Process for preparing halogenerated (alkylvinyl) ether monomers and fluorinated polymers prepared therewith

Abstract

A process for preparing a halogenated (alkylvinyl) ether, the process comprising heating a reaction mixture comprising a combination of: i) a metal; ii) a solvent; and iii) a halogenated (alkylethyl) ether according to formula (1) RCF2OC (H) (X) CF2Y (1) wherein R is independently H, F, Cl, Br, CF2H, CF3, CF2CF2H, 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 wherein X and Y are not both F; to form a reaction product mixture comprising a halogenated (alkylvinyl) ether, the solvent, an unreacted metal, and a metal salt.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] none Technical Field

[0003] The present invention generally relates to halo(alkyl vinyl) ether monomers, methods of making halo(alkyl vinyl) ether monomers, and fluorinated polymers made from halo(alkyl vinyl) ether monomers. Background Art

[0004] Fluoropolymers such as fluoroelastomers are known to have excellent mechanical properties, heat resistance, weather resistance, and chemical resistance. These properties make fluoroelastomers useful in many applications, such as O-rings, seals, hoses, non-slip materials, and coatings (e.g., metal gasket coatings) that may be exposed to harsh environments, including high temperatures and corrosive chemicals. Parts made from fluoroelastomers are used in many industries, including the automotive, chemical processing, semiconductor, aerospace, and petroleum industries.

[0005] Fluoropolymers are polymerized from fluoromonomers. One such fluoromonomer that has been used to prepare fluoroelastomers and fluororesins is perfluoromethyl vinyl ether (PMVE). PMVE has been polymerized to prepare homopolymers and copolymerized with other fluoromonomers to prepare different fluorinated copolymers.

[0006] Although it is known that PMVE can prepare fluoroelastomers with excellent properties, the properties of fluoromonomers and fluoropolymers in general produced from PMVE can still be improved. For example, fluoropolymers with better heat resistance, weather resistance, chemical resistance, or improved physical properties (such as increased or decreased flexibility) are desired compared to fluoropolymers prepared with PMVE.

[0007] Therefore, additional halogenated (alkyl vinyl) ethers other than PMVE are of potential interest for producing new fluoroelastomers having improved properties over existing fluoropolymers (e.g., those prepared with known monomers like PMVE). One such class of halogenated (alkyl vinyl) ethers of interest is the partially perhalogenated (alkyl vinyl) ethers. However, these partially halogenated alkyl vinyl ethers have proven difficult to manufacture in commercially viable quantities and yields.

[0008]

[0006] Therefore, there is a need for new methods of preparing partially halogenated (alkyl vinyl) ether monomers that can be used to produce fluoroelastomers having potentially improved properties over known fluoropolymers. Summary of the invention

[0009] The present invention relates to a method for preparing a halogenated (alkyl vinyl) ether, comprising the steps of: heating a reaction mixture comprising a combination of: i) a metal; ii) a solvent; and iii) a mixture of RCF according to formula (1) 2 OC(H)(X)CF 2 Y halo(alkylethyl)ether, wherein R is independently H, F, Cl, Br, CF 2 H.CF 3 CF 2 CF 2 H, 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, wherein X and Y are not both F; to form a reaction product mixture comprising a halogenated (alkyl vinyl) ether, a solvent, an unreacted metal, and a metal salt.

[0010] The present invention further relates to a fluoropolymer prepared by polymerizing the halo(alkyl vinyl) ether.

[0011] The present invention further relates to a fluoropolymer comprising: a repeating unit (I)-[(C(H)(R 1 )CF 2 )]-, where R 1 Yes - OCRF 2 , wherein R is independently H, F, Cl, Br, CF 2 H.CF 3 CF 2 CF 2 H. a linear perfluoroalkyl group having 1 to 12 carbon atoms, or a cyclic perfluoroalkyl group having 1 to 12 carbon atoms.

[0012] The process of the present invention allows the production of halo(alkyl vinyl)ethers in increased yields. The halo(vinyl ethers) produced can be used to prepare new fluoropolymers with improved properties. DETAILED DESCRIPTION

[0013] As used herein, the article "a" refers to one as well as more than one and does not necessarily limit its referent noun to the grammatical category of the singular.

[0014] 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" may refer to any article, thing, object, element, device, etc., in the form, shape, or structure that can be further processed to become a finished article. When the article is unfinished, the term "preform" may refer to the form, shape, or structure, any part of which may be further processed to become finished. As used herein, when the article is finished, the term "article" refers to an article, thing, object, element, device, etc. in a form, shape, or structure suitable for a specific use / purpose without further processing of the entire entity or a part thereof.

[0015] An article may include one or more elements or subassemblies that are partially completed and await further processing or assembly with other elements / subassemblies that together will constitute the finished article. Additionally, as used herein, the term "article" may refer to a system or configuration of articles.

[0016] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "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 the listed elements but may include other elements that are not expressly listed or inherent. In addition, unless expressly stated to the contrary, "or" refers to an inclusive "or" and not to an exclusive "or." For example, a condition A or B is satisfied by any 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).

[0017] As used herein, the terms "comprises / comprising," "includes / including," "has / having," "consisting essentially of," and "consisting of," or any other variation thereof, may refer to a non-exclusive inclusion or an exclusive inclusion. When these terms refer to a more exclusive inclusion, these terms limit the scope of the claim to those described materials or steps that substantially affect the novel elements of the described invention. When these terms refer to a full exclusive inclusion, these terms exclude any elements, steps, or components not expressly recited in a claim.

[0018] As used herein, the terms describing molecules or polymers follow the nomenclature in the IUPAC Compendium of Chemical Nomenclature version 2.15 as of September 7, 2009 (International Union of Pure and Applied Chemistry).

[0019] As used herein, the term "alkyl" refers to a straight chain, branched chain or cyclic hydrocarbon structure and combinations thereof. Alkyl does not include aromatic structures. Examples of straight chain alkyls include methyl, ethyl, propyl, butyl, pentyl and hexyl. Branched chain alkyls include, for example, sec-butyl and tert-butyl, and isopropyl. Examples of cyclic hydrocarbons include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

[0020] As used herein, the term "alkoxy" or "alkoxyl" refers to an alkyl group attached to an oxygen atom via a single bond. The other bond of the oxygen atom is attached to a carbon atom. Examples include methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy, and cyclohexyloxy.

[0021] As used herein, the term "compound" refers to a composition capable of being cured (i.e., a curable composition), and refers to a mixture of chemical entities comprising at least a fluoroelastomer and a curing agent. The mixture of chemical entities has not yet been cured or has not been subjected to processing conditions that would cause the curing of the mixture of chemical entities to undergo curing.

[0022] As used herein, the prefix term "fluoro" when placed as a prefix before a chemical entity name refers to a chemical entity 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 entity name explicitly includes "perfluoro" chemical entities. Thus, the prefix "fluoro" when preceding a chemical entity name refers to both "fluoro-" entities and "perfluoro-" entities.

[0023] As used herein, the term "cured" refers to a produced entity comprising a fluoroelastomer and which has been exposed to those conditions that cause the fluoroelastomer molecules to form sufficient cross-links among themselves (i.e., curing conditions) such that the produced entity assumes a form or shape or configuration or structure that cannot be reprocessed, molded, or extruded into a different form or shape or configuration or structure. That is, once a produced entity comprising a fluoroelastomer has been exposed to curing conditions and thereby cured, the entity cannot be recured to assume a substantially different form or structure.

[0024] As used herein, the term "curing" refers to the processing of a compound (also referred to herein as a curable composition) to produce a solid body that exhibits a form or shape or configuration or structure that cannot be reprocessed, molded, or extruded into a different form or shape or configuration or structure. Such processing is referred to as a "curing process / process" that requires the compound to be exposed to certain conditions in order to initiate the curing process, such conditions being referred to as curing conditions.

[0025] The resulting entity of the curing process is a "cured" entity, that is, an article as defined above. To be clear, curing produces a compound that takes on the form or shape or configuration or structure of an article. Cured articles of the compounds described herein include, but are not limited to, O-rings, seals, and gaskets.

[0026] The compound may be initially cured to achieve a non-reworkable form, shape, etc., which has been referred to herein as "cured". The cured compound may further be subjected to additional curing conditions that provide additional subsequent curing. Such additional curing conditions may be variously referred to herein as "curing" or "post-curing". That is, the terms "curing", "cured" refer to both the initial curing process that produces the first cured produced entity and also clearly refer to any subsequent curing process that produces the subsequently cured produced entity that may or may not have different materials or physical properties from those of the first cured produced entity.

[0027] Unless expressly stated otherwise, any ranges set forth herein expressly include their endpoints. Listing an amount, concentration, or other value or parameter as a range specifically discloses all possible ranges formed by any possible upper range limit and any possible lower range limit, regardless of whether such pairs of upper and lower range limits are expressly disclosed herein. The compounds, methods, and articles described herein are not limited to the specific values ​​disclosed when defining a range in the specification.

[0028] The disclosure herein of any variation of the methods, compounds, and articles described herein in terms of materials, chemical entities, methods, steps, values, and / or ranges, etc., whether or not identified as preferred, is specifically intended to include any possible combination of materials, methods, steps, values, ranges, etc. In order to provide detailed, precise, and sufficient support for the claims, any disclosed combination is a preferred variation of the methods, compounds, and articles described herein.

[0029] In this specification, if there is a naming error or typographical error about the chemical name of any chemical species described herein, the chemical structure takes precedence over the chemical name. And, if there is an error in the chemical structure of any chemical species described herein, the chemical structure of the chemical species that a person skilled in the art understands the intention of the specification shall prevail.

[0030] A method for preparing a halogenated (alkyl vinyl) ether, the method comprising the following steps:

[0031] heating a reaction mixture comprising:

[0032] i) metals;

[0033] ii) a solvent; and

[0034] iii) a halogenated (alkylethyl) ether according to formula (1)

[0035] RCF 2 OC(H)(X)CF 2 Y(1)

[0036] Wherein R is independently H, F, Cl, Br, CF 2 H.CF 3 CF 2 CF 2 H, 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, wherein X and Y are not both F;

[0037] To form a reaction product mixture comprising the halo(alkyl vinyl) ether, solvent, unreacted metal and metal salt.

[0038] The reaction mixture comprising the metal, solvent, and halo(alkylethyl)ether is heated to form a reaction product mixture comprising halo(alkylvinyl)ether, solvent, unreacted metal, and metal salt.

[0039] The metal is any metal that will cause the dehalogenation reaction of the halogenated (alkyl ethyl) ether according to formula (1) in a solvent according to the present invention, alternatively an alkali metal, alkaline earth metal or transition metal group metal that will cause the dehalogenation reaction of the halogenated (alkyl ethyl) ether according to formula (1) in a solvent, alternatively, the metal is zinc, magnesium, cadmium, or indium, alternatively zinc. Most metals are commercially available. Those skilled in the art will know how to obtain and use metals.

[0040] Solvent is enough to make the halogenated (alkyl ethyl) ether according to formula (1) and metal carry out dehalogenation reaction solvent, alternatively, solvent is anhydrous polar aprotic solvent, alternatively, solvent is dimethylformamide (DMF), N-methyl pyrrolidone (NMP), dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI), N, N'-dimethyl propylene urea (DMPU), acetonitrile (MeCN), ether or dimethylformamide (DMF), N-methyl pyrrolidone (NMP), dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI), N, N'-dimethyl propylene urea (DMPU), ether and acetonitrile (MeCN) in two or more mixtures. In one embodiment, solvent is anhydrous. The example of ether includes but is not limited to tetrahydrofuran (THF), dioxane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether. Many solvents that function in the present invention are commercially available.

[0041] According to the halogenated (alkylethyl) ether of formula (1)

[0042] RCF 2 OC(H)(X)CF 2 Y(1)

[0043] Where R is H, F, Cl, Br, CF 2 H.CF 3 CF 2 CF 2 H, 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, provided that X and Y are not both F.

[0044] Examples of halogenated (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)ethoxyperfluoro-sec-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 halogenated ethers according to formula (1) are commercially available or can be prepared by methods known in the art.

[0045] The halo(alkylethyl)ethers are prepared by methods known in the art.Many halo(alkylethyl)ethers are commercially available.

[0046] The reaction product mixture comprises the halo(alkyl vinyl) ether, solvent, unreacted metal and metal salt.

[0047] The solvent and unreacted metal in the reaction product mixture are as described above for the reaction mixture.

[0048] Metal salts are halides formed from halogens from halogenated (alkylethyl) ethers and metals. Examples of metal salts include, but are not limited to, halides comprising fluorine, chlorine and / or bromine and metals (including zinc, magnesium, cadmium, and / or indium metals), 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.

[0049] In one embodiment, the halogenated (alkyl vinyl) ether conforms to formula (2)

[0050] RCF 2 OC(H)CF 2 (2)

[0051] Where R is H, F, Cl, Br, CF 2 H.CF 3 CF 2 CF 2 R is H, a linear perfluoroalkyl group having 1 to 12 carbon atoms, or a cyclic perfluoroalkyl group having 1 to 12 carbon atoms; alternatively R is H, F, Cl or Br, alternatively R is F.

[0052] Examples of halo(alkyl vinyl)ethers according to formula (2) include, but are not limited to, 2-(difluoromethoxy)-1,1-difluoroethylene (HHPMVE), 1,1-difluoro-2-(trifluoromethoxy)ethylene, 1,1-difluoro-2-(chlorodifluoromethoxy)ethylene, 1,1-difluoro-2-(bromodifluoromethoxy)ethylene, 1,1-difluoro-2-(1,1,2,2-tetrafluoroethoxy)ethylene, 2-(pentafluoro)ethoxy-1,1-difluoroethylene, 1,1,2,2,3,3-hexafluoro-1-(1,1-difluorovinyloxy)propane, 1-(1,1 1-(1,1-difluorovinyloxy)perfluoropropane, 1-(1,1-difluorovinyloxy)perfluorobutane, 1-(1,1-difluorovinyloxy)perfluoroisobutane, 1-(1,1-difluorovinyloxy)perfluoro-sec-butane, 1-(1,1-difluorovinyloxy)perfluoropentane, 1-(1,1-difluorovinyloxy)perfluorohexane, 1-(1,1-difluorovinyloxy)perfluorocyclohexane, 1-(1,1-difluorovinyloxy)perfluorooctane, 1-(1,1-difluorovinyloxy)perfluorononane, and 1-(1,1-difluorovinyloxy)perfluorodecane.

[0053] The reaction mixture is formed by combining the metal, solvent and halogenated (alkyl ethyl) ether in a reaction vessel. Those skilled in the art will know how to combine the components of the reaction mixture. Any reaction vessel known for dehalogenation reactions can be used. For example, the reaction vessel can be a steel reactor, a three-necked round-bottomed glass flask, a sealed tubular reactor or an autoclave with a cooling coil and a pressure relief valve. The reaction vessel may or may not be equipped with a device for stirring the reaction mixture. For example, the reaction vessel may be equipped with a magnetic stirrer. Before use, the reaction vessel is usually purged with a non-reactive gas.

[0054] The method of merging reaction mixture components can vary. In one embodiment, there is no specific order in which the components of reaction mixture are added to the reaction vessel. For example, a solvent can be added to the reaction vessel, followed by a solvent, followed by a halo (alkyl ethyl) ether, or a metal can be first added, followed by a solvent and followed by a halo (alkyl ethyl) ether. In another embodiment, metal and solvent are added to the reaction vessel, followed by a halo (alkyl ethyl) ether. In one embodiment, halo (alkyl ethyl) ether is added to the reactor at 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 halo (alkyl ethyl) ether to control the reaction rate.

[0055] The reaction mixture comprising the halo(alkylethyl)ether, solvent and metal is heated. Methods known in the art for heating a reaction vessel can be used to heat the reaction mixture. For example, a heating mantle or a heating furnace can be used to heat the reactor, depending on the type of reaction vessel used. Those skilled in the art will know how to heat the reaction vessel.

[0056] 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 will readily occur, alternatively at a temperature below ambient to ambient or slightly above ambient, alternatively at a temperature below the boiling point of the components of the reaction mixture, alternatively at 0°C to 30°C.

[0057] The temperature to which the reaction mixture is heated can vary. Typically, the reaction mixture is heated to within the target temperature range, and then the reaction mixture temperature is maintained within the target temperature range until the reaction is fully completed. Those skilled in the art will know how to determine when the reaction is completed, 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 / minute, and the reaction can be monitored by chromatography.

[0058] The reaction mixture is heated to a temperature of 60°C to 200°C, alternatively 120°C to 180°C, alternatively 130°C to 160°C.

[0059] The time for maintaining the reaction mixture comprising the halogenated (alkyl ethyl) ether, the metal and the solvent 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 2-15 hours, alternatively 4 to 10 hours. Those skilled in the art will know how to determine how long to maintain the reaction mixture at the target temperature based on the progress of the reaction.

[0060] The boiling points of the solvent, halogenated (alkyl ethyl) ether and halogenated (alkyl vinyl) ether can be higher than the target temperature range of the reaction, so the reaction can occur under high pressure. The pressure will vary according to the temperature of the reaction mixture, the pressure or partial pressure of the solvent, halogenated (alkyl ethyl) ether and halogenated (alkyl vinyl) ether in the product mixture. Those 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, the pressure of the reaction mixture is increased to a pressure higher than the pressure generated by the components of the heating reaction mixture or the reaction product mixture without other means. Those skilled in the art will know to use an appropriate reactor at a reaction pressure higher than room pressure.

[0061] The weight ratio of the halo(alkylethyl)ether to the metal may 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. Those skilled in the art will know how to determine the weight ratio of the halo(alkylethyl)ether to the metal.

[0062] The amount of solvent in the reaction mixture comprising a halogenated (alkyl ethyl) ether, a solvent and a 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% (w / w), based on the weight of the solvent, the halogenated (alkyl ethyl) ether and the metal. Those skilled in the art will understand how to optimize the amount of solvent in the reaction mixture.

[0063] The halo (alkyl vinyl) ether product can be recovered from the reaction product mixture. The reaction product mixture can be cooled, alternatively cooled to about 25 ° C, alternatively to about 15 ° C, and any gas from the reaction vessel can be collected from the reactor using methods known in the art (e.g., gas collectors). 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.

[0064] In one embodiment of the invention, the halogenated (alkyl vinyl) ether is polymerized to form a fluoropolymer. The halogenated (alkyl vinyl) ether is as described above. The halogenated (alkyl vinyl) ether can be polymerized to form a homopolymer, or the halogenated (alkyl vinyl) ether can be polymerized with other known monomers for preparing fluoropolymers to form a copolymer, a terpolymer, etc.

[0065] Fluoropolymers can be cured, non-curable, or curable, alternatively the fluoropolymers are curable, alternatively non-curable, alternatively cured. Those skilled in the art will understand what is a cured, non-curable, or curable fluoropolymer and how to prepare non-curable or curable fluoropolymers. In one embodiment, a curable fluoropolymer can be prepared by polymerizing a halo(alkyl vinyl) ether with a monomer containing a cure site.

[0066] Fluoropolymers can be amorphous or non-amorphous. Examples of amorphous fluoropolymers include, but are not limited to, fluoroelastomer gums or perfluoroelastomer gums prepared from the halogenated (alkyl vinyl) ethers of the present invention, monomers having cure sites, and additional monomers that impart desired properties to the gum.

[0067] Examples of additional monomers that can be polymerized with the halogenated (alkyl vinyl) ether to form the fluoropolymer include, but are not limited to, perfluoroolefins, perfluoro(alkyl vinyl) ethers (PAVE) and perfluoroalkoxyalkyl vinyl ethers (PAAVE), fluoro(olefin ethers), halogenated fluoroolefins (such as chlorotrifluoroethylene (CTFE)), partially fluorinated olefins (such as vinyl fluoride (VF), vinylidene fluoride (VF2), trifluoroethylene, tetrafluoropropylene (TFP), pentafluoropropylene (HPFP), olefins in which less than half or less than a quarter of the hydrogen atoms are replaced by fluorine), according to the formula CX 2 =CXR olefins (wherein each X is independently hydrogen, fluorine or chlorine and R is hydrogen, fluorine or C 1 -C 12 Alternatively, C 1 To C 3 alkyl, provided that all X and R groups are not all fluorinated groups), hydrogen-containing monomers (such as ethylene, propylene, and other non-fluorinated α-olefins (such as C 2 To C 9 α-olefins), fluorinated ester ethers (such as fluorinated ester vinyl ethers), methyl perfluoro(5-methyl-4,7-dioxacyclohexane-8-enoic acid ethyl ester) (EVE), or perfluoro(4-methyl-3,6-dioxaoct-7-ene)sulfonyl fluoride (PSEPVE), perfluoro(3-methoxypropyl vinyl ether) (MV-31), and nitrogen-containing cure site monomers. Those skilled in the art will know where to find or how to prepare these additional monomers, and many of these additional monomers are commercially available.

[0068] Examples of perfluoroolefins include, but are not limited to, tetrafluoroethylene (TFE), hexafluoropropylene (HFP), or any fluoroolefin having the formula CF 2 =CF-R f Perfluoroolefins (where R f is fluorine or a perfluoroalkyl group having 1 to 8, alternatively 1 to 3, carbon atoms).

[0069] Examples of PAAVE monomers include, but are not limited to, 2 =CF-ORf (wherein Rf is a linear, branched or cyclic perfluorinated alkyl group optionally containing an ether linkage) and CF 2 =CF(OC n F 2n ) p ORf (wherein Rf is a perfluorinated (C 1 -C 8 ) alkyl, each n is independently 1 to 4, and p is 1 to 6). When there are more than one C n F 2n When the group is C, "n" can be independently selected, alternatively, n is 1 to 12, alternatively 1 to 6. However, in C n F 2n In the group, those skilled in the art will understand that "n" is not independently selected. n F 2n Can be straight chain or branched. In some embodiments, (OC n F 2n ) p By -O-(CF 2 ) 1-4 -[O(CF 2 ) 1-4 ] 0-1 Such perfluorinated ethers are described, for example, in U.S. Pat. Nos. 6,255,536 and 6,294,627 (each to Worm et al.). Examples of suitable PAAVE monomers include, but are not limited to, CF 2 =CFOCF 2 OCF 3 CF 2 =CFOCF 2 OCF 2 CF 3 CF 2 =CFOCF 2 CF 2 OCF 3 CF 2 =CFOCF 2 CF 2 CF 2 OCF 3 (MV-31), CF 2 =CFOCF 2 CF 2 CF 2 CF 2 OCF 3 CF 2 =CFOCF 2 CF2 OCF 2 CF 3 、CF 2 =CFOCF 2 CF 2 CF 2 OCF 2 CF 3 、CF 2 =CFOCF 2 CF 2 CF 2 CF 2 OCF 2 CF 3 、CF 2 =CFOCF 2 CF 2 OCF 2 OCF 3 、CF 2 =CFOCF 2 CF 2 OCF 2 CF 2 OCF 3 、CF 2 =CFOCF 2 CF 2 OCF 2 CF 2 CF 2 OCF 3 、CF 2 =CFOCF 2 CF 2 OCF 2 CF 2 CF 2 CF 2 OCF 3 、CF 2 =CFOCF 2 CF 2 OCF 2 CF 2 CF 2 CF 2 CF 2 OCF 3 、CF 2 =CFOCF 2 CF 2 (OCF 2 ) 3 OCF 3 、CF 2 =CFOCF 2 CF 2 (OCF 2 ) 4 OCF 3CF 2 =CFOCF 2 CF 2 OCF 2 OCF 2 OCF 3 CF 2 =CFOCF 2 CF 2 OCF 2 CF 2 CF 3 CF 2 =CFOCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 CF 3 CF 2 =CFOCF 2 CF(CF 3 )-OC 3 F 7 (PPVE-2), CF 2 =CF(OCF 2 CF(CF 3 )) 2 -OC 3 F 7 (PPVE-3), and CF 2 =CF(0CF 2 CF(CF 3 )) 3 -OC 3 F 7 (PPVE-4). Methods for preparing PAAVE monomers are known in the art. Many PAAVE monomers are commercially available.

[0070] Examples of suitable PAVE monomers include, but are not limited to, perfluoro(methyl vinyl) ether CF 2 =CFOCF 3 , Perfluoro(ethyl vinyl) ether CF 2 =CFOCF 2 CF 3 , and perfluoro(n-propyl vinyl) ether CF 2 =CFOCF 2 CF 2 CF 3 Mixtures of PAVE and PAAVE may also be employed. Methods for preparing PAVE monomers are known in the art. Many PAVE monomers are commercially available.

[0071] Examples of fluoro(olefin 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 2 =CFCF 2 (OC n F 2ll ) p Those represented by ORf, wherein n, p and Rf are as defined above for the PAAVE monomers. Examples of suitable fluoro(olefin ether) monomers include perfluoroalkoxyalkyl allyl ethers, such as CF 2 =CFCF 2 OCF 2 CF 2 OCF 3 CF 2 =CFCF 2 OCF 2 CF 2 CF 2 OCF 3 CF 2 =CFCF 2 OCF 2 OCF 3 CF 2 =CFCF 2 OCF 2 OCF 2 CF 3 CF 2 =CFCF 2 OCF 2 CF 2 CF 2 CF 2 OCF 3 CF 2 =CFCF 2 OCF 2 CF 2 OCF 2 CF 3 CF 2 =CFCF 2 OCF 2 CF 2 CF 2 OCF 2 CF 3 CF 2 =CFCF 2 OCF 2 CF 2 CF 2 CF 2 OCF 2 CF 3 CF 2=CFCF 2 OCF 2 CF 2 OCF 2 OCF 3 、CF 2 =CFCF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 3 、CF 2 =CFCF 2 OCF 2 CF 2 OCF 2 CF 2 CF 2 OCF 3 、CF 2 =CFCF 2 OCF 2 CF 2 OCF 2 CF 2 CF 2 CF 2 OCF 3 、CF 2 =CFCF 2 OCF 2 CF 2 OCF 2 CF 2 CF 2 CF 2 CF 2 OCF 3 、CF 2 =CFCF 2 OCF 2 CF 2 (OCF 2 ) 3 OCF 3 、CF 2 =CFCF 2 OCF 2 CF 2 (OCF 2 ) 4 OCF 3 、CF 2 =CFCF 2 OCF 2 CF 2 OCF 2 OCF 2 OCF 3 、CF 2 =CFCF 2 OCF2 CF 2 OCF 2 CF 2 CF 3 CF 2 =CFCF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 CF 3 CF 2 =CFCF 2 OCF 2 CF(CF 3 )-OC 3 F 7 , and CF 2 =CFCF 2 (OCF 2 CF(CF 3 )) 2 -OC 3 F 7 Many of these perfluoroalkoxyalkyl allyl ethers can be prepared, for example, according to the method described in U.S. Pat. No. 4,349,650 (Krespan). In addition, perfluoropropyl allyl ether (CF) can be prepared according to the method described in U.S. Pat. No. 5,891,965 (Worm). 2 =CF-CF 2 -OC 3 F 7 ) and perfluoromethoxyethyl allyl ether (CF 2 =CF-CF 2 -OC 2 F 4 OCF 3 ). Perfluoroalkoxyalkyl allyl ether can also be prepared by 2 =CF-CF 2 -OSO 2 Cl or CF 2 =CF-CF 2 -OSO 2 CF 3 The polyfluorinated compound comprising at least one ketone or carboxylic acid halide or a combination thereof and fluoride ions is prepared by combining at least one first component of the present invention and a polyfluorinated compound comprising at least one ketone or carboxylic acid halide or a combination thereof and fluoride ions. The polyfluorinated compound comprising 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. Pat. No. 4,349,650 (Krespan). Many fluoro(olefin ether) monomers, such as perfluoroalkoxyalkyl allyl ether monomers, are commercially available.

[0072] In one embodiment, the fluoropolymer comprises polymerized units derived from a halogenated (alkyl vinyl) ether according to formula (2), alternatively polymerized units derived from a halogenated (alkyl vinyl) ether according to formula (2) and additional monomers TFE, PAVE, PAAVE, VF2, VF and / or PMVE (alternatively one or more of TFE, VF2 and / or PMVE, alternatively TFE, alternatively VF2, alternatively PMVE), each of which may also contain monomer units having nitrogen-containing cure sites.

[0073] Liquid monomers including but not limited to halo(alkyl vinyl)ethers according to formula (2) used to prepare fluoropolymers may be pre-emulsified with an emulsifier prior to polymerization with other monomers (eg, addition of a gaseous fluoroolefin).

[0074] The fluoropolymer comprises at least 0.5% (w / w), alternatively at least 1% (w / w), alternatively 1% to 99.9% (w / w), alternatively 1% to 50% (w / w), alternatively 1% to 20% (w / w) of polymerized units derived from a halo(alkyl vinyl) ether according to formula (2).

[0075] The fluoropolymer may comprise additional monomers, alternatively 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) of polymerized units derived from one or more of the aforementioned additional monomers, based on the weight of the fluoropolymer.

[0076] Examples of fluoropolymers include, but are not limited to, 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 / CF 2 =CFOC 3 F 7 Copolymer, HHPMVE / TFE / CF 2 =CFOCF 3 / CF 2 =CFOC 3 F 7Copolymer, HHPMVE / TFE / ethyl vinyl ether (EtVE) copolymer, HHPMVE / TFE / butyl vinyl ether (BVE) copolymer, HHPMVE / TFE / EtVE / BVE copolymer, HHPMVE / VF2 / CF 2 =CFOC 3 F 7 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 / CF 2 =CFO(CF 2 ) 3 OCF 3 Copolymers, each of these polymers may also contain monomer units having nitrogen-containing cure sites.

[0077] In some embodiments, the fluoropolymer contains units derived from TFE, and the molar ratio of units derived from TFE to comonomer units derived from perfluoroalkyl vinyl ether or perfluoroalkyl allyl ether, or perfluoroalkoxyalkyl vinyl ether or perfluoroalkoxyalkyl allyl ether and the halogenated (alkyl vinyl) ether according to formula (2) described above is, for example, 1:1 to 4:1, wherein the unsaturated ether can be used as a single compound or as a combination of two or more unsaturated ethers. Typical compositions also contain 0.1%-10% (w / w) of a nitrogen-containing cure site monomer, the amount of which is selected so that the total amount is 100% (w / w). Other typical compositions contain about 1%-30% (w / w) HHPMVE, 17-30wt.% TFE, 25-38wt.% VF2, 28-42wt.% HFP and 0.1%-10wt.% nitrogen-containing cure site monomers, and 0%-10%wt. of other comonomers or modifiers, the amounts of these ingredients being selected so that the total is 100%wt.

[0078] The cure sites in the fluoropolymers enable the fluoropolymers to cure to form cured fluoropolymers (including fluoroelastomers). Examples of cure site components of fluoropolymers include nitrogen-containing groups. Examples of monomers containing nitrogen-containing groups that can be used to prepare fluoropolymers containing nitrogen-containing cure sites include free radical polymerizable nitriles, imidoesters, amidines, amides, imides, and amine oxides. Mixtures of any of these nitrogen-containing cure sites can be used in 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 CF 2 =CFO(CF 2 ) L CN、CF 2=CFO(CF 2 ) u OCF(CF 3 )CN、CF 2 =CFO[CF 2 CF(CF 3 )O] q (CF 2 O) y CF(CF 3 )CN、CF 2 =CFO[CF 2 FCF 3 O] n CF 2 -CFCF 3 CN or CF 2 =CF[OCF 2 CF(CF 3 )] r O(CF 2 ) t CN, wherein L is in the range of 2 to 12; u is in the range of 2 to 6; q is in the range of 0 to 4; y is in the range of 0 to 6; n is in the range of 0 to 4; r is in the range of 1 to 2; and t is in the range of 1 to 4. Examples of such nitrogen-containing cure site monomers include CF 2 =CFO(CF 2 ) 3 OCF(CF 3 )CN, perfluoro(8-cyano-5-methyl-3,6-dioxa-1-octene)(8-CNVE) and CF 2 =CFO(CF 2 ) 5 CN.

[0079] It is also possible to use selected chain transfer agents (e.g. I(CF 2 ) d CN, wherein d is 1 to 10 or 1 to 6) or by perfluorosulfinates (such as NC(CF 2 ) d SO 2 G, wherein G represents a hydrogen atom or a cation having a valence of 1 or 2) to incorporate nitrogen-containing cure sites into the curable fluoropolymer.

[0080] The nitrogen-containing monomers, chain transfer agents, and / or initiators typically comprise about 0.1 to 5 mole percent (in some embodiments, 0.3 to 2 mole percent) of the polymerization components.

[0081] Fluoropolymer provided herein can further or alternatively include at least one halogen atom curing site that can participate in peroxide curing reaction.The halogen that can participate in peroxide curing reaction can be bromine or iodine, alternatively iodine.The halogen atom that can participate in peroxide curing reaction can be located at the terminal position of main chain, alternatively located at the terminal position of main chain.However, when the position of the halogen atom that can participate in peroxide curing reaction is located at the terminal position, other reactive curing sites can also be present.The amount of iodine, bromine or its combination contained in fluoropolymer is between 0.001% and 5%, preferably between 0.01% and 2.5%, or is 0.1% to 1% or 0.2% to 0.6% by weight relative to the gross weight of fluoropolymer.

[0082] Examples of cure site monomers that are capable of participating in a peroxide cure reaction when incorporated into a fluoropolymer include, but are not limited to, CF 2 =CHBr, CH 2 =CHCH 2 Br, CF 2 =CFCF 2 Br, CH 2 =CHCF 2 CF 2 Br, CF 2 =CHI, CH 2 =CHCH 2 I. CF 2 =CFCF 2 I. CH 2 =CHCF 2 CF 2 I. CF 2 =CFOC 4 F 8 I(MV4I), CF 2 =CFOC 2 F 4 I. CF 2 =CFOCF 2 CF(CF 3 )OC 2 F 4 I. CH 2 =CHCF 2 CF 2 I. CF 2 =CFOCF 2 CF 2 CH 2 I. CF 2 =CFOCF 2 CF 2 CH 2 CH 2 I. CF 2=CFOC 4 F 8 CH 2 CH 2 I, and combinations thereof.

[0083] Fluoropolymer disclosed at present is typically prepared by a series of steps, and these steps may include polymerization, condensation, washing and drying. In certain embodiments, aqueous emulsion polymerization can be carried out continuously under steady-state conditions. For example, under optimal pressure and temperature conditions, an aqueous emulsion of monomer (for example including any one of those mentioned above), water, emulsifier, buffer and catalyst can be continuously fed into a stirred reactor, and the resulting emulsion or suspension is continuously taken out simultaneously. In certain embodiments, intermittent or semi-intermittent polymerization is by feeding the above-mentioned components into a stirred reactor and making them react at a set temperature for a specified time length or by loading these components into a reactor and feeding the monomer into the reactor to maintain a constant pressure until the polymer of the desired amount is formed to carry out. After polymerization, unreacted monomer is removed from the reactor effluent latex by reduced pressure vaporization. Fluoropolymer can be reclaimed from latex by condensation.

[0084] The polymerization is usually carried out in the presence of a free radical initiator system (such as ammonium persulfate, disodium hydrogen phosphate heptahydrate, potassium permanganate, AIBN, bis(perfluoroacyl) peroxide, or a combination of two or more thereof). In some embodiments, the polymerization is initiated with an initiator system selected from the following: a combination of a fluoroaliphatic sulfinate and an oxidant capable of oxidizing the sulfinate to a sulfonyl radical and / or a combination of a free radical initiator and a chloride salt. Examples of oxidants used as part of the initiator include, but are not limited to, free radical initiators such as persulfates, permanganic acid or its salts such as potassium permanganate. Examples of chloride salts used as part of the initiator include, but are not limited to, chloride salts with organic and inorganic cations, such as tetrabutylammonium chloride and ammonium chloride. Those skilled in the art will know initiators that work in similar polymerizations and how to initiate polymerization to form fluoropolymers.

[0085] The amount of initiator used to initiate polymerization to obtain the fluoropolymer can vary. In one embodiment, the amount of initiator used to initiate polymerization is an initiation-effective amount, alternatively 0.01% to 15% (w / w), alternatively 0.1% to 10% (w / w), alternatively 0.1% to 5% (w / w) of initiator based on the weight of all initiators and monomers. An "initiation-effective amount" of initiator means an amount sufficient to initiate the polymerization reaction. Those skilled in the art will know how to select and use and determine the appropriate amount of initiator for initiating polymerization.

[0086] Based on the disclosure herein, one skilled in the art will know how to optimize the temperature and pressure conditions, select an appropriate reaction vessel, and determine the percentages of monomers, initiators, and other components to polymerize to form the fluoropolymers of the present invention.

[0087] Fluoropolymers can also be described based on the repeating units in the fluoropolymer. In one embodiment, the fluoropolymer comprises a unit according to the formula: 1 )(H)CF 2 )-(3) repeating unit, wherein R 1 Yes - OCRF 2 , where R is H, F, Cl, Br, CF 2 H.CF 3 CF 2 CF 2 H, a linear perfluoroalkyl group having 1 to 12 carbon atoms, or a cyclic perfluoroalkyl group having 1 to 12 carbon atoms; alternatively comprising a repeating unit according to formula (3) and further comprising one or more repeating units (4)-(CF 2 CF 2 )-;(5)-(CH 2 -CF 2 )-;(6)-(CF 2 C(R 1 )F)-, where R 1 Yes-(OCF 2 C(F)(CF 3 )OCF 2 CF 2 C≡N); and / or (7)-(C(R 1 )(F)CF 2 )-.

[0088] Fluoropolymers comprising repeating units (3), and alternatively repeating units (3) and one or more of repeating units (4), (5), (6) and / or (7) can be prepared using the monomers, methods, conditions and reaction vessels described above for fluoropolymers prepared by polymerizing a halo(alkylethyl)ether according to formula (1). Based on the above disclosure, one skilled in the art will know how to prepare fluoropolymers having repeating units (3)-(7). In one embodiment, the fluoropolymer comprising repeating units (3)-(7) is made using a halo(alkylethyl)ether, which is made using the method for preparing the halo(alkyl ether) according to formula (1) described above.

[0089] The properties of the fluoropolymer comprising repeating unit (3), and alternatively comprising repeating unit (3) and one or more of repeating units (4), (5), (6) and / or (7) may have the same properties as the fluoropolymer prepared by polymerization with the halogenated (alkylethyl) ether according to formula (1) described above. For example, the fluoropolymer may be curable, non-curable, amorphous or non-amorphous.

[0090] Fluoropolymers may form part of the compound.

[0091] An article comprising a cured compound, said cured compound comprising, prior to curing, a fluoropolymer made by polymerizing a halo(alkyl vinyl) ether, wherein the halo(alkyl vinyl) ether and the method of preparing the halo(alkyl vinyl) ether are as described above. Examples of articles include, but are not limited to, gaskets, seals, tubing, sheets, washers, or O-rings.

[0092] An article comprising a cured compound, said cured compound comprising, prior to curing: a fluoropolymer. The fluoropolymer is as described above and contains repeating units also as described above. Examples of articles include, but are not limited to, gaskets, seals, tubing, sheets, washers, or O-rings.

[0093] The process claimed below allows the production of halo(alkyl vinyl)ethers in higher yields than known processes. Thus, the halo(vinyl ethers) produced can be produced economically and used to prepare new fluoropolymers having potentially improved properties compared to known fluoropolymers.

[0094] Examples

[0095] The following examples are given to better illustrate the method of the present invention, but should not be considered to limit the present invention described in the appended claims. Unless otherwise stated, all parts and percentages reported in the examples are by weight. The following table describes the abbreviations used in the examples:

[0096] Table 1. List of abbreviations used in the examples.

[0097]

[0098]

[0099] Example 1: Preparation of difluoromethyl 2,2-difluorovinyl ether (CF3C(Cl)(H)OCF2H) by dehalogenation of isoflurane (CF3C(Cl)(H)OCF2H) 2 =CHOCHF 2 )

[0100] Anhydrous zinc powder (492.0 g, 7.524 mol) and anhydrous DMF (1480 g) were loaded into a gallon Hastalloy-C autoclave with a cooling coil and a pressure relief device. 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. The contents were then cooled to 15 ° C and discharged. GC-FID analysis showed that isoflurane was completely converted into difluoromethyl 2,2-difluorovinyl ether. The mixture was filtered and cooled to remove excess zinc and zinc salts. The resulting filtrate was distilled under reduced pressure to obtain crude difluoromethyl 2,2-difluorovinyl ether (840 g) contaminated with trace amounts of DMF with a purity of >95% (w / w). The crude product was then redistilled at atmospheric pressure and the fractions collected at 17-20°C were combined to obtain difluoromethyl 2,2-difluorovinyl ether (759.8 g) as a clear colorless liquid with a purity >99% (w / w). The chemical structure was confirmed by NMR.

[0101] Example 2: Preparation of TFE-HHPMVE-8-CNVE copolymer

[0102] A polymer containing comonomers of tetrafluoroethylene (TFE), 2-(difluoromethoxy)-1,1-difluoroethylene (HHPMVE) and perfluoro-8(cyano-5-methyl-3,6-dioxa-1-octene) (8-CNVE) was prepared as follows. 2215 g of 2% (w / w) CF 3 CF 2 CF 2 OCF(CF 3 )CH 2 OPO(OH) 2The ammonium salt solution was loaded into a four-liter mechanically stirred water-jacketed stainless steel reactor and oxygen was removed by repeated pressurization / decompression cycles with nitrogen. Nitrogen was removed by repeated pressurization / decompression cycles with TFE. When the nitrogen content in the head space was less than 1% (w / w) and the reactor pressure was 0.03MPaG, 100ml of HHPMVE was fed into the reactor. The reactor was heated to 80°C and pressurized to 1.72MPaG with TFE. Then 3.6ml of 8-CNVE was loaded into the reactor. Then 40ml of an initiator solution of 2.5% (w / w) ammonium persulfate and 5.0% (w / w) disodium hydrogen phosphate heptahydrate was loaded into the reactor to start polymerization. Additional TFE was fed into the reactor to maintain a pressure of 1.72MPaG. When 70 grams of TFE were added, an additional 50ml of HHPMVE was fed into the reactor. When 100 grams of TFE were added, another 3.6 ml of 8-CNVE was fed into the reactor. When 140 grams of TFE were added, another 50 ml of HHPMVE was fed into the reactor. After a total of 200 grams of TFE were fed into the reactor, the reactor was vented to reduce the pressure and the polymerization was stopped. A 15.8% (w / w) solid emulsion was obtained by polymerization. The emulsion was coagulated with potassium aluminum sulfate and dried at 70°C. By NMR testing, the composition of the resulting polymer was 71.9 mol% TFE, 27.5 mol% HHPMVE, and 0.6 mol% 8-CNVE. The polymer had a glass transition temperature of 4.0°C and a melting temperature of 85.8°C.

[0103] Example 3: Preparation of VF2-HHPMVE binary copolymer

[0104] A polymer containing a comonomer of vinylidene fluoride (VF2) and 2-(difluoromethoxy)-1,1-difluoroethylene (HHPMVE) is prepared as follows. 2200 grams of deionized water is charged into a four-liter mechanically stirred water-jacketed stainless steel reactor and oxygen is removed by repeated pressurization / decompression cycles with nitrogen. Nitrogen is removed by repeated pressurization / decompression cycles with VF2. When the nitrogen content in the head space is less than 1% (w / w) and the reactor pressure is 0.03MPaG, 52ml of HHPMVE is fed into the reactor. The reactor is heated to 80°C and pressurized to 0.83MPaG with VF2. Then 20ml of an initiator solution of 10% (w / w) ammonium persulfate is charged into the reactor to start polymerization. Additional VF2 is fed into the reactor to maintain a pressure of 0.83MPaG. After 40, 80, 120, 160 and 200 grams of VF2 were fed, 24 ml portions of HHPMVE were fed into the reactor. After a total of 240 grams of VF2 were fed, the reactor was vented to reduce the pressure and the polymerization was stopped. An additional 89 ml of initiator solution was added throughout the polymerization to maintain the reaction. A 16.8% (w / w) solid emulsion was obtained from the 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.

[0105] Example 4: Preparation of TFE-HHPMVE binary copolymer

[0106] A polymer containing tetrafluoroethylene (TFE) and 2-(difluoromethoxy)-1,1-difluoroethylene (HHPMVE) as comonomers was prepared as follows. 2215 g of 2% (w / w) CF 3 CF 2 CF 2 OCF(CF 3 )CH 2 OPO(OH) 2The ammonium salt solution was charged into a four-liter mechanically stirred water-jacketed stainless steel reactor and oxygen was removed by repeated pressurization / decompression cycles with nitrogen. Nitrogen was removed by repeated pressurization / decompression cycles with TFE. When the nitrogen content in the head space was less than 1% (w / w) and the reactor pressure was 0.03MPaG, 71.5ml of HHPMVE was fed into the reactor. The reactor was heated to 80°C and pressurized to 1.72MPaG with TFE. Then 40ml of an initiator solution of 2.5% (w / w) ammonium persulfate and 5.0% (w / w) disodium hydrogen phosphate heptahydrate was charged into the reactor to start polymerization. Additional TFE was fed into the reactor to maintain a pressure of 1.72MPaG. After a total of 400 grams of TFE were fed, the reactor was vented to reduce the pressure and the polymerization was stopped. A 21.5% (w / w) solid emulsion was obtained by polymerization. The emulsion was coagulated with potassium aluminum sulfate and dried at 70°C. The polymer has a melting temperature of +304.4°C.

[0107] Example 5: Preparation of TFE / HHPMVE / PMVE / 8-CNVE tetrapolymer

[0108] A polymer containing comonomer units of tetrafluoroethylene (TFE), perfluoro(methyl vinyl ether) (PMVE), 2-(difluoromethoxy)-1,1-difluoroethylene (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 autoclave. The stream contained 0.09% (w / w) ammonium persulfate, 0.53% (w / w) disodium hydrogen phosphate heptahydrate, 3.1% (w / w) CF 3 CF 2 CF 2 OCF(CF 3 )CH 2 OPO(OH) 2 ammonium salt and 0.5% (w / w) carboxylic acid-terminated poly(hexafluoropropylene oxide) ( 157FSL). Using a diaphragm compressor, a mixture of TFE (67.4g / hr) and PMVE (97.5g / hr) was fed at a constant rate. HHPMVE was fed at a rate of 4.5g / hr and 8-CNVE was fed at a rate of 5.5g / hr. The temperature was maintained at 80°C and the pressure was maintained at 4.1MPaG throughout the reaction. The polymer emulsion was continuously discharged through a drain valve and the unreacted monomers were discharged. The polymer was coagulated with magnesium sulfate heptahydrate and dried at 70°C. The composition of the resulting polymer was 75.1mol% TFE, 22.5mol% PMVE, 1.7mol% HHPMVE and 0.7mol% 8-CNVE. The polymer has a viscosity of 0.1g polymer in 100g PP-11 (F2 Chemicals Ltd, Preston, UK) had an intrinsic viscosity of 1.33 measured in solution in 1% propylene glycol 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 melt transition.

Claims

1. A method for preparing a halogenated (alkyl vinyl) ether, the method comprising the following steps: heating a reaction mixture comprising a combination of: i) metals; ii) a solvent; and iii) a halogenated (alkylethyl) ether according to formula (1) RCF2OC(H)(X)CF2Y(1) wherein R is independently H, F, Cl, Br, CF2H, CF3, CF2CF2H, 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, wherein X and Y are not both F; to form a reaction product mixture comprising the halo(alkyl vinyl) ether, the solvent, unreacted metal and the metal salt.

2. The method according to claim 1, wherein: The halogenated (alkyl vinyl) ether conforms to formula (2) RCF2OC(H)=CF2 (2) wherein R is as defined for formula (1).

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

4. The method according to any one of the preceding claims, further comprising the steps of: (I) combining the metal and the solvent in a reactor; (II) flushing the metal and solvent combination with nitrogen; as well as (III) adding the halogenated (alkylethyl) ether to the combination of the metal and the solvent to form the reaction mixture; and (IV) maintaining the reaction mixture at a temperature of RT°C to 160°C for 2 to 15 hours, preferably 100°C-160°C, preferably 5-15 hours.

5. The method according to claim 3, further comprising the steps of: (IV) cooling the reaction product mixture to a temperature of 2°C to 20°C; and (V) filtering the reaction product mixture to remove the metal and metal salt to form a filtered reaction product mixture, the reaction product mixture comprising the solvent and the halo(alkyl vinyl) ether; and (VI) purifying the halo(alkyl vinyl) ether.

6. The method according to claim 4, wherein: The purification is carried out by distillation.

7. A method according to any one of the preceding claims, wherein: The molar ratio of metal to halogenated (alkylethyl) ether in the reaction mixture is 1:0.5 to 1:1.

5.

8. A fluoropolymer prepared by polymerizing a halo(alkyl vinyl) ether prepared by the process of any one of claims 1 to 7, wherein the fluoropolymer is curable.

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

10. The fluoropolymer according to claim 9, wherein The additional monomers are one or more monomers selected from the group consisting of tetrafluoroethylene (TFE), vinyl fluoride (VF), perfluoro(alkyl vinyl) ether (PAVE), ethylene, tetrafluoropropylene (TFP), ester vinyl ether, methyl perfluoro(5-methyl-4,7-dioxacyclohexane-8-enoic acid ethyl ester) (EVE), perfluoro(4-methyl-3,6-dioxaoct-7-ene)sulfonyl fluoride (PSEPVE), vinylidene fluoride (VF2), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), propylene (P), MOVE, pentafluoropropylene (HPFP), perfluoro(3-methoxypropyl vinyl) ether (MV-31), and the like.

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 a long-chain perfluorovinyl ether.

12. The fluoropolymer according to any one of claims 8 to 11, wherein The halo(alkyl vinyl) ether is further polymerized with a cure site monomer.

13. The fluoropolymer according to claim 12, wherein The cure site monomer is perfluoro(8-cyano-5-methyl-3,6-dioxaoct-1-ene), CF2=CF-O(CF2) n CN (straight chain CNVE), CF2=CF-O [CF2-CFCF3-O] n -CF2-CFCF3CN, or CF2=CF-[OCF2CFCF3] x -O-(CF2) n CN, CF2=CF-O-(CF2) n -O-CF(CF3)CN.

14. A fluoropolymer comprising: a. repeating unit (I), (I)-(C(R 1 )(H)CF2)-, where R 1 It is -OCRF2, wherein R is H, F, Cl, Br, CF2H, CF3, CF2CF2H, a linear perfluoroalkyl group having 1 to 12 carbon atoms, or a cyclic perfluoroalkyl group having 1 to 12 carbon atoms.

15. The fluoropolymer according to claim 14, further comprising b. having one or more repeating units of formula (II), (III), (IV), or (V): (II)-(CF2CF2)-; (III) -(CH2-CF2)-; (IV)-(CF2C(R 1 )F)-, where R 1 is -(OCF2C(F)(CF3)OCF2CF2C≡N); (V)-(C(R 1 )(F)CF2)-。 16. The fluoropolymer according to claims 8 to 15, wherein The fluoropolymer is curable.

17. An article comprising a cured compound, said cured compound comprising, prior to curing: a fluoropolymer prepared by polymerizing a halo(alkyl vinyl) ether made by the process of any one of claims 1-7.

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

19. An article comprising a cured compound comprising, prior to curing, the fluoropolymer according to any one of claims 14 or 15.

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