Sulfonated poly(phenylene ether) and method for producing the same

Abstract

Sulfonated poly(phenylene ethers) are described herein. The sulfonated poly(phenylene ethers) have a degree of sulfonation of 15 to 50%. At least 90% of the repeating units of the sulfonated poly(phenylene ethers) are monosubstituted. Methods for producing sulfonated poly(phenylene ethers) and articles prepared therefrom are also disclosed.

Description

[Technical Field]

[0001] This application relates to sulfonated poly(phenylene ether) and a method for producing sulfonated poly(phenylene ether).

[0002] (Cross-reference of related applications) This application claims priority and benefits from European Patent Application No. 23170792.8, filed on 28 April 2023, the contents of which are incorporated herein by reference in their entirety. [Background technology]

[0003] Sulfonated poly(phenylene ether) is a commercially attractive material due to its unique combination of physical, chemical, and electrical properties. Furthermore, combinations of poly(phenylene ether) with other polymers or additives result in blends that improve overall properties, including chemical resistance, high strength, and high fluidity. As novel commercial applications are sought, a variety of sulfonated grades of poly(phenylene ether) materials are desired.

[0004] Conventional methods for sulfonating poly(phenylene ether) result in heterogeneity as the sulfonation level progresses, affecting the reaction system and making further sulfonation impossible. [Overview of the project] [Problems that the invention aims to solve]

[0005] Therefore, there remains a continuing demand in the art for improved sulfonation processes that can provide high sulfonation levels (e.g., up to 50%) and further provide a high percentage of monosubstituted repeating units. It would be even more beneficial to provide sulfonated poly(phenylene ethers) with reduced levels of residual components, e.g., residual solvents.

Means for Solving the Problems

[0006] One aspect of the present disclosure is a formula

Chemical formula

[0007] Another aspect of the present disclosure is a membrane containing a sulfonated poly(phenylene ether).

[0008] Another aspect of the present disclosure is a method for producing a sulfonated poly(phenylene ether), comprising the steps of contacting poly(phenylene ether) with a sulfonating agent in the presence of a solvent containing 1,2-dichloroethane and an auxiliary solvent containing ethyl acetate, under conditions effective for obtaining a mixture containing the sulfonated poly(phenylene ether); and isolating the sulfonated poly(phenylene ether) from the mixture, wherein the poly(phenylene ether) is present in an amount of 8 weight percent or more based on the total weight of the poly(phenylene ether), sulfonating agent, solvent, and auxiliary solvent, preferably in an amount of 8 to 25 weight percent, the auxiliary solvent is present in an amount of 7 to 15 weight percent based on the total weight of the solvent and auxiliary solvent, and the sulfonating agent is present in a weight ratio of sulfonating agent to poly(phenylene ether) of less than 0.5:1, preferably 0.1:1 to 0.45:1.

[0009] The above and other characteristics are illustrated by the following drawings and detailed description.

[0010] The following drawings illustrate exemplary embodiments. [Brief explanation of the drawing]

[0011] [Figure 1] The chemical structure of an exemplary sulfonated poly(phenylene ether) according to one aspect of this disclosure is shown. [Modes for carrying out the invention]

[0012] The inventors have unexpectedly discovered that sulfonated poly(phenylene ethers) with a high degree of sulfonation can be obtained by selecting specific method conditions for the preparation of sulfonated poly(phenylene ethers). In a further beneficial property, sulfonated poly(phenylene ethers) can have a high degree of monosubstitution (i.e., at least 90% of the sulfonated repeating units have only one sulfonate group). The ability to efficiently produce poly(phenylene ethers) with sulfonation levels of 15-50% enables a wide variety of products. For example, ion exchange membranes for dialysis, proton conduction membranes for polymer electrolyte membrane fuel cells, ion exchange membranes for flow batteries, hollow fiber membranes, precursors for molecular sieve carbon membranes for gas separation, precursors for carbon electrodes for fuel cells, carbon membrane reactors, etc. Thus, a significant improvement is provided by this disclosure.

[0013] Accordingly, one aspect of the present disclosure is a method for producing sulfonated poly(phenylene ether). The degree of sulfonation can be controlled by adjusting the amounts of solvent and co-solvent in the process, adjusting the amount of sulfonating agent used, and adjusting the concentration of poly(phenylene ether) in the reaction mixture.

[0014] The process according to this disclosure comprises the step of sulfonating poly(phenylene ether) by contacting it with a sulfonating agent in the presence of a solvent and an auxiliary solvent. The solvent comprises 1,2-dichloroethane. The auxiliary solvent comprises at least one of methyl ethyl ketone, diethyl ether, methyl ethyl sulfone, ethyl acetate (EA), or tetramethylene sulfone. In one embodiment, the auxiliary solvent comprises at least one of ethyl acetate or tetramethylene sulfone. In a particular embodiment, the auxiliary solvent comprises ethyl acetate.

[0015] Poly(phenylene ether) is, [ka] [In the formula, Z 1 Each of these appearances independently requires that the halogen, hydrocarbyl group is not a tertiary hydrocarbyl, and that it be either unsubstituted or substituted C 1~12 Hydrocarbyl, C 1~12 Hydrocarbilthio, C 1~12 Hydrocarbyl oxy, or C in which the halogen and oxygen atoms are separated by at least two carbon atoms. 2~12 Contains halohydrocarbyl oxy, Z 2 Each of these appearances independently requires that the hydrogen, halogen, and hydrocarbyl group are not tertiary hydrocarbyl groups, and that the resulting C is either unsubstituted or substituted. 1~12 Hydrocarbyl, C 1~12 Hydrocarbilthio, C 1~12 Hydrocarbyl oxy, or C in which the halogen and oxygen atoms are separated by at least two carbon atoms. 2~12 [Contains halohydrocarbyl oxy] This includes those containing repeating structural units having . Where used herein, the term "hydrocarbyl" refers to a residue containing only carbon and hydrogen, whether used by itself or as a prefix, suffix, or fragment of another term. The residue may be aliphatic or aromatic, linear, cyclic, bicyclic, branched, saturated, or unsaturated. This may also include combinations of aliphatic, aromatic, linear, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, where a hydrocarbyl residue is described as substituted, it may optionally contain heteroatoms in addition to the carbon and hydrogen members of the substituted residue. Thus, where specifically described as substituted, a hydrocarbyl residue may also contain one or more carbonyl groups, amino groups, hydroxyl groups, etc., or may contain heteroatoms within the hydrocarbyl residue's backbone. As one example, Z 1 This could be a di-n-butylaminomethyl group formed by the reaction of a terminal 3,5-dimethyl-1,4-phenyl group with the di-n-butylamine component of an oxidative polymerization catalyst.

[0016] In one embodiment, poly(phenylene ether) comprises 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or a combination thereof. In one embodiment, poly(phenylene ether) is poly(2,6-dimethyl-1,4-phenylene ether). In one embodiment, poly(phenylene ether) comprises poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.03 to 2 deciliters (dl / g) per gram. For example, poly(phenylene ether) may have an intrinsic viscosity of 0.25 to 1.7 dl / g, more specifically 0.25 to 0.7 dl / g, more specifically 0.35 to 0.55 dl / g, and even more specifically 0.35 to 0.50 dl / g, as measured using an Ubbelohde viscometer in chloroform at 25°C.

[0017] In one embodiment, poly(phenylene ether) may include molecules having an aminoalkyl-containing terminal group typically located in the ortho position relative to the hydroxyl group. Tetramethyldiphenoquinone (TMDQ) terminal groups are also frequently present, typically obtained from 2,6-dimethylphenol-containing reaction mixtures that contain tetramethyldiphenoquinone byproducts. Poly(phenylene ether) may also be in the form of homopolymers, copolymers, graft copolymers, ionomers, block copolymers, or oligomers, or combinations thereof.

[0018] As used herein, poly(phenylene ether) may also refer to low molecular weight phenylene ether oligomers. In one embodiment, the phenylene ether oligomer comprises 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or a combination thereof. In one embodiment, the phenylene ether oligomer may have an intrinsic viscosity of 0.03–0.13 dl / g, or 0.05–0.1 dl / g, or 0.1–0.15 dl / g, as measured using an Ubbelohde viscometer in chloroform at 25°C. The phenylene ether oligomer may have a number-average molecular weight of 500–7,000 grams (g / mol) and a weight-average molecular weight of 500–15,000 g / mol, as determined by gel permeation chromatography using a polystyrene standard. In one embodiment, when determined by gel permeation chromatography using a polystyrene standard, the number-average molecular weight may be 750 to 4,000 g / mol, and the weight-average molecular weight may be 1,500 to 9,000 g / mol.

[0019] Phenylene ether oligomers can be monofunctional or difunctional. In one embodiment, a phenylene ether oligomer can be monofunctional. For example, it may have one functional group at one end of the polymer chain. The functional group may be, for example, a hydroxyl group or a (meth)acrylate group, preferably a (meth)acrylate group. In one embodiment, the phenylene ether oligomer includes poly(2,6-dimethyl-1,4-phenylene ether).

[0020] In one embodiment, the phenylene ether oligomer may be bifunctional. For example, it may have a functional group at both ends of the oligomer chain. The functional group may be, for example, a hydroxyl group or a (meth)acrylate group, preferably a (meth)acrylate group. A bifunctional polymer having a functional group at both ends of the polymer chain is also called a "telechelic" polymer. In one embodiment, the phenylene ether oligomer has a structure [ka] {In formula, Q 1 and Q 2 These are, independently, halogen, unsubstituted, or substituted C 1~12 Primary or secondary hydrocarbils, C 1~12 Hydrocarbilthio, C 1~12 Hydrocarbyl oxy, and C in which the halogen and oxygen atoms are separated by at least two carbon atoms. 2~12 Contains halohydrocarbyl oxy, Q 3 and Q 4 Each occurrence of hydrogen, halogen, unsubstituted or substituted C is independent of hydrogen, halogen, unsubstituted or substituted C. 1~12 Primary or secondary hydrocarbils, C 1~12 Hydrocarbilthio, C 1~12 Hydrocarbyl oxy, and C in which the halogen and oxygen atoms are separated by at least two carbon atoms. 2~12 It contains a halohydrocarbyloxy, where Z is hydrogen or (meth)acrylate, x and y are independently 0-30, or 0-20, or 0-15, or 0-10, or 0-8, provided that the sum of x and y is at least 2, or at least 3, or at least 4, and L is the structure [ka] [In the formula, R 3 and R 4 and R 5 and R 6 Each of these occurrences is independently hydrogen, halogen, unsubstituted or substituted C 1~12 Primary or secondary hydrocarbils, C 1~12 Hydrocarbilthio, C 1~12 Hydrocarbyl oxy, and C in which the halogen and oxygen atoms are separated by at least two carbon atoms. 2~12 It contains halohydrocarbyloxy, where z is 0 or 1, and Y is [ka] (In the formula, R 7Each of the appearances is independent of hydrogen and C 1~12 Contains hydrocarbil, R 8 and R 9 Each of the appearances of hydrogen and C is independent. 1~12 Hydrocarbil, and R 8 and R 9 Collectively C 4~12 C that forms an alkylene group 1~6 (Contains hydrocarbylene) [Having a structure that includes] } has It contains a bifunctional phenylene ether oligomer having [a specific characteristic].

[0021] In one embodiment, the phenylene ether oligomer has a structure [ka] [In the formula, Q 1 Q 2 Q 3 Q 4 L, x, and y are as defined above, and R 10 [It is methyl or hydrogen.] It contains a bifunctional phenylene ether oligomer having [a specific characteristic].

[0022] In the phenylene ether structure having (meth)acrylate termini described above, there are constraints on the variables x and y, which correspond to the number of phenylene ether repeating units at two different positions within the bifunctional phenylene ether oligomer. In this structure, x and y are independently 0 to 30, or 0 to 20, or 0 to 15, or 0 to 10, or 0 to 8. The sum of x and y is at least 2, or at least 3, or at least 4. To determine whether these constraints are met on average, the phenylene ether oligomer is subjected to proton nuclear magnetic resonance spectroscopy ( 1 It can be analyzed by 1H NMR. Specifically, 11H NMR can distinguish between protons associated with internal and terminal phenylene ether groups, protons associated with internal and terminal polyvalent phenol residues, and protons associated with terminal residues. Therefore, it is possible to determine the average number of phenylene ether repeating units per molecule, as well as the relative abundance of internal and terminal residues derived from divalent phenols.

[0023] In one embodiment, the phenylene ether oligomer has a structure [ka] [In the formula, Q 5 and Q 6 Each occurrence of independently comprises methyl, di-n-butylaminomethyl, or morpholinomethyl, and each occurrence of a and b independently ranges from 0 to 20, provided that the sum of a and b is at least 2, R 10 Each occurrence is either methyl or hydrogen. It includes a bifunctional phenylene ether oligomer having [a specific characteristic]. An example of a bifunctional phenylene ether oligomer is NORYL® resin SA9000, available from SABIC.

[0024] In one embodiment, the phenylene ether oligomer has a structure [ka] [In the formula, Q 5 and Q 6 Each occurrence of a independently comprises methyl, di-n-butylaminomethyl, or morpholinomethyl, and each occurrence of a and b independently ranges from 0 to 20, provided that the sum of a and b is at least 2. It includes a bifunctional phenylene ether oligomer having [a specific characteristic]. An example of a bifunctional phenylene ether oligomer is NORYL® resin SA90, available from SABIC.

[0025] In one embodiment, poly(phenylene ether) includes poly(phenylene ether) homopolymers, oligomers, or combinations thereof. Poly(phenylene ether) may preferably include poly(2,6-dimethyl-1,4-phenylene ether).

[0026] A process for sulfonating poly(phenylene ether) comprises the step of contacting the poly(phenylene ether) with a sulfonating agent in the presence of a solvent and an auxiliary solvent. In one embodiment, the method comprises the step of dissolving the poly(phenylene ether) in a solvent and an auxiliary solvent to form a poly(phenylene ether) mixture. The mixing of the components of the mixture can be carried out at a temperature of 10 to 60°C, for example, 25 to 40°C. The solvent comprises 1,2-dichloroethane and is present in an amount sufficient to dissolve the poly(phenylene ether). The amount of the auxiliary solvent is sufficient to prevent the sulfonated poly(phenylene ether) from precipitating before the desired degree of sulfonation is achieved.

[0027] The solvent mixture may contain 8% by weight or more of poly(phenylene ether), or more than 10% by weight of poly(phenylene ether), or more than 12% by weight of poly(phenylene ether). Within this range, the solvent mixture may contain 8 to 25% by weight, preferably 8 to 20% by weight, or 10 to 25% by weight, or more than 10% by weight to 25% by weight, or 10 to 20% by weight, or 15 to 25% by weight, or 15 to 20% by weight, based on the total weight of poly(phenylene ether), sulfonating agent, solvent, and auxiliary solvent.

[0028] The solvent (i.e., 1,2-dichloroethane) may be present in the reactants in amounts of 60–99% by weight, 70–95% by weight, or 70–85% by weight, based on the total weight of poly(phenylene ether), sulfonating agent, solvent, and co-solvent, respectively.

[0029] The auxiliary solvent may be present in the reactants in an amount of 7–15 weight percent based on the total weight of the solvent and the auxiliary solvent. For example, the auxiliary solvent may be present in an amount of 8–12 weight percent. In one embodiment, the auxiliary solvent may be present in an amount of at least 10 weight percent, for example, 10–15 weight percent, or more than 10–15 weight percent, or 11–15 weight percent, or 12–15 weight percent, based on the total weight of the solvent and the auxiliary solvent.

[0030] Poly(phenylene ether) is sulfonated by reacting it with a sulfonating agent. Sulfonation can be carried out at temperatures up to 85°C, for example, 10–60°C, or 25–40°C. The amount of sulfonating agent added to the reaction mixture can be selected so that the weight ratio of sulfonating agent to poly(phenylene ether) is less than 0.5:1. For example, the weight ratio of sulfonating agent to poly(phenylene ether) may be 0.1:1–0.45:1 or 0.2:1–0.4:1. In one embodiment, the sulfonating agent may be added slowly to the reaction mixture, for example, over a period of 15 to 60 minutes (for example, over a period of 30 minutes). After adding the sulfonating agent to the solvent mixture, the solvent mixture may be stirred for a period of 60–210 minutes, for example, before proceeding to the isolation of the sulfonation product.

[0031] The method further includes the step of isolating the sulfonated poly(phenylene ether) from the mixture. For example, after the poly(phenylene ether) is sulfonated, the sulfonated poly(phenylene ether) can be precipitated from the solvent mixture using, for example, an anti-solvent mixture containing deionized (DI) water and an organic solvent. Hexane, heptane, cyclopentane, or cycloheptane (together with deionized water) can be used as the organic solvent to induce the precipitation of sulfonated poly(phenylene ether) from the reaction solvent mixture. The inventors have found that certain organic solvents can be particularly useful. For example, the organic solvent is immiscible with water and does not form an azeotrope with either 1,2-dichloroethane or ethyl acetate. Preferably, the organic solvent includes cyclopentane or cycloheptane. In certain embodiments, the organic solvent is cyclopentane.

[0032] The reaction solvent mixture may be added (for example, slowly) to the poor solvent mixture, where the poor solvent mixture may be used in an amount sufficient to induce precipitation. For example, 100 grams (g) of the reaction mixture may be added to 300-700 g, preferably 390-595 g, of the poor solvent mixture. In one embodiment, the poor solvent may have a weight ratio of 1:1-1:1, 1:2-1:5, or 1:3-1:4.5 of organic solvent to water.

[0033] The precipitated sulfonated poly(phenylene ether) can be filtered and optionally washed and dried. The filtrate may be biphasic, with 1,2-dichloroethane, an auxiliary solvent, and optionally an organic substance that was part of the poor solvent mixture (e.g., cyclohexane or cycloheptane) as the organic phase, and water as the aqueous phase. Therefore, the filtrate may be further processed to recover at least one of 1,2-dichloroethane, the auxiliary solvent, or water, preferably 1,2-dichloroethane and the auxiliary solvent, and more preferably 1,2-dichloroethane, the auxiliary solvent, and water. Recovery of the material may involve decanting the biphasic filtrate to form an aqueous stream and an organic stream. The organic stream may be further processed, for example, by distillation, to recover 1,2-dichloroethane or the auxiliary solvent. The recovered material can be reused. The selection of poor solvents that do not form azeotropic mixtures with either 1,2-dichloroethane or ethyl acetate as described herein can, beneficially, lead to increased recovery of the solvent or auxiliary solvent for reuse and repurposing in subsequent processes.

[0034] The methods described herein can provide sulfonated poly(phenylene ether) having a high degree of sulfonation and a high degree of monosulfonation repeat units. Therefore, sulfonated poly(phenylene ether) represents another aspect of this disclosure.

[0035] The sulfonated poly(phenylene ether) used herein is of the formula [ka] [In the above formula, Z 1 In each instance, the condition is that the sulfonic acid group, sulfonyl chloride group, halogen, and hydrocarbyl group are not tertiary hydrocarbyl groups, and the C is either unsubstituted or substituted. 1~12 Hydrocarbyl, C 1~12 Hydrocarbilthio, C 1~12Hydrocarbyl oxy, or C in which the halogen and oxygen atoms are separated by at least two carbon atoms. 2~12 It is a halohydrocarbyloxy, Z 2 In each instance, the condition is that the sulfonic acid group, sulfonyl chloride group, hydrogen, halogen, and hydrocarbyl group are not tertiary hydrocarbyl groups, and the C is either unsubstituted or substituted. 1~12 Hydrocarbyl, C 1~12 Hydrocarbilthio, C 1~12 Hydrocarbyl oxy, or C in which the halogen and oxygen atoms are separated by at least two carbon atoms. 2~12 [It is a halohydrocarbyloxy] This refers to a polymer that includes repeating units by Z. In one embodiment, Z 2 At least one of the appearances is a sulfonic acid group or a sulfonyl chloride group. In one embodiment, Z 1 Each occurrence of C 1~6 The alkyl group is preferably a methyl group. In one embodiment, the sulfonated poly(phenylene ether) may be derived from poly(2,6-dimethyl-1,4-phenylene ether).

[0036] Sulfonated poly(phenylene ether) has a degree of sulfonation of 15-50%. The degree of sulfonation can be determined, for example, using nuclear magnetic resonance (NMR) spectroscopy. In one embodiment, sulfonated poly(phenylene ether) may have a degree of sulfonation of 15-40% or 15-30%. Sulfonated poly(phenylene ether) may therefore further contain unsulfonated repeating units.

[0037] In terms of beneficial properties, the sulfonated poly(phenylene ethers) according to this disclosure may have a high degree of monosubstitutedity. In other words, the majority of the sulfonated repeating units of the sulfonated poly(phenylene ether) may have a single sulfonate / sulfonic acid group (i.e., a monosubstituted repeating unit). For example, at least 90% of the sulfonated poly(phenylene ether) repeating units are monosubstituted. As used herein, the term “monosubstituted” is not equivalent to “uniformly substituted.” The term “uniformly substituted” refers to a sulfonated poly(phenylene ether) product having a specific degree of sulfonation that is uniform throughout the entire product mass. In contrast, as used herein, “monosubstituted” means that the sulfonated poly(phenylene ether) product has a specific (uniform) degree of sulfonation throughout the entire product mass, and furthermore, that at least 90% of the repeating units having a sulfonate group have only one sulfonate group. For example, a sulfonated poly(phenylene ether) product having a uniform 20% degree of substitution means that the degree of substitution is 20% throughout the entire product mass. In this application, a monosulfonated poly(phenylene ether) product having a 20% degree of substitution means, for example, that of 20 sulfonated repeating units (for ease of calculation, let's assume there are a total of 100 repeating units in the polymer), at least 90% of those 20 repeating units have only one sulfonate group (i.e., at least 18 of the 20 repeating units have only one sulfonate group).

[0038] The sulfonated poly(phenylene ether) may further have a total residual solvent content of less than 0.2 weight percent based on the total weight of the sulfonated poly(phenylene ether). The residual solvent content can be determined using gas chromatography. In one embodiment, the sulfonated poly(phenylene ether) may have a total residual ethyl acetate content of less than 0.05 weight percent based on the total weight of the sulfonated poly(phenylene ether) as determined by gas chromatography.

[0039] This disclosure is further illustrated by the following embodiments, but is not limited thereto. [Examples]

[0040] Sulfonated poly(phenylene) ethers were prepared and isolated according to the following procedure.

[0041] <Example 1> Poly(phenylene oxide) (PPO, 42 g) was dissolved in 1,2-dichloroethane (EDC, 378 g) and ethyl acetate (EA, 42 g) for 30 minutes at 45°C under stirring in a 500 ml glass reactor (9 cm inner diameter) with a 45° pitch blade turbine impeller (6 cm diameter). After the solution became homogenized and clear, chlorosulfonic acid (CSA, 17.22 g) was slowly added over a period of 30-40 minutes while maintaining a temperature of 45°C. The reaction was carried out for 3.5 hours with continuous agitation (300 rpm, tip velocity = 0.94 m / sec) after the addition of CSA. A portion of the reaction mixture (100 g) was quenched in a mixture of cold demineralized (DM) water (400 g) and n-hexane (100 g) maintained at 10-12°C. The quenched reaction mixture was then filtered using a Buchner funnel to separate the solvent and sulfonated PPE (sPPE). A wet sPPE cake (40 g) containing 80-85% water and hexane was then dried under vacuum (12 mmHg) at room temperature (e.g., 25-30°C) for 48 hours to obtain a residual moisture content of less than 5% by weight.

[0042] <Example 2> 75 g of PPO was dissolved in 300 g of 1,2-dichloroethane and 33.38 g of ethyl acetate at 45°C for 30 minutes under stirring in a 500 ml glass reactor (9 cm inner diameter) with a 45° pitch blade turbine impeller (6 cm diameter). After the solution became homogenized and clear, 28.84 g of chlorosulfonic acid was slowly added over a period of 30-40 minutes while maintaining the reactor temperature at 45°C. The reaction was carried out for 3.5 hours with continuous agitation (300 rpm, tip velocity = 0.94 m / sec) after the addition of CSA. A portion of the reaction mixture (100 g) was quenched in a mixture of 400 g of cold demineralized (DM) water and 100 g of n-hexane, maintained at 10-12°C. The quenched reaction mixture was then filtered using a Buchner funnel to separate the solvent and sulfonated PPE (sPPE). A wet sPPE cake (96 g) containing 80-85% water and hexane was then dried under vacuum (12 mmHg) at room temperature (25-30°C) for 48 hours to obtain a residual moisture content of less than 5% by weight.

[0043] <Comparative Example 3> PPO (42 g) was dissolved in 1,2-dichloroethane (394.38 g) and ethyl acetate (25.62 g) under stirring in a 500 ml glass reactor (9 cm inner diameter) with a 45° pitch blade turbine impeller (6 cm diameter) at 45°C for 30 minutes. After the solution became homogenized and clear, chlorosulfonic acid (23.94 g) was slowly added over a period of 30-40 minutes while maintaining the reactor temperature at 45°C. The reaction was carried out for 3.5 hours with continuous agitation (300 rpm, tip velocity = 0.94 m / sec) after the addition of CSA. A portion of the reaction mixture (100 g) was quenched in a mixture of cold demineralized (DM) water (400 g) and n-hexane (100 g) maintained at 10-12°C. The quenched reaction mixture was then filtered using a Buchner funnel to separate the solvent and sulfonated PPE (sPPE). A wet sPPE cake (40 g) containing 80-85% water and hexane was then dried under vacuum (12 mmHg) at room temperature (25-30°C) for 48 hours to obtain a residual moisture content of less than 5% by weight.

[0044] The results of Examples 1 and 2 and Comparative Example 3 are provided in Table 1. As shown in Table 1, sulfonation degrees in the range of 20-30% or 25-30% can be achieved using a homogeneous reaction mixture in which poly(phenylene ether) is present in the reaction mixture in an amount of up to 20 weight percent and the CSA / PPE ratio is less than 0.5.

[0045] [Table 1]

[0046] In current processes, hexane is typically used as a poor solvent for precipitating sulfonated products. Hexane forms azeotropic mixtures with ethyl acetate, dichloroethane, and water, which makes solvent recovery difficult. For example, when hexane is used as a poor solvent, an azeotropic agent is required for distillation to recover the pure solvent. Therefore, alternative co-solvents were investigated to provide an improved isolation procedure. Criteria for selecting a suitable poor solvent include: (1) being an organic solvent immiscible with water, (2) not dissolving sulfonated poly(phenylene ether), (3) being able to extract ethyl acetate and dichloroethane, (4) not forming azeotropic mixtures with either ethyl acetate or dichloroethane, and (5) being able to form azeotropic mixtures with water.

[0047] The following solvents were investigated for use in the isolation of sulfonated poly(phenylene ethers): hexane, cyclopentane, heptane, cycloheptane, n-octane, and i-octane. Table 2 outlines the solvents used in the reaction and their azeotropic behavior with each of these solvents.

[0048] [Table 2]

[0049] The extraction of EDC and EA in the various organic solvents described above was simulated at 25°C using a decanter model in ASPEN PLUS. The extracted and simulated volumes are provided in Table 3. In the simulation, the organic and aqueous layers were separated using a decanter model. The theoretical compositions of each supernatant organic layer are shown in Table 3. The compositions of each supernatant organic layer determined by the simulation are shown in Table 4. Based on the simulation and theoretical weight percentages of each solvent in the organic layer, the recovery percentages of each solvent were estimated as summarized in Table 5.

[0050] [Table 3]

[0051] [Table 4]

[0052] [Table 5]

[0053] Based on the quantities shown in Table 6, the theoretical composition of the supernatant organic layer was calculated. The actual composition of the organic layer is shown in Table 7. 1 The determination was made by 1H NMR analysis. Based on the actual and theoretical weight percentages of each solvent in the organic layer, the recovery percentage of each solvent was estimated as summarized in Table 8.

[0054] [Table 6]

[0055] [Table 7]

[0056] [Table 8]

[0057] Determination of substitution patterns in sulfonated PPE The sPPE sample prepared as described above was used to measure the degree of substitution (DS). 1 1H NMR is insufficient for determining substitution patterns (mono-substitution vs. di-substitution). This is because, 1 This is due to the low signal dispersion of the 1H NMR spectrum. The inventors have found a much higher signal dispersion. 13 This problem was solved by analyzing the C spectrum. 1Since the H resonance was well resolved, to relate the proton signal to the corresponding carbon resonance, 2D 1 H- 13 We performed a C-gradient-assisted heteronuclear single quantum coherence (gHSQC) experiment. C obtained from a substituted sPPE ring (shown in Figure 1) 13 The carbon peak is, 13 In 13C NMR, a well-resolved peak is obtained at approximately 14.6 ppm. The signal intensity of this peak is compared to that of the aromatic resonance at C6 in the substituted ring.

[0058] This ratio represents the apparent degree of monosubstitution, as shown in Table 9. DS(%) is also shown in Table 9. For the entire range of sulfonation degrees (20-35%) across the 11 samples analyzed, monosubstitution is clearly present in 90% or more cases.

[0059] [Table 9]

[0060] After identifying the above conditions and solvents for obtaining sulfonated poly(phenylene ether), the following examples were performed to determine the composition of the final sulfonated poly(phenylene ether) product.

[0061] <Example 15> Polyphenylene oxide (PPO, 75 g) was dissolved in 1,2-dichloroethane (EDC, 300 g) and ethyl acetate (EA, 33 g) at 60°C for 60 minutes under stirring in a 500 ml glass reactor (9 cm inner diameter) with a 45° pitch blade turbine impeller (6 cm diameter), using laboratory settings. After the solution became homogeneous and clear, chlorosulfonic acid (CSA, 28.875 g) was slowly added over a period of 30-40 minutes while maintaining the reactor temperature at 60°C, to achieve a target sulfonation degree (DS, %) of 28-30%. The reaction was carried out for 2 hours with continuous agitation (300 rpm, tip velocity = 0.94 m / sec) after the addition of CSA.

[0062] After the reaction was complete, 90 g of the reaction mass obtained from the above reaction was rapidly added to a 1-liter baffled precipitation reactor with a pitch blade turbine containing 360 g of water and 90 g of n-hexane, maintained at 8–10°C and 420 rpm. The formed slurry was maintained under agitation for 1 hour, after which the solid was filtered. The resulting wet cake was further washed to remove residue using the same reactor with 216 g of water and 54 g of n-hexane, under agitation at 300 rpm at 25°C for 1 hour. This washing process was repeated five times to obtain the desired residual solvent content in the final product. The washed wet cake was dried in a vacuum oven at 25°C under a vacuum of 10–20 mbar for 70–90 hours to obtain the final sulfonated PPE powder with a water content of less than 5% by weight.

[0063] <Example 16> 100g of PPO was dissolved in 400g of 1,2-dichloroethane and 33g of ethyl acetate at 60°C for 60 minutes under stirring in a 1-liter glass reactor (9cm inner diameter) with a 45° pitch blade turbine impeller (6cm diameter), using laboratory settings. After the solution became homogeneous and clear, 38.5g of CSA was slowly added over a period of 30-40 minutes while maintaining the reactor temperature at 60°C, to achieve a target DS of 28-30%. The reaction was carried out for 2 hours with continuous agitation (300 rpm, tip velocity = 0.94 m / sec) after the addition of CSA.

[0064] After the reaction was complete, 520 g of the reaction mass obtained from the above reaction was rapidly added to a 5-liter baffle-free precipitation reactor with a pitch blade turbine containing 2080 g of water and 520 g of cyclopentane (CP), maintained at 8–10°C and 750 rpm. The formed slurry was maintained under agitation for 2 hours, after which the solid was filtered. The resulting wet cake was further washed to remove residue using the same reactor with 1248 g of water and 312 g of cyclopentane, under agitation at 170 rpm at 25°C for 2 hours. This washing process was repeated five times to obtain the desired residual solvent content in the final wet cake. This cake was further dried in a vacuum oven at 25°C under a vacuum of 10–20 mbar for 70–90 hours to obtain the final sulfonated PPE powder with a water content of less than 5% by weight.

[0065] <Example 17> 100 g of PPO was dissolved in 400 g of 1,2-dichloroethane and 33 g of ethyl acetate at 60°C for 60 minutes under stirring in a 1-liter glass reactor (9 cm inner diameter) with a 45° pitch blade turbine impeller (6 cm diameter), using laboratory settings. After the solution became homogeneous and clear, 38.04 g of CSA was slowly added over a period of 30-40 minutes while maintaining the reactor temperature at 60°C, to achieve a target DS of 28-30%. The reaction was carried out for 2 hours with continuous agitation (300 rpm, tip velocity = 0.94 m / sec) after the addition of CSA.

[0066] After the reaction was complete, 520 g of the reaction mass obtained from the above reaction was rapidly added to a 5-liter baffle-free precipitation reactor with a pitch blade turbine containing 2080 g of water and 520 g of cyclopentane, maintained at 8–10°C and 750 rpm. The formed slurry was maintained under agitation for 2 hours, after which the solid was filtered. The resulting wet cake was further washed to remove residue using the same reactor with 1248 g of water and 312 g of cyclopentane, under agitation at 170 rpm at 25°C for 2 hours. This washing process was repeated five times to obtain the desired residual solvent content in the final wet cake. This cake was further dried in a vacuum oven at 25°C under a vacuum of 10–20 mbar for 70–90 hours to obtain the final sulfonated PPE powder with a water content of less than 5% by weight.

[0067] <Example 18> 100 g of PPO was dissolved in 400 g of 1,2-dichloroethane and 33 g of ethyl acetate at 60°C for 60 minutes under stirring in a 1-liter glass reactor (9 cm inner diameter) with a 45° pitch blade turbine impeller (6 cm diameter), using laboratory settings. After the solution became homogeneous and clear, 35.35 g of chlorosulfonic acid (CSA) was slowly added over a period of 30-40 minutes while maintaining the reactor temperature at 60°C, to achieve a target DS% of 24-26%. The reaction was carried out for 2 hours with continuous agitation (300 rpm, tip velocity = 0.94 m / sec) after the addition of CSA.

[0068] After the reaction was complete, 520 g of the reaction mass obtained from the above reaction was rapidly added to a 5-liter baffle-free precipitation reactor with a pitch blade turbine containing 2080 g of water and 520 g of cyclopentane, maintained at 8–10°C and 750 rpm. The formed slurry was maintained under agitation for 2 hours, after which the solid was filtered. The resulting wet cake was further washed to remove residue using the same reactor with 1248 g of water and 312 g of cyclopentane, under agitation at 170 rpm at 25°C for 2 hours. This washing process was repeated five times to obtain the desired residual solvent content in the final wet cake. This cake was further dried in a vacuum oven at 25°C under a vacuum of 10–20 mbar for 70–90 hours to obtain the final sulfonated PPE powder with a water content of less than 5% by weight.

[0069] <Example 19> 100 g of PPO was dissolved in 400 g of 1,2-dichloroethane and 33 g of ethyl acetate at 60°C for 60 minutes under stirring in a 1-liter glass reactor (9 cm inner diameter) with a 45° pitch blade turbine impeller (6 cm diameter), using laboratory settings. After the solution became homogeneous and clear, 35.0 g of CSA was slowly added over a period of 30-40 minutes while maintaining the reactor temperature at 60°C, to achieve a target DS% of 24-26. The reaction was carried out for 2 hours with continuous agitation (300 rpm, tip velocity = 0.94 m / sec) after the addition of CSA.

[0070] After the reaction was complete, 520 g of the reaction mass obtained from the above reaction was rapidly added to a 5-liter baffle-free precipitation reactor with a pitch blade turbine containing 2080 g of water and 520 g of cyclopentane, maintained at 8–10°C and 750 rpm. The formed slurry was maintained under agitation for 2 hours, after which the solid was filtered. The resulting wet cake was further washed to remove residue using the same reactor with 1248 g of water and 312 g of cyclopentane, under agitation at 170 rpm at 25°C for 2 hours. This washing process was repeated five times to obtain the desired residual solvent content in the final wet cake. This cake was further dried in a vacuum oven at 25°C under a vacuum of 10–20 mbar for 70–90 hours to obtain the final sulfonated PPE powder with a water content of less than 5% by weight.

[0071] <Example 20> 100g of PPO was dissolved in 400g of 1,2-dichloroethane and 33g of ethyl acetate at 60°C for 60 minutes under stirring in a 1-liter glass reactor (9cm inner diameter) with a 45° pitch blade turbine impeller (6cm diameter), using laboratory settings. After the solution became homogeneous and clear, 26.35g of CSA was slowly added over a period of 30-40 minutes while maintaining the reactor temperature at 60°C, to achieve a target DS of 20-22%. The reaction was carried out for 2 hours with continuous agitation (300 rpm, tip velocity = 0.94 m / sec) after the addition of CSA.

[0072] After the reaction was complete, 520 g of the reaction mass obtained from the above reaction was rapidly added to a 5-liter baffle-free precipitation reactor with a pitch blade turbine containing 2080 g of water and 520 g of cyclopentane, maintained at 8–10°C and 750 rpm. The formed slurry was maintained under agitation for 2 hours, after which the solid was filtered. The resulting wet cake was further washed to remove residue using the same reactor with 1248 g of water and 312 g of cyclopentane, under agitation at 170 rpm at 25°C for 2 hours. This washing process was repeated five times to obtain the desired residual solvent content in the final wet cake. This cake was further dried in a vacuum oven at 25°C under a vacuum of 10–20 mbar for 70–90 hours to obtain the final sulfonated PPE powder with a water content of less than 5% by weight.

[0073] <Example 21> 100g of PPO was dissolved in 400g of 1,2-dichloroethane and 33g of ethyl acetate at 60°C for 60 minutes under stirring in a 1-liter glass reactor (9cm inner diameter) with a 45° pitch blade turbine impeller (6cm diameter), using laboratory settings. After the solution became homogeneous and clear, 27.67g of CSA was slowly added over a period of 30-40 minutes while maintaining the reactor temperature at 60°C, to achieve a target DS% of 20-22. The reaction was carried out for 2 hours with continuous agitation (300 rpm, tip velocity = 0.94 m / sec) after the addition of CSA.

[0074] After the reaction was complete, 520 g of the reaction mass obtained from the above reaction was rapidly added to a 5-liter baffle-free precipitation reactor with a pitch blade turbine containing 2080 g of water and 520 g of cyclopentane, maintained at 8–10°C and 750 rpm. The formed slurry was maintained under agitation for 2 hours, after which the solid was filtered. The resulting wet cake was further washed to remove residue using the same reactor with 1248 g of water and 312 g of cyclopentane, under agitation at 170 rpm at 25°C for 2 hours. This washing process was repeated five times to obtain the desired residual solvent content in the final wet cake. This cake was further dried in a vacuum oven at 25°C under a vacuum of 10–20 mbar for 70–90 hours to obtain the final sulfonated PPE powder with a water content of less than 5% by weight.

[0075] <Example 22> 100g of PPO was dissolved in 400g of 1,2-dichloroethane and 33g of ethyl acetate at 60°C for 60 minutes under stirring in a 1-liter glass reactor (9cm inner diameter) with a 45° pitch blade turbine impeller (6cm diameter), using laboratory settings. After the solution became homogeneous and clear, 27.67g of CSA was slowly added over a period of 30-40 minutes while maintaining the reactor temperature at 60°C, to achieve a target DS of 20-22%. The reaction was carried out for 2 hours with continuous agitation (300 rpm, tip velocity = 0.94 m / sec) after the addition of CSA.

[0076] After the reaction was complete, 520 g of the reaction mass obtained from the above reaction was rapidly added to a 5-liter baffle-free precipitation reactor with a pitch blade turbine containing 2080 g of water and 520 g of cyclopentane, maintained at 8–10°C and 750 rpm. The formed slurry was maintained under agitation for 2 hours, after which the solid was filtered. The resulting wet cake was further washed to remove residue using the same reactor with 1248 g of water and 312 g of cyclopentane, under agitation at 170 rpm at 25°C for 2 hours. This washing process was repeated five times to obtain the desired residual solvent content in the final wet cake. This cake was further dried in a vacuum oven at 25°C under a vacuum of 10–20 mbar for 70–90 hours to obtain the final sulfonated PPE powder with a water content of less than 5% by weight.

[0077] <Example 23> 75g of PPO was dissolved in 300g of 1,2-dichloroethane and 33g of ethyl acetate at 60°C for 60 minutes under stirring in a 500ml glass reactor (9cm inner diameter) with a 45° pitch blade turbine impeller (6cm diameter), using laboratory settings. After the solution became homogeneous and clear, 21.6g of CSA was slowly added over a period of 30-40 minutes while maintaining the reactor temperature at 60°C, to achieve a target DS of 20-22%. The reaction was carried out for 2 hours with continuous agitation (300rpm, tip velocity = 0.94m / sec) after the addition of CSA.

[0078] After the reaction was complete, the 90 g reaction mass obtained from the above reaction was rapidly added to a 1 liter baffled precipitation reactor containing 360 g of water and 90 g of cyclopentane, maintained at 8–10°C and 420 rpm in a pitch blade turbine. The resulting slurry was maintained under agitation for 1 hour, after which the solid was filtered. The resulting wet cake was analyzed for residual solvent without drying.

[0079] <Example 24> 75g of PPO was dissolved in 300g of 1,2-dichloroethane and 33g of ethyl acetate at 60°C for 60 minutes under stirring in a 500ml glass reactor (9cm inner diameter) with a 45° pitch blade turbine impeller (6cm diameter), using laboratory settings. After the solution became homogeneous and clear, 21.6g of CSA was slowly added over a period of 30-40 minutes while maintaining the reactor temperature at 60°C, to achieve a target DS% of 20-22. The reaction was carried out for 2 hours with continuous agitation (300rpm, tip velocity = 0.94m / sec) after the addition of CSA.

[0080] After the reaction was complete, 90 g of the reaction mass obtained from the above reaction was rapidly added to a 1-liter baffled precipitation reactor with a pitch blade turbine containing 360 g of water and 90 g of cyclopentane, maintained at 8–10°C and 420 rpm. The resulting slurry was maintained under agitation for 1 hour, after which the solid was filtered. The resulting wet cake was dried in a vacuum oven at 25°C under a vacuum of 10–20 mbar for 70–90 hours to obtain a final sulfonated PPE powder with a water content of less than 5% by weight.

[0081] Samples were analyzed using an Agilent headspace gas chromatography (GC) instrument equipped with a CP-waX-52cb column measuring 50 m × 320 μm × 1.2 μm, with ultrapure helium as the carrier gas, at a column flow rate of 2 ml / min, a split ratio of 20:1, and an injector temperature of 240 °C. A flame ionization detector was used. The headspace oven was maintained at 80 °C, and the headspace vials were equilibrated for 30 minutes before injection.

[0082] To quantitatively analyze the residual solvent content, calibration was performed using an external solvent of known concentration. The vapor generated in each calibration sample was injected into a column, and the response was recorded using a flame ionization detector. A calibration curve was generated using the area under the curve of the specified chromatogram peak at the known concentration. The detection limit for this analysis was 5 ppm.

[0083] Samples of sulfonated poly(phenylene ether) (sPPE) according to the above-described examples were prepared by dissolving 0.5 grams of sPPE in 5 milliliters of NMP, and the samples were analyzed using gas chromatography. The concentration of residual solvent in each sample was determined using a calibration curve.

[0084] The experimental conditions and the resulting residual solvent content for each example are summarized in Table 10.

[0085] [Table 10]

[0086] [Table 11]

[0087] As shown in Table 10, EDC was not detected in any of the examples. Both EA and CP were observed to be present in acceptable amounts.

[0088] This disclosure further encompasses the following aspects:

[0089] Appearance 1: [ka] [In the above formula, Z 1is, in each occurrence independently, a sulfonic acid group, a sulfonyl chloride group, a halogen, a hydrocarbyl group that is not a tertiary hydrocarbyl, unsubstituted or substituted C 1~12 hydrocarbyl, C 1~12 hydrocarbylthio, C 1~12 hydrocarbyloxy, or C in which a halogen and an oxygen atom are separated by at least two carbon atoms 2~12 halohydrocarbyloxy, and Z 2 is, in each occurrence independently, a sulfonic acid group, a sulfonyl chloride group, hydrogen, a halogen, a hydrocarbyl group that is not a tertiary hydrocarbyl, unsubstituted or substituted C 1~12 hydrocarbyl, C 1~12 hydrocarbylthio, C 1~12 hydrocarbyloxy, or C in which a halogen and an oxygen atom are separated by at least two carbon atoms 2~12 halohydrocarbyloxy] A sulfonated poly(phenylene ether) containing a repeating unit of, wherein the sulfonated poly(phenylene ether) has a sulfonation degree of 15 to 50% when determined by nuclear magnetic resonance spectroscopy, and at least 90% of the sulfonated poly(phenylene ether) repeating units of the sulfonated poly(phenylene ether) are monosubstituted.

[0090] Aspect 2: The sulfonated poly(phenylene ether) according to Aspect 1, wherein the sulfonated poly(phenylene ether) has a total residual solvent content of less than 0.2 weight percent based on the total weight of the sulfonated poly(phenylene ether) when determined using gas chromatography.

[0091] Embodiment 3: A sulfonated poly(phenylene ether) according to Embodiment 1 or 2, characterized in that the sulfonated poly(phenylene ether) is produced by a method comprising the step of contacting poly(phenylene ether) with a sulfonating agent in the presence of a solvent containing 1,2-dichloroethane and an auxiliary solvent containing ethyl acetate to obtain a mixture containing the sulfonated poly(phenylene ether), wherein the poly(phenylene ether) is present in an amount of 8% by weight or more based on the total weight of the poly(phenylene ether), sulfonating agent, solvent and auxiliary solvent, preferably in an amount of 8 to 25% by weight, the auxiliary solvent is present in an amount of 7 to 15% by weight based on the total weight of the solvent and auxiliary solvent, and the sulfonating agent is present in a weight ratio of sulfonating agent to poly(phenylene ether) of less than 0.5:1, preferably 0.1:1 to 0.45:1.

[0092] Embodiment 4: A sulfonated poly(phenylene ether) according to Embodiment 3, characterized in that the sulfonated poly(phenylene ether) is produced by a method further comprising the steps of adding a mixture containing the sulfonated poly(phenylene ether) to a poor solvent containing water and an organic solvent that is immiscible with water and does not form an azeotrope with either 1,2-dichloroethane or ethyl acetate to form a slurry containing precipitated sulfonated poly(phenylene ether), and isolating the sulfonated poly(phenylene ether).

[0093] Embodiment 5: A sulfonated poly(phenylene ether) according to any one of Embodiments 1 to 4, wherein Z 2 A sulfonated poly(phenylene ether) characterized in that at least one of the groups is a sulfonic acid group or a sulfonyl chloride group.

[0094] Embodiment 6: A sulfonated poly(phenylene ether) according to any one of Embodiments 1 to 5, wherein Z 1A sulfonated poly(phenylene ether) characterized in that each of these is a methyl group.

[0095] Embodiment 7: A sulfonated poly(phenylene ether) according to any one of Embodiments 1 to 6, characterized in that the sulfonated poly(phenylene ether) has a total residual ethyl acetate content of less than 0.05 weight percent based on the total weight of the sulfonated poly(phenylene ether) as determined by gas chromatography.

[0096] Embodiment 8: The sulfonated poly(phenylene ether) according to Embodiment 1, wherein the sulfonated poly(phenylene ether) is of the formula [ka] Includes repeating units, The sulfonated poly(phenylene ether) has a degree of sulfonation of 15-40 percent as determined by nuclear magnetic resonance spectroscopy, at least 90% of the repeating units of the sulfonated poly(phenylene ether) are monosubstituted, the sulfonated poly(phenylene ether) has a total residual solvent content of less than 0.2 weight percent based on the total weight of the sulfonated poly(phenylene ether) as determined by gas chromatography, and the sulfonated poly(phenylene ether) is brought into contact with a sulfonating agent in the presence of a solvent containing 1,2-dichloroethane and an auxiliary solvent containing ethyl acetate to obtain a mixture containing the sulfonated poly(phenylene ether). A sulfonated poly(phenylene ether) characterized by being prepared by a method comprising the steps of: 1) the presence of poly(phenylene ether), a sulfonating agent, a solvent, and an auxiliary solvent in an amount of 8 to 25 weight percent based on the total weight of the solvent and the auxiliary solvent, the presence of the auxiliary solvent in an amount of 7 to 15 weight percent based on the total weight of the solvent and the auxiliary solvent, and the presence of the sulfonating agent in a weight ratio of sulfonating agent to poly(phenylene ether) of 0.1:1 to 0.45:1; 2) the addition of a mixture containing the sulfonated poly(phenylene ether) to a poor solvent containing water and an organic solvent that is immiscible with water and does not form an azeotrope with either 1,2-dichloroethane or ethyl acetate to form a slurry containing precipitated sulfonated poly(phenylene ether); and 3) the isolation of the precipitated sulfonated poly(phenylene ether).

[0097] Embodiment 9: A film characterized by containing a sulfonated poly(phenylene ether) as described in any one of Embodiments 1 to 8.

[0098] Embodiment 10: A method for producing sulfonated poly(phenylene ether), comprising the steps of: contacting poly(phenylene ether) with a sulfonating agent in the presence of a solvent containing 1,2-dichloroethane and an auxiliary solvent containing ethyl acetate, under conditions effective for obtaining a mixture containing sulfonated poly(phenylene ether); and isolating the sulfonated poly(phenylene ether) from the mixture, wherein the poly(phenylene ether) is present in an amount of 8% by weight or more based on the total weight of the poly(phenylene ether), sulfonating agent, solvent, and auxiliary solvent, preferably in an amount of 8 to 25% by weight, the auxiliary solvent is present in an amount of 7 to 15% by weight based on the total weight of the solvent and auxiliary solvent, and the sulfonating agent is present in a weight ratio of sulfonating agent to poly(phenylene ether) of less than 0.5:1, preferably 0.1:1 to 0.45:1.

[0099] Embodiment 11: A method according to Embodiment 10, further comprising the steps of: adding a mixture containing sulfonated poly(phenylene ether) to a poor solvent containing water and an organic solvent that is immiscible with water and does not form an azeotrope with 1,2-dichloroethane or ethyl acetate to form a slurry containing precipitated sulfonated poly(phenylene ether); isolating the sulfonated poly(phenylene ether); and optionally washing the isolated sulfonated poly(phenylene ether) with a poor solvent.

[0100] Embodiment 12: A method according to Embodiment 11, characterized in that the organic solvent comprises cyclopentane or cycloheptane, preferably cyclopentane.

[0101] Embodiment 13: A method according to any one of Embodiments 10 to 12, characterized in that the isolated sulfonated poly(phenylene ether) has a degree of sulfonation of 15 to 50 percent as determined by nuclear magnetic resonance spectroscopy, at least 90% of the sulfonation repeating units of the sulfonated poly(phenylene ether) are monosubstituted, and optionally, the isolated sulfonated poly(phenylene ether) has a total residual solvent content of less than 0.2 weight percent based on the total weight of the sulfonated poly(phenylene ether) as measured by gas chromatography.

[0102] Aspect 14: The method according to Aspect 10, comprising the steps of contacting poly(phenylene ether) with a sulfonating agent in the presence of a solvent containing 1,2-dichloroethane and an auxiliary solvent containing ethyl acetate, under conditions effective for obtaining a mixture containing sulfonated poly(phenylene ether), wherein poly(phenylene ether) is present in an amount of 8 to 25 weight percent based on the total weight of poly(phenylene ether), sulfonating agent, solvent, and auxiliary solvent, the auxiliary solvent is present in an amount of 7 to 15 weight percent based on the total weight of the solvent and auxiliary solvent, and the sulfonating agent is present in a weight ratio of sulfonating agent to poly(phenylene ether) of 0.1:1 to 0.45:1, and adding the mixture containing sulfonated poly(phenylene ether) to a poor solvent containing water and an organic solvent that is immiscible with water and does not form an azeotrope with either 1,2-dichloroethane or ethyl acetate. The method further comprises the steps of forming a slurry containing precipitated sulfonated poly(phenylene ether), isolating the precipitated sulfonated poly(phenylene ether), and optionally washing the isolated sulfonated poly(phenylene ether) with a poor solvent, wherein the organic solvent contains cyclopentane or cycloheptane, the isolated sulfonated poly(phenylene ether) has a degree of sulfonation of 15 to 50 percent as determined by nuclear magnetic resonance spectroscopy, at least 90% of the sulfonation repeating units of the sulfonated poly(phenylene ether) are monosubstituted, and optionally, the isolated sulfonated poly(phenylene ether) has a total residual solvent content of less than 0.2 weight percent based on the total weight of the sulfonated poly(phenylene ether) as determined by gas chromatography.

[0103] Embodiment 15: A sulfonated poly(phenylene ether) characterized by being produced by the method described in any one of Embodiments 10 to 14.

[0104] Compositions, methods, and articles may, by alternative means, include, be, or essentially consist of any suitable material, step, or component disclosed herein. Compositions, methods, and articles may, additionally or by alternative means, be formulated without, or substantially without, any material (or type), step, or component that is not essential for achieving the function or purpose of the composition, method, and article.

[0105] All scopes disclosed herein include endpoints, which are independently combinable. “Combinations” include blends, mixtures, alloys, reaction products, etc. Terms such as “first,” “second,” etc., do not indicate any order, quantity, or importance, but rather are used to distinguish one element from another. The terms “a,” “an,” and “the” do not indicate a limit on quantity and are considered to encompass both singular and plural forms unless otherwise explicitly indicated herein or clearly contradicted by the context. “Or” means “and / or” unless otherwise explicitly indicated. Throughout this specification, references to “an aspect” mean that a particular element described in relation to an aspect is included in at least one aspect described herein and may or may not be present in other aspects. As used herein, “their combinations” include, but are not limited to, one or more of the enumerated elements, and permit the presence of one or more similar elements not enumerated. In addition, it will be understood that the elements described may be combined in any preferred manner in various aspects.

[0106] Unless otherwise indicated herein, 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.

[0107] Unless otherwise defined, technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art in which this application pertains. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if any terminology in this application conflicts with or is inconsistent with any terminology in any of the references, the terminology in this application shall prevail over the conflicting terminology in the references.

[0108] The compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valence filled by the indicated bond or hydrogen atom. A dashed line ("-") that is not between two letters or symbols indicates a substituent bond point. For example, -CHO is bonded through the carbonyl group's carbon.

[0109] As used herein, the term "hydrocarbyl", whether used by itself or as a prefix, suffix, or fragment of another term, refers to a residue containing only carbon and hydrogen. The residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched-chain, saturated, or unsaturated. This can also include combinations of aliphatic, aromatic, straight-chain, cyclic, bicyclic, branched-chain, saturated, and unsaturated hydrocarbon moieties. However, when a hydrocarbyl residue is described as being substituted, it may optionally contain heteroatoms in addition to the carbon and hydrogen members of the substituent residue. Thus, when specifically described as being substituted, a hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, etc., or can contain heteroatoms within the backbone of the hydrocarbyl residue. The term "alkyl" means a branched or straight-chain saturated aliphatic hydrocarbon group, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, and n- and s-hexyl. The term "alkenyl" means a straight-chain or branched-chain monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH2)). The term "alkoxy" means an alkyl group linked through oxygen (i.e., alkyl-O-), such as methoxy, ethoxy, and sec-butoxy groups. The term "alkylene" means a straight-chain or branched-chain saturated divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-) or propylene (-(CH2)3-)). The term "cycloalkylene" means 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 having one or more rings and one or more carbon-carbon double bonds within the ring, where all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing a specified number of carbon atoms, e.g., phenyl, tropone, indanyl, or naphthyl. "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 of the fluoro, chloro, bromo, and iodo substituents. A combination of different halo atoms (e.g., bromo and fluoro), or just a chloro atom may be present. The prefix "hetero" means that a compound or group contains at least one ring member that is a heteroatom (e.g., one, two, or three heteroatoms), where each heteroatom is independently N, O, S, Si, or P. "Substituted" means that a compound or group has a hydrogen atom replaced by, independently, C. 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 can be a heteroaryl group and is substituted with at least one substituent (e.g., one, two, three, or four), but not exceeding the normal valency of the substituted atom. The number of carbon atoms shown in the group excludes any substituents. For example, -CH2CH2CN is a nitrile-substituted C2 alkyl group.

[0110] While specific embodiments are described, alternatives, variations, alterations, improvements, and substantial equivalents that are not anticipated or cannot be anticipated at present may be conceived by the applicant or other persons skilled in the art. Accordingly, the potentially amended appendix claims filed are intended to encompass all such alternatives, variations, alterations, improvements, and substantial equivalents.

Claims

1. formula 【Chemistry 1】 [In the above formula, Z １ In each instance, the condition is that the sulfonic acid group, sulfonyl chloride group, halogen, and hydrocarbyl group are not tertiary hydrocarbyl groups, and the C is either unsubstituted or substituted. １～１２ Hydrocarbil, C １～１２ Hydrocarbylthio, C １～１２ Hydrocarbyl oxy, or C in which the halogen and oxygen atoms are separated by at least two carbon atoms. ２～１２ It is a halohydrocarbyl oxy, Z ２ is, in each occurrence independently, a sulfonic acid group, a sulfonyl chloride group, hydrogen, a halogen, a hydrocarbyl group provided that the hydrocarbyl group is not a tertiary hydrocarbyl, an unsubstituted or substituted C １～１２ hydrocarbyl, C １～１２ hydrocarbylthio, C １～１２ hydrocarbyloxy, or a C ２～１２ halohydrocarbyloxy in which the halogen and oxygen atoms are separated by at least two carbon atoms] A sulfonated poly(phenylene ether) containing repeating units, The sulfonated poly(phenylene ether) has a degree of sulfonation of 15-50% as determined by nuclear magnetic resonance spectroscopy. At least 90% of the repeating units of the sulfonated poly(phenylene ether) are monosubstituted. A sulfonated poly(phenylene ether) characterized by the following features.

2. A sulfonated poly(phenylene ether) according to claim 1, characterized in that the sulfonated poly(phenylene ether) has a total residual solvent content of less than 0.2 weight percent based on the total weight of the sulfonated poly(phenylene ether) as determined by gas chromatography.

3. A sulfonated poly(phenylene ether) according to claim 1 or 2, wherein the sulfonated poly(phenylene ether) is The step involves contacting poly(phenylene ether) with a sulfonating agent in the presence of a solvent containing 1,2-dichloroethane and an auxiliary solvent containing ethyl acetate to obtain a mixture containing the sulfonated poly(phenylene ether). The poly(phenylene ether) is present in an amount of 8% by weight or more, based on the total weight of the poly(phenylene ether), the sulfonating agent, the solvent, and the auxiliary solvent, preferably in an amount of 8 to 25% by weight. The auxiliary solvent is present in an amount of 7 to 15 weight percent based on the total weight of the solvent and the auxiliary solvent. The sulfonating agent is present in a step where the weight ratio of the sulfonating agent to poly(phenylene ether) is less than 0.5:1, preferably 0.1:1 to 0.45:

1. A sulfonated poly(phenylene ether) characterized by being produced by a method comprising the above.

4. A sulfonated poly(phenylene ether) according to claim 3, characterized in that the sulfonated poly(phenylene ether) is produced by a method further comprising the steps of adding the mixture containing the sulfonated poly(phenylene ether) to a poor solvent containing water and an organic solvent that is immiscible with water and does not form an azeotrope with 1,2-dichloroethane or ethyl acetate to form a slurry containing precipitated sulfonated poly(phenylene ether), and isolating the sulfonated poly(phenylene ether).

5. A sulfonated poly(phenylene ether) according to any one of claims 1 to 4, wherein Z ２ A sulfonated poly(phenylene ether) characterized in that at least one of the groups is a sulfonic acid group or a sulfonyl chloride group.

6. A sulfonated poly(phenylene ether) according to any one of claims 1 to 5, wherein Z １ A sulfonated poly(phenylene ether) characterized in that each of these is a methyl group.

7. A sulfonated poly(phenylene ether) according to any one of claims 1 to 6, characterized in that the sulfonated poly(phenylene ether) has a total residual ethyl acetate content of less than 0.05% by weight, based on the total weight of the sulfonated poly(phenylene ether) as determined by gas chromatography.

8. The sulfonated poly(phenylene ether) according to claim 1, wherein the sulfonated poly(phenylene ether) is of the formula 【Chemistry 2】 Includes repeating units, The sulfonated poly(phenylene ether) has a degree of sulfonation of 15 to 40 percent when determined by nuclear magnetic resonance spectroscopy. At least 90% of the repeating units of the sulfonated poly(phenylene ether) are monosubstituted. The sulfonated poly(phenylene ether), when determined using gas chromatography, has a total residual solvent content of less than 0.2% by weight, based on the total weight of the sulfonated poly(phenylene ether). The aforementioned sulfonated poly(phenylene ether) The step involves contacting poly(phenylene ether) with a sulfonating agent in the presence of a solvent containing 1,2-dichloroethane and an ethyl acetate cosolvent to obtain a mixture containing the sulfonated poly(phenylene ether). The poly(phenylene ether) is present in an amount of 8 to 25 weight percent based on the total weight of the poly(phenylene ether), the sulfonating agent, the solvent, and the auxiliary solvent. The auxiliary solvent is present in an amount of 7 to 15 weight percent based on the total weight of the solvent and the auxiliary solvent. The sulfonating agent is present in a weight ratio of sulfonating agent to poly(phenylene ether) of 0.1:1 to 0.45:1, and the steps are as follows: The step of adding the mixture containing the sulfonated poly(phenylene ether) to a poor solvent containing water and an organic solvent that is immiscible with water and does not form an azeotrope with either 1,2-dichloroethane or ethyl acetate to form a slurry containing the precipitated sulfonated poly(phenylene ether), The steps include isolating the precipitated sulfonated poly(phenylene ether) and Produced by a method including A sulfonated poly(phenylene ether) characterized by the following features.

9. A film characterized by containing the sulfonated poly(phenylene ether) described in any one of claims 1 to 8.

10. A method for producing sulfonated poly(phenylene ether), The process involves contacting poly(phenylene ether) with a sulfonating agent in the presence of a solvent containing 1,2-dichloroethane and an auxiliary solvent containing ethyl acetate, under conditions effective for obtaining a mixture containing the sulfonated poly(phenylene ether), and The step is to isolate the sulfonated poly(phenylene ether) from the mixture, The poly(phenylene ether) is present in an amount of 8% by weight or more based on the total weight of the poly(phenylene ether), the sulfonating agent, the solvent, and the auxiliary solvent, preferably in an amount of more than 10% by weight and up to 25% by weight. The auxiliary solvent is present in an amount of 7 to 15 weight percent based on the total weight of the solvent and the auxiliary solvent. The sulfonating agent is present in a weight ratio of sulfonating agent to poly(phenylene ether) of less than 0.5:1, preferably 0.1:1 to 0.45:

1. Steps and A method characterized by including the following.

11. A method according to claim 10 or 11, The step of adding the mixture containing the sulfonated poly(phenylene ether) to a poor solvent containing water and an organic solvent that is immiscible with water and does not form an azeotrope with either 1,2-dichloroethane or ethyl acetate to form a slurry containing the precipitated sulfonated poly(phenylene ether), The steps include isolating the sulfonated poly(phenylene ether) and Optionally, the isolated sulfonated poly(phenylene ether) is washed with the poor solvent. A method characterized by further comprising:

12. A method according to claim 11, characterized in that the organic solvent comprises cyclopentane or cycloheptane, preferably cyclopentane.

13. A method according to any one of claims 10 to 12, characterized in that the isolated sulfonated poly(phenylene ether) has a degree of sulfonation of 15 to 50 percent as determined by nuclear magnetic resonance spectroscopy, at least 90% of the sulfonation repeating units of the sulfonated poly(phenylene ether) are monosubstituted, and optionally the isolated sulfonated poly(phenylene ether) has a total residual solvent content of less than 0.2 weight percent based on the total weight of the sulfonated poly(phenylene ether) as measured by gas chromatography.

14. The method according to claim 10, The step involves contacting the poly(phenylene ether) with the sulfonating agent in the presence of the solvent containing 1,2-dichloroethane and the auxiliary solvent containing ethyl acetate, under conditions effective for obtaining a mixture containing the sulfonated poly(phenylene ether). The poly(phenylene ether) is present in an amount of 8 to 25 weight percent based on the total weight of the poly(phenylene ether), the sulfonating agent, the solvent, and the auxiliary solvent. The auxiliary solvent is present in an amount of 7 to 15 weight percent based on the total weight of the solvent and the auxiliary solvent. The sulfonating agent is present in a weight ratio of sulfonating agent to poly(phenylene ether) of 0.1:1 to 0.45:1, and the steps are as follows: The step of adding the mixture containing the sulfonated poly(phenylene ether) to a poor solvent containing water and an organic solvent that is immiscible with water and does not form an azeotrope with either 1,2-dichloroethane or ethyl acetate to form a slurry containing the precipitated sulfonated poly(phenylene ether), The steps include isolating the precipitated sulfonated poly(phenylene ether), Optionally, the isolated sulfonated poly(phenylene ether) is washed with the poor solvent. Includes, The organic solvent includes cyclopentane or cycloheptane. The isolated sulfonated poly(phenylene ether) has a degree of sulfonation of 15 to 50 percent as determined by nuclear magnetic resonance spectroscopy, and at least 90% of the sulfonation repeating units of the sulfonated poly(phenylene ether) are monosubstituted. Optionally, the isolated sulfonated poly(phenylene ether) has a total residual solvent content of less than 0.2% by weight, based on the total weight of the sulfonated poly(phenylene ether), as determined by gas chromatography. A method characterized by the following:

15. A sulfonated poly(phenylene ether) characterized by being produced by the method described in any one of claims 10 to 14.

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