KR101327971B1 - Fabrication method for the grafted polymer membrane with vinyl ether based monomers having leaving group by simultaneous radiation - Google Patents

Abstract

The present invention relates to a method for producing a polymer film grafted with a vinyl ether monomer containing a leaving group, the production method according to the invention is simple because of the simultaneous irradiation method, excellent thermal stability, excellent graft rate However, since the graft rate can be adjusted, it may be useful for the preparation of cation exchange membranes, anion exchange membranes, adsorptive separation membranes, and the like.

Description

Fabrication method for the grafted polymer membrane with vinyl ether based monomers having leaving group by simultaneous radiation}

The present invention relates to a method for producing a polymer membrane usable as a polymer electrolyte membrane, an ion exchange membrane, a fuel cell membrane, etc., and to a method for producing a polymer membrane grafted with a vinyl ether monomer containing a leaving group using simultaneous irradiation will be.

Types of ionizing radiation having high energy levels include gamma rays, X-rays, and electron beams.The gamma rays emitted from Co ⁶⁰ have a high ability to penetrate materials and are widely used for sterilization of food and medical products and processing of polymer materials. In the case of an electron beam obtained by accelerating the electron beam, the transmission power is smaller than that of gamma rays, but it is widely used in tire and cable manufacturing because it can generate high energy in a short time.

Grafting technology using radiation has been studied for a long time, and the manufacturing method can be classified into a pre-irradiation method of irradiating a film and later grafting monomer and a simultaneous irradiation method of irradiating and grafting a film and a monomer simultaneously. .

In the case of gamma rays, the permeability of the material is good and can be used for both pre-irradiation and simultaneous irradiation. The graft technology using the radiation has the advantage that it can be evenly grafted to the inside of the material, it can be usefully used to give new functionality to the commercialized film.

The graft method using radiation can properly combine two or more different materials to produce a functional hybrid material capable of expressing the properties of each material. For example, tetrafluoroethylene-hexafluoropropylene (FEP), perfluoroalkyl vinyl ether (PFA), ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polytetrafluoroethylene Compared to fluorine polymer film and fluorine polymer film having high thermal stability and mechanical strength such as (PTFE), polyethylene (PE), polypropylene (PP), polyether ether ketone (PEEK), polysulfone (PSU), Radiation-grafted monomers suitable for hydrocarbon-based polymer films such as polyethersulfone (PES), polyimide (PI), polybenzylimidazole (PBI), and, if necessary, undergo additional processing to achieve high thermal stability and mechanical strength. It is possible to produce an ion conductive membrane with the same.

Vinyl and acrylic monomers such as styrene, vinyl chloride benzene, methacrylate, acrylate and acrylonitrile are widely used for radiation grafting. However, radiation grafts using vinyl ether monomers are extremely rare compared to the radiation graft methods using the aforementioned monomers.

Non-Patent Document 1 [Chen, J., Asano, M., Yamaki, T., Yoshida, M., 2005. Preparation of sulfonated crosslinked PTFE-graft-poly (alkyl vinyl ether) membranes for polymer electrolyte membrane fuel cells by radiation processing. J. Membrane Sci. 256, 3845.] discloses a method for producing a fuel cell membrane by irradiating an alkyl vinyl ether monomer to a PTFE film at the same time and then sulfonating with chlorosulfonic acid.

Non-Patent Document 2 [Abdel Aal, A., Khutoryanskiy, VV, Nurkeeva, ZS, Mun, GA, 2002. Radiation grafting of vinyl ether of monoethanolamine on polypropylene films for application in waste water treatment. J. Mater. Chem. 12, 2692-2695. Discloses a method for producing a heavy metal adsorbent by radiografting a vinyl ether monomer having a monoethanolamine onto a polypropylene (PP) film.

However, the radiation graft using the vinyl ether monomer, which is the method of Non-Patent Documents 1 and 2, requires not only high temperature and irradiation dose when irradiating, but also complicated manufacturing method such as using Lewis acid as an additive. In addition, there is a problem in that it is difficult to introduce a reactor through a chemical treatment because there is no leaving group in the monomer grafted on the film.

Thus, the inventors of the present invention while studying a method for producing a polymer film using a vinyl ether monomer containing a leaving group, the polymer film produced by the simultaneous irradiation method according to the present invention graft superior to the polymer film prepared under the conditions of the conventional simultaneous irradiation The present invention was completed by finding out that efficiency can be usefully used in cation exchange membranes, anion exchange membranes, adsorptive separation membranes, etc. by introducing a reactor (funcitional group) through chemical treatment in the leaving group included in the monomer.

An object of the present invention is to provide a method for producing a polymer film grafted with a vinyl ether monomer containing a leaving group.

Another object of the present invention is to provide a cation exchange membrane using a polymer membrane prepared by the method for producing a polymer membrane grafted with a vinyl ether monomer containing the leaving group.

Still another object of the present invention is to provide an anion exchange membrane using a polymer membrane prepared by a method for preparing a polymer membrane in which a vinyl ether monomer including the leaving group is grafted.

Another object of the present invention is to provide an adsorptive separation membrane using a polymer membrane prepared by a method for preparing a polymer membrane in which a vinyl ether monomer including the leaving group is grafted.

In order to achieve the above object, the present invention comprises the steps of preparing a monomer solution by dissolving a vinyl ether monomer containing a leaving group (X) represented by the formula (1) in a hydrocarbon solvent (step 1); And

It provides a method for producing a polymer membrane grafted with a vinyl ether monomer containing a leaving group comprising the step of immersing the polymer film in the monomer solution prepared in step 1 and irradiating (step 2):

[Formula 1]

In Formula 1,

X is halogen, diazonium salts, oxonium ions, fluorosulfonates, ammonium salts, nitrates, phosphates, tosylate tosylates, mesylates, triflates, or hydroxy,

n is an integer of 1-10.

In addition, the present invention provides a cation exchange membrane using a polymer membrane prepared by the method for producing a polymer membrane grafted with a vinyl ether monomer containing the leaving group.

Furthermore, the present invention provides an anion exchange membrane using a polymer membrane prepared by a method for preparing a polymer membrane in which a vinyl ether monomer including the leaving group is grafted.

The present invention also provides an adsorptive separation membrane using a polymer membrane prepared by a method of preparing a polymer membrane in which a vinyl ether monomer including a leaving group is grafted.

According to the present invention, a method of preparing a polymer membrane grafted with a vinyl ether monomer containing a leaving group according to the present invention is simple, a method of excellent thermal stability, excellent graft rate, and graft rate can be controlled using a simultaneous radiation method. , Cation exchange membranes, anion exchange membranes, adsorptive separation membranes and the like can be useful.

1 is a graph showing the graft ratio of a polymer film according to an embodiment of the present invention according to the radiation dose (Example 1: ETFE-g-CEVE, Example 2: ETFE-g-BDVE, Comparative Example 1: ETFE- g-BVE).
Figure 2 is a graph showing the graft rate according to the addition of the grafting catalyst when producing a polymer film according to an embodiment of the present invention.
3 is a graph showing the peak measured by the FT-IR polymer film according to an embodiment of the present invention (Example 1: ETFE-g-CEVE, Comparative Example 1: ETFE-g-BVE).
Figure 4 is an image taken with the EDX cross section of the polymer film according to an embodiment of the present invention.
5 is a graph showing a thermal decomposition curve of a polymer film grafted BVE according to an embodiment of the present invention (A: ETFE, B: ETFE-g-BVE (2.5%), C: ETFE-g-BVE (6.1%) )).
6 is a graph showing a thermal decomposition curve of the polymer membrane grafted CEVE according to an embodiment of the present invention (A: ETFE, B: ETFE-g-CEVE (13.5%), C: ETFE-g-CEVE (54%) )).
7 is a graph showing the graft ratio when the polymer membrane according to one embodiment of the present invention is prepared with hexane, toluene, acetone, DCM, and chloroform solvent.
8 is a graph showing the graft ratio when the polymer membrane according to one embodiment of the present invention is prepared with hexane, heptane, cyclohexane and octane solvent.
Figure 9 is a graph showing the graft rate when the polymer film according to one embodiment of the present invention is prepared by varying the concentration of the monomer.
10 is a graph showing the graft rate when the polymer film according to an embodiment of the present invention is manufactured by varying the radiation dose rate.

Hereinafter, the present invention will be described in detail.

The present invention comprises the steps of preparing a monomer solution by dissolving a vinyl ether monomer containing a leaving group (X) represented by the formula (1) in a hydrocarbon solvent (step 1); And

It provides a method for producing a polymer membrane grafted with a vinyl ether monomer containing a leaving group comprising the step of immersing the polymer film in the monomer solution prepared in step 1 and irradiating (step 2):

In Formula 1,

X is halogen, diazonium salts, oxonium ions, fluorosulfonates, ammonium salts, nitrates, phosphates, tosylate tosylates, mesylates, triflates, or hydroxy,

n is an integer of 1-10.

Preferably, in the above production method according to the present invention, X is chloro, bromo, iodo, fluoro or hydroxy,

n is an integer of 2-8.

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

In the method of preparing a polymer membrane according to the present invention, step 1 is a step of preparing a monomer solution.

Specifically, the monomer solution is prepared by dissolving a vinyl ether monomer including a leaving group represented by Chemical Formula 1 in a hydrocarbon solvent.

Vinyl ether monomer containing a leaving group represented by the formula (1) of the step 1 is grafted to the polymer film by the production method of the present invention, and then required functional groups (functional groups) through additional chemical treatment depending on the purpose of use It serves as an introduction part that can be used as a functional polymer membrane such as a cation exchange membrane, an anion exchange membrane, and an adsorption separation membrane.

The hydrocarbon solvent of step 1 serves to dissolve the monomer. The hydrocarbon solvent may be an aliphatic solvent, an aromatic solvent, a ketone solvent or a halogenated solvent, but is not limited thereto.

The aliphatic solvent may be pentane, hexane, heptane, cyclohexane, octane, nonane, decane, and the like. The aromatic solvent may be benzene, toluene, xylene or the like, and the ketone solvent may be acetone, methyl. Ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. can be used, and dichloromethane, chloroform, etc. can be used as said halogenation solvent.

Furthermore, the method for producing a polymer film according to the present invention can be grafted onto a polymer film using only monomers without using a hydrocarbon solvent. However, the method of the present invention excludes the use of only a monomer without a hydrocarbon solvent. no.

In the method of manufacturing a polymer membrane according to the present invention, step 2 is a step of immersing the polymer film in the monomer solution prepared in step 1 and irradiating the radiation.

Specifically, the polymer film is immersed in the monomer solution and then irradiated with radiation to graf the monomer onto the polymer film to prepare a polymer film. At this time, the radiation is irradiated to generate a radical on the polymer film and at the same time the monomer is grafted using a radiation simultaneous irradiation method.

The polymer film of step 2 serves as a basic skeleton of the polymer film to be prepared, and has excellent chemical stability, thermal stability, excellent mechanical properties, and a polymer film stable to radiation.

The polymer film is tetrafluoroethylene-hexafluoropropylene (FEP), perfluoroalkyl vinyl ether (PFA), ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polytetrafluoro Relatively cheaper polyethylene (PE), polypropylene (PP), polyether ether ketone (PEEK), polysulfone (PSU) than fluoropolymer films and fluoropolymer films with high thermal stability and mechanical strength such as ethylene (PTFE) , Hydrocarbon-based polymer films such as polyether sulfone (PES), polyimide (PI), polybenzylimidazole (PBI) and the like can be used.

In this case, the radiation generates radicals in the aliphatic chain of the polymer film serving as the basic skeleton and at the same time serves to graf the monomer to the polymer film. Gamma rays, ultraviolet rays, and electron beams can be used as the radiation, and gamma rays are preferably used.

The radiation is preferably irradiated by 50-600 kGy total dose at a dose rate of 1-20 kGy / h. If the dose rate is less than 1 kGy / h, there is a problem in that the manufacturing time is long, and if the dose rate is more than 20 kGy / h, the graft rate is lowered and the intermolecular breakage occurs, thereby deteriorating the mechanical strength due to molecular weight reduction. .

In addition, when the irradiation dose is less than 50 kGy, there is a problem that the graft rate is lowered, and when it exceeds 600 kGy, there is a problem that the degree of graft rate improvement is insignificant and the economy is inferior.

Additionally, impurities may be removed by performing the step of washing and drying the prepared polymer membrane after performing step 2.

According to the present invention, a method of preparing a polymer membrane grafted with a vinyl ether monomer containing a leaving group according to the present invention is simple, a method of excellent thermal stability, excellent graft rate, and graft rate can be controlled using a simultaneous radiation method. , Cation exchange membranes, anion exchange membranes, adsorptive separation membranes and the like can be useful.

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.

< Example  1> ETFE  On film CEVE end Grafted  Preparation of Polymer Membrane ETFE -g- CEVE )

Pretreatment: Preparation of Polymer Film

An ethylene tetrafluoroethylene film (ETFE) having a thickness of 25 μm was cut to 3 cm × 4 cm size, washed with acetone, and dried in a vacuum oven at 60 ° C. for 1 hour to prepare a film.

Step 1: Preparation of Monomer Solution

2-chloroethyl vinyl ether (CEVE) as a monomer containing a leaving group was mixed with heptane in a volume ratio of 1: 1 to prepare a monomer solution.

Step 2: Irradiation

The ETFE film prepared in the preparation step was immersed in the monomer solution prepared in Step 1, and gamma rays were irradiated until the irradiation dose (50-600 kGy) shown in Table 1 at a dose rate of 10 kGy / h.

Irradiation dose (kGy) Example 1a 50 Example 1b 100 Example 1c 200 Example 1d 300 Example 1e 400 Example 1f 600

After irradiation, the grafted ETFE film was washed with acetone for 24 hours to remove ungrafted homopolymer and unreacted monomer, and dried in a vacuum oven at 40 ° C. for 1 hour to prepare a polymer film grafted with CEVE on the ETFE film. It was.

< Example  2> ETFE  On film BDVE end Grafted  Preparation of Polymer Membrane ETFE -g- BDVE )

Polymer membrane grafted with BDVE on an ETFE film in the same manner as in Example 1 except that 1,4-butanediol vinyl ether (BDVE) was used instead of 2-chloroethyl vinyl ether (CEVE) as a monomer containing a leaving group. Was prepared.

Irradiation dose (kGy) Example 2a 50 Example 2b 100 Example 2c 200 Example 2d 300 Example 2e 400 Example 2f 600

< Comparative Example  1> ETFE  On film BVE end Grafted  Preparation of Polymer Membrane ETFE -g- BVE )

Except for using butyl vinyl ether (BVE) instead of 2-chloroethyl vinyl ether (CEVE) as a monomer without leaving group was carried out in the same manner as in Example 1 to prepare a polymer film grafted BVE to the ETFE film.

Irradiation dose (kGy) Comparative Example 1a 50 Comparative Example 1b 100 Comparative Example 1c 200 Comparative Example 1d 300 Comparative Example 1e 400 Comparative Example 1f 600

< Experimental Example  1> radiation To radiation dose  Following Graft rate  evaluation

In Example 1-2 and Comparative Example 1 to determine the graft rate according to the radiation dose was tested as follows.

Specifically, the weight (W ₀ ) of the polymer film prepared in the preparation step of Example 1-2 and Comparative Example 1 was measured, and the weight (W _g ) of the polymer film prepared by grafting the monomers of each example and the comparative example. After the measurement, the graft rate (%) was measured using Equation 1 below, and the results are shown in FIG. 1.

In the above equation (1)

W ₀ is the polymer film weight before grafting the monomer,

W _g is the weight of the polymer film after the monomer is grafted.

As shown in Figure 1, it shows that there are many differences in the graft rate according to the irradiation dose depending on the type of monomer. CEVE, a monomer of Example 1 (ETFE-g-CEVE), shows that the graft rate increases regularly with increasing dose, whereas BVE, a monomer of Comparative Example 1 (ETFE-g-BVE), shows very little graft rate. The BDVE, which is a monomer of Example 2 (ETFE-g-BDVE), was observed to form a homopolymer due to its high reactivity and gelation was observed. Therefore, it was confirmed that different graft rates were shown by the chemical properties of the monomers.

These results suggest that the electron donor group plays an active role in forming the polymer, and the Cl portion of CEVE, which is the monomer of Example 1, does not cause side reactions, resulting in a high graft rate. In order to obtain a sufficient graft ratio using CEVE as a monomer of Example 1, it was confirmed that an irradiation dose of 100 kGy or more is required.

Therefore, according to the present invention, the vinyl ether monomer-grafted polymer membrane can be introduced into the polymer film at a high graft rate by using a simple radiation simultaneous irradiation method. Thus, cation exchange membrane, anion exchange membrane, and adsorption It may be useful in the manufacture of the separator.

< Experimental Example  2> according to the addition of catalyst Graft rate  evaluation

In order to determine the graft rate according to the grafting catalyst addition was performed as follows.

Specifically, when preparing the monomer solution in Step 1 of Example 1 (ETFE-g-CEVE) and Comparative Example 1 (ETFE-g-BVE), 2 mg of AlCl ₃ was added as a grafting catalyst and 10 kGy / h of The graft rate of the prepared polymer membrane was measured until the dose was 200 kGy at the dose rate. In this case, the graft rate was measured in the same manner as in Experiment 1, and the results are shown in FIG. 2.

As shown in FIG. 2, no significant graft rate change was observed when the grafting catalyst was added and the monomer alone was added. This indicates that the production method of the present invention shows a high graft rate even without an additional catalyst.

Therefore, according to the present invention, the method for preparing a polymer membrane grafted with vinyl ether monomer can be introduced into the polymer membrane at a high graft rate without additional grafting catalyst by using a simple simultaneous irradiation method. It may be useful in the production of anion exchange membrane, adsorptive separation membrane and the like.

< Experimental Example  3> FT - IR  And EDX Using Graft  evaluation

In order to evaluate the graft presence of the polymer membrane prepared in Example 1 (ETFE-g-CEVE) and Comparative Example 1 (ETFE-g-BVE) was performed as follows.

Specifically, the grafted ETFE film and the same polymer membrane used in Experimental Example 2 were measured by FT-IR (model name: Tensor-37, manufacturer: Brucker) to evaluate the presence or absence of graft at the peaks. Is shown in FIG. 3.

In addition, the cross section of the polymer film prepared in Example 1 (irradiation dose: 200 kGy) was measured using Energy Dispersive X-ray spectroscopy (EDX) (model name: 7200-H, manufactured by HORIVA Company), and the results are illustrated in FIG. 4 is shown.

As shown in FIG. 3, 2870-2969 cm of peaks shown in the FTFE graph of the ETFE film before grafting and the polymer membranes prepared in Examples 1 and 1 (ETFE-g-CEVE and ETFE-g-BVE). an aliphatic group (-CH ₂ -) ^-1 was confirmed that the symmetric, asymmetric stretching peak appearing further embodiment the polymer membrane (ETFE-g-CEVE) prepared in example 1 is shown a C-Cl peak at about 742 cm ^-1 It was confirmed that CEVE and BVE were successfully grafted with monomers in the ETFE film.

As shown in FIG. 4, in the EDX image photographing the cross section of the polymer film prepared in Example 1, it was confirmed that the Cl element of the CEVE monomer was evenly distributed to the center portion of the polymer film, and thus the graft was successful. .

Therefore, according to the present invention, the vinyl ether monomer-grafted polymer membrane can be grafted by uniformly distributing the vinyl ether monomer on the polymer membrane using a simple simultaneous irradiation method. It may be useful in the manufacture of the separator.

< Experimental Example  4> On graft rate  Thermal stability evaluation

In order to determine the thermal stability of the ETFE film and the polymer membrane prepared in Example 1 (ETFE-g-CEVE) and Example 2 (ETFE-g-BDVE) as follows.

Specifically, using the thermogravimetric analyzer (model name: SDT Q600, manufacturer: TA instrument Korea) was measured the thermal decomposition curve of the ETFE film and the polymer film prepared in Example 1 and Comparative Example 1, the results are shown in Figures 5 and 6 Shown in

As shown in FIG. 5, the first degradation was observed at 490 ° C. for the ETFE film A, and the first degradation was observed at 310-410 ° C. for the BVE-grafted polymer film 2.5%. The first degradation was observed in the polymer membrane (C) where 6.1% of the BVE was grafted.

As shown in FIG. 6, the first degradation was observed at 490 in the ETFE film (A), and the first degradation was observed at 310-410 in the polymer film (B) grafted with 13.5% of the CEVE. 54% grafted polymer film (C) was also observed for the first degradation in 310-410. Since both polymer membranes do not deteriorate to 300, it can be seen that they have sufficiently high thermal stability compared to the operating temperature environment required for functional separation membranes such as cation exchange membranes and anion exchange membrane adsorption membranes.

At this time, the polymer film grafted CEVE at a high graft rate was confirmed that deterioration occurs twice, wherein the first degradation represents the weight loss due to the degradation of the CEVE monomer, the second degradation of the ETFE film Weight loss by

Therefore, the polymer membrane grafted with vinyl ether monomers prepared by the method for producing a polymer membrane grafted with vinyl ether monomers according to the present invention exhibits high thermal stability, and therefore, is useful for preparing cation exchange membranes, anion exchange membranes, adsorptive separation membranes, and the like. Can be useful.

< Experimental Example  5> according to the type of solvent Graft rate  evaluation

Considering that the monomers such as styrene and VBC have a high influence of the solvent on the graft reaction, the following experiment was performed to determine the graft rate according to the type of solvent when preparing the polymer membrane in Example 1.

Specifically, a monomer solution (monomer: solvent = 1: 1 volume) was prepared using hexane, cyclohexane, octane, toluene, acetone, DCM, and chloroform in addition to heptane as a solvent used in Example 1, and then 10 kGy / h. The polymer film was prepared by irradiating gamma rays to a dose rate of 200 and 400 kGy, respectively, and graft rates were measured by the same method as Experimental Example 1, and the results are shown in FIGS. 7 and 8.

As shown in FIG. 7 and FIG. 8, it was confirmed that the polymer film prepared using an aliphatic solvent (hexane, heptane, cyclohexane, octane) showed an average high graft rate, in particular, heptane showed a graft rate of 70% or more. It was found that heptane is the most suitable solvent for dissolving the vinyl ether monomer of the present invention.

Therefore, the method for preparing a polymer membrane grafted with vinyl ether monomers according to the present invention can use a variety of organic solvents, it can be useful for the preparation of cation exchange membrane, anion exchange membrane, adsorptive separation membrane and the like.

< Experimental Example  6> according to monomer concentration Graft rate  evaluation

In order to evaluate the change in the graft rate according to the concentration of the monomer in Example 1 was tested as follows.

Specifically, except that the monomers of 30, 50, 70, 100% (v / v) with respect to the heptane solvent in Example 1 to prepare each polymer membrane in the same manner as in Example 1, then Experimental Example 1 The graft rate was measured by the same method as described above, and the results are shown in FIG. 9.

As shown in Figure 9, it shows that the graft rate also increases as the monomer increases, it can be seen that higher graft rate can be obtained by increasing the monomer.

Therefore, the method for preparing a polymer membrane grafted with vinyl ether monomers according to the present invention can adjust the concentration of the monomer to adjust the graft rate, it can be useful for the preparation of cation exchange membrane, anion exchange membrane, adsorptive separation membrane and the like.

< Experimental Example  7> On dose rate  Following Graft rate  evaluation

In Example 1, the following experiment was conducted to evaluate the change of the graft rate according to the dose rate.

Specifically, instead of the 10 kGy / h dose rate used in Example 1, using the 5 kGy / h dose rate, the same method as in Example 1 except that the radiation was irradiated until 50, 100, 200 and 400 kGy doses Each polymer film was prepared, and the graft ratio was measured by the same method as Experimental Example 1, and the results are shown in FIG. 10.

As shown in FIG. 10, the lower the dose rate, the more the graft rate increased. This is believed to result from a slight increase in radical production in the polymer chains at lower dose rates. However, the overall graft rate does not show a significant difference, it was found that it is more preferable to use a 10 kGy / h dose rate in terms of reducing the manufacturing time.

Therefore, the method for preparing a polymer membrane grafted with vinyl ether monomer according to the present invention can increase the dose rate and shorten the production time, and thus may be useful for the preparation of cation exchange membranes, anion exchange membranes, adsorptive separation membranes, and the like.

Claims (10)

Preparing a monomer solution by dissolving a vinyl ether monomer including a leaving group (X) represented by Formula 1 in a heptane solvent (step 1); And
Immersing the polymer film in the monomer solution prepared in step 1 and irradiating gamma rays with an irradiation dose of 200-600 kGy at a dose rate of 3-15 kGy / h (step 2); vinyl ether containing a leaving group comprising a; Method for preparing a polymer film grafted with monomers:
[Chemical Formula 1]

(In Formula 1,
X is halogen
and n is an integer of 1-10.
delete The method of claim 1, wherein the polymer film of step 2 is tetrafluoroethylene-hexafluoropropylene (FEP), perfluoroalkyl vinyl ether (PFA), ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), Polyethylene (PE), Polypropylene (PP), Polyetheretherketone (PEEK), Polysulfone (PSU), Polyethersulfone (PES), Polyimide (PI) And polybenzylimidazole (PBI).
delete delete delete delete A cation exchange membrane using a polymer membrane prepared by the method of preparing a polymer membrane in which a vinyl ether monomer including the leaving group of claim 1 is grafted.
Anion exchange membrane using a polymer membrane prepared by the method for producing a polymer membrane grafted with a vinyl ether monomer containing a leaving group of claim 1.
Adsorption separation membrane using a polymer membrane prepared by a method for producing a polymer membrane grafted with a vinyl ether monomer containing a leaving group of claim 1.

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