Substituted polyphenylene ether, amino group-containing polyphenylene ether, and thermosetting polyphenylene ether

Abstract

Provided is a substituted polyphenylene ether having an enhanced ability to form an intermolecular or intramolecular network. Provided is a polyphenylene ether characterized by comprising at least one component represented by Formula (3) or Formula (4).

Description

Substituted polyphenylene ethers, amino group-containing polyphenylene ethers, and thermosetting polyphenylene ethers

[0001] This invention relates to substituted polyphenylene ethers. This invention relates to amino group-containing polyphenylene ethers, methods for producing the same, gas barrier membranes, gas barrier materials, and gas separation membranes. This invention relates to thermosetting polyphenylene ethers, methods for producing thermosetting polyphenylene ethers, and resin films.

[0002] Poly(2,6-cymethyl-1,4-phenylene ether) (hereinafter referred to as polyphenylene ether or PPE) has excellent high-frequency properties, flame retardancy, and heat resistance, and is therefore widely used as a material for products and components in the electrical and electronic fields, the automotive field, and other industrial materials fields.

[0003] Due to its polymeric properties, polyphenylene ether has limited applications. One specific example is industrial materials requiring gas barrier properties. PPE is attracting attention as a gas separation membrane material. This is because it has a rigid main chain skeleton and easily maintains gaps between polymer chains, resulting in excellent gas permeability. However, due to its high gas permeability, its application in food and beverage packaging and industrial materials requiring gas barrier properties has been difficult.

[0004] On the other hand, Patent Document 1 (Japanese Unexamined Patent Publication No. 57-117321) discloses techniques for benzylic halogenation and amination of PPE, and the introduction of polar functional groups reduces gas permeability compared to PPE.

[0005] However, these modified PPE rings or benzyl rings, while exhibiting reduced gas permeability, were not sufficiently improved and worsened thermal decomposition properties, making their application to industrial materials requiring heat resistance difficult.

[0006] PPE has also attracted attention as a gas separation membrane material, and Patent Document 1 (Japanese Patent Publication No. 57-117321) discloses techniques for benzylic halogenation and amination of PPE, stating that selective gas permeability is improved by introducing polar functional groups. However, while these modifications to the PPE ring or benzylic position improve selective permeability, it is not sufficient, and they worsen thermal decomposition, which can lead to degradation over time.

[0007] A second specific example is printed circuit boards or package substrates. With the remarkable progress of information network technology, or the expansion of services utilizing information networks, electronic devices are required to have larger data capacities and faster processing speeds. Against this backdrop, printed circuit boards mounted on electronic devices are required to have low dielectric loss tangents in order to reduce signal transmission loss.

[0008] Furthermore, in recent years, with the development of advanced road traffic systems such as advanced driver-assistance systems and autonomous driving, there is a growing demand for lower dielectric strength in printed circuit boards or package substrates, even in automotive applications where heat resistance is required.

[0009] In response to these demands, improvements are being made to epoxy resin compositions used in printed circuit boards or package substrates. For example, Patent Document 2 (Japanese Patent No. 7625940) discloses a curable resin composition that can exhibit high heat resistance, low dielectric properties, and high elastic modulus.

[0010] However, the resin compositions described in the above-mentioned literature had room for further improvement in terms of achieving both low transmission loss (low dielectric loss tangent) and heat resistance (high glass transition temperature).

[0011] Japanese Patent Application Laid-open No. 57-117321 Patent No. 7625940

[0012] Both of the aforementioned problems stem from the fact that the polymer chains in PPE cannot form a sufficient network.

[0013] Therefore, the present invention aims to provide a substituted polyphenylene ether with improved intermolecular or intramolecular network-forming ability.

[0014] Furthermore, one aspect of the present invention aims to provide an atom-containing polyphenylene ether and its gas barrier membrane that can improve gas barrier properties in gas permeation and have excellent thermal decomposition resistance. Another aspect of the present invention aims to provide an amino group-containing polyphenylene ether and its separation membrane that can improve selective gas permeability in gas permeation and have excellent thermal decomposition resistance.

[0015] Furthermore, one aspect of the present invention has been made in view of the above-mentioned problems, and aims to provide a thermosetting polyphenylene ether with excellent transmission loss and heat resistance. Another aspect of the present invention is to provide a prepreg formed using the thermosetting polyphenylene ether.

[0016] As a result of diligent research to solve the above problems, the present inventors have found that by introducing a predetermined nonionic substituent into the main chain skeleton of polyphenylene ether, a substituted polyphenylene ether with improved network-forming ability between polymer chains can be obtained.

[0017] In other words, the present invention is as follows: [1] A polyphenylene ether characterized by comprising at least one component represented by formula (3) or formula (4). (In equations (3) and (4), R ７ ~R ９ , R １０ and R １１ Each is independently at least one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, and a cyano group, R ７ and R ８ At least one of them is an alkyl group, R １０ and R １１At least one of them is an alkyl group, X is a divalent group that includes an alkylene group and may include a divalent group having a hetero atom, a divalent group including a divalent electron-withdrawing group and an arylene group, or a divalent group including a divalent electron-withdrawing group and an alkylene group, Z is a nonionic substituent having a hetero atom, the nonionic substituent has a substituent having an active hydrogen, a substituent having a double bond, or a substituent having an epoxy ring, and the double bond is any one of a carbon-carbon bond, a hetero atom-hetero atom bond, and a carbon atom-hetero atom bond.) [2] A polyphenylene ether characterized by containing at least a constituent component represented by formula (5) or formula (6). (In formula (5) and formula (6), １２ ~R １４ , R １５ and R １６ are each independently at least one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, and a cyano group, at least one of R １２ and R １３ is an alkyl group, R １５ and R １６At least one of the groups is an alkyl group, X is a divalent group comprising an alkylene group and may also comprise a divalent group having a heteroatom, a divalent group comprising a divalent electron-withdrawing group and an arylene group, or a divalent group comprising a divalent electron-withdrawing group and an alkylene group, T is an amino group, an ether group, or a thioether group, Z' is independently a nonionic or ionic substituent, at least one of Z' is a nonionic substituent, the nonionic substituent has an active hydrogen atom, a double bond, or an epoxy ring, the double bond is one of a carbon-carbon bond, a heteroatom heteroatom bond, or a carbon-carbon heteroatom bond, and n is 1 or 2. [3] The polyphenylene ether according to [2], characterized in that the nonionic substituent includes a group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, a hydroxyl group, a thiol group, a carboxyl group, a vinylbenzyl group, a vinyl group, an allyl group, a norbornene group, a methacrylic group, a maleimide group, a cinnamoyl group or a glycidyl group, an azo group, and an azide group. [4] A polyphenylene ether characterized in that it includes at least one component represented by formula (7) or formula (8). (In equations (7) and (8), R １７ ~R １９ , R ２０ and R ２１ Each is independently at least one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, and a cyano group, R １７ and R １８ At least one of them is an alkyl group, R ２０ and R ２１At least one of is an alkyl group, X is a divalent group including an alkylene group and may include a divalent group having a heteroatom, a divalent group including a divalent electron-withdrawing group and an arylene group, or a divalent group including a divalent electron-withdrawing group and an alkylene group, Y' is an amino group, A is a structure including an unsaturated or saturated carbon-carbon bond, at least one of A is a group including an unsaturated carbon-carbon bond, and n is 1 or 2.) [5] The polyphenylene ether according to [4], wherein the group including the unsaturated carbon-carbon bond is any of a vinylbenzyl group, an allyl group, a vinyl group, a norbornene group, a methacrylic group or a maleimide group. [6] A polyphenylene ether characterized by containing at least one component represented by formula (9) or formula (10). (In equations (9) and (10), R ２２ ~R ２４ , R ２５ and R ２６ Each is independently at least one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, and a cyano group, R ２２ and R ２３ At least one of them is an alkyl group, R ２５ and R ２６ At least one of them is an alkyl group, X is a divalent group containing an alkylene group and may contain a divalent group having a heteroatom, a divalent group containing a divalent electron-withdrawing group and an arylene group, or a divalent group containing a divalent electron-withdrawing group and an alkylene group, and Y is a structure containing an amino group.) [7] A step of obtaining a polyphenylene ether by oxidative polymerization of the phenol of formula (11), and the R of the polyphenylene ether ２８ A method for producing a polyphenylene ether according to [1], comprising: a modification step of introducing the nonionic substituent to at least one of to obtain a polyphenylene ether containing the components of formula (3) and / or formula (4); (In formula (11), R ２７Each of these is independently an optionally substituted C1-C6 alkyl group, an optionally substituted C6-C12 aryl group, or a halogen atom, R ２８Each of these is independently a hydrogen atom, an optionally substituted C1-C6 alkyl group, an optionally substituted C6-C12 aryl group, or a halogen atom.) [8] A method for producing a polyphenylene ether according to [2], comprising: a step of polymerizing an unmodified polyphenylene ether by oxidative polymerization of the phenol of formula (11); a step of synthesizing a modified polyphenylene ether by introducing into the unmodified polyphenylene ether an alkyl group which may contain a bonding group, a monovalent group which may contain a bonding group, or a monovalent group which may contain a bonding group, a divalent electron-withdrawing group, and an alkyl or alkylene group; a step of synthesizing a heteroatom group-containing polyphenylene ether by introducing a heteroatom group into the modified polyphenylene ether; and a step of introducing a nonionic substituent into the heteroatom group-containing polyphenylene ether. [9] A method for producing a polyphenylene ether according to [4], comprising: a step of polymerizing an unmodified polyphenylene ether by oxidative polymerization of a phenol of formula (11); a step of synthesizing a modified polyphenylene ether by introducing to the unmodified polyphenylene ether a monovalent group comprising an alkyl group which may contain a bonding group, a divalent electron-withdrawing group and an arylene group which may contain a bonding group, or a monovalent group comprising a divalent electron-withdrawing group and an alkyl group or alkylene group which may contain a bonding group; a step of synthesizing an amino group-containing polyphenylene ether by introducing an amino group to the modified polyphenylene ether; and a step of introducing to the amino group-containing polyphenylene ether a group which contains an unsaturated carbon-carbon bond.

[10] A method for producing a polyphenylene ether according to [6], comprising the steps of: polymerizing an unmodified polyphenylene ether by oxidative polymerization of the phenol of formula (11); synthesizing a modified polyphenylene ether by introducing to the unmodified polyphenylene ether a monovalent group comprising an alkyl group which may contain a bonding group, a divalent electron-withdrawing group and an arylene group which may contain a bonding group, or a monovalent group comprising a divalent electron-withdrawing group and an alkyl group or alkylene group which may contain a bonding group; and introducing an amino group to the modified polyphenylene ether.

[11] A polymer network comprising the polyphenylene ether according to any one of [1] to [6].

[12] A polyphenylene ether solution comprising the polyphenylene ether according to any one of [1] to [6].

[13] A thermosetting composition comprising the polyphenylene ether according to [4] or [5].

[14] A cured product comprising the thermosetting composition according to

[13] .

[15] A method for producing a cured product, comprising the step of heat-molding the thermosetting composition described in

[13] .

[16] A prepreg comprising a substrate and the thermosetting composition described in

[13] .

[17] A printed circuit board or package substrate comprising the thermosetting composition described in

[13] .

[18] A hydrogen-bonding polymer network comprising the polyphenylene ether described in [6].

[19] A gas barrier film or gas barrier material comprising the polyphenylene ether described in [6].

[0018] According to the present invention, it is possible to provide substituted polyphenylene ethers with improved intermolecular or intramolecular network-forming ability.

[0019] Furthermore, according to the present invention, it is possible to provide a heteroatom group-containing polyphenylene ether and its gas barrier membrane that can improve gas barrier properties in gas permeation and have excellent thermal decomposition resistance. In addition, it is possible to provide an amino group-containing polyphenylene ether and its separation membrane that can improve gas selective permeability in gas permeation and have excellent thermal decomposition resistance.

[0020] Furthermore, the present invention has been made in view of the above-mentioned problems and aims to provide a thermosetting polyphenylene ether with excellent transmission loss and heat resistance. The present invention can also provide a prepreg formed using the thermosetting polyphenylene ether.

[0021] The following describes in detail embodiments for carrying out the present invention (hereinafter referred to as "this embodiment"). It should be noted that the present invention is not limited to the following embodiments, and can be implemented in various modifications within the scope of its gist.

[0022] [Substituted Polyphenylene Ether] The substituted polyphenylene ether of this embodiment contains the constituent components shown in formula (1) or formula (2). (In equations (1) and (2), R １ ~R ３ Each is independently at least one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, and a cyano group, R １ and R ２ At least one of them is an alkyl group, R ５ and R ６ At least one of them is an alkyl group, R ４ (It is a nonionic reactive group containing a heteroatom.)

[0023] In this specification, "heteroatom" generally refers to atoms other than carbon and hydrogen that constitute organic compounds, such as boron, nitrogen, oxygen, silicon, phosphorus, sulfur, and halogen atoms (e.g., fluorine, chlorine, bromine, iodine), and more specifically, nitrogen, oxygen, and sulfur, but is not limited to these.

[0024] In this embodiment, the substituted polyphenylene ethers include the thermosetting polyphenylene ethers, heteroatom-containing polyphenylene ethers, and amino group-containing polyphenylene ethers described later.

[0025] The substituted polyphenylene ether of this embodiment may contain both the unit of formula (1) and the unit of formula (2).

[0026] An example of the substituted polyphenylene ether of this embodiment is preferably one which contains the constituent components represented by formula (3) or formula (4). (In equations (3) and (4), R ７ ~R ９ , R １０ and R １１ Each is independently at least one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, and a cyano group, R ７ and R ８ At least one of them is an alkyl group, R １０ and R １１ At least one of them is an alkyl group, X is a divalent group containing an alkylene group and may contain a divalent group having a heteroatom, a divalent group preferably containing a divalent electron-withdrawing group and an arylene group in series, or a divalent group preferably containing a divalent electron-withdrawing group and an alkylene group in series, Z is a nonionic substituent containing a heteroatom, the nonionic substituent having an active hydrogen atom, a substituent having a double bond, or a substituent having an epoxy ring, the double bond being any of a carbon-carbon bond, a heteroatom heteroatom bond, or a carbon-carbon heteroatom bond.) The substituted polyphenylene ether of this embodiment may contain both the (3) unit and the (4) unit. ７ and R ８ At least one of them is an alkyl group. １０ and R １１ At least one of the elements is an alkyl group. Having one element be an alkyl group suppresses the formation of branched structures and imparts heat resistance and mechanical strength.

[0027] Examples of the "divalent group having a heteroatom" in X include oxy, thio, aza (imino group, etc.). When X is a "divalent group containing an alkylene group and a divalent group having a heteroatom", preferred divalent groups include oxyalkylene groups, alkylene oxyalkylene groups, alkylene oxy groups, thioalkylene groups, alkylentioalkylene groups, alkylentio groups, azaalkylene groups, alkylene azaalkylene groups, and alkylene aza groups. Furthermore, when X is a "divalent group containing an alkylene group and possibly containing a divalent group having a heteroatom", other divalent groups may be further included in the structure. Examples of other divalent groups include divalent electron-withdrawing groups or arylene groups. The number of carbon atoms in the "alkylene group" in X is preferably 1 to 12, and more preferably 2 to 8. The divalent electron-withdrawing groups of X are -C(O)- (carbonyl group (keto group)), -S(O)- (sulfoxide), and -S(O). ２ Examples include -(sulfone), with -C(O)-(carbonyl group (keto group)) being preferred. Examples of the "arylene group" in X include a phenylene group, a naphthylene group, anthracenyl group, and a benzyl group, with a phenylene group being preferred. When X is a "divalent group preferably containing a divalent electron-withdrawing group and an arylene group in series" or a "divalent group preferably containing a divalent electron-withdrawing group and an alkylene group in series", it is preferable that the arylene group or alkylene group is bonded to the structure represented by Z.

[0028] Z is a nonionic substituent. A nonionic functional group is a functional group in which the entire group is electrically neutral and does not behave as an ion. For example, quaternary ammonium is not a nonionic substituent in this invention. Z may be a monovalent group including structures exemplified by T, Y, and A described later.

[0029] Z has a substituent with an active hydrogen atom, a substituent with a double bond, or a substituent with an epoxy ring, and the double bond is one of a carbon-carbon bond, a heteroatom heteroatom bond, or a carbon-carbon heteroatom bond.

[0030] Z is preferably a reactive group from the viewpoint of being able to form a polymer network. The reactive group is a substituent capable of forming intermolecular or intramolecular interactions through hydrogen bonding or covalent bonding. Examples of the reactive group include substituents having active hydrogen, substituents having a double bond, or substituents having an epoxy ring. Specifically, examples include substituents containing a group selected from the group consisting of primary amino groups, secondary amino groups, tertiary amino groups, hydroxyl groups, thiol groups, carboxyl groups, vinyl groups, allyl groups, norbornene groups, vinylbenzyl groups, methacrylic groups, maleimide groups, cinnamoyl groups, glycidyl groups, azo groups, or azide groups. Having a reactive group makes it possible to form a polymer interchain network of polyphenylene ether, and makes it possible to exhibit properties different from conventional polyphenylene ethers in which a polymer interchain network is not formed.

[0031] It is preferable that Z contains a heteroatom. When Z contains a heteroatom, it becomes possible to form an interchain network of polymers through interactions between the heteroatoms. Interactions between heteroatoms refer to interactions other than ionic bonds, such as hydrogen bonds and dipole-dipole interactions. Furthermore, since the active hydrogen adjacent to the heteroatom is highly reactive and substitution reactions proceed relatively easily, it is possible to substitute the active hydrogen with substituents that form a covalent network, thereby synthesizing polymers that can form a covalent interchain network of polymers.

[0032] An example of the substituted polyphenylene ether of this embodiment is preferably one which contains the constituent components represented by formula (5) or formula (6). (In equations (5) and (6), R １２ ~R １４ , R １５ and R １６ Each is independently at least one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, and a cyano group, R １２ and R １３ At least one of them is an alkyl group, R １５ and R １６At least one of the members is an alkyl group, X is a divalent group comprising an alkylene group and may also include a divalent group having a heteroatom, a divalent group comprising a divalent electron-withdrawing group and an arylene group preferably in series, or a divalent group comprising a divalent electron-withdrawing group and an alkylene group preferably in series, T is an amino group (preferably a secondary or tertiary amino group), an ether group, or a thioether group, Z' is each independently a nonionic or ionic substituent, at least one of Z' is a nonionic substituent, the nonionic substituent has an active hydrogen atom, a double bond, or an epoxy ring, the double bond is one of a carbon-carbon bond, a heteroatom heteroatom bond, or a carbon-carbon heteroatom bond, and n is a natural number from 1 to 3, preferably 1 or 2.) The substituted polyphenylene ether of this embodiment may contain both the (5) unit and the (6) unit. Also, in equations (5) and (6) -T-(Z') ｎ The structures represented by are the structures that -Z in equations (3) and (4) can take.

[0033] Examples of the "divalent group having a heteroatom" in X include oxy, thio, aza (imino group, etc.). When X is a "divalent group containing an alkylene group and a divalent group having a heteroatom", preferred divalent groups include oxyalkylene groups, alkylene oxyalkylene groups, alkylene oxy groups, thioalkylene groups, alkylentioalkylene groups, alkylentio groups, azaalkylene groups, alkylene azaalkylene groups, and alkylene aza groups. Furthermore, when X is a "divalent group containing an alkylene group and possibly containing a divalent group having a heteroatom", other divalent groups may be further included in the structure. Examples of other divalent groups include divalent electron-withdrawing groups or arylene groups. The number of carbon atoms in the "alkylene group" in X is preferably 1 to 12, and more preferably 2 to 8. The divalent electron-withdrawing groups of X are -C(O)- (carbonyl group (keto group)), -S(O)- (sulfoxide), and -S(O). ２Examples include -(sulfone), with -C(O)-(carbonyl group (keto group)) being preferred. Examples of the "arylene group" in X include phenylene group, naphthylene group, anthracenyl group, and benzyl group, with phenylene group being preferred.

[0034] T is an amino group (preferably a secondary or tertiary amino group), an ether group, or a thioether group, and it is preferable that the structure contains an amino group, and more preferably that it contains a secondary or tertiary amino group.

[0035] Each of Z' is independently a hydrogen atom, a nonionic substituent, or an ionic substituent. At least one of Z' is a nonionic substituent. When n is 2, each of Z' may independently be a hydrogen atom, an alkyl group, an alkylene group, or one of the aforementioned nonionic substituents. From the viewpoint of ease of manufacture, it is preferable that each of Z' is bonded to a heteroatom contained in T. It is preferable that n is a natural number of 1 or 2.

[0036] The nonionic substituent has an active hydrogen atom, a double bond, or an epoxy ring, and the double bond is one of a carbon-carbon bond, a heteroatom heteroatom bond, or a carbon-carbon heteroatom bond.

[0037] The nonionic substituent is preferably a nonionic reactive group, from the viewpoint of being able to form a polymer network. The nonionic reactive group is a substituent capable of forming intermolecular or intramolecular interactions through hydrogen bonding or covalent bonding. Having a reactive group makes it possible to form a polymer interchain network of the polyphenylene ether, and makes it possible to exhibit properties different from conventional polyphenylene ethers in which a polymer interchain network is not formed.

[0038] The nonionic substituent preferably includes a group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, a hydroxyl group, a thiol group, a carboxyl group, a vinyl group, an allyl group, a norbornene group, a vinylbenzyl group, a methacrylic group, a maleimide group, a cinnamoyl group, a glycidyl group, an azo group, or an azide group; more preferably includes a group selected from the group consisting of a vinylbenzyl group, a methacrylic group, a maleimide group, a glycidyl group, an azo group, or an azide group; even more preferably includes a group selected from the group consisting of a vinylbenzyl group, a methacrylic group, a maleimide group, or a glycidyl group; and most preferably is a vinylbenzyl group, a methacrylic group, or a maleimide group.

[0039] The embodiments in which the nonionic substituent is one of a primary amino group, a secondary amino group, a tertiary amino group, a hydroxyl group, a thiol group, or a carboxyl group are collectively referred to as heteroatom-containing polyphenylene ethers.

[0040] The embodiments in which the nonionic substituent is a primary amino group, a secondary amino group, or a tertiary amino group are collectively referred to as amino group-containing polyphenylene ethers.

[0041] The embodiments in which the nonionic substituent is any of a vinyl group, allyl group, norbornene group, vinylbenzyl group, methacrylic group, maleimide group, cinnamoyl group, glycidyl group, azo group, or azide group are collectively referred to as thermosetting polyphenylene ethers.

[0042] The substituted polyphenylene ether of this embodiment may contain the components represented by general formula (12). (In formula (12), R ２９ Each of these is independently an optionally substituted C1-C6 alkyl group, an optionally substituted C6-C12 aryl group, or a halogen atom, R ３０Each of these is independently a hydrogen atom, an optionally substituted C1-C6 alkyl group, an optionally substituted C6-C12 aryl group, or a halogen atom.

[0043] In the above formula (12), R ２９ Each of these is preferably an independently saturated hydrocarbon group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably a methyl group or a phenyl group, and even more preferably a methyl group. In formula (12), the two R ２９ It is preferable that both have the same structure. ２９ Substituents in saturated hydrocarbons having 1 to 6 carbon atoms and aryl groups having 6 to 12 carbon atoms include saturated or unsaturated hydrocarbon groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and halogen atoms.

[0044] In the above formula (12), R ３０ Each of these is preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or a methyl group. In formula (11), the two R ２８ These may be different, but it is preferable that one is a hydrogen atom and the other is a hydrocarbon group having 1 to 6 carbon atoms (preferably a methyl group). ３０ Examples of substituents on saturated hydrocarbons having 1 to 6 carbon atoms include saturated or unsaturated hydrocarbon groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and halogen atoms.

[0045] The substituted polyphenylene ether of this embodiment may contain the components represented by general formula (13). (In formula (13), R ３２ Each of these is independently a hydrogen atom, an optionally substituted C1-C20 alkyl or unsaturated hydrocarbon group, an optionally substituted C6-C12 aryl group, or a halogen atom, and two R ３２ Both are not hydrogen atoms, R ３１ This is a substructure represented by general formula (14). (In formula (14), R ３３ Each of these is independently a linear alkyl group having 1 to 8 carbon atoms, which may be substituted, or two R ３３These are bonded to each other to form a cyclic alkyl structure having 1 to 8 carbon atoms, R ３４ Each is independently an alkylene group having 1 to 8 carbon atoms, which may be substituted, and each is independently 0 or 1, R ３５ (This is a hydrogen atom, an optionally substituted C1-C8 alkyl group, or an optionally substituted phenyl group.)

[0046] In the above formula (13), R ３２ Each of these is preferably independently a hydrogen atom, a saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms, or an aryl group having 6 to 12 carbon atoms that may be substituted with an alkyl group having 1 to 6 carbon atoms; more preferably a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms that may be substituted with an alkyl group having 1 to 6 carbon atoms; and even more preferably a hydrogen atom or a methyl group. In formula (12), the two R ３０ These are preferably different, and more preferably one is a hydrogen atom and the other is a hydrocarbon group having 1 to 6 carbon atoms (preferably a methyl group). ３２ Examples of substituents in saturated hydrocarbons having 1 to 15 carbon atoms or aryl groups having 6 to 12 carbon atoms include saturated or unsaturated hydrocarbon groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, halogen atoms, and the like.

[0047] The substructure represented by formula (14) above is preferably a group containing secondary and / or tertiary carbons, such as an isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, tert-amyl group, 2,2-dimethylpropyl group, cyclohexyl group, or a structure having a phenyl group at its terminal, more preferably a tert-butyl group or a cyclohexyl group, and even more preferably a tert-butyl group.

[0048] The substituted polyphenylene ether of this embodiment may contain repeating units derived from the phenol of the following formula (6). (In formula (11), R ２７ Each of these is independently an optionally substituted C1-C6 alkyl group, an optionally substituted C6-C12 aryl group, or a halogen atom, R ２８Each of these is independently a hydrogen atom, an optionally substituted C1-C6 alkyl group, an optionally substituted C6-C12 aryl group, or a halogen atom.

[0049] Since the phenol of formula (11) does not have an unsubstituted ortho position (i.e., hydrogen atoms are not bonded to the two ortho carbon atoms of the carbon atom to which the hydroxyl group is bonded), it can react with other phenolic monomers only at the phenolic hydroxyl group and the para carbon atom. Therefore, the repeating units derived from formula (11) include repeating units having the structure of formula (12).

[0050] The substituted polyphenylene ether of this embodiment may include a unit derived from the phenol of formula (11) and a repeating unit derived from the phenol of the following formula (32). (In formula (32), R ５７ Each of these is independently a hydrogen atom, an optionally substituted C1-C20 alkyl or unsaturated hydrocarbon group, an optionally substituted C6-C12 aryl group, or a halogen atom, and two R ５８ These are not both hydrogen atoms, but rather substructures represented by general formula (13).

[0051] The phenol of formula (12) can react with another phenolic monomer at either the ortho or para position of the phenol, in addition to the phenolic hydroxyl group.

[0052] The substituted polyphenylene ether of this embodiment may further contain the component represented by formula (15). (In formula (15), R ３６ ~R ３８is, independently of each other, at least one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group and a cyano group, and X is a divalent group containing an alkylene group and optionally containing a divalent group having a hetero atom, a divalent group preferably containing a divalent electron-withdrawing group and an arylene group in series, or a divalent group preferably containing a divalent electron-withdrawing group and an alkylene group in series, and D is an alkyl group, a silyl group, a phosphate ester group or a nitro group.)

[0053] Examples of the "divalent group having a hetero atom" in X include oxy, thio, aza (imino group, etc.). When X is a "divalent group containing an alkylene group and a divalent group having a hetero atom", examples of such a divalent group include an oxyalkylene group, an alkyleneoxyalkylene group, an alkyleneoxy group, a thioalkylene group, an alkylenethioalkylene group, an alkylenethio group, an azalkylene group, an alkyleneazalkylene group, and an alkyleneaza group. When X is a "divalent group containing an alkylene group and optionally containing a divalent group having a hetero atom", the structure may further contain other divalent groups. Examples of other divalent groups include a divalent electron-withdrawing group or an arylene group. The number of carbon atoms of the "alkylene group" in X is preferably 1 to 12, more preferably 2 to 8. Examples of the divalent electron-withdrawing group of X include -C(O)- (carbonyl group (keto group)), -S(O)- (sulfoxide), -S(O) ２ -(sulfone), etc., and -C(O)- (carbonyl group (keto group)) is preferred. Examples of the "arylene group" in X include a phenylene group, a naphthylene group, an anthracenyl group, and a benzyl group, and a phenylene group is preferred. When X is a "divalent group preferably containing a divalent electron-withdrawing group and an arylene group in series" or a "divalent group preferably containing a divalent electron-withdrawing group and an alkylene group in series", it is preferred that the above aryl group or alkylene group is bonded to the structure represented by D.

[0054] D is an alkyl group, a silyl group, a phosphate ester group, or a nitro group, and various functions can be imparted by these functional groups. For example, if D is an alkyl group, it can impart fluidity; if it is a silyl group, it can impart adhesion to glass and metals; if it is a phosphate ester group, it can impart flame retardancy; and if it is a nitro group, it can impart optical properties. Multiple of these functional groups may be present. From the viewpoint of fluidity, D preferably has 1 to 20 carbon atoms, and from the viewpoint of heat resistance, it is more preferably 2 to 10 carbon atoms.

[0055] Furthermore, it is preferable that the constituent components represented by formula (15) are represented by formula (16). (In formula (16), R ３９ ~R ４１ Each of the following is independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, and a cyano group; X is an alkylene group, an arylene group containing a divalent electron-withdrawing group, or an alkylene group containing a divalent electron-withdrawing group; T is a structure containing an amino group, an ether group, a thioether group, or a keto group; and D is an alkyl group, a silyl group, a phosphate ester group, or a nitro group.

[0056] [Thermosetting polyphenylene ether] An example of the substituted polyphenylene ether of this embodiment is a thermosetting polyphenylene ether containing the components represented by formula (7) or formula (8).

[0057] By introducing an alkyl group, an arylene group containing a divalent electron-withdrawing group, and another alkyl group containing a divalent electron-withdrawing group into the main chain skeleton of polyphenylene ether, followed by the introduction of a structure containing an amino group, and then a structure containing an unsaturated hydrocarbon group, a thermosetting polyphenylene ether with excellent transmission loss and heat resistance can be obtained. This invention can be efficiently manufactured using a simple synthesis method and can utilize inexpensive general-purpose engineering plastics, making it economically advantageous. (In equations (7) and (8), R １７ ~R １９ Each is independently at least one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, and a cyano group, R１７ and R １８ At least one of them is an alkyl group, and R ２０ and R ２１ At least one of them is an alkyl group, and X is a divalent group containing an alkylene group and optionally containing a divalent group having a heteroatom, a divalent group preferably containing a divalent electron-withdrawing group and an arylene group in series, or a divalent group preferably containing a divalent electron-withdrawing group and an alkylene group in series, Y' is an amino group, A is a structure containing an unsaturated or saturated carbon-carbon bond, at least one of A is a group containing an unsaturated carbon-carbon bond, all of A are bonded to the nitrogen atom contained in Y', and n is 1 or 2.) The thermosetting polyphenylene ether of this embodiment may contain both the unit of formula (7) and the unit of formula (8). Also, the structure represented by -Y'-(A) in formula (7) and formula (8) ｎ is the structure that -Z in formula (3) and formula (4) can take.

[0058] Examples of the "divalent group having a heteroatom" in X include oxy, thio, aza (such as an imino group), etc. When X is a "divalent group containing an alkylene group and a divalent group having a heteroatom", examples of such a divalent group include an oxyalkylene group, an alkyleneoxyalkylene group, an alkyleneoxy group, a thioalkylene group, an alkylenethioalkylene group, an alkylenethio group, an azalkylene group, an alkyleneazalkylene group, and an alkyleneaza group. When X is a "divalent group containing an alkylene group and optionally containing a divalent group having a heteroatom", the structure may further contain other divalent groups. Examples of other divalent groups include a divalent electron-withdrawing group or an arylene group. The number of carbon atoms of the "alkylene group" in X is preferably 1 to 12, more preferably 2 to 8. Examples of the divalent electron-withdrawing group of X include -C(O)- (carbonyl group (keto group)), -S(O)- (sulfoxide), -S(O) ２Examples include -(sulfone), with -C(O)-(carbonyl group (keto group)) being preferred. Examples of the "arylene group" in X include phenylene group, naphthylene group, anthracenyl group, and benzyl group, with phenylene group being preferred.

[0059] Y' is an amino group.

[0060] A is a structure containing unsaturated or saturated carbon-carbon bonds. At least one of A's structures contains an unsaturated hydrocarbon group. n is a natural number of 1 or 2, and when n is 2, A may independently contain a hydrogen atom, an alkyl group, an alkylene group, or the aforementioned unsaturated hydrocarbon group. All A's are bonded to the nitrogen atom contained in Y'. An alkylene group A may bond to a part of Y' to form a ring structure, as shown in formula (18) below.

[0061] The structures of Y' and A are not particularly limited, but the structures shown in the following formulas (17), (18), and (19) are preferred.

[0062] In the above formula (17), R ４２ This represents an alkylene group with 2 to 6 carbon atoms or an oxybisalkylene group with a total of 2 to 6 carbon atoms. １ ~A ３ Each independently represents a structure containing hydrogen, an alkyl group having 1 to 6 carbon atoms, or an unsaturated hydrocarbon group, A １ ~A ３ The structure contains at least one unsaturated hydrocarbon group. n represents an integer from 1 to 5.

[0063] In the above formula (18), A ４ It has a structure containing an unsaturated hydrocarbon group.

[0064] In the above formula (19), A ５ and A ６ Each independently represents a structure containing hydrogen, an alkyl group having 1 to 6 carbon atoms, or an unsaturated hydrocarbon group, A ５ and A ６ At least one of the structures contains an unsaturated hydrocarbon group.

[0065] Structure A includes at least one unsaturated hydrocarbon group. The structure of A is not particularly limited, but the structures shown in the following formulas (20), (21), and (22) are preferred. It is more preferable that A is one of the following groups: vinylbenzyl group, allyl group, vinyl group, norbornene group, methacrylic group, or maleimide group. (In formula (21), R ４３ R is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, and the saturated or unsaturated hydrocarbon is R ４３ The substituents may be present within the range of 1 to 10 total carbon atoms. (In formula (22), R ４４ R is a saturated or unsaturated divalent hydrocarbon group having 1 to 10 carbon atoms, and the saturated or unsaturated divalent hydrocarbon is R ４４ R may have substituents within the range of 1 to 10 total carbon atoms. ４５ R is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, and the saturated or unsaturated hydrocarbon is R ４５ The substituents may differ in total carbon number by 1 to 10.

[0066] The structure of the thermosetting polyphenylene ether in this embodiment can be identified by analyzing it using methods such as NMR and mass spectrometry. Specific methods for identifying the structure of the polyphenylene ether include performing field desorption mass spectrometry (FD-MS), which is known to be less prone to fragmentation, and estimating the repeating units based on the spacing of the detected ions. Furthermore, a method for estimating the structure of the polyphenylene ether can be achieved by combining electron ionization (EI) peak analysis of fragment ions with structural analysis by NMR.

[0067] The thermosetting polyphenylene ether of this embodiment may contain components represented by general formula (12). (In formula (12), R ２９ Each of these is independently an optionally substituted C1-C6 alkyl group, an optionally substituted C6-C12 aryl group, or a halogen atom, R ３０Each of these is independently a hydrogen atom, an optionally substituted C1-C6 alkyl group, an optionally substituted C6-C12 aryl group, or a halogen atom.

[0068] In the above formula (12), R ２９ Each of these is preferably an independently saturated hydrocarbon group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably a methyl group or a phenyl group, and even more preferably a methyl group. In formula (12), the two R ２９ It is preferable that both have the same structure. ２９ Substituents in saturated hydrocarbons having 1 to 6 carbon atoms and aryl groups having 6 to 12 carbon atoms include saturated or unsaturated hydrocarbon groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and halogen atoms.

[0069] In the above formula (12), R ３０ Each of these is preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or a methyl group. In formula (11), the two R ２８ These may be different, but it is preferable that one is a hydrogen atom and the other is a hydrocarbon group having 1 to 6 carbon atoms (preferably a methyl group). ３０ Examples of substituents on saturated hydrocarbons having 1 to 6 carbon atoms include saturated or unsaturated hydrocarbon groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and halogen atoms.

[0070] The thermosetting polyphenylene ether substitution in this embodiment may include components represented by general formula (13). (In formula (13), R ３２ Each of these is independently a hydrogen atom, an optionally substituted C1-C20 alkyl or unsaturated hydrocarbon group, an optionally substituted C6-C12 aryl group, or a halogen atom, and two R ３２ Both are not hydrogen atoms, R ３１ This is a substructure represented by general formula (14). (In formula (14), R ３３ Each of these is independently a linear alkyl group having 1 to 8 carbon atoms, which may be substituted, or two R ３３These are bonded to each other to form a cyclic alkyl structure having 1 to 8 carbon atoms, R ３４ Each is independently an alkylene group having 1 to 8 carbon atoms, which may be substituted, and each is independently 0 or 1, R ３５ (This is a hydrogen atom, an optionally substituted C1-C8 alkyl group, or an optionally substituted phenyl group.)

[0071] In the above formula (13), R ３２ Each of these is preferably independently a hydrogen atom, a saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms, or an aryl group having 6 to 12 carbon atoms that may be substituted with an alkyl group having 1 to 6 carbon atoms; more preferably a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms that may be substituted with an alkyl group having 1 to 6 carbon atoms; and even more preferably a hydrogen atom or a methyl group. In formula (12), the two R ３０ These are preferably different, and more preferably one is a hydrogen atom and the other is a hydrocarbon group having 1 to 6 carbon atoms (preferably a methyl group). ３２ Examples of substituents in saturated hydrocarbons having 1 to 15 carbon atoms or aryl groups having 6 to 12 carbon atoms include saturated or unsaturated hydrocarbon groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, halogen atoms, and the like.

[0072] The substructure represented by formula (14) above is preferably a group containing secondary and / or tertiary carbons, such as an isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, tert-amyl group, 2,2-dimethylpropyl group, cyclohexyl group, or a structure having a phenyl group at its terminal, more preferably a tert-butyl group or a cyclohexyl group, and even more preferably a tert-butyl group.

[0073] Furthermore, in this embodiment, the thermosetting polyphenylene ether preferably has a total content of the constituent units of formula (7) and formula (8) in the range of 1 mol% to 50 mol%, and more preferably in the range of 2 mol% to 30 mol%, relative to a total of 100 mol% of the constituent units of formula (7), formula (8), and formula (12), from the viewpoint of heat resistance. When the total content of the constituent units of formula (7) and formula (8) is within these ranges, the cured product of the thermosetting polyphenylene ether can be obtained with a sufficiently low dielectric loss tangent and a high glass transition temperature.

[0074] The proportions of the constituent units in equation (7) and equation (8) are, for example, １ H-NMR, １３ It can be determined using analytical methods such as C-NMR, and more specifically, it can be measured by the method described in the examples below.

[0075] The thermosetting polyphenylene ether in this embodiment may contain a copolymer containing a structure derived from a divalent phenol of the following formula (23) as an impurity (in this specification, this may simply be referred to as "impurity"). The thermosetting polyphenylene ether in this embodiment may be a mixture of the above polyphenylene ether and the above impurity. The molar ratio of the impurity to 100 mol% of the polyphenylene ether in the embodiment is preferably 10 mol% or less, and more preferably 5 mol% or less.

[0076] The above-mentioned impurities can be synthesized, for example, as copolymers containing a structure derived from a divalent phenol with z=0 in formula (23) by the reaction of the following formula (24), which is generated as a byproduct during the oxidative polymerization of monovalent phenols, with a polyphenylene ether composed of monovalent phenols. (In formula (23), R ２９ and R ３０ This is the same as equation (12). n is 0 or 1, and B has the structure shown below: (In the formula, R ４６Each of these is independently one of the following: a hydrocarbon group having 1 to 6 carbon atoms, which may be substituted; an aryl group having 6 to 12 carbon atoms, which may be substituted; or a halogen atom. (In formula (24), R ２９ and R ３０ This is the same as equation (12).

[0077] [Amino group-containing polyphenylene ether] An example of the substituted polyphenylene ether of this embodiment is an amino group-containing polyphenylene ether containing the constituent components shown in formula (9) or formula (10). (In equations (9) and (10), R ２２ ~R ２４ , R ２５ and R ２６ Each is independently at least one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, and a cyano group, R ２２ and R ２３ At least one of them is an alkyl group, R ２５ and R ２６At least one of them is an alkyl group, X is a divalent group containing an alkylene group and may contain a divalent group having a heteroatom, a divalent group containing a divalent electron-withdrawing group and an arylene group preferably in series, or a divalent group containing a divalent electron-withdrawing group and an alkylene group preferably in series, and Y is a structure containing an amino group (e.g., a primary amino group, a secondary amino group, or a tertiary amino group). The thermosetting polyphenylene ether of this embodiment may contain both the (9) unit and the (10) unit. Examples of the "divalent group having a heteroatom" in X include oxy, thio, aza (imino group, etc.). When X is a "divalent group containing an alkylene group and a divalent group having a heteroatom," preferred divalent groups include oxyalkylene groups, alkylene oxyalkylene groups, alkylene oxy groups, thioalkylene groups, alkylentioalkylene groups, alkylentio groups, azaalkylene groups, alkylene azaalkylene groups, and alkylene aza groups. Furthermore, when X is a "divalent group containing an alkylene group and possibly containing a divalent group having a heteroatom," other divalent groups may be further included in the structure. Examples of other divalent groups include divalent electron-withdrawing groups or arylene groups. The number of carbon atoms in the "alkylene group" in X is preferably 1 to 12, more preferably 2 to 8. Examples of divalent electron-withdrawing groups in X include -C(O)- (carbonyl group (keto group)), -S(O)- (sulfoxide), and -S(O). ２ Examples include -(sulfone), with -C(O)-(carbonyl group (keto group)) being preferred. Examples of the "arylene group" in X include a phenylene group, a naphthylene group, anthracenyl group, and a benzyl group, with a phenylene group being preferred. When X is a "divalent group containing a divalent electron-withdrawing group and an arylene group preferably in series" or a "divalent group containing a divalent electron-withdrawing group and an alkylene group preferably in series", it is preferable that the arylene group or alkylene group is bonded to the structure represented by Y.

[0078] The amino group-containing polyphenylene ether of this embodiment may contain both the (9) unit and the (10) unit. When both the (9) unit and the (10) unit are included, although not particularly limited, the proportion of the (9) unit is preferably in the range of 1 mol% to 99 mol%, more preferably in the range of 10 mol% to 99 mol%, and even more preferably in the range of 30 mol% to 99 mol%, with respect to 100 mol% of the total of the (9) unit and the (10) unit. If the proportion of the (9) unit is 1 mol% or more, the ability to form intermolecular interactions tends to improve, and if it is 99 mol% or less, the resistance to thermal decomposition tends to be high.

[0079] In formulas (9) and (10), the following embodiments are preferred. In formulas (9) and (10), the following embodiments are preferred. R ２２ ~R ２６ The number of carbon atoms in the alkyl group and alkyl fluoride in R is preferably 1 to 12, and more preferably 1 to 4. ２２ ~R ２６ The allyl group is preferably a 2-propenyl group, a 2-methyl-2-propenyl group, or a 2-hexernyl group. ２２ ~R ２６ The preferred aryl group (i.e., on the main chain side) is a phenyl group or a benzyl group.

[0080] In formulas (9) and (10), the number of carbon atoms in the alkylene group of X is preferably 1 to 12, and more preferably 2 to 8. The divalent electron-withdrawing group of X is -C(O)- (carbonyl group (keto group)), -S(O)- (sulfoxide), -S(O) ２ Examples include -(sulfone), and -C(O)-(carbonyl group (keto group)). Examples of the aryl group containing the divalent electron-withdrawing group of X, the "arylene group", include phenylene group, naphthylene group, anthracenyl group, and benzyl group, with the phenyl group being preferred. The number of carbon atoms in the alkylene group containing the divalent electron-withdrawing group of X, the "alkylene group", is preferably 1 to 12, and more preferably 2 to 8.

[0081] In formulas (9), (10), and (9), Y is a structure containing a primary amino group, a secondary amino group, or a tertiary amino group. The structure of Y is not particularly limited, but the structures shown in the following general formulas (25) to (31) are preferred. In the above general formula (25), R ４７ R represents an alkylene group having 2 to 6 carbon atoms, or an oxybisalkylene group having a total of 2 to 6 carbon atoms. ４８ Each of these independently represents hydrogen, a C1-C3 alkyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, or a 2-hydroxyethoxyethyl group. n represents an integer from 1 to 5. In the above general formula (27), R ４９ This represents an alkyl group having 1 to 3 carbon atoms, a 2-hydroxyethyl group, or a 2-hydroxypropyl group. In the above general formula (28), R ５０ Each of these independently represents an alkyl group having 1 to 3 carbon atoms. ５１ R represents an alkylene group having 2 to 6 carbon atoms, or an oxybisalkylene group having a total of 2 to 6 carbon atoms. ５２ n represents an alkyl group having 1 to 3 carbon atoms, a 2-hydroxyethyl group, a 2-hydroxypropyl group, or a 2-hydroxyethoxyethyl group. n represents an integer from 1 to 4. In the above general formula (29), R ５３ Each of these independently represents an alkyl group having 1 to 3 carbon atoms. ５４ This represents an alkyl group having 1 to 3 carbon atoms, a 2-hydroxyethyl group, a 2-hydroxypropyl group, or a 2-hydroxyethoxyethyl group. In the above general formula (10), R ５５ This represents an alkyl group having 1 to 3 carbon atoms, a 2-hydroxyethyl group, a 2-hydroxypropyl group, or a 2-hydroxyethoxyethyl group. In the above general formula (11), R ５６ Each of these independently represents an alkyl group having 1 to 3 carbon atoms, a 2-hydroxyethyl group, or a 2-hydroxypropyl group.

[0082] The amino group-containing polyphenylene ether of this embodiment may contain the components represented by general formula (12). (In formula (12), R ２９ Each of these is independently an optionally substituted C1-C6 alkyl group, an optionally substituted C6-C12 aryl group, or a halogen atom, R ３０ Each of these is independently a hydrogen atom, an optionally substituted C1-C6 alkyl group, an optionally substituted C6-C12 aryl group, or a halogen atom.

[0083] In the above formula (12), R ２９ Each of these is preferably an independently saturated hydrocarbon group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably a methyl group or a phenyl group, and even more preferably a methyl group. In formula (12), the two R ２９ It is preferable that both have the same structure. ２９ Substituents in saturated hydrocarbons having 1 to 6 carbon atoms and aryl groups having 6 to 12 carbon atoms include saturated or unsaturated hydrocarbon groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and halogen atoms.

[0084] In formula (12) above, R30 is preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or a methyl group. In formula (11), the two R ２８ These may be different, but it is preferable that one is a hydrogen atom and the other is a hydrocarbon group having 1 to 6 carbon atoms (preferably a methyl group). ３０ Examples of substituents on saturated hydrocarbons having 1 to 6 carbon atoms include saturated or unsaturated hydrocarbon groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and halogen atoms.

[0085] The amino group-containing polyphenylene ether of this embodiment may also contain the component represented by general formula (13). (In formula (13), R ３２ Each of these is independently a hydrogen atom, an optionally substituted C1-C20 alkyl or unsaturated hydrocarbon group, an optionally substituted C6-C12 aryl group, or a halogen atom, and two R ３２ Both are not hydrogen atoms, R ３１ This is a substructure represented by general formula (14). (In formula (14), R ３３ Each of these is independently a linear alkyl group having 1 to 8 carbon atoms, which may be substituted, or two R ３３ These are bonded to each other to form a cyclic alkyl structure having 1 to 8 carbon atoms, R ３４ Each is independently an alkylene group having 1 to 8 carbon atoms, which may be substituted, and each is independently 0 or 1, R ３５ (This is a hydrogen atom, an optionally substituted C1-C8 alkyl group, or an optionally substituted phenyl group.)

[0086] In the above formula (13), R ３２ Each of these is preferably independently a hydrogen atom, a saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms, or an aryl group having 6 to 12 carbon atoms that may be substituted with an alkyl group having 1 to 6 carbon atoms; more preferably a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms that may be substituted with an alkyl group having 1 to 6 carbon atoms; and even more preferably a hydrogen atom or a methyl group. In formula (12), the two R ３０ These are preferably different, and more preferably one is a hydrogen atom and the other is a hydrocarbon group having 1 to 6 carbon atoms (preferably a methyl group). ３２ Examples of substituents in saturated hydrocarbons having 1 to 15 carbon atoms or aryl groups having 6 to 12 carbon atoms include saturated or unsaturated hydrocarbon groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, halogen atoms, and the like.

[0087] The substructure represented by formula (14) above is preferably a group containing secondary and / or tertiary carbons, such as an isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, tert-amyl group, 2,2-dimethylpropyl group, cyclohexyl group, or a structure having a phenyl group at its terminal, more preferably a tert-butyl group or a cyclohexyl group, and even more preferably a tert-butyl group.

[0088] In this embodiment, the structure of the amino group-containing polyphenylene ether can be identified by analyzing it using methods such as NMR and mass spectrometry. Specific methods for identifying the structure of the polyphenylene ether include field desorption mass spectrometry (FD-MS), which is known to be less prone to fragmentation, and estimating the repeating units based on the spacing of the detected ions. Furthermore, a method for estimating the structure of the polyphenylene ether can be proposed that combine electron ionization (EI) peak analysis of fragment ions with structural analysis by NMR.

[0089] The amino group-containing polyphenylene ether of this embodiment may contain units of formula (9), formula (10), and formula (12). Although not particularly limited, the total proportion of units of formula (9) and formula (10) relative to 100 mol% of the total of units of formula (9), formula (10), and formula (12) is preferably in the range of 1 mol% to 99 mol%, more preferably in the range of 10 mol% to 99 mol%, and even more preferably in the range of 30 mol% to 99 mol%. If the total proportion of units of formula (9) and formula (10) is 1 mol% or more, the ability to form intermolecular interactions tends to improve, and if it is 99 mol% or less, the resistance to thermal decomposition tends to be high.

[0090] The amino group-containing polyphenylene ether of this embodiment may contain units of formula (9), formula (10), and formula (13). Although not particularly limited, the total proportion of units of formula (9) and formula (10) is preferably in the range of 1 mol% to 99 mol%, more preferably in the range of 10 mol% to 99 mol%, and even more preferably in the range of 30 mol% to 99 mol%. If the total proportion of units of formula (9) and formula (10) is 1 mol% or more, the ability to form intermolecular interactions tends to improve, and if it is 99 mol% or less, the resistance to thermal decomposition tends to be high.

[0091] The amino group-containing polyphenylene ether of this embodiment may contain units of formula (9), formula (10), formula (12), and formula (13). While not particularly limited, it is preferable that, with respect to 100 mol% of the total of units of formula (9), formula (10), formula (12), and formula (13), the combined proportion of units of formula (9) and formula (10) is in the range of 1 mol% to 98 mol%, the proportion of unit of formula (11) is in the range of 1 mol% to 98 mol%, and the proportion of unit of formula (12) is in the range of 1 mol% to 98 mol%. Within these ranges, the ability to form intermolecular interactions tends to improve, the strength is sufficient, and the handling properties tend to be excellent. It is more preferable that the total proportion of units of formula (9) and formula (10) is in the range of 10 mol% to 98 mol%, the proportion of units of formula (11) is in the range of 1 mol% to 89 mol%, and the proportion of units of formula (12) is in the range of 1 mol% to 50 mol%.

[0092] The weight loss temperature (T) of the amino group-containing polyphenylene ether of this embodiment after a 5% weight loss. Ｄ５ The temperature is preferably 350°C or higher, and more preferably 370°C or higher. If the 5% weight loss temperature is 320°C or higher, the ability to form stable intermolecular interactions can be exhibited even in high-temperature environments. The 5% weight loss temperature can be measured by the method described in the examples below.

[0093] The proportions of each repeating unit of formula (9), formula (10), formula (12), and formula (13) are, for example, １ H-NMR, １３ It can be determined using analytical methods such as C-NMR, and more specifically, it can be measured by the method described in the examples below.

[0094] The reduced viscosity of the amino group-containing polyphenylene ether in this embodiment, measured with a chloroform solution at a concentration of 0.5 g / dL at 30°C, is not particularly limited, but is preferably 0.01 dL / g or higher, more preferably 0.06 dL / g or higher, preferably 1.00 dL / g or lower, and more preferably 0.80 dL / g or lower. A reduced viscosity of 0.01 dL / g or higher tends to result in superior strength, while a reduced viscosity of 1.00 dL / g or lower tends to result in improved handling properties. The reduced viscosity can be measured by the method described in the examples below.

[0095] The amino group-containing polyphenylene ether in this embodiment may contain a copolymer containing a structure derived from a divalent phenol of the following formula (23) as an impurity (in this specification, this may simply be referred to as "impurity"). The amino group-containing polyphenylene ether in this embodiment may be a mixture of the above polyphenylene ether and the above impurity. The molar ratio of the impurity to 100 mol% of the polyphenylene ether in this embodiment is preferably 10 mol% or less, and more preferably 5 mol% or less.

[0096] The above-mentioned impurities can be synthesized, for example, as copolymers containing a structure derived from a divalent phenol with z=0 in formula (23) by the reaction of the following formula (24), which is generated as a byproduct during the oxidative polymerization of monovalent phenols, with a polyphenylene ether composed of monovalent phenols. (In formula (23), R ２９ and R ３０ This is the same as equation (12). n is 0 or 1, and B has the structure shown below: (In the formula, R ４６ Each of these is independently one of the following: a hydrocarbon group having 1 to 6 carbon atoms, which may be substituted; an aryl group having 6 to 12 carbon atoms, which may be substituted; or a halogen atom. (In formula (24), R ２９ and R ３０ This is the same as equation (12).

[0097] [Method for producing substituted polyphenylene ether] The method for producing substituted polyphenylene ether according to this embodiment preferably includes at least the following two steps: A. A step of polymerizing the unmodified polyphenylene ether by oxidative polymerization of the phenol of formula (11) B. A modification step of introducing the nonionic substituent into the unmodified polyphenylene ether

[0098] The method for producing the substituted polyphenylene ether of this embodiment is not particularly limited, but it is preferable to include at least the following steps 1) to 3): 1) A step of polymerizing an unmodified polyphenylene ether by oxidative polymerization of the phenol of formula (11); 2) A step of synthesizing a modified polyphenylene ether by introducing into the unmodified polyphenylene ether an alkyl group which may contain a bonding group (e.g., halogen atoms such as fluorine, chlorine, bromine, or iodine), a monovalent group which preferably contains a divalent electron-withdrawing group and an aryl group in series and may contain a bonding group, or a monovalent group which preferably contains a divalent electron-withdrawing group and an alkyl group in series and may contain a bonding group; 3) A step of synthesizing a substituted polyphenylene ether by introducing a nonionic substituent into the modified polyphenylene ether (preferably at the bonding group introduction site in the modified polyphenylene ether). (In formula (11), R ２７ Each of these is independently an optionally substituted C1-C6 alkyl group, an optionally substituted C6-C12 aryl group, or a halogen atom, and R ２８ Each of these is independently a hydrogen atom, an optionally substituted C1-C6 alkyl group, an optionally substituted C6-C12 aryl group, or a halogen atom.

[0099] In the step of polymerizing the unmodified polyphenylene ether, phenol of formula (32) may be used as a polymerization raw material. (In formula (32), R ５７ Each of these is independently a hydrogen atom, an optionally substituted C1-C20 alkyl or unsaturated hydrocarbon group, an optionally substituted C6-C12 aryl group, or a halogen atom, and two R ５８These are not both hydrogen atoms, but rather substructures represented by general formula (14).

[0100] 1) Polymerization step of unmodified polyphenylene ether The polyphenylene ether is obtained by a method that includes, for example, a step of oxidative polymerization of a monovalent phenol compound represented by formula (11) and / or formula (32). The step of oxidative polymerization preferably involves oxidative polymerization of a raw material containing at least the phenol of formula (11).

[0101] Examples of monovalent phenol compounds represented by the above formula (11) include 2,6-dimethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-n-propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-n-butylphenol, 2,6-di-n-propylphenol, 2-ethyl-6-chlorophenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2-methyl-6-tolylphenol, 2,6-ditolylphenol, 2,3,6-trimethylphenol, 2,3-diethyl-6-n-propylphenol, 2,3,6-tributylphenol, 2,6-di-n-butyl-3-methylphenol, 2,6-dimethyl-3-n-butylphenol, and 2,6-dimethyl-3-t-butylphenol. Among these, 2,6-dimethylphenol, 2,3,6-trimethylphenol, and 2,6-diphenylphenol are particularly preferred because they are inexpensive and readily available. Examples of monovalent phenol compounds represented by formula (32) include 2-isopropyl-5-methylphenol, 2-cyclohexyl-5-methylphenol, 2-tert-butyl-5-methylphenol, and 2-isobutyl-5-methylphenol. From the viewpoint of suppressing multi-branching and gelation, 2-t-butyl-5-methylphenol and 2-cyclohexyl-5-methylphenol, which have bulky substituents, are more preferred. The monovalent phenol compounds represented by formula (32) may be used individually or in combination of multiple types.

[0102] In the polyphenylene ether production method of this embodiment, an aromatic solvent, which is a good solvent for polyphenylene ether, can be used as the polymerization solvent in the oxidative polymerization step. Here, a good solvent for polyphenylene ether is a solvent that can dissolve polyphenylene ether, and examples of such solvents include aromatic hydrocarbons such as benzene, toluene, xylene (including the o-, m-, and p- isomers), and ethylbenzene, as well as halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; nitro compounds such as nitrobenzene; and the like.

[0103] As the polymerization catalyst used in this embodiment, any known catalyst system that can be used in the production of polyphenylene ethers can be used. Commonly known catalyst systems consist of a transition metal ion having redox activity and an amine compound that can form a complex with the transition metal ion. Examples include catalyst systems consisting of a copper compound and an amine compound, a catalyst system consisting of a manganese compound and an amine compound, a catalyst system consisting of a cobalt compound and an amine compound, and so on. Since the polymerization reaction proceeds efficiently under slightly alkaline conditions, a small amount of alkali or further amine compounds may be added.

[0104] The polymerization catalyst preferred in this embodiment is a catalyst comprising a copper compound, a halogen compound, and an amine compound as catalyst components, and more preferably a catalyst containing a diamine compound represented by the following formula (29) as the amine compound. In formula (33), R ５９ , R ６０ , R ６１ , R ６２ Each of these is independently a hydrogen atom and a linear or branched alkyl group having 1 to 6 carbon atoms, and not all of them are hydrogen atoms at the same time. ６３ This is an alkylene group having 2 to 5 carbon atoms and being linear or methyl-branched.

[0105] Examples of copper compounds used as catalyst components are listed below. Suitable copper compounds include cuprous compounds, cupric compounds, or mixtures thereof. Examples of cupric compounds include cupric chloride, cupric bromide, cupric sulfate, and cupric nitrate. Examples of cuprous compounds include cuprous chloride, cuprous bromide, cuprous sulfate, and cuprous nitrate. Among these, particularly preferred metallic compounds are cuprous chloride, cupric chloride, cuprous bromide, and cupric bromide. These copper salts may also be synthesized at the time of use from oxides (e.g., cuprous oxide), carbonates, hydroxides, and corresponding halogens or acids. A frequently used method is to prepare them by mixing the previously exemplified cuprous oxide with hydrogen halides (or solutions of hydrogen halides).

[0106] Examples of halogen compounds include hydrogen chloride, hydrogen bromide, hydrogen iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, and tetraethylammonium iodide. These can be used as aqueous solutions or in solutions with a suitable solvent. These halogen compounds can be used individually or in combination of two or more. Preferred halogen compounds are aqueous solutions of hydrogen chloride and aqueous solutions of hydrogen bromide.

[0107] The amount of these compounds used is not particularly limited, but it is preferably 2 to 20 times the amount of halogen atoms relative to the molar amount of copper atoms, and the preferred amount of copper atoms to use per 100 moles of phenol compound added to the polymerization reaction is in the range of 0.02 moles to 0.6 moles.

[0108] Next, we list examples of diamine compounds that are catalyst components. For example, N,N,N',N'-tetramethylethylenediamine, N,N,N'-trimethylethylenediamine, N,N'-dimethylethylenediamine, N,N-dimethylethylenediamine, N-methylethylenediamine, N,N,N',N'-tetraethylethylenediamine, N,N,N'-triethylethylenediamine, N,N'-diethylethylenediamine, N,N'-diethylethylenediamine, N-ethylethylenediamine, N,N'-dimethyl-N'-ethylethylenediamine, N,N'-dimethyl-N-ethylethylenediamine, N-n-propylethylenediamine, N,N'-n-propylethylenediamine, N-i-propylethylenediamine, N,N'-i-propylethylenediamine, N-n-butylethylenediamine Examples include amines, N,N'-n-butylethylenediamine, N-i-butylethylenediamine, N,N'-i-butylethylenediamine, N-t-butylethylenediamine, N,N'-t-butylethylenediamine, N,N,N'-tetramethyl-1,3-diaminopropane, N,N,N'-trimethyl-1,3-diaminopropane, N,N'-dimethyl-1,3-diaminopropane, N,N'-methyl-1,3-diaminopropane, N,N,N',N'-tetramethyl-1,3-diamino-1-methylpropane, N,N,N',N'-tetramethyl-1,3-diamino-2-methylpropane, N,N,N',N'-tetramethyl-1,4-diaminobutane, N,N,N',N'-tetramethyl-1,5-diaminopentane, and the like. For this embodiment, preferred diamine compounds are those in which the alkylene group connecting the two nitrogen atoms has two or three carbon atoms. The amount of these diamine compounds used is not particularly limited, but it is preferably in the range of 0.01 moles to 10 moles per 100 moles of the phenol compound added to the polymerization reaction.

[0109] In this embodiment, the polymerization catalyst may include primary amines and secondary monoamines as constituent components. Examples of secondary monoamines, but not limited to the following, include dimethylamine, diethylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-t-butylamine, dipentylamines, dihexylamines, dioctylamines, didecylamines, dibenzylamines, methylethylamine, methylpropylamine, methylbutylamine, cyclohexylamine, N-phenylmethanolamine, N-phenylethanolamine, N-phenylpropanolamine, N-(m-methylphenyl)ethanolamine, N-(p-methylphenyl)ethanolamine, N-(2',6'-dimethylphenyl)ethanolamine, N-(p-chlorophenyl)ethanolamine, N-ethylaniline, N-butylaniline, N-methyl-2-methylaniline, N-methyl-2,6-dimethylaniline, and diphenylamine.

[0110] The polymerization catalyst in this embodiment may also include a tertiary monoamine compound. A tertiary monoamine compound is an aliphatic tertiary amine, including alicyclic tertiary amines. Examples include trimethylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, dimethylethylamine, dimethylpropylamine, allyldiethylamine, dimethyl-n-butylamine, diethylisopropylamine, and N-methylcyclohexylamine. These tertiary monoamines may be used individually or in combination of two or more types. The amount used is not particularly limited, but it is preferably in the range of 15 moles or less per 100 moles of the phenol compound added to the polymerization reaction.

[0111] In this embodiment, there are no restrictions on adding surfactants that have been conventionally known to have an effect of improving polymerization activity. Examples of such surfactants include trioctylmethylammonium chloride, known by the trade names Aliquat 336 and Capriquat. The amount used is preferably in a range not exceeding 0.1% by mass relative to 100% by mass of the total amount of the polymerization reaction mixture.

[0112] In this embodiment, the oxygen-containing gas used in polymerization can be pure oxygen, a mixture of oxygen and an inert gas such as nitrogen in any proportion, air, or a mixture of air and an inert gas such as nitrogen in any proportion. While atmospheric pressure is sufficient for the system pressure during the polymerization reaction, it can be reduced or increased as needed.

[0113] The polymerization temperature is not particularly limited, but if it is too low the reaction will not proceed easily, and if it is too high the reaction selectivity may decrease or a gel may form. Therefore, it is preferably 0°C or higher, more preferably 10°C or higher, preferably 60°C or lower, and more preferably 40°C or lower.

[0114] In the method for producing polyphenylene ether, polymerization can also be carried out in a poor solvent such as alcohol.

[0115] In this embodiment, there are no particular restrictions on the post-treatment method after the polymerization reaction is completed. Typically, an acid such as hydrochloric acid or acetic acid, or ethylenediaminetetraacetic acid (EDTA) and its salts, nitrilotriacetic acid and its salts, etc., are added to the reaction solution to deactivate the catalyst. In addition, the removal of divalent phenol by-products generated by the polymerization of polyphenylene ether can be carried out using conventionally known methods. If the metal ions that act as catalysts are substantially deactivated as described above, the mixture can be decolorized simply by heating it. Alternatively, it is also possible to add the required amount of a known reducing agent. Examples of known reducing agents include hydroquinone and sodium dithionite.

[0116] In the method for producing polyphenylene ether, water may be added to extract the compound from which the copper catalyst has been deactivated, followed by liquid-liquid separation into an organic phase and an aqueous phase. The copper catalyst may then be removed from the organic phase by removing the aqueous phase. This liquid-liquid separation step is not particularly limited, but examples include static separation and separation by centrifugation. To promote the above liquid-liquid separation, known surfactants may be used.

[0117] Next, in the method for producing polyphenylene ether according to this embodiment, the organic phase containing the polyphenylene ether after liquid-liquid separation may be concentrated and dried by volatilizing the solvent.

[0118] Methods for volatilizing the solvent contained in the organic phase are not particularly limited, but include methods such as transferring the organic phase to a high-temperature concentration tank and distilling off the solvent to concentrate it, or using equipment such as a rotary evaporator to distill off toluene and concentrate it.

[0119] The drying temperature in the drying process is preferably at least 60°C, more preferably 80°C or higher, even more preferably 120°C or higher, and most preferably 140°C or higher. Drying polyphenylene ether at a temperature of 60°C or higher efficiently reduces the content of high-boiling point volatile components in the polyphenylene ether powder.

[0120] To efficiently obtain polyphenylene ether, methods such as increasing the drying temperature, increasing the vacuum level in the drying atmosphere, and stirring during drying are effective, but increasing the drying temperature is particularly preferable from the viewpoint of manufacturing efficiency. In the drying process, it is preferable to use a dryer equipped with a mixing function. Examples of mixing functions include agitation type and tumbling type dryers. This allows for a larger processing volume and maintains high productivity.

[0121] 2) Synthesis Process of Modified Polyphenylene Ether The method for synthesizing modified polyphenylene ether is not particularly limited, but examples include introducing acyl groups, especially acyl groups having aromatic hydrocarbon groups; sulfone groups, especially sulfone groups having aromatic hydrocarbon groups; sulfinyl groups, especially sulfinyl groups having aromatic hydrocarbon groups; phosphonyl groups, especially phosphonyl groups having aromatic hydrocarbon groups; etc., to the aromatic ring skeleton of unmodified polyphenylene ether using a Friedel-Crafts acylation reaction. More specifically, in the Friedel-Crafts acylation reaction, unmodified polyphenylene ether is reacted with an acid halide, etc., in the presence of a Lewis acid (metal halide) such as aluminum chloride, tin chloride, or iron chloride.

[0122] Dichloromethane, chloroform, etc., are used as reaction solvents. The reaction conditions can be those described in Li, Q.; Liu, L.; Liang, S.; Li, Q.; Jin, B.; Bai, R.; Polym. Chem., 2014, 5, 2425-2432.

[0123] The above-mentioned acid halides are not particularly limited, but include compounds represented by the following formulas (34) and (35). (In formula (34), Ha is a halogen other than fluorine, and R ６４ ~R ６８ Each of these is independently a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, a cyano group, or a nitro group, where R ６４ ~R ６８ At least one of them is a hydrogen atom.) In equation (34), from the viewpoint of introducing a heteroatom, R ６６ A halogen atom is preferred, and a fluorine atom is more preferred. (In formula (35), Ha is a halogen other than fluorine, and R ６９ represents an alkyl group having 2 to 10 carbon atoms. The two Ha elements may have the same structure or different structures.

[0124] Furthermore, as acid halides, examples include compounds in which the side-chain aromatic hydrocarbon group bonded to the carbonyl group in formula (34) above is replaced with a polycyclic aromatic hydrocarbon group such as a naphthyl group or an anthracenyl group, instead of a phenyl group. In addition, examples include compounds in which the group bonded to the carbonyl group in formula (34) above is replaced with an aryl group (for example, a benzyl group) that allows the carbonyl group and the side-chain aromatic hydrocarbon group to be linked in a manner that an alkyl group is sandwiched between them.

[0125] Furthermore, as an acid halide, in formulas (34) and (35) above, the [-C(O)-] part is replaced with [-S(O) ２ Compounds with the -] portion (also called sulfonyl halogens); compounds in formulas (34) and (35) above with the -S(O)- portion replaced by the -C(O)- portion (also called sulfinyl halogens).

[0126] The acylated polyphenylene ether obtained by the Friedel-Crafts acylation reaction may be alkylated using a reducing agent. This reduction reaction is preferably carried out after introducing an amino group to the polyphenylene ether.

[0127] The method for synthesizing the modified polyphenylene ether is not particularly limited, but in addition to the Friedel-Crafts acylation reaction described above, other methods include introducing a chloromethyl group into the aromatic ring skeleton of the polyphenylene ether using Friedel-Crafts alkylation and chloromethylation reactions.

[0128] Specifically, the chloromethylation reaction involves generating a chloromethyltin intermediate using tin(IV) chloride, paraformaldehyde, and trimethylsilane. This intermediate then reacts with polyphenylene ether to introduce a chloromethyl group.

[0129] 3-1) Step for synthesizing amino group-containing polyphenylene ether The step for synthesizing the amino group-containing polyphenylene ether is not particularly limited, but for example, a method is carried out in which a modified polyphenylene ether and an amine compound are reacted in the absence of a solvent or in the presence of a solvent using an aromatic nucleophilic substitution reaction or a nucleophilic substitution reaction.

[0130] The amine compound is not particularly limited, but the structure shown in formula (36) below is preferred. It may also contain other heteroatoms such as aminomethylphenol or 2-aminoethanethiol. In formula (36), P is an alkylene group, an arylene group, an alkylene group containing a heteroatom, or an arylene group containing a heteroatom. As an example of the embodiment of formula (36), the structures shown in the following formulas (37), (38), and (39) are preferred. In the above formula (40), R ７０ R represents an alkylene group having 2 to 6 carbon atoms or an oxybisalkylene group having a total of 2 to 6 carbon atoms. ７１ ~R ７３ Each of these independently represents hydrogen and an alkyl group having 1 to 6 carbon atoms, R ７１ ~R ７３ At least one of them is a hydrogen atom. n represents an integer from 1 to 5. In the above formula (35), R ７４ and R ７５ Each of these independently represents hydrogen and an alkyl group having 1 to 6 carbon atoms, R ７４ and R ７５ At least one of them is a hydrogen atom.

[0131] The solvent is not particularly limited, but aprotic organic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, tetrahydrofuran, and dimethyl sulfoxide, as well as nonpolar solvents such as toluene and xylene, may be used. The reaction temperature is not particularly limited, but is usually 25 to 200°C, and the reaction time is usually 1 to 72 hours.

[0132] 3-2) Step for synthesizing ether group-containing polyphenylene ether The step for synthesizing the ether group-containing polyphenylene ether is not particularly limited, but for example, a method is carried out in which a modified polyphenylene ether is reacted with a phenol compound or an alcohol compound in the absence of a solvent or in the presence of a solvent, using an aromatic nucleophilic substitution reaction or a nucleophilic substitution reaction.

[0133] The phenol compound or alcohol compound is not particularly limited, but the structure represented by the following formula (40) is preferred. In formula (40), P is an alkylene group, an arylene group, an alkylene group containing a heteroatom, or an arylene group containing a heteroatom.

[0134] Examples of embodiments of formula (40) include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, 2,2-dimethylpropane-1,3-diol, diethylene glycol, triethylene glycol, tetraethylene glycol, octaethylene glycol, dipropylene glycol, N-methyldiethanolamine, p-xylylene glycol, 1,2 -Cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,6-decalindiol, 1,5-decalindiol, 2,3-decalindiol, 2,6-decalindimethanol, 1,5-decalindimethanol, 2,3-decalindimethanol, 2,3-norbornanediol, 2,5-norbornanediol, 2,3-norbornanedimethanol, 2,5-norbornanedimeth Condensed polycyclic ether diols such as 2,2-bis(4-hydroxycyclohexyl)-propane, 1,3-adamantanediol, 1,3-adamantanedimethanol, tricyclodecanedimethanol, isosorbide, 3,9-bis(2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-bis(2-hydroxy-1,1-diethylethyl)-2,4,8,10- Tetraoxaspiro[5.5]undecane, 3,9-bis(2-hydroxy-1,1-dipropylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,4-anhydroerythritol, 2-(5-ethyl-5-hydroxymethyl-1,3-dioxan-2-yl)-2-methylpropan-1-ol, 3,4-pyrrolidinediol, 3,4-dimethylpiperidinediol, N-ethyl-3,4-piperidinediol, N-ethyl-3,5-piperidinediol, deoxythiofructose, bisphenol A (2,Examples include 2-bis(4-hydroxyphenyl)propane, bisphenol C (2,2-bis(4-hydroxy-3-methylphenyl)propane), bisphenol Z (1,1-bis(4-hydroxyphenyl)cyclohexane), bisphenol 3MZ (1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane), bisphenol HTG (1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane), bisphenol-CDE (1,1-bis(4-hydroxyphenyl)cyclododecene), and 4,4'-dihydroxybiphenyl.

[0135] The solvent is not particularly limited, but aprotic organic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, tetrahydrofuran, and dimethyl sulfoxide, as well as nonpolar solvents such as toluene and xylene, may be used. The reaction temperature is not particularly limited, but is usually 25 to 200°C, and the reaction time is usually 1 to 72 hours.

[0136] 3-3) Step for synthesizing thioether group-containing polyphenylene ether The step for synthesizing the thioether group-containing polyphenylene ether is not particularly limited, but for example, a method is carried out in which a modified polyphenylene ether and a thiol compound are reacted in the absence of a solvent or in the presence of a solvent using an aromatic nucleophilic substitution reaction or a nucleophilic substitution reaction.

[0137] The thiol compound is not particularly limited, but the structure shown in formula (41) below is preferred. In formula (41), P is an alkylene group, an arylene group, an alkylene group containing a heteroatom, or an arylene group containing a heteroatom.

[0138] Examples of embodiments of formula (41) include methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, and 2-methyl methyl Examples include crohexane-2,3-dithiol, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, and 1,4-bis(mercaptoethyl)benzene.

[0139] The solvent is not particularly limited, but aprotic organic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, tetrahydrofuran, and dimethyl sulfoxide, as well as nonpolar solvents such as toluene and xylene, may be used. The reaction temperature is not particularly limited, but is usually 25 to 200°C, and the reaction time is usually 1 to 72 hours.

[0140] [Method for producing thermosetting polyphenylene ether] The thermosetting polyphenylene ether of this embodiment can be synthesized by including the following step 4) in addition to the steps 1) to 3) above. 4) A step of synthesizing thermosetting polyphenylene ether by introducing a structure containing an unsaturated hydrocarbon group into the substituted polyphenylene ether.

[0141] 4) Step for synthesizing thermosetting polyphenylene ether In the step for synthesizing the thermosetting polyphenylene ether, there are no particular limitations on the method for introducing a structure containing an unsaturated hydrocarbon group into the substituted polyphenylene ether, but for example, a nucleophilic substitution reaction is used to react the substituted polyphenylene ether with a haloalkane, carboxylic acid anhydride, or carboxylic acid chloride containing an unsaturated hydrocarbon group.

[0142] The haloalkanes, carboxylic acid anhydrides, and carboxylic acid chlorides containing unsaturated hydrocarbon groups are not particularly limited, but 4-(chloromethyl)styrene, 3-(chloromethyl)styrene, allyl chloride, allyl bromide, methacrylic anhydride, acrylic anhydride, maleic anhydride, methacryloyl chloride, and acryloyl chloride are preferred.

[0143] [Applications of Substituted Polyphenylene Ethers] The substituted polyphenylene ethers of this embodiment can form polymer networks through intermolecular interactions via nonionic substituents. By forming polymer networks, they have different properties from polyphenylene ethers that do not form polymer networks. For example, the polymer network exhibits significantly higher gas barrier properties and heat resistance compared to polyphenylene ethers that do not form polymer networks.

[0144] (Substituted Polyphenylene Ether Solution) The substituted polyphenylene ether solution of this embodiment contains a substituted polyphenylene ether and an organic solvent. From the viewpoint of solubility, the organic solvent is preferably an aromatic compound such as toluene or xylene, an aprotic organic solvent such as tetrahydrofuran, dimethyl sulfoxide, or methyl ethyl ketone (MEK), cyclopentanone, cyclohexanone, or chloroform. These solvents may be used individually or in combination of two or more.

[0145] (Thermosetting Composition) The polyphenylene ether of this embodiment can be used as a raw material for a thermosetting composition. The thermosetting composition is not particularly limited as long as it contains polyphenylene ether, but it is preferable to further contain an organic peroxide, and optionally further contain a thermoplastic resin, a flame retardant, other additives, silica filler, a solvent, etc. From the viewpoint of solubility, preferred solvents are aromatic compounds such as toluene and xylene, aprotic organic solvents such as tetrahydrofuran, dimethyl sulfoxide, and methyl ethyl ketone (MEK), cyclopentanone, cyclohexanone, and chloroform. These solvents may be used individually or in combination of two or more.

[0146] (Cured product, method for manufacturing the cured product) The cured product of this embodiment comprises a thermosetting polyphenylene ether or a thermosetting composition. The cured product of this embodiment can be obtained, for example, by curing the thermosetting composition by hot pressing at 180°C to 220°C. Because the cured product of this embodiment has excellent heat resistance and dielectric properties, it can be suitably used in, for example, communication equipment, substrate materials, resin-coated copper foil (RCC) and prepregs, adhesives, etc.

[0147] (Prepreg) The prepreg of this embodiment comprises a substrate and the thermosetting composition of this embodiment described above, and is preferably a composite comprising the substrate and the thermosetting composition of this embodiment impregnated or coated onto the substrate. The prepreg can be obtained, for example, by impregnating a substrate such as glass cloth with a varnish of the thermosetting composition, and then drying off the solvent using a hot air dryer or the like.

[0148] Examples of substrates include various glass cloths such as roving cloth, cloth, chopped mat, and surfacing mat; asbestos cloth, metal fiber cloth, and other synthetic or natural inorganic fiber cloths; woven or nonwoven fabrics obtained from liquid crystal fibers such as fully aromatic polyamide fibers, fully aromatic polyester fibers, and polybenzoxazole fibers; natural fiber cloths such as cotton cloth, linen cloth, and felt; natural cellulose-based substrates such as carbon fiber cloth, kraft paper, cotton paper, and cloths obtained from paper-glass blended yarns; and polytetrafluoroethylene porous films. Glass cloth is preferred among these. These substrates may be used individually or in combination of two or more types.

[0149] The proportion of the thermosetting composition solids (components of the thermosetting composition other than the solvent) in the prepreg of this embodiment is preferably 30 to 80% by mass, and more preferably 40 to 70% by mass. When the above proportion is 30% by mass or more, the insulation reliability tends to be even better when the prepreg is used for electronic circuit boards, etc. When the above proportion is 80% by mass or less, the mechanical properties such as the flexural modulus tend to be even better in applications such as electronic circuit boards.

[0150] (Laminate) The laminate of this embodiment preferably comprises a cured product of the prepreg of this embodiment and a metal foil, and is a metal-clad laminate obtained by laminating and curing the thermosetting composition of this embodiment or the prepreg of this embodiment and the metal foil. The metal-clad laminate preferably has a form in which the cured product of the prepreg (hereinafter also referred to as the "cured product composite") and the metal foil are laminated and in close contact, and is suitably used as a material for electronic substrates.

[0151] Examples of metal foils include aluminum foil and copper foil, and among these, copper foil is preferred because of its low electrical resistance.

[0152] The hardened composite material combined with the metal foil can consist of one or more sheets, and depending on the application, the metal foil is layered on one or both sides of the composite material to form a laminate.

[0153] One method for manufacturing a metal-clad laminate is to form a composite (e.g., the prepreg described above) consisting of a thermosetting composition and a substrate, then layer this with a metal foil, and finally cure the thermosetting composition to obtain a laminate in which a cured laminate and a metal foil are laminated together.

[0154] One particularly preferred application of the above-mentioned metal-clad laminate is a printed circuit board. Preferably, in a printed circuit board, at least a portion of the metal foil is removed from the metal-clad laminate.

[0155] (Printed Wiring Board) The thermosetting polyphenylene ether of this embodiment can be used to make a printed wiring board by removing at least a portion of the metal foil from a metal-clad laminate containing a cured prepreg and metal foil. The above printed wiring board can typically be formed by a pressure-heat molding method using the prepreg of this embodiment described above. The same prepregs as described above can be used as the substrate. Examples of metal foils include aluminum foil and copper foil, and among these, copper foil is preferred because of its low electrical resistance.

[0156] The hardened composite material combined with the metal foil can consist of one or more sheets, and depending on the application, the metal foil is layered on one or both sides of the composite material to form a laminate.

[0157] The printed circuit board described above, by containing the thermosetting composition of this embodiment, has excellent heat resistance and electrical properties (low dielectric constant and low dielectric loss tangent), can further suppress fluctuations in electrical properties due to environmental changes, and also has excellent insulation reliability and mechanical properties.

[0158] (Resin Film) The cured product of this embodiment can also be applied to curable resin films. The method for manufacturing the film is not particularly limited, but for example, it can be obtained by molding the thermosetting polyphenylene ether of this embodiment into a film or sheet.

[0159] (Gas Barrier Film) The gas barrier film of this embodiment is characterized by containing the amino group-containing polyphenylene ether of this embodiment. The content of the amino group-containing polyphenylene ether of this embodiment in the gas barrier film of this embodiment is particularly preferably 100% by mass (i.e., the gas barrier film of this embodiment consists of the amino group-containing polyphenylene ether of this embodiment), but it may contain other components, and is more preferably 95 to 100% by mass, and preferably 90 to 100% by mass. When the amino group of the above amino group-containing polyphenylene ether is a primary amino group or a secondary amino group, it becomes possible to form a polymer network by hydrogen bonding, and particularly excellent gas barrier performance can be obtained.

[0160] The gas barrier film of this embodiment can be manufactured, for example, by completely dissolving the above-mentioned amino group-containing polyphenylene ether in a solvent (organic solvent) such as dimethyl sulfoxide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, tetrahydrofuran, N,N-dimethylacetamide, or dimethyl sulfoxide, and then forming the solution into a film by casting onto a substrate, and then drying the resulting film. Specific casting methods include spraying, spin coating, and doctor spraying.

[0161] Examples of substrates used in the casting method include glass plates and plastic films. Preferably, the plastic film is polyethylene terephthalate film, polytetrafluoroethylene film, or polyimide film.

[0162] Examples of solvents for dissolving the above-mentioned amino group-containing polyphenylene ether include alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and propylene glycol monoethyl ether; ethers such as tetrahydrofuran and 1,3-dioxane; aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and acetonitrile; and alcohols such as methanol, ethanol, propanol, isopropyl alcohol, sec-butyl alcohol, and tert-butyl alcohol. These may be used individually or in combination of two or more.

[0163] The solid content concentration of the amino group-containing polyphenylene ether in the solution used for casting is 5 to 40% by mass, preferably 5 to 30% by mass, depending on the molecular weight of the polymer. If the polymer concentration is lower than the lower limit of the above range, it is difficult to form a thick film, and if it exceeds the upper limit of the above range, the solution viscosity becomes too high, making it difficult to form a film, and a uniform coating may not be obtained.

[0164] The drying process after film formation following the casting described above may be carried out at a temperature of 50 to 170°C for 0.1 to 12 hours.

[0165] The gas barrier film and gas barrier material composed of the amino group-containing polyphenylene ether of this embodiment can be suitably used in the food and beverage packaging field and in the industrial materials field where gas barrier properties are required.

[0166] (Gas Separation Membrane) The gas separation membrane of this embodiment is characterized by containing the amino group-containing polyphenylene ether of this embodiment. The content of the amino group-containing polyphenylene ether of this embodiment in the gas separation membrane of this embodiment is particularly preferably 100% by mass (i.e., the gas separation membrane of this embodiment consists of the amino group-containing polyphenylene ether of this embodiment), but it may contain other components, and is more preferably 95 to 100% by mass, and preferably 90 to 100% by mass. The gas separation performance is exhibited due to the interaction of the amino groups of the above amino group-containing polyphenylene ether with gases such as carbon dioxide. To obtain gas separation characteristics, it is preferable that the amino group-containing polyphenylene ether does not contain primary and secondary amines and has a structure that contains a tertiary amino group.

[0167] The gas separation membrane of this embodiment can be manufactured, for example, by completely dissolving the above-mentioned amino group-containing polyphenylene ether in a solvent (organic solvent) such as dimethyl sulfoxide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, tetrahydrofuran, N,N-dimethylacetamide, or dimethyl sulfoxide, then forming a film by casting this solution onto a substrate, and finally drying the resulting film. Specific casting methods include spraying, spin coating, and doctor spraying.

[0168] The selective permeability (α) of the gas separation membrane composed of the amino group-containing polyphenylene ether in this embodiment for a mixed gas of carbon dioxide and nitrogen is preferably 21 or higher, and more preferably in the range of 21 to 300. If the selective permeability (α) is 21 or higher, it tends to increase the purity of carbon dioxide in the separation of the mixed gas of carbon dioxide and nitrogen, and if it is 300 or lower, it tends to reduce the membrane area in the membrane separation process. The selective permeability can be measured by the method described in the examples below.

[0169] The gas separation membrane composed of the amino group-containing polyphenylene ether of this embodiment can be suitably used for carbon dioxide separation and recovery in thermal power plants, cement plants, blast furnaces in steel mills, and natural gas refining.

[0170] The embodiment will be described in detail below with reference to examples and comparative examples, but this embodiment is not limited to these examples. The evaluation method and measurement method used in this embodiment are as follows.

[0171] (Molar ratio of copolymer) The molar ratio of repeating units derived from formula (6) or formula (7) to the total of repeating units derived from formula (7) of phenol contained in the unmodified polyphenylene ether is described. The unmodified polyphenylene ether obtained in the examples and comparative examples was dissolved in deuterated chloroform, and tetramethylsilane was used as an internal standard. １¹H-NMR measurements were performed using a Bruker Biospin AvanceNEO600 (frequency: 600 MHz, pulse program: zg30, number of integrations: 16, temperature: 25°C). Before measurement, polyphenylene ether was held at 140°C and 1 mmHg for 8 hours to remove volatile components such as toluene and water, and was measured as dry, unmodified polyphenylene ether. The signals of the units derived from phenol in formulas (6) and (7) were identified, and their respective proportions were calculated. For example, in the unmodified polyphenylene ethers obtained in the Examples and Comparative Examples, the signal derived from the repeating unit derived from the phenol of formula (6), i.e., the 2,6-dimethylphenol-derived structure (2,6-dimethylphenylene unit), and the signal derived from the repeating unit derived from the phenol of formula (7), i.e., the 2-tert-butyl-5-methylphenol-derived structure (2-tert-butyl-5-methylphenylene unit), were analyzed as follows. The peaks of the repeating units derived from each phenol appear in the following regions. Peaks originating from the hydrogen atoms of the methyl groups of the 2,6-dimethylphenylene unit and the 2-tert-butyl-5-methylphenylene unit (6H and 3H, respectively): 1.60–2.50 ppm (excluding the peak originating from the hydrogen atoms of the methyl group of toluene) Peak originating from the hydrogen atoms of the tert-butyl group of the 2-tert-butyl-5-methylphenylene unit (9H): 1.00–1.52 ppm (excluding the peak originating from the hydrogen atoms of water) By examining the integral values ​​of the above signals, the integral value per proton of the peak originating from the hydrogen atoms of the methyl group of the 2,6-dimethylphenylene unit can be determined using the following formula (6).E = {C - 3 × (D / 9)} / 6 ... Formula (1) C: Integrated value of the methyl-derived peaks of the 2,6-dimethylphenylene unit and the 2-tert-butyl-5-methylphenylene unit D: Integrated value of the tert-butyl-derived peak of the 2-tert-butyl-5-methylphenylene unit E: Integrated value per proton of the methyl-derived peak of the 2,6-dimethylphenylene unit Furthermore, the percentage (mol%) of repeating units derived from phenol in formula (6) or formula (7) can be calculated using the following formulas (2) and (3). Percentage (mol%) of repeating units derived from phenol in formula (1) = E / {(D / 9) + E} × 100 ... Formula (2) Percentage (mol%) of repeating units derived from phenol in formula (2) = (D / 9) / {(D / 9) + E} × 100 ... Formula (3).

[0172] (Reduced viscosity) Prepare a 0.5 g / dL chloroform solution of unmodified polyphenylene ether and measure the reduced viscosity (η) at 30°C using an Ubbelohde viscous tube. ｓｐ We calculated (dL / g) (c).

[0173] (Denaturation Rate) Modified polyphenylene ethers, obtained by introducing spacers such as alkylene groups, aryl groups containing divalent electron-withdrawing groups, and alkylene groups containing divalent electron-withdrawing groups into unmodified polyphenylene ether, were dissolved in deuterated chloroform, and 1H-NMR measurements were performed using tetramethylsilane as an internal standard (Brker Biospin AvanceNEO600, frequency: 600 MHz, pulse program: zg30, number of integrations: 16, temperature: 25°C). The denaturation rate of the modified polyphenylene ether was calculated from the signal of the aromatic ring unit of equation (3) of the unmodified polyphenylene ether and the signal of the aromatic ring unit after denaturation. For example, in the unmodified polyphenylene ether obtained in the examples, the signals originating from the repeating unit of formula (3), i.e., the aromatic ring unit of the 2,6-dimethylphenylene-derived structure (2,6-dimethylphenylene unit), and the signals originating from the aromatic ring unit of the 2,6-dimethylphenylene-derived structure of compounds in which a 4-fluorobenzoyl group has been introduced at the 3rd or 5th position of 2,6-dimethylphenylene were analyzed as follows. The peaks of each repeating unit appear in the following regions. The peak (2H) originating from the hydrogen atom of the aromatic ring of the unmodified 2,6-dimethylphenylene unit appears at 6.40 to 6.60 ppm, and the peak (1H) originating from the hydrogen atom of the aromatic ring of the 2,6-dimethylphenylene unit of compounds in which a 4-fluorobenzoyl group has been introduced at the 3rd or 5th position of 2,6-dimethylphenylene appear at 5.90 to 6.30 ppm. By examining the integral values ​​of the above signals, the denaturation rate can be calculated from the following formula (4). X = 100 × Z / (Y / 2 + Z) ... Formula (4) X: Degradation rate Y: Integral value of the peak derived from the aromatic ring of the 2,6-dimethylphenylene unit Z: Integral value of the peak derived from the aromatic ring of the 2,6-dimethylphenylene unit of a compound in which a 4-fluorobenzoyl group has been introduced at the 3rd or 5th position of 2,6-dimethylphenol

[0174] (Thermal Stability) The polyphenylene ethers of the examples and comparative examples were measured using a TGA (STA7200, Hitachi High-Tech Science Corporation) under nitrogen and a heating rate of 10°C / min. From the TGA profile, the weight loss temperature T at which a 5% weight loss occurred from the initial weight was determined. Ｄ５ The temperature (°C) was measured.

[0175] (Gas Barrier Properties) Gas permeability was measured using a gas permeability measuring device (GTR-11A, manufactured by GTR Tech Co., Ltd.). Since the gas permeability of a film is inversely proportional to its film thickness, the gas permeability coefficient was calculated by multiplying the measured gas permeability by the film thickness in order to compare differences between materials. The unit of the gas permeability coefficient is Barr (1 Barr = 1 × 10⁻¹⁶). －１０ cm ３ (STP)・cm / (s・cm ２ The values ​​were expressed in cmHg. Specifically, a 30 μm film was prepared, and the permeability (unit: GPU) of carbon dioxide, nitrogen, and methane was measured at 25°C dry conditions. The gas permeability coefficient (unit: Barr) was then calculated by multiplying the measured film thickness by the measured values. Note that GPU (GPU) is the unit [1 GPU = 1 × 10⁻¹⁶]. －６ cm ３ (STP) / cm ２ It is [sec・cmHg].

[0176] (Gas Separability) Gas permeability was measured using a gas permeability measuring device (GTR-11A, manufactured by GTR Tech Co., Ltd.). Since the gas permeability of a film is inversely proportional to its film thickness, the gas permeability coefficient was calculated by multiplying the measured gas permeability by the film thickness in order to compare differences between materials. The unit of the gas permeability coefficient is Barr (1 Barr = 1 × 10⁻¹⁶). －１０ cm ３ (STP)・cm / (s・cm ２ The values ​​were expressed in cmHg. Specifically, a 30 μm film was prepared, and the permeability (unit: GPU) of each gas was measured using a mixed gas consisting of carbon dioxide / nitrogen = 90 / 10 under dry conditions at 25°C. The gas permeability coefficient (unit: Barr) was then calculated by multiplying the measured film thickness by the measured values. Note that GPU (GPU) is the unit [1 GPU = 1 × 10⁻¹⁶]. －６ cm ３ (STP) / cm ２ The value is [sec・cmHg]. The gas selectivity (α) was calculated from the gas permeability coefficient of each gas using the following formula (5): α = carbon dioxide permeability coefficient (Barr) / nitrogen permeability coefficient (Barr) ... formula (5)

[0177] (Dielectric Loss Tangent) The thermosetting resin powder of the example and the resin composition of the comparative example were heated at 200°C for 60 minutes under pressure in a hot press to obtain a film-like resin curing product. The obtained resin film was dried in an oven at 105°C for 1 hour, and then left to stand for 24 hours in an environment of 23°C and 50% relative humidity. Subsequently, the dielectric loss tangent (Df) at 10 GHz in an environment of 23°C and 50% relative humidity was measured using the split cylinder method. A network analyzer (N5227B, manufactured by KEYSIGHT TECHNOLOGIES) and a split cylinder resonator (CR-710, manufactured by EM Lab Co., Ltd.) were used as the measuring apparatus.

[0178] (Glass Transition Temperature) The glass transition temperature (Tg) of the cured products of the thermosetting resin powder in the examples and the resin composition in the comparative example was measured using a DSC (Discovery DSC2500, manufactured by TA Instruments). The thermosetting resin powder was heat-cured in the DSC by raising the temperature from 0°C to 300°C at a rate of 5°C per minute, then cooled to 0°C, and the temperature was raised again from 0°C to 300°C at a rate of 5°C per minute to measure the glass transition temperature.

[0179] (Example 1) A 40-liter jacketed polymerization tank equipped with a sparger for introducing oxygen-containing gas at the bottom of the tank, stirring turbine blades and baffles, and a reflux condenser in the vent gas line at the top of the polymerization tank, was filled with 4.57 g of cupric oxide, 24.18 g of 47% by mass aqueous solution of hydrogen bromide, 11.00 g of di-t-butylethylenediamine, 62.72 g of di-n-butylamine, 149.92 g of butyldimethylamine, 20.65 kg of toluene, and 3.12 kg of 2,6-dimethylphenol. The mixture was stirred until a homogeneous solution was formed and the internal temperature of the polymerization tank reached 25°C. Next, dry air was introduced into the polymerization tank through the sparger at a rate of 32.8 NL / min to start polymerization. Dry air was passed through for 140 minutes to obtain the polymerization mixture. The internal temperature was controlled to 40°C during polymerization. At the end of polymerization, the polymerization mixture (polymerization solution) was in a homogeneous solution state. The supply of dry air was stopped, and 10 kg of a 2.5 mass% aqueous solution of tetrasodium ethylenediaminetetraacetate (reagent manufactured by Dojin Chemical Research Institute) was added to the polymerization mixture. The polymerization mixture was stirred at 70°C for 150 minutes, then allowed to stand for 20 minutes, and the organic phase and aqueous phase were separated by liquid-liquid separation. The separated organic phase yielded a toluene solution containing 13.1 mass% polyphenylene ether. The above solution was placed in a jacketed stirring tank, and heated by flowing a heat transfer medium at 120°C through the jacket. The generated toluene-based vapor was cooled by a condenser to remove the toluene from the system, and the mixture was concentrated until the polymer concentration in the stirring tank reached 30 mass%. Methanol was mixed in such a ratio of 1.0 to the polymer solution, and the polymer was precipitated. Wet polyphenylene ether was obtained by vacuum filtration using a glass filter. Furthermore, the wet polyphenylene ether was washed with methanol in an amount such that the ratio of methanol to wet polyphenylene ether was 2.5. This washing operation was repeated three times. Then, the wet polyphenylene ether was held at 140°C and 1 mmHg for 120 minutes to obtain dry, unmodified polyphenylene ether. The reduced viscosity of the obtained unmodified polyphenylene ether was 0.57 dL / g.

[0180] In a 5 L four-necked flask purged with argon, the unmodified polyphenylene ether (90 g) obtained above and dichloromethane (2250 mL) were added and stirred. To the polyphenylene ether solution prepared above, a dichloromethane solution (750 mL) of aluminum chloride (109 g) and 4-fluorobenzoyl chloride (129 g) was added dropwise over 45 minutes at room temperature. After the addition was complete, the reaction solution was heated using a mantle heater and reacted at 40°C for 24 hours, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to methanol (18 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in chloroform (1.4 L), and the solution was added to methanol (10 L) for precipitation purification. The precipitate was filtered under reduced pressure to recover the modified (fluorobenzoylated) polyphenylene ether as the product. Structural identification of the modified polyphenylene ether was performed. １ Results obtained by 1H-NMR measurement showed that the degeneration rate was 100% using the method described above.

[0181] In a 2 L four-necked flask purged with argon, 100 g of the modified (fluorobenzoylated) polyphenylene ether obtained above was dissolved in 1.0 L of N,N-dimethylformamide, and 500 g of ethylenediamine was added as the amine starting material and stirred. The mixture was heated using an oil bath and incubated at 100°C for 24 hours under reflux, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to 10 L of deionized water to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in 1.0 L of N,N-dimethylformamide, and the solution was added to 10 L of deionized water for precipitation purification. The precipitate was filtered under reduced pressure and dried under reduced pressure at 50°C for 24 hours to recover the amino group-containing polyphenylene ether as the product. The obtained polymer was N,N-dimethylformamide-d ７ Dissolve in and use hexafluorobenzene as an internal standard. １９F-NMR measurements (JEOL ECS400, frequency: 400 MHz, number of integrations: 512, temperature: 25°C) confirmed the disappearance of the peak originating from the fluorobenzoyl group of the raw material, thus confirming amination. In addition, infrared spectrophotometer (Shimadzu MIRacle 10) measurements revealed a peak originating from fluorobenzoyl polyphenylene ether (1240 cm⁻¹). －１ ) disappears, and the peak derived from the amino group (1530 cm) －１ ) Its appearance was confirmed.

[0182] The obtained amino group-containing polyphenylene ether was dissolved in N,N-dimethylformamide to a solid content concentration of 10%, coated onto a glass substrate by casting, and dried at 110°C for 30 minutes to obtain a gas barrier film. The CO2 in this gas barrier film ２ The transmission coefficient is 0.5 Barre, N ２ The transmission coefficient is 0.03 Barre, CH ４ The transmittance coefficient was 0.04 Barre, and the 5% weight loss temperature was 385°C, which were both good.

[0183] (Example 2) The procedure was carried out in the same manner as in Example 1, except that N,N-dimethylethylenediamine was used as the amine raw material. The evaluation results of the obtained film are shown in Table 1.

[0184] (Example 3) The procedure was carried out in the same manner as in Example 1, except that diethylenetriamine was used as the amine raw material. The evaluation results of the obtained film are shown in Table 1.

[0185] (Example 4) The procedure was carried out in the same manner as in Example 1, except that N,N-dimethyldipropylenetriamine was used as the amine raw material. The evaluation results of the obtained film are shown in Table 1.

[0186] (Example 5) The procedure was carried out in the same manner as in Example 1, except that the amine raw material was triethylenetetramine. The evaluation results of the obtained film are shown in Table 1.

[0187] (Example 6) The procedure was carried out in the same manner as in Example 1, except that piperazine was used as the amine raw material. The evaluation results of the obtained film are shown in Table 1.

[0188] (Example 7) In a 5 L four-necked flask purged with argon, 90 g of unmodified polyphenylene ether obtained in the process of Example 1 and 2250 mL of dichloromethane were added and stirred. To the polyphenylene ether solution prepared above, a 750 mL solution of aluminum chloride (59 g) and 4-fluorobenzoyl chloride (70 g) in dichloromethane was added dropwise over 45 minutes at room temperature. After the addition was complete, the reaction solution was heated using a mantle heater and reacted at 40°C for 24 hours, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to methanol (18 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in chloroform (1.4 L), and the solution was added to methanol (10 L) for precipitation purification. The precipitate was filtered under reduced pressure to recover modified polyphenylene ether as the product. Structural identification of the modified polyphenylene ether was performed. １ Results obtained by 1H-NMR measurement showed that the degeneration rate was 50% using the method described above.

[0189] In a 2 L four-necked flask purged with argon, 100 g of the modified polyphenylene ether with a 50% modification rate obtained above was dissolved in 1.0 L of N,N-dimethylformamide, and 250 g of ethylenediamine was added as the amine starting material and stirred. The mixture was heated using an oil bath and incubated at 100°C for 24 hours under reflux, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to 10 L of deionized water to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in 1.0 L of N,N-dimethylformamide, and the solution was added to 10 L of deionized water for precipitation purification. The precipitate was filtered under reduced pressure and dried under reduced pressure at 50°C for 24 hours to recover the amino group-containing polyphenylene ether as the product. The obtained polymer was N,N-dimethylformamide-d ７ Dissolve in and use hexafluorobenzene as an internal standard. １９F-NMR measurements (JEOL ECS400, frequency: 400 MHz, number of integrations: 512, temperature: 25°C) confirmed the disappearance of the peak originating from the fluorobenzoyl group of the raw material, thus confirming amination. In addition, infrared spectrophotometer (Shimadzu MIRacle 10) measurements revealed a peak originating from fluorobenzoyl polyphenylene ether (1240 cm⁻¹). －１ ) disappears, and the peak derived from the amino group (1530 cm) －１ The appearance of the film was confirmed. The film formation method was the same as in Example 1. The evaluation results of the obtained film are shown in Table 1.

[0190] (Example 8) In a 5 L four-necked flask purged with argon, 90 g of unmodified polyphenylene ether obtained in the process of Example 1 and 2250 mL of dichloromethane were added and stirred. To the polyphenylene ether solution prepared above, a 750 mL solution of aluminum chloride (35 g) and 4-fluorobenzoyl chloride (42 g) in dichloromethane was added dropwise over 45 minutes at room temperature. After the addition was complete, the reaction solution was heated using a mantle heater and reacted at 40°C for 24 hours, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to methanol (18 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in chloroform (1.4 L), and the solution was added to methanol (10 L) for precipitation purification. The precipitate was filtered under reduced pressure to recover modified polyphenylene ether as the product. Structural identification of the modified polyphenylene ether was performed. １ Results obtained by 1H-NMR measurement showed a degeneration rate of 30% using the method described above.

[0191] In a 2 L four-necked flask purged with argon, 100 g of the modified polyphenylene ether with a 30% modification rate obtained above was dissolved in 1.0 L of N,N-dimethylformamide, and 200 g of ethylenediamine was added as the amine starting material and stirred. The mixture was heated using an oil bath and incubated at 100°C for 24 hours under reflux, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to 10 L of deionized water to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in 1.0 L of N,N-dimethylformamide, and the solution was added to 10 L of deionized water for precipitation purification. The precipitate was filtered under reduced pressure and dried under reduced pressure at 50°C for 24 hours to recover the amino group-containing polyphenylene ether as the product. The obtained polymer was N,N-dimethylformamide-d ７ Dissolve in and use hexafluorobenzene as an internal standard. １９ F-NMR measurements (JEOL ECS400, frequency: 400 MHz, number of integrations: 512, temperature: 25°C) confirmed the disappearance of the peak originating from the fluorobenzoyl group of the raw material, thus confirming amination. In addition, infrared spectrophotometer (Shimadzu MIRacle 10) measurements revealed a peak originating from fluorobenzoyl polyphenylene ether (1240 cm⁻¹). －１ ) disappears, and the peak derived from the amino group (1530 cm) －１ The appearance of the film was confirmed. The film formation method was the same as in Example 1. The evaluation results of the obtained film are shown in Table 1.

[0192] (Example 9) In a 5 L four-necked flask purged with argon, 90 g of unmodified polyphenylene ether obtained in the process of Example 1 and 2250 mL of dichloromethane were added and stirred. To the polyphenylene ether solution prepared above, a 750 mL solution of aluminum chloride (108 g) and 4-fluorobenzenesulfonyl chloride (158 g) in dichloromethane was added dropwise over 45 minutes at room temperature. After the addition was complete, the reaction solution was heated using a mantle heater and reacted at 40°C for 24 hours, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to methanol (18 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in chloroform (1.4 L), and the solution was added to methanol (10 L) for precipitation purification. The precipitate was filtered under reduced pressure to recover modified polyphenylene ether as the product. Structural identification of the modified polyphenylene ether was performed. １ Results obtained by 1H-NMR measurement showed that the degeneration rate was 100% using the method described above.

[0193] In a 2 L four-necked flask purged with argon, 100 g of the modified polyphenylene ether with a 100% modification rate obtained above was dissolved in N,N-dimethylformamide (1.0 L), and N,N-dimethylethylenediamine (200 g) was added as the amine starting material and stirred. The mixture was heated using an oil bath and incubated at 100°C for 24 hours under reflux, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to ion-exchanged water (10 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in N,N-dimethylformamide (1.0 L), and the solution was added to ion-exchanged water (10 L) for precipitation purification. The precipitate was filtered under reduced pressure and dried under reduced pressure at 50°C for 24 hours to recover the amino group-containing polyphenylene ether as the product. The obtained polymer was N,N-dimethylformamide-d ７ Dissolve in and use hexafluorobenzene as an internal standard. １９F-NMR measurements (JEOL ECS400, frequency: 400 MHz, number of integrations: 512, temperature: 25°C) confirmed the disappearance of the peak originating from the fluorobenzoyl group of the raw material, thus confirming amination. In addition, infrared spectrophotometer (Shimadzu MIRacle 10) measurements revealed a peak originating from fluorobenzenesulfonylated polyphenylene ether (1240 cm⁻¹). －１ ) disappears, and the peak derived from the amino group (1530 cm) －１ The appearance of the film was confirmed. The film formation method was the same as in Example 1. The evaluation results of the obtained film are shown in Table 1.

[0194] (Example 10) A 40-liter jacketed polymerization tank equipped with a sparger, stirring turbine blades and baffles at the bottom for introducing oxygen-containing gas, and a reflux condenser in the vent gas line at the top of the polymerization tank was mixed with 2.4 g of cupric oxide, 18.1 g of 47% by mass aqueous solution of hydrogen bromide, 5.8 g of di-t-butylethylenediamine, 28.1 g of di-n-butylamine, 85.6 g of butyldimethylamine, 17.9 kg of toluene, 1497 g of 2,6-dimethylphenol, and 503 g of 2-tert-butyl-5-methylphenol while blowing nitrogen gas at a flow rate of 17.1 L / min to form a homogeneous solution. Next, dry air was introduced into the polymerization tank from the sparger at a rate of 10.5 L / min to start polymerization. Dry air was passed through for 120 minutes to obtain the polymerization mixture. The internal temperature was controlled to 20°C during polymerization. At the end of polymerization, the polymerization mixture (polymerization solution) was in a homogeneous solution state. After stopping the supply of dry air, 25.9 g of tetrasodium ethylenediaminetetraacetate (reagent manufactured by Dojin Chemical Research Institute) was added to the polymerization mixture as an aqueous solution in 2 kg of water. The polymerization mixture was stirred at 70°C for 150 minutes, then allowed to stand for 20 minutes, and the organic phase and aqueous phase were separated by liquid-liquid separation. The organic phase was concentrated using a rotary evaporator until the polymer concentration reached 25% by mass. The above solution was mixed with methanol in a ratio of 6 to the polymer solution, and the polymer was precipitated. Wet polyphenylene ether was obtained by vacuum filtration using a glass filter. The wet polyphenylene ether was further washed with methanol in a ratio of 3 to the wet polyphenylene ether. The above washing operation was repeated three times. Then, the wet polyphenylene ether was held at 140°C and 1 mmHg for 120 minutes to obtain dry polyphenylene ether. The reduced viscosity of the obtained unmodified polyphenylene ether was 0.22 dL / g. Using the unmodified polyphenylene ether obtained above, the procedure was carried out in the same manner as in Example 7. The film formation method was carried out in the same manner as in Example 1. The evaluation results of the obtained film are shown in Table 1.

[0195] (Example 11) In a 5 L four-necked flask purged with argon, 90 g of unmodified polyphenylene ether obtained in the process of Example 1 and 2250 mL of chloroform were added and dissolved, and paraformaldehyde (107 g) was added and stirred for 1 hour. Next, at room temperature, SnCl ４ (19 g) was added. A solution of trimethylchlorosilane (264 g) dissolved in chloroform (500 mL) was added dropwise over 2 hours. After the dropwise addition was complete, the reaction solution was heated using a mantle heater and reacted at 40°C for 15 hours, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to methanol (18 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in chloroform (1.4 L), and the solution was added to methanol (10 L) for precipitation purification. The precipitate was filtered under reduced pressure to recover denatured (chloromethylated) polyphenylene ether as the product. Structural identification of the denatured polyphenylene ether was performed. １ ¹H-NMR measurements revealed that the denaturation rate was 30% using the method described above. The obtained modified polyphenylene ether was used, and the procedure was carried out in the same manner as in Example 8. The film formation method was the same as in Example 1. The evaluation results of the obtained film are shown in Table 1.

[0196] (Example 12) In a 5 L four-necked flask purged with argon, 90 g of unmodified polyphenylene ether obtained in the process of Example 1 and 2250 mL of dichloromethane were added and stirred. To the polyphenylene ether solution prepared above, a 750 mL solution of aluminum chloride (177 g) and 4-fluorobenzoyl chloride (210 g) in dichloromethane was added dropwise over 45 minutes at room temperature. After the addition was complete, the reaction solution was heated using a mantle heater and reacted at 40°C for 24 hours, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to methanol (18 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in chloroform (1.4 L), and the solution was added to methanol (10 L) for precipitation purification. The precipitate was filtered under reduced pressure to recover modified polyphenylene ether as the product. Structural identification of the modified polyphenylene ether was performed. １Results obtained by 1H-NMR measurement showed a degeneration rate of 150% using the method described above.

[0197] In a 2 L four-necked flask purged with argon, 100 g of the modified polyphenylene ether with a 150% modification rate obtained above was dissolved in N,N-dimethylformamide (1.0 L), and ethylenediamine (500 g) was added as the amine starting material and stirred. The mixture was heated using an oil bath and incubated at 100°C for 24 hours under reflux, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to ion-exchanged water (10 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in N,N-dimethylformamide (1.0 L), and the solution was added to ion-exchanged water (10 L) for precipitation purification. The precipitate was filtered under reduced pressure and dried under reduced pressure at 50°C for 24 hours to recover the amino group-containing polyphenylene ether as the product. The obtained polymer was N,N-dimethylformamide-d ７ Dissolve in and use hexafluorobenzene as an internal standard. １９ F-NMR measurements (JEOL ECS400, frequency: 400 MHz, number of integrations: 512, temperature: 25°C) confirmed the disappearance of the peak originating from the fluorobenzoyl group of the raw material, thus confirming amination. In addition, infrared spectrophotometer (Shimadzu MIRacle 10) measurements revealed a peak originating from fluorobenzoyl polyphenylene ether (1240 cm⁻¹). －１ ) disappears, and the peak derived from the amino group (1530 cm) －１ The appearance of the film was confirmed. The film formation method was the same as in Example 1. The evaluation results of the obtained film are shown in Table 1.

[0198] (Example 13) In a 5 L four-necked flask purged with argon, 90 g of unmodified polyphenylene ether obtained in the process of Example 1 and 2250 mL of dichloromethane were added and stirred. To the polyphenylene ether solution prepared above, a 750 mL solution of aluminum chloride (118 g) and 4-bromobutanoyl chloride (164 g) in dichloromethane was added dropwise over 45 minutes at room temperature. After the addition was complete, the reaction solution was heated using a mantle heater and reacted at 40°C for 24 hours, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to methanol (18 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in chloroform (1.4 L), and the solution was added to methanol (10 L) for precipitation purification. The precipitate was filtered under reduced pressure to recover modified (bromobutanoylated) polyphenylene ether as the product. Structural identification of denatured polyphenylene ethers １ Results obtained by 1H-NMR measurement showed that the degeneration rate was 100% using the method described above.

[0199] In a 2 L four-necked flask purged with argon, 100 g of the 100% denatured polyphenylene ether obtained above was dissolved in 1.0 L of N,N-dimethylformamide, and 250 g of ethylenediamine was added as the amine starting material and the mixture was stirred. The mixture was heated using an oil bath and incubated at 100°C for 24 hours under reflux, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to 10 L of deionized water to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in 1.0 L of N,N-dimethylformamide, and the solution was added to 10 L of deionized water for precipitation purification. The precipitate was filtered under reduced pressure, and the amino group-containing polyphenylene ether was recovered as the product by vacuum drying at 50°C for 24 hours. Infrared spectrophotometer (MIRacle 10, Shimadzu Corporation) measurement of the obtained polymer revealed a peak originating from bromobutanoylated polyphenylene ether (1400 cm⁻¹). －１ ) disappearance and the peak derived from the amino group (1530 cm) －１ The appearance of the film was confirmed. The film formation method was the same as in Example 1. The evaluation results of the obtained film are shown in Table 1.

[0200] (Example 14) In a 2 L four-necked flask purged with argon, 100 g of the 100% denatured (fluorobenzoylated) polyphenylene ether obtained in Example 1 was dissolved in N,N-dimethylformamide (1.0 L). 1,4-dihydroxybenzene (250 g) was added as the phenol starting material, and triethylamine (229 g) as the catalyst, and the mixture was stirred. The mixture was heated using an oil bath and incubated at 130°C for 24 hours under reflux, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to ion-exchanged water (10 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in N,N-dimethylformamide (1.0 L), and the solution was added to ion-exchanged water (10 L) for precipitation purification. The precipitate was filtered under reduced pressure, and the ether group-containing polyphenylene ether was recovered as the product by vacuum drying at 50°C for 24 hours. The obtained polymer is dissolved in N,N-dimethylformamide-d7, and hexafluorobenzene is used as an internal standard. １９ F-NMR measurements (JEOL ECS400, frequency: 400 MHz, number of integrations: 512, temperature: 25°C) confirmed the disappearance of the peak originating from the fluorobenzoyl group of the raw material, thus confirming amination. In addition, infrared spectrophotometer (Shimadzu MIRacle 10) measurements revealed a peak originating from fluorobenzoyl polyphenylene ether (1240 cm⁻¹). －１ The disappearance of ) was confirmed. The film formation method was carried out in the same manner as in Example 1. The evaluation results of the obtained film are shown in Table 1.

[0201] (Example 15) The procedure was carried out in the same manner as in Example 1, except that 4-hydroxybenzylamine was used as the amine raw material. The evaluation results of the obtained film are shown in Table 1.

[0202] (Example 16) In a 2 L four-necked flask purged with argon, 100 g of the 100% denatured (fluorobenzoylated) polyphenylene ether obtained in Example 1 was dissolved in N,N-dimethylformamide (1.0 L). 1,2-ethanedithiol (250 g) was added as the thiol starting material, and triethylamine (229 g) as the catalyst, and the mixture was stirred. The mixture was heated using an oil bath and incubated at 110°C for 24 hours under reflux, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to ion-exchanged water (10 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in N,N-dimethylformamide (1.0 L), and the solution was added to ion-exchanged water (10 L) for precipitation purification. The precipitate was filtered under reduced pressure, and the thioether group-containing polyphenylene ether was recovered as the product by vacuum drying at 50°C for 24 hours. The obtained polymer is dissolved in N,N-dimethylformamide-d7, and hexafluorobenzene is used as an internal standard. １９ F-NMR measurements (JEOL ECS400, frequency: 400 MHz, number of integrations: 512, temperature: 25°C) confirmed the disappearance of the peak originating from the fluorobenzoyl group of the raw material, thus confirming amination. In addition, infrared spectrophotometer (Shimadzu MIRacle 10) measurements revealed a peak originating from fluorobenzoyl polyphenylene ether (1240 cm⁻¹). －１ The disappearance of ) was confirmed. The film formation method was carried out in the same manner as in Example 1. The evaluation results of the obtained film are shown in Table 1.

[0203] (Comparative Example 1) The unmodified polyphenylene ether obtained in the process of Example 1 was dissolved in toluene to a solid content concentration of 10%, coated onto a glass substrate by casting, and dried at 110°C for 20 minutes to obtain a separation film. The evaluation results of the obtained film are shown in Table 1.

[0204] (Comparative Example 2) The unmodified polyphenylene ether obtained in the process of Example 10 was dissolved in toluene to a solid content concentration of 10%, coated onto a glass substrate by casting, and dried at 110°C for 20 minutes to obtain a separation film. The evaluation results of the obtained film are shown in Table 1.

[0205] (Comparative Example 3) Referring to Example 2 described in Japanese Patent Publication No. 57-117321, an aminerized 2,6-dimethyl-p-phenylene oxide was synthesized with a 44% modification rate, in which the methyl group of the 2,6-dimethylphenol unit was amine-modified. The evaluation results of the obtained film are shown in Table 1.

[0206] (Comparative Example 4) In a 500 mL four-necked flask purged with argon, 5 g of the unmodified polyphenylene ether obtained in the process of Example 1 and 150 mL of chloroform were added and dissolved. A mixture of 10 mL of nitric acid and 15 mL of sulfuric acid (25 mL) was added dropwise at 25°C for 5 minutes and stirred for 30 minutes. The reaction solution was added to methanol (1 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in chloroform (500 mL), and the solution was added to methanol (2 L) for precipitation purification to obtain a modified polymer (nitro group-containing polyphenylene ether) in which 15% of nitro groups were introduced at the 3rd or 5th position of 2,6-dimethylphenol. In a 500 mL four-necked flask purged with argon, 3 g of the polymer with 15% of nitro groups introduced at the 3rd or 5th position of 2,6-dimethylphenol and 15 mL of chloroform were added and dissolved. Add SnCl ２ ・2H ２ A solution of 30 g of oxygen (O) and 1 g of NaI (NaI) dissolved in a mixture of 48 mL of hydrochloric acid and 24 mL of glacial acetic acid (72 mL) was added dropwise at 60°C within 5 minutes. 15 mL of methanol was added, refluxed for 3 hours, and cooled to room temperature. The reaction mixture was poured into a 500 mL solution of 2N NaOH to precipitate the polymer. The precipitated polymer was washed with water until the pH was 7 and dried at room temperature. The dried polymer was dissolved in 15 mL of chloroform and purified by precipitation with 500 mL of methanol to obtain a polymer in which 15% of the amino group was introduced at the 3rd or 5th position of 2,6-dimethylphenol. The film formation method was the same as in Example 1. The evaluation results of the obtained films are shown in Table 1.

[0207]

[0208] As shown in Table 1, in Examples 1 to 16, hetero-containing polyphenylene ethers having polyphenylene ether, an inexpensive general-purpose engineering plastic, as the base structure exhibited high gas barrier properties and suppressed a decrease in thermal decomposition temperature. On the other hand, the amino-group-free polyphenylene ethers of Comparative Examples 1, 2, and 4 did not exhibit sufficient gas barrier properties, and the amino-group-containing polyphenylene ether of Comparative Example 3 was found to have a low thermal decomposition temperature.

[0209] (Example 17) A 40-liter jacketed polymerization tank equipped with a sparger for introducing oxygen-containing gas at the bottom of the polymerization tank, stirring turbine blades and baffles, and a reflux condenser in the vent gas line at the top of the polymerization tank, was inoculated with 4.57 g of cupric oxide, 24.18 g of 47% by mass aqueous solution of hydrogen bromide, 11.00 g of di-t-butylethylenediamine, 62.72 g of di-n-butylamine, 149.92 g of butyldimethylamine, 20.65 kg of toluene, and 3.12 kg of 2,6-dimethylphenol. The mixture was stirred until a homogeneous solution was formed and the internal temperature of the polymerization tank reached 25°C. Next, dry air was introduced into the polymerization tank through the sparger at a rate of 32.8 NL / min to start polymerization. Dry air was passed through for 140 minutes to obtain the polymerization mixture. The internal temperature was controlled to 40°C during polymerization. At the end of polymerization, the polymerization mixture (polymerization solution) was in a homogeneous solution state. The supply of dry air was stopped, and 10 kg of a 2.5 mass% aqueous solution of tetrasodium ethylenediaminetetraacetate (reagent manufactured by Dojin Chemical Research Institute) was added to the polymerization mixture. The polymerization mixture was stirred at 70°C for 150 minutes, then allowed to stand for 20 minutes, and the organic phase and aqueous phase were separated by liquid-liquid separation. The separated organic phase yielded a toluene solution containing 13.1 mass% polyphenylene ether. The above solution was placed in a jacketed stirring tank, and heated by flowing a heat transfer medium at 120°C through the jacket. The generated toluene-based vapor was cooled by a condenser to remove the toluene from the system, and the mixture was concentrated until the polymer concentration in the stirring tank reached 30 mass%. Methanol was mixed in such a ratio of 1.0 to the polymer solution, and the polymer was precipitated. Wet polyphenylene ether was obtained by vacuum filtration using a glass filter. Furthermore, the wet polyphenylene ether was washed with methanol in an amount such that the ratio of methanol to wet polyphenylene ether was 2.5. This washing operation was repeated three times. Then, the wet polyphenylene ether was held at 140°C and 1 mmHg for 120 minutes to obtain dry, unmodified polyphenylene ether. The reduced viscosity of the obtained unmodified polyphenylene ether was 0.57 dL / g.

[0210] In a 5 L four-necked flask purged with argon, the unmodified polyphenylene ether (90 g) obtained above and dichloromethane (2250 mL) were added and stirred. To the polyphenylene ether solution prepared above, a dichloromethane solution (750 mL) of aluminum chloride (109 g) and 4-fluorobenzoyl chloride (129 g) was added dropwise over 45 minutes at room temperature. After the addition was complete, the reaction solution was heated using a mantle heater and reacted at 40°C for 24 hours, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to methanol (18 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in chloroform (1.4 L), and the solution was added to methanol (10 L) for precipitation purification. The precipitate was filtered under reduced pressure to recover the modified (fluorobenzoylated) polyphenylene ether as the product. Structural identification of the modified polyphenylene ether was performed. １ Results obtained by 1H-NMR measurement showed that the degeneration rate was 100% using the method described above.

[0211] In a 2 L four-necked flask purged with argon, 100 g of the modified (fluorobenzoylated) polyphenylene ether obtained above was dissolved in 1.0 L of N,N-dimethylformamide, and 500 g of N,N,N'-trimethylethylenediamine was added as the amine starting material and stirred. The mixture was heated in an oil bath and incubated at 100°C for 24 hours under reflux, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to 10 L of deionized water to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in 1.0 L of N,N-dimethylformamide, and the solution was added to 10 L of deionized water for precipitation purification. The precipitate was filtered under reduced pressure and dried under reduced pressure at 50°C for 24 hours to recover the amino group-containing polyphenylene ether as the product. The obtained polymer was N,N-dimethylformamide-d ７ Dissolve in and use hexafluorobenzene as an internal standard. １９F-NMR measurements (JEOL ECS400, frequency: 400 MHz, number of integrations: 512, temperature: 25°C) confirmed the disappearance of the peak originating from the fluorobenzoyl group of the raw material, thus confirming amination. In addition, infrared spectrophotometer (Shimadzu MIRacle 10) measurements revealed a peak originating from fluorobenzoyl polyphenylene ether (1240 cm⁻¹). －１ ) disappears, and the peak derived from the amino group (1530 cm) －１ ) Its appearance was confirmed.

[0212] The obtained amino group-containing polyphenylene ether was dissolved in N,N-dimethylformamide to a solid content concentration of 10%, coated onto a glass substrate by casting, and dried at 110°C for 30 minutes to obtain a separation membrane. The gas separation performance α of this separation membrane was 36, and the weight loss temperature of 400°C was good.

[0213] (Example 18) The procedure was carried out in the same manner as in Example 17, except that dimethylamine was used as the amine raw material. The evaluation results of the obtained film are shown in Table 2.

[0214] (Example 19) The procedure was carried out in the same manner as in Example 17, except that 1-methylpiperazine was used as the amine raw material. The evaluation results of the obtained film are shown in Table 2.

[0215] (Example 20) The procedure was carried out in the same manner as in Example 17, except that the amine raw material was 3,3'-iminobis(N,N-dimethylpropylamine). The evaluation results of the obtained film are shown in Table 2.

[0216] (Example 21) The procedure was carried out in the same manner as in Example 17, except that the amine raw material was 1-[2-(2-hydroxyethoxy)ethyl]piperazine. The evaluation results of the obtained film are shown in Table 2.

[0217] (Example 22) In a 5 L four-necked flask purged with argon, 90 g of unmodified polyphenylene ether obtained in the process of Example 17 and 2250 mL of dichloromethane were added and stirred. To the polyphenylene ether solution prepared above, a 750 mL solution of aluminum chloride (59 g) and 4-fluorobenzoyl chloride (70 g) in dichloromethane was added dropwise over 45 minutes at room temperature. After the addition was complete, the reaction solution was heated using a mantle heater and reacted at 40°C for 24 hours, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to methanol (18 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in chloroform (1.4 L), and the solution was added to methanol (10 L) for precipitation purification. The precipitate was filtered under reduced pressure to recover modified polyphenylene ether as the product. Structural identification of the modified polyphenylene ether was performed. １ Results obtained by 1H-NMR measurement showed that the degeneration rate was 50% using the method described above.

[0218] In a 2 L four-necked flask purged with argon, 100 g of the modified polyphenylene ether with a 50% modification rate obtained above was dissolved in 1.0 L of N,N-dimethylformamide, and 250 g of 1-methylpiperazine was added as the amine starting material and stirred. The mixture was heated using an oil bath and incubated at 100°C for 24 hours under reflux, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to 10 L of deionized water to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in 1.0 L of N,N-dimethylformamide, and the solution was added to 10 L of deionized water for precipitation purification. The precipitate was filtered under reduced pressure and dried under reduced pressure at 50°C for 24 hours to recover the amino group-containing polyphenylene ether as the product. The obtained polymer was N,N-dimethylformamide-d ７ Dissolve in and use hexafluorobenzene as an internal standard. １９F-NMR measurements (JEOL ECS400, frequency: 400 MHz, number of integrations: 512, temperature: 25°C) confirmed the disappearance of the peak originating from the fluorobenzoyl group of the raw material, thus confirming amination. In addition, infrared spectrophotometer (Shimadzu MIRacle 10) measurements revealed a peak originating from fluorobenzoyl polyphenylene ether (1240 cm⁻¹). －１ ) disappears, and the peak derived from the amino group (1530 cm) －１ The appearance of the film was confirmed. The film formation method was carried out in the same manner as in Example 17. The evaluation results of the obtained film are shown in Table 2.

[0219] (Example 23) In a 5 L four-necked flask purged with argon, 90 g of unmodified polyphenylene ether obtained in the process of Example 17 and 2250 mL of dichloromethane were added and stirred. To the polyphenylene ether solution prepared above, a 750 mL solution of aluminum chloride (35 g) and 4-fluorobenzoyl chloride (42 g) in dichloromethane was added dropwise over 45 minutes at room temperature. After the addition was complete, the reaction solution was heated using a mantle heater and reacted at 40°C for 24 hours, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to methanol (18 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in chloroform (1.4 L), and the solution was added to methanol (10 L) for precipitation purification. The precipitate was filtered under reduced pressure to recover modified polyphenylene ether as the product. Structural identification of the modified polyphenylene ether was performed. １ Results obtained by 1H-NMR measurement showed a degeneration rate of 30% using the method described above.

[0220] In a 2 L four-necked flask purged with argon, 100 g of the modified polyphenylene ether with a 30% modification rate obtained above was dissolved in 1.0 L of N,N-dimethylformamide, and 200 g of 1-methylpiperazine was added as the amine starting material and stirred. The mixture was heated using an oil bath and incubated at 100°C for 24 hours under reflux, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to 10 L of deionized water to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in 1.0 L of N,N-dimethylformamide, and the solution was added to 10 L of deionized water for precipitation purification. The precipitate was filtered under reduced pressure and dried under reduced pressure at 50°C for 24 hours to recover the amino group-containing polyphenylene ether as the product. The obtained polymer was N,N-dimethylformamide-d ７ Dissolve in and use hexafluorobenzene as an internal standard. １９ F-NMR measurements (JEOL ECS400, frequency: 400 MHz, number of integrations: 512, temperature: 25°C) confirmed the disappearance of the peak originating from the fluorobenzoyl group of the raw material, thus confirming amination. In addition, infrared spectrophotometer (Shimadzu MIRacle 10) measurements revealed a peak originating from fluorobenzoyl polyphenylene ether (1240 cm⁻¹). －１ ) disappears, and the peak derived from the amino group (1530 cm) －１ The appearance of the film was confirmed. The film formation method was carried out in the same manner as in Example 17. The evaluation results of the obtained film are shown in Table 2.

[0221] (Example 24) In a 5 L four-necked flask purged with argon, 90 g of unmodified polyphenylene ether obtained in the process of Example 17 and 2250 mL of dichloromethane were added and stirred. To the polyphenylene ether solution prepared above, a 750 mL solution of aluminum chloride (108 g) and 4-fluorobenzenesulfonyl chloride (158 g) in dichloromethane was added dropwise over 45 minutes at room temperature. After the addition was complete, the reaction solution was heated using a mantle heater and reacted at 40°C for 24 hours, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to methanol (18 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in chloroform (1.4 L), and the solution was added to methanol (10 L) for precipitation purification. The precipitate was filtered under reduced pressure to recover modified (fluorobenzenesulfonylated) polyphenylene ether as the product. Structural identification of denatured polyphenylene ethers １ Results obtained by 1H-NMR measurement showed that the degeneration rate was 100% using the method described above.

[0222] In a 2 L four-necked flask purged with argon, 100 g of the 100% denatured polyphenylene ether obtained above was dissolved in 1.0 L of N,N-dimethylformamide, and 200 g of 1-methylpiperazine was added as the amine starting material and stirred. The mixture was heated using an oil bath and incubated at 100°C for 24 hours under reflux, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to 10 L of deionized water to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in 1.0 L of N,N-dimethylformamide, and the solution was added to 10 L of deionized water for precipitation purification. The precipitate was filtered under reduced pressure and dried under reduced pressure at 50°C for 24 hours to recover the amino group-containing polyphenylene ether as the product. The obtained polymer was N,N-dimethylformamide-d ７ Dissolve in and use hexafluorobenzene as an internal standard. １９F-NMR measurements (JEOL ECS400, frequency: 400 MHz, number of integrations: 512, temperature: 25°C) confirmed the disappearance of the peak originating from the fluorobenzoyl group of the raw material, thus confirming amination. In addition, infrared spectrophotometer (Shimadzu MIRacle 10) measurements revealed a peak originating from fluorobenzenesulfonylated polyphenylene ether (1220 cm⁻¹). －１ ) disappears, and the peak derived from the amino group (1500 cm) －１ The appearance of the film was confirmed. The film formation method was carried out in the same manner as in Example 17. The evaluation results of the obtained film are shown in Table 2.

[0223] (Example 25) A 40-liter jacketed polymerization tank equipped with a sparger, stirring turbine blades and baffles at the bottom for introducing oxygen-containing gas, and a reflux condenser in the vent gas line at the top of the polymerization tank was mixed with 2.4 g of cupric oxide, 18.1 g of 47% by mass aqueous solution of hydrogen bromide, 5.8 g of di-t-butylethylenediamine, 28.1 g of di-n-butylamine, 85.6 g of butyldimethylamine, 17.9 kg of toluene, 1497 g of 2,6-dimethylphenol, and 503 g of 2-tert-butyl-5-methylphenol while blowing nitrogen gas at a flow rate of 17.1 L / min to form a homogeneous solution. Next, dry air was introduced into the polymerization tank from the sparger at a rate of 10.5 L / min to start polymerization. Dry air was passed through for 120 minutes to obtain the polymerization mixture. The internal temperature was controlled to 20°C during polymerization. At the end of polymerization, the polymerization mixture (polymerization solution) was in a homogeneous solution state. After stopping the supply of dry air, 25.9 g of tetrasodium ethylenediaminetetraacetate (reagent manufactured by Dojin Chemical Research Institute) was added to the polymerization mixture as an aqueous solution in 2 kg of water. The polymerization mixture was stirred at 70°C for 150 minutes, then allowed to stand for 20 minutes, and the organic phase and aqueous phase were separated by liquid-liquid separation. The organic phase was concentrated using a rotary evaporator until the polymer concentration reached 25% by mass. The above solution was mixed with methanol in a ratio of 6 to the polymer solution, and the polymer was precipitated. Wet polyphenylene ether was obtained by vacuum filtration using a glass filter. The wet polyphenylene ether was further washed with methanol in a ratio of 3 to the wet polyphenylene ether. The above washing operation was repeated three times. Then, the wet polyphenylene ether was held at 140°C and 1 mmHg for 120 minutes to obtain dry polyphenylene ether. The reduced viscosity of the obtained unmodified polyphenylene ether was 0.22 dL / g. Using the unmodified polyphenylene ether obtained above, the procedure was carried out in the same manner as in Example 22. The film formation method was carried out in the same manner as in Example 17. The evaluation results of the obtained film are shown in Table 2.

[0224] (Example 26) In a 5 L four-necked flask purged with argon, 90 g of unmodified polyphenylene ether obtained in the process of Example 17 and 2250 mL of chloroform were added and dissolved, and paraformaldehyde (107 g) was added and stirred for 1 hour. Next, at room temperature, SnCl ４ (19 g) was added. A solution of trimethylchlorosilane (264 g) dissolved in chloroform (500 mL) was added dropwise over 2 hours. After the dropwise addition was complete, the reaction solution was heated using a mantle heater and reacted at 40°C for 15 hours, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to methanol (18 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in chloroform (1.4 L), and the solution was added to methanol (10 L) for precipitation purification. The precipitate was filtered under reduced pressure to recover denatured (chloromethylated) polyphenylene ether as the product. Structural identification of the denatured polyphenylene ether was performed. １ ¹H-NMR measurements revealed that the denaturation rate was 30% using the method described above. The obtained modified polyphenylene ether was used, and the procedure was carried out in the same manner as in Example 23. The film formation method was the same as in Example 17. The evaluation results of the obtained film are shown in Table 2.

[0225] (Comparative Example 5) The unmodified polyphenylene ether obtained in the process of Example 17 was dissolved in toluene to a solid content concentration of 10%, coated onto a glass substrate by casting, and dried at 110°C for 20 minutes to obtain a separation film. The evaluation results of the obtained film are shown in Table 2.

[0226] (Comparative Example 6) The unmodified polyphenylene ether obtained in the process of Example 25 was dissolved in toluene to a solid content concentration of 10%, coated onto a glass substrate by casting, and dried at 110°C for 20 minutes to obtain a separation film. The evaluation results of the obtained film are shown in Table 2.

[0227]

[0228] As shown in Table 2, in Examples 17 to 26, the amino group-containing polyphenylene ether, which has an inexpensive general-purpose engineering plastic polyphenylene ether as its base structure, was able to exhibit high gas selectivity and suppress the decrease in thermal decomposition temperature. On the other hand, it was found that the amino group-free polyphenylene ethers of Comparative Examples 5 and 6 did not exhibit sufficient gas selectivity.

[0229] (Example 27) A 40-liter jacketed polymerization tank equipped with a sparger, stirring turbine blades and baffles at the bottom for introducing oxygen-containing gas, and a reflux condenser in the vent gas line at the top of the polymerization tank was filled with 4.57 g of cupric oxide, 24.18 g of 47% by mass aqueous solution of hydrogen bromide, 11.00 g of di-t-butylethylenediamine, 62.72 g of di-n-butylamine, 149.92 g of butyldimethylamine, 20.65 kg of toluene, and 3.12 kg of 2,6-dimethylphenol, while blowing nitrogen gas at a flow rate of 0.5 L / min. The mixture was stirred until a homogeneous solution was formed and the internal temperature of the polymerization tank reached 25°C. Next, dry air was introduced into the polymerization tank through the sparger at a rate of 32.8 NL / min to start polymerization. Dry air was passed through for 90 minutes to obtain the polymerization mixture. The internal temperature was controlled to 40°C during polymerization. At the end of polymerization, the polymerization mixture (polymerization solution) was in a homogeneous solution state. The supply of dry air was stopped, and 10 kg of a 2.5 mass% aqueous solution of tetrasodium ethylenediaminetetraacetate (reagent manufactured by Dojin Chemical Research Institute) was added to the polymerization mixture. The polymerization mixture was stirred at 70°C for 150 minutes, then allowed to stand for 20 minutes, and the organic phase and aqueous phase were separated by liquid-liquid separation. The separated organic phase yielded a toluene solution containing 13.1 mass% polyphenylene ether. The above solution was placed in a jacketed stirring tank, and heated by flowing a heat transfer medium at 120°C through the jacket. The generated toluene-based vapor was cooled by a condenser to remove the toluene from the system, and the mixture was concentrated until the polymer concentration in the stirring tank reached 30 mass%. Methanol was mixed in such a ratio of 1.0 to the polymer solution, and the polymer was precipitated. Wet polyphenylene ether was obtained by vacuum filtration using a glass filter. Furthermore, the wet polyphenylene ether was washed with methanol in an amount such that the ratio of methanol to wet polyphenylene ether was 2.5. This washing procedure was repeated three times. Then, the wet polyphenylene ether was maintained at 140°C and 1 mmHg for 120 minutes to obtain dry, unmodified polyphenylene ether.

[0230] In a 10 L four-necked flask purged with argon, the unmodified polyphenylene ether (175 g) obtained above and dichloromethane (5 L) were added and stirred. To the polyphenylene ether solution prepared above, a dichloromethane solution (150 mL) of aluminum chloride (20 g) and 4-fluorobenzoyl chloride (24 g) was added dropwise over 45 minutes at room temperature. After the addition was complete, the reaction solution was heated using a mantle heater and reacted at 40°C for 24 hours, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to methanol (20 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in toluene (1 L), and the solution was added to methanol (10 L) for precipitation purification. The precipitate was filtered under reduced pressure to recover the modified (fluorobenzoyl) polyphenylene ether as the product. Structural identification of the modified polyphenylene ether was performed. １ Results obtained by 1H-NMR measurement showed that the degeneration rate was 1% using the method described above.

[0231] In a 2 L four-necked flask purged with argon, 100 g of the modified (fluorobenzoylated) polyphenylene ether obtained above, 500 mL of N,N-dimethylformamide, and 500 g of ethylenediamine as the amine starting material were added and stirred. The mixture was heated using an oil bath and incubated at 100°C for 24 hours under reflux, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to 10 L of deionized water to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in 500 mL of N,N-dimethylformamide, and the solution was added to 10 L of deionized water for precipitation purification. The precipitate was filtered under reduced pressure, and the amino group-containing polyphenylene ether was recovered as the product by vacuum drying at 50°C for 24 hours. The obtained polymer was N,N-dimethylformamide-d ７ Dissolve in and use hexafluorobenzene as an internal standard. １９F-NMR measurements (JEOL ECS400, frequency: 400 MHz, number of integrations: 512, temperature: 25°C) confirmed the disappearance of the peak originating from the fluorobenzoyl group of the raw material, thus confirming amination. In addition, infrared spectrophotometer (Shimadzu MIRacle 10) measurements revealed a peak originating from fluorobenzoyl polyphenylene ether (1240 cm⁻¹). －１ ) disappears, and the peak derived from the amino group (1530 cm) －１ ) Its appearance was confirmed.

[0232] In a 500 mL round-bottom flask, the amino group-containing polyphenylene ether (50 g) obtained above and toluene (100 mL) were added and stirred. Furthermore, tetrabutylammonium bromide (0.1 g), 4-(chloromethyl)styrene (3 g), and 48% sodium hydroxide solution (4 g) were added, and the mixture was heated and stirred at 80°C for 4 hours. The organic layer was then extracted from the reaction solution using toluene. The extracted organic layer was washed with deionized water, and then precipitated by dropping it into methanol (2 L). The precipitated polymer was filtered, washed with methanol, and then dried under reduced pressure at 50°C for 24 hours to obtain thermosetting polyphenylene ether. The obtained thermosetting polyphenylene ether was dissolved in deuterated chloroform, and tetramethylsilane was used as an internal standard. １ ¹H-NMR measurements were performed (Brker Biospin AvanceNEO600, frequency: 600 MHz, number of integrations: 16, temperature: 25°C). From the integral values ​​of the peaks originating from the introduced vinyl groups (5.2 ppm and 5.7 ppm), it was found that the content of formula (1) units in the repeating units of the polymer was 1%. Furthermore, the dielectric loss tangent (Df) and glass transition temperature (Tg) were measured using the method described above.

[0233] (Examples 28-36) The procedure was the same as in Example 27, except that the amount of reagent added and the type of amine raw material were changed as shown in Table 3 below, to obtain thermosetting polyphenylene ethers. In each example, the modified (fluorobenzoylated) polyphenylene ether of the intermediate was １ Structural identification was performed by 1H-NMR measurement. The results of the modification rate measurement are shown in Table 3. The obtained thermosetting polyphenylene ether was treated in the same manner as in Example 27.１ ¹H-NMR measurements were performed to determine the content ratio of the unit according to formula (1). Furthermore, the dielectric loss tangent (Df) and glass transition temperature (Tg) were measured using the method described above.

[0234]

[0235] (Comparative Example 7) EPICLON 850-S (manufactured by DIC Corporation) (2.2 g) was used as the epoxy resin, EPICLON HPC-8000-65T (manufactured by DIC Corporation) (7.8 g) was used as the curing agent, and 4-dimethylaminopyridine (0.05 g) was used as the curing catalyst. The solvent was then removed by vacuum distillation to obtain a resin composition. The dielectric loss tangent (Df) and glass transition temperature (Tg) of the obtained resin composition were measured using the method described above.

[0236] Table 4 shows the modification rate, type of amine raw material, dielectric loss tangent (Df), and glass transition temperature (Tg) of the thermosetting polyphenylene ethers obtained in each example and comparative example.

[0237]

[0238] As shown in Table 4, the thermosetting polyphenylene ethers of the examples exhibited lower dielectric loss tangents and higher glass transition temperatures compared to the comparative examples.

[0239] (Example 37) To 100 parts by weight of the thermosetting polyphenylene ether obtained in Example 29, 1 part by mass of organic peroxide (perbutyl P, manufactured by NOF Corporation) was added to toluene, stirred, and dissolved. The toluene was degassed by vacuum drying at 110°C to obtain a mixture of thermosetting polyphenylene ether and organic peroxide, and the dielectric loss tangent (Df) and glass transition temperature (Tg) were measured using the method described above.

[0240] (Example 38) In a 300 mL round-bottom flask, 20 g of the amino group-containing polyphenylene ether obtained in Example 29 and 80 g of toluene were added and stirred. 0.55 g of dimethylaminopyridine was added. When it appeared that all the solids had dissolved, 4.9 g of methacrylic anhydride was gradually added. The resulting solution was maintained at 85°C for 3 hours with continuous stirring. The solution was then cooled to room temperature and added dropwise over 30 minutes to 360 g of methanol in a 1 L beaker, which had been vigorously stirred with a magnetic stirrer. The resulting precipitate was filtered under reduced pressure through a membrane filter and then dried. The obtained thermosetting polyphenylene ether was dissolved in deuterated chloroform, and tetramethylsilane was used as an internal standard. １ ¹H-NMR measurements were performed (Brker Biospin AvanceNEO600, frequency: 600 MHz, number of integrations: 16, temperature: 25°C). From the integral value of the peak (5.8 ppm) derived from the introduced vinyl group, it was found that the content of formula (1) units in the repeating units of the polymer was 5%. To 100 parts by weight of the obtained thermosetting polyphenylene ether, 1 part by mass of organic peroxide (perbutyl P, NOF Corporation) was added to toluene, stirred, and dissolved. Toluene was degassed by vacuum drying at 110°C to obtain a mixture of thermosetting polyphenylene ether and organic peroxide, and the dielectric loss tangent (Df) and glass transition temperature (Tg) were measured by the method described above.

[0241] (Example 39) In a 500 mL round-bottom flask, 50 g of the amino group-containing polyphenylene ether obtained in Example 29 and toluene (100 mL) were added and stirred. Further, tetrabutylammonium bromide (0.1 g), 3-chloro-1-propene (1.5 g), and 48% sodium hydroxide solution (4 g) were added and the mixture was heated and stirred at 80°C for 4 hours. The organic layer was then extracted from the reaction solution using toluene. The extracted organic layer was washed with deionized water and then added dropwise to methanol (2 L) to precipitate the polymer. The precipitated polymer was filtered, washed with methanol, and then dried under reduced pressure at 50°C for 24 hours to obtain thermosetting polyphenylene ether. The obtained thermosetting polyphenylene ether was dissolved in deuterated chloroform, and tetramethylsilane was used as an internal standard.１ ¹H-NMR measurements were performed (AvanceNEO600, Bruker Biospin; frequency: 600 MHz; number of integrations: 16; temperature: 25°C). From the integral value of the peak (5.7 ppm) derived from the introduced vinyl group, it was found that the content of formula (1) units in the repeating units of the polymer was 5%. To 100 parts by weight of the obtained thermosetting polyphenylene ether, 1 part by mass of organic peroxide (perbutyl P, NOF Corporation) was added to toluene, stirred, and dissolved. Toluene was degassed by vacuum drying at 110°C to obtain a mixture of thermosetting polyphenylene ether and organic peroxide, and the dielectric loss tangent (Df) and glass transition temperature (Tg) were measured by the method described above.

[0242] (Example 40) Xylene (39.0 mL) and concentrated sulfuric acid (0.179 g) were added to a 1 L four-necked flask and stirred with a mechanical stirrer using a stirring blade. Dehydration was performed by heating and stirring under reflux at 140°C for 2 hours using an oil bath. 1.51 g of water was collected in a Dean Stark. The mixture was allowed to cool to an internal temperature of 60°C. Tributylamine (0.167 g) / xylene (39.0 mL) was added dropwise using a dropping funnel. Maleic anhydride (0.444 g) and 4-methoxyphenol (1.90 mg) were added and heated under reflux at 140°C using an oil bath. The amino group-containing polyphenylene ether (26.8 g) obtained in Example 29 was dissolved in xylene (268 mL) and added dropwise using a dropping funnel, and the mixture was heated and stirred at 140°C for 24 hours. After adding deionized water (54.0 mL) to the reaction mixture and stirring, the organic layer was recovered. This procedure was performed a total of four times. The organic layer was concentrated under reduced pressure and added dropwise to methanol (135 mL), and the precipitation of a pale yellow solid was observed. The precipitated solid was recovered by vacuum filtration. The solid was rinsed and washed with methanol (30 mL x 3). The obtained thermosetting polyphenylene ether was dissolved in deuterated chloroform, and tetramethylsilane was used as an internal standard. １¹H-NMR measurements were performed (Brker Biospin AvanceNEO600, frequency: 600 MHz, number of integrations: 16, temperature: 25°C). From the integral value of the peaks (7.0 to 7.1 ppm) derived from the introduced vinyl groups, it was found that the content of formula (1) units in the repeating units of the polymer was 5%. To 100 parts by weight of the obtained thermosetting polyphenylene ether, 1 part by mass of organic peroxide (perbutyl P, NOF Corporation) was added to toluene, stirred, and dissolved. Toluene was degassed by vacuum drying at 110°C to obtain a mixture of thermosetting polyphenylene ether and organic peroxide, and the dielectric loss tangent (Df) and glass transition temperature (Tg) were measured by the method described above.

[0243] (Comparative Example 8) A 1.5-liter jacketed reactor equipped with a sparger, stirring turbine blades and baffles at the bottom for introducing oxygen-containing gas, and a reflux condenser in the vent gas line at the top of the reactor was filled with a pre-prepared mixture of 0.10 g of cuprous oxide and 0.77 g of 47% hydrogen bromide, along with 0.25 g of N,N'-di-t-butylethylenediamine, 3.62 g of dimethyl-n-butylamine, 1.19 g of di-n-butylamine, 894 g of toluene, 79.45 g of 2,6-dimethylphenol, and 20.55 g of 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane. Then, while vigorously stirring, air was introduced into the reactor from the sparger at a rate of 1.05 L / min, and at the same time, the polymerization temperature was adjusted by passing a heat transfer medium through the jacket to maintain it at 40°C. 120 minutes after the introduction of air, the air supply was stopped, and the reactor was purged with nitrogen gas. Then, 1.10 g of ethylenediaminetetraacetate tetrahydrate (reagent manufactured by Dojin Chemical Laboratories) was added to the polymerization mixture as an aqueous solution in 100 g of water. Next, the mixture was heated to 70°C, and copper extraction was carried out at 70°C for 2 hours. After that, the mixture was separated into an unmodified polyphenylene ether solution (organic phase) and an aqueous phase to which the catalyst metal had been transferred by static separation. The organic phase was concentrated using a rotary evaporator until the polymer concentration reached 25% by mass. In a 500 ml tri-flask equipped with a line for introducing nitrogen gas at the top of the reactor and a reflux condenser in the vent gas line at the top of the reactor, the inside of the reactor was purged with nitrogen, and then 200 g of the above polyphenylene ether solution and 0.64 g of 4-dimethylaminopyridine were added. 21 mL of triethylamine was added using a syringe while stirring. Subsequently, 10.9 ml of methacryloyl chloride was taken into a syringe and added dropwise to the system at room temperature. After the addition was complete, the flask was heated in an oil bath for 1 hour and stirred at 90°C. Then, it was heated further in the oil bath and the reaction was continued under reflux. After 4 hours from the start of reflux, heating was stopped, and after returning to room temperature, 8 g of methanol was added to stop the reaction. Next, the reaction solution was filtered using a glass filter to obtain a solution from which the by-product triethylammonium salt had been removed. The above solution was mixed with methanol in a ratio of 10 to the polymer solution, and the polymer was precipitated.Wet polyphenylene ether was obtained by vacuum filtration using a glass filter. The wet polyphenylene ether was then washed with methanol in an amount such that the ratio of methanol to wet polyphenylene ether was 2.5. This washing procedure was repeated three times. Next, the wet polyphenylene ether was maintained at 100°C and 1 mmHg for 8 hours to obtain dry polyphenylene ether. １ ¹H NMR measurements were performed, and proton peaks originating from the olefin of the methacrylic group were confirmed at 4.4–5.8 ppm, leading to the conclusion that the hydroxyl groups had been modified into methacrylic groups. As described above, polyphenylene ether in which the hydroxyl group ends of the polymer main chain were modified into methacrylic was synthesized. To 100 parts by weight of the obtained polyphenylene ether, 1 part by weight of organic peroxide (perbutyl P, manufactured by NOF Corporation) was added to toluene, stirred, and dissolved. Toluene was degassed by vacuum drying at 110°C to obtain a mixture of thermosetting polyphenylene ether and organic peroxide, and the dielectric loss tangent (Df) and glass transition temperature (Tg) were measured using the method described above.

[0244] (Comparative Example 9) A 1.5-liter jacketed reactor equipped with a sparger for introducing oxygen-containing gas at the bottom of the reactor, stirring turbine blades and baffles, and a reflux condenser in the vent gas line at the top of the reactor, was filled with a pre-prepared mixture of 0.10 g of cuprous oxide and 0.77 g of 47% hydrogen bromide, along with 0.25 g of N,N'-di-t-butylethylenediamine, 3.62 g of dimethyl-n-butylamine, 1.19 g of di-n-butylamine, 894 g of toluene, 80.29 g of 2,6-dimethylphenol, and 19.71 g of 4,4'-dihydroxy-2,2',3,3',5,5'-hexamethylbiphenyl. Then, while vigorously stirring, air was introduced into the reactor from the sparger at a rate of 1.05 L / min, and at the same time, the polymerization temperature was adjusted by passing a heat transfer medium through the jacket to maintain a temperature of 40°C. 120 minutes after the introduction of air, the air supply was stopped, and the reactor was replaced with nitrogen gas. Then, 1.10 g of tetrasodium ethylenediaminetetraacetate tetrahydrate (reagent manufactured by Dojin Chemical Laboratories) was added to the polymerization mixture as an aqueous solution in 100 g of water. Next, the mixture was heated to 70°C, and copper extraction was carried out at 70°C for 2 hours. After that, the mixture was separated into an unmodified polyphenylene ether solution (organic phase) and an aqueous phase to which the catalyst metal had been transferred by static separation. The organic phase was concentrated using a rotary evaporator until the polymer concentration reached 25% by mass. In a 500 mL three-necked flask equipped with a temperature controller, stirrer, cooling equipment, and dropping funnel, 200 g of the above polyphenylene ether solution, 24 g of chloromethylstyrene (ratio of p-chloromethylstyrene to m-chloromethylstyrene 50 / 50, manufactured by Tokyo Chemical Industry Co., Ltd.), and 1.0 g of tetra-n-butylammonium bromide were added. The mixture was then stirred and dissolved, and the liquid temperature was raised to 85°C. A sodium hydroxide aqueous solution (4.2 g sodium hydroxide / 104 g water) was added dropwise to the mixture over 1 hour, and stirring was continued at 85°C for 5 hours. Next, the aqueous layer was removed using a separatory funnel to obtain a toluene layer (polymer solution) containing the polymer. The polymer solution was mixed with methanol in a ratio of 10 to the polymer solution, and the polymer was precipitated. Wet polyphenylene ether was obtained by vacuum filtration using a glass filter.Furthermore, the wet polyphenylene ether was washed with a washing solvent (methanol:water = 80:20) in an amount such that the ratio of the washing solvent to the wet polyphenylene ether was 2.5. After performing the above washing operation with the methanol-water mixed solvent three times, the wet polyphenylene ether was washed with methanol in an amount such that the ratio of methanol to the wet polyphenylene ether was 2.5. After performing the above washing operation with methanol twice, the wet polyphenylene ether was maintained at 100°C and 1 mmHg for 8 hours to obtain dry polyphenylene ether. １ ¹H NMR measurements were performed, and proton peaks originating from styryl groups were confirmed at 5–7 ppm, leading to the conclusion that the hydroxyl groups were modified to styryl groups (i.e., the substructure represented by formula (8)). As described above, polyphenylene ether was synthesized in which the hydroxyl group termini of the polymer main chain were modified to styryl groups (vinyl benzyl groups). To 100 parts by weight of the obtained polyphenylene ether, 1 part by mass of organic peroxide (perbutyl P, manufactured by NOF Corporation) was added to toluene, stirred, and dissolved. Toluene was degassed by vacuum drying at 110°C to obtain a mixture of thermosetting polyphenylene ether and organic peroxide, and the dielectric loss tangent (Df) and glass transition temperature (Tg) were measured using the method described above.

[0245]

[0246] As shown in Table 5, the thermosetting polyphenylene ethers in which unsaturated intercarbon bond-containing groups were introduced into the polymer main chain structure in the examples showed a lower dielectric loss tangent and a higher glass transition temperature compared to the polyphenylene ethers in which unsaturated intercarbon bond-containing groups were introduced at the polymer terminals in the comparative examples.

[0247] The present invention provides a substituted polyphenylene ether with improved intermolecular or intramolecular network-forming ability. Furthermore, the present invention provides a heteroatom group-containing polyphenylene ether and its gas barrier film that can improve gas barrier properties in gas permeation and have excellent thermal decomposition resistance. Furthermore, the present invention provides an amino group-containing polyphenylene ether and its separation film that can improve gas selective permeability in gas permeation and have excellent thermal decomposition resistance. Moreover, the present invention has been made in view of the above problems and aims to provide a thermosetting polyphenylene ether with excellent transmission loss and heat resistance. Furthermore, the present invention can provide a prepreg formed using the thermosetting polyphenylene ether. Thus, the present invention has industrial applicability.

Claims

A polyphenylene ether characterized by containing at least one component represented by formula (3) or formula (4). (In equations (3) and (4), R ７ ~R ９ , R １０ and R １１ Each of these is independently at least one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, and a cyano group. R ７ and R ８ At least one of them is an alkyl group, R １０ and R １１ At least one of them is an alkyl group, X is, A divalent group containing an alkylene group and which may contain a divalent group having a heteroatom, A divalent group containing a divalent electron-withdrawing group and an arylene group, or Divalent groups containing divalent electron-withdrawing groups and alkylene groups And, Z is a nonionic substituent having a heteroatom, The nonionic substituent has an active hydrogen atom, a double bond, or an epoxy ring. The aforementioned double bond is either a carbon-carbon bond, a heteroatom heteroatom bond, or a carbon-carbon heteroatom bond. 　 A polyphenylene ether characterized by containing at least one component represented by formula (5) or formula (6). (In equations (5) and (6), R １２ to R １４ , R １５ and R １６ each independently is at least one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, and a cyano group, R １２ and R １３ At least one of them is an alkyl group, R １５ and R １６ At least one of them is an alkyl group, X is, A divalent group containing an alkylene group and which may contain a divalent group having a heteroatom, A divalent group containing a divalent electron-withdrawing group and an arylene group, or Divalent groups containing divalent electron-withdrawing groups and alkylene groups And, T is, amino group, ether group, or thioether group And, Z' is a nonionic or ionic substituent, At least one of the Z' substituents is a nonionic substituent. The nonionic substituent has an active hydrogen atom, a double bond, or an epoxy ring. The aforementioned double bond is one of a carbon-carbon bond, a heteroatom heteroatom bond, or a carbon-carbon heteroatom bond. n is either 1 or 2. 　 The polyphenylene ether according to claim 2, characterized in that the nonionic substituent includes a group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, a hydroxyl group, a thiol group, a carboxyl group, a vinylbenzyl group, a vinyl group, an allyl group, a norbornene group, a methacrylic group, a maleimide group, a cinnamoyl group or a glycidyl group, an azo group, and an azide group. 　 A polyphenylene ether characterized by containing at least one component represented by formula (7) or formula (8). (In equations (7) and (8), R １７ ~R １９ , R ２０ and R ２１ Each of these is independently at least one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, and a cyano group. R １７ and R １８ At least one of them is an alkyl group, R ２０ and R ２１ At least one of them is an alkyl group, X is, A divalent group containing an alkylene group and which may contain a divalent group having a heteroatom, A divalent group containing a divalent electron-withdrawing group and an arylene group, or Divalent groups containing divalent electron-withdrawing groups and alkylene groups And, Y' is an amino group, Structure A contains unsaturated or saturated carbon-carbon bonds. At least one of A is a group containing an unsaturated carbon-carbon bond, n is either 1 or 2. 　 The polyphenylene ether according to claim 4, wherein the group containing the unsaturated carbon-carbon bond is any of the following groups: vinylbenzyl group, allyl group, vinyl group, norbornene group, methacrylic group, or maleimide group. 　 A polyphenylene ether characterized by containing at least one component represented by formula (9) or formula (10). (In equations (9) and (10), R ２２ ~R ２４ , R ２５ and R ２６ Each of these is independently at least one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, and a cyano group. R ２２ and R ２３ At least one of them is an alkyl group, R ２５ and R ２６ At least one of them is an alkyl group, X is, A divalent group containing an alkylene group and which may contain a divalent group having a heteroatom, A divalent group containing a divalent electron-withdrawing group and an arylene group, or Divalent groups containing divalent electron-withdrawing groups and alkylene groups And, Y is a structure that contains an amino group. 　 A step of obtaining polyphenylene ether by oxidative polymerization of phenol of formula (11), The R of the aforementioned polyphenylene ether ２８ A modification step to obtain a polyphenylene ether containing the components of formula (3) and / or formula (4) by introducing the nonionic substituent to at least one of the following: A method for producing polyphenylene ether according to claim 1, characterized by containing the following: (In formula (11), R ２７ Each of these is independently a C1-C6 alkyl group which may be substituted, a C6-C12 aryl group which may be substituted, or a halogen atom. R ２８ Each of these is independently a hydrogen atom, an optionally substituted C1-C6 alkyl group, an optionally substituted C6-C12 aryl group, or a halogen atom. 　 A step of polymerizing unmodified polyphenylene ether by oxidative polymerization of phenol of formula (11), To the aforementioned unmodified polyphenylene ether, Alkyl alkyl groups which may contain bonding groups A monovalent group comprising a divalent electron-withdrawing group and an arylene group, and which may also contain a bonding group, or A monovalent group comprising a divalent electron-withdrawing group and an alkyl or alkylene group, and which may also contain a bonding group. The process involves introducing a modified polyphenylene ether and A step of introducing heteroatomic groups into the modified polyphenylene ether to synthesize a heteroatomic group-containing polyphenylene ether, A step of introducing a nonionic substituent into the heteroatom group-containing polyphenylene ether, A method for producing polyphenylene ether according to claim 2, characterized by containing the following: 　 A step of polymerizing unmodified polyphenylene ether by oxidative polymerization of phenol of formula (11), To the aforementioned unmodified polyphenylene ether, Alkyl alkyl groups which may contain bonding groups A monovalent group comprising a divalent electron-withdrawing group and an arylene group, and which may also contain a bonding group, or A monovalent group comprising a divalent electron-withdrawing group and an alkyl or alkylene group, and which may also contain a bonding group. The process involves introducing a modified polyphenylene ether and A step of introducing an amino group into the modified polyphenylene ether to synthesize an amino group-containing polyphenylene ether, A step of introducing a group containing an unsaturated carbon-carbon bond into the aforementioned amino group-containing polyphenylene ether, A method for producing polyphenylene ether according to claim 4, characterized by containing the following: 　 The process involves oxidative polymerization of the phenol of formula (11) to polymerize the unmodified polyphenylene ether, To the aforementioned unmodified polyphenylene ether, Alkyl alkyl groups which may contain bonding groups A monovalent group comprising a divalent electron-withdrawing group and an arylene group, and which may also contain a bonding group, or A monovalent group comprising a divalent electron-withdrawing group and an alkyl or alkylene group, and which may also contain a bonding group. The process involves introducing a modified polyphenylene ether and The process involves introducing an amino group into the modified polyphenylene ether, A method for producing polyphenylene ether according to claim 6, characterized by containing the following: 　 A polymer network comprising the polyphenylene ether described in any one of claims 1, 4, and 6. 　 A polyphenylene ether solution comprising the polyphenylene ether described in any one of claims 1, 4, and 6. 　 A thermosetting composition comprising the polyphenylene ether described in claim 4 or 5. 　 A cured product comprising the thermosetting composition described in claim 13. 　 A method for producing a cured product, comprising the step of heating and molding the thermosetting composition described in claim 13. 　 A prepreg comprising a substrate and the thermosetting composition described in claim 13. 　 A printed circuit board or package substrate comprising the thermosetting composition described in claim 13. 　 A hydrogen-bonding polymer network comprising the polyphenylene ether described in claim 6. 　 A gas barrier film or gas barrier material comprising the polyphenylene ether described in claim 6.

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