Method for producing compound, and compound

Abstract

Provided is a method for producing a compound having a perfluoropolyether chain, the method involving irradiating a raw material composition containing a compound represented by formula (1) and a compound represented by formula (2) with ultraviolet rays having a wavelength of 150-300 nm under an inert gas flow. In formula (1), T11 and T12 each represent -R11–COOH or –R11–COOR12, R11 represents a perfluoroalkylene group, R12 represents an alkyl group, Rf1 represents (R13O)n1, R13 represents a perfluoroalkylene group, and n1 is an integer of 1 or more. In formula (2), L1 represents a divalent linking group, Z1 represents a functional group represented by –SO2F, –CN, –CH2OH, or –COOR22, and R22 represents an alkyl group.　Formula (1): T11-O-Rf1-T12 Formula (2):F2C=CF-O-L1-Z1

Description

Compound manufacturing method and compound

[0001] The present disclosure relates to methods for making compounds and to compounds.

[0002] Compounds having a perfluoropolyether chain (hereinafter also referred to as "PFPE chain") have excellent heat resistance, electrical insulation, and oxidation resistance, and a low glass transition temperature, and are therefore used in a variety of industrial applications. Compounds having a PFPE chain are expected to be applied to, for example, polymer electrolytes, crosslinked rubbers, gas-liquid separation membranes, optical element encapsulants, elastic adhesives, microchannel devices, etc. Patent Document 1, for example, discloses a compound having a PFPE chain with functional groups at both ends.

[0003] Japanese Unexamined Patent Publication No. 7-18083

[0004] When a compound having a PFPE chain (hereinafter also referred to as "PFPE compound") is used in applications such as polymer electrolytes, the PFPE compound may be required to have the type and amount of functional groups appropriate for the application. However, with PFPE compounds having functional groups at both ends, it is difficult to freely control the amount of functional groups. Furthermore, when a PFPE compound is used in an elastomer, properties that cannot be achieved by linking end groups as in conventional technology may be required. With PFPE compounds having functional groups only at the ends, it is difficult to freely control the amount of functional groups used as crosslinking groups. The present disclosure has been made in light of these circumstances, and one embodiment of the present disclosure aims to provide a method for producing a compound having a perfluoropolyether chain in which the amount of functional groups can be freely controlled, and a compound obtained by the production method.

[0005] The present disclosure includes the following aspects. <1> A method for producing a compound having a perfluoropolyether chain, comprising irradiating a raw material composition containing a compound (1) represented by the following formula (1) and a compound (2) represented by the following formula (2) with ultraviolet light having a wavelength of 150 to 300 nm under a flow of inert gas, thereby copolymerizing the compound (1) and the compound (2). １１ -O-Rf １ -T １２...Formula (1) F ２ C=CF-O-L １ -Z １ ...Formula (2) In formula (1), T １１ and T １２ are each independently -R １１ -COOH or -R １１ -COOR １２ and R １１ are each independently a perfluoroalkylene group, and R １２ are each independently an alkyl group, and Rf １ is (R １３ O) ｎ１ and R １３ are each independently a perfluoroalkylene group, n1 is an integer of 1 or more, and in formula (2), L １ is a divalent linking group, Z １ is -SO ２ F, —CN, —CH ２ OH or -COOR ２２ is a functional group represented by R ２２ is an alkyl group. <2> The method for producing the compound according to <1>, wherein the content of the compound (2) is 1 to 90 mass % with respect to the total mass of the raw material composition. <3> The method for producing the compound according to <1> or <2>, wherein the temperature of the raw material composition during the ultraviolet irradiation is 0 to 100°C. <4> A compound having a perfluoropolyether chain, comprising a unit (1) derived from a compound (1) represented by the following formula (1) and a unit (2) derived from a compound (2) represented by the following formula (2): T １１ -O-Rf １ -T １２ ...Formula (1) F ２ C=CF-O-L １ -Z １ ...Formula (2) In formula (1), T １１ and T １２ are each independently -R １１ -COOH or -R １１ -COOR １２ and R １１ are each independently a perfluoroalkylene group, and R１２ are each independently an alkyl group, and Rf １ is (R １３ O) ｎ１ and R １３ are each independently a perfluoroalkylene group, n1 is an integer of 1 or more, and in formula (2), L １ is a divalent linking group, Z １ is -SO ２ F, —CN, —CH ２ OH or -COOR ２２ is a functional group represented by R ２２ <5> The compound according to <4>, wherein the content of the unit (2) contained in one molecule is 1 to 90 mass %. <6> The compound according to <4> or <5>, wherein the number average molecular weight is 5,000 or more. <7> Z in the formula (2) １ The compound according to any one of <4> to <6>, wherein the content of the functional group represented by the formula (I) is 0.001 to 3 mmol / g relative to the total amount of the compound.

[0006] According to one embodiment of the present disclosure, there are provided a method for producing a compound having a perfluoropolyether chain in which the amount of functional groups can be freely controlled, and a compound obtained by the production method.

[0007] In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In numerical ranges described in stages in the present disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in numerical ranges described in the present disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. In the present disclosure, a compound represented by formula (X) may be referred to as compound (X) or compound X.

[0008] The meanings of the terms used in this disclosure are as follows: A perfluoroalkyl group refers to a group in which all hydrogen atoms of an alkyl group are substituted with fluorine atoms. A perfluoroalkylene group refers to a group in which all hydrogen atoms of an alkylene group are substituted with fluorine atoms. A perfluoropolyether chain (PFPE chain) refers to a structure having two or more perfluoroalkyleneoxy units. A raw material composition is composed of components that become units constituting a compound (copolymer) obtained by copolymerization, and does not include components that do not constitute the compound (solvent, etc.).

[0009] [Method for Producing Compound] A method for producing a compound according to an embodiment of the present disclosure is a method for producing a PFPE compound, which comprises irradiating a raw material composition containing a compound (1) represented by the following formula (1) and a compound (2) represented by the following formula (2) with ultraviolet light having a wavelength of 150 to 300 nm under a flow of an inert gas, thereby copolymerizing the compound (1) and the compound (2). １１ -O-Rf １ -T １２ ...Formula (1) F ２ C=CF-O-L １ -Z １ ...Formula (2) In formula (1), T １１ and T １２ are each independently -R １１ -COOH or -R １１ -COOR １２ and R １１ are each independently a perfluoroalkylene group, and R １２ are each independently an alkyl group, and Rf １ is (R １３ O) ｎ１ and R １３ are each independently a perfluoroalkylene group, n1 is an integer of 1 or more, and in formula (2), L １ is a divalent linking group, Z １ is -SO ２ F, —CN, —CH ２ OH or -COOR ２２ is a functional group represented by R ２２ is an alkyl group.２ F, —CN, —CH ２ OH and -COOR ２２ At least one selected from the group consisting of the following is also referred to as a "specific functional group".

[0010] As mentioned above, a PFPE compound may be required to have a type and amount of functional groups depending on the application. For example, when a PFPE compound is used as a material for a polymer electrolyte, it is necessary to add -SO ２ A PFPE compound having a large amount of functional groups such as -F is sometimes desired. Furthermore, when a PFPE compound is used as a material for crosslinked rubber, a PFPE compound having a large (or small) amount of functional groups such as -CN is sometimes desired in order to increase (or decrease) the crosslink density of the resulting crosslinked rubber. On the other hand, with conventional PTFE compounds having functional groups at both ends, it has been difficult to freely control the amount of functional groups.

[0011] In contrast, in the present embodiment, a raw material composition containing a compound (1) having a perfluoroalkyleneoxy unit and a terminal carboxy group or alkyloxycarbonyl group, and a compound (2) having a perfluorovinyl group and a specific functional group is used. This raw material composition is then irradiated with ultraviolet light under a flow of inert gas. Therefore, a PFPE compound having a specific functional group in the side chain rather than the terminal is obtained, and the amount of specific functional group introduced into the PFPE compound can be easily controlled by adjusting the amount of compound (2) contained in the raw material composition. Furthermore, since the molecular weight can be freely controlled, the flowability, solubility, mechanical properties, etc. can be adjusted as needed.

[0012] In the photopolymerization of the raw material composition, first, the —COOH or —COOR group at the end of the compound (1) is １２ By the elimination of -R １１ A radical is generated. Then, the generated -R １１ The radical is another -R １１ It is believed that polymerization proceeds by bonding to the radical or the perfluorovinyl group of compound (2).

[0013] Among the compounds (1) in this embodiment, T １１ and T１２ At least one of them is -R １１ When a compound having a -COOH group is used and irradiated with ultraviolet light without flowing an inert gas, the terminal of compound (1) is likely to be converted to a carbonyl fluoride group due to the action of a hydroxyl radical generated from the released COOH radical. When the terminal functional group is converted to a carbonyl fluoride group, the decomposition rate by ultraviolet light becomes extremely slow compared to that of a COOH group, and the target reaction does not proceed. On the other hand, in this embodiment, since ultraviolet light is irradiated using compound (1) and compound (2) under a flow of inert gas, even if a hydroxyl radical is generated, it is removed from the reaction system and carbonyl fluoride groups are unlikely to be generated, and radicals are generated at the terminal of compound (1) to form -R １１ Therefore, it is presumed that the amount of specific functional groups introduced into the PFPE compound can be easily controlled by adjusting the amount of compound (2) contained in the raw material composition.

[0014] In addition, among the compounds (1) in this embodiment, T １１ and T １２ At least one of them is -R １１ -COOR １２ Even when a compound having the formula (I) is used, polymerization does not proceed easily when irradiated with ultraviolet light without passing an inert gas. The reason why polymerization does not proceed easily is unclear, but it is thought that the alkyl radicals generated by further decomposition of the eliminated alkyloxycarbonyl group are converted into the aforementioned -R １１ It is presumed that this is because the addition of the specific functional group to the radical terminates the polymerization. On the other hand, in this embodiment, since the ultraviolet irradiation is performed under a flow of inert gas, even if an alkyl radical is generated, it is removed from the reaction system, making it difficult for the termination of the polymerization to occur. Therefore, it is presumed that a PFPE compound in which the amount of the specific functional group introduced into the PFPE compound is controlled can be obtained by adjusting the amount of compound (2) contained in the raw material composition.

[0015] <Raw Material Composition> (Compound (1)) Compound (1) used in the production method of this embodiment is a compound represented by the following formula (1): T １１ -O-Rf １ -T １２...Formula (1) In formula (1), T １１ and T １２ are each independently -R １１ -COOH or -R １１ -COOR １２ and R １１ are each independently a perfluoroalkylene group, and R １２ are each independently an alkyl group, and Rf １ is (R １３ O) ｎ１ and R １３ are each independently a perfluoroalkylene group, and n1 is an integer of 1 or more.

[0016] R １３ The number of carbon atoms in R is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2, from the viewpoints of excellent fluidity and solubility, and transparency depending on the application of the PFPE compound. １３ When R has 3 or more carbon atoms, it may be a linear perfluoroalkylene group, a branched perfluoroalkylene group, or a perfluoroalkylene group having a ring structure. １３ is preferably a linear perfluoroalkylene group or a branched perfluoroalkylene group, more preferably a linear perfluoroalkylene group, from the viewpoint of excellent fluidity. １３ may be the same as or different from each other. １ is two or more kinds of (R １３ O). １３ O) means that two or more (R １３ O) is present, and two or more types of (R １３ O) is present.

[0017] R １３ Specific examples of the group include -CF ２ -, -CF ２ CF ２ -, -CF(CF ３ ) -, -CF２ CF ２ CF ２ -, -CF(CF ３ )CF ２ -, -CF ２ CF ２ CF ２ CF ２ -, -CF(CF ３ )CF ２ CF ２ -, -CF ２ CF(CF ３ )CF ２ -, -CF ２ CF ２ CF ２ CF ２ CF ２ -, -CF(CF ３ )CF ２ CF ２ CF ２ -, -CF ２ CF(CF ３ )CF ２ CF ２ -, -CF[[ID=)56]] ２ CF ２ CF ２ CF ２ CF ２ CF ２ -, -CF(CF ３ )CF ２ CF ２ CF ２ CF ２ -, -CF ２ CF(CF ３ )CF ２ CF ２ CF ２ -, -CF ２ CF ２ CF(CF ３ )CF ２ CF ２ -, -cycloC ４ F[[ID=)100]] ６ -, -cycloC ５ F ８ -, and -cycloC ６ F １０ -, these combinations are included.

[0018] Here, -cycloC ４ F ６- means a perfluorocyclobutanediyl group. Examples of perfluorocyclobutanediyl groups include perfluorocyclobutane-1,2-diyl and perfluorocyclobutane-1,3-diyl groups. -cycloC ５ F ８ - means a perfluorocyclopentanediyl group. Examples of perfluorocyclopentanediyl groups include perfluorocyclopentane-1,2-diyl and perfluorocyclopentane-1,3-diyl groups. ６ F １０ - means a perfluorocyclohexanediyl group. Examples of the perfluorocyclohexanediyl group include a perfluorocyclohexane-1,2-diyl group, a perfluorocyclohexane-1,3-diyl group, and a perfluorocyclohexane-1,4-diyl group.

[0019] n1 is (R １３ is an integer of 1 or more representing the number of repetitions of the unit (2) derived from compound (2), and is preferably 1 to 1,000, more preferably 10 to 500, and even more preferably 30 to 300, from the viewpoint of controlling the molecular weight of the resulting PFPE compound and the content of the unit (2) derived from compound (2).

[0020] Rf １ is preferably represented by the following formula (3-1): -[(R ｆ１１ O) ｎ１１ (R ｆ１２ O) ｎ１２ (R ｆ１３ O) ｎ１３ (R ｆ１４ O) ｎ１４ (R ｆ１５ O) ｎ１５ (R ｆ１６ O) ｎ１６ ]- … (3-1) However, R ｆ１１ is a perfluoroalkylene group having one carbon atom, and R ｆ１２ is a perfluoroalkylene group having 2 carbon atoms, and R ｆ１３ is a perfluoroalkylene group having 3 carbon atoms, and R ｆ１４ is a perfluoroalkylene group having 4 carbon atoms, and R ｆ１５is a perfluoroalkylene group having 5 carbon atoms, and R ｆ１６ is a perfluoroalkylene group having 6 carbon atoms. n11, n12, n13, n14, n15, and n16 each independently represent an integer of 0 or 1 or more, and n11 + n12 + n13 + n14 + n15 + n16 = n1.

[0021] In addition, (R ｆ１１ O) ~ (R ｆ１６ O) may be bonded in any order. n11 to n16 in formula (3-1) are each ｆ１１ O) ~ (R ｆ１６ O), and does not represent the arrangement. For example, (R ｆ１５ O) ｎ１５ is (R ｆ１５ O) is n15, and (R ｆ１５ O) ｎ１５ Similarly, (R ｆ１１ O) ~ (R ｆ１６ The order of description of each unit does not represent the bonding order of the units.

[0022] Among them, -(R １３ O) ｎ１ - preferably includes at least one selected from the group consisting of structures represented by the following formulas (3-11) to (3-15), and more preferably includes a structure represented by formula (3-11). ｆ１１ O) ｎ１１ - (R ｆ１２ O) ｎ１２ -...(3-11) -(R ｆ１２ O) ｎ１２ - (R ｆ１４ O) ｎ１４ -...(3-12) -(R ｆ１３ O) ｎ１３ - (R ｆ１５ O) ｎ１５ -...(3-13) -(R ｆ１１ O) ｎ１１ - (R ｆ１２ O) ｎ１２ - (R ｆ１３ O) ｎ１３ -...(3-14) -(R ｆ１２ O) ｎ１２- (R ｆ１３ O) ｎ１３ - (3-15) where the symbols in the formulas (3-11) to (3-15) are the same as those in the formula (3-1).

[0023] In formula (3-11), (R ｆ１１ O) and (R ｆ１２ O) and (R ｆ１３ O) and (R ｆ１４ O) can be bonded in any order. For example, (R ｆ１１ O) and (R ｆ１２ O) may be arranged alternately, and (R ｆ１１ O) and (R ｆ１２ O) may be arranged in each block, and (R ｆ１１ O) and (R ｆ１２ O) and (R ｆ１３ O) and (R ｆ１４ O) may be arranged randomly. The same applies to formulas (3-12) to (3-15).

[0024] R １１ The perfluoroalkylene group represented by the formula (I) is the same as the above-mentioned R １３ Examples include the same perfluoroalkylene groups as those represented by R １１ is n1 R １３ and n1 R １３ may be different from any of the n1 R １３ It is preferable that the two R １１ may be the same as or different from each other. １１ From the viewpoint of availability, the number of carbon atoms in R is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. １１ may be the same as or different from each other.

[0025] R １２ From the viewpoint of suppressing inhibition of the reaction by decomposition products, the alkyl group represented by the formula (I) is preferably a methyl group or an ethyl group, and more preferably a methyl group. １１ and T １２ All of these are -R １１-COOR １２ When the two R １２ may be the same as or different from each other.

[0026] T in formula (1) １１ and T １２ are each independently -R １１ -COOH or -R １１ -COOR １２ From the viewpoint of ease of reaction and less influence of side reactions, -R １１ -COOH is preferred.

[0027] The number average molecular weight of compound (1) used in the production method of the present embodiment is preferably 100 to 100,000, more preferably 500 to 50,000, and even more preferably 1,000 to 10,000, from the viewpoint of controlling the molecular weight of the resulting PFPE compound and the content of unit (2) derived from compound (2).

[0028] In the present disclosure, the number average molecular weight of a compound is a value determined by the following method: adding p-bistrifluoromethylbenzene as an internal standard to the compound to be measured; １９ F-NMR measurement and １ The number average molecular weight is determined by H-NMR measurement. For example, when the compound to be measured is compound (1), １ The total amount of terminal groups (carboxy groups, alkyloxycarbonyl groups) determined by H-NMR measurement １９ The number average molecular weight of compound (1) is calculated from the total F number determined by F-NMR measurement. １９ The amount of peaks derived from the specific functional group was measured from the F-NMR spectrum to determine the content of the specific functional group relative to the total number of F in the PFPE compound, and then １ The total amount of terminal groups (carboxy groups, alkyloxycarbonyl groups) determined by H-NMR measurement １９ The number average molecular weight of the PFPE compound is calculated from the total F number and the content of the specific functional group determined by F-NMR measurement.

[0029] The raw material composition used in the production method of this embodiment may contain only one type of compound (1), or may contain two or more types of compound (1).

[0030] The compound (1) used in the production method of this embodiment may be a compound obtained by previously polymerizing the compound (4). The polymerization is carried out by photopolymerizing the compound (4) under an inert gas flow (for example, by irradiating it with ultraviolet light having a wavelength of 150 to 300 nm). ４１ -O-Rf ４ -T ４２ ...Formula (4) In formula (4), T ４１ and T ４２ are each independently -R ４１ -COOH or -R ４１ -COOR ４２ and R ４１ are each independently a perfluoroalkylene group, and R ４２ are each independently an alkyl group, and Rf ４ is (R ４３ O) ｎ４ and R ４３ are each independently a perfluoroalkylene group, and n4 is an integer of 1 to 115.

[0031] R ４３ From the viewpoint of excellent solubility, the number of carbon atoms in R is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2. ４３ When R has 3 or more carbon atoms, it may be a linear perfluoroalkylene group, a branched perfluoroalkylene group, or a perfluoroalkylene group having a ring structure. ４３ is preferably a linear perfluoroalkylene group or a branched perfluoroalkylene group, more preferably a linear perfluoroalkylene group, from the viewpoint of availability. ４３ may be the same as or different from each other. In other words, when n4 is 2 or more, the structure represented by formula (4) has two or more kinds of (R ４３ O). ４３ O) means that two or more (R ４３O) is present, and two or more types of (R ４３ O) is present. ４３ Specific examples of the above include the above-mentioned R １３ Specific examples similar to those mentioned above are given.

[0032] n4 is an integer of 1 to 115, and is preferably 10 to 100, more preferably 20 to 90, and even more preferably 30 to 70, from the viewpoint of excellent solubility and ease of synthesis of compound (1).

[0033] R ４１ The perfluoroalkylene group represented by the formula (I) is the same as the above-mentioned R １３ The two R ４１ may be the same as or different from each other. ４２ The alkyl group represented by T is preferably a methyl group or an ethyl group, and more preferably a methyl group. ４１ and T ４２ All of these are -R ４１ -COOR ４２ When the two R ４２ may be the same as or different from each other.

[0034] The number-average molecular weight of compound (4) is, for example, 300 to 5,000. The number-average molecular weight of the "compound obtained by photopolymerizing compound (4) under an inert gas flow" is, for example, 5,000 to 100,000. The procedures and conditions (ultraviolet wavelength, ultraviolet light source, ultraviolet irradiation intensity, type of inert gas, flow rate of inert gas, temperature, pressure, etc.) for photopolymerization of compound (4) are the same as those for the photopolymerization of the raw material composition described below. By using "a compound obtained by photopolymerizing compound (4) under an inert gas flow" as compound (1) contained in the raw material composition, a high-molecular-weight PFPE compound can be more easily obtained, for example, when the purpose is to produce an elastomer requiring a high molecular weight, compared to when compound (4) is used directly as compound (1).

[0035] (Compound (2)) The compound (2) used in the production method of this embodiment is a compound represented by the following formula (2): F ２ C=CF-O-L １ -Z １ ...Formula (2) In formula (2), L １ is a divalent linking group, Z １ is -SO ２ F, —CN, —CH ２ OH or -COOR ２２ is a functional group represented by R ２２ is an alkyl group.

[0036] R ２２ The alkyl group represented by the formula (I) is the same as the above-mentioned R １２ The T of the compound (1) contained in the raw material composition can be the same as the alkyl group represented by the following formula: １１ and T １２ At least one of them is -R １１ -COOR １２ and Z of compound (2) １ Ga-COOR ２２ In this case, from the viewpoint of facilitating reaction control, R ２２ The number of carbon atoms in the alkyl group represented by R １２ and the number of carbon atoms of the alkyl group represented by R １２ is a methyl group and R １２ It is more preferable that Z in formula (2) is an ethyl group. １ The functional group represented by is —SO ２ F, —CN, —CH ２ OH or -COOR ２２ From the viewpoint of availability and possibility of conversion to other functional groups, —SO ２ F, —CN, or —CH ２ OH is preferred, SO ２ F or —CN is more preferred.

[0037] L １ Examples of the divalent linking group represented by the formula (I) include an alkylene group, a perfluoroalkylene group, -O-, and a group formed by combining two or more of these groups.

[0038] L１ The divalent linking group represented by the formula (I) preferably contains a perfluoroalkylene group, and more preferably is a perfluoroalkylene group or a perfluoroalkylene group having —O— between carbon atoms. １ The total number of carbon atoms in the divalent linking group represented by the formula (I) is, for example, 1 to 10, and from the viewpoint of being less volatile and having high reactivity, it is preferably 3 to 8, and more preferably 3 to 5.

[0039] The molecular weight of the compound (2) used in the production method of this embodiment is preferably 250 to 1,000, more preferably 300 to 500, from the viewpoints of being less volatile and having high reactivity.

[0040] The raw material composition used in the production method of this embodiment may contain only one type of compound (2), or may contain two or more types. The content (mass%) of compound (2) is preferably 1 to 90 mass%, more preferably 5 to 80 mass%, and even more preferably 10 to 70 mass%, of the total raw material composition, from the viewpoint of the amount required to exhibit the function according to the intended application.

[0041] (Other Compounds) The raw material composition used in the production method of this embodiment contains at least compound (1) and compound (2), and may contain, as necessary or unavoidably, other compounds copolymerizable with compound (1) and compound (2). Examples of other compounds include compounds represented by the formula (1), such as T １１ or T １２ W-R １１ Compound (1A) having a structure in which —R is replaced by —F is exemplified. １１ -R in F １１ is T in formula (1) １１ and T １２ R included in １１ That is, the raw material composition used in the production method of this embodiment may contain compound (1), compound (2), and compound (1A). The total content of compound (1), compound (2), and compound (1A) relative to the entire raw material composition is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more.

[0042] <Irradiation of ultraviolet rays> The wavelength of ultraviolet rays irradiated onto the raw material composition is 150 to 300 nm, and from the viewpoint of obtaining a high-molecular-weight PFPE compound, it is preferably 180 to 280 nm, more preferably 200 to 260 nm. The light source of ultraviolet rays is not particularly limited, and may be a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, an excimer lamp (Ar ２ , Kr ２ , Xe ２ , KrCl, KrF, ArF, F ２ Examples of suitable light sources include a metal halide lamp, a flash lamp, an electrodeless lamp, an LED lamp, etc. The light source of ultraviolet light can be selected appropriately depending on the wavelength of the ultraviolet light to be irradiated. Specifically, when the wavelength of the ultraviolet light is 250 to 300 nm, a metal halide lamp is used, when the wavelength is 185 nm or 254 nm, a low-pressure mercury lamp is used, and when the wavelength is 157 nm, a F ２ Excimer laser, Xe for 172 nm ２ Examples of such excimer lamps include an ArF excimer laser for 193 nm, a KrCl excimer lamp for 222 nm, and a KrF excimer laser for 248 nm.

[0043] The irradiation intensity of the ultraviolet light is, for example, 1 to 100 mW / cm ２ From the viewpoint of obtaining a high molecular weight PFPE compound, 5 to 30 mW / cm ２ is preferred, and 10 to 20 mW / cm ２ The irradiation intensity of ultraviolet light is measured using an ultraviolet integrating actinometer. The irradiation time of ultraviolet light varies depending on the molecular weight of the target PFPE compound, etc., and may be, for example, 1 to 100 hours. From the viewpoint of balancing energy cost and a high molecular weight of the PFPE compound, 5 to 50 hours is preferred, and 10 to 20 hours is more preferred. The irradiation dose of ultraviolet light varies depending on the molecular weight of the target PFPE compound, etc., and may be, for example, 1 to 2,000 J / cm. ２ From the viewpoint of balancing energy cost and a high molecular weight of the PFPE compound, 10 to 1,000 J / cm ２ is preferred, and 20 to 500 J / cm ２ is more preferred.

[0044] The ultraviolet irradiation is carried out under a flow of inert gas. For example, depending on the application, such as crosslinked rubber, a PFPE compound having a high molecular weight and a large amount of functional groups may be desired. In this embodiment, ultraviolet irradiation is carried out under a flow of inert gas using compound (1) and compound (2), so that carbonyl fluoride groups are unlikely to be generated, as described above. Therefore, photopolymerization is likely to proceed, making it easy to obtain a high molecular weight, and the amount of specific functional groups introduced into the PFPE compound can be easily controlled by adjusting the amount of compound (2), making it possible to obtain a PFPE compound having a high molecular weight and a large amount of functional groups.

[0045] The inert gas is passed through the reactor by introducing the inert gas into the reactor. When the raw material composition is a liquid, the inert gas may be introduced (e.g., by bubbling) into the raw material composition (i.e., the liquid phase) in the reactor, or may be introduced into the gas phase in contact with the raw material composition. Examples of the inert gas include nitrogen gas, helium gas, neon gas, and argon gas. Nitrogen gas or helium gas is preferred, and nitrogen gas is preferred from the viewpoint of keeping costs low. From the viewpoint of suppressing the generation of carbonyl fluoride groups, the flow rate of the inert gas is preferably 0.1 L / min or more, more preferably 0.5 L / min or more, and even more preferably 1 L / min or more. The upper limit of the flow rate of the inert gas is not particularly limited, and may be, for example, 10 L / min. The flow rate of the inert gas is preferably 0.1 to 10 L / min, more preferably 0.5 to 10 L / min, and even more preferably 1 to 10 L / min.

[0046] The raw material composition is preferably irradiated with ultraviolet light while being stirred, from the viewpoint of suppressing the generation of carbonyl fluoride groups. The stirring means is not particularly limited, and examples thereof include a stirring bar, a stirring blade, a mixer, etc.

[0047] The irradiation of the raw material composition with ultraviolet rays may be carried out by irradiating a raw material composition containing no solvent with ultraviolet rays, or by irradiating a mixture of the raw material composition and a fluorine-containing solvent with ultraviolet rays. In particular, when the viscosity of the raw material composition is high, it is preferable to add a fluorine-containing solvent to reduce the viscosity and then irradiate with ultraviolet rays, from the viewpoint of suppressing the generation of carbonyl fluoride groups. Alternatively, after starting ultraviolet irradiation without adding a fluorine-containing solvent to the raw material composition, a fluorine-containing solvent may be added when the viscosity of the raw material composition increases, to reduce the viscosity and further irradiate with ultraviolet rays.

[0048] The fluorine-containing solvent dissolves the high molecular weight PFPE compound and forms -R １１ Preferably, the solvent has low activity against radicals. Furthermore, in order to pass an inert gas through the solvent, the boiling point of the fluorine-containing solvent is preferably higher than the temperature of the raw material composition during irradiation with ultraviolet light (i.e., the reaction temperature). Specific examples of the fluorine-containing solvent include perfluorodecalin, perfluorotributylamine, Fomblin Y series (manufactured by Solvay), Galden (manufactured by Solvay), fluoroalkanes such as 1H-perfluorodecane, and the like.

[0049] The temperature of the raw material composition during irradiation with ultraviolet light is preferably 0 to 100°C, more preferably 50 to 100°C, and even more preferably 50 to 70°C. Hereinafter, the temperature of the raw material composition during irradiation with ultraviolet light will also be referred to as the "reaction temperature." When the reaction temperature is equal to or higher than the lower limit, the photopolymerization of compound (1) and compound (2) is facilitated. When the reaction temperature is equal to or lower than the upper limit, the -R １１ The radical is added to the perfluorovinyl group of compound (2) to form -L of compound (2). １ -Z １The generation of carbonyl fluoride groups due to the elimination of fluorine is less likely to occur. Therefore, by suppressing side reactions, it is also easier to control the amount of functional groups. The pressure inside the reactor during ultraviolet irradiation is usually slightly increased because the reaction is carried out under a flow of inert gas, but when a solvent is used, it may be increased to a gauge pressure of 0.1 MPa or less to suppress its volatilization. This is also preferred in that the generation of carbonyl fluoride is suppressed even under reduced pressure. The photopolymerization of the raw material composition by ultraviolet irradiation may be carried out by a batch method or a continuous method.

[0050] [Compound] A compound according to an embodiment of the present disclosure is a PFPE compound containing a unit (1) derived from a compound (1) represented by the following formula (1) and a unit (2) derived from a compound (2) represented by the following formula (2): T １１ -O-Rf １ -T １２ ...Formula (1) F ２ C=CF-O-L １ -Z １ ...Formula (2) In formula (1), T １１ and T １２ are each independently -R １１ -COOH or -R １１ -COOR １２ and R １１ are each independently a perfluoroalkylene group, and R １２ are each independently an alkyl group, and Rf １ is (R １３ O) ｎ１ and R １３ are each independently a perfluoroalkylene group, n1 is an integer of 1 or more, and in formula (2), L １ is a divalent linking group, Z １ is -SO ２ F, —CN, —CH ２ OH or -COOR ２２ is a functional group represented by R ２２ is an alkyl group.

[0051] The PFPE compound according to this embodiment can be obtained, for example, by the above-described production method, which allows for the production of a PFPE compound having a PFPE chain in the main chain and a specific functional group in the side chain, with the content of the specific functional group being controlled.

[0052] The unit (1) is a functional group of —COOH or —COOR at both ends of the compound (1). １２ is eliminated, and is represented by, for example, the following formula (1-1). Unit (2) is a structural unit in which the carbon-carbon double bond of the perfluorovinyl group of compound (2) is cleaved, and is represented by, for example, the following formula (2-1). The PFPE compound according to this embodiment contains, for example, a unit represented by the following formula (1-1) and a unit represented by the following formula (1-2). １１ -O-Rf １ -R １１ -*...Formula (1-1) In formula (1-1), R １１ is T in formula (1) １１ and T １２ -R represented by １１ -COOH or -R １１ -COOR １２ R １１ and Rf １ is Rf in formula (1) １ and * denotes the bond between adjacent units.

[0053]

[0054] In formula (2-1), L １ is L in formula (2) １ is synonymous with Z １ is Z in formula (2) １ and * denotes the bond between adjacent units.

[0055] The PFPE compound according to the present embodiment may contain at least the unit (1) and the unit (2), and the terminal group of the PFPE compound is not particularly limited. The PFPE compound obtained by polymerization of a raw material composition consisting of the compound (1) and the compound (2) contains, for example, at least the unit (1) and the unit (2), and has the T in formula (1) as the terminal group. １１ and T１２ The PFPE compound obtained by polymerization of a raw material composition comprising the compound (1), the compound (2), and the compound (1A) contains, for example, at least the unit (1) and the unit (2), and has, as a terminal group, the T １１ and T １２ and -R １１ -F.

[0056] The PFPE compound according to this embodiment has a terminal group of -R １１ —COOH, —R １１ -COOR １２ , and -R １１ -F, and -R １１ -COOH and -R １１ It is more preferable that the PFPE compound according to this embodiment contains at least one selected from the group consisting of —SO ２ F, —CN, —CH ２ OH and -COOR ２２ and -SO ２ F, —CN, and —CH ２ It is preferable that the compound contains at least one selected from the group consisting of OH, and SO ２ It is more preferable that the group contains at least one selected from the group consisting of F and —CN.

[0057] The number average molecular weight of the PFPE compound according to this embodiment is, for example, 3,000 to 300,000. From the viewpoint of excellent thermal stability, the number average molecular weight of the PFPE compound according to this embodiment is preferably 5,000 or more, more preferably 10,000 or more, and when mechanical properties are important, it is even more preferably 30,000 or more, particularly preferably 50,000 or more, and extremely preferably 100,000 or more. The method for measuring the number average molecular weight is as described above.

[0058] The content (mass %) of the unit (2) contained in one molecule of the PFPE compound according to this embodiment is preferably 0.1 to 90 mass %, more preferably 1 to 90 mass %, based on the total mass of the PFPE compound, depending on the intended use. For polymer electrolyte applications, it is more preferably 10 to 90 mass %, even more preferably 30 to 70 mass %. When used as a crosslinking site of an elastomer, the content (mass %) of the unit (2) contained in one molecule of the PFPE compound is preferably 0.1 to 10 mass %. The content of the unit (2) contained in one molecule of the compound is １９ It is determined by F-NMR analysis.

[0059] The content of the specific functional group is preferably 0.001 to 3 mmol / g relative to the entire PFPE compound depending on the intended use, and for polymer electrolyte applications, it is more preferably 0.5 to 3 mmol / g, and even more preferably 1 to 2.5 mmol / g. １９ The unit (1) contained in the PFPE compound is T １１ and T １２ At least one of them is -R １１ -COOR １２ In the case where the unit is derived from the compound (1), the content of the specific functional group is -COOR which may be contained at the end of the main chain of the PFPE compound. １２ This value does not include the content of

[0060] The present disclosure will be described in detail below using examples. However, the present disclosure is not limited to these examples. Examples 1 to 7 are working examples.

[0061] [Example 1] A raw material composition, which was a mixture of 7 g of compound (11) and 7 g of compound (21), was stirred at 60°C under a nitrogen gas flow of 2.0 L / min, while being irradiated with ultraviolet light having a wavelength of 254 nm at an intensity of 15 mW / cm. ２ The mixture was irradiated with a low-pressure mercury lamp (manufactured by Sen Special Light Sources Co., Ltd.) for 38 hours to obtain PFPE compound (A1). Compound (11): Fomblin ZDIAC4000 manufactured by Solvay. The average value of n11 was 20, and the average value of n12 was 20. The number average molecular weight was 3,800. HOCOCF ２-O-(CF ２ O) ｎ１１ (CF ２ CF ２ O) ｎ１２ -CF ２ COOH...(11) Compound (21): CF ２ =CF-O-CF ２ CF (CF ３ ) OCF ２ CF ２ -SO ２ F... (21)

[0062] Reference Example 1 According to the method disclosed in the non-patent document (Journal of Fluorine Chemistry, 125 (2004) 243), the specific functional group —SO of the PFPE compound (A1) obtained in Example 1 was substituted with PFPE compound (A1). ２ F, -SO ２ N － (Li ＋ ) SO ２ CF ３ The compound obtained by the conversion of the functional group had good conductivity, and it was therefore confirmed that the PFPE compound (A1) was useful as a material for polymer electrolytes.

[0063] [Examples 2 to 3] PFPE compounds (A2) to (A3) were obtained in the same manner as in Example 1, except that the amount of compound (11), the amount of compound (21), and the irradiation time of ultraviolet light were changed as shown in Table 1.

[0064] [Example 4] While stirring 10 g of compound (11) at 90°C under a nitrogen gas flow of 2.0 L / min, the compound was irradiated with ultraviolet light having a wavelength of 254 nm at an intensity of 15 mW / cm ２ The mixture was irradiated with ultraviolet light for 12 hours (using a low-pressure mercury lamp (manufactured by Sen Special Light Sources Co., Ltd.)) to obtain compound (12) having a number average molecular weight of 18,000. PFPE compound (A4) was obtained in the same manner as in Example 1, except that 7 g of compound (12) and 4.5 g of compound (22) were used as the raw material composition and the ultraviolet light irradiation time was changed as shown in Table 1. Compound (22): CF ２ =CF-O-CF ２ CF (CF ３ ) OCF ２ CF ２ -CN ... (22)

[0065] (Reference Example 2) The PFPE compound (A4) obtained in Example 4 and 2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAOP) were kneaded and heated at 150°C for 1 hour to produce a crosslinked film. The crosslinked film obtained had strength and elasticity, confirming that the PFPE compound (A4) is useful as a material for crosslinked rubber.

[0066] [Example 5] Compound (13) having a number average molecular weight of 54,000 was obtained in the same manner as in the preparation of compound (12) in Example 4, except that the ultraviolet irradiation time was changed from 12 hours to 17 hours.

[0067] PFPE compound (A5) was obtained in the same manner as in Example 1, except that 10 g of compound (13) and 1 g of compound (22) were used as raw material compositions and the ultraviolet irradiation time was changed as shown in Table 1.

[0068] [Example 6] Compound (14) having a number average molecular weight of 11,000 was obtained in the same manner as in the preparation of compound (12) in Example 4, except that the ultraviolet irradiation time was changed from 12 hours to 7 hours. PFPE compound (A6) was obtained in the same manner as in Example 1, except that 10 g of compound (14) and 0.15 g of compound (23) were used as raw material compositions and the ultraviolet irradiation time was changed as shown in Table 1. Compound (23): CF ２ =CF-O-CF ２ CF ２ CF ２ -COOCH ３ …(23)

[0069] (Reference Example 3) The PFPE compound (A6) obtained in Example 6 was placed on a glass plate and heated at 90°C for 30 minutes to develop it into a film, which was then irradiated with ultraviolet light for 5 hours to produce a crosslinked film. The resulting crosslinked film had strength and elasticity, confirming that the PFPE compound (A6) is useful as a material for crosslinked rubber.

[0070] [Example 7] PFPE compound (A7) was obtained in the same manner as in Example 1, except that 6 g of compound (11) and 4 g of compound (24) were used as the raw material composition and the ultraviolet irradiation time and reaction temperature were changed as shown in Table 1. Compound (24): CF ２ =CF-O-CF ２ CF ２ CF ２ -CH ２ OH (24) Since the PFPE compound (A7) can dissolve Li salts, it was confirmed that the PFPE compound (A7) is useful as a material for polymer electrolytes.

[0071] <Measurement> p-bistrifluoromethylbenzene was added as an internal standard to the compound to be measured. １９ F-NMR measurement and １ The number average molecular weight was determined by H-NMR measurement. １９ The amount of peaks derived from the specific functional group is measured from the F-NMR spectrum to determine the content of the specific functional group relative to the total number of F in the PFPE compound, which is the compound to be measured, and then: １ The total amount of terminal groups (carboxy groups) determined by H-NMR measurement １９ The number average molecular weight of the resulting PFPE compound was calculated from the total F number and the content of the specific functional group determined by F-NMR measurement. The results are shown in Table 1.

[0072] Table 1 shows the content of compound (2) relative to the total raw material composition ("content of compound (2)" in the table). １９ The content of the specific functional group in the entire PFPE compound ("specific amount" in the table) was determined by F-NMR analysis. The results are shown in Table 1. The yield is also shown in Table 1.

[0073]

[0074] As shown in Table 1, by using compound (1) and compound (2) and irradiating them with ultraviolet light under an inert gas flow, it is possible to obtain PFPE compounds in which the amount of functional groups is freely controlled.

[0075] The compounds obtained by the compound production method of the present disclosure are useful as materials for polymer electrolytes, crosslinked rubbers, gas / liquid separation membranes, optical element encapsulants, contact lenses, elastic adhesives, microchannel devices, and the like.

[0076] The disclosure of Japanese Patent Application No. 2024-050201, filed on March 26, 2024, is incorporated herein by reference in its entirety. In addition, all documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A method for producing a compound having a perfluoropolyether chain, comprising irradiating a raw material composition containing a compound (1) represented by the following formula (1) and a compound (2) represented by the following formula (2) with ultraviolet light having a wavelength of 150 to 300 nm under a flow of inert gas, thereby copolymerizing the compound (1) and the compound (2). １１ -O-Rf １ -T １２ ...Formula (1) F ２ C=CF-O-L １ -Z １ ...Formula (2) In formula (1), T １１ and T １２ are each independently -R １１ -COOH or -R １１ -COOR １２ and R １１ are each independently a perfluoroalkylene group, and R １２ are each independently an alkyl group, and Rf １ is (R １３ O) ｎ１ and R １３ are each independently a perfluoroalkylene group, n1 is an integer of 1 or more, and in formula (2), L １ is a divalent linking group, Z １ is -SO ２ F, —CN, —CH ２ OH or -COOR ２２ is a functional group represented by R ２２ is an alkyl group.

2. The method for producing a compound according to claim 1, wherein the content of the compound (2) is 1 to 90 mass % based on the total mass of the raw material composition.

3. The method for producing a compound according to claim 1 or 2, wherein the temperature of the raw material composition during irradiation with ultraviolet light is 0 to 100°C.

4. A compound having a perfluoropolyether chain, comprising a unit (1) derived from a compound (1) represented by the following formula (1) and a unit (2) derived from a compound (2) represented by the following formula (2): T １１ -O-Rf １ -T １２ ...Formula (1) F ２ C=CF-O-L １ -Z １ ...Formula (2) In formula (1), T １１ and T １２ are each independently -R １１ -COOH or -R １１ -COOR １２ and R １１ are each independently a perfluoroalkylene group, and R １２ are each independently an alkyl group, and Rf １ is (R １３ O) ｎ１ and R １３ are each independently a perfluoroalkylene group, n1 is an integer of 1 or more, and in formula (2), L １ is a divalent linking group, Z １ is -SO ２ F, —CN, —CH ２ OH or -COOR ２２ is a functional group represented by R ２２ is an alkyl group.

5. The compound according to claim 4, wherein the content of the unit (2) contained in one molecule is 1 to 90% by mass.

6. The compound according to claim 4, having a number average molecular weight of 5,000 or more.

7. The compound of claim 5, having a number average molecular weight of 5,000 or more.

8. Z in the formula (2) １ The compound according to any one of claims 4 to 7, wherein the content of the functional group represented by the formula (I) is 0.001 to 3 mmol / g relative to the entire compound.

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