Process for producing perfluorocompounds and process for producing fluoropolymers

Abstract

Provided are a perfluorinated compound manufacturing method that can easily obtain a perfluorinated compound capable of producing a high-molecular-weight polymer in a polymerization reaction, the perfluorinated compound manufacturing method, and a fluorine-containing polymer manufacturing method using the same. A perfluorinated compound manufacturing method characterized by obtaining any of a crude product X of a crude product A or a crude product B by any of a process A or a process B, the process A being a process of obtaining the crude product A containing a perfluoroallyl ether compound by reacting a perfluoroalkoxide with a perfluoroallylating agent, the process B being a process of obtaining the crude product B containing a perfluoro-alpha-olefin compound by a dechlorination reaction of a chlorofluorocarbon compound, mixing the crude product X with a radical source, bringing a radical generated from the radical source into contact with the crude product X, and obtaining a crude product Y containing any of a perfluoroallyl ether compound or a perfluoro-alpha-olefin compound.

Description

Technical Field

[0001] This invention relates to methods for manufacturing perfluorinated compounds and methods for manufacturing fluoropolymers. Background Technology

[0002] Perfluorinated compounds, such as perfluoroallyl ether compounds and perfluoroalpha-olefin compounds, are used as monomers for manufacturing fluoropolymers.

[0003] As a method for manufacturing such a fluoropolymer, Patent Document 1 discloses the following method: after copolymerizing tetrafluoroethylene with a monomer represented by CF2=CFCF2OCF2CF2SO2F in the presence of a free radical polymerization initiator at a temperature of 100~200°C, the -SO2F group is hydrolyzed and acidified to convert it into a sulfonic acid group.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2010-18674 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] Polymers obtained using perfluorinated compounds sometimes require high molecular weights depending on their application. For example, when these polymers are used in the manufacture of electrolyte membranes, if the polymer has a low molecular weight, the mechanical strength of the electrolyte membrane will be insufficient. Therefore, high molecular weight polymers are particularly required in such fields.

[0009] The inventors manufactured a polymer by referring to the manufacturing method described in Patent Document 1, and found that the molecular weight was insufficient and there was room for improvement.

[0010] The present invention was made in view of the above-mentioned problems, and its objective is to provide a method for manufacturing a perfluorinated compound that can be easily obtained in a polymerization reaction to produce a high molecular weight polymer, a method for manufacturing a perfluorinated compound, and a method for manufacturing a fluoropolymer using the same.

[0011] Solution for solving the problem

[0012] The inventors conducted in-depth research on the above-mentioned issues and discovered that by including the following steps in the manufacturing method of perfluorinated compounds, a perfluorinated compound capable of producing high molecular weight polymers in a polymerization reaction using perfluorinated compounds can be obtained, thus completing the present invention. The steps are: obtaining a crude product containing any perfluorinated compound among perfluoroallyl ether compounds or perfluoroα-olefin compounds through a synthesis reaction, and then mixing the crude product X with a free radical source to bring the free radicals generated by the free radical source into contact with the crude product X.

[0013] That is, the inventors discovered that the above-mentioned problems can be solved by the following configuration.

[0014] [1] A method for manufacturing a perfluorinated compound, characterized in that crude product A or any crude product X from crude product B is obtained through any step A or step B, wherein step A is a step of reacting a perfluorinated alkoxide with a perfluorinated allylating agent to obtain crude product A containing a perfluorinated allyl ether compound, and step B is a step of obtaining crude product B containing a perfluorinated α-olefin compound through a dechlorination reaction of a chlorofluorocarbon compound.

[0015] The crude product X is mixed with a free radical source, and the free radical generated by the free radical source is brought into contact with the crude product X to obtain a crude product Y containing any perfluorinated compound among the aforementioned perfluoroallyl ether compound or the aforementioned perfluoro α-olefin compound.

[0016] [2] The method for manufacturing perfluorinated compounds according to [1] is carried out under the condition that the mixing of the crude product X and the free radical source is substantially free of polymerizable compounds other than the polymerizable compounds contained in the crude product X.

[0017] [3] According to the method for manufacturing perfluorinated compounds described in [1] or [2], wherein the ratio of the peak area of ​​the perfluorinated compound detected during gas chromatography analysis of the aforementioned crude product X to the sum of the peak areas is set as X%.

[0018] Furthermore, when the area of ​​the perfluorinated compound peak detected during gas chromatography analysis of the aforementioned crude product Y is defined as the ratio of the area of ​​all peaks to the total area of ​​all peaks, Y% is used.

[0019] The modification rate D calculated by the following formula (M) is less than 15%.

[0020] Modification rate D[%]=100×(XY) / X···(M)

[0021] [4] A method for manufacturing a perfluorinated compound according to any one of [1] to [3], wherein the aforementioned perfluorinated alkoxide is a compound represented by the following formula (S1), and the aforementioned perfluorinated allylating agent is a compound represented by the following formula (S2).

[0022] CF(-Q 11 (-Q) 12 )-OM···(S1)

[0023] CF2 = CFCF2 - Z S ...(S2)

[0024] In equation (S1), Q 11 and Q12 Each of the following can be independently a perfluoroalkyl group optionally having -SO2F, a monovalent group of a perfluoroalkyl group optionally having -SO2F whose -CF2- is replaced by an ether-like oxygen atom, or a fluorine atom. M is a monovalent metal element.

[0025] In equation (S2), Z S -OS(O)2R S1 , chlorine atom, bromine atom or iodine atom, R S1 It indicates a fluorine atom or a perfluoroalkyl group.

[0026] [5] According to the method for manufacturing perfluorinated compounds described in [4], the perfluorinated allyl ether compound obtained by reacting the compound shown in formula (S1) with the compound shown in formula (S2) is the compound shown in formula (F1).

[0027] CF(-Q 11 (-Q) 12 )-O-CF2CF=CF2···(F1)

[0028] Q in equation (F1) 11 and Q 12 respectively with Q in the aforementioned formula (S1) 11 and Q 12 They have the same meaning.

[0029] [6] The method for manufacturing a perfluorinated compound according to [4], wherein the compound represented by the aforementioned formula (S1) is the compound represented by the following formula (S1-1) or the compound represented by the following formula (S1-2).

[0030] FO2S-Q 21 -CF2-OM···(S1-1)

[0031] CF(-Q 22 -SO2F)(-Q 23 -SO2F)-OM···(S1-2)

[0032] In equation (S1-1), Q 21 It is a perfluoroalkyl group, or a divalent group of a perfluoroalkyl group whose -CF2- is replaced by an ether-oxygen atom.

[0033] In equation (S1-2), Q 22 and Q 23 Each is independently a perfluoroalkylene group, or a divalent group of a perfluoroalkylene group whose -CF2- is replaced by an ether-oxygen atom.

[0034] [7] According to the method for manufacturing perfluorinated compounds described in [6], the perfluorinated allyl ether compound obtained by reacting the compound shown in formula (S1-1) with the compound shown in formula (S2) is the compound shown in formula (F1-1), and the perfluorinated allyl ether compound obtained by reacting the compound shown in formula (S1-2) with the compound shown in formula (S2) is the compound shown in formula (F1-2).

[0035] FO2S-Q 21 -CF2-O-CF2CF=CF2···(F1-1)

[0036] CF(-Q 22 -SO2F)(-Q 23 -SO2F)-O-CF2CF=CF2···(F1-2)

[0037] Q in equation (F1-1) 21 Q in the aforementioned equation (S1-1) 21 They have the same meaning.

[0038] Q in equation (F1-2) 22 and Q 23 Each of them corresponds to Q in the aforementioned equation (S1-2) 22 and Q 23 They have the same meaning.

[0039] [8] A method for manufacturing a perfluorinated compound according to any one of [1] to [3], wherein the aforementioned chlorofluorocarbon compound is a compound represented by the following formula (S3).

[0040] ClCF2-CFCl-CF2-CF2-Q 13 -SO2F···(S3)

[0041] In equation (S3), Q 13 It is a single bond, an optional perfluoroalkylene group having -SO2F, or an optional perfluoroalkylene group having -SO2F and a -CF2- divalent group replaced by an ether-oxygen atom.

[0042] [9] According to the method for manufacturing perfluorinated compounds described in [8], the perfluorinated α-olefin compound obtained by the dechlorination reaction of the chlorofluorocarbon compound is a compound represented by the following formula (F2).

[0043] CF2 = CF - CF2 - CF2 - Q 13 -SO2F···(F2)

[0044] Q in equation (F2) 13 Q in the aforementioned equation (S3) 13 They have the same meaning.

[0045]

[10] The method for manufacturing a perfluorinated compound according to [9], wherein the compound represented by the aforementioned formula (F2) is the compound represented by the following formula (F2-1).

[0046] CF2 = CF - (CF2CF2) X2 -SO2F···(F2-1)

[0047] In equation (F2-1), x2 is an integer from 1 to 6.

[0048]

[11] The method for manufacturing a perfluorinated compound according to any one of [1] to

[10] , wherein the crude product Y is further purified.

[0049]

[12] The method for manufacturing perfluorinated compounds according to

[11] wherein the mixing of the crude product X with the free radical source and the purification of the crude product Y are carried out in the same apparatus.

[0050]

[13] A method for manufacturing a fluoropolymer, characterized in that a perfluorinated compound obtained by the manufacturing method of any one of the perfluorinated compounds described in [1] to

[12] is polymerized at a temperature of 100°C or higher to obtain a fluoropolymer.

[0051] The effects of the invention

[0052] According to the present invention, a method for manufacturing a perfluorinated compound that can be easily obtained in a polymerization reaction to produce a high molecular weight polymer, and a method for manufacturing a fluoropolymer using the perfluorinated compound are provided. Detailed Implementation

[0053] The meanings of the terms used in this invention are as follows.

[0054] α-olefins are olefins in which the carbon-carbon double bond exists at the terminal (α-position) carbon.

[0055] [Methods for manufacturing perfluorinated compounds]

[0056] The method for manufacturing perfluorinated compounds of the present invention includes either step A or step B. Step A involves reacting a perfluorinated alkoxide with a perfluorinated allylating agent to obtain a crude product A containing a perfluorinated allyl ether compound. Step B involves obtaining a crude product B containing a perfluorinated α-olefin compound through a dechlorination reaction of a chlorofluorocarbon compound. Through this process, any crude product X from crude product A or crude product B can be obtained.

[0057] The method for manufacturing perfluorinated compounds according to the present invention includes the following step (hereinafter also referred to as "step C"): mixing the crude product X with a free radical source, and contacting the free radical generated by the free radical source with the crude product X to obtain a crude product Y comprising any perfluorinated compound selected from the perfluoroallyl ether compound or the perfluoroalpha olefin compound. Hereinafter, step C performed using crude product A will be referred to as "step C1", and the obtained product will also be referred to as "crude product C1". Furthermore, step C performed using crude product B will be referred to as "step C2", and the obtained product will also be referred to as "crude product C2". Crude product Y is either crude product C1 or crude product C2.

[0058] According to this manufacturing method, perfluorinated compounds capable of producing high molecular weight polymers in polymerization reactions can be easily obtained. Here, "easily obtained perfluorinated compounds" refers to the excellent manufacturing efficiency and low cost of perfluorinated compounds.

[0059] The details of the reason are not yet clear, but it is speculated to be based on the following reasons.

[0060] In the synthesis of perfluoroallyl ethers and perfluoroalpha-olefins, various compounds are generated as impurities in the crude product X via side reactions during the synthesis process. Furthermore, when solvents are used in these reactions, residual solvents and solvent decomposition products are also included as impurities in the crude product X. If such impurities are present in the crude product X, its use in polymerization can sometimes lead to chain migration of impurities, making it difficult to obtain high molecular weight polymers. This tendency is particularly pronounced at high polymerization temperatures and can become a significant problem.

[0061] As a solution to this problem, there are methods to separate the aforementioned impurities from the perfluorinated compounds, which sometimes have similar volatility to the perfluorinated compounds. Therefore, when separating the perfluorinated compounds from the impurities in the crude product X for polymerization, obtaining perfluorinated compounds that can yield high molecular weight polymers requires the use of distillation columns with high theoretical plate numbers, which presents problems related to purification efficiency and cost.

[0062] Regarding this problem, the inventors hypothesize that by implementing the above-described step C, the impurities in the crude product X are decomposed or modified due to the action of free radicals, resulting in a perfluorinated compound that can produce high molecular weight polymers in the polymerization reaction.

[0063] Hereinafter, the method for manufacturing perfluorinated compounds of the present invention, having steps A and C1, will be described as the first embodiment, and the method for manufacturing perfluorinated compounds of the present invention, having steps B and C2, will be described as the second embodiment. Each embodiment will be described in detail.

[0064] [First Embodiment]

[0065] The method for manufacturing the perfluorinated compound in the first embodiment includes step A and step C1.

[0066] <Process A>

[0067] Step A is a step in which a perfluoroalkoxide is reacted with a perfluoroallylating agent to obtain a crude product A containing a perfluoroallyl ether compound.

[0068] As a perfluoroalkoxide, the compound shown in the following formula (S1) is preferred (hereinafter also referred to as "compound (S1)").

[0069] CF(-Q 11 (-Q) 12 )-OM···(S1)

[0070] In equation (S1), Q 11 and Q 12 Each is independently a perfluoroalkyl group optionally having -SO2F, a monovalent group of a perfluoroalkyl group optionally having -SO2F whose -CF2- is replaced by an ether-oxygen atom, or a fluorine atom.

[0071] The perfluoroalkyl group may be either linear or branched.

[0072] In terms of suppressing the decrease in the ion exchange capacity of the polymer, the perfluoroalkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and particularly preferably 1 to 4.

[0073] When a perfluoroalkyl group has -SO2F, the number of -SO2F atoms can be chosen to be one or more. -SO2F can be bonded to any carbon atom, but is preferably bonded to the terminal carbon atom.

[0074] The monovalent group may have one or more ether oxygen atoms, preferably two or fewer. The ether oxygen atoms are preferably located between carbon-carbon bonds of the perfluoroalkyl group.

[0075] In formula (S1), M is a monovalent metal element. Examples of monovalent metal elements include Na, K, Cs, and Ag, with K being the preferred choice.

[0076] From the viewpoint of being able to obtain a perfluoroallylic ether compound suitable for manufacturing a polymer for an electrolyte membrane, compound (S1) preferably has -SO2F, and is particularly preferred to be a compound shown in the following formula (S1-1) (hereinafter also referred to as "compound (S1-1)") or a compound shown in the following formula (S1-2) (hereinafter also referred to as "compound (S1-2)").

[0077] FO2S-Q 21 -CF2-OM···(S1-1)

[0078] CF(-Q 22 -SO2F)(-Q 23 -SO2F)-OM···(S1-2)

[0079] In equation (S1-1), Q 21 It is a perfluoroalkyl group, or a divalent group of a perfluoroalkyl group whose -CF2- is replaced by an ether-oxygen atom.

[0080] The perfluoroalkylene group may be either linear or branched.

[0081] In terms of suppressing the decrease in the ion exchange capacity of the polymer, the perfluoroalkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and particularly preferably 1 to 4.

[0082] The number of ether-containing oxygen atoms in the divalent group is optionally one or more, preferably two or fewer. The ether-containing oxygen atoms are preferably located between carbon-carbon bonds of the perfluoroalkyl group. Q in formula (S1-1) 21 The optimal choice is CF2.

[0083] In equation (S1-2), Q 22 and Q 23 Each is independently a perfluoroalkylene group, or a divalent group of a perfluoroalkylene group whose -CF2- is replaced by an ether-oxygen atom.

[0084] The perfluoroalkylene group may be either linear or branched.

[0085] In terms of suppressing the decrease in the ion exchange capacity of the polymer, the perfluoroalkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and particularly preferably 1 to 4.

[0086] The divalent group may have one or more ether oxygen atoms, preferably two or fewer. The ether oxygen atoms are preferably located between carbon-carbon bonds of the perfluoroalkyl group. Q in formula (S1-2) 22 and Q 23 The optimal choice for each is CF2.

[0087] As a perfluoroallylating agent, the compound shown in the following formula (S2) is preferred (hereinafter also referred to as "compound (S2)").

[0088] CF2 = CFCF2 - ZS…(S2)

[0089] In equation (S2), Z S -OS(O)2R S1 1. Chlorine atom, bromine atom, or iodine atom. R S1 It is a fluorine atom or a perfluoroalkyl group.

[0090] The perfluoroalkyl group may be either linear or branched.

[0091] The perfluoroalkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

[0092] Step A is preferably carried out in the presence of an organic solvent. Specific examples of organic solvents include monoglyme, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and acetonitrile.

[0093] In process A, fluoride salts such as potassium fluoride can be used further.

[0094] There are no special restrictions on the reaction conditions in process A; known reaction conditions can be used.

[0095] (Crude product A)

[0096] The crude product A obtained through process A contains a perfluoroallyl ether compound, which is the target compound and is a type of perfluorinated compound, and further contains impurities other than perfluorinated compounds.

[0097] Impurities in crude product A can include various compounds generated through side reactions and organic solvents used in process A.

[0098] The amount of perfluoroallyl ether compound contained in crude product A is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 85% by mass or more, and particularly preferably 95% by mass or more, relative to the total mass of crude product A.

[0099] From a manufacturing efficiency perspective, it is preferable that crude product A contains a relatively large amount of perfluoroallyl ether compound. However, even in small amounts, perfluoroallyl ether compounds with higher purity can be obtained, for example, through purification methods described later. Therefore, it is also acceptable for crude product A to contain a small amount of perfluoroallyl ether compound.

[0100] (Perfluoroallyl ether compounds)

[0101] Perfluoroallyl ether compounds are preferably those represented by the following formula (F1) (hereinafter also referred to as "monomer (F1)").

[0102] CF(-Q 11 (-Q) 12 )-O-CF2CF=CF2···(F1)

[0103] Q in equation (F1) 11 and Q 12 respectively with Q in equation (S1) 11 and Q 12 They have the same meaning.

[0104] From the perspective of being suitable for manufacturing polymers for electrolyte membranes, the monomer (F1) preferably has -SO2F, preferably a compound represented by the following formula (F1-1) (hereinafter also referred to as "monomer (F1-1)") or a compound represented by the following formula (F1-2) (hereinafter also referred to as "monomer (F1-2)").

[0105] FO2S-Q 21 -CF2-O-CF2CF=CF2···(F1-1)

[0106] CF(-Q 22 -SO2F)(-Q 23 -SO2F)-O-CF2CF=CF2···(F1-2)

[0107] Q in equation (F1-1) 21 Q in equation (S1-1) 21 They have the same meaning.

[0108] Q in equation (F1-2) 22 and Q 23 respectively with Q in equation (S1-2) 22 and Q 23 They have the same meaning.

[0109] <Process C1>

[0110] Step C1 is as follows: the crude product A is mixed with a free radical source, and the free radicals generated by the free radical source are brought into contact with the crude product A to obtain a crude product C1 containing the perfluoroallyl ether compound.

[0111] It is believed that the crude product C1 obtained through process C1 contains not only the perfluoroallyl ether compound, which is the target compound, but also impurities originally contained in the crude product A, as well as impurities generated by the decomposition or modification of these impurities due to the action of free radicals. It is speculated that through the decomposition and modification of impurities caused by the action of free radicals, the impurities contained in the crude product A are deactivated relative to free radicals, thereby enabling the polymer with a higher molecular weight to be obtained when the perfluoroallyl ether compound is used for polymerization.

[0112] Examples of free radical sources include organic peroxides, nitrogen-containing compounds, persulfates, halogen-containing compounds, sulfur-containing compounds, nitrogen-sulfur bond compounds, hydrogen peroxide, iodine, chlorine, bromine, and sulfur.

[0113] Examples of organic peroxides include acyl peroxides, alkyl peroxide esters, peroxydicarbonates, peroxycarbonates, peroxyketals, dialkyl peroxides, and hydroperoxides. Examples of nitrogen-containing compounds include azo compounds and amine compounds. Examples of sulfur-containing compounds include disulfides, monosulfides, sulfinic acids, and dialkyl sulfones. Examples of compounds containing nitrogen-sulfur bonds include sulfinamides.

[0114] In this regard, organic peroxides are preferred, dialkyl peroxides are more preferred, and bis(perfluoroalkyl) peroxides (e.g., (CF3)3COOC(CF3)3) and dialkyl peroxides (e.g., (CH3)3COOC(CH3)3) are particularly preferred, based on the principle of using the same initiator as the polymerization.

[0115] Two or more free radical sources can be used in combination.

[0116] From the perspective of further improving the effects of the present invention, the amount of free radical source added relative to 100 parts by weight of crude product A is preferably 0.01 to 2 parts by weight, more preferably 0.01 to 1 part by weight, and particularly preferably 0.03 to 0.3 parts by weight.

[0117] Process C1 is preferably carried out under heating conditions.

[0118] The heating temperature is preferably 120–180°C, and particularly preferably 150–170°C. If the heating temperature is above the lower limit, the heating time can be shortened, thus maximizing the efficiency of perfluorinated compound production. Conversely, if the heating temperature is below the upper limit, the decomposition and modification of the perfluorinated compound itself can be suppressed.

[0119] The heating time is preferably 1 to 120 hours, and particularly preferably 1 to 10 hours. If the heating time is above the lower limit, the residue of free radical sources can be suppressed. In addition, if the heating time is below the upper limit, the production efficiency of perfluorinated compounds can be improved.

[0120] The mixing of crude product A with the free radical source is preferably carried out under conditions where there are substantially no polymerizable compounds other than those contained in crude product A (hereinafter also referred to as "other polymerizable compounds A"). This suppresses the consumption of free radicals by other polymerizable compounds A, thus improving the reaction between the free radicals and impurities in crude product A.

[0121] Here, polymerizable compounds refer to compounds that have polymerizable groups. Examples of polymerizable groups include vinyl groups and fluorovinyl groups.

[0122] Examples of polymerizable compounds included in crude product A include perfluoroallyl ether compounds and compounds with polymerizable groups among the impurities. Examples of polymerizable compounds among the impurities include byproducts generated through the above-described process A.

[0123] Other polymeric compounds A include tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, fluorinated vinylidene fluoride, ethylene, and propylene.

[0124] In process C1, "under the condition that there are no other polymeric compounds A" means that the content of other polymeric compounds A is less than 0.1 parts by mass relative to 100 parts by mass of crude product A used in process C1.

[0125] The amount of perfluoroallyl ether compound contained in crude product C1 is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 85% by mass or more, and particularly preferably 95% by mass or more, relative to the total mass of crude product C1.

[0126] From a manufacturing efficiency perspective, it is preferable that the crude product C1 contains a relatively large amount of perfluoroallyl ether compound. However, even in the case of a small amount, perfluoroallyl ether compounds with higher purity can be obtained, for example, through purification as described later. Therefore, it is also acceptable for the crude product C1 to contain a small amount of perfluoroallyl ether compound.

[0127] As described above, in order to decompose and modify the aforementioned impurities through the action of free radicals, the contact between the free radicals and the crude product A in step C1 requires the application of appropriate temperature and time. During this process, due to the action of free radicals, the perfluoroallyl ether compound contained in the crude product A may sometimes decompose. From an efficiency standpoint, the decomposition of the perfluoroallyl ether compound is not preferred, but under contact conditions that inhibit the decomposition of the perfluoroallyl ether compound, the decomposition and modification of the aforementioned impurities may sometimes become insufficient.

[0128] Therefore, in this invention, from the perspective of fully decomposing and modifying the aforementioned impurities, it is preferable to perform step C1 under conditions where the perfluoroallyl ether compound undergoes a certain degree of decomposition. Specifically, it is preferable to set the contact conditions such that the modification rate D is below a certain value.

[0129] From the perspective of increasing the production of perfluorinated compounds, it is preferable to have a lower modification rate D calculated by the following formula (M). Specifically, the modification rate D is preferably 20% or less, more preferably 15% or less, and particularly preferably 5% or less.

[0130] The lower limit of the modification rate D is preferably 0%, and from the perspective of reliably decomposing and modifying impurities, it is preferably 0.5%, and more preferably 1.0%.

[0131] Modification rate D[%]=100×(XY) / X···(M)

[0132] In formula (M), X refers to the percentage (%) of the peak area of ​​the perfluoroallyl ether compound detected when performing gas chromatography analysis on the crude product A obtained in process A, relative to the sum of the peak areas of all peaks.

[0133] In formula (M), Y refers to the percentage (%) of the peak area of ​​the perfluoroallyl ether compound detected when the crude product C1 obtained in step C1 is analyzed by gas chromatography.

[0134] The modification rate D can be easily adjusted to the above values ​​by adjusting the amount of free radical source added, temperature, and time.

[0135] The crude product C1 containing the perfluoroallyl ether compound obtained in this way is preferably processed in step D1 described later, but it can also be used directly in the polymerization reaction. In this case, it is preferable that the impurities contained in the crude product C1 have little impact on the polymerization. For example, it is preferable to use perfluorinated peroxide as a free radical source, and to use the same solvent in step A as the solvent used to polymerize the perfluoroallyl ether compound.

[0136] <Process D1>

[0137] The method for manufacturing the perfluorinated compound in the first embodiment preferably includes a step D1 for purifying the crude product C1 after obtaining the crude product C1 in step C1. This yields a perfluorinated compound of high purity suitable for polymerization, specifically the perfluoroallyl ether compound of the first embodiment.

[0138] There are no particular limitations on the purification method; examples include washing with water, distillation, solvent-based extraction, or adsorption of impurities based on desiccants, adsorbents, etc., and multiple methods can be combined. Among these, distillation is preferred from the perspective of easily recovering high-purity perfluorinated compounds.

[0139] Distillation is preferably performed using a distillation apparatus equipped with a packed column or a plate column. The theoretical plate number of the packed column or plate column is preferably 10 to 100, and particularly preferably 10 to 80. According to the method for manufacturing perfluorinated compounds in the first embodiment, since step C1 is included, high-purity perfluorinated compounds can be obtained even with a low theoretical plate number in the packed column or plate column. The packing material in the packed column can be a regular packing material or an irregular packing material. Examples of packing materials include Helipack, coil rings, Pall rings, Dixon packing, and Goodroll Packing (all manufactured by TO-TOKU ENGINEERING CO.,LTD).

[0140] The amount of perfluoroallyl ether compound contained in the purified product obtained by step D1 is preferably 95 to 100% by mass relative to the total mass of the purified product, and particularly preferably 99 to 100% by mass.

[0141] From the perspective of simplifying the manufacture of perfluorinated compounds, steps C1 and D1 are preferably performed in the same apparatus. Examples of methods for performing this in the same manufacturing apparatus include: a method where, after step C1, composition A is not removed from the apparatus and step D1 is performed directly; or a method where crude product A and a free radical source are continuously supplied to the apparatus performing step D1, while steps C1 and D1 are performed simultaneously, and the compound from step D1 is continuously recovered. A more concrete example of this method is a method where a free radical source is supplied to a distillation column while distillation is being carried out.

[0142] Other processes can be performed between processes A, C1, and D1 in the first embodiment, or after process D1. For example, by performing processes such as washing, extraction and separation, and distillation between process A and process C1, perfluorinated compounds with higher purity can be obtained more efficiently.

[0143] <Applications>

[0144] When the perfluoroallyl ether compound obtained by the method for manufacturing perfluoro compounds in the first embodiment has a fluorosulfonyl group (-SO2F), the perfluoroallyl ether compound is suitable for use as a monomer component for manufacturing fluoropolymers containing sulfonic acid groups.

[0145] Fluoropolymers containing sulfonic acid groups are suitable for manufacturing electrolyte membranes.

[0146] [Second Implementation]

[0147] The method for manufacturing the perfluorinated compound in the second embodiment includes step B and step C2.

[0148] <Process B>

[0149] Process B is the process of obtaining crude product B containing perfluoroalpha olefins through the dechlorination reaction of chlorofluorocarbons.

[0150] From the perspective of obtaining perfluoroalpha olefin compounds suitable for manufacturing polymers for electrolyte membranes, chlorofluorocarbon compounds preferably have -SO2F, and compounds with the following formula (S3) are particularly preferred (hereinafter also referred to as "compound (S3)").

[0151] ClCF2-CFCl-CF2-CF2-Q 13 -SO2F···(S3)

[0152] In equation (S3), Q 13 It is a single bond, an optional perfluoroalkylene group having -SO2F, or an optional perfluoroalkylene group having -SO2F and a -CF2- divalent group replaced by an ether-oxygen atom.

[0153] The perfluoroalkylene group may be either linear or branched.

[0154] In terms of suppressing the decrease in the ion exchange capacity of the polymer, the perfluoroalkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and particularly preferably 1 to 4.

[0155] When the perfluoroalkyl group has -SO2F, the number of -SO2F atoms can be selected as one or more. -SO2F can be bonded to any carbon atom, and when the perfluoroalkyl group is branched, it is preferred to be bonded to the terminal carbon atom.

[0156] The number of ether oxygen atoms in the divalent group is optionally one or more, preferably two or less. The ether oxygen atoms are preferably located between carbon-carbon bonds of the perfluoroalkyl group.

[0157] Step B is preferably carried out in the presence of an organic solvent. Specific examples of organic solvents include ether-based organic solvents such as dioxane, alcohol-based organic solvents such as methanol, ethanol, isopropanol, and n-butanol, fatty acid-based organic solvents such as acetic acid, and amide-based organic solvents such as N,N-dimethylformamide and N,N-dimethylacetamide.

[0158] In process B, metals such as zinc can also be used.

[0159] The reaction conditions in process B are not particularly limited; for example, the reaction conditions described in Japanese Patent Publication No. 2002-528433 can be used.

[0160] (Crude product B)

[0161] The crude product B obtained through process B contains a perfluorinated α-olefin compound, which is the target compound and is a perfluorinated compound, and also contains impurities other than the perfluorinated compound.

[0162] Impurities in crude product B can include various compounds generated through side reactions and organic solvents used in process B.

[0163] The amount of perfluoroalpha olefin compound contained in crude product B is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 85% by mass or more, and particularly preferably 95% by mass or more, relative to the total mass of crude product B.

[0164] From a manufacturing efficiency perspective, it is preferable that crude product B contains a relatively large amount of perfluoroalpha-olefin compounds. However, even in small amounts, perfluoroalpha-olefin compounds of higher purity can be obtained, for example, through purification methods described later. Therefore, it is acceptable for crude product B to contain a small amount of perfluoroalpha-olefin compounds.

[0165] (Perfluoroalpha-olefin compounds)

[0166] From the perspective of polymers suitable for manufacturing electrolyte membranes, perfluoroalpha olefin compounds preferably have fluorosulfonyl groups, and compounds represented by the following formula (F2) are particularly preferred (hereinafter also referred to as "monomer (F2)").

[0167] CF2 = CF - CF2 - CF2 - Q 13 -SO2F···(F2)

[0168] Q in equation (F2) 13 With Q in equation (S3) 13 They have the same meaning.

[0169] From the perspective of ease of polymer manufacturing and ease of industrial implementation, the monomer (F2) is preferably a compound represented by the following formula (F2-1) (hereinafter also referred to as "monomer (F2-1)"). Particularly preferred is a compound represented by the following formula (F2-11) (hereinafter also referred to as "monomer (F2-11)").

[0170] CF2 = CF - (CF2CF2) X2 -SO2F···(F2-1)

[0171] CF2=CF-CF2CF2-SO2F···(F2-11)

[0172] In formula (F2-1), x2 is an integer from 1 to 6, preferably an integer from 1 to 3, and particularly preferably an integer from 1 to 2.

[0173] <Process C2>

[0174] Step C2 is as follows: mixing the crude product B with a free radical source, and contacting the free radicals generated by the free radical source with the crude product B to obtain the crude product C2 containing the perfluoro α-olefin compound.

[0175] It is believed that the crude product C2 obtained through process C2 contains not only the perfluoroalpha-olefin compound, which is the target compound, but also the impurities originally contained in the crude product B, and the impurities generated by the decomposition and modification of these impurities due to the action of free radicals. It is speculated that through the decomposition and modification of impurities caused by the action of free radicals, the impurities contained in the crude product B are deactivated relative to free radicals, thereby enabling the polymer with a high molecular weight to be obtained when the perfluoroalpha-olefin compound is used for polymerization.

[0176] The specific examples and optimization methods of the free radical source in process C2 are the same as those of the free radical source in process C1.

[0177] From the perspective of further improving the effects of the present invention, the amount of free radical source added is preferably 0.01 to 2 parts by mass relative to 100 parts by mass of crude product B, more preferably 0.01 to 1 part by mass, and particularly preferably 0.03 to 0.3 parts by mass.

[0178] Step C2 is preferably performed under heating conditions. The preferred methods for the heating temperature and heating time in step C2 are the same as those for the heating temperature and heating time in step C1.

[0179] The mixing of crude product B with the free radical source is preferably carried out under conditions where there are substantially no polymerizable compounds other than those contained in crude product B (hereinafter also referred to as "other polymerizable compounds B"). This suppresses the consumption of free radicals by other polymerizable compounds B, thus improving the reaction between the free radicals and impurities in crude product B.

[0180] The definition of polymeric compounds and specific examples of polymeric groups are as described above.

[0181] Examples of polymerizable compounds included in crude product B include perfluoroalpha-olefin compounds and compounds with polymerizable groups among the impurities. Examples of polymerizable compounds among the impurities include byproducts generated through the above-described process B.

[0182] The specific examples of other polymeric compounds B are the same as those of other polymeric compounds.

[0183] In step C2, "under the condition that there is no other polymerizable compound B in substance" means that the content of other polymerizable compound B is less than 0.1 parts by mass relative to 100 parts by mass of crude product B used in step C2.

[0184] The amount of perfluoroalpha olefin compounds contained in the crude product C2 is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 85% by mass or more, and particularly preferably 95% by mass or more, relative to the total mass of the crude product C2.

[0185] From a manufacturing efficiency perspective, it is preferable that the crude product C2 contains a relatively large amount of perfluoroalpha-olefin compounds. However, even in small amounts, perfluoroalpha-olefin compounds of higher purity can be obtained, for example, through purification methods described later. Therefore, it is also acceptable for the crude product C2 to contain a small amount of perfluoroalpha-olefin compounds.

[0186] As explained above, in step C1, from the perspective of fully decomposing and modifying the aforementioned impurities, step C2 is preferably carried out under conditions where the perfluoroα-olefin compound undergoes a certain degree of decomposition. Specifically, it is preferable to set the contact conditions such that the modification rate D is below a certain value.

[0187] From the perspective of increasing the yield of perfluorinated compounds, the lower the modification rate D calculated by the following formula (M), the better. Specifically, the modification rate D is preferably 20% or less, more preferably 15% or less, and particularly preferably 5% or less.

[0188] The lower limit of the modification rate D is preferably 0%, and from the perspective of reliably decomposing and modifying impurities, it is preferably 0.5%, and more preferably 1.0%.

[0189] Modification rate D[%]=100×(XY) / X···(M)

[0190] In formula (M), X refers to the percentage (%) of the peak area of ​​the perfluoro α-olefin compound detected when the crude product B obtained in process B is analyzed by gas chromatography relative to the sum of the peak areas of all peaks.

[0191] In formula (M), Y refers to the percentage (%) of the peak area of ​​the perfluoro α-olefin compound detected when the crude product C2 obtained in step C2 is analyzed by gas chromatography relative to the sum of the peak areas of all peaks.

[0192] By modulating the amount of free radical source added, the modification rate D can be easily adjusted to the above value.

[0193] The crude product C2 thus obtained, containing a perfluoroalpha olefin compound, is preferably processed through step D2 described later, or it can be directly used in the polymerization reaction. In this case, it is preferable that the impurities contained in the crude product C2 have a minimal impact on the polymerization; for example, it is preferable to use a perfluoroperoxide as the free radical source, and to use the same solvent in step B as the solvent used in the polymerization of the perfluoroalpha olefin compound.

[0194] <Process D2>

[0195] The method for manufacturing the perfluorinated compound in the second embodiment preferably includes a step D2 for purifying the crude product C2 after obtaining the crude product C2 in step C2. This yields a perfluorinated compound of high purity suitable for polymerization, the perfluorinated α-olefin compound of the second embodiment.

[0196] The specific examples and preferred methods of the purification method in step D2 are the same as those in step D1.

[0197] The content of perfluoroalpha olefin compounds in the purified product obtained by step D2 is preferably 95 to 100% by mass relative to the total mass of the purified product, and particularly preferably 99 to 100% by mass.

[0198] From the perspective of simplifying the manufacture of perfluorinated compounds, it is preferable to carry out process C2 and process D2 in the same apparatus.

[0199] Other processes can be performed between processes B, C2, and D2 in the second embodiment, or after process D2. Specific examples of these other processes are the same as in the first embodiment described above.

[0200] <Applications>

[0201] When the perfluorinated α-olefin compound obtained by the method for manufacturing the perfluorinated compound in the second embodiment has a fluorosulfonyl group (-SO2F), the perfluorinated α-olefin compound is suitable for use as a monomer component for manufacturing fluoropolymers containing sulfonic acid groups.

[0202] Fluoropolymers containing sulfonic acid groups are suitable for manufacturing electrolyte membranes.

[0203] [Manufacturing methods for fluoropolymers]

[0204] The method for manufacturing fluoropolymers of the present invention includes a polymerization step in which the perfluorinated compound (i.e., perfluoroallyl ether compound or perfluoroalpha olefin compound) obtained by the above method is polymerized at 100°C or above.

[0205] According to the method for manufacturing fluoropolymers of the present invention, since a perfluorinated compound obtained by the above method is used, a high molecular weight fluoropolymer can be obtained.

[0206] Examples of polymerization methods include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.

[0207] The polymerization process is preferably carried out under conditions that generate free radicals. Methods for generating free radicals include irradiation with ultraviolet light, gamma rays, electron beams, etc., and adding free radical polymerization initiators.

[0208] Specific examples of free radical polymerization initiators are the same as those shown above as free radical sources. The polymerization initiator described in Japanese Patent No. 5217708 is particularly preferred.

[0209] In the polymerization process, monomers other than the perfluorinated compounds mentioned above (hereinafter also referred to as "other monomers") can be used. Examples of other monomers include tetrafluoroethylene (hereinafter also referred to as "TFE"), trichlorofluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, ethylene, propylene, etc., among which TFE is preferred.

[0210] The polymerization temperature is above 100℃, preferably above 150℃, and particularly preferably above 160℃. The manufacturing efficiency of fluoropolymers is superior when the polymerization temperature is above 150℃.

[0211] The polymerization temperature is preferably below 190°C, and particularly preferably below 180°C. When the polymerization temperature is below 190°C, the decomposition rate of the free radical polymerization initiator becomes too fast, which is excellent in terms of making the polymerization control easier.

[0212] Polymerization conditions other than polymerization temperature can be appropriately adopted using well-known conditions.

[0213] When the fluoropolymer obtained in this manufacturing method has a fluorosulfonyl group (-SO2F), it can be used as a precursor polymer for manufacturing fluoropolymers containing sulfonic acid groups.

[0214] The Q value of the fluoropolymer obtained in this manufacturing method is preferably 0.2 to 60.0 mm. 3 / second, more preferably 0.5 to 55 mm 3 / second, further optimized to 0.8~50mm 3 / second, with a preferred thickness of 3.0–45mm. 3 / Second.

[0215] Here, a lower Q value for the fluoropolymer indicates a larger molecular weight, while a higher Q value indicates a smaller molecular weight. If the Q value of the fluoropolymer falls within the above range, the molecular weight is sufficiently high, and therefore, the solid polymer electrolyte membrane obtained using the fluoropolymer exhibits superior hot water resistance. The Q value was determined using the method described in the Examples section below.

[0216] Example

[0217] The present invention will be described in detail below with examples. Examples 1-1 to 1-8, 2-1 to 2-8, and 3-1 to 3-8 are examples, and examples 1-9 to 1-13, 2-9 to 2-13, and 3-9 to 3-12 are comparative examples.

[0218] The crude product Y described in the examples is designated as "monomer F", and the crude product X described in the comparative examples is designated as "monomer F'". Furthermore, the fluorosulfonyl-containing polymer of the examples is designated as "polymer F", and the fluorosulfonyl-containing polymer of the comparative examples is designated as "polymer F'". Additionally, the sulfonic acid-containing polymer of the examples is designated as "polymer H", and the sulfonic acid-containing polymer of the comparative examples is designated as "polymer H'". However, the present invention is not limited to these examples.

[0219] It should be noted that, unless otherwise specified, the mixing amounts of each component in the tables described below represent the quality benchmark.

[0220] [Monomer purity determination]

[0221] The purity of perfluoroallyl ether compounds or any perfluorinated compound (also referred to as "monomer" in the table) in the crude product was determined by gas chromatography (GC analysis) under the following conditions.

[0222] Device: Shimadzu Corporation GC-2030

[0223] Column: DB-1 (60m long, 0.25mm inner diameter ID, 1.00μm film thickness in liquid phase) Oven temperature: 40℃ (10 minutes) - 10℃ / minute - 240℃ (25 minutes)

[0224] Inlet temperature: 250℃

[0225] Flow split ratio: 1 / 50

[0226] Control mode: Pressure 100.0 kPa

[0227] Injection volume: 0.5 μL

[0228] Detector: FID

[0229] Detector temperature: 250℃

[0230] After the implementation of step A (or step B) and before the implementation of step C1 (or step C2), GC analysis of the crude product is performed under the above conditions. The ratio of the peak area of ​​any perfluorinated compound in the detected perfluoroallyl ether compound or perfluoro α-olefin compound to the sum of the peak area values ​​of all peaks is calculated, and this value is set as the monomer purity X [%).

[0231] In addition, after the implementation of step C1 (or step C2) and before the implementation of step D1 (or step D2), GC analysis of the crude product is performed under the above conditions. The ratio of the peak area of ​​any perfluorinated compound in the detected perfluoroallyl ether compound or perfluoro α-olefin compound to the sum of the peak area values ​​of all peaks is calculated, and this value is set as the monomer purity Y [%).

[0232] In addition, after the implementation of step D1 (or step D2), GC analysis of the purified product is performed under the above conditions. The ratio of the peak area of ​​any perfluorinated compound in the detected perfluoroallyl ether compound or perfluoro α-olefin compound to the sum of the peak area values ​​of all peaks is calculated, and this value is set as the monomer purity Z [%).

[0233] Using the obtained purity values ​​X and Y, the modification rate D (%) is calculated using the following formula (M).

[0234] Modification rate D[%]=100×(XY) / X···(M)

[0235] [Theoretical plate number of the distillation column]

[0236] The crude product is distilled using a glass or stainless steel distillation column filled with an irregular packing material (Helipack No. 1).

[0237] The theoretical plate number of a distillation column is determined by distilling a mixed solution containing two components with known relative volatility. Specifically, the concentration is calculated based on the rate of change of the composition ratio of the two components in the distillate solution relative to the composition ratio of the two components in the input solution, and the calculation is performed based on the concentration and relative volatility as follows.

[0238] Concentration = (Composition ratio of the two components in the distillate solution) / (Composition ratio of the two components in the added solution)

[0239] Theoretical plate number = Log 10 (Concentration) / Log 10 (Relative volatility) -1

[0240] In this specification, the theoretical plate number is determined using a mixed solution of HCFC-225ca (chemical formula: CF3CF2CHCl2) and HCFC-225cb (chemical formula: CClF2CF2CHClF) (relative volatility = 1.1423).

[0241] [Ion exchange capacity]

[0242] Acid-type fluoropolymer containing sulfonic acid groups was vacuum dried at 120°C for 12 hours, then impregnated in a 0.85 mol / g sodium hydroxide solution (solvent: water / methanol = 10 / 90 (mass ratio)) to neutralize the ion exchange groups. The neutralized sodium hydroxide solution was back-titrated with 0.1 mol / L hydrochloric acid to determine the ion exchange capacity of the acid-type fluoropolymer containing sulfonic acid groups.

[0243] [Proportions of each constituent unit]

[0244] Regarding the proportions of TFE units, PSAE units, and other constituent units in fluoropolymers containing fluorosulfonyl groups, for each polymer... 19 The results of the F-NMR measurements were obtained.

[0245] 19 F-NMR was performed at 282.7 MHz, with hexafluorobenzene as the solvent and CFCl3 as the chemical shift standard.

[0246] It should be noted that the proportions of each constituent unit in fluorinated polymers containing sulfonic acid groups are the same as those in fluorinated polymers containing fluorosulfonyl groups.

[0247] [Q value]

[0248] Using a flow testing apparatus (Shimadzu Corporation capillary rheometer flow testing apparatus, CFT-500D) equipped with a nozzle having an inner diameter of 1 mm and a length of 1 mm, fill the container to a cross-sectional area of ​​1 cm². 2 Polymer F or polymer F' is extruded from the nozzle at 260°C, 30 kg load, and a pressure of 2.94 MPa. The volumetric flow rate (mm) of the extruded polymer at which the extrusion speed stabilizes is then recorded. 3 ( / second) is set as the Q value.

[0249] [abbreviation]

[0250] For tetrafluoroethylene, perfluoroallyl ether compounds, free radical polymerization initiators, and organic solvents, use the following abbreviations.

[0251] TFE: Tetrafluoroethylene

[0252] PSAE: CF2=CFCF2OCF2CF2SO2F

[0253] BSAE: CF2=CFCF2OCF(-CF2SO2F)2

[0254] tBPO:(CH3)3COOC(CH3)3

[0255] PFtBPO:(CF3)3COOC(CF3)3

[0256] HFE-347pc-f:CF3CH2OCF2CF2H

[0257] HFC-52-13p: CF3(CF2)5H

[0258] HCFC-141b: CH3CCl2F

[0259] [Manufacturing of perfluorinated compounds]

[0260] <Example 1-1>

[0261] The crude product A-1 containing PSAE (perfluoroallyl ether compound) (monomer purity X: 97.00%) was synthesized via the synthetic route shown below (step A) according to the method described in the examples of U.S. Patent Application Publication No. 2005 / 0037265.

[0262] Option A

[0263]

[0264] 2500 g of crude product A-1 containing PSAE and 3.00 g of PFtBPO (1200 ppm relative to crude product A-1) were placed in an autoclave (hereinafter referred to as A / C, internal volume 2500 mL, stainless steel) and degassed by cooling with liquid nitrogen. Nitrogen was introduced into the gas phase section, and the autoclave was heated to an internal temperature of 160°C using an oil bath. The internal temperature was maintained at 160°C for 3 hours. After cooling to below 30°C, the gas inside the autoclave was purged to obtain crude product C1-1 containing PSAE (step C1). This was designated as monomer F-1. It should be noted that stirring during heating and cooling was performed using a double helix with blades, and the stirring speed was set to 250 rpm. The results are shown in Table 1.

[0265] <Example 1-2>

[0266] The crude product A-2 (monomer purity X: 97.10%) containing PSAE (perfluoroallyl ether compound) was synthesized in the same manner as in Example 1-1 (step A).

[0267] 2029 g of crude product A-2 containing PSAE and 0.7457 g of tBPO (368 ppm relative to crude product A-2) were placed in an autoclave (hereinafter referred to as A / C, internal volume 1500 mL, stainless steel) and degassed by cooling with liquid nitrogen. Nitrogen gas was introduced into the gas phase section, and the autoclave was heated to an internal temperature of 160°C using an oil bath. The internal temperature was maintained at 160°C for 3 hours. After cooling to below 30°C, the gas inside the autoclave was purged to obtain crude product C1-2 containing PSAE (step C1). It should be noted that stirring during heating and cooling was performed using anchor blades at a stirring speed of 250 rpm.

[0268] Next, the crude product C1-2 is distilled to obtain a purified product containing PSAE (step D1). It should be noted that the distillation column is made of glass and the packing material is Helipack No.1.

[0269] The purified product containing PSAE was designated as monomer F-2. The results are shown in Table 1.

[0270] <Example 1-3>

[0271] The crude product A-3 (monomer purity X: 99.49%) containing PSAE (perfluoroallyl ether compound) was synthesized in the same manner as in Example 1-1 (step A).

[0272] Using the crude product A-3 thus obtained, the conditions were changed as shown in Table 1, except that the process was the same as in Examples 1-2, to obtain crude product C1-3 and monomer F-3 (a purified product containing PSAE) obtained from it. The results are shown in Table 1.

[0273] <Example 1-4>

[0274] The crude product A-4 (monomer purity X: 99.82%) containing PSAE (perfluoroallyl ether compound) was synthesized in the same manner as in Example 1-1 (step A).

[0275] Next, 31.5 kg of crude product A-4 containing PSAE and 25.2 g of tBPO (800 ppm relative to crude product A-4) were added to a 40 L distillation column (material: stainless steel, packing: Helipack No. 2, theoretical plate number: 70, reflux ratio: 1) that had been pre-degassed and nitrogen-purged. The column was heated in an oil bath to an internal temperature of 160 °C and maintained at 160 °C for 3 hours. After cooling to an internal temperature of 30 °C, crude product C1-4 containing PSAE was obtained (step C1). It should be noted that the reflux ratio in this specification refers to the ratio of reflux flow rate to distillate flow rate (reflux flow rate / distillate flow rate).

[0276] Subsequently, the crude product C1-4 is not removed from the distillation column and is directly distilled to obtain a purified product containing PSAE (step D1). It should be noted that steps C1 and D1 are carried out in the same reaction vessel (distillation column).

[0277] The purified product containing PSAE was designated as monomer F-4. The results are shown in Table 1.

[0278] <Example 1-5>

[0279] Using the crude product A-2 obtained in Example 1-2, the conditions were changed as shown in Table 1, and the process was otherwise the same as in Example 1-2, to obtain the crude product C1-5 and the purified monomer F-5 (a purified product containing PSAE). The results are shown in Table 1.

[0280] <Example 1-6>

[0281] Crude product A-6 (monomer purity X: 99.90%) containing PSAE (perfluoroallyl ether compound) was synthesized in the same manner as in Example 1-1 (Step A).

[0282] Next, 589.5 g of crude product A-6 containing PSAE and 9.45 g of tBPO (16000 ppm relative to the mass of crude product A-6) were placed in an autoclave (hereinafter referred to as A / C, internal volume 1500 mL, stainless steel). The internal temperature was heated to 160°C using an oil bath and maintained at 160°C for 3 hours. After cooling to 30°C, crude product C1-6 containing PSAE was obtained (step C1).

[0283] Next, the crude product C1-6 is distilled to obtain a purified product containing PSAE (step D1). It should be noted that the distillation column is made of glass and the packing material is Helipack No.1.

[0284] The purified product containing PSAE was designated as monomer F-6. The results are shown in Table 1.

[0285] <Example 1-7>

[0286] The crude product A-7 (monomer purity X: 98.50%) containing BSAE (perfluoroallyl ether compound) was synthesized via the synthetic route shown below (step A) according to the method described in the examples of International Publication No. 2019-045063.

[0287]

[0288] Next, 200g of crude product A-7 containing BSAE and 0.032g of tBPO (160ppm relative to the mass of crude product A-7) were placed into an autoclave (hereinafter referred to as A / C, internal volume 200mL, stainless steel). The autoclave was heated in an oil bath until the internal temperature reached 160°C, and then maintained at 160°C for 3 hours. After cooling to 30°C, crude product C1-7 containing BSAE was obtained (step C1).

[0289] Next, the crude product C1-7 is distilled to obtain a purified product containing BSAE (step D1). It should be noted that the distillation column is made of glass and the packing material is Helipack No.1.

[0290] The purified product containing BSAE was designated as monomer F-7. The results are shown in Table 1.

[0291] <Example 1-8>

[0292] The crude product B-1 (monomer purity X: 99.44%) containing the perfluoro α-olefin compound shown in formula (F2-1) was synthesized using the chlorofluorocarbon compound shown in formula (S3-1) according to the method described in Example 1 of Japanese Patent Publication No. 2002-528433 (step A).

[0293] CF2=CF-CF2-CF2-SO2F···(F2-1)

[0294] ClCF2-CFCl-CF2-CF2-SO2F···(S3-1)

[0295] Next, 200g of crude perfluoroalpha olefin compound B-1 (containing formula (F2-1)) and 0.08g of PFtBPO (400ppm relative to the mass of crude product B-1) were placed into an autoclave (hereinafter referred to as A / C, internal volume 200mL, stainless steel). The autoclave was heated in an oil bath until the internal temperature reached 160°C, and then maintained at 160°C for 3 hours. After cooling to 30°C, crude perfluoroalpha olefin compound C2-1 (process C2) was obtained.

[0296] Next, the crude product C2-1 is distilled to obtain a purified product containing the perfluoroα-olefin compound represented by formula (F2-1) (step D2). It should be noted that the distillation column is made of glass and the packing material is Helipack No. 1.

[0297] The purified product containing the perfluoro α-olefin compound represented by formula (F2-1) was designated as monomer F-8. The results are shown in Table 1.

[0298] <Example 1-9~Example 1-11>

[0299] Instead of step C1 in Example 1-1, step D1 (distillation) was performed only under the conditions described in Table 1 to obtain monomers F'-1 to F'-3 (purified products containing PSAE) as in Examples 1-9 to 1-11. The results are shown in Table 1.

[0300] <Example 1-12>

[0301] Instead of step C1 in Examples 1-7, step D1 (distillation) was performed only under the conditions described in Table 1 to obtain monomer F'-4 (a purified product containing BSAE) as in Examples 1-7. The results are shown in Table 1.

[0302] <Example 1-13>

[0303] Instead of step C2 in Examples 1-8, step D2 (distillation) was performed only under the conditions described in Table 1 to obtain monomer F'-5 (a purified product containing the perfluoro α-olefin compound represented by formula (F2-1)) in Examples 1-8. The results are shown in Table 1.

[0304] [Table 1]

[0305]

[0306] [Manufacturing of polymer F and polymer F']

[0307] <Example 2-1>

[0308] The pressure in the autoclave (2500 mL internal volume, stainless steel) was reduced. 2252.50 g of monomer F-1 (crude product containing PSAE) obtained in Example 1-1 was aspirated and added to the autoclave. The process of pressurizing to 0.3 MPa (gauge pressure) with nitrogen and then depressurizing to 0.05 MPa was repeated five times to remove dissolved oxygen. Nitrogen was introduced into the gas phase, and the autoclave was heated in an oil bath until the internal temperature reached 160°C. The pressure at this point was 1.101 MPa (gauge pressure). Next, 34.32 g of TFE was introduced into the autoclave. The pressure at this point was 1.410 MPa (gauge pressure), and the partial pressure of TFE at the polymerization temperature was 0.309 MPa.

[0309] PFtBPO, used as an initiator, was dissolved in monomer F-1 at a concentration of 140 ppm, and 0.72 g of the resulting initiator solution was added to initiate copolymerization. At this point, the amount of PFtBPO added was 0.10 mg, and the concentration of PFtBPO in the autoclave was 0.045 ppm of the mass of monomer F-1 added to the autoclave before copolymerization. The pressure was maintained at 1.410 MPa (gauge pressure), and TFE was continuously added, continuing polymerization for 5 hours. During this time, to maintain the PFtBPO concentration at 0.045 ppm relative to the mass of monomer F-1 added to the autoclave before copolymerization, the initiator solution was continuously added at a rate of 35.7 g / h (equivalent to 5.00 mg / h based on the mass of PFtBPO), stopping after 4 hours and 30 minutes. Through the above operations, the total amount of monomer F-1 added to the autoclave was 2413.14 g, and the total amount of PFtBPO added to the autoclave was 22.5 mg. Therefore, the average polymerization time per hour was 1.9 ppm, with the ratio of the total PFtBPO addition to the total F-1 monomer addition. Additionally, the additional TFE addition was 22.20 g. It should be noted that stirring during copolymerization was performed using a double-helix bladed mixer at a speed of 150 rpm.

[0310] The mixture was cooled until the internal temperature dropped below 30°C, and then the gas inside the autoclave was purged. 6033 g of HFE-347pc-f (2.5 times the mass of monomer F-1) was added to the reaction solution to cause polymer coagulation and filtration. The polymer was then stirred in the same amount of HFE-347pc-f and washed with HFE-347pc-f, repeated twice. Vacuum drying at 180°C yielded 62.1 g of the TFE / PSAE copolymer, polymer F-1. The Q value was 8.9 mm. 3 / second. The results are shown in Table 2.

[0311] It should be noted that in Table 2, the productivity index (Rp) represents the amount of polymer (g) generated when the average total amount of SO2F-based monomers input before and during copolymerization is 100g and the average polymerization time is 1 hour.

[0312] <Example 2-2>

[0313] 525.0 g of monomer F-2 (hereinafter, the purified product containing PSAE) obtained in Example 1-2 was placed in an autoclave equipped with an air condenser (hereinafter referred to as A / C; internal volume 500 mL, Hastelloy alloy). The autoclave was cooled with liquid nitrogen and degassed. Nitrogen gas was introduced into the gas phase, and the autoclave was heated in an oil bath until the internal temperature reached 160°C. The pressure at this point was 0.502 MPa (gauge pressure). Next, 10.40 g of TFE was introduced into the autoclave. The pressure at this point was 0.892 MPa (gauge pressure), and the partial pressure of TFE at the polymerization temperature was 0.390 MPa.

[0314] tBPO, used as an initiator, was dissolved in monomer F-2 at a concentration of 667 ppm by mass. 0.79 g of the resulting initiator solution was added to initiate copolymerization. At this point, the amount of tBPO added was 0.53 mg, and the concentration of tBPO in the autoclave was 1.0 ppm by mass of monomer F-2 added to the autoclave before copolymerization. The pressure was maintained at 0.892 MPa (gauge pressure), and TFE was continuously added, continuing polymerization for 5 hours. During this period, 0.66 g of the aforementioned initiator solution (equivalent to 0.44 mg of tBPO by mass) was added nine times every 30 minutes, introducing a total of 3.98 mg of tBPO into the autoclave. In other words, tBPO was added at a concentration of 1.0 ppm immediately after addition, relative to the mass of monomer F-2 added to the autoclave before copolymerization. Through the above operations, the total amount of monomer F-2 added to the autoclave was 531.1 g, and the total amount of tBPO added was 4.51 mg. Therefore, in terms of the ratio of the total amount of tBPO added to the total amount of monomer F-2 added, the average polymerization time per hour is 1.7 ppm by mass (denoted as "time-average initiator ratio" in the table). Additionally, the additional amount of TFE added is 8.73 g. It should be noted that stirring during copolymerization is carried out using anchor blades at a stirring speed of 250 rpm.

[0315] The mixture was cooled until the internal temperature dropped below 30°C, and then the gas inside the autoclave was purged. Monomer F-2 and 1060 g of HFE-347pc-f (twice the mass) were added to the reaction mixture, causing the polymer to coagulate and filter. Then, the polymer was stirred in the same amount of HFE-347pc-f, washed with HFE-347pc-f, and this operation was repeated twice. Vacuum drying was performed at 180°C to obtain 19.44 g of the TFE / PSAE copolymer, i.e., polymer F-2. The Q value was 14.0 mm. 3 / second. The results are shown in Table 2.

[0316] <Example 2-3>

[0317] 80.02 g of monomer F-3 (a purified product containing PSAE) obtained in Examples 1-3 was placed in an autoclave equipped with an air condenser (hereinafter referred to as A / C; internal volume 100 mL, stainless steel) and degassed by cooling with liquid nitrogen. Nitrogen gas was introduced into the gas phase, and the autoclave was heated in an oil bath until the internal temperature reached 160°C. The pressure at this point was 0.460 MPa (gauge pressure). Next, 3.19 g of TFE was introduced into the autoclave. The pressure at this point was 0.850 MPa (gauge pressure), and the partial pressure of TFE at the polymerization temperature was 0.390 MPa.

[0318] tBPO, used as an initiator, was dissolved in monomer F-3 at a concentration of 250 ppm by mass. 0.32 g of the resulting initiator solution was added to initiate copolymerization. At this point, the amount of tBPO added was 0.08 mg, and the concentration of tBPO in the autoclave was 1.0 ppm by mass of monomer F-3 added to the autoclave before copolymerization. The pressure was maintained at 0.850 MPa (gauge pressure), and TFE was continuously added, continuing polymerization for 6 hours. During this time, 0.27 g of the aforementioned initiator solution (0.07 mg by mass of tBPO) was added 11 times every 30 minutes, introducing a total of 0.77 mg of tBPO into the autoclave. In other words, tBPO was added at a concentration of 1.0 ppm immediately after addition, relative to the mass of monomer F-3 in the autoclave before copolymerization. Through the above operations, the total amount of monomer F-3 added to the autoclave was 83.31 g, and the total amount of tBPO added was 0.85 mg. Therefore, in terms of the ratio of the total amount of tBPO added to the total amount of monomer F-3 added, the average polymerization time per hour is 1.7 ppm by mass (denoted as "time-average initiator ratio" in the table). Additionally, the additional amount of TFE added is 1.72 g. It should be noted that stirring during copolymerization is carried out using a double helix with blades, and the stirring speed is set to 250 rpm.

[0319] The mixture was cooled until the internal temperature dropped below 30°C, and then the gas inside the autoclave was purged. Monomer F-3 and 166g of HFE-347pc-f (twice the mass) were added to the reaction mixture, causing the polymer to coagulate and filter. The polymer was then stirred in the same amount of HFE-347pc-f, washed with HFE-347pc-f, and this process was repeated twice. Vacuum drying at 180°C yielded 2.8g of the TFE / PSAE copolymer, polymer F-3. The Q value was 7.9mm. 3 / second. The results are shown in Table 2.

[0320] <Example 2-4>

[0321] As shown in Table 2, the conditions of Example 2-2 were changed, except that the process was the same as in Example 2-2, to obtain polymer F-4 in Example 2-4. The results are shown in Table 2.

[0322] <Example 2-5>

[0323] As shown in Table 2, the conditions of Example 2-1 were changed, except that the process was the same as in Example 2-1, to obtain polymer F-5 in Example 2-5. The results are shown in Table 2.

[0324] <Example 2-6>

[0325] As shown in Table 2, the conditions of Example 2-2 were changed, except that the process was the same as in Example 2-2, to obtain polymer F-6 in Example 2-6. The results are shown in Table 2.

[0326] <Example 2-7>

[0327] 69.99 g of monomer F-7 (a purified product containing BSAE) obtained in Examples 1-7 was placed in an autoclave equipped with an air condenser (hereinafter referred to as A / C; internal volume 100 mL, stainless steel) and degassed by cooling with liquid nitrogen. Nitrogen gas was introduced into the gas phase, and the autoclave was heated in an oil bath until the internal temperature reached 160°C. The pressure at this point was 0.300 MPa (gauge pressure). Next, 2.97 g of TFE was introduced into the autoclave. The pressure at this point was 0.800 MPa (gauge pressure), and the partial pressure of TFE at the polymerization temperature was 0.500 MPa.

[0328] tBPO, used as an initiator, was dissolved in monomer F-7 at a concentration of 2000 ppm by mass. 0.18 g of the resulting initiator solution was added to initiate copolymerization. At this point, the amount of tBPO added was 0.35 mg, and the concentration of tBPO in the autoclave was 5.0 ppm by mass of monomer F-7 added to the autoclave before copolymerization. The pressure was maintained at 0.800 MPa (gauge pressure), and TFE was continuously added, continuing polymerization for 8.5 hours. During this time, 0.15 g of the aforementioned initiator solution (equivalent to 0.36 mg of tBPO by mass) was added 16 times every 30 minutes, introducing a total of 5.70 mg of tBPO into the autoclave. In other words, tBPO was added at a concentration of 5.0 ppm immediately after addition, relative to the mass of monomer F-7 added to the autoclave before copolymerization. Through the above operations, the total amount of monomer F-7 added to the autoclave was 73.13 g, and the total amount of tBPO added was 6.05 mg. Therefore, in terms of the ratio of the total amount of tBPO added to the total amount of monomer F-7 added, the average polymerization time per hour is 9.7 ppm by mass (denoted as "time-average initiator ratio" in the table). Additionally, the additional amount of TFE added is 6.85 g. It should be noted that stirring during copolymerization is carried out using a double helix with blades, and the stirring speed is set to 180 rpm.

[0329] The mixture was cooled until the internal temperature dropped below 30°C, and then the gas inside the autoclave was purged. The reaction solution was diluted with HFC-52-13p, and HFE-347pc-f was added to cause polymer coagulation, followed by filtration. The polymer was then stirred in the HFC-52-13p and re-coagulated with HFE-347pc-f, repeated twice. Vacuum drying at 120°C yielded 13.92 g of the TFE / BSAE copolymer, polymer F-7. The Q value was 27.2 mm. 3 / second. The results are shown in Table 2.

[0330] <Example 2-8>

[0331] As shown in Table 2, the conditions of Examples 2-3 were modified (in Example 2-8, nitrogen was not introduced into the gas phase of the autoclave). Additionally, monomer F-8 (a purified product containing the perfluoroα-olefin compound represented by formula (F2-1)) and HCFC-141b were added to the reaction solution in four times the amount (by mass) to obtain 400 g of polymer, which was then allowed to coagulate and filtered. The polymer was then stirred in the same amount of HCFC-141b, washed with HCFC-141b, and this operation was repeated twice. Otherwise, the process was the same as in Example 2-3, yielding polymer F-8 as in Example 2-8. The results are shown in Table 2.

[0332] <Example 2-9~Example 2-10>

[0333] As shown in Table 2, the conditions of Example 2-2 were changed, and the process was otherwise carried out in the same manner as in Example 2-2 to obtain polymers F'-1 to F'-2 in Examples 2-9 to 2-10. The results are shown in Table 2.

[0334] <Example 2-11>

[0335] As shown in Table 2, the conditions of Example 2-3 were changed, except that the process was the same as in Example 2-3, to obtain polymer F'-3 in Example 2-11. The results are shown in Table 2.

[0336] <Example 2-12>

[0337] As shown in Table 2, the conditions of Example 2-7 were changed, except that the process was the same as in Example 2-7, to obtain polymer F'-4 in Example 2-12. The results are shown in Table 2.

[0338] <Example 2-13>

[0339] As shown in Table 2, the conditions of Example 2-8 were changed, except that the process was the same as in Example 2-8, to obtain polymer F'-5 in Example 2-13. The results are shown in Table 2.

[0340] [Table 2-1]

[0341]

[0342] [Table 2-2]

[0343]

[0344] [Manufacturing of polymer H and polymer H']

[0345] <Example 3-1>

[0346] Using the polymer F-1 obtained as described above, a membrane of polymer F-1 was obtained by pressure pressing at 260°C and 4 MPa (gauge pressure). The polymer F-1 membrane was immersed in an alkaline aqueous solution (aqueous solution A: potassium hydroxide / water = 20 / 80 (mass ratio)) at 80°C for 16 hours to hydrolyze the -SO2F of polymer F-1, converting it to -SO3K. Then, the polymer membrane was immersed in a 3 mol / L hydrochloric acid aqueous solution at 80°C for 30 minutes, followed by immersion in ultrapure water at 80°C for 30 minutes. A total of 5 cycles of immersion in hydrochloric acid aqueous solution and immersion in ultrapure water were performed to convert the -SO3K of the polymer to -SO3H. Washing with ultrapure water was repeated until the pH of the water used to immerse the polymer membrane became 7. The polymer membrane was then air-dried while held in filter paper to obtain the polymer H-1 membrane of Example 3-1. The results are shown in Table 3.

[0347] <Example 3-2~Example 3-12>

[0348] Polymer F-1 was changed to polymers F-2 to F-8, F'-1 to F'-2, and F'-4 to F'-5. Otherwise, the same procedure as in Example 3-1 was followed to obtain polymers H-2 to H-8 in Examples 3-2 to 3-8, polymers H'-1 to H'-2 in Examples 3-9 to 3-10, and polymers H'-4 to H'-5 in Examples 3-11 to 3-12. The results are shown in Table 3.

[0349] [Table 3]

[0350]

[0351]

[0352] As shown in Tables 1 and 2, if step C1 or step C2 is performed during monomer manufacturing, high molecular weight polymers F (Examples 1-1 to 1-8, Examples 2-1 to 2-8) can be obtained even without distillation or by simplifying the distillation conditions during monomer manufacturing.

[0353] In contrast, it is shown that in order to obtain high molecular weight polymer F'-1 using monomer F'-1 (without performing steps C1 and C2), the distillation conditions during monomer manufacturing become complicated (Examples 1-9, 2-9).

[0354] In addition, it was shown that monomers F'-2 to F'-5 obtained by simplifying the distillation conditions during monomer manufacturing without performing steps C1 and C2 could not be used to manufacture high molecular weight polymers (Examples 1-10 to 1-13, Examples 2-10 to 2-13).

[0355] It should be noted that the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2021-112875, filed on July 7, 2021, are incorporated herein as a disclosure of the specification of this invention.

Claims

1. A method for manufacturing a perfluorinated compound, characterized in that, Crude product A or any crude product X from crude product B is obtained through any step in step A or step B, wherein step A is a step of reacting a perfluoroalkoxide with a perfluoroallylating agent to obtain crude product A containing a perfluoroallyl ether compound, and step B is a step of obtaining crude product B containing a perfluoroα-olefin compound through a dechlorination reaction of a chlorofluorocarbon compound. The crude product X is mixed with a free radical source, and the free radicals generated by the free radical source are brought into contact with the crude product X to obtain a crude product Y containing any perfluorinated compound from the perfluoroallyl ether compound or the perfluoroalpha olefin compound. The amount of the perfluoroallyl ether compound contained in the crude product A is more than 95% by mass relative to the total mass of the crude product A. The amount of the perfluoroalpha olefin compound contained in the crude product B is more than 95% by mass relative to the total mass of the crude product B. The mixing of the crude product X with the free radical source is carried out under the condition that the content of polymerizable compounds other than those contained in the crude product X is less than 0.1 parts by mass relative to 100 parts by mass of the crude product X. The mixing of the crude product X with the free radical source is carried out under heating conditions, with a heating temperature of 120~180℃ and a heating time of 1~120 hours. The free radical source is an organic peroxide, and the amount of the free radical source added is 0.01 to 2 parts by mass relative to 100 parts by mass of the crude product X. The ratio of the peak area of ​​perfluorinated compounds detected during gas chromatography analysis of the crude product X to the sum of the peak areas is set as X%. Furthermore, when the area of ​​the perfluorinated compound peak detected during gas chromatography analysis of the crude product Y is set as Y% relative to the sum of the area values ​​of all peaks, The modification rate D, calculated using the following formula (M), is 0.5% to 20%. Modification rate D [%] = 100 × (XY) / X … (M).

2. The method for manufacturing a perfluorinated compound according to claim 1, wherein, The ratio of the peak area of ​​perfluorinated compounds detected during gas chromatography analysis of the crude product X to the sum of the peak areas is set as X%. Furthermore, when the area of ​​the perfluorinated compound peak detected during gas chromatography analysis of the crude product Y is set as Y% relative to the sum of the area values ​​of all peaks, The modification rate D, calculated using the following formula (M), is 0.5% to 15%. Modification rate D [%] = 100 × (XY) / X … (M).

3. The method for manufacturing a perfluorinated compound according to claim 1, wherein, The perfluoroalkoxide is a compound represented by the following formula (S1). The perfluoroallylating agent is a compound represented by the following formula (S2). CF(-Q 11 )(-Q 12 )-O-M …(S1) CF2=CFCF2-Z S …(S2) In equation (S1), Q 11 and Q 12 Each of these can be independently a perfluoroalkyl group optionally having -SO2F, a monovalent group of a perfluoroalkyl group optionally having -SO2F whose -CF2- is replaced by an ether-like oxygen atom, or a fluorine atom, where M is a monovalent metal element. In formula (S2), Z S -OS(O)2R S1 , chlorine atom, bromine atom or iodine atom, R S1 It indicates a fluorine atom or a perfluoroalkyl group.

4. The method for manufacturing a perfluorinated compound according to claim 3, wherein, The perfluoroallyl ether compound obtained by reacting the compound represented by formula (S1) with the compound represented by formula (S2) is the compound represented by formula (F1). CF(-Q 11 )(-Q 12 )-O-CF2CF=CF2…(F1) Q in equation (F1) 11 and Q 12 respectively with Q in the above formula (S1) 11 and Q 12 They have the same meaning.

5. The method for manufacturing a perfluorinated compound according to claim 3, wherein, The compound represented by formula (S1) is either the compound represented by formula (S1-1) or the compound represented by formula (S1-2). FO2S-Q 21 -CF2-O-M …(S1-1) CF(-Q 22 -SO2F)(-Q 23 -SO2F)-O-M …(S1-2) In equation (S1-1), Q 21 It is a perfluoroalkylene group, or a divalent group of a perfluoroalkylene group whose -CF2- is replaced by an ether-like oxygen atom. In equation (S1-2), Q 22 and Q 23 Each is independently a perfluoroalkylene group, or a divalent group of a perfluoroalkylene group whose -CF2- is replaced by an ether-oxygen atom.

6. The method for manufacturing a perfluorinated compound according to claim 5, wherein, The perfluoroallyl ether compound obtained by reacting the compound shown in formula (S1-1) with the compound shown in formula (S2) is the compound shown in formula (F1-1), and the perfluoroallyl ether compound obtained by reacting the compound shown in formula (S1-2) with the compound shown in formula (S2) is the compound shown in formula (F1-2). FO2S-Q 21 -CF2-O-CF2CF=CF2 …(F1-1) CF(-Q 22 -SO2F)(-Q 23 -SO2F)-O-CF2CF=CF2 …(F1-2) Q in equation (F1-1) 21 With Q in the above formula (S1-1) 21 Same meaning Q in equation (F1-2) 22 and Q 23 Each of them corresponds to Q in the aforementioned equation (S1-2) 22 and Q 23 They have the same meaning.

7. The method for manufacturing a perfluorinated compound according to claim 1, wherein, The chlorofluorocarbon compound is a compound represented by the following formula (S3). ClCF2-CFCl-CF2-CF2-Q 13 -SO2F …(S3) In equation (S3), Q 13 It is a single bond, an optional perfluoroalkylene group having -SO2F, or an optional perfluoroalkylene group having -SO2F and a -CF2- divalent group replaced by an ether-oxygen atom.

8. The method for manufacturing a perfluorinated compound according to claim 7, wherein, The perfluoroalpha olefins obtained by the dechlorination reaction of chlorofluorocarbons are compounds represented by the following formula (F2). CF2=CF-CF2-CF2-Q 13 -SO2F …(F2) Q in equation (F2) 13 With Q in the above formula (S3) 13 They have the same meaning.

9. The method for manufacturing a perfluorinated compound according to claim 8, wherein, The compound represented by formula (F2) is the same as the compound represented by formula (F2-1) below. CF2=CF-(CF2CF2) X2 -SO2F …(F2-1) In equation (F2-1), x2 is an integer from 1 to 6.

10. The method for producing a perfluorinated compound according to any one of claims 1 to 9, wherein, The crude product Y was further purified.

11. The method for manufacturing a perfluorinated compound according to claim 10, wherein, The mixing of the crude product X with the free radical source and the purification of the crude product Y are carried out in the same apparatus.

12. A method for manufacturing a fluoropolymer, characterized in that, A fluorinated polymer is obtained by polymerizing the perfluorinated compound obtained by the manufacturing method of any one of claims 1 to 11 at a temperature of 100°C or higher.

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