KR101267979B1 - Hydrocarbon polymer proton exchange membranes having improved thermal and dimension stability and fabrication method thereof - Google Patents

Abstract

The present invention relates to a method for producing a hydrocarbon-based polymer electrolyte membrane and a hydrocarbon-based polymer electrolyte membrane prepared according to the above, and more particularly, a crosslinking agent mixture and a hydrocarbon-based polymer are added in an optimum composition ratio and irradiated with a hydrocarbon-based polymer It relates to a method for producing an electrolyte membrane. Since the polymer electrolyte membrane according to the preparation method of the present invention significantly improves high temperature and dimensional stability, it may be usefully used as a polymer electrolyte membrane such as an ion exchange membrane, a fuel cell membrane, or a separator for a battery.

Description

Hydrocarbon polymer proton exchange membranes having improved thermal and dimension stability and fabrication method

The present invention relates to a method for producing a hydrocarbon-based polymer electrolyte membrane and a polymer electrolyte membrane prepared accordingly.

The conventional polymer electrolyte membrane mainly used sulfonated fluorine-based polymer, and a representative material is Nafion ^® . These fluorine-based polymers have excellent mechanical properties, chemical stability, and ion conductivity, but have disadvantages such as high price, low driving temperature (less than 100 ° C.), and low stability in methanol.

Therefore, in order to compensate for this, the development of hydrocarbon-based polymers has been actively performed. Representative examples include sulfonate poly (ether ether ketone, SPEEK), sulfonate poly (aryl ether sulfone), sulfonate phenol formal resin, sulfonate poly (phenylene oxide), phosphonic poly (Phenylene oxide) and sulfonate poly (benzylimidazole).

These hydrocarbon-based polymers have very good mechanical strength and chemical properties, and have low merit of manufacturing cost and sulfonation degree, so that the ionic conductivity can be adjusted.

However, when the degree of sulfonation is excessively increased, dimensional stability and mechanical strength due to moisture are reduced. Therefore, many researches are actively being made to compensate for these disadvantages.

American Journal of Membrane Science In 2009 , 345, 119, 2,4,5-triaminopyrimidine and Closilite were used to prepare nanocomposite membranes based on sulfonate poly (ether ether ketone) to increase dimensional stability and ionic conductivity. The contents are disclosed.

American Journal of Power Sources 2007 , 168, 154 disclose a polymer electrolyte membrane having a crosslinked structure using an ultraviolet curing method by introducing a sulfonate poly (ether ether ketone) as a basic structure and introducing a functional group having a double bond structure in the side chain. .

American Radiation Physics and Chemistry 2008 , 77, 617 discloses a method of grafting sulfonate styrene using poly (ether ether ketone) irradiation techniques.

However, the above-described prior arts have a problem in that they are difficult to be used widely commercially because of the disadvantages of synthesizing new polymers and requiring a long time crosslinking process.

Accordingly, the inventors of the present invention, while conducting research to solve this problem, by mixing the crosslinking agent mixture and the hydrocarbon-based polymer in an optimum composition ratio and irradiating the radiation of the appropriate irradiation dose to produce a hydrocarbon-based polymer electrolyte membrane, stability at high temperatures The present invention was completed by finding out that the dimensional stability was improved.

It is an object of the present invention to provide a method for producing a hydrocarbon-based polymer electrolyte membrane in which a crosslinking agent mixture and a hydrocarbon-based polymer are mixed and irradiated with radiation.

Another object of the present invention is to provide a hydrocarbon-based polymer electrolyte membrane having improved high temperature and dimensional stability produced by the above method.

Still another object of the present invention is to provide an ion exchange membrane using the polymer electrolyte membrane.

Another object of the present invention is to provide a fuel cell membrane using the polymer electrolyte membrane.

Still another object of the present invention is to provide a battery separator using the electrolyte polymer membrane.

In order to achieve the above object,

The present invention is to prepare a crosslinking agent mixture by mixing 35 to 60% by weight of monofunctional crosslinking agent, 0 to 35% by weight of polyester acrylic oligomer crosslinking agent and 5 to 45% by weight of polyfunctional crosslinking agent (step 1);

Preparing a mother liquor by dissolving 1 to 10% by weight of the crosslinking agent mixture prepared in Step 1 and 1 to 10% by weight of a hydrocarbon-based polymer in 85 to 95% by weight of a solvent (step 2);

Casting and drying the mother liquor prepared in step 2 onto a glass plate (step 3); And

It provides a method for producing a hydrocarbon-based polymer electrolyte membrane comprising the step of irradiating and drying the radiation (step 4).

In addition, it provides a hydrocarbon-based polymer electrolyte membrane prepared by the above production method.

Furthermore, an ion exchange membrane using the polymer electrolyte membrane is provided.

In addition, a fuel cell membrane using the polymer electrolyte membrane is provided.

Furthermore, it provides a battery separator using the polymer electrolyte membrane.

The hydrocarbon-based polymer electrolyte membrane prepared by mixing the crosslinking agent mixture and the hydrocarbon-based polymer according to the present invention at an optimum composition ratio and irradiating with radiation is not only stable at high temperatures but also has improved dimensional stability, such as an ion exchange membrane, a fuel cell membrane, a battery separator, and the like. It can be usefully used as a polymer electrolyte membrane of.

1 is a schematic view showing a manufacturing process of a polymer electrolyte membrane according to the present invention.
Figure 2 is a graph measuring the dynamic / mechanical properties of the polymer electrolyte membrane according to an embodiment of the present invention.
Figure 3 is a graph measuring the ion conductivity of the polymer electrolyte membrane according to an embodiment of the present invention.
Figure 4 is a graph measuring the weight change to infer the chemical stability of the polymer electrolyte membrane according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The present invention is to prepare a crosslinking agent mixture by mixing 35 to 60% by weight of monofunctional crosslinking agent, 0 to 35% by weight of polyester acrylic oligomer crosslinking agent and 5 to 45% by weight of polyfunctional crosslinking agent (step 1);

Preparing a mother liquor by dissolving 1 to 10% by weight of the crosslinking agent mixture prepared in Step 1 and 1 to 10% by weight of a hydrocarbon-based polymer in 85 to 95% by weight of a solvent (step 2);

Casting and drying the mother liquor prepared in step 2 onto a glass plate (step 3); And

It provides a method for producing a hydrocarbon-based polymer electrolyte membrane comprising the step of irradiating and drying the radiation (step 4).

Hereinafter, the present invention will be described in detail step by step.

In the method for preparing a hydrocarbon-based polymer electrolyte membrane according to the present invention, step 1 is a step of preparing a crosslinking agent mixture. Specifically, a monofunctional crosslinking agent, a polyester acrylic oligomer crosslinking agent, and a polyfunctional crosslinking agent are mixed at an optimum ratio to prepare a crosslinking agent mixture.

The monofunctional crosslinking agent of the present step 1 serves to dissolve the polyester acrylic oligomer crosslinking agent and the polyfunctional crosslinking agent and to appropriately control the flexibility of the electrolyte membrane. The monofunctional crosslinking agent may be used alone or in combination of EOEOEA (2- (2-ethoxyethoxy) ethyl acrylate), HEA (Hydroxyethyl acrylate), EHA (ethylhexyl acrylate).

At this time, it is preferable to add 35 to 45% by weight of the monofunctional crosslinking agent to prepare a crosslinking agent mixture.

If the monofunctional crosslinking agent is added in an amount of less than 35% by weight, there is a problem in that the membrane is easily broken due to increased physical strength but reduced flexibility. When added in excess of 45% by weight, the flexibility is increased, but there is a problem that it is difficult to secure numerical stability.

The polyester acrylic oligomer crosslinking agent of the present step 1 serves to properly control the flexibility of the electrolyte membrane together with the monofunctional crosslinking agent. Polyester acryl etc. can be used as said polyester acrylic oligomer crosslinking agent.

At this time, it is preferable to add 0 to 35% by weight of the polyester acrylic oligomer crosslinking agent to prepare a crosslinking agent mixture.

If the polyester acrylic oligomer crosslinking agent is added in excess of 35% by weight, there is a problem that the mechanical strength is excessively increased and the chemical resistance is lowered.

The multifunctional crosslinking agent of the present step 1 serves to enhance the degree of crosslinking and to increase the mechanical strength and the degree of crosslinking of the membrane. As the multifunctional crosslinking agent, trimethylol propane trimethacrylate (TMPTA), hexanediol diacrylate (Hexanedioldiacrylate, HDDA) and the like may be used alone or in combination.

At this time, it is preferable to prepare a crosslinking agent mixture by adding 5 to 25% by weight of the multifunctional crosslinking agent.

If the multifunctional crosslinking agent is added in less than 5% by weight, there is a problem of decreasing mechanical strength and lowering of dimensional stability, and when it is added in excess of 25% by weight, the crosslinking density is increased so that impact strength is lowered. There is.

In the method for preparing a hydrocarbon-based polymer electrolyte membrane according to the present invention, step 2 is a step of preparing a mother liquid of a hydrocarbon-based polymer electrolyte membrane. Specifically, the hydrocarbon-based polymer and the crosslinking agent mixture prepared in Step 1 are dissolved in a solvent at room temperature to prepare a mother liquid.

The solvent of step 2 dissolves the hydrocarbon-based polymer and in step 1 It serves to mix the prepared crosslinker mixture. As the solvent, polar solvents such as N, N-dimethylacetamide (DMAc), 1-methyl-2-pyrrolidinone (NMP), and dimethyl sulfoxide (DMSO) may be used alone or in combination.

At this time, it is preferable to prepare the mother liquid by adding 85 to 95% by weight of the solvent.

If the solvent is added below 85% by weight, there is a problem of dispersing the solvent and increasing the crosslinking density, and when adding the solvent in excess of 95% by weight, it is difficult to form a film.

The hydrocarbon-based polymer of this step 2 serves to form the basic skeleton of the polymer electrolyte membrane. As the hydrocarbon-based polymer, sulfonate poly (ether ether ketone) (SPEEK), sulfonate poly (aryl ether sulfone), sulfonate poly (imide), sulfonate poly (phenylene oxide) and the like can be used.

At this time, it is preferable to prepare the mother liquid by adding 1 to 10% by weight of the hydrocarbon-based polymer.

If the hydrocarbon-based polymer is added in less than 1% by weight, there is a problem in that it does not have sufficient ionic conductivity, and when added in excess of 10% by weight, dimensional stability is deteriorated.

In the method for preparing a hydrocarbon-based polymer electrolyte membrane according to the present invention, step 3 is a step of casting and drying the mother liquid on a glass plate. Specifically, using a solution casting method evenly sprayed on a glass plate of the appropriate size at room temperature, and dried for 1 to 2 hours at a high temperature of 60 ~ 80 ℃ to evaporate the solvent.

In the method for producing a hydrocarbon-based polymer electrolyte membrane according to the present invention, step 4 is a step of irradiating and drying the radiation. Specifically, in step 3 by evaporating the solvent to irradiate the film formed on the glass plate with radiation, and vacuum dried at 100 ~ 140 ℃ for 10 to 14 hours to remove the remaining solvent and cooled to room temperature, the prepared polymer electrolyte The membrane may be separated from the glass plate using distilled water to prepare a hydrocarbon-based polymer electrolyte membrane according to the present invention.

In this case, the radiation serves to improve the mechanical strength by crosslinking the crosslinking agent and the hydrocarbon-based polymer. As said radiation, it is preferable to irradiate 1 or more types chosen from the group which consists of a gamma ray, an ultraviolet-ray, and an electron beam, and it is more preferable to irradiate an electron beam.

In addition, the radiation is preferably irradiated by 80 ~ 120 kGy irradiation dose at a dose rate of 4 ~ 8 kGy / min, by 90 ~ 110 kGy irradiation dose at a dose rate of 5 ~ 7 kGy / min It is more preferable to give.

If the irradiation dose of the radiation is less than 80 kGy / min, there is a problem that sufficient crosslinking does not occur, and if it exceeds 120 kGy / min, intermolecular breakage occurs and there is a problem of lowering mechanical strength due to molecular weight reduction. .

Additionally, after performing step 4, impurities may be removed by washing and drying the polymer electrolyte membrane. For example, it may be placed in about 1M HCl aqueous solution for 36 to 60 hours to remove impurities and dry.

The hydrocarbon-based polymer electrolyte membrane according to the present invention can be used in a high-temperature operating environment (about 180 ° C., see FIG. 2) by mixing and adding a crosslinking agent mixture and a hydrocarbon-based polymer in an optimum composition ratio, and manufacturing by irradiating with radiation. However, since the dimensional stability is improved, it can be usefully used as a polymer electrolyte membrane such as an ion exchange membrane, a fuel cell membrane, a battery separator.

Hereinafter, the present invention will be described in detail with reference to 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> SPEEK As the base skeleton Of polymer electrolyte membrane  Produce

Hydrocarbon-based polymer electrolyte membranes based on sulfonate poly (ether ether ketone) (SPEEK) with improved high temperature and dimensional stability according to the present invention were prepared as shown in FIG.

Specifically,

Step 1: Cross-linking agent  Preparing the mixture

The crosslinking agents were prepared at room temperature by mixing the crosslinking agents in the composition ratios (C1 to C7) shown in Table 1 below.

Step 2: Mother liquor  Steps to manufacture

The mother liquor was prepared at room temperature by mixing sulfonate poly (etheretherketone) (SPEEK) and the crosslinking agent mixture prepared in step 1 in an N, N-dimethyl acetamide (DMAc) solvent in the composition ratio shown in Table 1 below.

Step 3: Mother liquor  Cast on glass Desiccant  step

The mother liquor prepared in step 2 was evenly sprayed on a 15 cm × 15 cm glass plate at room temperature using a solution casting method. The glass plate in which the mother liquid was dispersed was dried at a high temperature of 70 ° C. to evaporate the solvent N, N-dimethyl acetamide (DMAc) for 1 hour.

Step 4: Irradiate Desiccant  step

The glass plate from which the solvent was evaporated in step 3 was irradiated with 100 kGy of electron beam at a dose rate of 6 kGy / min. The irradiated glass plate was vacuum dried at 120 ° C. for about 12 hours to remove residual DMAc solvent, cooled to room temperature, and the polymer electrolyte membrane thus prepared was separated from the glass plate using distilled water. Finally, the polymer electrolyte membrane prepared above was placed in a 1M HCl aqueous solution for 48 hours to remove impurities, thereby preparing a hydrocarbon-based polymer electrolyte membrane according to the present invention.

% By weight of crosslinker mixture

Name of sample
Cross-linking agent
C1 C2 C3 C4 C5 C6 C7


Crosslinker mixture
Polyester acrylate
30.0
26.3
22.2
17.6
12.5
6.9
0
TMPTA
10.0
10.5
11.1
11.7
12.5
13.3
14.3
HDDA
20.0 21.1 22.2 23.6 25.0 26.7 28.6 EOEOEA
40.0 42.1 44.5 47.1 50.0 53.3 57.1 % By weight of mother liquor


Mother liquor
Crosslinker mixture
5 5 5 5 5 5 5 SPEEK
5 5 5 5 5 5 5 DMAc
90 90 90 90 90 90 90

< Experimental Example  1> Gelation degree  Measure

In order to determine the gelation degree of the polymer electrolyte membrane prepared in Example 1, the experiment was performed as follows.

Specifically, the polymer electrolyte membrane prepared in Example 1 was immersed in DMAc, a solvent used before electron beam irradiation, for one day, and then observed the weight change, thereby measuring the degree of gelation by Equation 1 below, and the results are shown in Table 2 below. It was.

In Equation 1, W _dry is the weight of the polymer electrolyte membrane before immersion in DMAc solvent, W _dissolved is the weight of the electrolyte membrane after immersion in DMAc solvent for one day.

Name of sample
Gelation degree (%)
C1
65.0 ± 0.5 C2
53.3 ± 2.1 C3
42.1 ± 0.8 C4
46.7 ± 0.5 C5
56.2 ± 0.6 C6
58.6 ± 0.2 C7
62.1 ± 0.6

As shown in Table 2, the average gelation degree of the polymer electrolyte membrane prepared by the C1 ~ C7 composition ratio was confirmed that more than 50%.

Therefore, since the polymer electrolyte membrane according to the present invention has a sufficient gelling rate, it can be usefully used as a hydrocarbon-based polymer electrolyte membrane such as an ion exchange membrane, a fuel cell membrane, and a battery separator.

< Experimental Example  2> ion exchange capacity ( Ion exchange capacity , IEC ) Measure

In order to determine the IEC of the polymer electrolyte membrane prepared in Example 1, the following experiment was performed using a neutralization titration method.

Specifically, the polymer electrolyte membrane prepared in Example 1 was placed in 3M NaCl solution for 24 hours to neutralize the H ⁺ of the sulfone group in the form of Na ⁺ , followed by reverse neutralization titration using 0.1 M NaOH. Automatic titrator DL22 (Mettler Toledo Company, Switzerland) was used for accurate neutralization titration, and IEC value was calculated using Equation 2 below, and the results are shown in Table 3 below.

In Equation 2, C _NaOH is the concentration of NaOH solution, V _NaOH is the volume of 0.1M NaOH solution used in the neutralization titration, W _dry is the weight of the dry state of the cross-linked polymer electrolyte membrane.

Name of sample
IEC (meq / g)
C1
0.90 C2
1.06 C3
0.93 C4
0.94 C5
1.04 C6
1.03 C7
1.02

As shown in Table 3, the average ion exchange capacity of the polymer electrolyte membrane prepared in the C1 ~ C7 composition ratio was confirmed to be 0.98 meq / g.

Therefore, since the polymer electrolyte membrane according to the present invention has a sufficient ion exchange capacity, it can be usefully used as a hydrocarbon-based polymer electrolyte membrane such as an ion exchange membrane, a fuel cell membrane, and a battery separator.

< Experimental Example  3> Moisture absorption rate measurement

In order to determine the water absorption of the polymer electrolyte membrane prepared in Example 1, the experiment was performed as follows.

Specifically, after immersing the polymer electrolyte membrane prepared in Example 1 in distilled water for 24 hours at room temperature to remove the moisture present on the surface of the electrolyte membrane and observed the weight change, the water absorption was measured by the following equation (3), The results are shown in Table 4.

In Equation 3, W _d is the weight of the dried film, W _s is the weight of the film absorbing moisture.

Name of sample
Water absorption rate (%)
C1
22.3 ± 0.5 C2
23.4 ± 0.8 C3
23.0 ± 0.2 C4
23.3 ± 0.1 C5
23.4 ± 0.7 C6
22.1 ± 0.2 C7
23.9 ± 0.5

As shown in Table 4, the water absorption of the polymer electrolyte membrane prepared by the C1 ~ C7 composition ratio was confirmed to appear to about 23%.

Therefore, since the polymer electrolyte membrane according to the present invention has an appropriate water absorption, it can be usefully used as a hydrocarbon-based polymer electrolyte membrane such as an ion exchange membrane, a fuel cell membrane, or a battery separator.

< Experimental Example  4> Dynamic / mechanical property measurement

In order to determine the dynamic / mechanical properties of the polymer electrolyte membrane prepared in Example 1, the experiment was performed as follows.

Specifically, the dynamic / mechanical properties of the polymer electrolyte membrane prepared with the C1, C3, C5, and C7 compositions in Example 1 were measured using TA DMA Q800 (TA Instruments, USA).

Experimental conditions were used as the tensile method, the experiment was performed at a frequency of 1Hz in the temperature range of -50 ~ 300 ℃, the temperature rise rate was set to 2 ℃ / min to measure the dynamic / mechanical properties, the results are shown in Figure 2 Indicated.

Figure 2 is a graph measuring the dynamic / mechanical properties of the polymer electrolyte membrane according to an embodiment of the present invention.

As shown in FIG. 2, the polymer electrolyte membrane prepared by adding the crosslinking agent mixture in Example 1 shows a glass phase, glass transition temperature, ionic modulus, and glass transition temperature of the polymer main chain as the temperature increases. It was confirmed that it has a flowing property. In addition, it can be seen that the temperature at which the flow of all the crosslinked polymer electrolyte membrane starts is about 190 ° C.

Therefore, the polymer electrolyte membrane according to the present invention can be used at a maximum of 180 ℃, it can be usefully used as a hydrocarbon-based polymer electrolyte membrane, such as ion exchange membrane, fuel cell membrane, battery separator membrane.

< Experimental Example  5> Ionic Conductivity ( Proton conductivity ) Measure

In order to determine the ionic conductivity of the polymer electrolyte membrane prepared in Example 1, the experiment was performed as follows.

Specifically, the resistance of the electrolyte was measured using an AC impedance analyzer (SI 1260, Solatron Company) of the polymer electrolyte membrane prepared in the C1, C3, C5 and C7 composition in Example 1.

At this time, the impedance measurement was measured by recording according to the temperature change in the frequency range of 0.01 to 100 kHz, the hydrogen ion conductivity was calculated using Equation 4 below, the results are shown in FIG.

In Equation 4, L is the distance between the two electrodes, A is the width in the thickness direction of the polymer electrolyte membrane, R is the electrical resistance value.

Figure 3 is a graph measuring the ion conductivity of the polymer electrolyte membrane according to an embodiment of the present invention.

As shown in FIG. 3, the ion conductivity of the polymer electrolyte membrane prepared in Example 1 was confirmed that all of the ion conductivity of the polymer electrolyte membrane prepared with the C1, C3, C5 and C7 compositions increased with increasing temperature. However, in the case of the electrolyte membrane using only SPEEK without adding a crosslinking agent, since the electrolyte membrane swells and breaks after about 45 ° C., the ion conductivity can no longer be measured.

Therefore, the polymer electrolyte membrane according to the present invention can be said to have excellent hydration stability, and excellent ion conductivity even at high temperature and high humidity, and thus can be usefully used as a hydrocarbon-based polymer electrolyte membrane such as an ion exchange membrane, a fuel cell membrane, and a battery separator. .

< Experimental Example  6> Chemical stability evaluation

In order to determine the chemical stability of the polymer electrolyte membrane prepared in Example 1, the experiment was performed as follows.

Specifically, the polymer electrolyte membrane prepared in the C1, C3, C5 and C7 composition in Example 1 is immersed in distilled water for one day and then made into a sufficiently swollen state. The initial weight of the swelled electrolyte membrane was measured (at this time, the moisture on the surface of the electrolyte membrane was removed after sufficient removal as in the water absorption rate measurement method of Experimental Example 3), followed by Fenton's in 3% hydrogen peroxide (H ₂ O ₂ ) at 60 ° C. the reagent is placed into the Fe ^{2 +} 4 ppm solution added. After that, the polymer electrolyte membrane of Example 1 The change in weight was measured to infer chemical stability, and the results are shown in FIG. 4.

Figure 4 is a graph measuring the weight change to infer the chemical stability of the polymer electrolyte membrane according to an embodiment of the present invention.

As shown in FIG. 4, it was observed that the SPEEK electrolyte membrane without the crosslinking agent was rapidly increased in weight after 30 minutes, and thus the chemical stability of the SPEEK electrolyte membrane was decreased so that the weight change could not be measured anymore after 60 minutes. However, in the case of the polymer electrolyte membrane prepared in Example 1, it was confirmed that there was no significant weight change after 400 minutes and had chemical stability.

Therefore, the polymer electrolyte membrane according to the present invention is excellent in chemical stability even for long time use, and thus can be usefully used as a hydrocarbon-based polymer electrolyte membrane such as an ion exchange membrane, a fuel cell membrane, or a battery separator.

Claims (13)

Preparing a crosslinking agent mixture by mixing 35 to 60 wt% of a monofunctional crosslinking agent, 0 to 35 wt% of a polyester acrylic oligomer crosslinking agent and 5 to 45 wt% of a multifunctional crosslinking agent (step 1);
Preparing a mother liquor by dissolving 1 to 10% by weight of the crosslinking agent mixture prepared in Step 1 and 1 to 10% by weight of a hydrocarbon-based polymer in 85 to 95% by weight of a solvent (step 2);
Casting and drying the mother liquor prepared in step 2 onto a glass plate (step 3); And
Method for producing a hydrocarbon-based polymer electrolyte membrane comprising the step of irradiating and drying the radiation (step 4).
The method of claim 1, wherein the monofunctional crosslinking agent of step 1 is at least one selected from the group consisting of EOEOEA (2- (2-ethoxyethoxy) ethyl acrylate), HEA (Hydroxyethyl acrylate) and EHA (ethylhexyl acrylate). Method of producing a hydrocarbon-based polymer electrolyte membrane.
The method of claim 1, wherein the polyesteracryl-based oligomer crosslinking agent of step 1 is polyesteracrylic.
The method of claim 1, wherein the multifunctional crosslinking agent of step 1 is at least one selected from the group consisting of trimethylol propane trimethacrylate (TMPTA) and hexanediol diacrylate (Hexanedioldiacrylate, HDDA). A method for producing a hydrocarbon-based polymer electrolyte membrane.
The solvent of claim 1, wherein the solvent of step 2 is selected from the group consisting of N, N-dimethylacetamide (DMAc), 1-methyl-2-pyrrolidinone (NMP), and dimethyl sulfoxide (DMSO). A method for producing a hydrocarbon-based polymer electrolyte membrane, characterized in that above.
The method of claim 1, wherein the hydrocarbon polymer of step 2 is sulfonate poly (ether ether ketone) (SPEEK), sulfonate poly (aryl ether sulfone), sulfonate poly (imide) and sulfonate poly (phenylene oxide) A method for producing a hydrocarbon-based polymer electrolyte membrane, characterized in that at least one member selected from the group consisting of
The method according to claim 1, wherein the radiation of step 4 is one selected from the group consisting of gamma rays, ultraviolet rays and electron beams.
The method of claim 7, wherein the radiation is an electron beam.
The method according to claim 7, wherein the radiation is irradiated by a radiation dose of 80 to 120 kGy at a dose rate of 4 to 8 kGy / min.
A hydrocarbon-based polymer electrolyte membrane prepared by the method according to any one of claims 1 to 9.
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