Halomethylated polyphenylene ether and method for producing the same

Abstract

This is a halomethylated polyphenylene ether containing a specific amount of repeating units represented by structural formulas (I), (II), and (III) (wherein X is chlorine or bromine). This halomethylated polyphenylene ether is considered particularly suitable for subsequent quaternization. The use of the described material in applications such as ion exchange membranes is also discussed. JPEG2026520833000067.jpg27170(I) JPEG2026520833000068.jpg34170(II) JPEG2026520833000069.jpg26170(III)

Description

[Technical Field]

[0001] This application relates to halomethylated polyphenylene ether and a method for producing the same. [Background technology]

[0002] (Cross-reference of related applications) This application claims priority and benefits of European Patent Application Publication No. 23169594.1, filed on 24 April 2023, which is incorporated herein by reference in its entirety.

[0003] Halomethylated polyphenylene ethers (e.g., chloromethylated and bromomethylated polyphenylene ethers) are considered useful for a variety of applications, including electrochemical applications (e.g., battery components). More specifically, halomethylated polyphenylene ethers can serve as precursors to quaternized polyphenylene ethers, which are particularly well-suited for use in ion separation membranes of electrochemical devices or fuel cells. Conventional methods for preparing halomethylated polyphenylene ethers often yield halomethylated polyphenylene ethers with a relatively low degree of substitution (i.e., less than 30%). Furthermore, controlling the uniformity of the halomethylation product (e.g., the ratio of monosubstituted to disubstituted products, and the distribution of functional groups along the polymer backbone) is considered difficult. [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] In this technology, improvements to halomethylated polyphenylene ethers, particularly chloromethylated and bromomethylated polyphenylene ethers, are needed. The presentation of chloromethylated or bromomethylated polyphenylene ethers with a predetermined degree of chloromethylation or bromomethylation, respectively, is considered particularly beneficial. Furthermore, the presentation of chloromethylated or bromomethylated polyphenylene ethers in which halomethyl groups are more uniformly substituted on the polymer backbone would also be beneficial. [Means for solving the problem]

[0005] A halomethylated polyphenylene ether, wherein the halomethylated polyphenylene ether is 35 to 89 mole percent (mol%) of the first repeating unit represented by structural formula (I), [ka] (I) 10 to 65 mol% of the second repeating unit represented by structural formula (II), [ka] (II) Less than 1 mol% of the third repeating unit represented by structural formula (III) and [ka] (III) The ether contains (wherein X in structural formula (II) is bromine (Br) or chlorine (Cl)), and, as measured by nuclear magnetic resonance spectroscopy, at least 90% of the halomethylation repeating units are monohalomethylation repeating units represented by structural formula (II), and the halomethylated polyphenylene ether has a residual zinc content of less than 1000 ppm relative to the total mass of the halomethylated polyphenylene ether.

[0006] A method for producing a halomethylated polyphenylene ether, the method comprising the steps of contacting a polyphenylene ether with chloromethyl ethyl ether or bromomethyl methyl ether to produce a mixture containing a halomethylated polyphenylene ether, and isolating the halomethylated polyphenylene ether from the mixture.

[0007] A quaternary amine-containing polyphenylene ether derived from the aforementioned halomethylated polyphenylene ether is another embodiment disclosed herein.

[0008] An article containing the aforementioned halomethylated polyphenylene ether is another embodiment disclosed herein.

[0009] An anion exchange membrane containing a quaternary amine-containing polyphenylene ether is another aspect disclosed in the present application.

[0010] The above and other features will be described by way of example in the following detailed description.

Mode for Carrying Out the Invention

[0011] The inventor of the present invention has discovered that it is possible to produce a halomethylated polyphenylene ether having characteristics of a favorable combination, such as a high degree of monohalomethylation (i.e., one halomethyl group per repeating unit). For the sake of simplicity in indicating chloromethylated polyphenylene ether and bromomethylated polyphenylene ether, in the text, the term "halomethylated polyphenylene ether" will be used. The halomethylated polyphenylene ethers presented in the text (e.g., chloromethylated polyphenylene ether and bromomethylated polyphenylene ether) can be used as precursors to their quaternized products and are thus considered to be particularly well-suited for use in ion separation membranes for electrochemical applications.

[0012] Therefore, one of the aspects disclosed in the present application is a halomethylated polyphenylene ether. This halomethylated polyphenylene ether contains a specific amount of repeating units represented by structural formulas (I), (II), and (III).

Chemical formula

Chemical formula

Chemical formula

[0013] In one embodiment, the halomethylated polyphenylene ether may further contain one or more repeating units represented by structural formulas (IV) to (IX). [ka] (IV) [ka] (V) [ka] (VI) [ka] (VII) [ka] (VIII) [ka] (IX) In the formulas, X is either Cl or Br in each of structural formulas (IV) to (IX). Each repeating unit shown in structural formulas (IV) to (IX) can independently be present in the halomethylated polyphenylene ether in an amount of 1 mol% or less.

[0014] In one embodiment, the halomethylated polyphenylene ether contains a specific amount of repeating units represented by structural formulas (I) to (IX). For example, the halomethylated polyphenylene ether contains 35 to 89 mol%, 55 to 85 mol%, or 60 to 80 mol% of the units represented by structural formula (I), 10 to 65 mol%, 15 to 45 mol%, or 30 to 40 mol% of the units represented by structural formula (II), and 1 mol% or less of the units represented by structural formulas (III) to (IX).

[0015] In one particular embodiment, the halomethylated polyphenylene ether may be a chloromethylated polyphenylene ether and may contain certain amounts of repeating units represented by structural formulas (IA), (IIA), and (IIIA). [ka] (IA) [ka] (IIA) [ka] (IIIA) In one embodiment, the chloromethylated polyphenylene ether comprises 35 to 89 mol%, 55 to 85 mol%, or 60 to 80 mol% of units represented by structural formula (I), 10 to 65 mol%, 15 to 45 mol%, or 30 to 40 mol% of units represented by structural formula (II), and 1 mol% or less of units represented by structural formula (III).

[0016] In one embodiment, the chloromethylated polyphenylene ether may further contain one or more repeating units represented by structural formulas (IVA) to (IXA). [ka] (IVA) [ka] (VA) [ka] (VIA) [ka] (VIIA) [ka] (VIIIA) [ka] (IXA) Each repeating unit represented by structural formulas (IVA) to (IXA) can independently be present in the chloromethylated polyphenylene ether in an amount of 1 mol% or less.

[0017] In another detailed embodiment, the halomethylated polyphenylene ether may be a bromomethylated polyphenylene ether and may contain certain amounts of repeating units represented by structural formulas (IB), (IIB), and (IIIB). [ka] (IB) [ka] (IIB) [ka] (IIIB) In one embodiment, the bromomethylated polyphenylene ether comprises 35 to 89 mol%, 55 to 85 mol%, or 60 to 80 mol% of the units represented by structural formula (I), 10 to 65 mol%, 15 to 45 mol%, or 30 to 40 mol% of the units represented by structural formula (II), and 1 mol% or less of the units represented by structural formula (III).

[0018] In one embodiment, the bromomethylated polyphenylene ether may further contain one or more repeating units represented by structural formulas (IVB) to (IXB). [ka] (IVB) [ka] (VB) [ka] (VIB) [ka] (VIIB) [ka] (VIIIB) [ka] (IXB) The repeating units represented by structural formulas (IVB) to (IXB) can each be independently present in the bromomethylated polyphenylene ether in an amount of 1 mol% or less.

[0019] The halomethylated polyphenylene ethers disclosed herein have an overall degree of halomethylation (also referred to as the degree of substitution) of 10 to 70%. In other words, 10 to 70% of the repeating units of the halomethylated polyphenylene ether contain at least one halomethyl group. The overall degree of substitution can be determined using nuclear magnetic resonance (NMR) spectroscopy. The method for determining the degree of substitution will be further described in later examples. Within the range of 10 to 70%, the halomethylated polyphenylene ethers disclosed herein may have an overall degree of halomethylation of 20 to 80%, 30 to 70%, or 20 to 70%.

[0020] At least 90% of the substituted repeating units are monosubstituted or monohalomethylated. In other words, at least 90% of the halomethylated repeating units have only one halomethyl group per repeating unit (i.e., as shown in structural formula (II)). In some embodiments, at least 92%, at least 93%, at least 94%, 90 to 100%, 90 to 99%, 90 to 98%, 92 to 99%, or 92 to 98% of the halomethylated repeating units are monohalomethylated. Note that the term “monosubstituted” as used in this text is not the same as “uniformly substituted.” The term “uniform substitution” refers to a substituted poly(phenylene ether) product in which the entire product has a uniform degree of substitution (e.g., halomethylation). In contrast, the term "mono-substituted" as used in this text means that the halomethylated poly(phenylene ether) product has a certain (uniform) degree of halomethylation throughout the entire product, and furthermore, at least 90% of the repeating units with halomethyl groups have only one halomethyl group. For example, a halomethylated poly(phenylene ether) product with a uniform degree of substitution of 20% means that the degree of substitution is 20% throughout the entire product. In this application, a monohalomethylated poly(phenylene ether) product with a degree of substitution of 20% means, for example, that of 20 halomethylated repeating units (for simplicity of calculation, let's assume there are a total of 100 repeating units in the polymer), at least 90% of these 20 repeating units have only one halomethyl group (i.e., at least 18 of the 20 repeating units have one halomethyl group). In one embodiment, the ratio of monochloromethylated to dichloromethylated polyphenylene ether repeating units is greater than 0.94.

[0021] The distribution of halomethylated repeating units (i.e., structural formulas (II) and (IV)-(IX)) and non-halomethylated repeating units (i.e., structural formula (I)) can be random or blocky, where blocky refers to "clusters" of adjacent or very close-proximity halomethylated repeating units. In some embodiments, adjacent or close-proximity halomethylated repeating units can constitute the majority of the halomethylated repeating units. For example, adjacent or close-proximity halomethylated repeating units can constitute at least 80%, at least 85%, or at least 90% of the total amount of halomethylated repeating units. The halomethylated polyphenylene ether can also include randomly arranged repeating units in which the halomethylated repeating units are not adjacent to or close to other halomethylated repeating units. In one embodiment, isolated halomethylated repeat units may constitute less than 20%, less than 15%, less than 10%, less than 5%, less than 1%, less than 0.5%, or less than 0.1% of the total amount of halomethylated repeat units.

[0022] This halomethylated polyphenylene ether can have a minimum mass-average molecular weight of 40,000 g / mol. The molecular weight can be determined by gel permeation chromatography, eluting with chloroform and comparing with a polystyrene standard. Within this range, this halomethylated polyphenylene ether can have a mass-average molecular weight of 40,000 to 150,000 g / mol.

[0023] This halomethylated polyphenylene ether can have a low oligomer content. For example, the phenylene ether oligomer with a mass-average molecular weight of less than 1,000 g / mol contained in this halomethylated polyphenylene ether can be less than 2% by mass, less than 1.5% by mass, or less than 1.3% by mass, where the mass percentage is relative to the total mass of the halomethylated polyphenylene ether. The phenylene ether oligomer with a mass-average molecular weight of less than 500 g / mol contained in this halomethylated polyphenylene ether can be less than 1% by mass, less than 0.95% by mass, less than 0.92% by mass, or less than 0.90% by mass, where the mass percentage is relative to the total mass of the halomethylated polyphenylene ether.

[0024] A method for producing the halomethylated polyphenylene ether is another embodiment disclosed herein. In one embodiment, the method includes the step of contacting a polyphenylene ether with chloromethyl ethyl ether to produce a chloromethylated polyphenylene ether. In another embodiment, the method includes the step of contacting a polyphenylene ether with bromomethyl methyl ether to produce a bromomethylated polyphenylene ether.

[0025] The polyphenylene ether starting material can be a polyphenylene ether represented by the following structural formula. [ka]

[0026] The step of producing the halomethylated polyphenylene ether can be carried out at a temperature of 25 to 75°C, 30 to 70°C, greater than 30 to less than 70°C, greater than 30 to 65°C, 40 to 60°C, or 45 to 55°C for 1 to 10 hours or 2 to 6 hours. In some embodiments, the reaction time can be less than 5 hours, for example, 1 to less than 5 hours. The step of contacting the polyphenylene ether with chloromethyl ethyl ether or bromomethyl methyl ether can be carried out in the presence of a solvent, preferably an organic solvent selected to dissolve the polyphenylene ether. Examples of solvents include halogenated aromatic solvents such as chlorobenzene and o-dichlorobenzene. The polyphenylene ether starting material and solvent can be present in amounts such that the polyphenylene ether is present in a solution of 5 to 25% by mass, 10 to 25% by mass, 12 to 25% by mass, 10 to 20% by mass, 12 to 20% by mass, or 12 to 18% by mass, relative to the total mass of the polyphenylene ether and the solvent. In the contact step, a polyphenylene ether:chloromethyl ethyl ether molar ratio or polyphenylene ether:bromomethyl methyl ether molar ratio of 1.9:1 to 2.1:1, preferably 1.95:1 to 2.05:1 or 1.99:1 to 2.01:1, most preferably 2:1 can be used.

[0027] The process of contacting polyphenylene ether with chloromethyl ethyl ether or bromomethyl methyl ether in the presence of a catalyst can be carried out to produce chloromethylated polyphenylene ether or bromomethylated polyphenylene ether, respectively. In one embodiment, the catalyst can be a Lewis acid catalyst, for example, a zinc-containing catalyst. In one specific embodiment, the catalyst can be zinc chloride (ZnCl2). The amount of catalyst can be 1 to 10% by mass, 2 to 7% by mass, 3 to 7% by mass, or 4 to 6% by mass, relative to the mass of the polyphenylene ether starting material. In one embodiment, the reaction mixture containing the catalyst is homogeneous. For example, a homogeneous reaction mixture can be obtained by pre-dissolving the catalyst in a suitable solvent and then adding it to the reaction mixture. For example, the catalyst can be pre-dissolved in a solvent such as a dialkoxymethane (e.g., diethoxymethane), as will be further described in later examples. Although not intended to be theoretically restrictive, heterogeneous reaction mixtures (e.g., including insoluble catalysts) are thought to lead to problems with reproducibility and an increase in the amount of catalyst remaining in the product. In one embodiment, the catalyst can be added to the reaction mixture as a powder.

[0028] In some embodiments, chloromethyl ethyl ether or bromomethyl methyl ether can be added using a pump to ensure a constant rate. In some embodiments, chloromethyl ethyl ether or bromomethyl methyl ether can be added for 45 minutes or less, preferably 30 minutes or less, preferably 25 minutes or less, 20 minutes or less, or 15 minutes or less. Adding chloromethyl ethyl ether or bromomethyl methyl ether for a long period of time (e.g., 30 minutes or more or 45 minutes or more) or by manual addition may result in loss of control over molecular weight and degree of substitution.

[0029] The present manufacturing method may further include a step of isolating the halomethylated polyphenylene ether from a reaction mixture containing the halomethylated polyphenylene ether. The isolation step may include one or more of the following steps: precipitating the halomethylated polyphenylene ether from the mixture in a poor solvent, preferably methanol or methanolic hydrochloric acid; washing the halomethylated polyphenylene ether, preferably with water, hydrochloric acid, or a combination thereof; or adding a chelating agent, an ion exchange resin, carbon, or a combination thereof to the mixture. In one embodiment, the isolation step of the halomethylated polyphenylene ether may include precipitating the halomethylated polyphenylene ether from the mixture in a poor solvent and washing the halomethylated polyphenylene ether. The poor solvent may include methanol or methanolic hydrochloric acid, and the washing step may be carried out with water, hydrochloric acid, or a combination thereof. In one embodiment, the poor solvent may not include water. In one embodiment, the washing step of the halomethylated polyphenylene ether may not include washing with water. In one embodiment, the isolation step of halomethylated polyphenylene ether may include the steps of precipitating the halomethylated polyphenylene ether from the mixture in a poor solvent, isolating the precipitate by some solid-liquid separation technique (e.g., filtration), and redissolving the filtered halomethylated polyphenylene ether in, for example, chlorobenzene or o-dichlorobenzene (which may optionally further contain a dialkoxymethane; for example, chlorobenzene containing a dialkoxymethane such as dimethoxymethane or diethoxymethane, or o-dichlorobenzene containing a dialkoxymethane such as dimethoxymethane or diethoxymethane). A chelating agent may be added to the halomethylated polyphenylene ether solution. The halomethylated polyphenylene ether can be reprecipitated, isolated, and washed as necessary.

[0030] Methods for producing and isolating halomethylated polyphenylene ethers will be further illustrated with examples in later examples.

[0031] Advantageously, the halomethylated polyphenylene ether can have a low concentration of residual catalyst. For example, the residual catalyst content of the halomethylated polyphenylene ether can be less than 1000 ppm, less than 500 ppm, less than 100 ppm, less than 50 ppm, or less than 20 ppm relative to the total mass of the halomethylated polyphenylene ether. In one embodiment, the halomethylated polyphenylene ether can be prepared using a zinc-containing catalyst, and the residual zinc content of the resulting halomethylated polyphenylene ether can be less than 1000 ppm, less than 500 ppm, less than 100 ppm, less than 50 ppm, or less than 20 ppm relative to the total mass of the halomethylated polyphenylene ether. The residual catalyst content can be determined, for example, by inductively coupled plasma emission spectroscopy or inductively coupled plasma mass spectrometry.

[0032] The inventors of the present invention have also noticed that various dialkoxyalkanes (e.g., dialkoxymethanes such as diethoxymethane and dimethoxymethane) may be formed as byproducts during the reaction and / or precipitation steps of a method for producing halomethylated polyphenylene ethers. The halomethylated polyphenylene ethers disclosed herein may have a dialkoxyalkane content of less than 20 ppm or less than 10 ppm relative to the total mass of the halomethylated polyphenylene ether. In one embodiment, the halomethylated polyphenylene ether may have a combined content of less than 20 ppm or less than 10 ppm of diethoxymethane and dimethoxymethane relative to the total mass of the halomethylated polyphenylene ether. The residual dialkoxyalkane content can be determined, for example, by nuclear magnetic resonance (NMR) spectroscopy or head space gas chromatography (GC-HS).

[0033] The halomethylated polyphenylene ethers disclosed herein can be used as precursors for producing the corresponding quaternary amine-containing polyphenylene ethers. Accordingly, the quaternary amine-containing polyphenylene ethers derived from the halomethylated polyphenylene ethers described herein are another embodiment disclosed herein.

[0034] Quaternized polyphenylene ethers may contain repeating units shown in the following structural formula. [ka] In the formula, each instance of R is independent of C. 1~12 Alkyl groups, such as methyl groups, are present. Due to the presence of quaternary ammonium groups, the quaternized polyphenylene ether can have a positive net charge overall. In some embodiments, the quaternized polyphenylene ether may further contain repeating units represented by structural formulas (I) and (III) to (IX) (wherein X is substituted with a -NR3 group). The amount of each repeating unit may be the same as that previously described for halomethylation precursors.

[0035] Quaternized polyphenylene ethers can be prepared by any method suitable for the substitution of the halo group with an amine. For example, a halomethylated polyphenylene ether can be dissolved in a solvent and contacted with a trialkylamine (e.g., trimethylamine) to produce a quaternized polyphenylene ether. An example of a synthetic procedure for preparing quaternized polyphenylene ethers is also described in Int. J. Mol. Sci. 2019, 20, 3678, and its contents are entirely referenced and incorporated herein.

[0036] The quaternated polyphenylene ethers disclosed herein can have a total quaternary amine substitution degree of 10 to 70%. In other words, 10 to 70% of the repeating units of the quaternated polyphenylene ether contain at least one quaternary amine group. The total substitution degree can be determined by nuclear magnetic resonance (NMR) spectroscopy. Within the range of 10 to 70%, the total quaternary amine substitution degree can be 20 to 80%, 30 to 70%, or 20 to 70%.

[0037] Of the substituted repeating units, at least 90% of the quaternized repeating units may have one quaternary amine group per repeating unit. In one embodiment, at least 92%, at least 93%, at least 94%, 90 to 100%, 90 to 99%, 90 to 98%, 92 to 99%, or 92 to 98% of the quaternized repeating units have only one quaternization group.

[0038] This chloromethylated polyphenylene ether or its corresponding quaternary derivative can be used in the manufacture of various articles. For example, this chloromethylated polyphenylene ether or its corresponding quaternary derivative can be molded into articles, for example, by injection molding or extrusion molding.

[0039] The chloromethylated polyphenylene ether and, in particular, the corresponding quaternized derivative are considered useful for a variety of applications, such as electrochemical equipment. In one specific embodiment, the quaternized polyphenylene ether disclosed herein is considered particularly useful for the manufacture of membranes, especially ion exchange membranes. The membrane can be prepared, for example, by dissolving the quaternized polyphenylene ether in a suitable solvent and casting the solution to form a film.

[0040] The contents of this application will be further explained by the following embodiments, but are not limited to these. [Examples]

[0041] Chloromethylated poly(phenylene ethers) were prepared according to the following examples. The same general methods described herein are considered applicable to the bromomethylated polyphenylene ethers disclosed herein.

[0042] Chloromethylated poly(phenylene ether) was prepared according to the following general method. To a chlorobenzene or o-dichlorobenzene solution of 15% by mass of poly(phenylene ether) (relative to the amount of solvent) with 5% by mass of ZnCl2 (relative to the amount of poly(phenylene ether) added, chloromethyl ethyl ether (CMEE, 2 equivalents) was added over 15 to 45 minutes at 30 to 50°C to synthesize chloromethylated poly(phenylene ether) with a degree of substitution ranging from 36 to 65%. The initial poly(phenylene ether) was poly(2,6-dimethyl-1,4-phenylene ether) with an intrinsic viscosity of 0.46 deciliters / gram (dL / g) measured at 25°C in chloroform using an Ubbelohde viscometer. The reaction was continued for 4.5 hours at a temperature range of 30 to 70°C. Table 1 summarizes the detailed conditions and reactant amounts for each example.

[0043] [Table 1]

[0044] The polymer was precipitated at the end of the reaction. The precipitation conditions for each example were as follows:

[0045] Example 1: The reaction was stopped by adding 50 mL of 2 M HCl. The chloromethylated polyphenylene ether resin was precipitated in 700 g of methanol. The precipitate was filtered off, air-dried, and dissolved in 100 mL of chlorobenzene. To this, 10 mL of dimethoxymethane and 30 mL of 2 M HCl were added. The polymer was reprecipitated in 700 g of methanol. The above steps, including redissolution and reprecipitation, were repeated one or more times. The polymer was filtered off and washed twice with 150 mL of 2 M HCl at 50°C for 2 hours with stirring. The polymer was filtered off and washed again twice with water at 50°C for 2 hours with stirring. Finally, the polymer was washed with 100 mL of methanol. The polymer was filtered off and air-dried for 24 hours.

[0046] Example 2: The reaction product was precipitated in 364 g of methanol. The polymer was filtered and washed twice with 150 mL of 1 M HCl at 50°C for 2 hours with stirring. The polymer was filtered and washed again twice with water at 50°C for 2 hours with stirring. Finally, the polymer was washed with 100 mL of methanol. The polymer was filtered and air-dried for 24 hours.

[0047] Example 3: The reaction was stopped by adding 30 mL of 2 M HCl. The polymer was precipitated in 700 g of methanol. The precipitate was filtered, air-dried, and dissolved in 100 mL of chlorobenzene, to which 30 mL of 2 M HCl was added. The polymer was reprecipitated in 700 g of methanol. The above steps, including redissolution and reprecipitation in methanol, were repeated one or more times. The polymer was filtered and washed twice with 150 mL of 2 M HCl at 50°C for 2 hours with stirring. The polymer was filtered and washed again twice with water at 50°C for 2 hours with stirring. Finally, the polymer was washed with 100 mL of methanol. The polymer was filtered and air-dried for 24 hours.

[0048] Example 4: The polymer was precipitated in 364 g of methanol. The polymer was filtered and washed twice with 150 mL of 1 M HCl with stirring at room temperature for 2 hours. The polymer was filtered and washed again twice with water with stirring at room temperature for 2 hours. Finally, the polymer was washed with 100 mL of methanol. The polymer was filtered and air-dried for 24 hours.

[0049] Example 5, 6: The reaction was stopped with 10 mL of 1 M HCl, and then precipitated in 364 g of methanol. The polymer was filtered and washed twice with 150 mL of 1 M HCl with stirring at 50°C for 2 hours. The polymer was filtered and washed again twice with 150 mL of water with stirring at 50°C for 2 hours. Finally, the polymer was washed with 100 mL of methanol at 50°C. The polymer was filtered and air-dried for 24 hours.

[0050] Example 7: The polymer was precipitated in 364 g of methanol. The precipitate was filtered, air-dried, and dissolved in 100 mL of chlorobenzene. To this polymer solution, 3% by mass of nitriloacetic acid (NTA) added to 25 mL of water was added and the mixture was gently stirred for 15 minutes. 364 g of methanol was added dropwise. The polymer precipitated as a fine powder. The polymer was filtered and washed with 150 mL of water at 50°C for 2 hours with stirring. Finally, the polymer was washed with 100 mL of methanol. The polymer was filtered and air-dried for 24 hours.

[0051] Example 8: The reaction was stopped with 20 mL of 2 M HCl, and then precipitated in 728 g of methanol. The polymer was filtered and air-dried. The polymer was redissolved in 200 mL of chlorobenzene, to which 20 mL of 2 M HCl was added. The polymer solution was reprecipitated in 728 g of methanol. The precipitate was washed twice with 300 mL of 2 M HCl at 50°C for 2 hours with stirring. The polymer was filtered and washed again twice with 300 mL of water at 50°C for 2 hours with stirring. Finally, the polymer was washed with 200 mL of methanol at 50°C. The polymer was filtered and air-dried for 24 hours.

[0052] Examples 9 and 10: Precipitation / purification was carried out in the same manner as in Example 3, but with the amount of all solvents doubled.

[0053] Examples 11 and 12: The polymer was precipitated in 50 mL of methanol. The polymer was air-dried for 24 hours.

[0054] Example 13: The sample from Example 8 was further dried at 65°C for 5 hours.

[0055] Example 14: The sample from Example 8 was dried at 65°C for 1 day.

[0056] Example 15: The sample from Example 8 was dried at 65°C for 2 days.

[0057] Example 16: The sample from Example 8 was dried at 65°C for 5 days.

[0058] Example 17: The polymer was precipitated in 182 g of 1 M methanolic HCl. The polymer was filtered and washed twice with 75 mL of 1 M HCl at room temperature (RT) for 2 hours with stirring. The polymer was filtered and washed again twice with water at room temperature for 2 hours with stirring. Finally, the polymer was washed with 50 mL of methanol. The polymer was filtered and air-dried for 24 hours.

[0059] Example 18: Precipitation / purification was carried out in the same manner as in Example 8, but with 75% less solvent used than in Example 8.

[0060] Example 19: Precipitation / purification was carried out in the same manner as in Example 3, but with 50% less solvent used than in Example 3.

[0061] Example 20: The reaction of the chloromethylated poly(phenylene ether) polymer was stopped by adding 10 mL of 2 M HCl. Next, the polymer was precipitated in 364 g of ethanol. The precipitate was filtered off, air-dried, and dissolved in 100 mL of chlorobenzene (containing 10 mL of diethoxymethane). 25 mL of 2 M HCl was added dropwise to this solution. Next, 364 g of ethanol was added dropwise, causing the polymer to precipitate as a fine powder. The polymer was filtered off and washed twice with 150 mL of 2 M HCl at 50°C for 2 hours with stirring. The polymer was filtered off and washed again twice with water at 50°C for 2 hours with stirring. Finally, the polymer was washed with 100 mL of methanol. The polymer was filtered off and air-dried for 24 hours. Next, the sample was dried in an oven at 60°C for 5 hours.

[0062] Example 21: The polymer was precipitated in 182 g of methanol. The polymer was washed with 100 mL of methanol. The polymer was filtered off and air-dried for 24 hours.

[0063] Example 22: The polymer was precipitated in 22 g of methanol. The precipitate was filtered, air-dried, and dissolved in 7 mL of chlorobenzene, to which 2 mL of water was added. 3% by mass of ion exchange resin (IER) was added to this polymer solution and gently stirred for 8 hours. 22 g of methanol was added dropwise. The polymer precipitated as a fine powder. The polymer was filtered and washed with 10 mL of water at 50°C for 2 hours with stirring. Finally, the polymer was washed with 10 mL of methanol. The polymer was filtered and air-dried for 24 hours.

[0064] Example 23: The polymer was precipitated in 22 g of methanol. The precipitate was filtered, air-dried, and dissolved in 7 mL of chlorobenzene, to which 2 mL of water was added. 3% by mass of activated carbon was added to this polymer solution and gently stirred for 8 hours. 22 g of methanol was added dropwise. The polymer precipitated as a fine powder. The polymer was filtered and washed with 10 mL of water at 50°C for 2 hours with stirring. Finally, the polymer was washed with 10 mL of methanol. The polymer was filtered and air-dried for 24 hours.

[0065] The properties of the obtained chloromethylated poly(phenylene) ether were determined by proton nuclear magnetic resonance ( 1 The oligomer content of various polymer samples was determined using 1H NMR spectroscopy and gel permeation chromatography (GPC). In GPC, the oligomers were eluted with chloroform containing 50 ppm DBA, and their molecular weight was determined by comparing them with a polystyrene standard.

[0066] 1 Using 1H NMR spectroscopy, the molar ratio of mono-substituted to di-substituted chloromethylated phenylene ether repeating units and the total degree of substitution (DS) were determined.

[0067] 1 H-13 Using C heteronuclear single quantum coherence NMR (HSQC NMR), the relative positions of the chloromethylated repeating units with respect to each other were investigated. For example, the presence of peaks at 4.92 ppm ( 1 H) / 38.23 ppm ( 13 C) ppm is considered to correspond to chloromethylated repeating units that are adjacent or close to each other (hereinafter referred to as "major components"). The degree of substitution (DS%) corresponding to the major component is referred to as "major DS%". In contrast, the presence of peaks at 4.72 ppm ( 1 H) / 65.52 ppm ( 13 C) ppm is considered to correspond to chloromethylated repeating units that are not adjacent or close to other chloromethylated repeating units (hereinafter referred to as "minor components"). The DS% corresponding to the minor component is referred to as "minor DS%".

[0068] The properties of the chloromethylated poly(phenylene ether) of Examples 1 to 23 are shown in Tables 2a and 2b.

[0069] [Table 2]

[0070] [Table 3]

[0071] As shown in Table 2, chloromethylated poly(phenylene ether) having a DS of 35 to 65% was obtained. Furthermore, this chloromethylated poly(phenylene ether) showed a 1-substituted:2-substituted ratio greater than 0.94, and the abundance of the major component exceeded 72%. Since the 1-substituted ratio was greater than 0.94 in all examples (Tables 2a and 2b), most of the major and minor components are 1-substituted. Put another way, regardless of how the substituted repeating units are assembled (or not), most of the chloromethylated repeating units are 1-substituted.

[0072] Examples 3-7 and 17-19 demonstrate the reproducibility and consistency of the degree of product substitution when the product is added under controlled conditions using a pump over a specific time period. In contrast, manual addition resulted in some variability in the product.

[0073] Example 9 demonstrates the advantages of adding a catalyst pre-dissolved in the solvent. Pre-dissolving the catalyst resulted in a more homogeneous reaction mixture, allowing the desired degree of substitution to be achieved in a shorter time (i.e., 3.5 hours compared to 4.5 hours in other examples). This preliminary dissolution also led to the repeated and reproducible acquisition of the desired product.

[0074] Furthermore, despite various drying conditions, a small amount of precipitated solvent (methanol) remained in the sample, suggesting a strong association between methanol and the minor component. For example, the polymer in Example 8 showed a methanol:minor component molar ratio of 0.43, and even after drying at 65°C for 5 days (Example 16), the methanol:minor component ratio remained at 0.45.

[0075] Table 2 further shows the concentrations of organic residues, specifically dimethoxymethane (DMM), diethoxymethane (DEM), methanol (MeOH), ethanol (EtOH), and chlorobenzene (ClBz), obtained by GS-MS and GS-MS for the polymers of Examples 1 and 20. 1 The results of the 1H NMR analysis are shown. Note that both GC-MS and NMR indicate the situ generation of dialkoxymethanes such as DMM and DEM during the reaction and / or precipitation steps. Also note that ethanol is a byproduct of this reaction.

[0076] As shown in Table 2, the samples were also analyzed for the presence of residual zinc (i.e., from the catalyst). From Table 2, it can be seen that the amount of residual zinc is somewhat affected by the precipitation and washing conditions. For example, when the polymer was purified as in Example 1, the residual zinc content could be reduced to less than 0.5 ppm.

[0077] Table 2 also shows that the molecular weight of the final chloromethylated poly(phenylene ether) is sensitive to the rate of addition of the CMEE reactants.

[0078] The effect of the solvent selected for the chloromethylation reaction was also investigated. o-dichlorobenzene (ODCB), 1,2-dichloroethane (EDC), and toluene were tested. Chlorobenzene (CB) was found to be preferable and was used in the previous examples. Toluene was simultaneously chloromethylated, producing a less substituted polyphenylene ether. 1,2-dichloroethane formed a gel in the presence of a catalyst. The results of these experiments are shown in Table 3. Molecular weight and DS% were measured in the same manner as described above.

[0079] [Table 4]

[0080] The effect of the method of adding the CMEE reactants to the reaction mixture was also investigated. The use of a dropping funnel and a pump was tested. With the dropping funnel, it was generally difficult to control the molecular weight and DS% of the chloromethylated polyphenylene ether product. The results of manual addition using a dropping funnel are summarized in Table 4.

[0081] [Table 5]

[0082] The effect of reaction temperature was investigated. In the following examples, the same synthesis method as described in Table 1 was used, except that the reaction temperature was raised to 70°C (addition was performed using a peristaltic pump). The results are shown in Table 5. As can be seen from Table 5, the product was only partially soluble in chloroform. The molecular weight and DS% in Table 5 indicate the molecular weight and DS% of the dissolved portion.

[0083] [Table 6]

[0084] The effect of the CMEE addition rate was also investigated. Tests were conducted with varying addition rates, and the results are summarized in Table 6. When the product is only partially soluble, the molecular weight and DS% shown refer only to the soluble portion.

[0085] [Table 7]

[0086] A comparison of the results shown in Table 6 with those shown in Table 2 suggests that a faster addition rate is desirable to prevent the formation of insoluble products.

[0087] The effect of catalyst residence time was investigated. In the following examples, the ZnCl2 catalyst was added to the reaction mixture one hour before adding the CMEE reactants. As can be seen from Table 7, this resulted in a product with low solubility. The molecular weight and DS% shown are for soluble components only.

[0088] [Table 8]

[0089] As an additional comparative example, chloromethylated polyphenylene ether was produced according to the procedure described in Int. J. of Hydrogen Energy, 39 (2014), 2659-2668. Briefly, 2 g of polyphenylene ether was dissolved in chlorobenzene at 30°C (15% by mass solution). When zinc chloride (5% by mass relative to the polymer mass) was added to the reaction mixture as a catalyst, a heterogeneous reaction mixture was formed because the catalyst was insoluble in chlorobenzene. Chloromethyl ethyl ether (CMEE) was added dropwise to the polyphenylene ether mixture. This mixture was stirred at 50°C for 5 hours and then cooled. After cooling, the product was precipitated with methanol (34 mL), filtered, washed twice with distilled water (34 mL each time), and dried in an oven at 70°C for 24 hours.

[0090] The results are shown in Table 8. As shown in Table 8, the comparative method produced chloromethylated polyphenylene ether with higher residual amounts of dimethoxymethane and chlorobenzene compared to the chloromethylated polyphenylene ether produced by the method disclosed in this application. Furthermore, the comparative method produced chloromethylated polyphenylene ether with a high residual zinc concentration (average 4000 ppm). The high zinc content and the observed range are due to the heterogeneity of the obtained sample.

[0091] [Table 9]

[0092] The disclosures of this application further include the following aspects:

[0093] Embodiment 1: A halomethylated polyphenylene ether, wherein the halomethylated polyphenylene ether is 35 to 89 mol% of the first repeating unit represented by structural formula (I), [ka] (I) 10 to 65 mol% of the second repeating unit represented by structural formula (II), [ka] (II) Less than 1 mol% of the third repeating unit represented by structural formula (III) and [ka] (III) The formula contains (wherein X in structural formula (II) is bromine or chlorine), and, as measured by nuclear magnetic resonance spectroscopy, at least 90% of the halomethylation repeating units are monohalomethylation repeating units represented by structural formula (II), and the halomethylated polyphenylene ether has a residual zinc content of less than 1000 ppm relative to the total mass of the halomethylated polyphenylene ether.

[0094] Embodiment 2: The halomethylated polyphenylene ether of Embodiment 1, further, Less than 1 mol% of the fourth repeating unit represented by structural formula (IV), [ka] (IV) Less than 1 mol% of the fifth repeating unit represented by structural formula (V), [ka] (V) Less than 1 mol% of the sixth repeating unit represented by structural formula (VI), [ka] (VI) Less than 1 mol% of the seventh repeating unit represented by structural formula (VII), [ka] (VII) Less than 1 mol% of the eighth repeating unit represented by structural formula (VIII), [ka] (VIII) It contains 1 mol% or less of the ninth repeating unit represented by structural formula (IX). [ka] (IX)

[0095] Embodiment 3: A halomethylated polyphenylene ether according to Embodiment 1 or 2, wherein the halomethylated polyphenylene ether has a mass-average molecular weight of at least 40,000 g / mol, preferably 40,000 to 150,000 g / mol, as measured by gel permeation chromatography, eluted with chloroform, and compared to a polystyrene standard.

[0096] Embodiment 4: A halomethylated polyphenylene ether according to any of Embodiments 1 to 3, wherein the halomethylated polyphenylene ether has a residual zinc content of less than 500 ppm, less than 100 ppm, less than 50 ppm, or less than 20 ppm relative to the total mass of the halomethylated polyphenylene ether, a dialkoxyalkane content of less than 20 ppm or less than 10 ppm relative to the total mass of the halomethylated polyphenylene ether, an oligomer content of less than 1% by mass relative to the total mass of the halomethylated polyphenylene ether, or a combination thereof, preferably the halomethylated polyphenylene ether has a combined content of diethoxymethane and dimethoxymethane of less than 20 ppm or less than 10 ppm relative to the total mass of the halomethylated polyphenylene ether, and the oligomer is a phenylene ether oligomer having a mass-average molecular weight of less than 1000 g / mol.

[0097] Embodiment 5: A halomethylated polyphenylene ether according to any of Embodiments 1 to 4, wherein the halomethylated polyphenylene ether is produced by a method comprising the steps of contacting a polyphenylene ether with chloromethyl ethyl ether to produce a chloromethylated polyphenylene ether, or contacting a polyphenylene ether with bromomethyl methyl ether to produce a bromomethylated polyphenylene ether.

[0098] Embodiment 6: A halomethylated polyphenylene ether according to Embodiment 5, wherein the contact step for producing the halomethylated polyphenylene ether is carried out for 1 to 10 hours at a temperature of 25 to 75°C, preferably 30 to 75°C, greater than 30 to less than 70°C, greater than 30 to 65°C, 40 to 60°C, or 45 to 55°C, using a polyphenylene ether:chloromethyl ethyl ether molar ratio or polyphenylene ether:bromomethyl methyl ether molar ratio of 1.9:1 to 2.1:1, preferably 2:1, at a temperature of 25 to 75°C, preferably 30 to 75°C, greater than 30 to less than 70°C, greater than 30 to 65°C, 40 to 60°C, or 45 to 55°C, and the contact step is carried out in the presence of a solvent, preferably chlorobenzene or o-dichlorobenzene, and the contact step is carried out in the presence of a catalyst, preferably a Lewis acid catalyst, more preferably a zinc-containing Lewis acid catalyst, wherein the amount of the catalyst is 3 to 7% by mass relative to the mass of the polyphenylene ether.

[0099] Embodiment 7: A method for producing a halomethylated polyphenylene ether, the method comprising the steps of: contacting a polyphenylene ether with chloromethyl ethyl ether to produce a mixture containing chloromethylated polyphenylene ether; or contacting a polyphenylene ether with bromomethyl methyl ether to produce bromomethylated polyphenylene ether; and isolating the halomethylated polyphenylene ether from the mixture, wherein the isolation step of the halomethylated polyphenylene ether is carried out using a poor solvent, preferably methanol or methanol. The process includes: precipitating a halomethylated polyphenylene ether from a mixture in hydrochloric acid; filtering off the precipitated halomethylated polyphenylene ether; washing the halomethylated polyphenylene ether preferably with water, hydrochloric acid, or a combination thereof; dissolving the filtered halomethylated polyphenylene ether in a solvent to produce a purified halomethylated polyphenylene ether solution; and adding a chelating agent, an ion exchange resin, a carbonaceous material, or a combination thereof to the purified halomethylated polyphenylene ether solution.

[0100] Embodiment 8: A method for producing Embodiment 7, wherein the polyphenylene ether comprises poly(2,6-dimethyl-1,4-phenylene ether).

[0101] Embodiment 9: A method for producing Embodiment 7 or 8, wherein the contact step uses a polyphenylene ether:chloromethyl ethyl ether molar ratio or polyphenylene ether:bromomethyl methyl ether molar ratio of 1.9:1 to 2.1:1, preferably 2:1, and the contact step is carried out for 1 to 10 hours at a temperature of 25 to 75°C, preferably 30 to 75°C, greater than 30 to less than 70°C, greater than 30 to 65°C, 40 to 60°C, or 45 to 55°C, and the contact step is carried out in the presence of a catalyst, preferably a Lewis acid catalyst, more preferably a zinc-containing Lewis acid catalyst, wherein the amount of the catalyst is 3 to 7% by mass relative to the mass of the polyphenylene ether.

[0102] Embodiment 10: A method for producing the material according to Embodiment 9, wherein the catalyst is dissolved in a solvent before the contact step in order to produce a homogeneous mixture.

[0103] Embodiment 11: A method for producing any of Embodiments 7 to 10, wherein the halomethylated polyphenylene ether has a degree of halomethylation of 5 to 100% as measured by nuclear magnetic resonance spectroscopy, and at least 90% of the halomethylated repeating units are monohalomethylated.

[0104] Embodiment 12: A method for producing any of Embodiments 7 to 11, wherein the halomethylated polyphenylene ether is 35 to 89 mol% of the first repeating unit represented by structural formula (I), [ka] (I) 10 to 65 mol% of the second repeating unit represented by structural formula (II), [ka] (II) Less than 1 mol% of the third repeating unit represented by structural formula (III) and [ka] (III) The formula contains (wherein X in structural formula (II) is bromine or chlorine), and the halomethylated polyphenylene ether has a residual zinc content of less than 1000 ppm relative to the total mass of the halomethylated polyphenylene ether.

[0105] Embodiment 13: A quaternary amine-containing polyphenylene ether derived from any of the halomethylated polyphenylene ethers of Embodiments 1 to 6.

[0106] Embodiment 14: An article comprising a halomethylated polyphenylene ether according to any of Embodiments 1 to 6, a halomethylated polyphenylene ether produced by any of the production methods of Embodiments 7 to 12, or a quaternary amine-containing polyphenylene ether according to Embodiment 13, wherein the article is preferably a membrane, and more preferably an ion separation membrane.

[0107] Embodiment 15: An anion exchange membrane containing a quaternary amine-containing polyphenylene ether according to Embodiment 13.

[0108] The compositions, methods, and articles may optionally include, consist of, or essentially consist of any suitable material, step, or component disclosed herein. The compositions, methods, and articles may also be configured, additionally or selectively, to exclude or substantially omit any material (or type), step, or component that is not necessarily required for achieving the function or purpose of the compositions, methods, and articles.

[0109] All scopes disclosed in the text include their endpoints, and these endpoints are independently combinable with one another. "Combinations" include blends, mixtures, alloys, reaction products, etc. Terms such as "first," "second," etc., do not indicate order, quantity, or importance, but are used to distinguish one element from another. Terms such as "a," "an," and "the" do not indicate a limit on quantity and should be interpreted as including both singular and plural forms unless otherwise indicated or clearly negated by the context. "Or" means "and / or" unless otherwise explicitly stated. A reference in the specification to "an aspect" means that a particular element described in relation to that aspect is included in at least one aspect described in the text, but may or may not be present in other aspects. The term “combination thereof” as used in this text includes one or more of the listed components, is open, and may include one or more similar components not listed. Furthermore, it goes without saying that the elements described can be combined in any suitable way in various aspects.

[0110] Unless otherwise stated in the text, all test standards are the most recent standards in effect as of the filing date of this application, or, if priority is claimed, as of the filing date of the earliest priority application in which the test standards are described.

[0111] Unless otherwise defined, technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art in the field to which this application pertains. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, in the event of any conflict or inconsistency between terms in this application and terms in any of the references, the terms in this application shall prevail over the conflicting terms in the references.

[0112] Compounds are described using standard nomenclature. For example, any position not substituted by a specified group is assumed to be bonded by the specified bond or to have its valence filled with hydrogen atoms. A dash ("-") not flanked by two letters or symbols is used to indicate the position of a substituent. For example, -CHO is bonded to the carbonyl group's carbon.

[0113] As used in this text, the term "hydrocarbyl" refers to a residue containing only carbon and hydrogen, whether used alone or as a prefix, suffix, or part of another term. This residue can be aliphatic or aromatic, linear, cyclic, bicyclic, branched, saturated, or unsaturated. It can also include combinations of aliphatic, aromatic, linear, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon groups. However, if a hydrocarbyl residue is described as substituted, it may, if necessary, contain heteroatoms in addition to the carbon and hydrogen that make up the substituent residue. That is, if it is explicitly stated as substituted, this hydrocarbyl residue may contain one or more carbonyl groups, amino groups, hydroxyl groups, etc., or it may contain heteroatoms in the main chain of the hydrocarbyl residue. The term "alkyl" means branched or linear, saturated aliphatic hydrocarbon groups, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, n- and s-hexyl. "Alkenyl" refers to a branched or linear, monovalent hydrocarbon group containing at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH2)). "Alkoxy" refers to an alkyl group bonded via oxygen (i.e., alkyl-O-), e.g., methoxy, ethoxy, sec-butyloxy groups. "Alkylene" refers to a branched or linear, saturated divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-), propylene (-(CH2)3-)). "Cycloalkylene" refers to a divalent cyclic alkylene group -C n H 2n-x(wherein x is the number of hydrogens replaced by cyclization) "Cycloalkenyl" means a monovalent group (e.g., cyclopentyl, cyclohexyl) containing one or more rings and one or more carbon-carbon double bonds within the rings, where all ring members are carbon. "Aryl" means an aromatic hydrocarbon group (e.g., phenyl, tropone, indanyl, naphthyl) containing the specified number of carbon atoms. "Arylene" means a divalent aryl group. "Alkylarylene" means an arylene group substituted with an alkyl group. "Arylalkylene" means an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" means a group or compound containing one or more fluoro, chloro, bromo, or iodo substituents. Different combinations of halo atoms (e.g., bromo and fluoro), or only chloro atoms may be present. The prefix "hetero" means a compound or group that contains at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatoms), where each heteroatom is independently N, O, S, Si, or P. "Substituted" means that the compound or group has at least one (e.g., 1, 2, 3, or 4) substituents instead of hydrogen (each independently C), provided that the valence of the substituted atom does not exceed the normal valence of the substituted atom. 1~9 Alkoxy, C 1~9 Haloalkoxy, nitro(-NO2), cyano(-CN), C 1~6 Alkylsulfonyl (-S(=O)2-alkyl), C 6~12 Arylsulfonyl (-S(=O)2-aryl), thiol (-SH), thiocyano (-SCN), tosyl (CH3C6H4SO2-), C 3~12 Cycloalkyl, C 2~12 Alkenil, C 5~12 Cycloalkenyl, C 6~12 Ariel, C 7~13 Arylalkylene, C 4~12 Heterocycloalkyl, and C 3~12This means that it is substituted with a heteroaryl group. The number of carbon atoms shown for a group does not include the substituent. For example, -CH2CH2CN is a nitrile-substituted C2 alkyl group.

[0114] While specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are not anticipated or are not anticipated at present may be devised by the applicant or other persons skilled in the art. Accordingly, the claims in filing and any potentially amended appendices should encompass all of these alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A halomethylated polyphenylene ether, The aforementioned halomethylated polyphenylene ether 35 to 89 mole percent (mol%) of the first repeating unit represented by structural formula (I), 【Chemistry 1】 （I） 10 to 65 mol% of the second repeating unit represented by structural formula (II), 【Chemistry 2】 (II) Less than 1 mol% of the third repeating unit represented by structural formula (III) and 【Transformation 3】 (III) (In the formula, X in structural formula (II) is bromine or chlorine) Measurements by nuclear magnetic resonance spectroscopy revealed that at least 90% of the halomethylation repeating units are monohalomethylation repeating units represented by structural formula (II). The halomethylated polyphenylene ether is characterized in that the halomethylated polyphenylene ether has a residual zinc content of less than 1000 ppm relative to the total mass of the halomethylated polyphenylene ether.

2. The halomethylated polyphenylene ether according to claim 1, further, A fourth repeating unit represented by structural formula (IV) in an amount of 1 mol% or less, 【Chemistry 4】 (IV) A fifth repeating unit represented by structural formula (V) in an amount of 1 mol% or less, 【Transformation 5】 （V） Less than 1 mol% of the sixth repeating unit represented by structural formula (VI), 【Transformation 6】 (VI) Less than 1 mol% of the seventh repeating unit represented by structural formula (VII), 【Transformation 7】 (VII) Less than 1 mol% of the eighth repeating unit represented by structural formula (VIII), 【Transformation 8】 (VIII) Less than 1 mol% of the ninth repeating unit represented by structural formula (IX) and 【Chemistry 9】 (IX) A halomethylated polyphenylene ether characterized by containing the following:

3. A halomethylated polyphenylene ether according to claim 1 or 2, characterized in that the halomethylated polyphenylene ether has a mass-average molecular weight of at least 40,000 g / mol (g / mol), preferably 40,000 to 150,000 g / mol, as measured by gel permeation chromatography, eluted with chloroform, and compared with a polystyrene standard.

4. A halomethylated polyphenylene ether according to any one of claims 1 to 3, The aforementioned halomethylated polyphenylene ether Residual zinc content less than 500 ppm, less than 100 ppm, less than 50 ppm, or less than 20 ppm relative to the total mass of halomethylated polyphenylene ether. Dialkoxyalkane content of less than 20 ppm or less than 10 ppm relative to the total mass of halomethylated polyphenylene ether, Oligosaccharide content of less than 1 mass percent (mass%) relative to the total mass of halomethylated polyphenylene ethers, Or have a combination of these, Preferably, the halomethylated polyphenylene ether has a combined content of diethoxymethane and dimethoxymethane of less than 20 ppm or less than 10 ppm relative to the total mass of the halomethylated polyphenylene ether. The halomethylated polyphenylene ether is characterized in that the oligoma is a phenylene ether oligoma having a mass-average molecular weight of less than 1000 g / mol.

5. A halomethylated polyphenylene ether according to any one of claims 1 to 4, The aforementioned halomethylated polyphenylene ether A process of producing chloromethylated polyphenylene ether by contacting polyphenylene ether with chloromethyl ethyl ether, or A process to produce bromomethylated polyphenylene ether by contacting polyphenylene ether with bromomethylmethyl ether. A halomethylated polyphenylene ether characterized by being manufactured by a method comprising the above.

6. The halomethylated polyphenylene ether according to claim 5, In the aforementioned contact step, a molar ratio of polyphenylene ether to chloromethyl ethyl ether or polyphenylene ether to bromomethyl methyl ether of 1.9:1 to 2.1:1, preferably 2:1, is used. The contact step for producing the halomethylated polyphenylene ether is carried out at a temperature of 25 to 75°C, preferably 30 to 75°C, greater than 30 to less than 70°C, greater than 30 to 65°C, 40 to 60°C, or 45 to 55°C for 1 to 10 hours. The contact step is carried out in the presence of a solvent, preferably chlorobenzene or o-dichlorobenzene. The above contact step is carried out in the presence of a catalyst, preferably a Lewis acid catalyst, more preferably a zinc-containing Lewis acid catalyst. A halomethylated polyphenylene ether characterized in that the amount of the catalyst present is 3 to 7% by mass relative to the mass of the polyphenylene ether.

7. A method for producing the aforementioned halomethylated polyphenylene ether, The aforementioned manufacturing method A step of contacting polyphenylene ether with chloromethyl ethyl ether to produce a mixture containing chloromethylated polyphenylene ether, or a step of contacting polyphenylene ether with bromomethyl methyl ether to produce bromomethylated polyphenylene ether, A step of isolating halomethylated polyphenylene ether from the mixture. Includes, The isolation step described above involves, A step of precipitating the halomethylated polyphenylene ether from the mixture in a poor solvent, preferably methanol or methanolic hydrochloric acid, A step of filtering off the precipitated halomethylated polyphenylene ether, The process involves washing the halomethylated polyphenylene ether, preferably with water, hydrochloric acid, or a combination thereof. The filtered halomethylated polyphenylene ether is dissolved in a solvent to produce a solution of purified halomethylated polyphenylene ether, and a chelating agent, an ion exchange resin, a carbonaceous material, or a combination thereof is added to the purified halomethylated polyphenylene ether solution. A manufacturing method characterized by including the following.

8. A method for producing according to claim 7, characterized in that the polyphenylene ether comprises poly(2,6-dimethyl-1,4-phenylene ether).

9. A manufacturing method according to claim 7 or 8, In the aforementioned contact step, a molar ratio of polyphenylene ether to chloromethyl ethyl ether or polyphenylene ether to bromomethyl methyl ether of 1.9:1 to 2.1:1, preferably 2:1, is used. The contact step is carried out at a temperature of 25 to 75°C, preferably 30 to 75°C, greater than 30 to less than 70°C, greater than 30 to 65°C, 40 to 60°C, or 45 to 55°C for 1 to 10 hours. The above contact step is carried out in the presence of a catalyst, preferably a Lewis acid catalyst, more preferably a zinc-containing Lewis acid catalyst. A method for producing the catalyst, characterized in that the amount of the catalyst present is 3 to 7% by mass relative to the mass of the polyphenylene ether.

10. A manufacturing method according to claim 9, characterized in that the catalyst is dissolved in a solvent before the contact step in order to produce a homogeneous mixture.

11. A manufacturing method according to any one of claims 7 to 10, The aforementioned halomethylated polyphenylene ether has a degree of halomethylation of 5 to 100% as measured by nuclear magnetic resonance spectroscopy. A method for producing the product, characterized in that at least 90% of the halomethylation repeating units are monohalomethylated products.

12. A manufacturing method according to any one of claims 7 to 11, The aforementioned halomethylated polyphenylene ether 35 to 89 mol% of the first repeating unit represented by structural formula (I), 【Chemistry 10】 （I） 10 to 65 mol% of the second repeating unit represented by structural formula (II), 【Chemistry 11】 (II) Less than 1 mol% of the third repeating unit represented by structural formula (III) and 【Chemistry 12】 (III) (In the formula, X in structural formula (II) is bromine or chlorine) A method for producing the halomethylated polyphenylene ether characterized in that the halomethylated polyphenylene ether has a residual zinc content of less than 1000 ppm relative to the total mass of the halomethylated polyphenylene ether.

13. A quaternary amine-containing polyphenylene ether characterized by being derived from a halomethylated polyphenylene ether according to any one of claims 1 to 6.

14. An article comprising a halomethylated polyphenylene ether according to any one of claims 1 to 6, a halomethylated polyphenylene ether produced by a manufacturing method according to any one of claims 7 to 12, or a quaternary amine-containing polyphenylene ether according to claim 13, wherein the article is preferably a membrane, and more preferably an ion separation membrane.

15. An anion exchange membrane characterized by containing the quaternary amine-containing polyphenylene ether described in claim 13.

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