Method for preparing sulfonated poly(phenylene ether) and articles prepared therefrom

Abstract

A method for sulfonating a poly(phenylene ether) may include: in a mixing container, dissolving a poly(phenylene ether) comprising 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl ether units, or a combination thereof in a mixture of 1,2-dichloroethane and a co-solvent to form a solvent mixture, wherein the co-solvent comprises at least one of methyl ethyl ketone, diethyl ether, methyl ethyl sulfone, ethyl acetate, or tetramethylene sulfone; combining a sulfonating agent with the solvent mixture, wherein the sulfonating agent reacts with the poly(phenylene ether) to form a sulfonated poly(phenylene ether); precipitating the sulfonated poly(phenylene ether); and filtering the precipitated sulfonated poly(phenylene ether) to form a sulfonated poly(phenylene ether) precipitate and a filtrate; wherein the sulfonated poly(phenylene ether) has a sulfonation level of 20 to 50%.

Description

Background Art

[0001] Disclosed herein is a method for preparing sulfonated poly(phenylene ether).

[0002] Poly(phenylene ether) is a commercially attractive material due to a unique combination of physical, chemical and electrical properties. In addition, the combination of poly(phenylene ether) with other polymers or additives provides blends that improve overall properties, including chemical resistance, high strength and high flow. As new commercial applications are explored, various sulfonated grades of poly(phenylene ether) materials are needed.

[0003] Conventional methods for sulfonation of poly(phenylene ether) produce heterogeneity as the sulfonation level increases, affecting the reaction system and making further sulfonation impossible.

[0004] There is a need in the art for a scalable process for the sulfonation of poly(phenylene ether) to levels as high as 50% sulfonation and preferably with improved efficiency. Summary of the invention

[0005] Disclosed herein are methods for the sulfonation of poly(phenylene ether).

[0006] A method for sulfonating a poly(phenylene ether) may include: dissolving a poly(phenylene ether) comprising 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl ether units, or a combination thereof in a mixture of 1,2-dichloroethane and a co-solvent to form a solvent mixture, wherein the co-solvent comprises at least one of methyl ethyl ketone, diethyl ether, methyl ethyl sulfone, ethyl acetate, or tetramethylene sulfone; combining a sulfonating agent with the solvent mixture, wherein the sulfonating agent reacts with the poly(phenylene ether) to form a sulfonated poly(phenylene ether); precipitating the sulfonated poly(phenylene ether); and filtering the precipitated sulfonated poly(phenylene ether) to form a sulfonated poly(phenylene ether) precipitate and a filtrate, wherein the sulfonation level of the sulfonated poly(phenylene ether) is 20 to 50%. BRIEF DESCRIPTION OF THE DRAWINGS

[0007] Reference is now made to the accompanying drawings which are illustrative and non-limiting.

[0008] Figure 1 is a schematic diagram of one embodiment of a system for sulfonation of poly(phenylene ether).

[0009] Figure 2 is a schematic diagram of another embodiment of a system for sulfonation of poly(phenylene ether).

[0010] Figure 3 is a schematic diagram of another embodiment of a system for sulfonation of poly(phenylene ether).

[0011] Figure 4 The NMR graph shows the degree of sulfonation. DETAILED DESCRIPTION

[0012] A method has been developed for reliably sulfonating poly(phenylene ether) to a degree of sulfonation of 20 to 50%. The method is scalable and allows the production of poly(phenylene ether) having different levels of sulfonation. For example, the method is capable of sulfonating poly(phenylene ether) to a sulfonation level of up to 50% while maintaining homogeneity, and preferably is capable of recovering and recycling the solvent. This is accomplished using a reaction solvent mixture comprising 1,2-dichloroethane and a cosolvent, such as at least one of ethyl acetate or tetramethylene sulfone. The presence of the cosolvent enables reaction homogeneity to be achieved at progressive poly(phenylene ether) sulfonation levels when relatively high stoichiometric amounts of a sulfonating agent, such as chlorosulfonic acid, are involved. For example, poly(phenylene ether) can be sulfonated to 20 to 50% while maintaining a homogeneous system.

[0013] It has been determined that inhibiting precipitation during the sulfonation process can control the level of sulfonation. Preferably, in order to make the process scalable and efficient, it is important to effectively treat the effluent from the process. In the present process, the solvent can be recovered and recycled at a rate greater than or equal to 80 weight percent (wt%) based on the total weight of the solvent introduced into the system.

[0014] The ability to efficiently produce poly(phenylene ether) with 20 to 50% sulfonation levels allows for the production of a variety of different products, such as ion exchange membranes for dialysis, proton conducting 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.

[0015] The degree of sulfonation can be controlled by adjusting the amount of solvent, and in particular the co-solvent, in the process and by the amount of the sulfonating agent used. The process comprises dissolving a poly(phenylene ether) in a solvent, adding a sulfonating agent to the mixture, and sulfonating the poly(phenylene ether). The solvent comprises 1,2-dichloroethane. The co-solvent comprises at least one of methyl ethyl ketone, diethyl ether, methyl ethyl sulfone, ethyl acetate (EA), or tetramethylene sulfone; preferably comprises at least one of ethyl acetate or tetramethylene sulfone, and more preferably comprises ethyl acetate.

[0016] Poly(phenylene ether)s include those comprising repeating structural units having the formula

[0017]

[0018] Each occurrence of Z 1 independently contain halogen, unsubstituted or substituted C1-C 12Hydrocarbon (provided that the hydrocarbon group is not a tertiary hydrocarbon group), C1-C 12 Hydrocarbon thio group, C1-C 12 Hydroxyl or C2-C 12 haloalkyloxy, wherein at least two carbon atoms separate the halogen from the oxidogen; and each occurrence of Z 2 independently contain hydrogen, halogen, unsubstituted or substituted C1-C 12 Hydrocarbon (provided that the hydrocarbon group is not a tertiary hydrocarbon group), C1-C 12 Hydrocarbon thio group, C1-C 12 Hydroxyl or C2-C 12 A halogenated hydrocarbon group, in which at least two carbon atoms separate the halogen from the oxygen atom. As used herein, the term "hydrocarbyl", whether used alone 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, saturated or unsaturated. It can also contain a combination of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated and unsaturated hydrocarbon parts. However, when a hydrocarbyl hydrocarbyl residue is described as being substituted, it may optionally contain heteroatoms in addition to the carbon and hydrogen members of the substituent residue. Therefore, when specifically described as being substituted, the hydrocarbyl residue may also contain one or more carbonyl groups, amino groups, hydroxyl groups, etc., or it may contain heteroatoms in the main chain of the hydrocarbyl residue. As an example, Z 1 It may be a di-n-butylaminomethyl group formed by reacting a terminal 3,5-dimethyl-1,4-phenyl group with a di-n-butylamine component of an oxidative polymerization catalyst.

[0019] In some embodiments, the poly(phenylene ether) comprises 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or combinations thereof. In some embodiments, the poly(phenylene ether) is poly(2,6-dimethyl-1,4-phenylene ether). In some embodiments, the poly(phenylene ether) comprises poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.03 to 2 deciliters per gram (dl / g). For example, the intrinsic viscosity of the poly(phenylene ether) can be 0.25 to 1.7 dl / g, 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.

[0020] In some embodiments, the poly(phenylene ether) may include molecules having aminoalkyl-containing end groups, typically located in an ortho position to the hydroxyl group. Tetramethyldiphenoquinone (TMDQ) end groups are also frequently present, typically obtained from a reaction mixture containing 2,6-dimethylphenol in which tetramethyldiphenoquinone byproduct is present. The poly(phenylene ether) may be in the form of a homopolymer, copolymer, graft copolymer, ionomer, block copolymer, or oligomer, and combinations thereof.

[0021] As used herein, poly(phenylene ether) may also refer to low molecular weight phenylene ether oligomers. In some embodiments, 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 some embodiments, the intrinsic viscosity of the phenylene ether oligomer may be 0.03 to 0.13 deciliters / gram, or 0.05 to 0.1 deciliters / gram, or 0.1 to 0.15 deciliters / gram, measured in chloroform at 25°C using an Ubbelohde viscometer. The number average molecular weight of the phenylene ether oligomer may be 500 to 7,000 g / mole and the weight average molecular weight may be 500 to 15,000 g / mole, as determined by gel permeation chromatography using a polystyrene standard. In some embodiments, the number average molecular weight may be 750 to 4,000 g / mole and the weight average molecular weight may be 1,500 to 9,000 g / mole as determined by gel permeation chromatography using polystyrene standards.

[0022] The phenylene ether oligomer can be monofunctional or difunctional. In some embodiments, the phenylene ether oligomer can be monofunctional. For example, it can have a functional group at one end of the polymer chain. The functional group can be, for example, a hydroxyl group or a (meth) acrylate group, preferably a (meth) acrylate group. In some embodiments, the phenylene ether oligomer comprises poly (2,6-dimethyl-l,4-phenylene ether).

[0023] In some embodiments, the phenylene ether oligomer may be bifunctional. For example, it may have functional groups at both ends of the oligomer chain. The functional groups may be, for example, hydroxyl groups or (meth)acrylate groups, preferably (meth)acrylate groups. Bifunctional polymers having functional groups at both ends of the polymer chain are also referred to as "telechelic" polymers. In some embodiments, the phenylene ether oligomer comprises a bifunctional phenylene ether oligomer having the following structure,

[0024]

[0025] Where Q 1 and Q 2 Each independently contains halogen, unsubstituted or substituted C1-C12 Primary or secondary hydrocarbon, C1-C 12 Hydrocarbon thio group, C1-C 12 Alkyloxy and C2-C 12 A haloalkyloxy group in which at least two carbon atoms separate the halogen from the oxygen atom; each occurrence of Q 3 and Q 4 independently contain hydrogen, halogen, unsubstituted or substituted C1-C 12 Primary or secondary hydrocarbon, C1-C 12 Hydrocarbon thio group, C1-C 12 Alkyloxy and C2-C 12 a halohydrocarbyloxy group in which at least two carbon atoms separate the halogen and oxygen atoms; Z is hydrogen or (meth)acrylate; x and y are independently 0 to 30, specifically 0 to 20, more specifically 0 to 15, still more specifically 0 to 10, even more specifically 0 to 8, provided that the sum of x and y is at least 2, specifically at least 3, more specifically at least 4; and L has the structure

[0026]

[0027] Each occurrence of R 3 and R 4 and R 5 and R 6 independently contain hydrogen, halogen, unsubstituted or substituted C1-C 12 Primary or secondary hydrocarbon, C1-C 12 Hydrocarbon thio group, C1-C 12 Alkyloxy and C2-C 12 a haloalkyloxy group in which at least two carbon atoms separate the halogen and oxygen atoms; z is 0 or 1; and Y has a structure comprising the formula,

[0028]

[0029] Each occurrence of R 7 independently contain hydrogen and C1-C 12 hydrocarbon group, and each occurrence of R 8 and R 9 independently contain hydrogen, C1-C 12 Hydrocarbyl and C1-C6 alkylene (where R 8 and R 9 Together they form C 4- C 12 alkylene).

[0030] In one embodiment, the phenylene ether oligomer comprises a difunctional phenylene ether oligomer having the structure,

[0031]

[0032] Where Q 1 , Q 2 , Q 3 , Q 4 , L, x and y are as defined above, R 10 Methyl or hydrogen.

[0033] In the above (meth)acrylate terminated phenylene ether structure, there are restrictions on variables x and y, which correspond to the number of phenylene ether repeating units at two different positions in the difunctional phenylene ether oligomer. In the structure, x and y are independently 0 to 30, specifically 0 to 20, more specifically 0 to 15, even more specifically 0 to 10, and even more specifically 0 to 8. The sum of x and y is at least 2, specifically at least 3, and more specifically at least 4. The proton nuclear magnetic resonance spectroscopy ( 1 H NMR) analysis of the phenylene ether oligomers to determine whether, on average, these constraints are met. Specifically, 1 H NMR can distinguish between protons associated with internal and terminal phenylene ether groups, protons associated with internal and terminal residues of polyphenols, and protons associated with terminal residues. Thus, it is possible to determine the average number of phenylene ether repeat units per molecule and the relative abundance of internal and terminal residues derived from dihydric phenols.

[0034] In some embodiments, the phenylene ether oligomer comprises a difunctional phenylene ether oligomer having the structure,

[0035]

[0036] Each occurrence of Q 5 and Q 6 independently comprises methyl, di-n-butylaminomethyl or morpholinomethyl; and each occurrence of a and b is independently 0 to 20, provided that the sum of a to b is at least 2; and each occurrence of R 10 is methyl or hydrogen. Exemplary difunctional phenylene ether oligomers include NORYL available from SABIC Innovative Plastics TM ResinSA9000.

[0037] In some embodiments, the phenylene ether oligomer comprises a difunctional phenylene ether oligomer having the structure,

[0038]

[0039] Each occurrence of Q 5 and Q 6independently comprises methyl, di-n-butylaminomethyl or morpholinomethyl; and each occurrence of a and b is independently 0 to 20, provided that a and b are followed by at least 2. Exemplary difunctional phenylene ether oligomers include NORYL available from SABIC Innovative Plastics TM Resin SA90.

[0040] In some embodiments, the poly(phenylene ether) comprises a poly(phenylene ether) homopolymer, an oligomer, or a combination thereof. The poly(phenylene ether) may preferably comprise poly(2,6-dimethyl-1,4-phenylene ether).

[0041] The poly(phenylene ether) composition may optionally include one or more additives, provided that the one or more additives do not significantly adversely affect one or more desired properties of the poly(phenylene ether) composition. Exemplary additives may include stabilizers, mold release agents, lubricants, processing aids, anti-drip agents, nucleating agents, UV blockers, dyes, pigments, antioxidants, antistatic agents, foaming agents, mineral oils, metal deactivators, anti-blocking agents, and combinations thereof. When present, such additives are typically used in a total amount less than or equal to 10 weight percent, specifically less than or equal to 5 weight percent, based on the total weight of the poly(phenylene ether) composition.

[0042] The method for sulfonating the poly(phenylene ether) comprises dissolving the poly(phenylene ether) in a solvent (preferably a solvent and a co-solvent) to form a solvent mixture. The mixing can be carried out at a temperature of 10°C to 60°C, such as 25°C to 40°C. 1,2-dichloroethane is present in a sufficient amount to dissolve the poly(phenylene ether). The amount of co-solvent is sufficient to prevent the sulfonated poly(phenylene ether) from precipitating before the desired degree of sulfonation is obtained. Based on 100 wt% of the solvent mixture, the solvent mixture can include 1 wt% to 20 wt%, preferably 5 wt% to 10 wt% poly(phenylene ether); 80 wt% to 99 wt%, preferably 90 wt% to 95 wt% 1,2-dichloroethane; and 0 to 10 wt% (e.g., greater than 0), preferably greater than 0 to 6.0 wt% co-solvent. The amount of co-solvent is determined based on the desired degree of sulfonation. For example, for 10 to 20% sulfonation, the solvent mixture may contain 1 wt% to 20 wt%, preferably 5 wt% to 10 wt% poly(phenylene ether); 80 wt% to 99 wt%, preferably 90 wt% to 95 wt% 1,2-dichloroethane; no co-solvent is required. However, for uniform sulfonation above 20%, the presence of a co-solvent is desirable. For example, for a uniform sulfonation level of 25% to 50%, based on 100 wt% weight of the solvent mixture, the solvent mixture may contain 1 wt% to 10 wt%, preferably 5 wt% to 10 wt% poly(phenylene ether); 70 wt% to 90 wt%, preferably 80 wt% to 90 wt% 1,2-dichloroethane, and 1 to 10 wt%, preferably 2 to 6.0 wt% co-solvent.

[0043] The solvent mixture can then be reacted with a sulfonating agent to sulfonate the poly(phenylene ether). The sulfonation can be carried out at a temperature of up to 85°C, such as 10°C to 60°C or 25°C to 40°C. The amount of sulfonating agent added to the solvent mixture can be 0.5 to 1 mole, preferably 0.25 to 0.9 mole, based on a total of 1 mole of poly(phenylene ether) dissolved in the solvent mixture. The specific amount of sulfonating agent added depends on the desired sulfonation level in the sulfonation reaction product. Preferably, the sulfonating agent is slowly added to the solvent mixture, such as over a period of 15 minutes (min) to 60 min (e.g., over a period of 30 min). Once the sulfonating agent is added to the solvent mixture, the solvent mixture can be stirred before precipitation, such as for a period of 60 to 210 min.

[0044] Once the poly(phenylene ether) has been sulfonated, the sulfonated poly(phenylene ether) can be precipitated from the reaction solvent mixture using a reaction mixture, such as an anti-solvent mixture containing deionized (DI) water. For example, at least one of hexane and heptane can be used with deionized water to cause the sulfonated poly(phenylene ether) to precipitate from the reaction solvent mixture. The reaction solvent mixture can be added (e.g., slowly) to the anti-solvent mixture, wherein the anti-solvent mixture can be used in an amount sufficient to cause precipitation. For example, 100 grams (g) of the solvent mixture can be added to 300 g to 700 g, preferably 390 g to 595 g, of an anti-solvent mixture having a weight ratio of hexane to water ranging from 0 to 1.15.

[0045] The precipitated sulfonated poly(phenylene ether) can be filtered and optionally washed and dried. The filtrate can be biphasic, with 1,2-dichloroethane, co-solvent, and optionally organic matter (e.g., hexane) as part of the anti-solvent mixture as the organic phase, and water as the aqueous phase. Therefore, the filtrate can be further processed to recover at least one of 1,2-dichloroethane, co-solvent, or water; preferably 1,2-dichloroethane and co-solvent are recovered, more preferably 1,2-dichloroethane, co-solvent, and water are recovered. Recovering the material can include decanting the biphasic filtrate to form an aqueous stream and an organic stream. The organic stream can be further processed, such as distilled, to recover 1,2-dichloroethane and / or co-solvent. The recovered material can be recycled.

[0046] See now Figure 1, wherein the method is schematically shown. As shown, the method requires the introduction of poly(phenylene ether), 1,2-dichloroethane into a mixing container 10. The mixing container can be maintained at room temperature up to 85°C, for example, 30°C to 60°C, preferably 30°C to 45°C. In the mixing container 10, the poly(phenylene ether), 1,2-dichloroethane and the co-solvent can be mixed, for example, until homogeneous, to form a solvent mixture. Optionally, mixing can be continued until a uniform clear solution is obtained. The solvent mixture from the mixing container 10 can be treated with a sulfonating agent in a reaction vessel 20. The sulfonated poly(phenylene ether) can then be precipitated from the mixture in a precipitation unit 30, for example, once the desired degree of sulfonation is reached. For example, the reaction solvent mixture can be slowly added to an anti-solvent mixture (e.g., a mixture of hexane and deionized water) to induce precipitation of the sulfonated poly(phenylene ether). For example, the precipitated sulfonated poly(phenylene ether) can be separated from the liquid phase in filtration unit 40, and then optionally washed (such as with DI water) in washing units 50, 52, and dried, for example, in dryer 54. At the same time, the liquid phase from filtration unit 40 can be treated to remove water, for example, using liquid-liquid separation in decantation unit 60. The water recovery phase from decantation unit 60 can be treated in a multiple effect evaporator (MEE) 70 to recover water. The resulting water can optionally be recycled to, for example, washing unit 52 or precipitation unit 30. The 1,2-dichloroethane (EDC) stream from decantation unit 60 can be further treated to separate the EDC by distillation in unit 80. The separated EDC can optionally be recycled to, for example, mixing vessel 10.

[0047] See now Figure 2, wherein the method is schematically shown. As shown, the method requires the introduction of poly(phenylene ether), 1,2-dichloroethane and a cosolvent (here ethyl acetate) into a mixing vessel 10. The mixing vessel can be maintained at room temperature up to 85°C, such as 30°C to 60°C, preferably 30°C to 45°C. In the mixing vessel 10, the poly(phenylene ether), 1,2-dichloroethane and the cosolvent can be mixed, for example, until homogeneous to form a solvent mixture. Optionally, mixing can be continued until a uniform clear solution is obtained. The solvent mixture from the mixing vessel 10 can be treated with a sulfonating agent in a reaction vessel 20. For example, once the degree of sulfonation has been obtained, the sulfonated poly(phenylene ether) can be precipitated in a precipitation unit 30. For example, the reaction solvent mixture can be slowly added to an anti-solvent mixture (e.g., DI water) to induce precipitation of the sulfonated poly(phenylene ether). The precipitated sulfonated poly(phenylene ether) may be separated from the liquid phase, for example, in filtration unit 40, and then optionally reslurried with a DI water-hexane mixture, for example, followed by washing (e.g., using DI water) in units 50, 52, and drying in dryer 54. The wash liquor from washing units 50, 52 may optionally be separated into a water stream and a hexane stream in decanting unit 56. The hexane stream may optionally be recycled to reslurry unit 50. Meanwhile, the liquid phase from filtration unit 40 may be treated to remove water using liquid-liquid separation, for example, in decanting unit 60. The aqueous phases from decanting unit 60 and decanting unit 56 may be treated in multiple-effect evaporator 70. The resulting water may optionally be recycled, for example, to reslurry unit 50, washing unit 52, or precipitation unit 30; and is preferably recycled to reslurry unit 50. The EDC stream from the decantation unit 60 may be further processed to separate the EDC, such as by distillation from organics and / or residues in unit 80. The separated EDC may optionally be recycled to, for example, the mixing vessel 10.

[0048] See now Figure 3, wherein the method is schematically shown. As shown, the method requires the introduction of poly(phenylene ether), 1,2-dichloroethane and a cosolvent (e.g., tetramethylene sulfone) into a mixing vessel 10. The mixing vessel can be maintained at room temperature up to 85°C, such as 30°C to 60°C, preferably 30°C to 45°C. Within the mixing vessel 10, the poly(phenylene ether), 1,2-dichloroethane and the cosolvent can be mixed, for example, until homogeneous to form a solvent mixture. Optionally, mixing is continued until a uniform clear solution is obtained. The solvent mixture from the mixing vessel 10 can be treated with a mixing agent in a reaction vessel 20. For example, once the desired degree of sulfonation has been obtained, the sulfonated poly(phenylene ether) can be precipitated from the mixture in a precipitation unit 30. For example, the reaction solvent mixture can be slowly added to DI water (used as an anti-solvent mixture) to induce precipitation of the sulfonated poly(phenylene ether). The precipitated sulfonated poly(phenylene ether) may be separated from the liquid phase, for example, in filtration unit 40, and then optionally reslurried in a DI water-hexane mixture, for example, followed by washing (e.g., using DI water) in units 50, 52, and drying, for example, in dryer 54. The wash liquor from washing units 50, 52 may optionally be separated into a water stream and a hexane stream in decanting unit 56. The hexane stream may optionally be recycled to reslurry unit 50. Meanwhile, the liquid phase from filtration unit 40 may be treated to remove water using liquid-liquid separation, for example, in decanting unit 60. The aqueous phases from decanting unit 60 and decanting unit 56 may be treated in multiple-effect evaporator 70. The resulting water may optionally be recycled, for example, to reslurry unit 50, washing unit 52, or precipitation unit 30; and is preferably recycled to reslurry unit 50. The EDC stream from the decantation unit 60 may be further processed to separate the EDC, for example by distillation from organics and / or residues in unit 80. The separated EDC may optionally be recycled to, for example, the mixing vessel 10.

[0049] The present disclosure is further illustrated by the following non-limiting examples.

[0050] Example

[0051] Example 1: Simulated method for preparing sulfonated polyphenylene ether (sPPE) having 1.5-1.6 milliequivalent / gram (meq / g) ion exchange capacity (IEC). Figure 1 The scheme is shown.

[0052] A 3-neck round bottom glass flask equipped with a TEFLON stirrer, a reflux condenser and a pressure equalizing dropping funnel was maintained at 35°C. 10.0 grams (g) of NORYL PPO TM646-poly(phenylene ether) resin (commercially available from SABIC) was dissolved in 95 g of 1,2-dichloroethane (EDC) until a uniform, clear solution was obtained; 60 minutes (min). The temperature was then lowered to 25 °C. 2.37 g of chlorosulfonic acid was transferred to a pressure equalizing dropping funnel and added to the 1,2-dichloroethane solution over a period of 30 minutes under vigorous stirring. The dropping funnel was rinsed with 5 g of 1,2-dichloroethane. Despite rapid stirring, a nitrogen purge was maintained. At the end of the addition, the stirred solution became slightly turbid. Stirring was continued for an additional 60 minutes at 25 °C. The reaction mass was then slowly transferred to a 2 liter (L) baffled precipitation vessel maintained at 10°C and equipped with a 4-blade agitator of approximately 60 millimeters (mm) in diameter, running at 1,000 revolutions per minute (rpm) with a tip speed of 3.14 meters per second (m / s) along with hexane-deionized (DI) water ((350 milliliters (ml):200 ml) anti-solvent mixture). The temperature was then raised to 25°C after 1 hour. Stirring was continued for a total of 8 hours. Thereafter, filtration was performed. The residue (sulfonated poly(phenylene ether) (sPPE)) was then re-slurried in DI water and re-filtered. The residue was thoroughly washed with DI water to a neutral pH. The sulfonated material was then vacuum dried at room temperature for 48 hours (h).

[0053] An industrial process scheme for making sulfonated polyphenylene ether (sPPE) includes dissolving polyphenylene ether (PPE) in 1,2-dichloroethane (based on 100 kilograms per hour (kg / h) of poly(phenylene ether)) with a residence time of 10 to 15 minutes. The dissolved 1,2-dichloroethane enters a reaction vessel, where a reaction with chlorosulfonic acid (23.7 kg / h) is carried out, and the molar ratio of chlorosulfonic acid to poly(phenylene ether) is 0.249. The reaction temperature is 25° C. and the residence time is 30 min. The hydrochloride (HCl) gas formed in the process is discharged from the reactor and washed using an alkaline scrubber. The reaction mass from the reactor is precipitated in a precipitation vessel, and the volume ratio of the starting poly(phenylene ether) to the anti-solvent mixture is 1:55.

[0054] The precipitated material was filtered, the wet sPPE was passed through two wash vessels for purification and dried in a dryer at a temperature of 50 to 60°C under a reduced pressure of 100 millimeters of mercury (mmHg). The filtrate was biphasic, with 1,2-dichloroethane (EDC) and hexane as the organic phase and water as the aqueous phase. Decantation (liquid-liquid separation) was performed to separate the EDC layer from the water, and then distillation was performed to separate the EDC from the heavies. EDC forms a heterogeneous azeotrope with water. The distillation operation separates the EDC into a distillate (which can be recycled) and the organic heavies at the bottom. The recycling efficiency of water and solvent is over 90%. The entire scheme was simulated in Aspen to understand the recovery and recycling.

[0055] Example 2: Simulated method for preparing sPPE with IEC of 1.8-2.0 meq / g. Figure 2 The scheme is shown.

[0056] A 3-neck round bottom glass flask equipped with a TEFLON stirrer, a reflux condenser and a pressure equalizing dropping funnel was maintained at 40°C. 10.0 g of NORYL PPO TM 646-poly(phenylene ether) resin was dissolved in a mixture of 1,2-dichloroethane and ethyl acetate (EA) (179.5 g: 11.7 g) until a uniform clear solution was obtained; 60 min. The temperature was maintained at 40 ° C. 5.85 g of chlorosulfonic acid was transferred to a pressure equalizing dropping funnel and added to the 1,2-dichloroethane-ethyl acetate solution mixture over a period of 30 minutes under vigorous stirring. A nitrogen purge was continuously introduced under rapid stirring. At the end of the addition, the stirred solution became slightly turbid. Stirring was continued at 40 ° C for an additional 210 minutes. The reaction mass was then slowly transferred to a 2L baffled precipitation vessel with 1,200 ml of DI water (e.g., as an anti-solvent mixture), which was maintained at 10 ° C and equipped with a 4-blade stirrer with a diameter of about 60 mm, which was operated at 1,000 rpm with a tip speed of 3.14 m / s. Subsequently, the temperature was raised to 25 ° C after 1 hour. Stirring was continued for a total of 30 min. Thereafter, filtration was performed. The residue (sulfonated PPO) was then re-slurried in a DI water-hexane (500 ml:70 ml) mixture and re-filtered. The residue was washed thoroughly with DI water to a neutral pH. The sulfonated material was then dried under vacuum at room temperature for 48 hours.

[0057] The industrial process scheme for making sulfonated PPO (sPPE) includes dissolving poly(phenylene ether) in 1,2-dichloroethane and ethyl acetate (based on 100 kg / h poly(phenylene ether)) in an amount of 89.2 wt% EDC, 4.97 wt% poly(phenylene ether) and 5.83 wt% EA based on the total weight of poly(phenylene ether), EA and EDC. The residence time is 10 to 15 minutes. The dissolved poly(phenylene ether) is carried out in a reaction vessel, in which a reaction with chlorosulfonic acid (58.5 kg / h) is carried out, and the molar ratio of chlorosulfonic acid to poly(phenylene ether) is 0.613. The reaction temperature is 40°C and the residence time is 30 min. The HCl gas generated in the process is discharged from the reactor and washed using an alkaline scrubber. The reaction mass from the reactor is deposited in a precipitation vessel, with a starting poly(phenylene ether):water volume ratio of 1:120.

[0058] The precipitated material was filtered, the wet sPPE was passed through two wash vessels for purification, and dried in a dryer at a temperature of 50 to 60° C. under a reduced pressure of 100 millimeters of mercury (mmHg). The filtrate was biphasic, with 1,2-dichloroethane and EA as the organic phase, and water as the aqueous phase. Decantation (liquid-liquid separation) was performed to separate EDC and EA from water, and then distillation was performed to separate EDC and EA. Both EDC and EA form heterogeneous azeotropes with water. The distillation operation separated EDC and EA as recyclable distillates, and the organic heavies were at the bottom. The recycling efficiency of water and solvent exceeded 90%. The entire scheme was simulated in Aspen to understand the recovery and recycling.

[0059] Example 3: Simulated method for preparing sPPE with IEC of 1.8-2.0 meq / g. Figure 2 The scheme is shown.

[0060] A 3-neck round bottom glass flask equipped with a TEFLON stirrer, a reflux condenser and a pressure equalizing dropping funnel was maintained at 40°C. 10.0 g of NORYL PPO TM 646-poly(phenylene ether) resin was dissolved in a mixture of 1,2-dichloroethane and ethyl acetate (93.9 g:6.12 g) until a uniform clear solution was obtained; 60 min. The temperature was maintained at 40 ° C. Chlorosulfonic acid (5.9 g) was accurately transferred to a pressure equalizing dropping funnel and added to the 1,2-dichloroethane and ethyl acetate mixture over a period of 30 min under vigorous stirring. Despite rapid stirring, nitrogen purge was maintained. At the end of the addition, the stirred solution became slightly turbid. Stirring was continued at 40 ° C for an additional 210 minutes. The reaction mass was then slowly transferred to a 2L baffled precipitation vessel along with 500 ml of DI water (used as an anti-solvent mixture), which was maintained at 10 ° C and equipped with a 4-blade stirrer with a diameter of about 60 mm, which was operated at 1,000 rpm with a tip speed of 3.14 m / s. Subsequently, the temperature was raised to 25 ° C after 1 hour. Stirring was continued for a total of 30 min. Thereafter, filtration was performed. The residue (sPPE) was then re-slurried in a DI water / hexane (435 ml:65 ml) mixture and re-filtered. The residue was washed thoroughly with DI water to a neutral pH. The sulfonated poly(phenylene ether) was then vacuum dried at room temperature for 48 hours.

[0061] The industrial process scheme for making sulfonated poly(phenylene ether) comprises dissolving poly(phenylene ether) in 1,2-dichloroethane and ethyl acetate (based on 100 kg / h poly(phenylene ether)) in an amount of 85.33 wt% EDC, 9.09 wt% poly(phenylene ether) and 5.58 wt% EA with a residence time of 10 to 15 minutes. The dissolved poly(phenylene ether) is introduced into a reaction vessel, where a reaction with chlorosulfonic acid (59.1 kg / h) is carried out, the molar ratio of chlorosulfonic acid relative to poly(phenylene ether) being 0.62. The reaction temperature is 40° C. and the residence time is 30 min. The HCl gas generated in the process is discharged from the reactor and washed using an alkaline scrubber. The reaction mass from the reactor is precipitated in a precipitation vessel, the poly(phenylene ether):water volume ratio being 1:50.

[0062] The precipitated material was filtered, the wet sPPE was purified by passing it through two wash vessels and dried in a dryer at a temperature of 50 to 60°C and a reduced pressure of 100 mmHg. The filtrate was biphasic, with 1,2-dichloroethane and EA as the organic phase and water as the aqueous phase. Decantation (liquid-liquid separation) was performed to separate EDC and EA from water, followed by distillation to separate EDC and EA. Both EDC and EA form heterogeneous azeotropes with water. The distillation operation separated EDC and EA as distillates, which could be recycled at the bottom along with the organic heavies. The recycling efficiency of water and solvent exceeded 90%. The entire scheme was simulated in Aspen to understand the recovery and recycling.

[0063] Additional reactions were performed to determine the desired sulfonation reaction time in Example 3 after the addition of chlorosulfonic acid. Figure 2 The scheme is shown.

[0064] Embodiment 4:

[0065] A 3-neck round bottom glass flask equipped with a TEFLON stirrer, a reflux condenser and a pressure equalizing dropping funnel was maintained at 40°C. 10.0 g of NORYL PPO TM646-poly(phenylene ether) resin was dissolved in a mixture of 1,2-dichloroethane and ethyl acetate (93.9 g: 6.12 g) until a uniform clear solution was obtained; 60 min. The temperature was maintained at 40 ° C. Chlorosulfonic acid (5.9 g) was accurately transferred to a pressure equalizing dropping funnel and added to the 1,2-dichloroethane and ethyl acetate mixture over a period of 30 min under vigorous stirring. Despite rapid stirring, nitrogen purge was maintained. At the end of the addition, the stirred solution became slightly turbid. Stirring was continued for an additional 60 minutes at 40 ° C. The reaction mass was then slowly transferred to a 2L baffled precipitation vessel along with 500 ml of DI water (used as an anti-solvent mixture), which was maintained at 10 ° C and equipped with a 4-blade stirrer of about 60 mm in diameter, which was operated at 1,000 rpm with a tip speed of 3.14 m / s. Subsequently, the temperature was raised to 25 ° C after 1 hour. Stirring was continued for a total of 30 min. Thereafter, filtration was performed. The residue (sPPE) was then re-slurried in a DI water / hexane (435 ml:65 ml) mixture and re-filtered. The residue was washed thoroughly with DI water to a neutral pH. The sulfonated material was then dried under vacuum at room temperature for 48 hours.

[0066] Embodiment 5:

[0067] A 3-neck round bottom glass flask equipped with a TEFLON stirrer, a reflux condenser and a pressure equalizing dropping funnel was maintained at 40°C. 10.0 g of NORYL PPO TM 646-poly(phenylene ether) resin was dissolved in a mixture of 1,2-dichloroethane and ethyl acetate (93.9 g: 6.12 g) until a uniform clear solution was obtained; 60 min. The temperature was maintained at 40 ° C. Chlorosulfonic acid (5.9 g) was accurately transferred to a pressure equalizing dropping funnel and added to the 1,2-dichloroethane and ethyl acetate mixture over a period of 30 min under vigorous stirring. Despite rapid stirring, nitrogen purge was maintained. At the end of the addition, the stirred solution became slightly turbid. Stirring was continued for an additional 120 minutes at 40 ° C. The reaction mass was then slowly transferred to a 2L baffled precipitation vessel together with 500 ml of DI water (used as an anti-solvent mixture), which was maintained at 10 ° C and equipped with a 4-blade stirrer with a diameter of about 60 mm, which was operated at 1,000 rpm with a tip speed of 3.14 m / s. Subsequently, the temperature was raised to 25 ° C after 1 hour. Stirring was continued for a total of 30 min. Thereafter, filtration was performed. The residue (sPPE) was then re-slurried in a DI water / hexane (435 ml:65 ml) mixture and re-filtered. The residue was washed thoroughly with DI water to a neutral pH. The sulfonated material was then dried under vacuum at room temperature for 48 hours.

[0068] Embodiment 6:

[0069] A 3-neck round bottom glass flask equipped with a TEFLON stirrer, a reflux condenser and a pressure equalizing dropping funnel was maintained at 40°C. 10.0 g of NORYL PPO TM 646-poly(phenylene ether) resin was dissolved in a mixture of 1,2-dichloroethane and ethyl acetate (93.9 g: 6.12 g) until a uniform clear solution was obtained; 60 min. The temperature was maintained at 40 ° C. Chlorosulfonic acid (5.9 g) was accurately transferred to a pressure equalizing dropping funnel and added to the 1,2-dichloroethane and ethyl acetate mixture over a period of 30 min under vigorous stirring. Despite rapid stirring, nitrogen purge was maintained. At the end of the addition, the stirred solution became slightly turbid. Stirring was continued for an additional 180 minutes at 40 ° C. The reaction mass was then slowly transferred to a 2L baffled precipitation vessel along with 500 ml of DI water (used as an anti-solvent mixture), which was maintained at 10 ° C and equipped with a 4-blade stirrer of about 60 mm in diameter, which was operated at 1,000 rpm with a tip speed of 3.14 m / s. Subsequently, the temperature was raised to 25 ° C after 1 hour. Stirring was continued for a total of 30 min. Thereafter, filtration was performed. The residue (sPPE) was then re-slurried in a DI water / hexane (435 ml:65 ml) mixture and re-filtered. The residue was washed thoroughly with DI water to a neutral pH. The sulfonated material was then dried under vacuum at room temperature for 48 hours.

[0070] Embodiment 7:

[0071] A 3-neck round bottom glass flask equipped with a TEFLON stirrer, a reflux condenser and a pressure equalizing dropping funnel was maintained at 40°C. 10.0 g of NORYL PPO TM646-poly(phenylene ether) resin was dissolved in a mixture of 1,2-dichloroethane and ethyl acetate (93.9 g:6.12 g) until a uniform clear solution was obtained; 60 min. The temperature was maintained at 40 ° C. Chlorosulfonic acid (5.9 g) was accurately transferred to a pressure equalizing dropping funnel and added to the 1,2-dichloroethane and ethyl acetate mixture over a period of 30 min under vigorous stirring. Despite rapid stirring, a nitrogen purge was maintained. At the end of the addition, the stirred solution became slightly turbid. Stirring was continued at 40 ° C for an additional 210 minutes. The reaction mass was then slowly transferred to a 2L baffled precipitation vessel along with 500 ml of DI water (used as an anti-solvent mixture), which was maintained at 10 ° C and equipped with a 4-blade stirrer of approximately 60 mm in diameter, which was operated at 1,000 rpm with a tip speed of 3.14 m / s. Subsequently, the temperature was raised to 25 ° C after 1 hour. Stirring was continued for a total of 30 min. Thereafter, filtration was performed. The residue (sPPE) was then re-slurried in a DI water / hexane (435 ml:65 ml) mixture and re-filtered. The residue was washed thoroughly with DI water to a neutral pH. The sulfonated material was then dried under vacuum at room temperature for 48 hours.

[0072] The corresponding data for the product characteristics given in the table below show that the target ion exchange capacity (IEC) can be achieved within 2 hours after the addition of chlorosulfonic acid.

[0073] Example 8: Simulated method for preparing sPPE with IEC of 2.5-3.0 meq / g. Figure 2 The scheme is shown in .

[0074] A 3-neck round bottom glass flask equipped with a TEFLON stirrer, a reflux condenser and a pressure equalizing dropping funnel was maintained at 40°C. 10.0 g of NORYL PPO TM646-poly(phenylene ether) resin was dissolved in a mixture of 1,2-dichloroethane and ethyl acetate (179.5 g: 11.7 g) until a uniform clear solution was obtained; 60 min. The temperature was maintained at 40 ° C. Chlorosulfonic acid (8.78 g) was transferred to a pressure equalizing dropping funnel and added to the mixture of 1,2-dichloroethane and ethyl acetate over a period of 30 minutes under vigorous stirring. A nitrogen purge was continuously introduced under rapid stirring. At the end of the addition, the stirred solution became slightly turbid. Stirring was continued at 40 ° C for an additional 210 minutes. The reaction mass was then slowly transferred to a 2L baffled precipitation vessel along with 1,200 ml of DI water, which was maintained at 10 ° C and equipped with a 4-blade stirrer of approximately 60 mm in diameter, which was operated at 1,000 rpm with a tip speed of 3.14 m / s. Subsequently, the temperature was raised to 25 ° C after 1 hour. Stirring was continued for a total of 30 min. Thereafter, filtration was performed. The residue (sPPE) was reslurried in a mixture of DI water and hexane (500 ml:70 ml) and refiltered. The residue was washed thoroughly with DI water to neutral pH and then dried under vacuum at room temperature for 48 hours.

[0075] The industrial process scheme for making sPPE comprises dissolving poly(phenylene ether) in 1,2-dichloroethane and ethyl acetate (based on 100 kg / h poly(phenylene ether)) in an amount of 89.2 wt% EDC, 4.97 wt% poly(phenylene ether) and 5.83 wt% EA based on the total weight of poly(phenylene ether), EA and EDC, with a residence time of 10 to 15 minutes. The dissolved poly(phenylene ether) is passed into a reaction vessel, where a reaction with chlorosulfonic acid (87.8 kg / h) is carried out, the molar ratio of chlorosulfonic acid relative to PPO being 0.92. The reaction temperature is 40° C. and the residence time is 30 min. The HCl gas generated in the process is discharged from the reactor and washed using an alkaline scrubber. The reaction mass from the reactor is precipitated in a precipitation vessel, with a poly(phenylene ether):water volume ratio of 1:50.

[0076] The precipitated material was filtered, the wet sPPE was passed through two wash containers for purification, and dried in a dryer at a temperature of 50 to 60°C and a reduced pressure of 100 mmHg. The filtrate was biphasic, with 1,2-dichloroethane and EA as the organic phase and water as the aqueous phase. Decantation (liquid-liquid separation) was performed to separate EDC and EA from water, and then distillation was performed to separate EDC and EA. Both EDC and EA form heterogeneous azeotropes with water. The distillation operation separated EDC and EA into recyclable distillates and organic heavies at the bottom. The recycling efficiency of water and solvent exceeded 90%. The entire scheme was simulated in Aspen to understand recovery and recycling.

[0077] Example 9. Method for preparing sulfonated polyphenylene ether having an ion exchange capacity of 2.5-3.0 meq / g. Figure 3 The scheme is shown in .

[0078] A 3-neck round bottom glass flask equipped with a Teflon stirrer, a reflux condenser and a pressure equalizing dropping funnel was maintained at 40°C. 10.0 g of NORYL PPO TM 646-poly (phenylene ether) resin is dissolved in 1,2-dichloroethane and tetramethylene sulfone (179.5g: 11.7g) solvent mixture until a uniform clear solution is obtained. The temperature is maintained at 40°C. 5.85g chlorosulfonic acid is accurately transferred to a pressure equalizing dropping funnel and added to the 1,2-dichloroethane-tetramethylene sulfone solution mixture over a period of 30 minutes under vigorous stirring. Despite rapid stirring, nitrogen purge is maintained. At the end of the addition, the stirred solution becomes slightly turbid. Stirring is continued for an additional 210 minutes at 40°C. The reaction mass is then slowly transferred to a 2L baffled precipitation vessel together with 1200ml DI water-hexane (50: 50w / w) (used as an anti-solvent mixture), which is maintained at 10°C and equipped with a 4-blade stirrer with a diameter of about 60mm, which is operated at 1000rpm with a tip speed of 3.14m / s. Subsequently, the temperature is raised to 25°C after 1 hour. Stirring was continued for a total of 30 min. Filtration was then performed. The residue (sulfonated poly(phenylene ether)) was then re-slurried in 500 ml of DI water and re-filtered. The residue was washed thoroughly with DI water to a neutral pH. The sulfonated material was then vacuum dried at room temperature for 48 hours.

[0079] The industrial process scheme for making sulfonated poly(phenylene ether) consists of dissolving poly(phenylene ether) in 1,2-dichloroethane and tetramethylene sulfone (based on 100 kg / h poly(phenylene ether)) in an amount of 89.2 wt% EDC, 4.97 wt% poly(phenylene ether) and 5.83 wt% tetramethylene sulfone based on the total weight of poly(phenylene ether), tetramethylene sulfone and EDC, with a residence time of 10 to 15 minutes. The dissolved poly(phenylene ether) is passed into a reaction vessel, where a reaction with chlorosulfonic acid (58.5 kg / h) is carried out, the molar ratio of chlorosulfonic acid relative to poly(phenylene ether) being 0.613. The reaction temperature is 40° C. and the residence time is 30 min. The HCl gas generated in the process is discharged from the reactor and washed using an alkaline scrubber. The reaction mass from the reactor is precipitated in a precipitation vessel, with a starting poly(phenylene ether): anti-solvent mixture volume ratio of 1:120.

[0080] The precipitated material was filtered, the wet sPPE was passed through two wash vessels for purification, and dried in a dryer at a temperature of 50 to 60°C and a reduced pressure of 100 mmHg. The filtrate was biphasic, with 1,2-dichloroethane and tetramethylene sulfone as the organic phase and water as the aqueous phase. Decantation (liquid-liquid separation) was performed to separate EDC and tetramethylene sulfone from water, followed by distillation to separate EDC and tetramethylene sulfone. The distillation operation separated EDC and tetramethylene sulfone into a distillate that could be recycled, with the organic heavies at the bottom. The recycling efficiency of water and solvent exceeded 90%. The entire scheme was simulated in Aspen to understand the recovery and recycling.

[0081] Example 10. Scale-up (500:1 from Example 1): Method for preparing 5 kilograms (kg) of sulfonated polyphenylene ether (sPPE) having an ion exchange capacity (IEC) of 1.5-1.6 milliequivalents / gram (meq / g).

[0082]

[0083] A 100 L multi-neck reactor equipped with an overhead stirrer, reflux condenser, addition port, and nitrogen purge was charged with NORYL PPO TM 646 poly(phenylene ether) resin (at a reaction temperature (RT) of 25 to 30°C) and 1,2-dichloroethylene (EDC). The reaction mass (RM) was heated to 30 to 35°C under stirring to obtain a clear solution. Chlorosulfonic acid was added under nitrogen purge over a period of 20 to 25 minutes under vigorous stirring. The reaction mass was further vigorously stirred for 90 min at RT under nitrogen. The reaction mass was added to a 500 L reactor containing a pre-cooled mixture of 175 L hexane and 100 L DI water. The resulting precipitate was allowed to reach RT and stirred at the same temperature for 10 hours. The solid was filtered and spin dried by a centrifuge, and the wet solid was unloaded. The wet solid was stirred for 4 h at RT using 250 L DI water. The solid was filtered by a centrifuge; the wet solid was fully spin dried and unloaded. The wet solid was re-slurried at RT at neutral pH using an additional 250 L DI water for 14 hours to isolate the sulfonated product.

[0084] The solid was dried in a vacuum tray dryer (VTD) at 35 to 40° C. for 72 h. The obtained sulfonated polymer weighed: about 5.25 kg.

[0085] Example 11: Method for preparing sPPE with IEC of 1.8-2.0 meq / g to determine the effect of co-solvent. Figure 2 The scheme is shown.

[0086] Example 2 was repeated without using a co-solvent. A 3-neck round bottom glass flask equipped with a TEFLON stirrer, a reflux condenser and a pressure equalizing dropping funnel was maintained at 40°C. 10.0 g of NORYL PPO TM 646-poly(phenylene oxide) resin was dissolved in a mixture of 1,2-dichloroethane (179.5 g) until a homogeneous clear solution was obtained; 60 min. The temperature was maintained at 40°C. 5.85 g of chlorosulfonic acid was transferred to a pressure equalizing dropping funnel and added to the 1,2-dichloroethane solution mixture over a period of 30 minutes under vigorous stirring. A nitrogen purge was continuously introduced under rapid stirring. At the end of this addition, the reaction mass developed heterogeneity and the product precipitated from the reaction mass. Stirring was continued at 40°C for an additional 210 minutes. The reaction mass was then slowly transferred to a 2L baffled precipitation vessel along with 1,200 ml of DI water (e.g., as an anti-solvent mixture), which was maintained at 10°C and equipped with a 4-blade stirrer of approximately 60 mm in diameter, which was operated at 1,000 rpm with a tip speed of 3.14 m / s. Subsequently, the temperature was raised to 25°C after 1 hour. Stirring was continued for a total of 30 min. Thereafter, filtration was performed. The residue (sulfonated PPO) was then re-slurried and re-filtered in a DI water-hexane (500 ml:70 ml) mixture. The residue was washed thoroughly with DI water to a neutral pH. The sulfonated material was then dried under vacuum at room temperature for 48 hours.

[0087] Once isolated using the exact procedure as described in Example 2, the sulfonated product has a degree of sulfonation of 20 to 24% (non-uniform) as measured by NMR. This level is lower than the degree of sulfonation of 31.42% in Example 2 using ethyl acetate as a co-solvent. The development of heterogeneity in the sulfonated polymer and the subsequent phase separation prevented further sulfonation beyond 24%. However, as shown in Examples 2 to 9, the inclusion of a co-solvent ensures reaction homogeneity during the sulfonation process, resulting in a higher degree of sulfonation in the product, such as 24% here and 31% in Example 2.

[0088] Ion exchange capacity determined by potentiometric method: The ion exchange capacity (IEC) indicates the number of milliequivalents of ions in 1 g of dry polymer. The degree of substitution (DS) indicates the percentage of repeating units carrying sulfonic acid groups along the sulfonated polymer molecule chain. The method comprises dissolving the sPPE in a dimethylacetamide / isopropanol mixture and titrating with alcoholic potassium hydroxide by potentiometric titration. This non-aqueous titration is performed using a Solvatrode (commercially available from Metrohm USA) as an electrode. This method uses two solvent systems. Therefore, a sharp and reproducible endpoint is obtained.

[0089] The sample was dissolved in dimethylacetamide and diluted with isopropanol to obtain reproducible ion exchange capacity. When using dimethylacetamide alone, no sharp endpoint was obtained and there was considerable variability in repeated analyses. Without being limited by theory, it is believed that this dual solvent system helps control polarity and achieve a reproducible, sharp endpoint.

[0090]

[0091] Where: A = volume of 0.1N potassium hydroxide (KOH) solution required for titration, in ml;

[0092] B = volume of 0.1N KOH solution required for blank, in ml;

[0093] F = normality of 0.1 N KOH solution; and

[0094] S = sample weight, in grams.

[0095] Degree of sulfonation (DS) (also called sulfonation level) determined by nuclear magnetic resonance spectroscopy (NMR): The samples were dissolved in dimethyl sulfoxide-d6 (DMSO-d6, also called deuterated DMSO) (with the assistance of shaking overnight in a horizontal shaker), 32 scans were averaged with a delay of 5 seconds. In the case of undissolved parts, the solvent vial was sonicated in a water bath at 45°C for 15-30 minutes. Figure 4 An example of the resulting spectrum is shown in .

[0096] The degree of sulfonation can be calculated from aliphatic or aromatic protons:

[0097] Consider the aromatic protons:

[0098]

[0099] Consider aliphatic protons:

[0100]

[0101] Where I is the integrated value of the NMR chemical shift at a given ppm. Reference is made to the NMR spectra in this disclosure.

[0102] Molecular weight: A gel permeation chromatography (GPC) method for estimating the molecular weight (weight average molecular weight (Mw) and number average molecular weight (Mn)) of sPPE was developed using dimethylformamide as a mobile phase with 0.1 wt% (based on the weight of the mobile phase) of lithium bromide as an additive. Agilent 2x (e.g., 2 columns) PLgel 5 microns (μm) MIXED-B, 300x 7.5 mm with one guard column was used to elute the sPPE at a flow rate of 1 milliliter per minute (ml / min) and a column temperature of 400°C. The GPC chromatogram of sPPE was recorded using an ultraviolet (UV) detector (at 254 nanometers (nm)) with an elution time of 30 min. The sample was slowly dissolved in dimethylformamide solvent at a concentration of 2 grams per milliliter (mg / ml) in a horizontal shaker for about 4 to 6 hours. The solution was filtered through a 0.45 μm PTFE filter into a GPC autosampler sample bottle for analysis. The GPC system was calibrated using polystyrene standards ranging from 180 Daltons (Da) to 6870 kDa. Baseline points were set using Agilent ChemStation software.

[0103] Polydispersity Index (PDI or ): can be determined by the following formula:

[0104]

[0105] Estimation of solubility: 0.1 g of sPPE was placed in 10 ml of the corresponding solvent in a polypropylene centrifuge tube. The solvents were tetrahydrofuran (THF), methanol (MeOH), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF) and dimethylacetamide (DMAc). It was kept in a shaker for 24 hours. Any inhomogeneity of the solution was then observed.

[0106]

[0107]

[0108]

[0109] Recovery and recycling of solvents and co-solvents have been studied through simulations and demonstrated in laboratory scale to understand the commercial feasibility of the process involving recovery and recycling of solvent streams. The amount and type of solvents have been selected taking into account the recyclability of the solvent as one of the principles in the claimed scheme.

[0110] In this process, the main solvent used in all examples is 1,2-dichloroethane, which is distilled from traces of water in a distillation unit (80) and recycled. In all cases, the recovery is higher than 99% with respect to 1,2-dichloroethane.

[0111] In Examples 2, 3-7 and 8, ethyl acetate was used as a co-solvent together with 1,2-dichloroethane. Ethyl acetate can be distilled together with 1,2-dichloroethane in the distillation unit (80) and recycled for the sulfonation reaction. The recovery rate of ethyl acetate is higher than 97%.

[0112] In all the above embodiments, the recycling of water is common, after the aqueous phase is separated from the organic phase in the decanter (60), the aqueous layer (mainly water) is evaporated in a multiple effect evaporator and recycled, for example, to the precipitation and / or filtration unit. The recycled water accounts for 90% of the total amount of water, preferably 94% or more.

[0113] Thus, the commercial feasibility of this sulfonation process has been demonstrated, wherein poly(phenylene ether) is sulfonated to 20%-50% using 1,2-dichloroethane and a cosolvent. The cosolvent may be at least one of methyl ethyl ketone, diethyl ether, methyl ethyl sulfone, ethyl acetate, or tetramethylene sulfone, although ethyl acetate has greater recyclability.

[0114] The compositions, methods and articles may alternatively comprise, consist of or consist essentially of any suitable material, step or component disclosed herein. The compositions, methods and articles may additionally or alternatively be formulated so as to lack or be essentially free of any material (or species), step or component that is not necessary to achieve the function or purpose of the compositions, methods and articles.

[0115] A method for sulfonation of poly(phenylene ether) may include: dissolving the poly(phenylene ether) in a mixture of 1,2-dichloroethane and a co-solvent in a mixing container to form a solvent mixture, wherein the co-solvent comprises at least one of methyl ethyl ketone, diethyl ether, methyl ethyl sulfone, ethyl acetate, or tetramethylene sulfone; combining a sulfonating agent with the solvent mixture, wherein the sulfonating agent reacts the poly(phenylene ether) to form a sulfonated poly(phenylene ether); precipitating the sulfonated poly(phenylene ether); and filtering the precipitated sulfonated poly(phenylene ether) to form a sulfonated poly(phenylene ether) precipitate and a filtrate; wherein the sulfonation level of the sulfonated poly(phenylene ether) is 20 to 50%.

[0116] The following aspects further define the method.

[0117] Aspect 1: A method for sulfonation of poly(phenylene ether), comprising: dissolving a poly(phenylene ether) comprising 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl ether units, or a combination thereof in a mixture of 1,2-dichloroethane and a preferred co-solvent to form a solvent mixture; combining a sulfonating agent with the solvent mixture, wherein the sulfonating agent reacts with the poly(phenylene ether) to form a sulfonated poly(phenylene ether); precipitating the sulfonated poly(phenylene ether); and filtering the precipitated sulfonated poly(phenylene ether) to form a sulfonated poly(phenylene ether) precipitate and a filtrate; wherein the sulfonation level of the sulfonated poly(phenylene ether) is 20 to 50%.

[0118] Aspect 2: A method for sulfonation of poly(phenylene ether), comprising: in a mixing container, dissolving the poly(phenylene ether) in a mixture of 1,2-dichloroethane and a preferred co-solvent to form a solvent mixture; combining a sulfonating agent with the solvent mixture, wherein the sulfonating agent reacts with the poly(phenylene ether) to form a sulfonated poly(phenylene ether); precipitating the sulfonated poly(phenylene ether); and filtering the precipitated sulfonated poly(phenylene ether) to form a sulfonated poly(phenylene ether) precipitate and a filtrate; wherein the sulfonated poly(phenylene ether) has a uniform sulfonation level, and the sulfonation level is in the range of 20 to 50%.

[0119] Aspect 3: A method for sulfonation of poly(phenylene ether), comprising: determining a desired sulfonation level; if the desired sulfonation level is greater than 20%, dissolving the poly(phenylene ether) in a mixture of 1,2-dichloroethane and a cosolvent in a mixing container to form a solvent mixture, and if the sulfonation level is less than or equal to 20%, dissolving the poly(phenylene ether) in a mixture of 1,2-dichloroethane and no cosolvent in a mixing container to form a solvent mixture; then combining a sulfonating agent with the solvent mixture, wherein the sulfonating agent reacts with the poly(phenylene ether) to form a sulfonated poly(phenylene ether); precipitating the sulfonated poly(phenylene ether); and filtering the precipitated sulfonated poly(phenylene ether) to form a sulfonated poly(phenylene ether) precipitate and a filtrate. Preferably, the sulfonated poly(phenylene ether) has a uniform sulfonation level.

[0120] Aspect 4: The method according to any one of the preceding aspects, wherein the solvent mixture comprises the co-solvent, and wherein the co-solvent comprises at least one of methyl ethyl ketone, diethyl ether, methyl ethyl sulfone, ethyl acetate, or tetramethylene sulfone.

[0121] Aspect 5: The method according to any one of the preceding aspects, wherein the co-solvent comprises at least one of ethyl acetate or tetramethylene sulfone.

[0122] Aspect 6: The method according to any one of the preceding aspects, wherein the co-solvent comprises ethyl acetate.

[0123] Aspect 7: The method according to any one of the preceding aspects, wherein the co-solvent is ethyl acetate.

[0124] Aspect 8: The method according to any one of the preceding aspects, wherein the dissolving is performed at a temperature of 30°C to 60°C.

[0125] Aspect 9: A method according to any of the preceding aspects, wherein the solvent mixture comprises: 1 to 20 wt% of the poly(phenylene ether); 80 to 99 wt% of 1,2-dichloroethane; and 0 to 10 wt% of the co-solvent, preferably greater than 0 to 10 wt%; wherein the weight percentages are based on 100 wt% of the solvent mixture.

[0126] Aspect 10: A method according to any one of the preceding aspects, wherein the solvent mixture comprises: 1 to 10 wt%, preferably 5 to 10 wt% of poly(phenylene ether); 70 to 90 wt%, preferably 80 to 90 wt% of 1,2-dichloroethane; and 1 to 10 wt%, preferably 2 to 6 wt% of the co-solvent; wherein the weight percentages are based on 100 wt% of the solvent mixture.

[0127] Aspect 11: The method according to any one of the preceding aspects, further comprising recovering the solvent and co-solvent.

[0128] Aspect 12: The method according to aspect 11, wherein recovering the solvent and co-solvent comprises decanting the filtrate to form an organic stream, and distilling the organic stream.

[0129] Aspect 13: The method according to any one of aspects 11-12, further comprising recycling the solvent and co-solvent to the mixing vessel.

[0130] Aspect 14: The method according to any one of the preceding aspects, wherein the sulfonation level determined by NMR is from 25% to 50%, preferably from 28% to 50%.

[0131] Aspect 15: The method according to any of the preceding aspects, wherein the sulfonated poly(phenylene ether) has a uniform sulfonation level, as determined by NMR, in the range of 20 to 50%, preferably in the range of 25 to 50%, more preferably 28 to 50%.

[0132] Aspect 16: The method according to any one of the preceding aspects, wherein greater than 97 wt%, preferably greater than or equal to 99 w%, of the 1,2-dichloroethane is recycled.

[0133] Aspect 17: The method according to any one of the preceding aspects, wherein greater than 95 wt%, preferably greater than or equal to 97 w% of the co-solvent is recycled.

[0134] Aspect 18: The method according to any of the preceding aspects, wherein greater than 90 wt%, preferably greater than or equal to 93 w%, of the water used in the process is recycled.

[0135] All ranges disclosed herein include endpoints, and the endpoints can be combined independently of each other (e.g., the range "up to 25wt%, or more specifically 5wt% to 20wt%" includes the endpoints of the range "5wt% to 25wt%" and all intermediate values, etc.). "Combination" includes blends, mixtures, alloys, reaction products, etc. The terms "first", "second", etc. do not indicate any order, quantity, or importance, but are used to distinguish one element from another. The terms "a" and "an" and "the" do not indicate a number limit, but should be interpreted as covering the singular and plural, unless otherwise specified herein or clearly contradictory to the context. "Or" means "and / or", unless otherwise explicitly stated. References to "some embodiments", "one embodiment", etc. throughout the specification mean that the specific elements described in conjunction with the embodiments are included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it should be understood that the described elements can be combined in any suitable manner in various embodiments. "Combinations thereof" is open ended and includes any combination comprising at least one of the listed components or properties, optionally together with unlisted similar or equivalent components or properties.

[0136] As used herein, the term "hydrocarbyl", whether used alone 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, saturated or unsaturated. It can also contain a combination of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated and unsaturated hydrocarbon parts. However, when the hydrocarbyl residue is described as substituted, in addition to the carbon and hydrogen members of the substituent residue, it can optionally contain heteroatoms. Therefore, when specifically described as substituted, the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, etc., or it can contain heteroatoms within the backbone of the hydrocarbyl residue.

[0137] As used herein, "homogeneous" means having the same degree of sulfonation in a separate mass of the sulfonated polymer product, as determined by sieving at least five small samples taken from the entire product mass. 1 Confirmed by H-NMR.

[0138] All mass percentages are based on a total amount of 100% by weight.

[0139] Unless otherwise specified herein, all test standards are the most current standards in effect as of the filing date of this application or, if priority is claimed, the filing date of the earliest priority application in which the test standards appear.

[0140] Unless otherwise defined, the technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which this application belongs. All cited patents, patent applications and other references are incorporated herein by reference in their entirety. However, if a term in this application contradicts or conflicts with a term incorporated in a reference, the term in this application takes precedence over the conflicting term incorporated in the reference.

[0141] Compounds are described using standard nomenclature. For example, any position not substituted by any specified group is understood to have its valence filled by the specified bond or hydrogen atom. A dash ("-") that is not between two letters or symbols is used to indicate the point of attachment of a substituent. For example, -CHO is attached through the carbon of the carbonyl group.

[0142] Although specific embodiments have been described, the applicant or other persons skilled in the art may think of alternatives, modifications, variations, improvements, and substantial equivalents that are not currently foreseeable or may not be foreseeable. Therefore, the appended claims as filed and as they may be amended are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A method for the sulfonation of poly(phenylene ether), comprising: dissolving a poly(phenylene ether) comprising 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl ether units, or a combination thereof in a mixture of 1,2-dichloroethane and a co-solvent to form a solvent mixture, the co-solvent comprising at least one of methyl ethyl ketone, diethyl ether, ethyl acetate, or a combination thereof; combining a sulfonating agent with the solvent mixture, wherein the sulfonating agent reacts with the poly(phenylene ether) to form a sulfonated poly(phenylene ether); precipitating the sulfonated poly(phenylene ether); and filtering the precipitated sulfonated poly(phenylene ether) to form a sulfonated poly(phenylene ether) precipitate and a filtrate; Wherein the sulfonated poly(phenylene ether) has a sulfonation level of 20 to 50%.

2. The method according to claim 1, wherein the co-solvent further comprises at least one of methyl ethyl sulfone, tetramethylene sulfone, or a combination thereof.

3. The method according to claim 1 or 2, wherein the co-solvent comprises ethyl acetate and tetramethylene sulfone.

4. The method of claim 1 or 2, comprising 2 to 6 wt% of a co-solvent, and wherein the co-solvent comprises ethyl acetate.

5. The method according to claim 1, wherein the co-solvent is ethyl acetate.

6. The method according to claim 1 or 2, wherein the dissolving is performed at a temperature of 30°C to 60°C.

7. The method according to claim 1 or 2, wherein the solvent mixture comprises: 1 to 20 wt% of said poly(phenylene ether); 80 to 99 wt% 1,2-dichloroethane; and greater than 0 to 10 wt % of said co-solvent; The weight percentages are based on 100 wt % of the solvent mixture.

8. The method according to claim 1 or 2, wherein the solvent mixture comprises: 1 to 10 wt% of said poly(phenylene ether); 70 to 90 wt% 1,2-dichloroethane; and 1 to 10 wt % of the co-solvent; The weight percentages are based on 100 wt % of the solvent mixture.

9. The method of claim 1 or 2, wherein the method further comprises recovering the solvent and the co-solvent.

10. The method of claim 9, wherein recovering the solvent and co-solvent comprises decanting the filtrate to form an organic stream, and distilling the organic stream.

11. The method of claim 9, further comprising recycling solvent and the co-solvent to the mixing vessel.

12. The method of claim 1 or 2, wherein the sulfonation level is 25% to 50% as determined by NMR.

13. The method of claim 1 or 2, wherein the sulfonated poly(phenylene ether) has a uniform sulfonation level of 20 to 50% as determined by NMR.

14. The method according to any one of claims 1 or 2, in, Greater than 97 wt% of the 1,2-dichloroethane is recycled; and / or wherein greater than 95 wt% of the co-solvent is recycled; and / or Therein, more than 90 wt % of the water used in the process is recycled.

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