KR20150070577A - Crosslinked hydrocarbon polymer electrolyte membranes with diols by radiation and manufacturing method thereof - Google Patents

Abstract

According to the present invention, a cross-linked hydrocarbon-based polymer electrolyte membrane is formed by mixing a hydrocarbon-based polymer and a diol cross-linking agent at the optimal ratio and irradiating radiation beams onto the mixture. The membrane is formed by a cross-linking reaction at the room temperature rapidly to be prepared with a simple cross-linking process. The present invention has a sufficient gel transition rate and moisture absorbing rate to be used at a high temperature up to 180°C. The present invention also has the hydrogen ion conductivity higher than a conventionally used polymer electrolyte membrane to be used as an ion exchange membrane or a fuel cell membrane.

Description

Technical Field [0001] The present invention relates to a diol crosslinked hydrocarbon polymer electrolyte membrane using radiation, and a process for producing the crosslinked hydrocarbon polymer electrolyte membrane,

The present invention relates to a hydrocarbon-based polymer electrolyte membrane that is crosslinked with a diol using radiation, and a method for producing the same.

The fuel cell is a new power generation system that converts the energy generated by electrochemically reacting fuel gas and oxidizer gas into electric energy. It is more efficient than conventional internal combustion engine and can reduce carbon dioxide emissions, SO _x ) and oxides of nitrogen (NO _x ). Also, since it can be miniaturized and various fuels can be used, it can be applied to a wide range of fields such as a portable power source for mobile communication equipment, a power source for transporting automobiles, and a household and military power generation system.

Fuel cells can be classified into polymer electrolyte fuel cell (PEFC), alkaline fuel cell (AFC), phosphoric acid fuel cell (PAFC) A molten carbonate fuel cell (MCFC), and a solid oxide fuel cell (SOFC). Particularly, the polymer electrolyte fuel cell has attracted attention as a fuel cell due to its low operating temperature, high output density, and low environmental load. The proton exchange membrane fuel cell, in which hydrogen gas is used as fuel, PEMFC) and a direct methanol fuel cell (DMFC) in which methanol is used as a direct fuel without a reformer.

Polymer electrolyte membranes for fuel cells require high hydrogen ion conductivity and chemical, thermal, mechanical and electrochemical stability. In dehydration, the conductivity of hydrogen ion is drastically decreased, so it must be resistant to dehydration. In addition, it must be durable, thermally, physically and chemically stable to operate at temperatures as high as 90 ° C and in extreme acidic environments. For this reason, the study of polymer electrolyte membranes is recognized as a key factor in fuel cell development.

Conventional polymer electrolyte membranes mainly use sulfonated fluorinated polymers. Typically, there is Nafion R, a perfluorosulfonic acid cation exchange membrane of DuPont, USA. These fluorine-based polymers have excellent mechanical properties, chemical stability and ionic conductivity, but are complicated in the synthesis of synthesis materials and manufacturing processes, have a high production cost, have a low driving temperature (less than 1,000 ° C.) It has disadvantages.

Therefore, in order to compensate for this, the development cost of the hydrocarbon-based polymer made of low-cost materials has been actively developed or the total production cost has been reduced. Representative examples include sulfonate poly (ether ether ketone) (SPEEK), sulfonate poly (aryl ether sulfone), sulfonate phenol formalin, sulfonate poly (phenylene oxide), phosphonic poly (Phenylene oxide), and sulfonate poly (benzylimidazole).

Such a hydrocarbon-based polymer has excellent mechanical strength and chemical properties, is inexpensive to manufacture, and can control ion conductivity of a fuel cell membrane by controlling a cation exchange functional group (for example, a sulfonic acid group) introduced into a hydrocarbon-based polymer It has advantages.

However, when cation exchange functional groups are excessively introduced to increase the ionic conductivity, the hydrophilicity of the membrane is increased and the dimensional stability and mechanical strength are decreased. Therefore, studies are being actively carried out to introduce cross - linking structures to overcome these shortcomings.

US Journal of Membrane In Science 2009 , 345, 119, nanocomposite membranes based on sulfonate poly (etheretherketone) were prepared using 2,4,5-triaminopyrimidine and closilite to increase the dimensional stability and ionic conductivity Is disclosed.

US Journal of Power Source 2007 , 168, 154 describes a polymer electrolyte membrane having a crosslinked structure by using a sulfonate poly (ether ether ketone) as a basic structure, introducing a functional group having a double bond structure into a side chain, and using an ultraviolet curing method have.

United States Radiation Physics and Chemistry 2008 , 77, 617 discloses a method of grafting sulfonate styrene to a poly (etheretherketone) using an irradiation technique.

US Journal of Membrane Science 2008 , 332, 67 and Journal of Membrane Science 2006 , 285, 306 discloses a method for producing a fuel cell membrane having a crosslinked structure by thermally curing a diol to a sulfonated poly (ether ether ketone).

The prior art described above has a problem that it is difficult to widely use commercially because there are disadvantages such as synthesis of new polymer, long crosslinking process at high temperature, reduction of ion exchange capacity due to crosslinking, and the like.

Radiation-induced polymer crosslinking technology can form radicals without initiator as compared with formation of crosslinked structure by heat, ultraviolet ray, and plasma, and it does not cause decrease in weatherability due to initiator, and has a dense crosslinking structure to the inside of polymer due to high permeability of radiation And further, since no additional heat treatment is required, the crosslinked structure is formed in a short time, which is advantageous in energy efficiency.

Accordingly, the inventors of the present invention have conducted studies to solve the above problems, and have found that by mixing a diol crosslinking agent and a hydrocarbon resin at an optimal composition ratio and irradiating a radiation of an appropriate irradiation dose at room temperature to produce a crosslinked hydrocarbon- Crosslinkable hydrocarbon polymer membrane can be produced by a short-time crosslinking process, and the thermal stability is improved, thereby completing the present invention.

Journal of Membrane Science 2009, 345, 119 Journal of Power Source 2007, 168, 154 Radiation Physics and Chemistry 2008, 77, 617 Journal of Membrane Science 2008, 332, 67 Journal of Membrane Science 2006, 285, 306

An object of the present invention is to provide a process for producing a diol crosslinked hydrocarbon-based polymer electrolyte membrane by mixing a diol cross-linking agent and a hydrocarbon-based polymer and irradiating the radiation.

Another object of the present invention is to provide a diol crosslinked hydrocarbon-based polymer electrolyte membrane having improved thermal stability, which is produced by the above-described process.

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

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

The present invention relates to a process for producing a diol crosslinked hydrocarbon-based polymer electrolyte membrane and a polymer electrolyte membrane using the same.

According to an aspect of the present invention,

a) preparing a mother liquor comprising a diol crosslinking agent, a hydrocarbon resin and a solvent represented by the general formula (1); And

b) casting said mother liquor and irradiating it with radiation;

Based polymer electrolyte membrane.

[Chemical Formula 1]

이고;(Wherein A in the above formula

ego;

Each R ₁ and R ₃ are independently (C1-C20) alkylene, (C3-C20) cycloalkylene, (C3-C20) heterocycloalkyl alkylene, (C6-C20) arylene or (C6-C20) Lt; / RTI > and heteroarylene;

,

로 이루어진 군에서 선택되는 어느 하나일 수 있으며;Wherein R < ₂ > is a single bond,

,

≪ / RTI >

M and n are each independently an integer of 0 to 10, except when m and n are 0 at the same time.

Another aspect of the present invention relates to a diol bridged hydrocarbon-based polymer electrolyte membrane produced by the above method.

Another aspect of the present invention relates to an ion exchange membrane or fuel cell membrane comprising the diol bridged hydrocarbon-based polymer electrolyte membrane.

The crosslinked hydrocarbon polymer electrolyte membrane prepared by mixing the diol crosslinking agent mixture and the hydrocarbon polymer according to the present invention at an optimal composition ratio and irradiating the crosslinking agent is crosslinked at a room temperature for a short time to perform a crosslinking process. In addition, it exhibits sufficient gelation rate and water absorption rate and can be used at high temperatures up to 180 ° C. In addition, it has superior thermal stability and thermal curing, and exhibits a hydrogen ion conductivity higher than that of conventionally used polymer electrolyte membranes, and thus can be effectively used as a polymer electrolyte membrane such as an ion exchange membrane and a fuel cell membrane.

FIG. 1 shows a process of manufacturing a polymer electrolyte membrane according to an embodiment of the present invention.
2 is a graph showing the gelation degree of the polymer electrolyte membrane according to Examples 1 to 42 of the present invention.
3 is a graph showing the ion exchange capacity of the polymer electrolyte membrane according to Examples 5, 11, 17, 23, 29, 35, 41 and Comparative Examples 1 to 7 of the present invention.
4 is a graph showing dynamic / mechanical properties of a polymer electrolyte membrane according to Examples 5, 17, 29 and 41 of the present invention.
5 is a graph showing the ionic conductivity of the polymer electrolyte membranes according to Examples 5, 17, 29, 41 and Comparative Examples 1, 3, 5, and 7 of the present invention.

Hereinafter, an apparatus for selectively separating iodine in radioactive wastewater according to the present invention will be described in detail with reference to specific examples or examples. It should be understood, however, that the invention is not limited thereto and that various changes and modifications may be made without departing from the spirit and scope of the invention.

Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

Also, the singular forms as used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly indicates otherwise.

A process for producing a diol crosslinked hydrocarbon-based polymer electrolyte membrane according to the present invention comprises the steps of: a) preparing a mother liquor comprising a diol crosslinking agent represented by the general formula (1), a hydrocarbon resin and a solvent; And b) casting the mother liquor and irradiating it with radiation.

Hereinafter, the present invention will be described in detail.

The diol crosslinked hydrocarbon-based polymer electrolyte membrane according to the present invention starts by preparing a mother liquor containing a diol crosslinking agent, a hydrocarbon resin and a solvent represented by the general formula (1) as in step a).

The diol cross-linking agent according to the present invention improves the dimensional stability of the polymer electrolyte membrane, and may have a structure represented by the following formula (1).

[Chemical Formula 1]

이고;(Wherein A in the above formula

ego;

Each R ₁ and R ₃ are independently (C1-C20) alkylene, (C3-C20) cycloalkylene, (C3-C20) heterocycloalkyl alkylene, (C6-C20) arylene or (C6-C20) Lt; / RTI > and heteroarylene;

,

로 이루어진 군에서 선택되는 어느 하나일 수 있으며;Wherein R < ₂ > is a single bond,

,

≪ / RTI >

M and n are each independently an integer of 0 to 10, except when m and n are 0 at the same time.

More specifically, A in formula (1) may have a structure represented by the following formulas (2) to (6).

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(In the formula (2), 1 is an integer of 2 to 10)

More specifically, the diol cross-linking agent may have a structure of the following formulas (7) to (13).

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

The diol crosslinking agent according to the present invention is preferably added in an amount of 0.5 to 15% by weight based on 100% by weight of the whole mother liquor. When the diol cross-linking agent is added in an amount of less than 0.5 wt%, crosslinking reaction does not occur and dimensional stability is difficult to secure. When the diol cross-linking agent is added in an amount of more than 15 wt%, the ionic conductivity and ion exchange capacity are deteriorated.

The hydrocarbon resin serves to form the basic skeleton of the polymer electrolyte membrane. As the hydrocarbon resin, for example, any one or a mixture of two or more selected from the group consisting of sulfonate polyether ether ketone, sulfonate polyaryl ether sulfone, sulfonate polyimide and sulfonate polyphenylene oxide can be used , But the present invention is not limited thereto.

The hydrocarbon resin is preferably added in an amount of 5 to 30% by weight based on 100% by weight of the whole mother liquor. When the amount is less than 5% by weight, the polymer electrolyte membrane is not properly formed. When the amount is more than 30% by weight, the dimensional stability is greatly reduced.

The solvent is not limited to any kind as long as it is a substance capable of effectively dissolving a hydrocarbon resin and a diol cross-linking agent as mother liquor constituents in the present invention. Examples of the solvent include N, N-dimethyl acetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, And 1,3,5-trimethylbenzene. Preferred examples of the solvent include N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide May be used alone or in combination, but the present invention is not limited thereto.

The solvent is preferably added in an amount of 65 to 90% by weight based on 100% by weight of the mother liquor. When the amount is less than 65% by weight, the dispersion of the solvent may not occur properly and the crosslinking density may increase. When the amount exceeds 90% by weight, the polymer electrolyte membrane may not be formed properly.

When the mother liquor is produced, the step of casting the mother liquor and irradiating the mother liquor as in the step b) may be performed to complete the polymer electrolyte membrane. Specifically, the step b) may include a step of casting the mother liquor on a glass plate and drying, followed by irradiating and drying the radiation.

The mother liquor can be cast by a method commonly used in the art, such as a solution casting method, by applying the mother liquor to a glass plate having a proper size at a room temperature at a predetermined thickness in the step b) Lt; 0 > C for 1 to 2 hours to evaporate the solvent. When the drying process is performed within the above-mentioned range, the solvent has some viscosity so that the solution does not flow.

After the mother liquor is cast and dried as described above, the resulting film is irradiated with radiation to cause crosslinking, thereby improving the mechanical strength of the polymer electrolyte membrane.

As the radiation, one or two or more selected from the group consisting of gamma rays, ultraviolet rays and electron rays may be irradiated, and it is preferable to irradiate electron rays.

The radiation is preferably irradiated at an irradiation dose of 50 to 600 kGy at a dose rate of 0.1 to 10 kGy / min, more preferably at an irradiation dose of 200 to 400 kGy at a dose rate of 1 to 7 kGy / min. When the irradiation dose of the radiation is less than 0.1 kGy / min, the reaction is too slow to increase the production time of the electrolyte membrane. When the irradiation dose exceeds 10 kGy / min, the crosslinking is not uniformized or the intermolecular bond is broken, do.

The crosslinked electrolyte membrane was vacuum dried at 100 to 140 ° C for 10 to 14 hours to remove residual solvent, cooled to room temperature, and then the diol crosslinked hydrocarbon-based polymer electrolyte membrane was separated from the glass plate to obtain a diol crosslinked hydrocarbon- A polymeric cation exchange membrane can be produced.

The method may further include a step of removing the impurities by washing and drying the cation exchange membrane prepared additionally. In one embodiment of the impurity removal process, the prepared cation exchange membrane may be immersed in an aqueous solution of 0.5 to 2 M HCl and distilled water for 12 to 72 hours to remove impurities and then dried.

The hydrocarbon-based polymer electrolyte membrane according to the present invention can be produced by mixing a diol cross-linking agent and a hydrocarbon-based resin at an optimum composition ratio and irradiating it with radiation to produce a cross-linking reaction at room temperature for a short time, It has a water absorption rate and thermal stability that can be used even at high temperatures up to 180 ° C. It has a hydrogen ion conductivity higher than that of a thermo-cured polymer electrolyte membrane and can be used as a polymer electrolyte membrane such as an ion exchange membrane and a fuel cell membrane have.

Hereinafter, the diol crosslinked hydrocarbon-based polymer electrolyte membrane according to the present invention will be described in more detail. However, the following examples are only illustrative of the present invention in further detail, and the present invention is not limited by the following examples.

Physical properties of the polymer electrolyte membrane prepared through the following examples and comparative examples were measured as follows.

(Degree of gelation)

The resulting polymer electrolyte membrane was immersed in DMAc for one day, and the change in weight was measured, and then the degree of gelation was measured by the following formula 1, and it is shown in FIG.

[Formula 1]

(W _dry in the above formula 1 is the weight of the polymer electrolyte membrane before being immersed in the DMAc solvent, and W _dissolved is the weight of the electrolyte membrane after immersing in the DMAc solvent.)

(Ion exchange capacity, IEC)

The polymer electrolyte membranes prepared in Examples 5, 11, 17, 23, 29, 35 and 41 were placed in a 3M NaCl solution for 24 hours to neutralize H + of the sulfone group into Na + form, Respectively. For accurate neutralization titration, an automatic titrator DL22 (Mettler Toledo Company, Switzerland) was used and the IEC value was calculated using the following equation 2 and shown in FIG.

[Formula 2]

(In the formula 2, C _NaOH is the concentration of NaOH, V _NaOH is the volume of 0.1 M NaOH solution used during neutralization titration, and W _dry is the _dry weight of the crosslinked polymer electrolyte membrane).

(Water absorption rate)

After the polymer electrolyte membranes prepared in Examples 5, 11, 17, 23, 29, 35 and 41 were immersed in distilled water for 24 hours at room temperature, water present on the surface of the electrolyte membrane was removed, 3, and the results are shown in Table 4 below.

[Formula 3]

(Where W _d is the weight of the dried film and W _s is the weight of the film that has absorbed water).

(Dynamic / mechanical properties)

The dynamic and mechanical properties of the polymer electrolyte membranes prepared in Examples 5, 17, 29 and 41 were tested at a frequency of 1 Hz in a temperature range of -50 to 300 ° C using a TA DMA Q800 (TA Instruments, USA) Is set at 2 [deg.] C / min and measured values are shown in Fig.

(Ion conductivity)

The polymer electrolyte membranes prepared in Examples 5, 17, 29 and 41 and the polymer electrolyte membranes prepared in Comparative Examples 1, 3, 5 and 7 were measured for the resistance of the electrolyte using an AC impedance analyzer (SI 1260, Solatron Company) . At this time, the impedance measurement was recorded according to the temperature change in the frequency range of 0.01 to 100 kHz, and the hydrogen ion conductivity was calculated using the following equation 4, and the results are shown in FIG.

[Formula 4]

(Where L is the distance between two electrodes, A is the width in the thickness direction of the polymer electrolyte membrane, and R is the electrical resistance)

< Example  1> Crosslinking using radiation crosslinking method SPEEK As a basic skeleton Polymer electrolyte membrane  Produce

A polymer electrolyte membrane having a hydrocarbon-based crosslinking structure having SPEEK (sulfonate poly (ether ether ketone)) as a basic skeleton having improved high-temperature and dimensional stability according to the present invention was prepared as shown in Fig.

Specifically,

Step 1: Mother liquor  Steps to manufacture

Sulfonate poly (ether ether ketone) (SPEEK) and a crosslinking agent represented by the formula (1) were mixed in the N, N-dimethylacetamide (DMAc) solvent at the composition ratios shown in Table 1 below to prepare a mother liquor at room temperature.

Step 2: Mother liquor  Cast on a glass plate Dry  step

The mother liquor prepared in the step 1 was uniformly sprayed on a 15 cm x 15 cm glass plate at room temperature using a solution casting method. The glass plate on which the mother liquor was dispersed was dried at 70 캜 and N, N-dimethylacetamide (DMAc) as a solvent was evaporated for 1 hour.

Step 3: Exposure to radiation Dry  step

The glass plate on which the solvent was evaporated in the step 2 was irradiated with an irradiation dose shown in Table 1 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, and then cooled to room temperature. Then, the prepared polymer electrolyte membrane was separated from the glass plate using distilled water. Finally, the polyelectrolyte membrane prepared above was placed in a 1 M HCl aqueous solution for 48 hours to remove impurities to prepare a crosslinked hydrocarbon-based polymer electrolyte membrane according to the present invention.

Examples 1 to 42 were prepared as shown in Tables 1 and 2 below.

[Table 1]

[Table 2]

< Comparative Example > Thermal crosslinking  Bridging method SPEEK As a basic skeleton Polymer electrolyte membrane  Produce

A polymer electrolyte membrane having a hydrocarbon bridge structure having a basic skeleton of PEEK (sulfonate poly (ether ether ketone)) using a thermosetting method which has been used in the prior art was prepared.

Specifically,

Step 1: Mother liquor  Steps to manufacture

Sulfonate poly (ether ether ketone) (SPEEK) and a crosslinking agent represented by the formula (1) were mixed in a N, N-dimethylacetamide (DMAc) solvent at the composition ratios shown in Table 2 below to prepare a mother liquor at room temperature.

Step 2: Mother liquor  Cast on a glass plate Dry  step

The mother liquor prepared in the step 1 was uniformly sprayed on a 15 cm x 15 cm glass plate at room temperature using a solution casting method. The glass plate on which the mother liquor was dispersed was dried at a high temperature of 80 캜, and N, N-dimethylacetamide (DMAc) as a solvent was evaporated for 12 hours.

Step 3: Cross-linking step using thermosetting

The glass plate in which the solvent was evaporated in the step 2 was thermally crosslinked under vacuum drying conditions at 60 ° C for 2 hours, 80 ° C for 2 hours, 100 ° C for 2 hours, 120 ° C for 2 hours and 135 ° C for 16 hours After cooling to room temperature, the prepared polymer electrolyte membrane was separated from the glass plate using distilled water. Finally, the polyelectrolyte membrane prepared above was placed in a 1 M aqueous HCl solution for 48 hours to remove impurities, and a polymer electrolyte membrane having a hydrocarbon crosslinked structure was prepared.

Comparative Examples 1 to 7 were prepared as shown in Table 3 below.

[Table 3]

First, in the case of gelation degree, as shown in FIG. 2, the gelation degree of the polymer electrolyte membrane prepared at the C5 to C60 composition ratio is more than 40% at the irradiation rate of 200 kGy. Also, even if the irradiation rate is less than 200 kGy, the degree of gelation tends to increase as the crosslinking agent content increases.

In the case of the ion exchange capacity, it can be seen that the EB-irradiation embodiment prepared by the radiation crosslinking method as shown in Fig. 3 has better ion exchange capacity than the thermal curing comparative example . In particular, it can be confirmed that the ion exchange capacity is 1.61 meq / g in all the examples.

As shown in Table 4 below, the moisture absorption rate was found to be less than about 48%.

[Table 4]

In the case of the dynamic / mechanical properties, as shown in FIG. 4, the polymer electrolyte membrane prepared by adding the crosslinking agent mixture in the Examples shows a glass transition temperature, ionic modulus, ionic bond After showing the transition temperature, it was confirmed that it had a flowing property. Also, it was confirmed that the temperature at which the flow of all the crosslinked polymer electrolyte membranes starts is about 190 ° C.

In the case of ionic conductivity, as shown in FIG. 5, it was confirmed that the hydrogen ion conductivity of the polyelectrolyte membrane according to each example increased with increasing temperature. However, in the case of Example 5, the ionic conductivity decreases when the temperature rises above 60 ° C. This phenomenon is caused by the absorption of too much moisture and the decrease in mechanical strength. Therefore, it is understood that a film having a gelation rate of 50% or more is required to have hydration stability. On the other hand, when the thermosetting composition was prepared as in the comparative example, it was confirmed that the ion conductivity was lower than that of the examples.

Therefore, the polymer electrolyte membrane according to the present invention has a simple crosslinking process at a room temperature for a short period of time, has a sufficient gelation rate and water absorption rate, can be used even at a high temperature of 180 ° C, The polymer electrolyte membrane exhibits a higher hydrogen ion conductivity than the polymer electrolyte membrane and can be usefully used as a polymer electrolyte membrane such as an ion exchange membrane fuel cell membrane.

Claims (12)

a) preparing a mother liquor comprising a diol crosslinking agent, a hydrocarbon resin and a solvent represented by the general formula (1); And
b) casting said mother liquor and irradiating it with radiation;
Based polymer electrolyte membrane.
[Chemical Formula 1]

(Wherein A in the above formula

ego;
Each R ₁ and R ₃ are independently (C1-C20) alkylene, (C3-C20) cycloalkylene, (C3-C20) heterocycloalkyl alkylene, (C6-C20) arylene or (C6-C20) Lt; / RTI &gt; and heteroarylene;
Wherein R &lt; ₂ &gt; is a single bond,

,

&Lt; / RTI &gt;
M and n are each independently an integer of 0 to 10, except when m and n are 0 at the same time. The method according to claim 1,
Wherein A is any one selected from the group consisting of the following formulas (2) to (6).
(2)
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(In the formula (2), 1 is an integer of 2 to 10) The method according to claim 1,
Wherein the diol cross-linking agent is any one or two or more selected from the following formulas (7) to (13).
(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

The method according to claim 1,
Wherein the mother liquor comprises 0.5 to 15% by weight of a diol cross-linking agent, 5 to 30% by weight of a hydrocarbon-based resin and 65 to 90% by weight of a solvent. The method according to claim 1,
The solvent is selected from the group consisting of N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, tetrahydrofuran, dimethylformamide, toluene, cyclohexane, benzene, chlorobenzene, , 5-trimethylbenzene, or a mixture of two or more thereof. The method according to claim 1,
Wherein the hydrocarbon resin is at least one selected from the group consisting of a sulfonate polyether ether ketone, a sulfonate polyaryl ether sulfone, a sulfonate polyimide, and a sulfonate polyphenylene oxide, wherein the diol crosslinked hydrocarbon polymer electrolyte &Lt; / RTI &gt; The method according to claim 1,
Wherein the radiation is any one selected from the group consisting of gamma rays, ultraviolet rays, and electron beams. 8. The method of claim 7,
Wherein the radiation is an electron beam. 8. The method of claim 7,
Wherein the radiation is irradiated at an irradiation dose of 50 to 600 kGy at a dose rate of 0.1 to 10 kGy / min. 10. A diol crosslinked hydrocarbon-based polymer electrolyte membrane produced by any one of the methods selected from the group consisting of the first to the ninth aspects. An ion exchange membrane comprising the diol bridged hydrocarbon-based polymer electrolyte membrane of claim 10. A fuel cell membrane comprising the diol bridged hydrocarbon-based polymer electrolyte membrane of claim 10.

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