Method for producing halo(alkyl vinyl) ether monomer and fluorinated polymer produced from halo(alkyl vinyl) ether monomer

Abstract

A process for producing a halo(alkyl vinyl) ether, comprising heating a reaction mixture comprising a combination of i) a metal, ii) a solvent, and iii) a halo(alkyl ethyl) ether according to the formula (1) RCF2OC(H)(X)CF2Y (1) (wherein 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, and X and Y are not both F) to form a reaction product mixture comprising a halo(alkyl vinyl) ether, a solvent, unreacted metal, and a metal salt.

Description

Technical Field

[0001] The present invention generally relates to halo(alkyl vinyl) ether monomers, methods for producing halo(alkyl vinyl) ether monomers, and fluorinated polymers produced from halo(alkyl vinyl) ether monomers.

Background Art

[0002] (Cross-reference to Related Applications) None

[0003] (Background Art) Fluoropolymers such as fluoroelastomers are known to have excellent mechanical properties, heat resistance, weather resistance, and chemical resistance. Such properties make fluoroelastomers useful in many applications such as O-rings, seals, hoses, lubricants, and coatings (e.g., metal gasket coatings) that can be exposed to harsh environments such as high temperatures and corrosive chemicals. Parts made of fluoroelastomers find uses in many industries such as automotive, chemical processing, semiconductor, aerospace, and petroleum industries.

[0004] Fluoropolymers are produced by the polymerization of fluoromonomers. One such fluoromonomer that has been used to produce fluoroelastomers and fluororesins is perfluoromethyl vinyl ether (PMVE). PMVE has been polymerized to produce homopolymers and copolymerized with other fluoromonomers to produce different fluorinated copolymers.

[0005] PMVE is known to produce fluoroelastomers with excellent properties, but the properties of fluoromonomers and generally fluoropolymers produced by PMVE can still be improved. For example, a fluoropolymer having improved physical properties such as better heat resistance, weather resistance, chemical resistance, or increased or decreased flexibility compared to fluoropolymers produced with PMVE is desirable.

[0006] Accordingly, additional halo(alkyl vinyl) ethers different from PMVE are potentially interesting because they can lead to fluoroelastomers having improved properties over prior fluoropolymers made from known monomers such as PMVE. One such class of interesting halo(alkyl vinyl) ethers are the partially perhalogenated (alkyl vinyl) ethers. However, it has been found that these partially halogenated alkyl vinyl ethers are difficult to produce in commercially viable amounts and yields. SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION

[0007] Therefore, there is a need for a novel process for producing partially halogenated (alkyl vinyl) ether monomers that can be used in the production of fluoroelastomers having potentially improved properties over known fluoropolymers. MEANS FOR SOLVING THE PROBLEM

[0008] The present invention relates to a process for producing a halo(alkyl vinyl) ether, comprising heating a reaction mixture comprising i) a metal, ii) a solvent, and iii) a halo(alkyl ethyl) ether according to formula (1) RCF2OC(H)(X)CF2Y (wherein 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, and X and Y are not both F) to form a reaction product mixture comprising a halo(alkyl vinyl) ether, a solvent, unreacted metal, and a metal salt.

[0009] The present invention further relates to a fluoropolymer produced by polymerizing a halo(alkyl vinyl) ether.

[0010] The present invention still further relates to a fluoropolymer comprising repeating unit (I)-[(C(H)(R 1 ))CF2]-(wherein R 1 is -OCRF2 and 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).

[0011] The method of the present invention enables the production of halo(alkyl vinyl) ethers in increased yields. The produced halo(vinyl ether) can be used to produce novel fluoropolymers having improved properties.

DETAILED DESCRIPTION OF THE INVENTION

[0012] As used herein, the article "a" refers to one and more than one and does not necessarily limit the noun it modifies to the singular grammatical category.

[0013] As used herein, the term "article" refers to an unfinished or finished article, thing, object or an element or feature of an unfinished or finished article, thing or object. As used herein, when the article is unfinished, the term "article" can refer to any article, thing, object, element, device, etc. having a form, shape, configuration that can undergo further processing to become a finished product. When the article is unfinished, the term "preform" can refer to that form, shape, configuration of which any part can undergo further processing to become a finished product. As used herein, when the article is finished, the term "article" refers to an article, thing, object, element, device, etc. in a form, shape, configuration suitable for a particular use / purpose without further processing of the whole or a part thereof.

[0014] The article may include one or more elements or sub-assemblies that are either partially completed and awaiting further processing or are assemblies with other elements / sub-assemblies that will together contain the finished product. Further, as used herein, the term "article" may refer to a system or configuration of an article.

[0015] As used herein, the terms "comprising," "comprises," "including," "includes," "having," "has," or any other variations thereof refer to non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not limited to only the listed elements, and may include other elements not expressly listed or inherent thereto. Further, unless expressly stated to the contrary, "or" refers to an inclusive or and not an exclusive or. For example, the 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 both A and B are true (or present).

[0016] As used herein, the terms "comprising," "comprises," "including," "includes," "having," "has," "consisting essentially of," and "consisting of" or any other variations thereof may refer to either non-exclusive inclusion or exclusive inclusion. When these terms refer to more exclusive inclusion, these terms limit the scope of the claim to the enumerated materials or steps that substantially affect the novel elements of the invention described. When these terms refer to complete exclusive inclusion, these terms exclude any element, step, or component not expressly enumerated in the claims.

[0017] As used herein, terms describing a molecule or polymer follow the terminology in the IUPAC Compendium of Chemical Terminology version 2.15 (International Union of Pure and Applied Chemistry) as of September 7, 2009.

[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, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups.

[0019] As used herein, the term "alkoxy" or "alkoxyl" refers to an alkyl group bonded to an oxygen atom by a single bond. The other bond of the oxygen atom is bonded 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 and a mixture of chemical substances comprising at least a fluoroelastomer and a curing agent. The mixture of chemical substances is not cured and has not been subjected to the processing conditions that would cause curing of the mixture of chemical substances for curing.

[0021] As used herein, the prefix term "fluoro", when placed as a prefix before a chemical name, refers to a chemical substance 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, clearly includes "perfluoro" chemicals. Thus, the prefix "fluoro", when preceding a chemical name, indicates both "fluoro" and "perfluoro" forms.

[0022] As used herein, the term "cured" refers to a resulting substance that includes a fluoroelastomer and has been exposed to conditions (i.e., curing conditions) that cause sufficient cross-linking to form between the fluoroelastomer molecules such that the resulting substance takes a form, or shape, or configuration, or structure that cannot be reprocessed, shaped, or extruded into a different one. That is, when a resulting substance that includes a fluoroelastomer is exposed to and thereby cured under curing conditions, the substance cannot be re-cured to take a substantially different form or structure.

[0023] As used herein, the term "curing" refers to the process of that compound (also referred to herein as a curable composition) that results in a substance that takes a form, or shape, or configuration, or structure that cannot be reprocessed, shaped, or extruded into a different one. Such a process refers to a "curing process / treatment" that requires the compound to be exposed to specific conditions (such conditions are referred to as curing conditions) to initiate the curing process.

[0024] The substance resulting from the hardening process is a "hardened" substance, i.e., an article as defined above herein. To be clear, hardening results in a compound that takes on the form, or shape, or configuration, or structure of the article. Hardened articles of the compounds described herein include, but are not limited to, O-rings, seals, and gaskets.

[0025] The compound can first be hardened to achieve a non-reprocessable form, shape, etc., which is referred to herein as "hardening". The hardened compound of the compound can be further subjected to additional hardening conditions, which provide additional subsequent hardening. Such additional hardening conditions can be variously referred to herein as either "hardening" or "post-curing". That is, the terms "hardening", "hardened" refer to the initial hardening process that results in the first-hardened, resulting substance and also clearly refer to any subsequent hardening process that results in a subsequently-hardened, resulting substance that may or may not have different materials or physical properties from that of the first-hardened, resulting substance.

[0026] Unless otherwise specified, any range recited herein clearly encompasses its endpoints. The recitation of a range of amounts, concentrations, or other values or parameters discloses specifically all possible ranges formed from any possible upper limit of such a range and any possible lower limit, whether or not such a pair of upper and lower limits of the range is explicitly disclosed herein. The compounds, processes, and articles described herein are not limited to the specific values disclosed when defining the ranges in this description.

[0027] Any disclosure in this specification of variations of the processes, compounds and materials of the articles, chemical substances, methods, procedures, values and / or ranges etc. described herein is specifically intended to include - whether specified as preferred or not - any possible combination of materials, methods, procedures, values, ranges etc. For the purpose of providing accurate 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 are any naming errors or typos regarding the chemical names of any chemical species described herein, the chemical structure takes precedence over the chemical name. Also, if there are any errors in the chemical structure of any chemical species described herein, the chemical structure of the chemical species that a person skilled in the art would understand as the intended description takes precedence.

[0029] A method for producing a halo(alkyl vinyl) ether, comprising: i) a metal, ii) a solvent, iii) a halo(alkyl ethyl) ether according to formula (1) RCF2OC(H)(X)CF2Y (1) (wherein 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, and X and Y are not both F) and heating a reaction mixture containing to form a reaction product mixture containing a halo(alkyl vinyl) ether, a solvent, unreacted metal and a metal salt. A method comprising the steps of.

[0030] The reaction mixture containing a metal, a solvent and a halo(alkyl ethyl) ether is heated to form a reaction product mixture containing a halo(alkyl vinyl) ether, a solvent, unreacted metal and a metal salt.

[0031] The metal is any metal that would cause dehalogenation of the halo(alkylethyl)ether according to formula (1) in the solvent according to the present invention, or instead an alkali, alkaline earth or transition metal that would cause dehalogenation of the halo(alkylethyl)ether according to formula (1) in the solvent, or instead the metal is zinc, magnesium, cadmium or indium, or instead zinc. Most metals are commercially available. Those skilled in the art will know how to obtain and use the metal.

[0032] The solvent is a solvent sufficient for the dehalogenation reaction of the halo(alkylethyl)ether according to formula (1) with the metal, or instead the solvent is an anhydrous polar aprotic solvent, or instead the solvent is dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI), N,N'-dimethylpropyleneurea (DMPU), acetonitrile (MeCN), ether or a mixture of two or more of dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI), N,N'-dimethylpropyleneurea (DMPU), ether and acetonitrile (MeCN). In one embodiment, the solvent is anhydrous. Examples of ethers include, but are not limited to, tetrahydrofuran (THF), dioxane, diglyme, triglyme and tetraglyme. Many of the solvents that will function in the present invention are commercially available.

[0033] Formula (1) RCF2OC(H)(X)CF2Y (1) (wherein R is 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, provided that X and Y are not both F) Halo(alkylethyl)ethers according to

[0034] Examples of halo(alkylethyl)ethers according to formula (1) include, but are not limited to, 2-chloro-2-(difluoromethoxy)-1,1,1-trifluoro-ethane, 2-chloro-2-(chlorodifluoromethoxy)-1,1,1-trifluoro-ethane, 2-chloro-2-(bromodifluoromethoxy)-1,1,1-trifluoro-ethane, 2-chloro-2-(1-chloro-2,2,2-trifluoroethoxy)-1,1,2,2-tetrafluoro-ethane, 2-chloro-2-(pentafluoroethoxy)-1,1,1-trifluoro-ethane, 1,1,2,2,3,3-hexafluoro-1-(2-chloro-1,1,1-trifluoroethoxy)-propane, 1-(1-chloro-2,2,2-trifluoro)ethoxyperfluoropropane, 1-(1-chloro-2,2,2-trifluoro)ethoxyperfluorobutane, 1-(1-chloro-2,2,2-trifluoro)ethoxyperfluoroisobutane, 1-(1-chloro-2,2,2-trifluoro)ethoxyperfluorosec-butane, 1-(1-chloro-2,2,2-trifluoro)ethoxyperfluoropentane, 1-(1-chloro-2,2,2-trifluoro)ethoxyperfluorohexane, 1-(1-chloro-2,2,2-trifluoro)ethoxyperfluorocyclohexane, 1-(1-chloro-2,2,2-trifluoro)ethoxyperfluorooctane, 1-(1-chloro-2,2,2-trifluoro)ethoxyperfluorononane, 1-(1-chloro-2,2,2-trifluoro)ethoxyperfluorodecane, 1-(1-chloro-2,2,2-trifluoro). Many of the halogenated ethers according to formula (1) are commercially available or can be produced by methods known in the art.

[0035] Halo(alkylethyl)ethers are produced by methods known in the art. Many halo(alkylethyl)ethers are commercially available.

[0036] The reaction product mixture comprises a halo(alkyl vinyl) ether, a solvent, unreacted metal, and a metal salt.

[0037] The solvent and the unreacted metal in the reaction product mixture are as described above for the reaction mixture.

[0038] The metal salt is a halide formed from the halogen and the metal from the halo(alkyl ethyl) ether. Examples of metal salts include, but are not limited to, halides containing fluorine, chlorine and / or bromine, such as zinc fluoride, zinc chloride, zinc bromide, magnesium fluoride, magnesium chloride, magnesium bromide, cadmium fluoride, cadmium chloride, cadmium bromide, indium fluoride, indium chloride and indium bromide and mixtures thereof, and metals containing zinc, magnesium, cadmium and / or indium metals.

[0039] In one embodiment, the halo(alkyl vinyl) ether has the formula (2) RCF2OC(H)CF2(2) (wherein R is 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, alternatively, R is H, F, Cl or Br, alternatively, R is F) and follows.

[0040] Examples of halo(alkyl vinyl) ethers according to formula (2) 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, 1-(1,1-difluoroethenoxy)perfluorobutane, 1-(1,1-difluoroethenoxy)perfluoroisobutane, 1-(1,1-difluoroethenoxy)perfluorosec-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, 1-(1,1-difluoroethenoxy)perfluorodecane, but are not limited thereto.

[0041] The reaction mixture is formed by combining a metal, a solvent, and a halo(alkyl ethyl) ether in a reactor. One of ordinary skill in the art will know how to combine the components of the reaction mixture. Any reactor known for use in a dehalogenation reaction can be used. For example, the reactor can be a steel reactor, a three-neck round-bottom glass flask, a sealed tube reactor, or an autoclave having a cooling coil and a pressure safety valve. The reactor may or may not be equipped with means for stirring the reaction mixture. For example, the reactor can be equipped with a magnetic stirrer. The reactor is typically purged with an inert gas before use.

[0042] The method of combining the components of the reaction mixture can vary. In one embodiment, there is no specific order for adding the components of the reaction mixture to the reactor. For example, the solvent can be added to the reactor, followed by the halo(alkylethyl)ether, or the metal can be added first, followed by the solvent and then the halo(alkylethyl)ether. In another embodiment, the metal and the solvent are added to the reactor before the halo(alkylethyl)ether. In one embodiment, the halo(alkylethyl)ether is added to the reactor last, and the addition rate is controlled to control the reaction rate. Those skilled in the art will know how to control the addition of the halo(alkylethyl)ether to control the reaction rate.

[0043] A reaction mixture comprising a halo(alkylethyl)ether, a solvent, and a metal is heated. Methods known in the art for heating the reactor can be used to heat the reaction mixture. For example, the reactor can be heated using a heating mantle or a furnace depending on the type of reactor used. Those skilled in the art will know how to heat the reaction vessel.

[0044] The temperature at which the components of the reaction mixture are combined can vary. For example, the components of the reaction mixture can be combined at a temperature below the temperature at which the reaction would occur immediately, instead at a temperature below ambient temperature to ambient temperature or slightly above ambient temperature, instead at a temperature below the boiling point of the components of the reaction mixture, instead at 0 °C to 30 °C.

[0045] The temperature at which the reaction mixture is heated can vary. Typically, the reaction mixture is heated within a target temperature range, and then the reaction mixture temperature is maintained within that target temperature range until the reaction is sufficiently complete. Those skilled in the art will know how to determine when the reaction is complete and how to heat the reaction mixture as discussed above. For example, the reaction mixture can be heated to increase the temperature of the reaction mixture at a rate of about 10 °C per minute, and the reaction can be monitored by chromatography.

[0046] The reaction mixture is heated at 60 °C to 200 °C, alternatively at 120 °C to 180 °C, alternatively at 130 °C to 160 °C.

[0047] The time for which the reaction mixture containing the halo(alkylethyl)ether, the metal and the solvent is maintained within the target temperature range can vary. Alternatively, the time is until the reaction is complete or nearly complete, alternatively 1 to 20 hours, alternatively 2 to 15 hours, alternatively 4 to 10 hours. One skilled in the art will know how to determine how long to hold the reaction mixture at the target temperature depending on the progress of the reaction.

[0048] The solvent, the halo(alkylethyl)ether and the halo(alkylvinyl)ether may have boiling points above the target temperature range for the reaction and thus the reaction can be carried out at elevated pressure. The pressure will vary depending on the temperature of the reaction mixture and the pressure or partial pressure of the solvent, the halo(alkylethyl)ether and the halo(alkylvinyl)ether in the product mixture. One skilled in the art will know how to determine the reaction pressure based on the components of the reaction mixture and the reaction product mixture. Typically, no other means are taken to increase the pressure of the reaction mixture beyond the pressure generated from heating the components of the reaction mixture or the reaction product mixture. One skilled in the art will know suitable reactors for use at elevated reaction pressures above ambient pressure.

[0049] The weight ratio of the halo(alkylethyl)ether to the metal can vary. Alternatively, the weight ratio of the halo(alkylethyl)ether to the metal is 1:0.01 to 1:0.75, alternatively 1:0.1 to 1:0.5, alternatively 1:0.2 to 1:0.4. One skilled in the art will know how to determine the weight ratio of the halo(alkylethyl)ether to the metal.

[0050] The amount of solvent in the reaction mixture containing halo(alkyl ethyl) ether, solvent, and metal can vary. In one embodiment, the solvent is 10% (w / w) to 95% (w / w), alternatively 25% (w / w) to 80% (w / w), alternatively 40% (w / w) to 70% based on the weight of the solvent, halo(alkyl ethyl) ether, and metal. Those skilled in the art will understand how to optimize the amount of solvent in the reaction mixture.

[0051] The halo(alkyl vinyl) ether product can be recovered from the reaction product mixture. The reaction product mixture can be cooled to about 25°C, alternatively about 15°C, and any gas from the reactor can be collected from the reactor using methods known in the art, such as a gas trap. The halo(alkyl vinyl) ether can then be recovered from the reaction product mixture by methods known in the art. For example, the halo(alkyl vinyl) ether can be recovered using distillation or gas chromatography. Those skilled in the art will recognize that there are different methods that can be used to recover the halo(alkyl vinyl) ether product.

[0052] In one embodiment of the present invention, the halo(alkyl vinyl) ether can be polymerized to form a fluoropolymer. The halo(alkyl vinyl) ether is as described above. The halo(alkyl vinyl) ether can be fused to form a homopolymer, or the halo(alkyl vinyl) ether can be polymerized with additional known monomers used to produce fluoropolymers to form copolymers, terpolymers, etc.

[0053] The fluoropolymer can be cured, non-curable or curable. Instead, the fluoropolymer is curable, instead non-curable, instead cured. One skilled in the art will understand what a cured, non-curable or curable fluoropolymer is and how to manufacture a non-curable or curable fluoropolymer. In one embodiment, the curable fluoropolymer can be produced by polymerizing a halo(alkyl vinyl) ether with a monomer containing a curing site.

[0054] The fluoropolymer can be amorphous or non-amorphous. Examples of amorphous fluoropolymers include fluoroelastomer rubbers or perfluoroelastomer rubbers produced from the halo(alkyl vinyl) ethers of the present invention, monomers having a curing site, and additional monomers to provide a rubber having desired properties, but are not limited thereto.

[0055] Examples of additional monomers that can be polymerized with halo(alkyl vinyl) ethers to form fluoropolymers include perfluorolefins, perfluoro(alkyl vinyl) ethers (PAVE) and perfluoroalkoxyalkyl vinyl ethers (PAAVE), fluoro(alkene ethers), halogenated fluoroolefins such as chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), vinylidene fluoride (VF2), trifluoroethylene, tetrafluoropropene (TFP), pentafluoropropene (HPFP) and other partially fluorinated olefins, olefins in which less than half or less than 1 / 4 of the hydrogen atoms are replaced by fluorine, and olefins of the formula CX2 = CXR, where each X is independently hydrogen, fluoro or chloro, and R is hydrogen, fluoro or C1-C 12, instead, olefins conforming to C1-C3, alkyl (provided that not all X and R are fluoro groups), ethylene, propylene and other non-fluorinated alpha-olefins, such as hydrogen-containing monomers like C2-C9 alpha-olefins, fluorinated ester vinyl ethers, fluorinated ester ethers like methyl perfluoro(5-methyl-4,7-dioxanon-8-enoate) (EVE) or perfluoro(4-methyl-3,6-dioxaocta-7-ene) sulfonyl fluoride (PSEPVE), perfluoro(3-methoxypropyl vinyl ether) (MV-31) and nitrogen-containing curing site monomers can be mentioned, but are not limited thereto. Those skilled in the art know where additional monomers can be found or the manufacturing methods of additional monomers, and many of these additional monomers are commercially available.

[0056] Examples of perfluoroolefins include tetrafluoroethylene (TFE), hexafluoropropylene (HFP) or the formula CF2=CF-R f (wherein R f is fluorine or a perfluoroalkyl of 1 to 8, instead 1 to 3 carbon atoms) of any perfluoroolefin can be mentioned, but is not limited thereto.

[0057] Examples of PAAVE monomers include those conforming to the formula CF2=CF-ORf (wherein Rf is a linear, branched or cyclic perfluorinated alkyl group optionally containing an ether bond) and CF2=CF(OC n F 2n ) p 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), but are not limited thereto. When two or more C n F 2n groups are present, "n" can be independently selected, instead, n is 1 to 12, instead 1 to 6. However, C n F 2nThose skilled in the art will understand that "n" is not independently selected within the base. C n F 2n can be linear or branched. In some embodiments, (OC n F 2n ) p is represented by -O-(CF2) 1~4 -[O(CF2) 1~4 0~1 . Such perfluorinated ethers are described, for example, in U.S. Pat. Nos. 6,255,536 and 6,294,627 (each issued to Worm et al.). Examples of suitable PAAVE monomers include, but are not limited to, CF2=CFOCF2OCF3, CF2=CFOCF2OCF2CF3, CF2=CFOCF2CF2OCF3, CF2=CFOCF2CF2CF2OCF3 (MV-31), CF2=CFOCF2CF2CF2CF2OCF3, CF2=CFOCF2CF2OCF2CF3, CF2=CFOCF2CF2CF2OCF2CF3, CF2=CFOCF2CF2CF2CF2OCF2CF3, CF2=CFOCF2CF2OCF2OCF3, CF2=CFOCF2CF2OCF2CF2OCF3, CF2=CFOCF2CF2OCF2CF2CF2OCF3, CF2=CFOCF2CF2OCF2CF2CF2CF2OCF3, CF2=CFOCF2CF2OCF2CF2CF2CF2CF2OCF3, CF2=CFOCF2CF2(OCF2)3OCF3, CF2=CFOCF2CF2(OCF2)4OCF3, CF2=CFOCF2CF2OCF2OCF2OCF3, CF2=CFOCF2CF2OCF2CF2CF3CF2=CFOCF2CF2OCF2CF2OCF2CF2CF3, CF2=CFOCF2CF(CF3)-O-C3F7 (PPVE-2), CF2=CF(OCF2CF(CF3))2-O-C3F7 (PPVE-3), and CF2=CF(OCF2CF(CF3))3-O-C3F7 (PPVE-4). Methods for producing PAAVE monomers are known in the art. Many PAAVE monomers are commercially available.

[0058] ​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 can also be used. Methods for producing PAVE monomers are known in the art. Many PAVE monomers are commercially available.

[0059] Examples of fluoro(alkene ether) monomers include, but are not limited to, those described in U.S. Patent Nos. 5,891,965 (Worm et al.) and 6,255,535 (Schulz et al.). Such monomers include the formula CF2=CFCF2(OC n F 2ll ) pThose represented by ORf (wherein n, p and Rf are as defined above for the PAAVE monomer) may be mentioned. Examples of suitable fluoro(alkene ether) monomers include CF2=CFCF2OCF2CF2OCF3, CF2=CFCF2OCF2CF2CF2OCF3, CF2=CFCF2OCF2OCF3CF2=CFCF2OCF2OCF2CF3, CF2=CFCF2OCF2CF2CF2CF2OCF3, CF2=CFCF2OCF2CF2OCF2CF3, CF2=CFCF2OCF2CF2CF2OCF2CF3, CF2=CFCF2OCF2CF2CF2CF2OCF2CF3, CF2=CFCF2OCF2CF2OCF2OCF3, CF2=CFCF2OCF2CF2OCF2CF2OCF3, CF2=CFCF2OCF2CF2OCF2CF2CF2OCF3, CF2=CFCF2OCF2CF2OCF2CF2CF2CF2OCF3, CF2=CFCF2OCF2CF2OCF2CF2CF2CF2CF2OCF3, CF2=CFCF2OCF2CF2(OCF2)3OCF3, CF2=CFCF2OCF2CF2(OCF2)4OCF3, CF2=CFCF2OCF2CF2OCF2OCF2OCF3, CF2=CFCF2OCF2CF2OCF2CF2CF3, CF2=CFCF2OCF2CF2OCF2CF2OCF2CF2CF3, CF2=CFCF2OCF2CF(CF3)-O-C3F7 and CF2=CFCF2(OCF2CF(CF3))2-O-C3F7, etc., perfluoroalkoxyalkyl allyl ethers. 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, a polyfluorinated compound containing at least one ketone or carboxylic acid halide or a combination thereof, and fluoride ions. The polyfluorinated compound containing at least one ketone or carboxylic acid halide or a combination thereof and fluoride ions can be any of those described, for example, in U.S. Patent No. 4,349,650 (Krespan). Many fluoro(alkene ether) monomers, such as perfluoroalkoxyalkyl allyl ether monomers, are commercially available.

[0060] In one embodiment, the fluoropolymer comprises polymerized units derived from a halo(alkyl vinyl) ether according to formula (2), instead of a halo(alkyl vinyl) ether according to formula (2) and one or more of additional monomers TFE, PAVE, PAAVE, VF2, VF, and / or PMVE, instead of one or more of TFE, VF2, and / or PMVE, instead of TFE, instead of VF2, instead of PMVE, and each of those polymers may also contain monomer units having a nitrogen-containing curing site.

[0061] Liquid monomers, including but not limited to, halo(alkyl vinyl) ethers according to formula (2), used to produce fluoropolymers can be pre-emulsified with an emulsifier prior to polymerization with other monomers, such as the addition of gaseous fluoroolefins.

[0062] The fluoropolymer contains at least 0.5% (w / w), instead of at least 1% (w / w), instead of 1% - 99.9% (w / w), instead of 1 - 50% (w / w), instead of 1% - 20% (w / w) of polymerized units derived from a fluoro(alkyl vinyl) ether according to formula (2).

[0063] The fluoropolymer may contain polymerization units derived from one or more of the above additional monomers in an amount of 0 to 99.5% (w / w), alternatively 0% to 99% (w / w), alternatively 0.1% (w / w) to 99% (w / w), alternatively 80% (w / w) to 99% (w / w), alternatively 50% to 99% (w / w), based on the weight of the fluoropolymer.

[0064] Examples of fluoropolymers include HHPMVE homopolymers, HPPMVE / TFE copolymers, HHPMVE / VF2 copolymers, HHPMVE / TFE / PMVE copolymers, and HHPMVE / VF2 / PMVE copolymers, and HHPMVE / TFE / propylene copolymers, HHPMVE / TFE / propylene / VF2 copolymers, HHPMVE / VF2 / HFP copolymers, HHPMVE / TFE / VF2 / HFP copolymers, HHPMVE / TFE / CF2=CFOC3F7 copolymers, HHPMVE / TFE / CF2=CFOCF3 / CF2=CFOC3F7 copolymers, HHPMVE / TFE / ethyl vinyl ether (EtVE) copolymers, HHPMVE / TFE / butyl vinyl ether (BVE) copolymers, HHPMVE / TFE / EtVE / BVE copolymers, HHPMVE / VF2 / CF2=CFOC3F7 copolymers, HHPMVE / ethylene / HFP copolymers, HHPMVE / TFE / HFP copolymers, HHPMVE / CTFE / VF2 copolymers, HHPMVE / TFE / VF2 copolymers, HHPMVE / TFE / VF2 / PMVE / ethylene copolymers and HHPMVE / TFE / VF2 / CF2=CFO(CF2)3OCF3 copolymers, but are not limited thereto, and each of these copolymers may also contain monomer units having a nitrogen-containing curing site.

[0065] In some embodiments, the fluoropolymer contains units derived from TFE having a molar ratio of units derived from TFE to comonomer units derived from perfluoroalkyl vinyl or allyl ethers or perfluoroalkoxyalkyl vinyl or allyl ethers and halo(alkyl vinyl)ethers according to formula (2) above of, for example, 1:1 to 4:1, and the unsaturated ether can be used as a single compound or a combination of two or more unsaturated ethers. Typical compositions also include 0.1 to 10% (w / w) of a nitrogen-containing cure site monomer, and the amounts of the raw materials are selected such that the total amount is 100% (w / w). Other typical compositions include about 1 to 30% (w / w) HHPMVE, 17 to 30 wt% TFE, 25 to 38 wt% VF2, 28 to 42 wt% HFP and 0.1 to 10 wt% nitrile-containing cure site monomer and 0 to 10 wt% of other comonomers or modifiers, and the amounts of the raw materials are selected such that the total amount is 100 wt%.

[0066] The cure sites in the fluoropolymer enable the fluoropolymer to be cured to form a cured fluoropolymer such as a fluoroelastomer. Examples of cure site components of the fluoropolymer include nitrogen-containing groups. Examples of monomers containing nitrogen-containing groups useful for preparing fluoropolymers containing nitrogen-containing cure sites include free-radically polymerizable nitriles, imidates, amidines, amides, imides and amine-oxides. Any mixture of these nitrogen-containing cure sites can be useful in the fluoropolymer compositions according to the present disclosure. Useful nitrogen-containing cure site monomers include nitrile-containing fluorinated olefins and nitrile-containing fluorinated vinyl ethers, such as CF2=CFO(CF2) 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 (wherein 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 nitrogen-containing curing site monomers include CF2=CFO(CF2)3OCF(CF3)CN, perfluoro(8-cyano-5-methyl-3,6-dioxo-1-octene) (8-CNVE), and CF2=CFO(CF2)5CN.

[0067] The nitrogen-containing curing site can be incorporated into the curable fluoropolymer by using a selected chain transfer agent (e.g., I(CF2) d CN (wherein d is 1 to 10 or 1 to 6)) or in the presence of a perfluorosulfinate such as NC(CF2) d SO2G (wherein G represents a hydrogen atom or a cation having a valence of 1 or 2) by carrying out free radical polymerization.

[0068] The nitrogen-containing monomer, chain transfer agent, and / or initiator typically constitute about 0.1 to 5 mole percent (in some embodiments 0.3 to 2 mole percent) of the polymerization components.

[0069] The fluoropolymers provided herein can further or alternatively include at least one halogen atom curing site that can participate in a peroxide curing reaction. The halogen that can participate in the peroxide curing reaction can be bromine or iodine, alternatively iodine. The halogen atom that can participate in the peroxide curing reaction can be placed at the terminal position of the main chain, alternatively at the terminal position of the main chain. However, when the position of the halogen atom that can participate in the peroxide curing reaction is placed at the terminal position, there can also be a more reactive curing site. The amount of iodine, bromine, or a combination thereof contained in the fluoropolymer is 0.001 to 5%, preferably 0.01 to 2.5% or 0.1 to 1% or 0.2 to 0.6% by weight based on the total weight of the fluoropolymer.

[0070] Examples of curing site monomers that can participate in peroxide curing reactions when incorporated into fluoropolymers 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.

[0071] The presently disclosed fluoropolymers are typically prepared by a series of steps that may include polymerization, coagulation, washing, and drying. In some embodiments, aqueous emulsion polymerization can be carried out continuously under steady-state conditions. For example, an aqueous emulsion of monomers (such as any of those described above), water, emulsifier, buffer, and catalyst can be continuously fed into a stirred reactor under optimal pressure and temperature conditions while continuously removing the resulting emulsion or suspension. In some embodiments, batch or semi-batch polymerization is carried out by feeding the aforementioned raw materials into a stirred reactor, reacting them at a set temperature for a predetermined time, or charging the raw materials into the reactor and feeding monomers into the reactor until the desired amount of polymer is formed while maintaining a constant pressure. After polymerization, unreacted monomers are removed from the reactor effluent latex by evaporation under reduced pressure. The fluoropolymer can be recovered from the latex by coagulation.

[0072] Coincidence is generally carried out in the presence of a free radical initiator system such as ammonium persulfate, disodium phosphate heptahydrate, potassium permanganate, AIBN, bis(perfluoroacyl)propoxide or a combination of two or more thereof. In some embodiments, the polymerization is initiated with an initiator system selected from a combination of a fluoroaliphatic sulfinate and an oxidizing agent capable of oxidizing the sulfinate to a sulfonyl radical and / or a combination of a free radical initiator and a chloride salt. Examples of oxidizing agents used as part of the initiator include, but are not limited to, free radical initiators such as persulfates, permanganic acid or salts thereof such as potassium permanganate. Examples of chloride salts used as part of the initiator include, but are not limited to, chloride salts having organic and inorganic cations such as tetrabutylammonium chloride and ammonium chloride. Those skilled in the art will know initiators that function in similar polymerizations and methods for initiating polymerizations to form fluoropolymers.

[0073] The amount of initiator used to initiate the polymerization of the fluoropolymer can vary. In one embodiment, the amount of initiator used to initiate the polymerization is an initiation effective amount, alternatively 0.01% - 15% (w / w) based on the weight of all the initiator and monomer, alternatively 0.1% - 10% (w / w), alternatively 0.1% - 5% (w / w) of the initiator. The "initiation effective amount" of the initiator means an amount sufficient to initiate the polymerization reaction. Those skilled in the art will know how to select, use and determine the appropriate amount of initiator for use in initiating the polymerization.

[0074] Based on the disclosure herein, those skilled in the art will know how to optimize the temperature and pressure conditions for carrying out the polymerization to form the fluoropolymers of the present invention, select the appropriate reactor, and determine the monomer, initiator and other component percentages.

[0075] The fluoropolymer can also be described according to the repeating units in the fluoropolymer. In one embodiment, the fluoropolymer has the formula (C(R 1)(H)CF2) (3) (wherein R 1 contains a repeating unit according to -OCRF2 (where R is 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 instead contains a repeating unit according to formula (3), and one or more repeating units (4) (CF2CF2)-, (5)-(CH2-CF2)-, (6)-(CF2C(R 1 )F) (where R 1 is -(OCF2C(F)(CF3)OCF2CF2C≡N)), and / or (7)-(C(R 1 )(F)CF2).

[0076] A fluoropolymer containing repeating unit (3) and instead repeating unit (3) and one or more of repeating units (4), (5), (6) and / or (7) can be produced using the above-described monomers, processes, conditions and reactors for fluoropolymers produced by polymerizing a halo(alkyl ethyl) ether according to formula (1). Those skilled in the art will know how to produce a fluoropolymer having repeating units (3) to (7) based on the above disclosure. In one embodiment, a fluoropolymer containing repeating units (3) to (7) is produced using a halo(alkyl ethyl) ether produced using the method for producing a halo(alkyl ether) according to formula (1) above.

[0077] The properties of a fluoropolymer containing repeating unit (3) and instead repeating unit (3) and one or more of repeating units (4), (5), (6) and / or (7) can have the same properties as a fluoropolymer produced by polymerizing with a halo(alkyl ethyl) ether according to formula (1) above. For example, the fluoropolymer can be curable, non-curable, amorphous or non-amorphous.

[0078] The fluoropolymer can form part of a compound.

[0079] An article comprising a cured compound containing a fluoropolymer produced by polymerizing a halo(alkyl vinyl) ether before curing, wherein the halo(alkyl vinyl) ether and the method for producing the halo(alkyl vinyl) ether are as described above. Examples of the article include, but are not limited to, gaskets, seals, tubes, sheets, washers or O-rings.

[0080] An article comprising a cured compound containing a fluoropolymer before curing. The fluoropolymer is as described above and contains repeating units that are also as described above. Examples of the article include, but are not limited to, gaskets, seals, tubes, sheets, washers or O-rings.

[0081] The method claimed below enables the production of halo(alkyl vinyl) ethers in increased yields beyond known methods. Thus, the produced halo(vinyl ether) can be used to produce novel fluoropolymers that are produced economically and have potentially improved properties compared to known fluoropolymers.

Examples

[0082] The following examples are presented to better illustrate the method of the present invention, but should not be considered as limiting the present invention as precisely described in the appended claims. Unless otherwise specified, all parts and percentages reported in these examples are by weight. The following table explains the abbreviations used in these examples.

[0083]

Table 1

[0084] Example 1: Preparation of difluoromethyl 2,2-difluoroethenyl ether (CF2=CHOCHF2) by dehalogenation of isoflurane (CF3C(Cl)(H)OCF2H) A 1 - gallon Hastelloy - C autoclave equipped with a cooling coil and a pressure removal device was charged with anhydrous zinc powder (492.0 g, 7.524 mol) and anhydrous DMF (1480 g). The mixture was thoroughly flushed with nitrogen, and isoflurane (1195 g, 6.477 mol) was fed into the reactor. The reactor was heated at 140 °C for 10 h. Then the contents were cooled to 15 °C and discharged. GC - FID analysis showed complete conversion of isoflurane to difluoromethyl 2,2 - difluoroethenyl ether. The mixture was filtered cold to remove excess zinc and zinc salts. The resulting filtrate was distilled under reduced pressure to obtain crude difluoromethyl 2,2 - difluoroethenyl ether (840 g) with a purity of over 95% (w / w) contaminated with trace amounts of DMF. Then the crude product was redistilled at atmospheric pressure, and the fractions collected at 17 - 20 °C were combined to obtain difluoromethyl 2,2 - difluoroethenyl ether (759.8 g) as a clear colorless liquid with a purity of over 99% (w / w). The chemical structure was confirmed by NMR.

[0085] Example 2: Preparation of TFE - HHPMVE - 8 - CNVE Copolymer A polymer containing copolymerized monomers of tetrafluoroethylene (TFE), 2-(difluoromethoxy)-1,1-difluoroethene (HHPMVE) and perfluoro-8-(cyano-5-methyl-3,6-dioxaoctene) (8-CNVE) was prepared as follows. A 2% (w / w) solution of 2215 grams of the ammonium salt of CF3CF2CF2OCF(CF3)CH2OPO(OH)2 was loaded into a 4-liter, mechanically stirred, water-jacketed stainless steel reactor and deoxygenated by repeated pressurization / depressurization cycles with nitrogen. Nitrogen was removed by repeated pressurization / depressurization cycles with TFE. When the nitrogen content in the headspace was less than 1% (w / w) and the reactor pressure was 0.03 MPaG, 100 ml of HHPMVE was fed into the reactor. The reactor was heated to 80 °C and pressurized to 1.72 MPaG with TFE. Then, 3.6 ml of 8-CNVE was loaded into the reactor. Next, 40 ml of an initiator solution of 2.5% (w / w) ammonium persulfate and 5.0% (w / w) disodium phosphate heptahydrate was charged into the reactor to initiate polymerization. Additional TFE was fed into the reactor to maintain a pressure of 1.72 MPaG. When 70 grams of TFE was added, an additional 50 ml of HHPMVE was fed into the reactor. When 100 grams of TFE was added, another 3.6 ml charge of 8-CNVE was loaded into the reactor. When 140 grams of TFE was added, an additional 50 ml of HHPMVE was fed into the reactor. After a total of 200 grams of TFE was fed into the reactor, the reactor was degassed to reduce the pressure and polymerization was stopped. A 15.8% (w / w) solids emulsion was obtained from this polymerization. The emulsion was coagulated with potassium aluminum sulfate and dried at 70 °C. The resulting polymer had a composition of 71.9 mol% TFE, 27.5 mol% HHPMVE and 0.6 mol% 8-CNVE by NMR testing. The polymer had a glass transition temperature of 4.0 °C and a melting temperature of 85.8 °C.

[0086] Example 3: Preparation of VF2-HHPMVE Dipolymer A polymer containing a copolymerized monomer of vinylidene fluoride (VF2) and 2-(difluoromethoxy)-1,1-difluoroethene (HHPMVE) was prepared as follows. 2200 grams of deionized water was loaded into a 4-liter, mechanically stirred, water-jacketed stainless steel reactor and deoxygenated by repeated pressurization / depressurization cycles with nitrogen. Nitrogen was removed by repeated pressurization / depressurization cycles with VF2. When the nitrogen content in the headspace was less than 1% (w / w) and the reactor pressure was 0.03 MPaG, 52 ml of HHPMVE was fed into the reactor. The reactor was heated to 80 °C and pressurized to 0.83 MPaG with VF2. 20 ml of an initiator solution of 10% (w / w) ammonium persulfate was charged into the reactor to initiate polymerization. Additional VF2 was fed into the reactor to maintain a pressure of 0.83 MPaG. After 40, 80, 120, 160 and 200 grams of VF2 were fed, 24 ml portions of HHPMVE were fed into the reactor. When a total of 240 grams of VF2 was fed, the reactor was vented to reduce the pressure and polymerization was stopped. An additional 89 ml of the initiator solution was added throughout the polymerization to maintain the reaction. A 16.8% (w / w) solids emulsion was obtained from this polymerization. The emulsion was coagulated with potassium aluminum sulfate and dried at 70 °C. The polymer had a glass transition temperature of -4.7 °C and a melting temperature of 91.1 °C.

[0087] Example 4: Preparation of TFE-HHPMVE Dipolymer A polymer containing a copolymerized monomer of tetrafluoroethylene (TFE) and 2-(difluoromethoxy)-1,1-difluoroethene (HHPMVE) was prepared as follows. A 2% (w / w) solution of 2215 grams of the ammonium salt of CF3CF2CF2OCF(CF3)CH2OPO(OH)2 was loaded into a 4-liter, mechanically stirred, water-jacketed stainless steel reactor and the oxygen was removed by repeated pressurization / de-pressurization cycles with nitrogen. Nitrogen was removed by repeated pressurization / de-pressurization cycles with TFE. When the nitrogen content in the headspace was less than 1% (w / w) and the reactor pressure was 0.03 MPaG, 71.5 ml of HHPMVE was fed into the reactor. The reactor was heated to 80 °C and pressurized to 1.72 MPaG with TFE. Then, 40 ml of an initiator solution of 2.5% (w / w) ammonium persulfate and 5.0% (w / w) disodium phosphate heptahydrate was charged into the reactor to initiate the polymerization. Additional TFE was fed into the reactor to maintain a pressure of 1.72 MPaG. When a total of 400 grams of TFE was fed, the reactor was degassed to reduce the pressure and the polymerization was stopped. A 21.5% (w / w) solids emulsion was obtained from this polymerization. The emulsion was coagulated with potassium aluminum sulfate and dried at 70 °C. The polymer had a melting temperature of +304.4 °C.

[0088] Example 5: Preparation of TFE / HHPMVE / PMVE / 8-CNVE Tetrapolymer A polymer containing copolymerized monomers of tetrafluoroethylene (TFE), perfluoro(methyl vinyl ether) (PMVE), 2-(difluoromethoxy)-1,1-difluoroethene (HHPMVE) and perfluoro 8-(cyano-5-methyl-3,6-dioxa-1-octene) (8-CNVE) was prepared as follows. An aqueous stream was continuously fed at a rate of 235 cc / hr into a 1-liter mechanically stirred, water-jacketed stainless steel reactor. This stream contained 0.09% (w / w) ammonium persulfate, 0.53% (w / w) disodium phosphate heptahydrate, 3.1% (w / w) ammonium salt of CF3CF2CF2OCF(CF3)CH2OPO(OH)2 and 0.5% (w / w) ammonium salt of carboxylic acid-terminated poly(hexafluoropropylene oxide) (Krytox® 157 FSL). A mixture of TFE (67.4 g / hr) and PMVE (97.5 g / hr) was fed at a constant rate using a diaphragm compressor. HHPMVE was fed at a rate of 4.5 g / hr and 8-CNVE was fed at a rate of 5.5 g / hr. The temperature was maintained at 80 °C and the pressure was maintained at 4.1 MPaG throughout the reaction. The polymer emulsion was continuously removed using a let-down valve and the unreacted monomers were degassed. The polymer was coagulated with magnesium sulfate heptahydrate and dried at 70 °C. The resulting polymer had a composition of 75.1 mol% TFE, 22.5 mol% PMVE, 1.7 mol% HHPMVE and 0.7 mol% 8-CNVE. The polymer had an intrinsic viscosity of 1.33 measured in a solution of 0.1 g of polymer in 100 g of Flutec® PP-11 (F2 Chemicals Ltd, Preston, UK) and a Mooney viscosity (1+10) of 92.5 measured at 175 °C. The polymer had a glass transition temperature of -0.5 °C and no melting transition.

Claims

1. A method for producing a halo(alkylvinyl) ether, i) Metals and, ii) Solvent and, iii) Formula (1) RCF 2 OC(H)(X)CF 2 Y (1) (In the formula, R is independently H, F, Cl, Br, CF) 2 H, CF 3 CF 2 CF 2 H is a linear perfluoroalkyl group having 1 to 12 carbon atoms or a cyclic perfluoroalkyl group having 1 to 12 carbon atoms, and X and Y are independently Cl, Br, I, or F, and X and Y cannot both be F. Halo(alkylethyl) ethers according to the following A reaction mixture containing the combination of the above is heated to form a reaction product mixture containing a halo(alkyl vinyl) ether, the solvent, an unreacted metal, and a metal salt. A method that includes this.

2. The aforementioned halo(alkylvinyl) ether is of formula (2) RCF 2 OC(H)=CF 2 (2) (In the formula, R is as defined for formula (1)) The method according to claim 1.

3. The method according to claim 1, wherein the metal is zinc, magnesium, cadmium, or indium, the solvent is an anhydrous polar aprotic solvent, the halo(alkylethyl) ether is anhydrous isoflurane, and the halo(alkylvinyl) ether is difluoromethyl 2,2-difluoroethenyl ether.

4. (I) A step of combining the metal and the solvent in a reactor, (II) A step of flashing the combination of the metal and solvent with nitrogen, (III) A step of adding the halo(alkylethyl) ether to the combination of the metal and solvent to form the reaction mixture, (IV) A step of maintaining the reaction mixture at a temperature of room temperature to 160°C for 2 to 15 hours, preferably at 100 to 160°C for 5 to 15 hours. The method according to claim 1, further comprising:

5. (V) A step of cooling the reaction product mixture to a temperature of 2°C to 20°C, (VI) A step of filtering the reaction product mixture to remove the metal and metal salt to form a filtered reaction product mixture containing the solvent and the halo(alkylvinyl) ether, (VII) A step of purifying the halo(alkylvinyl) ether and The method according to claim 4, further comprising:

6. The method according to claim 5, wherein the purification is performed by distillation.

7. The method according to claim 1, wherein the molar ratio of metal to halo(alkylethyl) ether in the reaction mixture is 1:0.5 to 1:1.

5.

8. A fluoropolymer produced by polymerizing a halo(alkylvinyl) ether produced by the method described in claim 1, wherein the fluoropolymer is curable.

9. The fluoropolymer according to claim 8, wherein the halo(alkylvinyl) ether is polymerized with one or more additional monomers.

10. The fluoropolymer according to claim 9, wherein the additional monomer is one or more monomers selected from the group consisting of 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-dioxaocta-7-ene) sulfonyl fluoride (PSEPVE), vinylidene fluoride (VF2), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), propylene (P), perfluoromethoxyvinyl ether (MOVE), pentafluoropropene (HPFP), perfluoro(3-methoxypropyl vinyl) ether (MV-31), and analogs thereof.

11. The fluoropolymer according to claim 10, wherein the perfluoro(alkyl vinyl) ether is perfluoromethyl vinyl ether (PVME), perfluoro(ethyl vinyl) ether (PEVE), perfluoro(propyl vinyl) ether (PPVE), or long-chain perfluorovinyl ether.

12. The fluoropolymer according to claim 8, wherein the halo(alkylvinyl) ether is further polymerized with the curing site monomer.

13. The curing site monomer is perfluoro(8-cyano-5-methyl-3,6-dioxaocta-1-ene), CF 2 =CF-O(CF 2 ) n CN (linear 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 CN, CF 2 =CF-O-(CF 2 ) n -O-CF(CF 3 )CN as described in claim 12 of the fluoropolymer.​

14. a. Repeating unit (I) (I) - (C(R 1 ) (H) CF 2 ) - (wherein, R 1 is, -OCRF 2 And R is H, F, Cl, Br, CF 2 H, CF 3 CF 2 CF 2 H is a linear perfluoroalkyl group having 1 to 12 carbon atoms or a cyclic perfluoroalkyl group having 1 to 12 carbon atoms. A fluoropolymer containing [a specific component].

15. b. Formulas (II), (III), (IV), or (V): (II)-(CF) 2 CF 2 )-、 (III)-(CH 2 -CF 2 )-、 (IV) - (CF 2 C(R 1 )F)-(wherein, R 1 is, -(OCF 2 C(F)(CF 3 ) OCF 2 CF 2 C≡N) (V)-(C(R 1 )(F)CF 2 )- one or more repeating units The fluoropolymer according to claim 14, further comprising:

16. The fluoropolymer according to claim 8, which is curable.

17. An article comprising a cured compound that, before curing, contained a fluoropolymer produced by polymerizing a halo(alkyl vinyl) ether produced by the method of claim 1.

18. The article according to claim 17, in the form of a gasket, seal, tube, sheet, washer, or O-ring.

19. An article comprising a cured compound that contained the fluoropolymer described in claim 14 before curing.