KR20180075018A - Crosslinked cation exchange resin (CER)/ cation exchange polymer composite membrane by radiation and fabrication thereof - Google Patents

Abstract

The present invention relates to a crosslinked cation-exchange resin/cation-exchange polymer composite membrane comprising a crosslinker having three or more radiation-crosslinkable vinyl groups, a cation-exchange polymer, and a cation-exchange resin, and to a preparation method for the same. According to the present invention, the crosslinked cation-exchange resin/cation-exchange polymer composite membrane is prepared by mixing a crosslinker having three or more vinyl groups in which a crosslinking structure can be introduced by radiation, a cation-exchange resin having high ion-exchange capacity, and a cation-exchange polymer in an appropriate ratio, and irradiating the mixture with radiation; can be prepared at room temperature in a short time; and has high dimensional stability as well as high permeation selectivity while maintaining high ion exchange capacity, and thus may be utilized in an ion exchange membrane, a fuel cell membrane, a flow battery membrane for a large-capacity secondary battery, a water treatment membrane, and the like.

Description

Technical Field [0001] The present invention relates to a cation exchange resin / cation exchange polymer composite membrane by radiation crosslinking and a method for producing the same,

The present invention relates to a crosslinked cation-exchange resin / cation-exchange polymer composite membrane comprising a crosslinking agent having three or more vinyl groups capable of crosslinking by radiation, a cation-exchange polymer and a cation-exchange resin, and a process for producing the same.

Ion exchange membranes have been widely applied in many industrial fields since their introduction in 1890, when Maigrot and Sabate first removed inorganic ions from sugar syrup using permanganate paper as a separator. The process of separating and purifying a substance using an ion exchange membrane is simple and has excellent selectivity for a specific ion and has a wide range of applications. Particularly, the ion exchange membrane is capable of selectively separating cations and anions in an aqueous solution, and thus can be used for a fuel cell, a secondary battery, a flow cell, a water electrolysis electrodialysis for acid and base recovery, diffusion dialysis for recovering acid and metal species from a pickling effluent, Ultrapure water process and the like.

Currently commercially available ion exchange membranes include Nafion from Dupont, fluorine-based ion exchange membranes such as R-1010 and R-1030 from RAI Research, non-fluorine ion exchange membranes such as AMX, CMX from Tokuyama Soda, and S-SEBS from Kraton Polymers And the fluorine-based ion exchange membrane has an advantage of being excellent in chemical stability due to the introduction of a fluorine group into the main chain of the polymer, but its disadvantage is that it is limited in use in various fields due to complicated manufacturing process, reduction of ionic conductivity at a high price and high temperature Have. On the other hand, the non-fluorine-based ion exchange membrane has a relatively low cost compared to the fluorine-based ion exchange membrane and has a simple manufacturing process. However, when the ion exchange capacity is increased by introducing excessive ion exchange function to improve the performance of the ion exchange membrane, The volume strain is increased and the durability of the membrane is decreased.

In order to solve these problems, various methods such as introduction of inorganic particles, blending of polymers, and crosslinking of polymers are used. Among them, the crosslinking method has been applied to many fields because it has the advantages of improving the mechanical strength and thermal stability, improving the disadvantages of the ion exchange membrane having high water content and low dimensional stability.

Various methods have been used to introduce ion exchange membrane crosslinking structures. In the case of thermal crosslinking, a crosslinking process at a high temperature is required for a long time, and crosslinking using UV is disadvantageous in that it can not form a crosslinked structure uniformly due to contamination due to the use of an initiator and low permeability. The crosslinking technique using radiation does not require an initiator and can form a dense crosslinked structure to the inside of the ion exchange membrane due to high permeability of radiation, and it can shorten the time required for the manufacturing process.

Accordingly, the present inventors have conducted studies on cation exchange membranes having high ion exchange capacity and excellent dimensional stability and permeation selectivity, and have found that cation exchange resins having high ion exchange capacity, crosslinking agents having three vinyl groups capable of crosslinking by radiation, and cation exchange polymers And then irradiated with an electron beam at an appropriate irradiation dose at room temperature to obtain a crosslinked ion exchange resin / ion exchange polymer composite cation exchange membrane having a crosslinked structure. And that the dimensional stability and transmission selectivity are improved due to the formation of a crosslinked structure by radiation, thus completing the present invention.

Patent Registration No. 10-1655409

An object of the present invention is to provide a radiation crosslinked cation exchange resin / cation exchange polymer composite membrane having a high ion exchange capacity and improved dimensional stability.

Another object of the present invention is to provide a process for producing the crosslinked cation-exchange resin / cation-exchange polymer composite membrane.

It is another object of the present invention to provide a cation exchange membrane comprising the crosslinked cation exchange resin / cation exchange polymer composite membrane.

Another object of the present invention is to provide a water treatment membrane comprising the crosslinked cation exchange resin / cation exchange polymer composite membrane.

Another object of the present invention is to provide a fuel cell membrane comprising the crosslinked cation-exchange resin / cation-exchange polymer composite membrane.

In order to achieve the above object,

The present invention relates to a cation exchange polymer;

A crosslinking agent having three or more vinyl groups; And

Cation exchange resin;

Exchange resin / cation-exchange polymer composite membrane.

The present invention also relates to a method for preparing a cation exchange resin, comprising the steps of: dissolving a cation exchange polymer, a crosslinking agent having three or more vinyl groups in a solvent, adding and dispersing a cation exchange resin to prepare a mother liquor (step 1);

Casting the mother liquor prepared in step 1 on a glass plate and drying (step 2); And

Irradiating and drying the radiation (step 3);

Exchange resin / cation-exchange polymer composite membrane.

Furthermore, the present invention provides a cation exchange membrane comprising the crosslinked cation exchange resin / cation exchange polymer composite membrane.

The present invention also provides a water treatment membrane comprising the crosslinked cation exchange resin / cation exchange polymer composite membrane.

Further, the present invention provides a fuel cell membrane comprising the crosslinked cation-exchange resin / cation-exchange polymer composite membrane.

A crosslinking agent having three or more vinyl groups capable of introducing a crosslinking structure by radiation according to the present invention, a cation exchange resin having a high ion exchange capacity, a crosslinking cation exchange resin / cation exchange resin prepared by mixing a cation exchange polymer with an appropriate composition ratio, The polymer composite membrane can be manufactured at room temperature in a short time, and it can be used for an ion exchange membrane, a fuel cell membrane, a flow cell membrane for a large-capacity secondary battery, and a water treatment membrane because it has high dimensional stability and high permeation selectivity while maintaining high ion exchange capacity .

1 is a schematic view showing a process for producing a crosslinked cation-exchange resin / cation-exchange polymer composite membrane according to the present invention.
FIG. 2 is a graph showing a gelation rate of a crosslinked cation-exchange resin / cation-exchange polymer composite membrane according to one embodiment of the present invention and a comparative example.
3 is a graph showing the ion exchange capacity of a crosslinked cation-exchange resin / cation-exchange polymer composite membrane according to one embodiment of the present invention and a comparative example.
4 is a graph showing the water content of a crosslinked cation-exchange resin / cation-exchange polymer composite membrane according to one embodiment of the present invention and a comparative example.
5 is a graph illustrating the dimensional stability of a crosslinked cation exchange resin / cation exchange polymer composite membrane according to an embodiment of the present invention.
FIG. 6 is a graph showing transmission selectivity of a crosslinked cation-exchange resin / cation-exchange polymer composite membrane according to an embodiment of the present invention and a comparative example.

Hereinafter, the present invention will be described in detail.

Crosslinked cation exchange resin / cation exchange polymer composite membrane

The present invention relates to a cation exchange polymer;

A crosslinking agent having three or more vinyl groups; And

Cation exchange resin;

Exchange resin / cation-exchange polymer composite membrane.

The crosslinked cation-exchange resin / cation-exchange polymer composite membrane comprises 30 to 75 parts by weight of a cation-exchange polymer; 5-40 parts by weight of a crosslinking agent having 3 or more vinyl groups; And 10-50 parts by weight of a cation exchange resin.

The cation exchange polymer may be selected from the group consisting of sulfonated polystyrene (SPS), sulfonated poly (ether ether ketone), SPEEK, sulfonated polysulfone (SPSu), sulfonated poly (SPES), sulfonated polyimide (SPI), sulfonated poly (phenylene oxide), SPPO), or the like can be used alone or in combination with one or more of the above-mentioned sulfonated poly (ether sulfone) But the present invention is not limited thereto.

Here, the cation exchange polymer is a polymer containing a sulfonic acid group and serves to facilitate cation exchange.

The cation exchange polymer may be used in an amount of 30-75 parts by weight, preferably 35-70 parts by weight. If it is added in an amount of less than 30 parts by weight, it may be difficult to form a film, and when it is added in an amount exceeding 75 parts by weight, it may be difficult to secure dimensional stability of the film.

The three vinyl group-containing crosslinking agents may be selected from the group consisting of trimethylolpropane ethoxylate triacrylate (TMPETA), trimethylolpropane trimethacrylate (TMPTA), triallyl isocyanurate , TAIC), pentaerythritol triallyl ether (PETALE), etc. may be used alone or in combination.

Here, the crosslinking agent having three vinyl groups serves to improve the dimensional stability of the composite membrane.

The content of the crosslinking agent having three vinyl groups may be 5-40 parts by weight, preferably 7-35 parts by weight. If it is added in an amount of less than 5 parts by weight, there may be a problem of decrease in mechanical strength and dimensional stability, and when it is added in an amount exceeding 40 parts by weight, flexibility may be decreased and the film may be fragile.

The cation exchange resin is a sulfonated polystyrene (SPS) crosslinked with divinyl benzene (DVB), and may be particles having a size of 1-25 탆. The particle size of the cation exchange resin is preferably 1-25 탆, and when it is more than 25 탆, dispersion by a solvent may be difficult.

Here, the cation exchange resin serves to improve ion exchange capacity and dimensional stability. The cation exchange resin is preferably immersed in a 1 M aqueous hydrochloric acid solution for 24 hours to replace sodium ions remaining in the cation exchange resin with hydrogen ions. If acid treatment is not carried out, there may be a problem of causing a decrease in ion exchange capacity.

The content of the cation exchange resin may be 10-50 parts by weight, preferably 20-40 parts by weight, more preferably 25-35 parts by weight. If it is added in an amount of less than 10 parts by weight, there may be a problem that the dimensional stability to water is lowered, and when it is added in an amount exceeding 50 parts by weight, there may be a problem that the film flexibility is lowered.

Manufacturing method

The present invention relates to a method for producing a cation exchange resin, comprising the steps of: dissolving a cation exchange polymer, a crosslinking agent having three or more vinyl groups in a solvent, adding and dispersing a cation exchange resin to prepare a mother liquor (step 1);

Casting the mother liquor prepared in step 1 on a glass plate and drying (step 2); And

Irradiating and drying the radiation (step 3);

Exchange resin / cation-exchange polymer composite membrane.

In the manufacturing method according to the present invention, step 1 is a step of dissolving a cation-exchange polymer, a crosslinking agent having three or more vinyl groups in a solvent, adding a cation-exchange resin, and dispersing the solution to prepare a mother liquor. Specifically, Step 1 is a step of dissolving 3 to 21.5 wt% of a cation exchange polymer, 3 to 11 wt% of a crosslinking agent having 3 or more vinyl groups in 70 to 90 wt% of a solvent, adding 2.5 to 9.5 wt% And then dispersed to prepare a mother liquor.

The method may further include a step of holding the cation exchange resin in an aqueous hydrochloric acid solution for 12 to 36 hours before the step 1, followed by washing and drying. It is preferable to replace sodium ions remaining in the cation exchange resin with hydrogen ions. If acid treatment is not performed, there may be a problem of causing a decrease in ion exchange capacity.

The cation exchange polymer, the cross-linking agent and the cation exchange resin are as described above.

The solvent in this Step 1 serves to dissolve the cation exchange polymer and the crosslinking agent having three or more vinyl groups. As the solvent, a polar solvent such as N, N-dimethylacetamide (DMAc), 1-methyl-2-pyrrolidinone (NMP) or dimethylsulfoxide (DMSO) may be used alone or in combination.

At this time, the solvent is preferably added in an amount of 70 to 90% by weight to prepare a mother liquor. If the solvent is added in an amount of less than 70% by weight, there may be a problem of dispersion of a solvent and an increase in cross-linking density, and addition of more than 90% by weight may cause difficulty in film formation.

In the manufacturing method according to the present invention, the step 2 is a step of casting the mother liquor prepared in the step 1 on a glass plate and drying it.

Specifically, the solution is uniformly sprayed on a glass plate having an appropriate size at room temperature using a solution casting method, and the solvent is evaporated by drying at 60-80 ° C for 1-2 hours. When dried under these conditions, some of the solvent remains to have such a viscosity that the solution does not flow.

In the production method according to the present invention, step 3 is a step of irradiating and drying the radiation.

Specifically, in step 2, the solvent was evaporated to irradiate the film formed on the glass plate with radiation, vacuum-dried at room temperature for 10-14 hours to remove the remaining solvent, and then the resulting crosslinked cation exchange resin / cation exchange polymer composite The membrane can be separated from the glass plate using distilled water to produce the crosslinked cation-exchange resin / cation-exchange polymer composite membrane according to the present invention.

At this time, the radiation serves to improve the dimensional stability and mechanical strength by crosslinking the crosslinking agent and the cation exchange polymer / cation exchange resin. As the radiation, it is preferable to irradiate one species selected from the group consisting of gamma ray, ultraviolet ray and electron ray, and it is more preferable to irradiate with electron rays.

Preferably, the radiation is irradiated at a dose rate of 0.1 to 20 kGy / pass at an irradiation dose of 50 to 300 kGy, and irradiated at a dose rate of 1 to 10 kGy / pass at an irradiation dose of 100 to 200 kGy It is more desirable to give.

If the irradiation dose of the electron beam is less than 50 kGy, there may be a problem that sufficient crosslinking does not occur. If the irradiation dose exceeds 300 kGy, there is a possibility that the molecular weight is cut off, have.

A cation exchange membrane, a water treatment membrane, a fuel cell membrane

The present invention provides a cation exchange membrane comprising the crosslinked cation exchange resin / cation exchange polymer composite membrane.

The present invention also provides a water treatment membrane comprising the crosslinked cation exchange resin / cation exchange polymer composite membrane.

Further, the present invention provides a fuel cell membrane comprising the crosslinked cation-exchange resin / cation-exchange polymer composite membrane.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

EXAMPLES Preparation of Crosslinked Cation-Exchange Resin / Cation-Exchange Polymer Composite Membrane Using Radiation Crosslinking Method

Crosslinked sulphonated polystyrene having cation exchange resin and sulfonated polystyrene (SPS) with high ion exchange capacity and improved dimensional stability and permeation selectivity according to the present invention Radiation crosslinked cation exchange resin / cation exchange polymer composite A cation exchange membrane was prepared.

Step 1: Cation exchange polymer / Cross-linking agent / Cation exchange resin Mother liquor  Steps to manufacture

After dissolving the polystyrene polymer in dichloroethane solvent, sulfuric acid was added to the polystyrene at 60/40 molar ratio of styrene and sulfuric acid, and the sulfonated polystyrene was poured into boiling distilled water at 60 ° C for 1 hour to precipitate sulfonated polystyrene, Polystyrene cation exchange polymer was prepared. The cation exchange resin was immersed in a 1 M HCl solution for 24 hours. Subsequently, the sodium ion of the cation exchange resin was replaced with hydrogen ion, and then washed in distilled water at 80 ° C for 6 hours and dried in a vacuum oven at 50 ° C for 12 hours. The cation - exchange resin substituted with hydrogen ion was milled with a zirconium wheel at 320 rpm for 4 hours using a zirconium cylinder and 25 ㎛ of powder was obtained. After dissolving the prepared cation exchange polymer and a crosslinking agent trimethylolpropane ethoxylate triacrylate (TMPETA) having three or more vinyl groups in N, N-dimethylacetamide (DMAc), the pretreated cation exchange The resin was dispersed to prepare an ion exchange polymer / crosslinking agent / cation exchange resin mother liquor.

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 60 DEG C to evaporate N, N-dimethylacetamide (DMAc) as a solvent for 1 hour.

Step 3: Exposure to radiation Dry  step

The glass plate on which the solvent was evaporated in step 2 was irradiated with electron beams of 100 kGy and 200 kGy with a dose rate of 10 kGy / pass. The irradiated glass plate was vacuum dried at 100 ° C for about 12 hours to remove the residual DMAc solvent, cooled to room temperature, and then the resulting crosslinked cation-exchange resin / cation-exchange polymer composite membrane was separated from the glass plate using distilled water. Finally, the crosslinked cation-exchange resin / cation-exchange polymer composite membrane prepared above was dried in a vacuum oven at 60 ° C. for 12 hours to prepare a crosslinked cation-exchange resin / cation-exchange polymer composite membrane according to the present invention.

Examples 1 to 6 were prepared as shown in Table 1 below.

Example SPS
Ion exchange capacity (meq / g) SPS
content(%) TMPETA
Crosslinker content
(%) Cation exchange resin Ion exchange capacity (meq / g) Cation exchange resin content (%) Irradiation dose (kGy) One 1.32 70 0 3.97 30 200 2 1.32 63 7 3.97 30 200 3 1.32 49 21 3.97 30 100 4 1.32 49 21 3.97 30 200 5 1.32 35 35 3.97 30 100 6 1.32 35 35 3.97 30 200

≪ Comparative Example 1 > Preparation of sulfonated polystyrene cation exchange membrane

A cation exchange polymer membrane was prepared by sulfonated polystyrene prepared by sulfonating polystyrene.

Step 1: Step of preparing a sulfonated polystyrene cation-exchange polymer

After dissolving the polystyrene polymer in dichloroethane solvent, the molar ratio of styrene and sulfuric acid in polystyrene was added at 50/50 molar ratio and sulfuric acid was added. The sulfonated polystyrene was poured into boiling distilled water at 60 ° C for 1 hour to precipitate sulfonated polystyrene, Polystyrene cation exchange polymer was prepared.

Step 2: Step of preparing a sulfonated polystyrene cation exchange membrane

The sulfonated polystyrene prepared in the step 1 was dissolved in DMAc solvent at a concentration of 10% by weight, and sprayed uniformly on a 15 cm × 15 cm glass plate at room temperature using a solution casting method. The glass plate in which the sulfonated polystyrene solution was dispersed was vacuum dried at 60 ° C for 12 hours, and then the sulfonated polystyrene cation exchange polymer membrane was separated from the glass plate using distilled water. Finally, the polystyrene cation exchange membrane prepared above was dried in a vacuum oven at 60 DEG C for 12 hours to prepare a comparative polystyrene cation exchange membrane of the present invention.

Experimental Example 1 Gelation degree measurement

The gelation degree of the crosslinked cation exchange resin / cation exchange polymer composite membrane prepared in Examples 1 to 6 was examined in the following manner. Specifically, the crosslinked cation-exchange resin / cation-exchange polymer composite membrane prepared in Examples 1 to 6 was immersed in DMAc, a solvent used before electron beam irradiation, for one day, and the change in weight was observed. The results are shown in Fig.

In the above equation (1)

W _dry is the weight of the crosslinked cation-exchange resin / cation-exchange polymer composite membrane before being immersed in the DMAc solvent,

W _dissolved is the weight of the crosslinked cation exchange resin / cation exchange polymer composite membrane after being soaked in the DMAc solvent for one day.

2 is a graph showing a gelation rate of a crosslinked cation-exchange resin / cation-exchange polymer composite membrane according to one embodiment of the present invention and a comparative example.

As shown in FIG. 2, it was confirmed that the crosslinking occurred in the TMPETA crosslinking agent content of 30 wt% or more (Example 3, Example 4, Example 5, Example 6), and particularly, the irradiation dose of the electron beam was 200 kGy , Example 6) showed a high gelation rate of 96% or more, thus confirming that sufficient crosslinking occurred.

EXPERIMENTAL EXAMPLE 2 Measurement of Ion Exchange Capacity (IEC)

In order to examine the IEC of the crosslinked cation-exchange resin / cation-exchange polymer composite membrane prepared in Examples 1, 2, 4, and 6, the following experiment was conducted using a neutralization titration method.

Specifically, the prepared crosslinked cation-exchange resin / cation-exchange polymer composite membrane was immersed in a 3 M NaCl solution for 24 hours to neutralize H ⁺ of the sulfone group to Na ⁺ form and then reverse-neutralize with 0.1 M NaOH. 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). The results are shown in FIG.

In Equation (2)

C _NaOH is the concentration of the NaOH solution, V _NaOH is the volume of the 0.1 M NaOH solution used during neutralization titration,

W _dry is the _dry weight of the crosslinked cation exchange resin / cation exchange polymer composite membrane.

3 is a graph showing ion exchange capacity of an ion exchange resin / ion exchange polymer composite cation exchange membrane having a crosslinked structure prepared according to one embodiment of the present invention and a comparative example.

As shown in FIG. 3, the cross-linked ion exchange resin / ion-exchange polymer composite prepared by the radiation crosslinking method of Examples 1, 2, 4, and 6 and having the ion exchange capacity of 1.93 meq / It was also confirmed that the cation exchange membrane had similar ion exchange capacity in the range of 1.93 to 2.11 meq / g.

Experimental Example 3 Measurement of Moisture Content

In order to examine the water content of the crosslinked cation exchange resin / cation exchange polymer composite membrane prepared in Comparative Example 1 and Examples 4 and 6, the following experiment was conducted.

Specifically, the crosslinked cation-exchange resin / ion-exchange polymer composite membrane prepared in Comparative Example 1 and Examples 4 and 6 was immersed in distilled water at 25 ° C and 60 ° C depending on the temperature, and then the water present on the surface of the prepared cation- And the weight change was observed. The moisture absorption rate was measured by the following equation (3), and the results are shown in FIG.

In Equation (3)

W _d is the weight of the dried film,

W _s is the weight of the film that absorbs moisture.

4 is a graph showing the water content of the ion exchange resin / ion exchange polymer composite cation exchange membrane according to the comparative example of the present invention and one embodiment.

As shown in FIG. 4, it was confirmed that the cross-linked composite cation exchange membranes prepared in Examples 4 and 6 had a water content lower than that of the cation exchange membrane prepared in Comparative Example 1 by about 50% at 25 and 60 ° C. It was confirmed that the water content was decreased by the ion exchange resin and cross-linking agent.

<Experimental Example 4> Measurement of dimensional change

The following experiments were performed to examine the dimensional changes of the ion exchange resin / ion exchange polymer composite cation exchange membranes prepared in Comparative Example 1 and Examples 4 and 6.

Specifically, the crosslinked cation-exchange resin / cation-exchange polymer composite membrane prepared in Comparative Example 1 and Examples 4 and 6 was immersed in distilled water at 25 ° C and 60 ° C depending on the temperature, and then the water present on the surface of the prepared cation- And the change in the area of the membrane was observed. The change in dimension was measured by the following equation (4), and the results are shown in FIG.

In Equation (4)

A _i is the area of the dried film,

A _s is the area of the membrane that has absorbed water.

As shown in FIG. 5, it was confirmed that the crosslinked composite cation exchange membranes prepared in Examples 4 and 6 had significantly less dimensional changes at 25 ° C and 60 ° C than the cation exchange membranes prepared in Comparative Example 1. It was confirmed that the dimensional stability was improved by reducing the dimensional change due to the radiation crosslinking by the ion exchange resin and the crosslinking agent.

Experimental Example 5 Evaluation of permselectivity

The permeation selectivity of the cation exchange membranes prepared in Comparative Examples 1 and 4 and 6 was examined in the following manner.

Specifically, the crosslinked composite cation exchange membranes of Examples 4 and 6 and the cation exchange membrane of Comparative Example 1 were mounted on a measurement cell, and 0.1 M NaCl solution was supported on one cell and supported on 0.5 M NaCl on the other cell, The potential difference was measured at 25 캜 using AgCl as a reference electrode, and the permeation selectivity was calculated from the equation (5). The results are shown in Fig.

In Equation (5)

V _meas is the potential difference of the prepared film,

V _theo is the theoretical potential difference obtained by the Nernst equation of the fabricated film.

6 shows the results of evaluating the permeation selectivity of the cation exchange membrane prepared according to one embodiment of the present invention and the comparative example.

As shown in FIG. 6, the permeation selectivity of the cation exchange membrane without the ion exchange resin and the crosslinking agent (Comparative Example 1) was 63%, while the permeation selectivity of the crosslinked composite cation exchange membrane prepared by one example was 92% The permeation selectivity to cations is high. These results show that although the ion exchange capacity is high, the permeation selectivity is increased due to the radiation crosslinking due to addition of the cation exchange resin and the crosslinking agent.

The crosslinked cation-exchange resin / cation-exchange polymer composite membrane prepared by mixing at least three vinyl groups-capable crosslinking agent, cation-exchange resin, and cation-exchange polymer at a suitable composition ratio and irradiating the crosslinked structure, It can be manufactured in a short time and has high dimensional stability and high permeation selectivity while maintaining high ion exchange ability, so it can be used for ion exchange membrane, fuel cell membrane, flow cell membrane for large capacity secondary battery and water treatment membrane.

Claims (15)

Cation exchange polymers;
A crosslinking agent having three or more vinyl groups; And
Cation exchange resin;
/ RTI &gt; wherein the crosslinked cation-exchange resin / cation-exchange polymer composite membrane comprises: &lt; RTI ID = 0.0 &gt;
The method according to claim 1,
30 to 75 parts by weight of a cation exchange polymer; 5-40 parts by weight of a crosslinking agent having 3 or more vinyl groups; And 10-50 parts by weight of a cation exchange resin. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
The method according to claim 1,
The cation exchange polymer may be selected from the group consisting of sulfonated polystyrene (SPS), sulfonated poly (ether ether ketone), SPEEK, sulfonated polysulfone (SPSu), sulfonated poly (SPES), sulfonated polyimide (SPI), and sulfonated poly (phenylene oxide) (SPPO). The term &quot; sulfonated poly (ether sulfone) And at least one kind selected from the group consisting of polyvinyl alcohol and polyvinyl alcohol.
The method according to claim 1,
The three vinyl group-containing crosslinking agents may be selected from the group consisting of trimethylolpropane ethoxylate triacrylate (TMPETA), trimethylolpropane trimethacrylate (TMPTA), triallyl isocyanurate , TAIC), pentaerythritol triallyl ether (PETALE), and the like.
The method according to claim 1,
Wherein the cation exchange resin is a copolymer of sulfonated polystyrene (SPS) with divinyl benzene (DVB) and having a particle size of 1-25 탆.
Dissolving a cation exchange polymer, a crosslinking agent having three or more vinyl groups in a solvent, adding and dispersing a cation exchange resin to prepare a mother liquor (step 1);
Casting the mother liquor prepared in step 1 on a glass plate and drying (step 2); And
Irradiating and drying the radiation (step 3);
Exchange resin / cation-exchange polymer composite membrane.
The method according to claim 6,
In step 1, 3 to 21.5 weight% of a cation exchange polymer, 3 to 11 weight% of a crosslinking agent having three or more vinyl groups, is dissolved in 70 to 90 weight% of a solvent, 2.5 to 9.5 weight% of a cation exchange resin is added and dispersed Wherein a mother liquor is prepared.
The method according to claim 6,
Further comprising the step of supporting the cation exchange resin in an aqueous hydrochloric acid solution for 12 to 36 hours before the step 1, followed by washing and drying.
The method according to claim 6,
The solvent of step 1 is at least one selected from the group consisting of N, N-dimethylacetamide (DMAc), 1-methyl-2-pyrrolidinone (NMP) and dimethylsulfoxide (DMSO) Way.
The method according to claim 6,
Wherein the radiation of step (3) is one kind selected from the group consisting of gamma ray, ultraviolet ray and electron ray.
11. The method of claim 10,
Wherein the radiation of step 3 is an electron beam.
11. The method of claim 10,
Wherein the radiation is irradiated at a dose rate of 0.1 - 20 kGy / pass by a dose of 50 - 300 kGy irradiation.
A cation exchange membrane comprising the crosslinked cation exchange resin / cation exchange polymer composite membrane of claim 1.
A water treatment membrane comprising the crosslinked cation exchange resin / cation exchange polymer composite membrane of claim 1.
A fuel cell membrane comprising the crosslinked cation exchange resin / cation exchange polymer composite membrane of claim 1.

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