KR101017649B1 - Post-sulfonated copolymers including perfluorocyclic butane group, preparation method thereof and use thereof - Google Patents

Abstract

The present invention relates to a later-fonned copolymer comprising a perfluorocyclobutane group, a method for producing the same, and a use thereof, wherein the below-fonned copolymer comprising a perfluorocyclobutane group according to the present invention is in solution or molten state. It can be easily produced, the prepared electrolyte membrane has a high hydrogen ion conductivity, excellent mechanical properties and chemically stable, can control the distribution, position, number, etc. of sulfonic acid groups in the polymer skeleton, furthermore sulfonic acid Since it does not accompany the decrease of membrane properties due to the increase of the group, it is processed into various types of polymer blend membrane, polymer crosslinked membrane, polymer composite membrane, flat membrane, hollow fiber membrane, and tube membrane, and thus fuel cell membrane, ion exchange membrane, dehumidification membrane, and humidification membrane. It can be usefully used.

Perfluorocyclobutane groups, fonned later, copolymers, electrolyte membranes, fuel cells, hydrogen ion conductivity

Description

Post-sulfonated copolymers including perfluorocyclic butane group, preparation method according to perfluorocyclobutane group, and preparation thereof

The present invention relates to a later-fonned copolymer comprising a perfluorocyclobutane group, a preparation method thereof, and a use thereof.

Fuel cell is an energy conversion system that converts chemical energy into electrical energy, and is actively researched due to its environmentally friendly features, which require the development of alternative energy due to the explosive increase in electric demand, high energy efficiency and low pollutant emission. Fuel cells are classified according to the electrolyte material or operating temperature used. Among them, polymer electrolyte membrane fuel cells (PEMFCs) can be used for small combined cycle power generation that supplies power and heat simultaneously. Compared to the battery, it has excellent energy conversion characteristics and power density characteristics, can operate at low temperature, and has many advantages such as stability against mechanical shock, and thus, has been in the spotlight as a power source for automobiles and electronic components.

Such polymer electrolyte membranes require high ionic conductivity, safety against redox, high mechanical strength, and the like. Commercially available fuel cell membranes include, for example, Nafion ™ from Dupont, an Allex-based ion exchange membrane, and Asiplex ™ from Asahi Chemical. However, these all-fluorine-based polymer electrolyte membranes have a problem of high cost and excellent efficiency compared to excellent performance. In addition, when such a membrane is used in a direct methanol fuel cell (DMFC), in addition to the above-described problems, there is a problem that methanol is ejected from the anode to the cathode through the membrane (methanol crossover). In order to solve this problem, various researches are being conducted to replace the perfluorinated layer with a non-fluorine-based or partial fluorine-based layer.

US Patent No. 5,602, 185 discloses a process for preparing a polymer electrolyte membrane by copolymerizing a partially fluorine-based trifluorostyrene derivative. However, since the above method uses a palladium catalyst in the manufacturing process, the production cost of the monomer increases, the mechanical properties decrease due to the rigid structure of the polystyrene itself, and the distribution, position, and number of sulfonic acid groups in the polymer skeleton are controlled. Not only is it difficult, there is a problem that the water content of the membrane is increased as the sulfonic acid group increases, the physical properties of the electrolyte membrane is lowered.

U.S. Patent No. 6,090,895 also discloses a crosslinking process of sulfonated polymers such as sulfonated polyetherketones, sulfonated polyethersulfones and sulfonic acid polystyrenes. However, when producing a large amount of thin film from the cross-linked sulfonic acid polymer has not been proposed an effective method for properly processing.

On the other hand, European Patent Publication No. 1,113,517 A2 discloses a block copolymer polymer electrolyte membrane having a sulfonic acid group and a sulfonic acid group. The sulfonated aromatic block using sulfuric acid is a block copolymer composed of an aliphatic block and an aromatic block, but there is a problem in that the aliphatic polymer bond is chemically decomposed during the sulfonation process.

In addition, US Patent Publication No. 2004-186262 discloses a method for producing a multiblock copolymer polymer electrolyte membrane in which hydrophobic blocks made of hydrocarbons and hydrophilic blocks are alternately made. Due to the low solubility of the multiblock copolymer, the -SO ₃ K type copolymer was converted to -SO ₂ Cl using thionyl chloride to impart hydrogen ion conductivity to the polymer membrane. However, the method has a problem in that the manufacturing process is complicated, there is a problem of toxicity during the manufacturing process, and the mechanical integrity of the polymer thin film does not reach the level required for driving the fuel cell.

Accordingly, the present inventors have made efforts to improve the problem of the polymer used in the conventional electrolyte membrane, as a result, a copolymer from a high sulfonation activity monomer and a low sulfonation activity monomer containing a perfluorovinyloxy group in the sock end After the synthesis, the phonation described later can not only easily prepare the sulfonated copolymer, but also modify the polymer membrane including the copolymer through various processes such as fuel cell membrane, ion exchange membrane, dehumidification membrane, humidification membrane, and the like. It has been found that the use can be used and the present invention has been completed.

It is an object of the present invention to provide a later-fonned copolymer comprising a perfluorocyclobutane group represented by the formula (1).

Another object of the present invention is to provide a method for preparing the above-mentioned fonned copolymer.

Still another object of the present invention is to provide a polymer membrane including the later-fonned copolymer of Formula 1 above.

Another object of the present invention is to provide a use of the polymer membrane comprising the copolymerized later described in the formula (1).

Another object of the present invention to provide a method for producing a polymer film comprising a copolymerized later described in the formula (1).

In order to achieve the above object, the present invention provides a later-fonned copolymer represented by the formula (1):

[Formula 1]

(In Formula 1, R, R ', R ", n, m ₁ and m ₂ are as defined in the specification).

In addition, the present invention is to prepare a copolymer compound (4) having a perfluorocyclobutane ring by polymerizing a monomer compound (2) having a low sulfonation activity and a monomer compound (3) having a high sulfonation activity ( Step 1); And a perfluorocyclobutane group comprising a perfluorocyclobutane group comprising the copolymer compound (4) prepared in step 1 to be later fonned using a sulfonating agent to prepare a copolymer of Formula 1 (step 2). It provides a process for the preparation of the copolymer.

Furthermore, the present invention provides a polymer film including a copolymer fonned later, including a perfluorocyclobutane group represented by Chemical Formula 1.

In addition, the present invention provides a variety of uses for use in fuel cell membranes, ion exchange membranes, dehumidification membranes, humidification membranes and the like of a polymer membrane comprising a copolymerized later described in the formula (1).

Furthermore, the present invention is to dissolve the below-coated copolymer of the formula (1), and to coat it on a suitable support or solid surface used for film coating to form a film, and then under atmospheric pressure or vacuum in the temperature range of 50-250 ℃ It provides a method for producing a polymer membrane comprising the copolymerized later described formula of Formula 1 comprising the step of drying for 10 minutes to 48 hours.

The later-fonned copolymer including the perfluorocyclobutane group of Formula 1 according to the present invention can be easily prepared in solution or in a molten state, and the polymer membrane including the same exhibits excellent hydrogen ion conductivity and excellent mechanical properties. In addition, it is not only chemically stable but also can control the distribution, position, number, etc. of sulfonic acid groups in the polymer skeleton, and because it does not involve deterioration of membrane properties due to the increase of sulfonic acid groups, polymer blend membranes, polymer crosslinked membranes, and polymers It is processed into various types of composite membranes, flat membranes, hollow fiber membranes, and tube membranes, and can be usefully used in fuel cell membranes, ion exchange membranes, dehumidification membranes, humidification membranes, and the like.

The present invention provides a later-fonned copolymer comprising a perfluorocyclobutane group represented by the following formula (1).

Hereinafter, the present invention will be described in detail.

In Chemical Formula 1 according to the present invention,

R is an inert organic compound which contains at least one benzene ring but does not induce a chemical reaction and has a low sulfonation activity, wherein when R comprises two benzene rings, the benzene rings are directly connected to each other or- Connected via any one selected from the group consisting of (CO)-,-(SO ₂ )-,-(SO)-,-(PO)-, and-(C (CF ₃ ) ₂ )-;

R ′ is an aromatic compound having a high sulfonation activity including at least one benzene ring, wherein when R ′ includes two benzene rings, the benzene rings are directly connected to each other or -O-, -S-,- (CH ₂ )-,-(C (CH ₃ ) ₂ )-,-(PO)-,-(Si (CH ₃ ) ₂ )-,-(Si (C ₆ H ₅ ) ₂ )-, -NH- , -NR ₁ -and -R ₂ -are connected via any one selected from the group consisting of, wherein R ₁ is alkyl or aryl having 1 to 25 carbon atoms, R ₂ is alkylene having 1 to 25 carbon atoms Or arylene;

R ″ is a form in which R ′ is fonned below by introducing —SO ₃ H into R ′;

N, m ₁ and m ₂ are integers, where m ₁ is 0 when all R's are later fonned, and 10 ≦ n + m ₁ + m ₂ ≦ 100,000.

Preferably,

,

,

,

,

등이 될 수 있다. R is

,

,

,

,

And so on.

Preferably,

,

,

,

,

,

,

,

,

,

,

,

등이 될 수 있다. R 'is

,

,

,

,

,

,

,

,

,

,

,

And so on.

In addition, the present invention as shown in Scheme 1,

Preparing a copolymer compound (4) having a perfluorocyclobutane ring formed by polymerizing a monomer compound (2) having low sulfonation activity and a monomer compound (3) having high sulfonation activity (step 1); And

The copolymerized compound (4) prepared in step 1 to be later described by using a sulfonating agent to prepare a copolymer of the formula (1) described later comprising the perfluorocyclobutane group comprising a step (step 2) Provided are methods for preparing the copolymers:

(In Scheme 1, R, R ', R ", n, m ₁ , m ₂ are as defined in the formula (1), m is an integer, 10≤n + m≤100,000).

Hereinafter, the method for preparing the later-fonned copolymer of Formula 1 according to the present invention will be described in more detail step by step.

Step 1:

Step 1 according to the present invention is a step of preparing a copolymer compound (4) having a perfluorocyclobutane ring by polymerizing a monomer compound (2) having a low sulfonation activity and a monomer compound (3) having a high sulfonation activity. to be.

The monomer compound having low sulfonation activity (2) and the monomer compound having high sulfonation activity (3) used as starting materials have a perfluorovinyloxy group at both ends in common. As a result of the copolymerization reaction, the perfluorovinyloxy group undergoes a cyclization reaction to form a perfluorocyclobutane ring.

The polymerization reaction of step 1 according to the present invention is preferably carried out in an inert gas atmosphere. As said inert gas, nitrogen or argon atmosphere is mentioned, for example.

In addition, the polymerization of step 1 is preferably carried out in a molten state or a solution state by heating for 30 minutes to 72 hours in the temperature range of 130-450 ℃. If the reaction temperature is less than 130 ℃ cyclobutane ring reaction does not occur, or there is a problem that occurs very slowly. On the other hand, when the reaction temperature exceeds 450 ℃ there is a problem that the copolymer is decomposed.

Furthermore, when the polymerization reaction of step 1 is carried out in a solution state, the reaction solvent is not particularly limited as long as it is a solvent capable of appropriately dissolving the reactants and the product. Preferably, aprotic polar solvents such as dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF) and dimethylacetamide (DMAC) are used, or diphenyl ether A solvent having a breaking point of 130 ° C. or higher can be used, such as (DPE) and 1,3,5-trimethylbenzene.

Step 2:

Step 2 according to the present invention is a step of preparing a copolymer of Chemical Formula 1 by fonning the copolymer compound (4) prepared in Step 1 later using a sulfonating agent.

The above-mentioned fonning may be performed by using a known method, and as the sulfonating agent that can be used, there is no particular limitation as long as it is a material capable of introducing -SO ₃ H into the polymer. Preferably, chlorosulfonic acid, sulfur trioxide, sulfuric acid, fuming sulfuric acid, acyl sulfate and the like can be used.

Step 2 is a hydrophobic moiety that maintains the mechanical density of the thin film by sulfonating a monomer (R ') moiety having a high sulfonation activity of the copolymer compound (4) prepared in step 1, and imparts ion conductivity to the thin film. Ensure that the hydrophilic moieties are alternately linked by chemical bonds.

The later-fonned copolymer according to the production method according to the present invention is characterized in that the sulfonated activity monomer (2) and the sulfonated activity monomer (3) are bonded to each other after being fonned later. Therefore, by adjusting the ratio of the compound (2) and compound (3), it is possible to easily control the distribution and number of sulfonic acid groups in the polymer skeleton.

In another aspect, the present invention provides a polymer membrane comprising a later-fonned copolymer comprising a perfluorocyclobutane group represented by the formula (1).

The polymer membrane may be used by various processing in the form of a polymer blend membrane, a polymer crosslinked membrane, a polymer composite membrane, a hollow fiber membrane, a tube membrane and the like by a processing method commonly used in the art.

In addition, the polymer membrane according to the present invention can be used for applications such as fuel cell membrane, ion exchange membrane, dehumidification membrane, humidification membrane.

Experimental Example 1 in which the polymer membranes of Examples 1 to 3 for the polymer membrane according to the present invention were measured in comparison with Nafion 115, which has been used as a conventional polymer membrane, is hydrogen ion conductivity of the polymer membrane according to the present invention. It is much improved than Nafion 115, showing at least an equivalent degree of hydrogen ion conductivity (see FIG. 1 ).

In addition, the polymer membrane according to the present invention not only includes perfluorocyclobutane groups known as chemically stable materials having excellent mechanical properties, but also regulates the proportion of monomers during polymerization, such as the number, distribution and position of sulfonic acid groups in the polymer skeleton. It is possible to control the characteristics of the membrane property is prevented from being deteriorated with the increase of sulfonic acid groups. As a result, the polymer membrane according to the present invention can be usefully used as electrolyte membranes such as fuel cell membranes and ion exchange membranes, dehumidification membranes, humidification membranes and the like.

Furthermore, the present invention provides a method for producing the polymer membrane.

The steps are as follows.

The method for producing a polymer membrane according to the present invention comprises the following steps:

Subsequently fonned copolymers containing the perfluorocyclobutane group represented by the formula (1) include dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF) and dimethylacetamide An aprotic polar solvent selected from the group consisting of (DMAC); Or dissolving in a polar solvent selected from the group consisting of methanol, ethanol and isopropanol to prepare a polymer solution (step A-1);

Coating the polymer solution prepared in step A-1 on a glass, metal, porous polymer support (ceramic, polysulfone, polyisamide, etc.) or a solid surface used for film coating to form a film (step A-2 ); And

Drying the film formed in step A-2 for 10 minutes to 48 hours at atmospheric pressure or vacuum in the temperature range of 50-250 ° C (step A-3).

Hereinafter, the present invention will be described in detail by way of examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

Example 1 Preparation of Biphenyl Copolymer and Sulfonyl Biphenyl Copolymer, and Films Comprising the Same

4,4'-bis (trifluorovinyloxy) biphenyl, a monomer having high sulfonation activity, and 4,4'-sulfonyl-bis, a monomer having low sulfonation activity (Trifluorovinyloxy) biphenyl (4,4'-sulfonyl-bis (trifluorvinyloxy) biphenyl) was heated at 250 ° C. for 5 hours at a weight ratio of 1: 1, 1: 5, and 1:10, respectively, under a nitrogen atmosphere. After cooling slowly to room temperature. The obtained polymer was dissolved in DMAC, slowly added dropwise into excess methanol, precipitated and filtered to obtain a copolymer (Compound (4)). The copolymer was dissolved in dichloroethane at a concentration of 1 wt% under a nitrogen atmosphere, and then chlorosulfonic acid was slowly added dropwise to 4 moles of the biphenyl repeating unit, and then fonned later for 7 hours. The solvent of the mixture was removed and washed several times with distilled water to prepare a later-fonned copolymer of Chemical Formula 1.

As a result of measuring the inherent viscosity (Cannon-Fenske viscometer) of the prepared copolymer, 1.2 (g / dl) ^-1 for 1: ¹ , 1.1 (g / dl) ^-1 , 1:10 for 1: 5 Case 1.1 (g / dl) ^-1 is shown. The polymer thus obtained was dissolved in DMAC at a concentration of 15 wt%, cast on a glass plate, and then the thickness of the copolymer solution on the glass plate was adjusted with a film applicator, and then dried in an oven at 80 ° C. for 1 day, and then in a 140 ° C. oven. Vacuum drying for a time to prepare a later-fonned copolymer polymer membrane of 50 ~ 120 ㎛ thickness.

<Example 2> Diphenyl sulfide-based and benzophenone-based copolymer, and the production of a film comprising the same

4,4'-bis (2-trifluorovinyloxy) diphenyl sulfide (4,4'-Bis (2-trifluorovinyloxy) diphenyl sulfide) which is a monomer having high sulfonation activity and a monomer having low sulfonation activity 4, 4'-bis (2-trifluorovinyloxy) benzophenone (4,4'-Bis (2-trifluorovinyloxy) benzophenone) in a weight ratio of 1: 1, 1: 5, and 1:10, respectively, was added to diphenyl ether. 20 wt% was added, followed by heating at 200 ° C. under nitrogen for one day, and then slowly cooling to room temperature. The obtained polymer solution was slowly added dropwise into excess methanol, precipitated, filtered, and dried to obtain a copolymer corresponding to compound (4). After dissolving the copolymer at 1 wt% in dichloroethane under a nitrogen atmosphere, acetylsulfate (acetic anhydride / condensed sulfuric acid, 1.5 mol / 1 mol) was slowly added dropwise to 4 mol times the diphenylsulfide repeat unit. To be phoned later for 7 hours. The solvent of the mixture was removed and washed several times with distilled water to prepare a later-fonned copolymer of Chemical Formula 1.

As a result of measuring the intrinsic viscosity (Cannon-Fenske viscometer) of the prepared copolymer, 1.0 (g / dl) ^-1 for 1: ¹ , 0.9 (g / dl) ^-1 , 1:10 for 1: 5 Case 1.0 (g / dl) ⁻¹ is shown. The polymer thus obtained was dissolved in 15 wt% of DMAC and cast on a glass plate. Then, the thickness of the copolymer solution on the glass plate was controlled by a film applicator, dried in an oven at 80 ° C. for one day, and then in a 140 ° C. oven for 10 hours. Vacuum drying to prepare a later-fonned copolymer polymer membrane having a thickness of 50 ~ 120 ㎛.

Example 3 Preparation of Bisphenol-Based and Fluorophenyl-Based Copolymers, and Films Comprising the Same

2,2-bis (4-trifluorovinyloxyphenyl) propane, a monomer having high sulfonation activity, and 1,4-bis, a monomer having low sulfonation activity, Trifluorovinyloxy) tetrafluorobenzene (1,4-Bis (trifluorovinyloxy) tetrafluorobenzene) was added at a weight ratio of 1: 1, 1: 5, and 1:10, respectively, in 20 wt% of diphenyl ether, followed by nitrogen It was heated at 200 ℃ for one day and then slowly cooled to room temperature. The obtained polymer was slowly added dropwise into excess methanol, precipitated, filtered, and dried to obtain a copolymer of Compound (4). The copolymer was dissolved in dichloroethane at 1 wt% under a nitrogen atmosphere, and then chlorosulfonic acid was slowly added dropwise to 4 moles of the biphenyl repeating unit, and then fonned later for 7 hours. The solvent of the mixture was removed and washed several times with distilled water to prepare a later-fonned copolymer of Chemical Formula 1.

As a result of measuring the inherent viscosity (Cannon-Fenske viscometer) of the prepared copolymer, 1.1 (g / dl) ^-1 for 1: ¹ , 1.2 (g / dl) ^-1 , 1:10 for 1: 5 Case 1.0 (g / dl) ^-1 was shown. The polymer thus obtained was dissolved in DMAC at a concentration of 15 wt%, cast on a glass plate, and then the thickness of the copolymer solution on the glass plate was adjusted with a film applicator, and then dried in an oven at 80 ° C. for 1 day, and then in a 140 ° C. oven. Vacuum drying for a time to prepare a later-fonned copolymer polymer membrane of 50 ~ 120 ㎛ thickness.

Experimental Example 1 Measurement of Hydrogen Ion Conductivity

In the sulfonated copolymer polymer membranes prepared in Examples 1 to 3, the hydrogen ion conductivity of the polymer membrane in which the monomer having high sulfonation activity and the monomer having low sulfonation activity was adjusted in a weight ratio of 1: 1 by a potentiostatic potential 2 probe It was measured by the (potentiostatic two-probe) method. 1 x 1 cm ² and 1.5 x 1.5 cm ² carbon paper electrodes are placed on each side of the specimen with an area of 2 x 2 cm ² at a constant pressure, and an ultra-pure water is allowed to flow out of it. A frequency of MHz-100 Hz was applied. At this time, the impedance was obtained through an alternating current applied to both ends of the electrode, and the hydrogen ion conductivity of each of the fonned copolymer polymer films described below was measured using the same, and the results are shown in Table 1 and FIG. 1. As a comparative example, Nafion 115, which has been used as a conventional polymer membrane, was used.

Temperature (℃) Hydrogen ion conductivity (S / cm) Example 1 Example 2 Example 3 Nafion 115 30 0.0880 0.0810 0.0580 0.0650 40 0.0940 0.0850 0.0630 0.0730 50 0.1050 0.0920 0.0720 0.0860 60 0.1150 0.1090 0.0830 0.0900 70 0.1300 0.1120 0.0870 0.0930 80 0.1410 0.1230 0.0900 0.0960 90 0.1510 0.1400 0.1040 0.1200 100 0.1670 0.1450 0.1210 0.1100

As shown in Table 1 and FIG. 1, the fonned copolymer polymer membranes prepared in Example 1 (◆), Example 2 (■) and Example 3 (●) according to the present invention have been used as conventional polymer membranes. It can be seen that the hydrogen ion conductivity is equivalent to or better than that of Nafion 115 (o). In particular, the polymer membrane including the biphenyl-based and sulfonyl biphenyl-based copolymers of Example 1 was about 0.0230 S / cm at 30 ° C. and about 0.0570 S / cm at 100 ° C., compared to Nafion 115. Hydrogen ion conductivity is shown.

From this, it can be seen that the below-coated copolymer containing the perfluorocyclobutane group of the formula 1 according to the present invention can be usefully used as an electrolyte membrane such as a fuel cell membrane or an ion exchange membrane that requires excellent hydrogen ion conductivity. have.

1 is a graph showing the results of measuring the hydrogen ion conductivity of the polymer film prepared in Examples 1 to 3 of the present invention and the polymer film (Nafion 115) of the comparative example.

Claims (12)

delete delete delete As shown in Scheme 1 below, Preparing a copolymer compound (4) having a perfluorocyclobutane ring formed by polymerizing a monomer compound (2) having low sulfonation activity and a monomer compound (3) having high sulfonation activity (step 1); And The copolymerized compound (4) prepared in step 1 to be described later by using a sulfonating agent to form a copolymer of formula (1) to be described later comprising a perfluorocyclobutane group comprising the step (step 2) Manufacturing method of: Scheme 1

(In Scheme 1, R is an inert organic compound which contains at least one benzene ring but does not induce a chemical reaction and is an aromatic compound having low sulfonation activity, wherein when R comprises two benzene rings, the benzene rings are directly connected to each other or Connected via any one selected from the group consisting of (CO)-,-(SO ₂ )-,-(SO)-,-(PO)-, and-(C (CF ₃ ) ₂ )-; R ′ is an aromatic compound having a high sulfonation activity including at least one benzene ring, wherein when R ′ includes two benzene rings, the benzene rings are directly connected to each other or -O-, -S-,- (CH ₂ )-,-(C (CH ₃ ) ₂ )-,-(PO)-,-(Si (CH ₃ ) ₂ )-,-(Si (C ₆ H ₅ ) ₂ )-, -NH- , -NR ₁ -and -R ₂ -are connected via any one selected from the group consisting of, wherein R ₁ is alkyl or aryl having 1 to 25 carbon atoms, R ₂ is alkylene having 1 to 25 carbon atoms Or arylene; R ″ is a form in which R ′ is fonned below by introducing —SO ₃ H into R ′; N, m ₁ and m ₂ are integers, where m ₁ is 0 when all R ′ are fonned below, and 10 ≦ n + m ₁ + m ₂ ≦ 100,000; M is an integer and 10 ≦ n + m ≦ 100,000). The method of claim 4, wherein the polymerization of step 1 is carried out in an inert gas atmosphere. The method according to claim 4, wherein the polymerization reaction of step 1 is performed below in a molten state or a solution state by heating for 30 minutes to 72 hours at a temperature range of 130 to 450 ° C. Process for the preparation of fonned copolymers. The reaction solvent of the polymerization reaction of step 1 is dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF) and dimethylacetamide (DMAC) An aprotic polar solvent selected from the group consisting of: Or a difluoroether (DPE) and a perfluorocyclobutane group, characterized in that the solvent has a breaking point of 130 ° C or higher selected from the group consisting of 1,3,5-trimethylbenzene. The sulfonated copolymer of claim 4, wherein the sulfonating agent of step 2 is selected from the group consisting of chlorosulfonic acid, sulfur trioxide, sulfuric acid, fuming sulfuric acid and acylsulfate. Manufacturing method. delete delete delete delete

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