are not limited to, minimum S' torque (M L ), the maximum S' torque achieved during a specific period (M H ), M L The time it takes to increase torque by 1 unit (scorch) from S' (ts1), M L The time it takes to increase the torque by 2 units (scorch time) (ts2), M L From M H Time (t) until 50% increase in torque (S') 50 ), and / or M L From M H Time (t) until 90% increase in torque (S') 90 Such cured fluoroelastomer properties may include, but are not limited to, compression set resistance, tensile strength (TS), elongation at break (EB), and modulus at 100% (M100), and / or fluid aged properties.

[0062] In an exemplary embodiment, the curing agent is a curing agent of Formula 1:

[0063] [ka] wherein R1 and R5 are independently H, halogen, or optionally partially or completely halogenated C 1~18 Alkyl, optionally partially or fully halogenated C 1~18 alkoxy, and X, wherein R2, R3, and R4 are independently selected from the group consisting of OH, H, halogen, and optionally partially or fully halogenated C 1~18 Alkyl, optionally partially or fully halogenated C 1~18alkoxy, and X, provided that at least one of R, R, and R is OH, and provided that no more than three of R, R, R, R, and R are halogen; X is selected from the group consisting of Formula 2 and Formula 3;

[0064] [ka] In the formula, R6, R7, R8, R9, and R 10 are independently H, C which may be partially or fully halogenated 1~18 Alkyl, optionally partially or fully halogenated C 1~18 and R is selected from the group consisting of alkoxy, partially or fully fluorinated phenyl, acetyl or methylsulfonyl which may be alkyl- or aryl-substituted or partially or fully halogenated, nitro, nitrile, and halogen, with the proviso that N may be substituted at exactly one of C2, C3, or C4, in which case the respective R6, R7, or R8 is absent, such that the ring in formula 2 is a pyridinyl ring, and R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 are independently H, C which may be partially or fully halogenated 1~18 Alkyl, optionally partially or fully halogenated C 1~18 is selected from the group consisting of alkoxy, nitro, nitrile, and halogen, 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-, Y is selected from the group consisting of -SO2-, -C(O)-, -C(CF3)2-, and -O-, and n is 0 or 1, provided that at least one of R1, R2, R3, R4, and R5 is fluorine, fluorine-containing C(CF3)2-, or 1~18 Alkyl, Fluorine-containing C 1~18 Alkoxy, or X, provided that X is present and R1, R2, R3, R4, and R5 are all fluorine, fluorine-containing C 1~18 Alkyl or fluorine-containing C 1~18 If not alkoxy, 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 groups is fluorine or fluorine-containing C 1~18 Alkyl, partially or fully fluorinated phenyl, or fluorine-containing C 1~18 It is an alkoxy.

[0065] In some embodiments, the ring in Formula 2 is a benzyl ring.

[0066] In some embodiments, N is substituted at exactly one of C2, C3, or C4, and the ring in formula 2 is a pyridinyl ring.

[0067] In some embodiments, at least one of R1 and R5 is H.

[0068] In some embodiments, at least one of R1, R2, R3, R4, and R5 is H when it is a substituent adjacent to OH.

[0069] In some embodiments, no more than one of R1, R2, R3, R4, and R5 is X.

[0070] In some embodiments, no more than two of R1, R2, R3, R4, and R5 are halogen.

[0071] In some embodiments, only one of R2, R3, and R4 is OH.

[0072] In some embodiments, either R2 or R4 is OH.

[0073] In some embodiments, R and R are H, fluorine, or optionally partially or fully fluorinated C 1~18 Alkyl, optionally partially or fully fluorinated C 1~18 alkoxy, and X, wherein R2, R3, and R4 are independently selected from the group consisting of OH, H, fluorine, and optionally partially or fully fluorinated C 1~18 Alkyl, optionally partially or fully fluorinated C 1~18 alkoxy, and X.

[0074] In some embodiments, one of R1, R2, R3, R4, and R5 is X, and X is Formula 2.

[0075] In some embodiments, R, R, R, R, and R 10 are independently H, fluorine, or C, which may be partially or fully fluorinated. 1~6 Alkyl and optionally partially or fully fluorinated C 1~6 alkoxy; R, R, R, R, and R 10 At least one of the C groups may be fluorine, partially or completely fluorinated. 1~6 alkyl, or optionally partially or fully fluorinated C 1~6 It is an alkoxy.

[0076] In some embodiments, R, R, R, R, and R 10are independently selected from the group consisting of H, fluorine, perfluoromethyl, and perfluoromethoxy; R, R, R, R, and R 10 At least one of is fluorine, perfluoromethyl, or perfluoromethoxy.

[0077] In some embodiments, n is 0.

[0078] In some embodiments, -Y- is -O-.

[0079] In some embodiments, the curing agent is a fluorinated resorcinol analog. Exemplary fluorinated resorcinol analogs may include, but are not limited to:

[0080] [ka]

[0081] [ka]

[0082] In some embodiments, the curing agent is a fluorinated hydroquinone analog. Exemplary fluorinated hydroquinone analogs include, but are not limited to, the following:

[0083] [ka]

[0084] In some embodiments, the curing agent has the following structure:

[0085] [ka] is selected from.

[0086] In some embodiments, the curative is part of a curable fluoroelastomer composition that further comprises a polyhydroxy curable fluoroelastomer and an acid acceptor.

[0087] 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.

[0088] The fluoroelastomer may be any polyhydroxy-curable fluoroelastomer. As used herein, "polyhydroxy-curable" refers to fluoroelastomers known to crosslink with polyhydroxy curatives, such as BPAF. Such fluoroelastomers include, but are not limited to, those with multiple carbon-carbon double bonds along the elastomeric polymer backbone and those containing sites that can be readily dehydrofluorinated. 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 ethers), 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 an iodine-, bromine-, or chlorine-containing elastomer.For example, small amounts (0.01-1 wt%) of chlorine, bromine, or iodine can be introduced with a telogen such as CH2I2 or I(CF2)4I, or a monomer such as CH2=CHCF2CF2X (X=Br, I) or chlorotrifluoroethylene. In some embodiments, the polyhydroxy curable fluoroelastomer is, for example, a bisolefin, such as CH2=CH(CF2). n CH=CH2 (wherein n=2 to 8) or CF2=CFO(CF2) n Contains OCF=CF2 (wherein n=2 to 8).

[0089] Suitable acid acceptors may 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.

[0090] In some embodiments, the curable composition includes an organic base. Suitable organic bases may include, but are not limited to, 1,8-diazobicyclo[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.

[0091] 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.

[0092] In some embodiments, the fluoroelastomer masterbatch comprises a curative and a polyhydroxy curable fluoropolymer.

[0093] In some embodiments, the mixture of curing agent and cure accelerator comprises a curing agent and a cure accelerator.

[0094] Suitable cure accelerators include, but are not limited to, tertiary sulfonium salts, such as [(C6H5)2S + (C6H 13 )][Cl] - , and [(CH 13 )2S(C6H5)] + [CH3CO2] - , as well as quaternary ammonium salts of the formula R5R6R7R8Y + X - and R5, R6, R7, and R8 are each independently selected from the group consisting of 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 20Alkyl, 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-undecenium chloride, diphenylmethyltriphenylphosphonium chloride, allyltriphenyl-phosphonium 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.

[0095] In some embodiments, the cure accelerator includes a quaternary phosphonium salt, a quaternary ammonium salt, or a tertiary sulfonium salt.

[0096] In some embodiments, the cure accelerator includes benzyltriphenylphosphonium chloride or tetrabutylammonium hydrogen sulfate.

[0097] In some embodiments, the curing agent and curing accelerator in the curing agent and curing accelerator mixture are in a weight ratio ranging 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.

[0098] In some embodiments, the curing agent and curing accelerator are pre-reacted to form a salt of the curing agent and curing accelerator. In some embodiments, the curing agent is in a 2- to 6-fold molar excess, alternatively a 2- to 5-fold molar excess, alternatively a 3- to 6-fold molar excess, alternatively about a 3.5-fold molar excess, alternatively about a 5.3-fold molar excess, or any value, range, or subrange therebetween, relative to the amount of curing accelerator.

[0099] In some embodiments, the pre-reacted curing agent-cure accelerator salt provides similar cure properties to the same curing agent and cure accelerator without the pre-reacted salt, but provides significantly better compression set to the cured polymer than the same curing agent and cure accelerator without the pre-reacted salt. In some embodiments, the compression set is reduced by at least 10% with the pre-reacted salt. In some embodiments, the compression set is reduced by at least 30% with the pre-reacted salt. In some embodiments, the compression set is reduced by a greater percentage than when BPAF is used as the curing agent.

[0100] In some embodiments, the phenoxide derived from the curing agent of Formula 1 is in the form of a quaternary phosphonium salt or quaternary ammonium salt for use as a fluoroelastomer curative and cure accelerator.

[0101] In some embodiments, the process cures a polyhydroxy curable fluoropolymer with a curing agent.

[0102] In some embodiments, the process comprises forming a mixture of a polyhydroxy curable fluoropolymer, a curing agent, at least one acid acceptor, and a cure accelerator.

[0103] 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 0.6 parts by weight, of the cure accelerator per 100 parts by weight of fluoroelastomer, or any value, range, or subrange therebetween.

[0104] In some embodiments, the mixture further comprises a filler. The filler may be one or more inorganic fillers, one or more polymeric fillers, or a combination thereof. In some embodiments, the filler is medium thermal carbon black. Other suitable inorganic fillers may include, but are not limited to, silica, talc, titanium dioxide (TiO), barium sulfate (BaSO), calcium carbonate (CaCO), or a combination thereof. Suitable polymeric fillers may 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 filler per 100 parts by weight of fluoroelastomer, or any value, range, or subrange therebetween.

[0105] 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.

[0106] 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.

[0107] In some embodiments, the curing agent provides curing properties similar to those of BPAF. Such properties include, but are not limited to, M 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.

[0108] In some embodiments, the curing agent provides a cured fluoroelastomer with properties similar to those of cured fluoroelastomers 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 modulus at 100%. In some embodiments, the 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 value of BPAF as the curing agent.

[0109] In some embodiments, a method of curing a polyhydroxy curable fluoroelastomer comprises 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.

[0110] In some embodiments, the curable fluoroelastomer composition is free or substantially free of 2,2-bis(4 hydroxyphenyl)hexafluoropropane.

[0111] In some embodiments, the article is cured by a curing method.

[0112] In some embodiments, the article is free or substantially free of 2,2-bis(4 hydroxyphenyl)hexafluoropropane.

[0113] In another embodiment, the compound is of formula 1A:

[0114] [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 selected from the group consisting of Formula 2A and Formula 3A;

[0115] [ka] wherein R5, R6, R7, R8, and R9 are independently selected from the group consisting of H, F, CF3, partially or fully fluorinated phenyl, OCF3, CH3, nitro, and nitrile, provided that at least one of R5, R6, R7, R8, and R9 is selected from the group consisting of F, CF3, partially or fully fluorinated phenyl, and OCF3, provided that R5, R6, R7, R8, and R9 are independently selected from H and F. at least two are H and at least two are F, with the proviso that when R is OH, R is Formula 2A, and R, R, R, R, and R are independently selected from the group consisting of H and CF, then at least one of R and R is H, with the proviso that N is optionally substituted at exactly one of C, C, or C, in which case the respective R, R, or R is absent.

[0116] Applications for the cured fluoropolymers described herein may include, but are not limited to, sealing materials, shaft seals, O-rings, containers, hoses, or wearable applications such as, for example, watch bands.

[0117] 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.

[0118] Although the curing agents are described herein for curing curable fluoroelastomers, the curing agents may have other uses as well. In some embodiments, the curing agents react with polyisocyanates to form polyurethanes.

[0119] 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 material may be a liquid crystalline aromatic polyester. The introduction of fluorinated aromatic side groups may result in good polymer processability, good thermal stability, and / or good oxidative stability.

[0120] In other embodiments, the curing agent is included in the polyimide, polyamide, polycarbonate, and / or epoxy resin.

[0121] Test Method Moving die rheometer (MDR) measurements Cure properties were measured on approximately 8 grams of the fluoroelastomer cured composition according to ASTM D5289 using an MDR-2000 Rheometer (Alpha Technologies, Bellingham, WA). The cure temperature was 177°C and the cure time was 24 minutes. The moving die frequency was 1.66 Hz and the vibration amplitude was 0.5°.

[0122] The reported hardening properties are expressed in units of M in dN m. L , M in dN m H , ts1 in minutes, ts2 in minutes, t in minutes 50 , and t in minutes 90 Includes:

[0123] Measurement of fluoroelastomer properties Compression set resistance was determined for fluoroelastomers according to ASTM D395, Test Method B, using a compression device to compress fluoroelastomer samples to 25% deflection. 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).

[0124] Tensile properties were determined for unaged fluoroelastomers at 23°C according to ISO 37:2005 C or 1 2008 test protocols. Prior to tensile testing, the fluoroelastomers were post-cured at 232°C for 16 hours. Measured tensile properties included tensile strength in MPa, elongation at break in %, and modulus at 100% in MPa.

[0125] Certain fluoroelastomer O-rings were fluid aged by placing them in sulfuric acid at 70° C. for 168 hours. Prior to fluid aging, the fluoroelastomer was post-cured at 232° C. for 16 hours. Following fluid aging, the fluoroelastomer swell was measured as a weight percent and compression set (CS1) was performed on the samples. [Example]

[0126] Synthesis Example Twenty-nine fluorinated resorcinol or hydroquinone analogs were prepared for evaluation as curing agents. The chemical structures of these Inventive Examples (IE) are shown in Table 1.

[0127] The starting material for inventive Example 1 was obtained from MilliporeSigma (Burlington, Mass.) and further purified by column chromatography on silica gel.

[0128] The fluorinated resorcinol analogs of Examples 2-12, 15-19, 21-27, and 29 of the present invention, as well as the fluorinated hydroquinone analog of Example 20 of the present invention, were prepared by a palladium-catalyzed synthetic methodology often used for the coupling of arylboronic acids with aryl bromides as building blocks. When the aromatic hydroxy group of the building block was protected with a methyl group, an additional hydrolysis step of the methoxy group was used to generate the fluorinated resorcinol and hydroquinone analogs.

[0129] For example, in the synthesis of Example 2 of the present invention, 3,5-dimethoxyphenylboronic acid (12.5 g), 1-bromo-2,3,5-trifluorobenzene (11 g), potassium carbonate (13.8 g), Pd(PPh3)4 (0.36 g), water (44 g), and toluene (132 g) were stirred and refluxed under nitrogen for 4 hours. The resulting toluene solution was separated and dried over MgSO4. The toluene was removed by distillation, and the resulting (MeO)2C6H3-C6F3H2 was distilled under high vacuum (120-142 °C / 0.6-0.8 Torr). Next, (MeO)2C6H3-C6F3H2 (6.3 g) was diluted with dichloromethane (22 g) and a 1 M solution of BBr3 in dichloromethane (52 mL) was added at a temperature of -7 to 0 °C. The mixture was stirred and allowed to warm to room temperature overnight. The mixture was then cooled to 0°C, water was carefully added dropwise, and the product was extracted with ethyl acetate. The extract was dried, filtered, and the solvent was evaporated to give the final yellow powder of Example 2 of the present invention (4.4 g, mp=187°C, 3,5-(HO)2C6H3-C6F3H2).

[0130] [Table 1]

[0131] [Table 2]

[0132] In Example 12 of the present invention, 3,5-difluorophenylboronic acid (16.08 g), 1-bromo-3,5-dimethoxy-benzene (17 g), potassium carbonate (19.5 g), Pd(PPh3)4 (0.45 g), water (68 g), and toluene (206 g) were stirred and refluxed under nitrogen for 4 hours. The resulting toluene solution was separated and dried over MgSO4. The toluene was removed by distillation, and the resulting (MeO)2C6H3-C6F2H3 was distilled under high vacuum (141-145 °C / 1.3 Torr). The resulting (MeO)2C6H3-C6F2H3 (11.8 g) was reacted with 48% hydrobromic acid (39 g) and acetic acid (34.6 g) at 114 °C for 20 hours. Most of the acid was removed by distillation under high vacuum, and the distillation residue was neutralized with 6.9 g of 25% aqueous NaOH, extracted with ethyl acetate, and dried over MgSO. The ethyl acetate was removed by distillation, and the resulting 3,5-(HO)CH-CFH was recrystallized to give the final off-white solid (7.55 g, mp=144°C) of Example 12 of the present invention.

[0133] In Example 13 of the present invention, a 250 mL reactor was charged with potassium carbonate (17.7 g), N,N-dimethylformamide (DMF, 65.56 g), and pentafluorobenzene (10.6 g) and preheated to 80 °C. A mixture of 3,5-dimethoxyphenol (9.8 g) and DMF (11.9 g) was added via a dropping funnel over 20 minutes. The mixture was stirred and heated to 90 °C over 8 hours. An additional 1.9 g of pentafluorobenzene was then added, and heating was continued for 9 hours, achieving 98% conversion of 3,5-dimethoxyphenol by GC / MS. Water (150 g) was added, and the crude 3,5-dimethoxyphenyl 2,3,5,6-tetrafluorophenyl ether was filtered as a solid and purified by high-vacuum distillation at 102-118 °C / 0.6-0.8 Torr. Next, 3,5-dimethoxyphenyl 2,3,5,6-tetrafluorophenyl ether (MeO)C6H3-O-C6F4H (12.9 g) was diluted with dichloromethane (68 g) and a 1 M solution of BBr3 in dichloromethane (60 mL) was added over 15 minutes at -14 to -3 °C, stirred, and allowed to warm slowly to room temperature overnight. The mixture was cooled in an ice-water bath, and water was carefully added dropwise. The product was extracted with ethyl acetate. The extract was dried, filtered, and the solvent was evaporated to give the final yellow powder (11 g, mp = 142 °C) of Example 13 of the present invention.

[0134] For Inventive Example 14, 85 g (0.34 mol) of boron tribromide was added dropwise to a vigorously stirred solution of 25 g (0.16 mol) of 3,5-dimethoxy-1-fluorobenzene in 200 mL of dichloromethane at 0-3°C (ice-water cooling bath). Stirring of the reaction mixture continued while the reaction mixture warmed to room temperature, and then the mixture was left at room temperature overnight. The reaction mixture was then cooled in ice water and quenched with deionized water. The solvent was removed on a rotary evaporator, and the crude product was extracted from the mixture with diethyl ether. The crude product was purified by passing through a silica gel column. This synthesis was repeated using the same loading of starting material, and the products from two batches were combined. The combined material was recrystallized from toluene and dried to remove residual solvent, yielding 27.5 g (67% average of the two batches) of Inventive Example 14.

[0135] In Example 28 of the present invention, a solution of 3,5-dimethoxy-phenylmagnesium bromide (32 mL, 0.71 mol) in 2-methyltetrahydrofuran was added to a flask containing pentafluoropyridine (9.5 g, 0.56 mol) at 10° C. over 5 minutes. After reacting at room temperature for 40 minutes, the reaction was heated to 52° C. for 24 hours. The reaction was then quenched with water, washed, and dried over MgSO4. The removed solvent was removed on a rotary evaporator under high vacuum to give the crude adduct (13.1 g), which was 1 H and 19 F NMR showed that it contained 4-(3,5-dimethoxyphenyl)-2,3,5,6-tetrafluoropyridine and 2-(3,5-dimethoxyphenyl)-3,4,5,6-tetrafluoropyridine (ratio of 64.5:35.5 by GC / MS). After two recrystallizations from toluene, 4-(3,5-dimethoxyphenyl)-2,3,5,6-tetrafluoropyridine and 2-(3,5-dimethoxyphenyl)-3,4,5,6-tetrafluoropyridine (ratio of 64.5:35.5 by GC / MS) were obtained. 19A white crystalline solid containing 99:1 methylpropanol (as determined by F NMR) was obtained. 5.6 g of the recrystallized product was reacted with 48% hydrobromic acid (19 g) and acetic acid (27 g) at 114-116 °C for 12 hours. After confirming complete conversion by GC / MS, most of the excess acid was removed by distillation under high vacuum. The distillation residue was diluted with ethyl acetate and neutralized with 6.4 g of 25% aqueous NaOH. The organic layer was washed with water and dried over MgSO. The ethyl acetate was removed by rotary evaporation and high vacuum drying to yield 4.6 g (mp = 214-218 °C) of Example 28 of the present invention (5-(2,3,5,6-tetrafluoropyridin-4-yl)benzene-1,3-diol) as a white solid.

[0136] The melting points of the examples of the present invention, except for IE20, were determined and are shown in Table 2.

[0137] [Table 3]

[0138] Comparative Fluoroelastomer Curing Examples Because the conditions for each set of cure trials were slightly different, 2,2-bis(4-hydroxyphenyl)hexafluoropropane (BPAF) (Comparative Examples A-P) was used as the curing agent for comparison of each set of cure trials for the inventive examples of curing agents.

[0139] The comparative fluoroelastomer curable compositions contained 100 parts by weight of Viton™ A-500 (The Chemours Company FC LLC, Wilmington, DE) as a polyhydroxy-curable fluoroelastomer, 30 parts by weight of medium thermal carbon black (MT Black) as a filler, 3 parts by weight of powdered MgO (Elastomag® 170, Akrochem Corporation, Akron, OH) as an acid acceptor, 6 parts by weight of calcium hydroxide (Hallstar International, Chicago, IL) as an acid acceptor, 2 parts by weight of BPAF, and 0.55 parts by weight of benzyltriphenolphosphonium chloride (BTPPC) as a cure accelerator. The only exception was Comparative Example B, which contained 3.3 parts by weight of powdered MgO instead of 3 parts by weight.

[0140] In an additional comparative example, 2,3,5,6-tetrafluorohydroquinone obtained from Synquest Laboratories, Inc. (Alachua, FL) was tested as a polyfluorinated hydroquinone curing agent with fluorine atoms at the R1, R2, R4, and R5 sites. The cure response was extremely slow, with very low M values ​​of 3.77 and 5.36 dN m. H Only values ​​were achieved which were too low in state of cure to be molded and the physical properties measured.

[0141] Fluoroelastomer Curing Examples of the Invention The prepared fluorinated resorcinol and hydroquinone analogs were evaluated as curing agents in curable compositions (Inventive Examples 1-29).

[0142] 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 the filler, 3 parts by weight of powdered MgO as the acid acceptor, 6 parts by weight of calcium hydroxide as the acid acceptor, 1.02 to 2.42 parts by weight of a curing agent, and 0.25 to 0.60 parts by weight of BTPPC as a cure accelerator. The amounts of curing agent and BTPPC for each curable composition are shown in Table 3. In Example 20 of the present invention, the curing agent was provided in a form of 10% by weight of the MT Black, for a total amount of 19.33 parts by weight.

[0143] [Table 4]

[0144] In some cases, several trials were performed using the same curative, and the amounts of curative and BTPPC were adjusted based on previous results to obtain more similar cure and / or fluoroelastomer properties compared to when BPAF was used as the curative.

[0145] Fluoroelastomer cure results The cure properties of the inventive examples from Table 1 and their respective comparative examples in the cured compositions of Table 3 are shown in Tables 4-7. Each comparative example is listed immediately before an inventive example from the same set of MDR runs. When multiple runs were run with the same curative, only the run with the best combination of cure and fluoroelastomer properties was selected for inclusion in the tables.

[0146] [Table 5]

[0147] [Table 6]

[0148] [Table 7]

[0149] [Table 8]

[0150] Tables 4-7 show that the examples of the present invention provided hardening properties similar to those of BPAF. L The value is in the range of 0.57 to 1.59 dN m, and M H The values ​​range from 19.73 to 26.3 dN m, the ts1 values ​​range from 0.54 to 1.56 min, the ts2 values ​​range from 0.63 to 1.90 min, and the t 50 The values ​​range from 1.10 to 3.48 min, and t 90 The values ​​ranged from 1.91 to 6.61 min.

[0151] Fluoroelastomer Properties The fluoroelastomer properties of the fluoroelastomers formed from the inventive examples in Table 1 and their respective comparative examples in the cured compositions of Table 3 are shown in Tables 8-11. When multiple runs were performed with the same curative, only the run with the best combination of cure and fluoroelastomer properties was selected for inclusion in the tables.

[0152] [Table 9]

[0153] [Table 10]

[0154] [Table 11]

[0155] [Table 12]

[0156] Tables 8-11 show that the inventive examples provided cured fluoroelastomers with similar properties to cured fluoroelastomers formed using BPAF as the curing agent. Tables 8-11 show that for the inventive examples, TS values ​​ranged from 13.2 to 17.1 MPa, EB values ​​ranged from 135 to 215%, M100 values ​​ranged from 3.06 to 8.69 MPa, CS1 values ​​ranged from 15.7 to 25.6%, CS2 values ​​ranged from 23.6 to 40.7%, and CS3 values ​​ranged from 55.8 to 80.2%.

[0157] Finally, Inventive Example 1 was fluid aged and then tested. The swelling of the fluid-aged fluoroelastomer formed using Inventive Example 1 as the curing agent was 3.5 wt. % with a standard deviation of 0.2 wt. %, and the CS1 of the fluid-aged fluoroelastomer formed using Inventive Example 1 as the curing agent was 22.0%. These results indicate that the acid resistance of the fluoroelastomers formed using fluorinated resorcinol and hydroquinone analogs as curing agents was excellent.

[0158] Hardener Salt Example Hardener salt formation To form the hardener salt of the inventive example, Inventive Example 9 (IE9) was pre-reacted with BTPPC by the following procedure. IE9 (20.34 g, 0.0847 mol) and methanol (45 g) were charged to a 500 mL round-bottom flask equipped with a magnetic stir bar and a dropping funnel topped with a nitrogen T-tube. 25 wt% sodium methylate in methanol (18.53 g, 0.0857 mol) was then added rapidly via the addition funnel, and the solution was stirred at room temperature for 15 minutes. Next, a solution of BTPPC (33.0 g, 0.0849 mol) in methanol (17.9 g) was added rapidly via the addition funnel. The mixture was stirred for 30 minutes, during which time sodium chloride precipitated. The slurry was filtered through a polypropylene filter funnel with a 10 micron polyethylene frit to remove the sodium chloride, and then BTPP was added. + IE9 - The salt-containing filtrate was combined with a 3.5-fold molar excess of IE9 (71.34 g, 0.297 mol) dissolved in methanol (200 mL). Most of the methanol was removed on a rotary evaporator, and then the remaining methanol was removed under high vacuum with magnetic stirring at 150 °C / 30 torr. While the mixture was still molten, an aliquot was removed, rapidly cooled with liquid nitrogen, and then dried under high vacuum at room temperature for 18 hours. A solid (65.2 g), designated IE9 / PRC1, was recovered and dissolved in MeOH-d4. 1 The ratio of IE9 to BTPP was determined to be 4.50:1 IE9:BTPP+ mol:mol by H NMR. The remainder of the molten mixture was cooled to room temperature and then dried in a high vacuum oven at 80 °C for 18 hours. A solid (53.0 g), designated IE9 / PRC2, was recovered and dissolved in MeOH-d 1 The molar ratio of IE9:BTPP was determined to be 4.49:1 by H NMR. The overall yield was 98.7%. + IE9 - The structure of the salt is shown in Formula 4.

[0159] [ka]

[0160] Similarly, BTPP was reacted with IE9 in a 3-fold molar excess. + IE9 - The product isolated by flash cooling was designated IE9 / PRC3 and dissolved in MeOH-d 1 Determined by 1 H NMR to be 4.07:1 IE9:BTPP+ mol:mol.

[0161] Similarly, BTPP was reacted with IE9 at a 4-fold molar excess. + IE9 - The product isolated by flash cooling was designated IE9 / PRC4 and was dissolved in MeOH-d 1 Determined by 1 H NMR to be 5.08:1 IE9:BTPP+ mol:mol.

[0162] To form the hardener salt of this inventive example, inventive example 23 (IE23) was pre-reacted with BTPPC by a procedure similar to that for IE9, using a 3-fold molar excess of IE23 to give BTPP + IE9 - A salt was formed. While the product mixture was still molten, an aliquot was removed, rapidly cooled with liquid nitrogen, and then dried under high vacuum at room temperature for 18 hours. A solid (5.09 g), designated IE23 / PRC1, was recovered and dissolved in MeOH-d 1 The ratio was determined to be 4.05:1 I-23:BTPP+ mol:mol by H NMR. The remainder of the molten mixture was cooled to room temperature and then dried in a high vacuum oven at 80 °C for 18 hours. A solid (6.56 g), designated IE23 / PRC2, was recovered and dissolved in MeOH-d 1 Determined by H NMR to be 4.00:1 IE23:BTPP+ mol:mol. Overall yield was 100%.

[0163] For comparison, Viton™ VC-50, a pre-reacted salt blend of BPAF and BTPP+ available from Chemours, was used.

[0164] Hardening example using hardener salt The comparative and inventive fluoroelastomer cured compositions contained 100 parts by weight of Viton™ B-600 as the polyhydroxy-curable fluoroelastomer, 30 parts by weight of MT Black as the filler, 3 parts by weight of powdered MgO as the acid acceptor, 6 parts by weight of calcium hydroxide as the acid acceptor, and equimolar amounts of BPAF and IE9 (either not pre-reacted or pre-reacted with BTPPC). Viton™ B-600 fluoroelastomer is a terpolymer of hexafluoropropylene, vinylidene fluoride, and tetrafluoroethylene available from Chemours. The cure was complete in less than 3 minutes. 90 The amount of pre-reacted salt was adjusted to cure up to 100 mg / kg of BPAF. For example, IE9 required slightly less salt to do this. Curing was then compared at fixed levels of BPAF and IE9 or IE23. In the case of IE9 / PRC1 and IE9 / PRC2, for example, IE9 cures with less BTPP+, so an additional 0.35 phr of IE9 was added to achieve an equimolar loading of IE9.

[0165] The curing properties of cured compositions with non-pre-reacted or pre-reacted curing agents are shown in Table 12. In the first set of MDR trials, the curing agents were BPAF (BPAF1), pre-reacted BPAF (BPAFS), IE9 (IE91), IE9 / PRC1 (9 / 1), and IE9 / PRC2 (9 / 2). In the second set of MDR trials, the curing agents were BPAF (BPAF2), IE9 (IE92), IE9 / PRC3 (9 / 3), and IE9 / PRC4 (9 / 4). In the third set of MDR trials, the curing agents were BPAF (BPAF3), IE23 (IE23), IE23 / PRC1 (23 / 1), and IE23 / PRC2 (23 / 2).

[0166] [Table 13]

[0167] Table 12 shows that both the non-pre-reacted and pre-reacted inventive examples provided cure properties similar to those of BPAF.

[0168] Fluoroelastomer Properties Fluoroelastomer properties for the fluoroelastomers whose cure properties are shown in Table 12 are shown in Table 13.

[0169] [Table 14]

[0170] Table 13 shows that the fluoroelastomer properties of fluoroelastomers formed with IE9 / PRC1 and IE9 / PRC2 were virtually identical. For fluoroelastomers formed in the first set of MDR runs, the pre-reacted curatives of the present invention showed significantly greater improvements in CS1 (ΔCS1), CS2 (ΔCS1), and CS3 (ΔCS1) compared to BPAF compared to their non-pre-reacted counterparts. Positive ΔCS values ​​indicate a decrease in CS. The improvement in CS provided by the pre-reacted IE9 catalyst salt was surprisingly significantly greater than that of BPAF. In addition, the pre-reacted BPAF CS was actually worse at 250°C (CS3), while the pre-reacted IE9 CS improved by 10.4 to 10.7 points.

[0171] A second set of MDR runs was performed, with IE9:BTPPC molar ratios either slightly lower or slightly higher than in the first set of MDR runs, showing a similar trend as the ΔCS values, although the improvement was not as good and was still substantial.

[0172] For the third set of MDR runs, IE23 / PRC1 showed a significant, but less significant, improvement in ΔCS values ​​than IE9. Interestingly, the cure rate and compression set of IE23 / PRC1 were superior to those of IE23 / PRC2, which showed little improvement and in fact was slightly worse at 200°C for 168 hours (CS2). This indicates that in some cases it may be advantageous to rapidly cool, dry, and store the molten eutectic catalyst mixture at room temperature before compounding, rather than slowly cooling to room temperature before drying at 80°C.

[0173] All of the above references are incorporated herein by reference.

[0174] 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. A curable fluoroelastomer composition, Polyhydroxycurable fluoroelastomers, Hardener of formula 1: 【Chemistry 1】 (In the formula, R １ and R ５ However, independently, H, halogen, and C which may be partially or completely halogenated. １～１８ C, which may be alkyl, partially or completely halogenated. １～１８ Selected from the group consisting of alkoxy and X, R ２ , R ３ , and R ４ are each independently selected from the group consisting of OH, H, halogen, C １～１８ alkyl which may be partially or fully halogenated, C １～１８ alkoxy which may be partially or fully halogenated, and X. However, R ２ , R ３ , and R ４ At least one of them is OH, However, R １ , R ２ , R ３ , R ４ , and R ５ One of them is X, However, R １ , R ２ , R ３ , R ４ , and R ５ Three or fewer of these are halogens. X is selected from the group consisting of equations 2 and 3. 【Chemistry 2】 In the formula, R ６ , R ７ , R ８ , R ９ , and R １０ However, independently, H, and C, which may be partially or completely halogenated, may be present. １～１８ C, which may be alkyl, partially or completely halogenated. １～１８ Selected from the group consisting of alkoxy, partially or completely fluorinated phenyl, alkyl-substituted or aryl-substituted or partially or completely halogenated acetyl or methylsulfonyl, nitro, nitrile, and halogen, wherein N is C ２ , C ３ , or C ４ It is also possible that the substitution occurs in exactly one of the R, in which case each R ６ , R ７ , or R ８ It does not exist, R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ , and R １８ However, independently, H, and C, which may be partially or completely halogenated, may be present. １～１８ C, which may be alkyl, partially or completely halogenated. １～１８ Selected from the group consisting of alkoxy, nitro, nitrile, and halogen, however, 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 -SO ２ -, -C(O)-, -C(CF ３ ) ２ Selected from the group consisting of - and -O-, n is 0 or 1, However, R １ , R ２ , R ３ , R ４ , and R ５ At least one of them is fluorine, fluorine-containing C １～１８ Alkyl, fluorine-containing C １～１８ It is an alkoxy or X, However, X exists and R １ , R ２ , R ３ , R ４ , and R ５ All of these are fluorine, fluorine-containing C １～１８ Alkyl or fluorine-containing C １～１８ If it is not an alkoxy, 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 them is fluorine, fluorine-containing C １～１８ Alkyl or fluorine-containing C １～１８ (It is an alkoxy) Acid receptors and A curable fluoroelastomer composition containing the following:

2. R １ and R ５ The curable fluoroelastomer composition according to claim 1, wherein at least one of the elements is H.

3. R １ 、R ２ 、R ３ 、R ４ 、and R ５ When at least one of them is a substituent adjacent to OH, it is H. The curable fluoroelastomer composition according to claim 1.

4. R １ 、R ２ 、R ３ 、R ４ 、and R ５ The curable fluoroelastomer composition according to claim 1, wherein one or less of them is X.

5. R １ , R ２ , R ３ , R ４ , and R ５ The curable fluoroelastomer composition according to claim 1, wherein two or fewer of these atoms are halogens.

6. R ２ , R ３ , and R ４ The curable fluoroelastomer composition according to claim 1, wherein only one of the groups is an OH group.

7. R ２ or R ４ The curable fluoroelastomer composition according to claim 6, wherein any of the elements is OH.

8. R １ and R ５ However, H, fluorine, and C which may be partially or completely fluorinated. １～１８ Alkyl, partially or completely fluorinated C １～１８ Selected from the group consisting of alkoxy and X, R ２ , R ３ , and R ４ However, independently, OH, H, fluorine, and C which may be partially or completely fluorinated may exist. １～１８ Alkyl, partially or completely fluorinated C １～１８ A curable fluoroelastomer composition according to claim 1, selected from the group consisting of alkoxy and X.

9. A curable fluoroelastomer composition according to claim 1, wherein X is formula 2.

10. R ６ , R ７ , R ８ , R ９ , and R １０ However, independently, H, fluorine, and C which may be partially or completely fluorinated. １～６ Alkyl and C which may be partially or completely fluorinated. １～６ Selected from the group consisting of alkoxys, R ６ , R ７ , R ８ , R ９ , and R １０ At least one of them may be fluorinated, partially or completely fluorinated C １～６ C may be alkyl, or partially or completely fluorinated. １～６ The curable fluoroelastomer composition according to claim 9, wherein the alkoxy is present.

11. R ６ , R ７ , R ８ , R ９ , and R １０ However, independently selected from the group consisting of H, fluorine, perfluoromethyl, and perfluoromethoxy, R ６ , R ７ , R ８ , R ９ , and R １０ The curable fluoroelastomer composition according to claim 9, wherein at least one of the elements is fluorine, perfluoromethyl, or perfluoromethoxy.

12. The aforementioned curing agent, 【Transformation 3】 A curable fluoroelastomer composition according to claim 1, selected from the group consisting of the following.

13. The curable fluoroelastomer composition according to claim 1, comprising 0.1 to 10 parts by weight of the curing agent per 100 parts by weight of the fluoroelastomer.

14. The curable fluoroelastomer composition according to claim 1, wherein the polyhydroxycurable fluoroelastomer is a copolymer of hexafluoropropylene and vinylidene fluoride.

15. The curable fluoroelastomer composition according to claim 1, wherein the polyhydroxycurable fluoroelastomer is a terpolymer of hexafluoropropylene, vinylidene fluoride, and tetrafluoroethylene.

16. The curable fluoroelastomer composition according to claim 1, further comprising a curing accelerator.

17. The curable fluoroelastomer composition according to claim 16, wherein the curing accelerator is in the form of a salt obtained by pre-reacting with a portion of the curing agent.

18. The curable fluoroelastomer composition according to claim 17, wherein the curing agent is present in a molar excess of three to four times the amount of the curing accelerator.

19. A fluoroelastomer masterbatch comprising a polyhydroxycurable fluoropolymer and a curing agent of formula 1: 【Chemistry 4】 (In the formula, R １ and R ５ However, independently, H, halogen, and C which may be partially or completely halogenated. １～１８ C, which may be alkyl, partially or completely halogenated. １～１８ Selected from the group consisting of alkoxy and X, R ２ , R ３ , and R ４ However, independently, OH, H, halogen, and C which may be partially or completely halogenated may be present. １～１８ C, which may be alkyl, partially or completely halogenated. １～１８ Selected from the group consisting of alkoxy and X, However, R ２ , R ３ , and R ４ At least one of them is OH, However, R １ , R ２ , R ３ , R ４ , and R ５ One of them is X, However, R １ , R ２ , R ３ , R ４ , and R ５ Three or fewer of these are halogens. X is selected from the group consisting of equations 2 and 3. 【Transformation 5】 In the formula, R ６ , R ７ , R ８ , R ９ , and R １０ However, independently, H, and C, which may be partially or completely halogenated, may be present. １～１８ C, which may be alkyl, partially or completely halogenated. １～１８ Selected from the group consisting of alkoxy, partially or completely fluorinated phenyl, alkyl-substituted or aryl-substituted or partially or completely halogenated acetyl or methylsulfonyl, nitro, nitrile, and halogen, wherein N is C ２ , C ３ , or C ４ It is also possible that the substitution occurs in exactly one of the R, in which case each R ６ , R ７ , or R ８ It does not exist, R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ , and R １８ However, independently, H, and C, which may be partially or completely halogenated, may be present. １～１８ C, which may be alkyl, partially or completely halogenated. １～１８ Selected from the group consisting of alkoxy, nitro, nitrile, and halogen, however, 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 -SO ２ -, -C(O)-, -C(CF ３ ) ２ Selected from the group consisting of - and -O-, where n is 0 or 1, However, R １ , R ２ , R ３ , R ４ , and R ５ At least one of them is fluorine, fluorine-containing C １～１８ Alkyl, fluorine-containing C １～１８ It is an alkoxy or X, However, if X exists, R １ , R ２ , R ３ , R ４ , and R ５ All of these are fluorine, fluorine-containing C １～１８ Alkyl or fluorine-containing C １～１８ If it is not an alkoxy, 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 them is fluorine, fluorine-containing C １～１８ Alkyl or fluorine-containing C １～１８ (It is an alkoxy) Includes, A fluoroelastomer masterbatch containing the curing agent at a concentration of approximately 1% to 50% by weight.

20. The fluoroelastomer masterbatch according to claim 19, wherein the concentration of the curing agent is 20% by weight to 40% by weight.

21. A mixture of a hardening agent and a hardening accelerator, wherein the hardening agent is of formula 1: 【Transformation 6】 (In the formula, R １ and R ５ However, independently, H, halogen, and C which may be partially or completely halogenated. １～１８ C, which may be alkyl, partially or completely halogenated. １～１８ Selected from the group consisting of alkoxy and X, R ２ , R ３ , and R ４ However, independently, OH, H, halogen, and C which may be partially or completely halogenated may be present. １～１８ C, which may be alkyl, partially or completely halogenated. １～１８ Selected from the group consisting of alkoxy and X, However, R ２ , R ３ , and R ４ At least one of them is OH, However, R １ , R ２ , R ３ , R ４ , and R ５ One of them is X, However, R １ , R ２ , R ３ , R ４ , and R ５ Three or fewer of these are halogens. X is selected from the group consisting of equations 2 and 3. 【Transformation 7】 In the formula, R ６ , R ７ , R ８ , R ９ , and R １０ However, independently, H, and C, which may be partially or completely halogenated, may be present. １～１８ C, which may be alkyl, partially or completely halogenated. １～１８ Selected from the group consisting of alkoxy, partially or completely fluorinated phenyl, alkyl-substituted or aryl-substituted or partially or completely halogenated acetyl or methylsulfonyl, nitro, nitrile, and halogen, wherein N is C ２ , C ３ , or C ４ It is also possible that the substitution occurs in exactly one of the R, in which case each R ６ , R ７ , or R ８ It does not exist, R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ , and R １８ However, independently, H, and C, which may be partially or completely halogenated, may be present. １～１８ C, which may be alkyl, partially or completely halogenated. １～１８ Selected from the group consisting of alkoxy, nitro, nitrile, and halogen, however, 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 -SO ２ -, -C(O)-, -C(CF ３ ) ２ Selected from the group consisting of - and -O-, where n is 0 or 1, However, R １ , R ２ , R ３ , R ４ , and R ５ At least one of them is fluorine, fluorine-containing C １～１８ Alkyl, fluorine-containing C １～１８ It is an alkoxy or X, However, X exists and R １ , R ２ , R ３ , R ４ , and R ５ All of these are fluorine, fluorine-containing C １～１８ Alkyl or fluorine-containing C １～１８ If it is not an alkoxy, 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 them is fluorine, fluorine-containing C １～１８ Alkyl or fluorine-containing C １～１８ (It is an alkoxy) A curing accelerator selected from the group consisting of quaternary phosphonium salts, quaternary ammonium salts, and tertiary sulfonium salts, A mixture of a hardening agent and a hardening accelerator, including [the specified substance].

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

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

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

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

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

27. The mixture of the curing agent and the curing accelerator according to claim 21, wherein the curing accelerator is in the form of a salt that has pre-reacted with a portion of the curing agent.

28. The mixture of the curing agent and the curing accelerator according to claim 27, wherein the curing agent is present in a molar excess of three to four times the amount of the curing accelerator.

29. A salt for use as a fluoroelastomer curing agent and curing accelerator, comprising the compound of formula 1: 【Transformation 8】 (In the formula, R １ and R ５ However, independently, H, halogen, and C which may be partially or completely halogenated. １～１８ C, which may be alkyl, partially or completely halogenated. １～１８ Selected from the group consisting of alkoxy and X, R ２ , R ３ , and R ４ However, independently, OH, H, halogen, and C which may be partially or completely halogenated may be present. １～１８ C, which may be alkyl, partially or completely halogenated. １～１８ Selected from the group consisting of alkoxy and X, However, R ２ , R ３ , and R ４ At least one of them is OH, However, R １ , R ２ , R ３ , R ４ , and R ５ One of them is X, However, R １ , R ２ , R ３ , R ４ , and R ５ Three or fewer of these are halogens. X is selected from the group consisting of equations 2 and 3. 【Chemistry 9】 In the formula, R ６ , R ７ , R ８ , R ９ , and R １０ However, independently, H, and C, which may be partially or completely halogenated, may be present. １～１８ C, which may be alkyl, partially or completely halogenated. １～１８ Selected from the group consisting of alkoxy, partially or completely fluorinated phenyl, alkyl-substituted or aryl-substituted or partially or completely halogenated acetyl or methylsulfonyl, nitro, nitrile, and halogen, wherein N is C ２ , C ３ , or C ４ It is also possible that the substitution occurs in exactly one of the R, in which case each R ６ , R ７ , or R ８ It does not exist, R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ , and R １８ However, independently, H, and C, which may be partially or completely halogenated, may be present. １～１８ C, which may be alkyl, partially or completely halogenated. １～１８ Selected from the group consisting of alkoxy, nitro, nitrile, and halogen, however, 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 -SO ２ -, -C(O)-, -C(CF ３ ) ２ Selected from the group consisting of - and -O-, where n is 0 or 1, However, R １ , R ２ , R ３ , R ４ , and R ５ At least one of them is fluorine, fluorine-containing C １～１８ Alkyl, fluorine-containing C １～１８ It is an alkoxy or X, However, X exists and R １ , R ２ , R ３ , R ４ , and R ５ All of these are fluorine, fluorine-containing C １～１８ Alkyl or fluorine-containing C １～１８ If it is not an alkoxy, 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 them is fluorine, fluorine-containing C １～１８ Alkyl or fluorine-containing C １～１８ A salt comprising a quaternary phosphonium salt or quaternary ammonium salt derived from an alkoxy.

30. The salt according to claim 29, wherein the salt is the quaternary ammonium salt.

31. The salt according to claim 30, wherein the quaternary ammonium salt is tetrabutylammonium hydrogen sulfate.

32. The salt according to claim 29, wherein the salt is the quaternary phosphonium salt.

33. The salt according to claim 32, wherein the quaternary phosphonium salt is a benzyltriphenylphosphonium salt.

34. The salt according to claim 29, wherein the curing accelerator is in the form of a salt that has pre-reacted with a portion of the curing agent.

35. The salt according to claim 34, wherein the curing agent is present in a molar excess of three to four times the amount of the curing accelerator.

36. A method for curing a polyhydroxycurable fluoroelastomer, wherein the method is a curable fluoroelastomer composition, The aforementioned polyhydroxycurable fluoroelastomer, Hardener of formula 1: 【Chemistry 10】 (In the formula, R １ and R ５ However, independently, H, halogen, and C which may be partially or completely halogenated. １～１８ C, which may be alkyl, partially or completely halogenated. １～１８ Selected from the group consisting of alkoxy and X, R ２ , R ３ , and R ４ However, independently, OH, H, halogen, and C which may be partially or completely halogenated may be present. １～１８ C, which may be alkyl, partially or completely halogenated. １～１８ Selected from the group consisting of alkoxy and X, However, R ２ , R ３ , and R ４ At least one of them is OH, However, R １ , R ２ , R ３ , R ４ , and R ５ One of them is X, However, R １ , R ２ , R ３ , R ４ , and R ５ Three or fewer of these are halogens. X is selected from the group consisting of equations 2 and 3. 【Chemistry 11】 In the formula, R ６ , R ７ , R ８ , R ９ , and R １０ However, independently, H, and C, which may be partially or completely halogenated, may be present. １～１８ C, which may be alkyl, partially or completely halogenated. １～１８ Selected from the group consisting of alkoxy, partially or completely fluorinated phenyl, alkyl-substituted or aryl-substituted or partially or completely halogenated acetyl or methylsulfonyl, nitro, nitrile, and halogen, wherein N is C ２ , C ３ , or C ４ It is also possible that the substitution occurs in exactly one of the R, in which case each R ６ , R ７ , or R ８ It does not exist, R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ , and R １８ However, independently, H, and C, which may be partially or completely halogenated, may be present. １～１８ C, which may be alkyl, partially or completely halogenated. １～１８ Selected from the group consisting of alkoxy, nitro, nitrile, and halogen, however, 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 -SO ２ -, -C(O)-, -C(CF ３ ) ２ Selected from the group consisting of - and -O-, where n is 0 or 1, However, R １ , R ２ , R ３ , R ４ , and R ５ At least one of them is fluorine, fluorine-containing C １～１８ Alkyl, fluorine-containing C １～１８ It is an alkoxy or X, However, X exists and R １ , R ２ , R ３ , R ４ , and R ５ All of these are fluorine, fluorine-containing C １～１８ Alkyl or fluorine-containing C １～１８ If it is not an alkoxy, 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 them is fluorine, fluorine-containing C １～１８ Alkyl or fluorine-containing C １～１８ (It is an alkoxy) Acid receptors and A step of forming a curable fluoroelastomer composition, including, A step of heating the curable fluoroelastomer composition to cure the polyhydroxycurable fluoroelastomer, Methods that include...

37. The method according to claim 36, wherein the curable fluoroelastomer composition further comprises a curing accelerator.

38. The method according to claim 37, wherein the curing accelerator is in the form of a salt that has pre-reacted with a portion of the curing agent.

39. The method according to claim 38, wherein the curing agent is present in a molar excess of three to four times the amount of the curing accelerator.

40. An article cured by the method described in claim 36.

41. The article according to claim 40, wherein the article does not contain 2,2-bis(4-hydroxyphenyl)hexafluoropropane.

42. The compound of formula 1A, 【Chemistry 12】 In the formula, R １ and R ２ One of them is H, and the other is OH. R ３ and R ４ One of them is H, and the other is selected from the group consisting of formulas 2A and 3A. 【Chemistry 13】 In the formula, R ５ , R ６ , R ７ , R ８ , and R ９ These are H, F, and CF, independently. ３ , partially or completely fluorinated phenyl, OCF ３ ,CH ３ Selected from the group consisting of nitro and nitrile, However, R ５ , R ６ , R ７ , R ８ , and R ９ At least one of them is F, CF ３ , partially or completely fluorinated phenyl, and OCF ３ Selected from the group consisting of, However, R ５ , R ６ , R ７ , R ８ , and R ９ However, if selected independently from the group consisting of H and F, then at least two are H and at least two are F. However, R １ OH is R ３ Equation 2A is given, and R ５ , R ６ , R ７ , R ８ , and R ９ However, independently, H and CF ３ When selected from the group consisting of, R ６ and R ８ At least one of them is H, However, N is C ２ , C ３ , or C ４ It is also possible that the substitution occurs in exactly one of the R, in which case each R ５ , R ６ , or R ７ It does not exist. compound.

43. R １ OH is R ２ The compound according to claim 42, wherein is H.

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