Fluoropolymer compositions and articles made therefrom

Abstract

A fluoropolymer composition comprising a fluoropolymer and one or more heat-resistant additives selected from acridone, anthrone, diaminoanthraquinone, acridine, substituted acridone, substituted anthrone, substituted diaminoanthraquinone, and substituted acridine, and a cured fluoropolymer composition formed by curing the fluoropolymer composition.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS none

[0002] FIELD OF THE INVENTION The present invention relates to fluoropolymer compositions comprising a fluoropolymer and one or more heat resistant additives, and to articles cured from these fluoropolymer compositions. [Background technology]

[0003] Elastomer compositions containing fluoropolymers have enjoyed significant commercial success due to their ability to be used in harsh environments, particularly during exposure to high temperatures and highly reactive chemicals. For example, compositions containing fluoroelastomers are used in seals for hot sections of aircraft engines, in oil well rigs, as sealing elements in industrial equipment operating at high temperatures, and in high-temperature, high-pressure, aqueous environments.

[0004] The properties of cured compositions containing fluoropolymers are primarily due to the stability and inertness of the copolymerized fluorinated monomers that make up the majority of the polymeric backbone of these compounds. Such monomers include tetrafluoroethylene and perfluoro(alkyl vinyl) ethers. To fully develop their elastomeric properties, fluoroelastomers are typically crosslinked, i.e., vulcanized or cured. For this purpose, a small percentage of a cure site monomer is copolymerized with the fluorinated monomer. During crosslinking, the cure site monomer reacts with a curing agent to form a crosslinked fluoroelastomer in the form of an article. A variety of cure site monomers can be used. For example, nitrile-group-containing cure site monomers or halogen-containing cure site monomers can be used. Perfluoroelastomers containing cure site monomers can be cured with any curing agent suitable for use with the type of cure site monomer employed.

[0005] Although fluoroelastomers perform well in harsh environments, their performance can still be improved. In particular, because cured fluoropolymer compositions are used in high-heat environments, there is a continuing need for fluoropolymer compositions with improved heat resistance. Summary of the Invention [Means for solving the problem]

[0006] The present invention relates to a fluoropolymer composition comprising a fluoropolymer and one or more heat resistant additives selected from acridone, anthrone, diaminoanthraquinone, acridine, substituted acridone, substituted anthrone, substituted diaminoanthraquinone, and substituted acridine.

[0007] The present invention further relates to a process comprising curing a composition comprising a fluoropolymer and one or more heat resistant additives selected from acridone, anthrone, diaminoanthraquinone, acridine, substituted acridone, substituted anthrone, substituted diaminoanthraquinone, and substituted acridine.

[0008] The present invention also relates to an article formed from a fluoropolymer composition comprising a fluoropolymer and one or more heat resistant additives selected from acridone, anthrone, diaminoanthraquinone, acridine, substituted acridone, substituted anthrone, substituted diaminoanthraquinone, and substituted acridine.

[0009] The compositions of the present invention provide superior heat resistance over conventional fluoropolymer compositions and over articles formed from fluoropolymer compositions that do not contain a heat resistant additive selected from acridone, anthrone, diaminoanthraquinone, acridine, substituted acridone, substituted anthrone, substituted diaminoanthraquinone, and substituted acridine. DETAILED DESCRIPTION OF THE INVENTION

[0010] As used herein, the article "a" means more than one as well as one and does not necessarily restrict its referent noun to the grammatical category of singular.

[0011] As used herein, the terms "about" and "exactly or approximately," when used to modify an amount or value, refer to an approximation of an amount or value that is greater than or less than the exact amount or value recited in a claim or the present specification. The exact value of an approximation is determined by what a person skilled in the art would recognize as an appropriate approximation to the exact value. As used herein, terms conveying similar values ​​that are not exactly recited in a claim or the present specification can produce results or effects equivalent to those recited in the claim or the present specification, and therefore, a person skilled in the art would recognize them as acceptable results of similar values.

[0012] As used herein, the term "article" means an unfinished or finished item, thing, object, or element or feature of an unfinished or finished item, thing, or object. As used herein, when the article is unfinished, the term "article" can refer to any item, thing, object, element, device, etc. that has a form, shape, configuration that can be further processed to become a finished product. When the article is unfinished, the term "preform" can refer to a form, shape, configuration, or any part that can be further processed to become a finished product.

[0013] As used herein, the term "article" refers to an item, thing, object, element, device, etc. that is in a form, shape, or configuration suitable for a particular use / purpose without further processing in whole or in part, when the article is completed. An article may include one or more elements or assemblies that are either partially completed and awaiting further processing, or are an assembly with other elements / assemblies that together comprise a completed product. Additionally, as used herein, the term "article" may refer to a system or configuration of articles.

[0014] As used herein, the terms "comprises," "comprising," "includes," "having," or any other variation thereof, refer to a non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of elements is not limited to only the listed elements and may include other elements not expressly listed or inherent. Furthermore, unless expressly stated to the contrary, "or" refers to an inclusive or, not an exclusive one. For example, condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), and A and B are both true (or present).

[0015] As used herein, the terms "comprises," "comprising," "includes," "having," "consisting essentially of," and "consisting of," or any other variation thereof, may refer to either a non-exclusive inclusion or an exclusive inclusion. When these terms refer to a more exclusive inclusion, they limit the scope of the claim to those recited materials or steps that materially affect the recited novel element of the invention. When these terms refer to a completely exclusive inclusion, they exclude any element, step, or ingredient not expressly recited in the claim.

[0016] As used herein, terms describing molecules or polymers follow the terminology in the IUPAC Compendium of Chemical Terminology version 2.15 of September 7, 2009 (International Union of Pure and Applied Chemistry).

[0017] As used herein, the term "unsaturated fluorinated olefin" refers to a linear, branched, or cyclic hydrocarbon structure containing at least one unsaturated double bond and containing at least one fluorine atom.

[0018] As used herein, the term "alkyl" refers to linear, branched, or cyclic hydrocarbon structures and combinations thereof. Alkyl does not include aromatic structures. Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Examples of branched alkyl groups include, for example, s- and t-butyl, and isopropyl groups. Examples of cyclic hydrocarbon groups include cyclopropyl, cyclopentyl, cyclohexyl, cyclobutyl, and cyclooctyl groups.

[0019] As used herein, the term "alkoxy" or "alkoxyl" refers to an alkyl group attached to an oxygen atom by a single bond. The oxygen atom's other bond is to a carbon atom. Examples include methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy, and cyclohexyloxy.

[0020] As used herein, the term "compound" refers to a composition that is curable, i.e., a curable composition, as well as a mixture of chemicals that includes at least a fluoroelastomer or fluoropolymer and a curing agent. The mixture of chemicals has not been cured or subjected to processing conditions that would cause the mixture of chemicals to undergo curing. As used herein, the term may be used interchangeably with the term "composition" when used to refer to a curable composition.

[0021] As used herein, the prefix "fluoro," when placed as a prefix before a chemical name, refers to a chemical having at least one fluorine atom, as exemplified by the following names: fluoroelastomer, perfluoroelastomer, fluorovinyl, and perfluorovinyl ether. The prefix "fluoro," when placed as a prefix before a chemical name, specifically includes "perfluoro" chemicals. Thus, the prefix "fluoro," when preceding a chemical name, denotes both "fluoro" and "perfluoro" forms.

[0022] As used herein, the term "aromatic" refers to a chemical compound containing at least one unsaturated ring of atoms stabilized by the interaction of the bonds that form the ring, exemplified by benzene and naphthalene.

[0023] As used herein, the term "phenyl" refers to a chemical compound having the formula -CH, derived from benzene by removing one hydrogen atom. The carbon atom missing the hydrogen atom is used to form a bond with another chemical compound.

[0024] As used herein, the term "cured" refers to a resultant material comprising a fluoroelastomer and / or a fluoropolymer, and that has been exposed to those conditions (i.e., cure conditions) that cause the fluoroelastomer or fluoropolymer molecules to form sufficient crosslinks between them so that the resultant material assumes a form, shape, configuration, or structure that cannot be reprocessed, molded, or extruded into a different one. That is, once a resultant material comprising a fluoroelastomer or a fluoropolymer has been exposed to cure conditions and thereby cured, the material cannot be recured to assume a substantially different form or structure.

[0025] As used herein, the term "curing" refers to the treatment of a compound (also referred to herein as a curable composition) that results in a material that assumes a form, shape, configuration, or structure that cannot be reprocessed, molded, or extruded into something different. Such treatment refers to a "curing process / treatment" that requires exposure of the compound to specific conditions (such conditions are referred to as cure conditions) to initiate the curing process. The material resulting from the curing process is a "cured" material, i.e., an article as defined herein above. For clarity, curing results in a compound that assumes the form, shape, configuration, or structure of an article. Cured articles of the compounds described herein include, but are not limited to, O-rings, seals, and gaskets. The terms "cure" and "cured" also explicitly include varying degrees of treatment of the compound, such that the resulting material assumes a form, shape, configuration, or structure that cannot be reprocessed, molded, or extruded into something different and may exhibit specific physical properties as a result of curing. In essence, these compounds can be initially cured to reach a non-reprocessable form, shape, etc., which is referred to herein as "curing." The cured compound can be further subjected to additional curing conditions that provide additional, subsequent cure. Such additional curing conditions may be variously referred to herein as either "curing" or "post-curing." That is, the terms "cure" and "cured" refer to the initial curing process that results in an initially cured, resulting material, and also specifically refer to any subsequent curing processes that result in a subsequently cured, resulting material that may or may not have different material or physical properties than those of the initially cured, resulting material.

[0026] Any range set forth herein expressly includes its endpoints unless otherwise specified. The setting out of an amount, concentration, or other value or parameter as a range specifically discloses all possible ranges formed from every possible upper range limit and every possible lower range limit, whether or not such upper and lower range limit pairs are expressly disclosed herein. The compounds, processes, and articles described herein are not limited to the specific values ​​disclosed in defining ranges in this description.

[0027] The disclosure herein of any variations on the materials, chemicals, methods, steps, values, and / or ranges, etc., of the processes, compounds, and articles described herein is specifically intended to include—whether identified as preferred or non-preferred—any possible combinations of materials, methods, steps, values, ranges, etc. For purposes of providing precise and sufficient support for the claims, any disclosed combination is a preferred variation of the processes, compounds, and articles described herein.

[0028] In this description, if there is a nomenclature error or typographical error regarding the chemical name of any chemical species described herein, the chemical structure takes precedence over the chemical name. Also, if there is an error in the chemical structure of any chemical species described herein, the chemical structure of the chemical species that one skilled in the art would understand to be the intended description takes precedence.

[0029] a. Fluoropolymers; and b. One or more heat-resistant additives selected from acridone, anthrone, diaminoanthraquinone, acridine, substituted acridone, substituted anthrone, substituted diaminoanthraquinone, and substituted acridine 1. A fluoropolymer composition comprising:

[0030] The fluoropolymer composition includes a fluoropolymer. The fluoropolymer includes polymerized units of one or more, or two or more, fluorinated olefins. The fluorinated olefins can be the same or different, or, when two or more fluorinated olefins are copolymerized, the fluorinated olefins are different from each other. Each fluorinated olefin is independently selected from the group consisting of fluorovinyl ethers, unsaturated fluorinated olefins, unsaturated olefins, and mixtures of fluorovinyl ethers, unsaturated fluorinated olefins, and unsaturated olefins.

[0031] In one embodiment, the fluorinated vinyl olefin contains, in addition to fluorine, additional hologen atoms, alternatively chlorine.

[0032] Examples of fluorinated olefins include halo(alkyl vinyl) ethers, perfluoroolefins, perfluoro(alkyl vinyl) ethers (PAVE) and perfluoroalkoxyalkyl vinyl ethers (PAAVE), fluoro(methoxy vinyl) ethers (MOVE), fluoro(alkene ethers), halogenated fluoroolefins such as chlorotrifluoroethylene (CTFE), partially fluorinated olefins such as vinyl fluoride (VF), vinylidene fluoride (VF2), trifluoroethylene, tetrafluoropropene (TFP), pentafluoropropene (HPFP), olefins in which less than half or less than one-quarter of the hydrogen atoms are replaced by fluorine, olefins of the formula CX2=CXR, where each X is independently hydrogen, fluoro, or chloro, and R is hydrogen, fluoro, or C1-C 12or C1-C3, alkyl (provided that not all X and R are fluoro groups), hydrogen-containing monomers such as ethylene, propylene, and other non-fluorinated alpha-olefins, e.g., C2-C9 alpha-olefins, fluorinated ester vinyl ethers, fluorinated ester ethers such as methyl perfluoro(5-methyl-4,7-dioxanon-8-enoate) (EVE) or perfluoro(4-methyl-3,6-dioxaoct-7-ene)sulfonyl fluoride (PSEPVE), perfluoro(3-methoxypropyl vinyl ether) (MV-31), perfluoro- and nitrogen-containing cure site monomers. Those skilled in the art will know where to find or how to make fluorinated olefins, and many of these additional monomers are commercially available.

[0033] Examples of halo(alkyl vinyl) ethers include 2-(difluoromethoxy)-1,1-difluoroethene (HHPMVE), 1,1-difluoro-2-(trifluoromethoxy)ethene, 1,1-difluoro-2-(chlorodifluoromethoxy)ethene, 1,1-difluoro-2-(bromodifluoromethoxy)ethene, 1,1-difluoro-2-(1,1,2,2-tetrafluoroethoxy)ethene, 2-(pentafluoro)ethoxy-1,1-difluoroethene, 1,1,2,2,3,3-hexafluoro-1-(1,1-difluoroethenoxy)propane, 1-(1,1-difluoroethenoxy)perfluoropropane, Examples of perfluoroethenoxy perfluoropropanes include, but are not limited to, 1-(1,1-difluoroethenoxy)perfluorobutane, 1-(1,1-difluoroethenoxy)perfluoroisobutane, 1-(1,1-difluoroethenoxy)perfluoro-sec-butane, 1-(1,1-difluoroethenoxy)perfluoropentane, 1-(1,1-difluoroethenoxy)perfluorohexane, 1-(1,1-difluoroethenoxy)perfluorocyclohexane, 1-(1,1-difluoroethenoxy)perfluorooctane, 1-(1,1-difluoroethenoxy)perfluorononane, and 1-(1,1-difluoroethenoxy)perfluorodecane.

[0034] Halo(alkyl vinyl) ethers can be prepared by heating a reaction mixture containing a metal; a solvent; and a halo(alkylethyl) ether of the formula RCF2OC(H)(X)CF2Y (where R is independently H, F, Cl, Br, CF2H, CF3, CF2CF2H, a linear perfluoroalkyl having 1 to 12 carbon atoms, or a cyclic perfluoroalkyl having 1 to 12 carbon atoms, and X and Y are independently Cl, Br, I, or F, where X and Y are not both F) to form a reaction product mixture containing the halo(alkyl vinyl) ether, the solvent, unreacted metal, and a metal salt. Other methods known in the art can also be used to prepare halo(alkyl vinyl) ethers.

[0035] Examples of perfluoroolefins include tetrafluoroethylene (TFE), hexafluoropropylene (HFP) or perfluoroolefins of the formula CF2=CF-R f (In the formula, R f is fluorine or a perfluoroalkyl of 1 to 8, or 1 to 3 carbon atoms).

[0036] Examples of PAAVE monomers include those of the formula CF2=CF-ORf, where Rf is a linear, branched, or cyclic perfluorinated alkyl group optionally containing an ether linkage, and CF2=CF(OC n F 2n ) p Examples of suitable fluorinated alkyl groups include, but are not limited to, those according to the formula ORf (wherein Rf is a perfluorinated (C1-C8) alkyl group optionally containing an ether bond, each n is independently 1 to 4, and p is 1 to 6). n F 2n When a group is present, "n" can be independently selected, alternatively n is 1 to 12, alternatively 1 to 6. However, C n F 2n Within a group, one of skill in the art will understand that "n" is not independently selected. n F 2ncan be linear or branched. In some embodiments, (OC n F 2n ) p is -O-(CF2) 1~4 -[O(CF2) 1~4 ] 0~1 Such perfluorinated ethers are described, for example, in U.S. Patent Nos. 6,255,536 and 6,294,627, each to Worm et al. Examples of suitable PAAVE monomers include CF2=CFOCF2OCF3, CF2=CFOCF2OCF2CF3, CF2=CFOCF2CF2OCF3, CF2=CFOCF2CF2CF2OCF3, CF2=CFOCF2CF2CF2OCF3 (MV-31), CF2=CFOCF2CF2CF2CF2OCF3, CF2=CFOCF2CF2CF2CF2OCF2CF3, CF2=CFOCF2CF2CF2CF2OCF2CF3, CF2=CFOCF2CF2CF2CF2OCF2CF3, CF2=CFOCF2CF2CF2OCF2CF3, CF2=CFOCF2CF2CF2OCF2CF3, CF2=CFOCF2CF2OCF2CF2OCF3, CF2=CFOCF2CF2OCF2CF2CF2OCF3 CF2CF(CF3)-O-C3F7 (PPVE-2), CF2CF(OCF2CF(CF3))-O-C3F7 (PPVE-3), and CF2CF(OCF2CF(CF3))-O-C3F7 (PPVE-4). Methods for producing PAAVE monomers are known in the art. Many of the PAAVE monomers are commercially available.

[0037] Examples of suitable PAVE monomers include, but are not limited to, perfluoro(methyl vinyl) ether CF2=CFOCF3, perfluoro(ethyl vinyl) ether CF2=CFOCF2CF3, and perfluoro(n-propyl vinyl) ether CF2=CFOCF2CF2CF3. Mixtures of PAVE and PAAVE may also be used. Methods for producing PAVE monomers are known in the art. Many of the PAVE monomers are commercially available.

[0038] Examples of suitable MOVE monomers include, but are not limited to, MOVE monomers defined in U.S. Pat. No. 7,160,967 B2, such as perfluoro-3,5-dioxa-1-heptene (MOVE1) (CF₂=CFOCF₂OCF₂CF₃) and perfluoro-3,5,8-trioxa-1-nonene (CF₃OCF₂CF₂OCF₂OCF₂=CF₂) (MOVE2). Those skilled in the art will know how to prepare MOVE monomers. Many MOVE monomers are commercially available.

[0039] Examples of fluoro(alkene ether) monomers include, but are not limited to, those described in U.S. Pat. Nos. 5,891,965 (Worm et al.) and 6,255,535 (Schulz et al.). Such monomers include those of the formula CF═CFCF(OC n F 211 ) pORf, where n, p, and Rf are as defined above for the PAAVE monomer. Examples of suitable fluoro(alkene ether) monomers include those represented by CF2=CFCF2OCF2CF2OCF3, CF2=CFCF2OCF2CF2CF2OCF3, CF2=CFCF2OCF2CF2CF2OCF3, CF2=CFCF2OCF2CF2CF2OCF3, CF2=CFCF2OCF2CF2CF2OCF3, CF2=CFCF2OCF2CF2CF2OCF3, CF2=CFCF2OCF2CF2CF2OCF3, CF2=CFCF2OCF2CF2CF2OCF3, CF2=CFCF2OCF2CF2CF2OCF3, CF2=CFCF2OCF2CF2CF2OCF3, CF2=CFCF2OCF2CF2CF2OCF3, CF2=CFCF2OCF2CF2CF2OCF3, CF2=CFCF2OCF2CF2CF2OCF3, CF2=CFCF2OCF2CF2CF2OCF2 OCF3, CF2=CFCF2OCF2CF2CF2CF2CF2CF2CF2CF3, CF2=CFCF2OCF2CF2CF2CF2CF2CF2CF2CF3, CF2=CFCF2OCF2CF2CF2CF2CF2CF3, CF2=CFCF2OCF2CF2(OCF2)3OCF3, CF2=CFCF2OCF2CF2(OCF2)4OCF3, CF2=CFCF2OCF2CF2CF2OCF2OCF2CF3, CF2=CFCF2OCF2CF2CF2CF2CF3, CF2=CFCF2OCF2CF2CF2OCF2CF3, CF2=CFCF20CF2CF(CF3)-0-C3F7 and CF2=CFCF2(0CF2CF(CF3))2-0-C3F7. These perfluoroalkoxyalkyl allyl ethers can be prepared, for example, according to the method described in U.S. Patent No. 4,349,650 (Krespan). Perfluoropropyl allyl ether (CF2=CF-CF2-OC3F7) and perfluoromethoxyethyl allyl ether (CF2=CF-CF2-OC2F4OCF3) can also be prepared according to the method described in U.S. Patent No. 5,891,965 (Worm).Perfluoroalkoxyalkyl allyl ethers can also be prepared by combining a first component containing at least one of CF₂=CF-CF₂-OSO₂C₁ or CF₂=CF-CF₂-OSO₂CF₃ with a polyfluorinated compound containing at least one ketone or carboxylic acid halide or a combination thereof, and fluoride ion. The polyfluorinated compound containing at least one ketone or carboxylic acid halide or a combination thereof and the fluoride ion can be, for example, any of those described in U.S. Pat. No. 4,349,650 (Krespan). Many fluoro(alkene ether) monomers, such as perfluoroalkoxyalkyl allyl ether monomers, are commercially available.

[0040] In one embodiment, the fluorinated polymer further comprises, as polymerized units, one or more cure site monomers. The cure site in the fluoropolymer allows the fluoropolymer to be cured to form a cured fluoropolymer, such as a fluoroelastomer. In one embodiment, the cure site monomer is selected from the group consisting of nitrile-containing fluorinated olefins and nitrile-containing fluorinated vinyl ethers. Examples of cure sites in the cure site monomer include, but are not limited to, free-radically polymerizable nitriles, imidates, amidines, amides, imides, and amine oxides. Mixtures of any of these cure site monomers may be useful in the fluoropolymer compositions according to the present disclosure. Useful nitrile-containing fluorinated olefins and fluorinated vinyl ethers include CF═CFO(CF═). L CN, CF2 = CFO(CF2) u OCF(CF3)CN, CF2=CFO[CF2CF(CF3)O] q (CF2O) y CF(CF3)CN, CF2=CFO[CF2FCF3O] n CF2-CFCF3CN or CF2=CF[OCF2CF(CF3)] r O(CF2) tCN, where L ranges from 2 to 12, u ranges from 2 to 6, q ranges from 0 to 4, y ranges from 0 to 6, n ranges from 0 to 4, r ranges from 1 to 2, and t ranges from 1 to 4. Examples of such nitrile-containing cure site monomers include, but are not limited to, CF2=CFO(CF2)3OCF(CF3)CN, perfluoro(8-cyano-5-methyl-3,6-dioxa-1-octene) (8-CNVE), and CF2=CFO(CF2)5CN.

[0041] The nitrile-containing cure site is a polymerizable compound that reacts with a selected chain transfer agent (e.g., I(CF2) d CN (wherein d is 1 to 10 or 1 to 6) or NC(CF2) d They can also be incorporated into curable fluoropolymers by carrying out free radical polymerization in the presence of perfluorosulfinates such as SO2G (where G represents a hydrogen atom or a cation having a valence of 1 or 2).

[0042] The nitrile-containing monomer, chain transfer agent, and / or initiator typically comprise about 0.1 to 5 mole percent (in some embodiments, 0.3 to 2 mole percent) of the polymerization components.

[0043] The fluoropolymers provided herein may also or alternatively include at least one halogen atom cure site capable of participating in, for example, a peroxide cure reaction. For example, the halogen capable of participating in a peroxide cure reaction may be bromine or iodine, or alternatively, iodine. The halogen atom capable of participating in a peroxide cure reaction may be located at the terminal or internal position of the backbone, or may be located at the terminal position of the backbone. However, when the halogen atom capable of participating in a peroxide cure reaction is located at the terminal position, more reactive cure sites may also be present. The amount of iodine, bromine, or a combination thereof contained in the fluoropolymer is 0.001 to 5 wt %, preferably 0.01 to 2.5 wt %, 0.1 to 1 wt %, or 0.2 to 0.6 wt %, based on the total weight of the fluoropolymer.

[0044] In one embodiment, halogen cure sites are incorporated into the perfluoropolymer by incorporating a monomer containing one or more bromine atoms and / or one or more iodine atoms, or a mixture of monomers containing bromine and / or iodine atoms, and / or nitrile-containing groups.

[0045] Such fluorinated monomers containing one or more bromine atoms and / or one or more iodine atoms have the formula (I) or (II): CR 2 R 2 =(CR 3 R 4 ) n -CR 5 R 6 (I) (wherein n is 1 to 4; R 1 , R 2 , R 3 , R 4 , and R 5 is H or F, where R 1 ~R 5 At least one of is F; R 6 is Br or I, preferably I); or CF2 = CF-O(CR 7 R 8 ) n -R 9 (II) (wherein n is 1 to 4; R 7 and R 8 is H or F, where R 7 or R 8 At least one of the is F; R 9 is Br or I, or I) by.

[0046] Examples of cure site monomers that can participate in a peroxide cure reaction when incorporated into a fluoropolymer include, but are not limited to, CF2=CHBr, CH2=CHCH2Br, CF2=CFCF2Br, CH2=CHCF2CF2Br, CF2=CHI, CH2=CHCH2I, CF2=CFCF2I, CH2=CHCF2CF2I, CF2=CFOC4F8I(MV4I), CF2=CFOC2F4I, CF2=CFOCF2CF(CF3)OC2F4I, CH2=CHCF2CF2I, CF2=CFOCF2CF2CH2I, CF2=CFOCF2CF2CH2CH2I, CF2=CFOC4F8CH2CH2I and combinations thereof.

[0047] Perfluoroelastomers containing cure sites can also be obtained by polymerization processes which include bromine or iodine compounds as chain transfer agents and / or are carried out using chain transfer compounds.

[0048] Typical examples of bromine or iodine chain transfer compounds that may be used include those of formula (III): R 10 I x Br y (III) (wherein x and y are each an integer of 0 to 2, satisfying 1≦x+y≦2; and R10 is a saturated or unsaturated fluorohydrocarbon group or chiorofluorocarbon group having 1 to 16 carbon atoms, or a hydrocarbon group having 1 to 3 carbon atoms optionally containing an oxygen atom). By using a bromine compound or an iodine compound, iodine or bromine can be introduced into the polymer and function as a crosslinking point.

[0049] Examples of bromine compound or iodine compound chain transfer agents include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, 1,5-diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane, diiodomethane, 1,2-diiodoethane, 1,3-diiodo-n-propane, CF2Br2, BrCF2CF2Br, CF3CFBrCF2Br, C Examples of suitable iodoperfluorocarbons include, but are not limited to, FClBr, BrCFCFClBr, CFBrClCFClBr, BrCFCFCFBr, BrCFCFBrOCF, 1-bromo-2-iodoperfluoroethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3-iodoperfluorobutane, 3-bromo-4-iodoperfluorobutene-1,2-bromo-4-iodoperfluorobutene, and monoiodomonobromo-substituted products, diiodomonobromo-substituted products, and (2-iodoethyl)- and (2-bromoethyl)-substituted products of benzene. These compounds may be used alone or in combination. Among these, 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 2-iodoperfluoropropane are preferred in terms of polymerization reactivity, crosslinking reactivity, and availability.

[0050] The liquid monomers used to make the fluoropolymer may be pre-emulsified with an emulsifier, such as by the addition of a gaseous fluoroolefin, before polymerization with other monomers.

[0051] Fluoropolymers can be cured, non-curable, or curable; alternatively, fluoropolymers can be curable, non-curable, or cured. Those skilled in the art will understand what cured, non-curable, or curable fluoropolymers are and how to make non-curable or curable fluoropolymers. In one embodiment, curable fluoropolymers can be made by copolymerizing with monomers containing cure sites.

[0052] The fluoropolymer can be amorphous or non-amorphous. Examples of amorphous fluoropolymers include, but are not limited to, fluoroelastomer or perfluoroelastomer rubbers made from the halo(alkyl vinyl) ethers of the present invention, a monomer having a cure site, and additional monomers to provide the rubber with desired properties.

[0053] The fluoropolymer composition comprises one or more heat-resistant additives selected from acridone, anthrone, diaminoanthraquinone, acridine, substituted acridone, substituted anthrone, substituted diaminoanthraquinone, and substituted acridine; or one or more heat-resistant additives selected from acridone, anthrone, diaminoanthraquinone, and acridine; or the heat-resistant additive is acridone, or anthrone, or diaminoanthraquinone, or acridine. In one embodiment, the heat-resistant additive is diaminoanthraquinone, or 1,5-diaminoanthraquinone.

[0054] In one embodiment, the substituents of the substituted acridone, substituted anthrone, substituted diaminoanthraquinone, and substituted acridine may be known substituents, or may include, but are not limited to, linear and / or branched alkyl, haloalkyl, alkenyl, alkynyl, acrylate functional groups, and methacrylate functional groups; halo, glycidyl, amine, ether, cyanate ester, isocyano, ester, carboxylic acid, carboxylate, succinate, anhydride, mercapto, sulfide, sulfate, sulfinyl, sulfonyl, azide, phosphonate, phosphine, masked isocyano, hydroxyl, and organic functional groups containing any of the foregoing groups.

[0055] The structures of the heat-resistant additives acridone, anthrone, diaminoanthraquinone, and acridine are as follows:

[0056] [ka]

[0057] Methods for preparing acridone, anthrone, diaminoanthraquinone, acridine and substituted acridone, anthrone, diaminoanthraquinone, acridine compounds are known in the art. Acridone, anthrone, diaminoanthraquinone, acridine and many substituted acridone, anthrone, diaminoanthraquinone, acridine compounds are commercially available.

[0058] The perfluoroelastomers used in the compounds of the present invention can be crosslinked with any of the known curing agents for perfluoroelastomers, including, but not limited to, polyhydroxy compounds such as combinations of organic peroxides and polyfunctional crosslinking coagents (U.S. Pat. Nos. 4,214,060; 4,983,680), organotins (U.S. Pat. No. 5,789,489), bis(aminophenols) such as diaminobisphenol AF (U.S. Pat. No. 6,211,319 B1), aromatic tetraamines such as 3,3'-diaminobenzidine, 2,2-bis[3-amino-4-(N-phenylamino)phenyl]hexafluoropropane, ammonia-generating compounds such as urea, urea derivatives such as guanylthiourea, and other compounds disclosed in U.S. Pat. No. 6,281,296 and WO 01 / 27194.

[0059] One curing agent that can be used is an organic peroxide / multifunctional coagent system. Useful organic peroxides are those that generate free radicals at the curing temperature. Dialkyl peroxides or bis(dialkyl peroxides) that decompose at temperatures above 50°C are particularly preferred. In many cases, it is preferred to use ditertiary butyl peroxide, which has a tertiary carbon atom attached to the peroxy oxygen. Among the most useful peroxides of this type are 2,5-dimethyl-2,5-di(tertiary butylperoxy)hexyne-3 and 2,5-dimethyl-2,5-di(tertiary butylperoxy)-hexane. Other peroxides can be selected from compounds such as dicumyl peroxide, dibenzoyl peroxide, tertiary butyl perbenzoate, and di[1,3-dimethyl-3-(t-butylperoxy)butyl]carbonate. When present in the curable compositions of the present invention, 1 to 5 phr of peroxide is typically used.

[0060] The polyfunctional coagent used with the organic peroxide is a polyunsaturated compound capable of synergizing with the peroxide to provide a useful cure. These coagents can be added in amounts equal to 0.1 to 10 phr, preferably 2 to 5 phr. The coagent can be one or more of the following compounds: triallyl cyanurate; triallyl isocyanurate; polytriallyl isocyanurate; tri(methallyl)isocyanurate; tris(diallylamine)-s-triazine; triallyl phosphite; N,N-diallylacrylamide; hexaallyl phosphoramide; N,N,N',N'-tetraalkyltetraphthalamide; N,N,N',N'-tetraallylmalonamide; trivinyl isocyanurate; 2,4,6-trivinylmethyltrisiloxane; and tri(5-norbornene-2-methylene)cyanurate. Triallyl isocyanurate (TAIC) is particularly useful.

[0061] Other curing agents that may be used in the compounds of the present invention include bis(aminophenols) such as diaminobisphenol AF, tetraamines, organotins, and compounds that decompose to form ammonia at cure temperatures, such as urea. When present in the compounds of the present invention, typically 0.1 to 7 phr of any one of the latter curing agents is used.

[0062] The additional additives commonly used in curable fluoropolymer compositions may be included in the curable fluoropolymer composition of the present invention.Those skilled in the art will be familiar with the commonly used additives, such as fillers; metal sulfides, perfluoro-free elastomers that can crosslink independently with any perfluoroelastomer (A) cure site; stabilizers; plasticizers; lubricants; fillers; and processing aids.

[0063] Examples of metal sulfides include, but are not limited to, calcium sulfide, magnesium sulfide, manganese sulfide, iron sulfide, and copper sulfide. The concentration of the metal sulfide is generally about 0.1 to 20 phr, preferably 1 to 20 phr, and more preferably 5 to 20 phr.

[0064] Examples of perfluoro-free elastomers are those having at least one crosslinkable group selected from the group consisting of cyano (-CN), carboxyl (-COOH), alkoxycarbonyl (-COOR9 (where R9 is a monovalent organic group), and acid halide group (-COX1 (where X1 is a halogen atom)) at least in either its main chain or at the end of its side chain, which can crosslink with the perfluoroelastomer (A).

[0065] Examples of perfluoro-free elastomers include, but are not limited to, fluorine-containing but perfluoro-free rubber; thermoplastic fluorine-containing rubber; and rubber compositions containing fluorine-containing rubber.

[0066] The fluorine-containing rubber may contain monomer units independently selected from the group consisting of vinylidene fluoride (VDF), tetrafluoroethylene, and hexafluoropropylene, and at least one additional monomer such as tetrafluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl ether), chlorotrifluoroethylene, trifluoroethylene, trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, vinyl fluoride, and iodine-containing fluorinated vinyl ether, ethylene, propylene, alkyl vinyl ether, and combinations thereof. Those skilled in the art will know how to prepare non-perfluoro-containing elastomers.

[0067] Examples of fillers include, but are not limited to, carbon black and non-carbon black fillers such as anhydrous silica (e.g., acidic silica or fumed silica). Such silicas are available from Degussa Aktiengesellschaft (Frankfurt, Germany) under the Aerosil® trademark. A particularly useful type is Aerosil® 200 silica. Other suitable silicas include Reolosil® silicas, such as Reolosil® QS13, Reolosil® QS102, and Reolosil® QS30, available from Tokuyama Corporation (Tokyo, Japan). The amount of filler ranges from 1 to 25 phr, but is preferably 1 to 7 phr or less.

[0068] Additional types of fillers include fine powders or fluoroadditives. Fine powders are usually partially crystalline polymers. Fine powders include finely divided, easily dispersible plastic fluoropolymers that are solid at the highest temperatures used in the manufacture and curing of the compounds described herein. The term "solid" refers to plastic fluoropolymers that have a crystalline melting temperature above the processing temperature of the compounds described herein.

[0069] Fine powders that can be used in these compounds include, but are not limited to, those based on the group of polymers known as tetrafluoroethylene (TFE) polymers. This group includes polytetrafluoroethylene (PTFE) and copolymers of TFE with a low concentration of about 1 mole percent or less of at least one copolymerizable modifying monomer, so that the fine powder does not melt or soften during processing of the fluoroelastomer A containing the fine powder. The modifying monomer can be, for example, hexafluoropropylene (HFP), perfluoro(propyl vinyl) ether (PPVE), perfluorobutylethylene, chlorotrifluoroethylene, or another monomer that introduces a side group into the polymer molecule.

[0070] Tetrafluoroethylene polymers used as additives in these compounds include copolymers of TFE having a sufficient concentration of copolymerized units of one or more monomers to lower the melting point below that of PTFE. Such copolymers typically have a concentration of 0.5 to 60 x 10 3 They have melt viscosities in the Pa·s range, although viscosities outside this range are known. Perfluoroolefins and perfluoro(alkyl vinyl) ethers are preferred comonomers. Hexafluoropropylene and perfluoro(propyl vinyl) ether are most preferred. Examples of TFE copolymers include TFE / hexafluoropropylene copolymers and TFE / perfluoro(propyl vinyl) ether copolymers, provided that the melt temperature constraints relative to the processing temperature of the perfluoroelastomer are met. These copolymers may be utilized in powder form as isolated from the polymerization medium, provided the particle size is acceptable, or they may be milled to the appropriate particle size from larger size starting materials.

[0071] The fluoropolymer compositions described herein may be compounds that can be prepared by mixing the perfluoropolymer, heat-resistant additive, and any other components in the fluoropolymer composition, such as curing agents and fillers, until homogeneous using known rubber compounding procedures, such as a two-roll rubber mill, an internal mixer, or an extruder. These compositions and compounds can be cured, for example, by applying sufficient heat and / or pressure to cause the curing agent to form crosslinks with the cure site, or a dual cure system can also be used. When compression molding is used for curing, the press cure cycle is preferably followed by a post-cure cycle to achieve an optimal cure state, during which the press-cure compound is heated at an elevated temperature of over 200°C for several hours.

[0072] When cured, the compositions described herein become the articles described herein, which exhibit thermal stability and chemical resistance suitable for the applications in which they are used. These articles are useful as seals and gaskets for high temperature conditions and in a wide range of chemical environments, as seals for high temperature automotive applications, and as O-rings.

[0073] The compounds of the present invention are useful for the manufacture of gaskets, tubing, seals, and other molded parts. Such articles are generally produced by molding a composite blend of fluoropolymer compositions with various additives under pressure, curing the part, and then subjecting it to a post-cure cycle. The cured compositions have excellent mechanical properties and excellent thermal stability and chemical resistance.

[0074] The fluoropolymer compositions of the present invention exhibit improved weight loss and compression set properties. [Example]

[0075] The following examples are presented to better illustrate the method of the present invention, but should not be construed as limiting the invention as properly described in the appended claims. Unless otherwise specified, all parts and percentages reported in the examples are by weight. The following table explains the abbreviations used in the examples.

[0076] [Table 1]

[0077] FFKM1: An uncured perfluorinated fluoropolymer prepared using the nitrile cure site monomers described above and at least one fluorine-containing monomer. FFKM2: Uncured perfluorinated fluoropolymer prepared with iodine cure site FFKM3: Uncured perfluorinated fluoropolymer prepared with iodine cure site Weight Loss: Cured O-rings were tested for weight loss by placing them in an air oven at 300° C. for 6 weeks. After each week, the parts were removed, weighed, and the weight loss was calculated.

[0078] Composition Formulation: Curable compositions containing the ingredients shown in Tables 2, 3, and 4 were prepared by blending these ingredients in a conventional manner using an internal mixer and / or a two-roll rubber mill. The composition properties are also shown in Tables 2, 3, and 4.

[0079] O-Rings: O-rings for weight loss testing were manufactured by molding and curing using conventional methods.

[0080] Curing: Curing was done by conventional methods and tested using an MDR to ensure proper cure.

[0081] Compression Set: Compression set was performed according to ASTM D395 under the conditions listed in Tables 3 and 4.

[0082] [Table 2]

[0083] [Table 3]

[0084] [Table 4]

Claims

1. 1. A fluoropolymer composition comprising: a. fluoropolymer and b. one or more heat-resistant additives selected from acridone, anthrone, diaminoanthraquinone, acridine, substituted acridone, substituted anthrone, substituted diaminoanthraquinone, and substituted acridine; 1. A fluoropolymer composition comprising:

2. c) further comprising a curing agent; 10. The fluoropolymer composition of claim 1, wherein the fluoropolymer is curable and is a copolymer derived from a cure site monomer and at least one fluorine-containing monomer.

3. The fluoropolymer compound of claim 2, wherein the cure site monomer is a nitrile cure site monomer. A dependent claim is added: guanyl thyrourea.

4. The cure site monomer is perfluoro(8-cyano-5-methyl-3,6-dioxaoct-1-ene), CF ２ =CF-O(CF ２ ) ｎ CN (chained CNVE), CF ２ =CF-O[CF ２ -CFCF ３ O] ｎ -CF ２ -CFCF ３ CN or CF ２ =CF-[OCF ２ CFCF ３ ] ｘ -O-(CF ２ ) ｎ C.N., C.F. ２ =CF-O-(CF ２ ) ｎ -O-CF(CF ３ ) CN. The fluoropolymer compound of claim 3.

5. The fluorine-containing monomer is tetrafluoroethylene (TFE), vinyl fluoride (VF), perfluoro(alkyl vinyl) ether (PAVE), ethylene, tetrafluoropropene (TFP), ester vinyl ether, methyl perfluoro(5-methyl-4,7-dioxanone-8-enoate) (EVE), perfluoro(4-methyl-3,6-dioxaoct-7-ene)sulfonyl fluoride (PSEPVE), vinylidene fluoride (VF2), hexafluoropropylene (HFP), chlorotrifluoroethylene, methyl ...

3. The fluoropolymer composition of claim 2, wherein the monomer is one or more monomers selected from the group consisting of fluoroethylene (CTFE), propylene (P), perfluoro-3,5-dioxa-1-heptene (MOVE 1) and perfluoro-3,5,8-trioxa-1-nonene (MOVE 2), pentafluoropropene (HPFP), perfluoro(3-methoxypropyl vinyl) ether (MV-31), 2-(difluoromethoxy)-1,1-difluoroethene (HHPMVE), and analogs thereof.

6. 6. The fluoropolymer composition of any one of claims 1 to 5, wherein the substituted acridone, substituted anthrone, substituted diaminoanthraquinone, and substituted acridine are substituted with a group selected from linear alkyl, branched alkyl, haloalkyl, alkenyl, alkynyl, acrylate and methacrylate functional groups; halo, glycidyl, amine, ether, cyanate ester, isocyano, ester, carboxylic acid, carboxylate salt, succinate, anhydride, mercapto, sulfide, sulfate, sulfinyl, sulfonyl, azide, phosphonate, phosphine, masked isocyano, and hydroxyl.

7. The fluoropolymer composition of any one of claims 1 to 6, wherein the diaminoanthraquinone is 1,5-diaminoanthraquinone.

8. The fluoropolymer of any one of claims 1 to 7, wherein the curing agent is an ammonia-generating compound.

9. 9. The fluoropolymer of any one of claims 1 to 8, wherein the curative is 0.1 to 7 phr of the fluoropolymer composition and the heat resistance additive is 1 to 10 phr of the fluoropolymer composition.

10. The fluoropolymer of any one of claims 1 to 9, wherein the fluoropolymer composition is amorphous.

11. A cured fluoropolymer composition formed by curing the fluoropolymer composition of any one of claims 1-10.

12. 12. The cured fluoropolymer composition of claim 11, wherein the cured fluoropolymer composition is an elastomer.

13. 13. The cured fluoropolymer composition of claim 11 or 12, wherein the cured fluoropolymer composition is in the form of a seal.

14. A method comprising the step of curing a composition according to any one of claims 1 to 10.

15. 13. An article comprising the cured composition of claim 11 or 12.

16. The article of claim 15, wherein the article is in the form of a gasket, a seal, a tube, a sheet, a washer, or an O-ring.

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