KR102278518B1 - A partially crosslinked poly(phenylene oxide)-based polymer, method for preparation thereof and anion exchange membrane using the same - Google Patents

Abstract

The present invention relates to a partially crosslinked polyphenylene oxide(PPO)-based polymer, a manufacturing method thereof, and an anion exchange membrane using the same, and more specifically, to a partially crosslinked PPO-based polymer, which is partially crosslinked with dimethylhexadecylammonium groups to exhibit excellent water absorption and swelling properties and have high ion exchange capacity at the same time, and has high electrical conductivity and low electrical resistance to be applicable as a microbial fuel cell, a manufacturing method thereof, and an anion exchange membrane using the same.

Description

Partially crosslinked polyphenylene oxide-based polymer, manufacturing method thereof, and anion exchange membrane using the same {A partially crosslinked poly(phenylene oxide)-based polymer, method for preparation thereof and anion exchange membrane using the same}

The present invention relates to a polymer based on partially crosslinked poly(phenylene oxide) (PPO), a method for preparing the same, and an anion exchange membrane using the same, and more particularly, to a dimethylhexadecylammonium group and Partially cross-linked PPO-based polymer that exhibits excellent water absorption and swelling properties, high ion exchange capacity, high electrical conductivity and low electrical resistance, and is applicable as a microbial fuel cell, manufacturing method thereof, and using same It relates to an anion exchange membrane.

A fuel cell is a power generation system that continuously supplies fuel and an oxidizer and extracts chemical energy when they react as electric power. Depending on the type of electrolyte used, the fuel cell may be an alkaline fuel cell, a phosphoric acid fuel cell, and a solid polymer electrolyte fuel cell having a relatively low operating temperature, or a molten carbonate fuel cell or a solid oxide electrolyte fuel cell operating at a high temperature. is distinguished by

On the other hand, in the case of a fuel cell using an anion exchange membrane (AEM), the availability of non-noble metal electrocatalyst, easy oxidation of fuel, fast reduction rate of oxygen, crossover of reduced fuel, enhanced carbon monoxide of catalyst Due to its many advantages such as resistance and relatively simple water management, it has recently received a lot of attention compared to the proton exchange membrane fuel cell (PEMFC), and accordingly, research on an anion exchange membrane as an alternative to the proton exchange membrane (PEM) is in progress.

In order to prepare such an anion exchange membrane, a chloromethylating agent reaction is performed in a hydrocarbon-based polymer, and an amination reaction is performed to prepare an anion exchange membrane having increased ion conductivity and thermal stability. In addition, a study in which polyarylene ether sulfone containing quaternary ammonium is applied to a solid alkaline exchange membrane fuel cell is presented.

However, when an anion exchange membrane is manufactured using the polymer prepared by the above manufacturing methods, there is a disadvantage in that processability is poor, and research is required to solve this problem.

Therefore, in order to supplement the above problems, the present inventors have found that if a polymer with excellent processability can be synthesized as a separator, it maintains improved ionic conductivity, and has excellent ionic conductivity stability and improved physical strength as an anion exchange membrane for a microbial fuel cell. Recognizing that development is urgent, the present invention was completed.

Japanese Laid-Open Patent Publication No. 10-2010-0107010 Korean Patent Publication No. 10-1545229 Korean Patent Publication No. 10-0776375

Jieun Choi et. al. Int. J. Hydrogen, 39, 21223-21230 (2014)

It is an object of the present invention to be partially crosslinked with a dimethylhexadecylammonium group to exhibit excellent water absorption and swelling properties, and at the same time have high ion exchange capacity, high electrical conductivity and low electrical resistance, so that it can be applied as a microbial fuel cell To provide a partially crosslinked PPO-based polymer, a method for preparing the same, and an anion exchange membrane using the same.

The technical problems to be achieved by the invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by those of ordinary skill in the art from the description of the present invention.

In order to achieve the above object, the present invention provides a polymer based on partially crosslinked poly(phenylene oxide, PPO), a method for preparing the same, and an anion exchange membrane using the same.

Hereinafter, the present specification will be described in more detail.

The present invention provides a polymer based on partially cross-linked polyphenylene oxide, characterized in that represented by the following [Formula 1].

[Formula 1]

In [Formula 1], a and b are 1 to 30, m, n and l are 1 to 100, and x is 1 to 100,000,000.

In addition, the present invention provides a method for producing a polymer based on partially crosslinked polyphenylene oxide, characterized in that it comprises the following steps.

(A1) N-bromosuccinimide (NBS) and 2,2′-azobis (2) on poly(2,6-dimethylphenylene oxide) -Methylpropionitrile) (2,2'-azobis(2-methylpropionitrile), AIBN) was added to prepare a first polymer represented by the following [Formula 2];

(A2) preparing a second polymer represented by the following [Formula 3] by adding N,N-dimethyl-1-hexadecylamine (DMHDA) to the first polymer step; and

(A3) N,N,N',N'-tetramethyl-1,6-hexanediamine (N,N,N',N'-tetramethyl-1,6-hexanediamine, TMHDA) to the second polymer Preparing a polymer based on partially cross-linked polyphenylene oxide represented by the following [Formula 1] by adding.

[Formula 1]

[Formula 2]

[Formula 3]

In [Formula 1], a and b are 1 to 30, m, n and l are 1 to 100, and x is 1 to 100,000,000.

In the present invention, the step (A1) is characterized in that it consists of the following steps.

(A1a) dissolving poly(2,6-dimethylphenylene oxide) in a first solvent;

(A1b) preparing a mixture by adding NBS and AIBN to the dissolved poly(2,6-dimethylphenylene oxide); and

(A1c) adding a first solvent to the mixture to obtain a first polymer represented by the above [Formula 2] as a precipitate.

In the present invention, the first solvent in step (A1) is a C1 to C4 low-cost alcohol, glycerin, butylene glycol, propylene glycol, methyl acetate, ethyl acetate, acetone, benzene, hexane, diethyl ether, chloroform, chloroform It is characterized in that at least one selected from the group consisting of benzene and dichloromethane.

In the present invention, the step (A2) is characterized in that it consists of the following steps.

(A2a) dissolving the first polymer in methylpyrrolidone (N-methyl-2-pyrrolidone, NMP);

(A2b) adding DMHDA to the dissolved first polymer to prepare a mixture; and

(A2c) adding a second solvent to the mixture to obtain a second polymer represented by the above [Formula 3].

In the present invention, the second solvent in step (A2) is a C1 to C4 low-cost alcohol, glycerin, butylene glycol, propylene glycol, methyl acetate, ethyl acetate, acetone, benzene, hexane, diethyl ether, chloroform, chloroform It is characterized in that at least one selected from the group consisting of benzene and dichloromethane.

In addition, the present invention provides an anion exchange membrane comprising a polymer based on partially cross-linked polyphenylene oxide represented by the above [Formula 1].

In the present invention, the anion exchange membrane is characterized in that it is a transparent membrane having a thickness of 150 to 350 ㎛.

In addition, the present invention provides a method for producing an anion exchange membrane, characterized in that it comprises the following steps.

(B1) heating a polymer based on partially crosslinked polyphenylene oxide (poly(phenylene oxide), PPO) represented by the following [Formula 1];

(B2) N,N,N′,N′-tetramethyl-1,6-hexanediamine (N,N,N′,N′-tetramethyl-1,6-hexanediamine, TMHDA) in the heated polymer adding to prepare a membrane; and

(B3) washing and drying the immersed membrane;

[Formula 1]

In the above [Formula 1],

wherein a and b are 1 to 30,

Wherein m, n and l are 1 to 100,

wherein x is 1 to 100,000,000.

All matters mentioned in the above partially crosslinked polyphenylene oxide-based polymer, its preparation method, an anion exchange membrane using the same, and an anion exchange membrane manufacturing method using the same apply unless contradictory.

The partially cross-linked PPO-based polymer of the present invention, a method for preparing the same, and an anion exchange membrane using the same are partially cross-linked with a dimethylhexadecylammonium group to exhibit excellent water absorption and swelling properties, and at the same time have a high ion exchange capacity. , it has high electrical conductivity and low electrical resistance, so it can be applied as a microbial fuel cell.

Effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description of the claims.

^{1 is a 1} H NMR spectrum of a first polymer (Example 1) represented by [Formula 2] according to the present invention.
2 is an FT-IR spectrum of a polymer (Example 1) based on PPO represented by [Formula 1] according to the present invention.
3 is an X-ray photoelectron spectroscopy (XPS) spectrum of a polymer (Example 1) based on PPO represented by [Formula 1] according to the present invention.
4 is a thermogravimetric (TGA) spectrum of a polymer (Example 1) based on PPO represented by [Formula 1] according to the present invention.
5 is a Scanning Electron Microscopy (SEM) image of an anion exchange membrane (Example 2) including a polymer based on PPO represented by [Formula 1] according to the present invention.
6 is an atomic force microscopy (AFM) image of an anion exchange membrane (Example 2) including a polymer based on PPO represented by [Formula 1] according to the present invention.
7 is a Synchrotron Small-Angle X-ray Scattering (SAXS) spectrum of an anion exchange membrane (Example 2) comprising a polymer based on PPO represented by [Formula 1] according to the present invention; to be.
8 is a graph showing the water absorption rate of an anion exchange membrane (Example 2) including a polymer based on PPO represented by [Formula 1] according to the present invention.
9 is a graph showing the water swelling rate of an anion exchange membrane (Example 2) including a polymer based on PPO represented by [Formula 1] according to the present invention.
10 is a power density vs. power density of a microbial fuel cell using an anion exchange membrane (Example 2) containing a polymer based on PPO represented by [Formula 1] according to the present invention. It is a graph showing the current density curve.

The terms used in this specification have been selected as currently widely used general terms as possible while considering the functions in the present invention, which may vary depending on the intention or precedent of a person skilled in the art, the emergence of new technology, and the like. In addition, in a specific case, there is a term arbitrarily selected by the applicant, and in this case, the meaning will be described in detail in the description of the corresponding invention. Therefore, the term used in the present invention should be defined based on the meaning of the term and the overall content of the present invention, rather than the name of a simple term.

Unless defined otherwise, all terms used herein, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

Numerical ranges are inclusive of the values defined in that range. Every maximum numerical limitation given throughout this specification includes all lower numerical limitations as if the lower numerical limitation were expressly written. Every minimum numerical limitation given throughout this specification includes all higher numerical limitations as if the higher numerical limitation were expressly written. Any numerical limitation given throughout this specification shall include all numerical ranges within the broader numerical range, as if the narrower numerical limitation were expressly written.

Hereinafter, examples of the present invention will be described in detail, but it is obvious that the present invention is not limited by the following examples.

Polymers based on PPO

The present invention provides a polymer based on partially cross-linked polyphenylene oxide (poly(phenylene oxide), PPO), characterized in that represented by the following [Formula 1].

[Formula 1]

In [Formula 1], a and b may be 1 to 30, preferably, in [Formula 1], a is 1 to 25, and b may be 1 to 10.

In [Formula 1], m, n and l may be 1 to 100, preferably, m, n and l may be 10 to 80, and most preferably, in [Formula 1], m and m are 20 to 60, and l may be 1 to 40.

In [Formula 1], x may be 1 to 100,000,000.

Method for the preparation of polymers based on PPO

The present invention provides a method for preparing a polymer based on partially crosslinked poly(phenylene oxide) (PPO), characterized in that it comprises the following steps.

(A1) N-bromosuccinimide (NBS) and 2,2′-azobis (2) on poly(2,6-dimethylphenylene oxide) -Methylpropionitrile) (2,2'-azobis(2-methylpropionitrile), AIBN) was added to prepare a first polymer represented by the following [Formula 2];

(A2) preparing a second polymer represented by the following [Formula 3] by adding N,N-dimethyl-1-hexadecylamine (DMHDA) to the first polymer step; and

(A3) N,N,N',N'-tetramethyl-1,6-hexanediamine (N,N,N',N'-tetramethyl-1,6-hexanediamine, TMHDA) to the second polymer Preparing a polymer based on partially crosslinked PPO represented by the following [Formula 1] by adding.

[Formula 1]

[Formula 2]

[Formula 3]

In [Formula 1], a and b are 1 to 30, m, n and l are 1 to 100, and x is 1 to 100,000,000.

The polymer based on PPO represented by the above-mentioned [Formula 1] is the same as mentioned above.

The step (A1) is a step of preparing the first polymer represented by the [Formula 2], and may consist of the following steps.

(A1a) dissolving poly(2,6-dimethylphenylene oxide) in a first solvent;

(A1b) preparing a mixture by adding NBS and AIBN to the dissolved poly(2,6-dimethylphenylene oxide); and

(A1c) adding a first solvent to the mixture to obtain a first polymer represented by the above [Formula 2] as a precipitate.

More specifically, the first solvent in step (A1a) is a C1 to C4 low-cost alcohol, glycerin, butylene glycol, propylene glycol, methyl acetate, ethyl acetate, acetone, benzene, hexane, diethyl ether, chloroform, chlorobenzene And it may be at least one selected from the group consisting of dichloromethane, preferably at least one selected from the group consisting of benzene, hexane, diethyl ether, chloroform, chlorobenzene and dichloromethane, most preferably chloroform, chloro It may be at least one selected from the group consisting of benzene and dichloromethane.

In step (A1b), the NBS and AIBN may be mixed and added at a molar ratio of 1 to 20: 1, preferably 1 to 15: 1 to be mixed and added at a molar ratio of 1 can

After performing step (A1b), stirring the mixture at 55 to 95 °C for 1 to 12 hours; and cooling the mixture to room temperature; and diluting the mixture with one or more solvents selected from the group consisting of chloroform, chlorobenzene and dichloromethane.

The step (A1c) may be a step of obtaining the first polymer represented by the [Formula 2] as a precipitate by adding a first solvent to the mixture.

The first solvent in step (A1c) is a C1 to C4 low-cost alcohol, glycerin, butylene glycol, propylene glycol, methyl acetate, ethyl acetate, acetone, benzene, hexane, diethyl ether, chloroform, chlorobenzene and dichloromethane. It may be one or more selected from the group consisting of, preferably 1 to C4 low-cost alcohol, glycerin, butylene glycol, propylene glycol, methyl acetate, ethyl acetate and acetone may be one or more selected from the group consisting of, most preferably may be at least one selected from the group consisting of 1 to C4 low-cost alcohols, methyl acetate, ethyl acetate, and acetone.

The precipitate obtained in step (A1c) may be washed with a low-cost alcohol of 1 to C4 and dried to prepare the first polymer represented by the above [Formula 2].

The low-cost alcohol of 1 to C4 may be methanol, ethanol, isopropyl alcohol, or butanol.

The step (A2) is a step of preparing the second polymer represented by the [Formula 3], and may consist of the following steps.

(A2a) dissolving the first polymer in methylpyrrolidone (N-methyl-2-pyrrolidone, NMP);

(A2b) adding DMHDA to the dissolved first polymer to prepare a mixture; and

(A2c) adding a second solvent to the mixture to obtain a second polymer represented by the above [Formula 3].

The DMHDA added in step (A2b) may be functionalized with Br (bromine) of the first polymer represented by Formula 2 above.

After performing the step (A2b), the step of stirring may be additionally included. The stirring is performed by primary stirring at 65 to 95 °C for 1 to 6 hours; and after the first stirring, the second stirring at room temperature for 12 to 36 hours; may be performed.

The second solvent in step (A2c) is a C1 to C4 low-cost alcohol, glycerin, butylene glycol, propylene glycol, methyl acetate, ethyl acetate, acetone, benzene, hexane, diethyl ether, chloroform, chlorobenzene and dichloromethane. It may be at least one selected from the group consisting of, preferably at least one selected from the group consisting of C1 to C4 low-cost alcohol, glycerin, butylene glycol, propylene glycol, methyl acetate, ethyl acetate and acetone, most preferably may be at least one selected from the group consisting of methyl acetate, ethyl acetate and acetone.

The precipitate obtained in step (A2c) may be washed with hexane and dried to prepare a second polymer represented by the above [Formula 3].

Step (A2) may be performed by a Menshutkin reaction.

The Menshkin reaction refers to a reaction in which a tertiary amine is converted into a quaternary ammonium salt by reaction with an alkyl halide as shown in the following reaction scheme. In the present invention, the second polymer in the form of a quaternary amine is prepared by reacting the first polymer containing bromine with DMHDA, which is a tertiary amine.

[General reaction formula of Menshutkin reaction]

The step (A3) may be a step of preparing a polymer based on the partially cross-linked PPO represented by the [Formula 1].

More specifically, N,N,N',N'-tetramethyl-1,6-hexanediamine (N,N,N',N'-tetramethyl-1,6-hexanediamine, TMHDA) in the second polymer and partially crosslinking the second polymer to prepare a polymer represented by the [Formula 1]; may be.

Anion exchange membrane (AEM) comprising polymer based on PPO and method for preparing same

The present invention provides an anion exchange membrane (Anion Exchange Membrane, AEM) comprising a polymer based on partially crosslinked polyphenylene oxide (PPO) represented by the following [Formula 1] to provide.

[Formula 1]

In the above [Formula 1],

wherein a and b are 1 to 30,

Wherein m, n and l are 1 to 100,

wherein x is 1 to 100,000,000.

A polymer based on PPO represented by the above-mentioned [Formula 1] and a method for preparing the same are the same as described above.

The anion exchange membrane may be a transparent membrane having a thickness of 150 to 350 μm.

In addition, the present invention provides a method for manufacturing an anion exchange membrane comprising the following steps.

(B1) heating a polymer based on partially crosslinked polyphenylene oxide (poly(phenylene oxide), PPO) represented by the following [Formula 1];

(B2) N,N,N′,N′-tetramethyl-1,6-hexanediamine (N,N,N′,N′-tetramethyl-1,6-hexanediamine, TMHDA) in the heated polymer adding to prepare a membrane; and

(B3) washing and drying the immersed membrane.

[Formula 1]

In the above [Formula 1],

wherein a and b are 1 to 30,

Wherein m, n and l are 1 to 100,

wherein x is 1 to 100,000,000.

A polymer based on PPO represented by the above-mentioned [Formula 1], a method for preparing the same, and an anion exchange membrane comprising the same are the same as described above.

In step (B1), the polymer based on the partially crosslinked PPO represented by the [Formula 1] is heated at 40 to 60 ° C. to remove the solvent present in the polymer based on the PPO represented by the [Formula 1]. removing; may be.

Step (B2) is a step of preparing a membrane by adding an excess of TMHDA to the polymer; the immersion may be performed for 12 to 60 hours.

Step (B3) is a step of finally preparing an anion exchange membrane, and may be a step of washing and drying the membrane.

More specifically, the washing in step (B3) is a C1 to C4 low-cost alcohol, glycerin, butylene glycol, propylene glycol, methyl acetate, ethyl acetate, acetone, benzene, hexane, diethyl ether, chloroform, chlorobenzene and dichloro It may be carried out with one or more solvents selected from the group consisting of methane. Preferably, the solvent may be at least one selected from the group consisting of C1 to C4 low alcohol alcohol, glycerin, butylene glycol, propylene glycol, methyl acetate, ethyl acetate and acetone, most preferably methyl acetate, ethyl acetate and acetone. It may be at least one selected from the group consisting of.

In addition, the drying in step (B3) may be performed at 50 to 70 °C for 12 to 60 hours, and may be dried under vacuum, but is not limited thereto.

Advantages and features of the present invention, and methods for achieving them, will become apparent with reference to the embodiments described below in detail. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms, and only the embodiments allow the disclosure of the present invention to be complete, and common knowledge in the technical field to which the present invention pertains It is provided to fully inform those who have the scope of the invention, and the present invention is only defined by the scope of the claims.

Example 1. Polymers based on PPO

1.1 Preparation of the first polymer represented by Formula 2

Polyphenylene oxide (poly(phenylene oxide), PPO) powder (12 g, 100 mmol) was dissolved in chlorobenzene (100 ml) in a three necked round-bottom flask, NBS (30.5 g) , 170 mmol) and AIBN (2.8 g, 17 mmol) were added to the flask to make a mixture, then equipped with a condenser and nitrogen. The mixture was stirred at 85° C. for 4 hours under a nitrogen environment, and the mixture was cooled to room temperature and then diluted with _{chloroform (CHCl 3 ).} Next, an excess of ethanol was slowly added to the mixture to form a precipitate, and the precipitate was filtered. The precipitate was washed three times with methanol, and after vacuum drying at 50° C., a first polymer represented by the above [Formula 2] was prepared.

1.2 Preparation of the second polymer represented by Formula 3

The second polymer may be performed by a Menshutkin reaction. More specifically, the first polymer (3 g, 17 mmol) of the synthesized [Formula 2] was dissolved in NMP (30 ml), and DMHDA (7.22 g, 26 mmol) was added thereto. After the addition of DMHDA, the mixture was first stirred at 85° C. under a nitrogen environment for 4 hours, and secondarily stirred at room temperature for 24 hours. To the mixture, ethyl acetate (EA) was added to prepare a second polymer represented by [Formula 3].

1.3 Preparation of a polymer based on PPO represented by [Formula 1]

TMHDA (74 mg, 0.4 mmol) was added to the synthesized second polymer represented by [Formula 3] and stirred to prepare a PPO-based polymer represented by [Formula 1] according to the present invention.

Example 2. Anion Exchange Membrane Comprising Polymer Based on PPO

The polymer based on the PPO represented by [Formula 1] prepared in Example 1 was poured into a petri dish, and heated at 55° C. for 24 hours. Then, an excess of TMHDA was added to the pet tea dish and left for 2 days to prepare a membrane. The membrane was removed from the excess TMHDA, washed with ethyl acetate (EA), and vacuum dried at 60° C. for 24 h. An anion exchange membrane containing a transparent PPO-based polymer with a thickness of 200-300 μm. was prepared.

Experimental Example 1. ^One H NMR analysis

¹ H NMR spectrum analysis was performed to confirm that the first polymer represented by [Formula 2] prepared in Example 1 was prepared.

¹ H NMR spectra were obtained from CDCl ₃ (δ(1H)=7.26 ppm) and DMSO-d ₆ (δ(1H)=2.50 ppm; at 40 ^o C) with a Varian Unity Inova 500 spectrometer (400 MHz) and Agilent Superconducting FT- It was measured using an NMR spectrometer (500 MHz), and the results are shown in FIG. 1 .

^{1 is a 1} H NMR spectrum of a first polymer represented by [Formula 2], it can be confirmed that a peak of ~ 4.3 ppm corresponds to about 60.5% of selective bromination at the benzyl position of PPO.

Experimental Example 2. FT-IR analysis

FT-IR analysis was performed to confirm that the polymer based on the PPO represented by [Formula 1] prepared in Example 1 was prepared, and the FT-IR used for this analysis was a Nicole 6700 FT-IR spectrophotometer. was measured, and the results are shown in FIG. 2 .

Referring to FIG. 2 , it can be confirmed that a CN infrared vibration absorption peak appears at ^{1646 cm -1} corresponding to a quaternary ammonium group or an amine group. Also, ^{the peaks at 1187 cm -1} and 1303 cm ^-1 are due to symmetric and asymmetric CO stretching in the aryl ether linkage, whereas ^{the peaks at 1600 cm -1} and 1470 cm ^-1 are aromatic CC stretching. ), and the peak of ^{2870-2940 cm -1} can be confirmed to appear due to _{-CH 2} - and -CH _{3 stretching.} ^{In addition, the broadband of ~3300 cm -1} in the FT-IR spectrum can be attributed to the OH stretching vibration from absorbed moisture due to the hydrophilicity of the polymer represented by [Formula 1]. Therefore, as can be seen from the FT-IR spectrum, it can be confirmed that the PPO-based polymer represented by [Formula 1] according to the present invention was successfully synthesized.

Experimental Example 3. X-ray photoelectron spectroscopy (XPS) analysis

X-ray photoelectron spectrum analysis was performed to confirm the degree of crosslinking in which chemical bonding was made by measuring the photoelectron kinetic energy of the polymer based on the PPO represented by [Formula 1] prepared in Example 1, and used in this analysis X-ray photoelectron spectroscopy (XPS) was measured using an AR-XPS system (Theta probe), and the results are shown in FIG. 3 .

3, the high BE (Binding energy, eV) peak (398.6 eV) corresponds to the 1s-electron of N in the quaternary ammonium group, while the low BE peak (396.3 eV) is tertiary ) It can be confirmed that it corresponds to the 1s-electron of N present in the amine group. In addition, the peak area and strength of the quaternary ammonium group increase as the degree of crosslinking increases, which is why TMHDA was effectively used as a crosslinking agent for a higher level of crosslinking, and the PPO-based compound represented by [Formula 1] according to the present invention It can be confirmed that the polymer was successfully synthesized.

Experimental Example 4. Thermogravimetric (TGA)

Thermogravimetric analysis (TGA) was measured to confirm the thermal stability of the polymer based on the PPO represented by [Formula 1] prepared in Example 1 above.

Thermogravimetric (TGA) was measured at a heating rate of 10 °C/min under nitrogen using a TGA Q5000 (TA Instruments) to check the decomposition temperature, and the sample was preheated at 100 °C under vacuum for 12 hours or more. Moisture was removed, and the results are shown in FIG. 4 .

4, it is confirmed that the weight loss in the range of 200-370 °C is a gradual decomposition of the quaternary ammonium group, and the decomposition starting at 370 °C is followed by decomposition of the backbone of the polymer (Formula 1) according to the present invention. . These results can be said that the polymer based on PPO represented by [Formula 1] according to the present invention exhibits high thermal stability that satisfies various electrochemical application requirements.

Experimental Example 5. Morphology analysis

Scanning Electron Microscopy (SEM) was measured to confirm the morphology of the anion exchange membrane including the polymer based on PPO represented by [Formula 1] prepared in Example 2 above.

A Philips XL 30 FEG microscope having an acceleration voltage of 10 kV was used as the scanning electron microscope (SEM) used for this analysis, and the results are shown in FIG. 5 .

Referring to FIG. 5 , it can be seen that, while the surface (a & b) of the membrane is smooth and homogeneous, cracks occur in the cross-sectional area (c & d) due to strong bonding by cross-linking. However, it can be seen that the rough surface is sandwiched between relatively smooth thin layers. Through the above results, it can be said that the anion exchange membrane according to the present invention can provide improved stability.

Experimental Example 6. Atomic Force Microscopy (AFM)

Atomic force microscopy (AFM) was measured to confirm the hydrophilic and hydrophobic phase separation of the anion exchange membrane including the polymer based on PPO represented by [Formula 1] prepared in Example 2 above.

The atomic force microscope used in this analysis was confirmed in tapping mode with an n-Tracer SPM (Nanofocus) with a silicon curvature of <8 nm and a resonance frequency of ~ 320 kHz, and the results are shown in FIG. 6 .

Referring to FIG. 6 , dark regions indicate hydrophilic domains and bright regions indicate hydrophobic domains. It can be seen that the hydrophobic alkyl chain grafted in the structure of the membrane according to the present invention (Example 2) is an interconnected hydrophilic network of small ionic domains with a size of ~ 5 nm, which induces clear hydrophilicity and hydrophobic phase separation. From the above results, the anion exchange membrane according to the present invention can provide a better ion transport path.

Experimental Example 7. Synchrotron Small-Angle X-ray Scattering (SAXS)

Synchrotron Small-Angle X-ray Scattering (SAXS) analysis to analyze the morphology of the anion exchange membrane containing the PPO-based polymer represented by [Formula 1] prepared in Example 2 was performed.

Synchrotron small-angle X-ray scattering (SAXS) used in this analysis was performed using a BL4C beamline at Pohang Accelerator Laboratory (PAL). In addition, data were confirmed in ^{the q-range 0.1-1.8 nm −1} using the wavelength (λ) of the incident X-ray beam at 0.07 nm and the Rayonix 2D SX 165 detector. The scattering vector (q) was calculated from q=4πsinθ/λ, where θ is the scattering angle between incident and scattered radiation, λ is the wavelength of the X-ray beam source, and characteristic separation length (d) was calculated using Bragg's law (d=2π/q), and the results are shown in FIG. 7 .

Referring to FIG. 7 , it can be seen that the scattering vector (q) of the anion exchange membrane (Example 2) according to the present invention has a distinct ionomeric peak at ^{max to 1.56 nm −1 .} In addition, the anion exchange membrane according to the present invention (Example 2) exhibits a large ionic domain size of 4.16 nm, which includes a hydrophilic main chain including a quaternary ammonium ion and a hydrophobic aliphatic side chain. ) due to the high degree of nanophase separation between In addition, it can be confirmed that the arrangement of the ordered structures of ion domains can be maintained over a wide range that can facilitate ion transport.

Experimental Example 8. Confirmation of water absorption rate and swelling rate

An experiment was performed to confirm the water absorption and swelling of the anion exchange membrane comprising a polymer based on PPO represented by [Formula 1] prepared in Example 2 above.

Water absorption and swelling were used by drying the weight, length and thickness (approximately 5 cm x 1 cm) of an anion exchange membrane (Example 2) according to the present invention at 90° C. under vacuum for 24 hours. Then, the dried anion exchange membrane was immersed in deionized water for 24 hours, the membrane was taken out and the membrane was wiped with paper, the weight, length and thickness of the membrane were measured, and the water absorption amount (water uptake, WU _W ) was calculated using the following formula.

[Water uptake (WU _W )]

Where W _wet and W _dry are the weights of the absorbent and dry membranes, respectively.

In addition, the swelling ratio (swelling ratio) was calculated through the following formula.

[swelling ratio]

where l and t are the length and thickness of each membrane.

The moisture absorption rate and swelling rate were confirmed using the conditions and formulas as described above, and the results are shown in FIGS. 8, 9 and [Table 1].

[Table 1]

Referring to [Table 1] and FIG. 8, the moisture absorption of the anion exchange membrane comprising a polymer based on PPO represented by [Formula 1] according to the present invention is 63%, and the By comparison, it can be seen that they have excellent moisture absorption.

In addition, referring to [Table 1] and FIG. 9, the moisture swelling of the anion exchange membrane containing the polymer based on PPO represented by [Formula 1] according to the present invention is 8.7%, and the comparative example 1 and 2, it can be seen that the water absorption rate is excellent.

Experimental Example 9. Power density vs. Check current density

9.1 Fabrication of Microbial Fuel Cells

Microbial Fuel Cell (MFC) used a 250 ml glass bottle with anode and cathode chambers with a glass side arm (13 mm diameter) and a connecting glass tube (21 mm diameter) for a reference electrode. Carbon felt (40 mm × 50 mm NARA Cell-tech Co., Korea) for the positive electrode and negative electrode was used as the electrode, and between the glass bottles based on PPO represented by [Formula 1] prepared in Example 2 A microbial fuel cell reactor was fabricated by clamping an anion exchange membrane comprising a polymer.

In addition, a comparative microbial fuel cell was used in the same manner as above using Nafion (nafion 117, Dufont, USA) and a conventional anion exchange membrane (AEM, FAB-PK-130, Fumasep, Fumatech BWT GmbH, Germany) as a control. Reactors 1 and 2 were fabricated.

9.2 Microbial fuel cell environment

The anode chamber of the microbial fuel cell was inoculated with anaerobic secondary digester sludge (10% v/v) and obtained from a wastewater treatment plant (Suyeong WWT Plant, Busan, Korea). The media of the two chambers (anode and cathode) were 50 mM phosphate buffer (pH 7.0), CH ₃ COONa (3.28 g/L); It _{consisted of a mixture of NH 4} Cl (0.23 g/L), NaCl (0.04 g/L), MgSO _{4 .H 2} O (0.01 g/L) and KCl (0.02 g/L). In addition, in the anolyte, 0.02 g/L of yeast extract was added for replenishment of an unknown mineral, whereas in the catholyte, potassium ferricyanide (potassium ferricyanide ( potassium ferricyanide, 0.1M, 0.323 g/L) was added. Finally, the reactor was incubated at 30 °C in a thermostatically controlled room.

9.3 Power Density vs. Check current density

Power density vs. power density of a microbial fuel cell using an anion exchange membrane comprising a polymer based on PPO represented by [Formula 1] prepared in Example 2 above. An experiment was performed to confirm the current density, and the results are shown in FIG. 10 .

^{10 , the microbial fuel cell reactor according to the present invention is about 0.68 to 0.71 V and 184.4 mW/m 2} at an open circuit voltage compared to comparative microbial fuel cell 1 (Nafion) and comparative microbial fuel cell 2 (AEM). showed high voltage and power density. In addition, it can be seen that the microbial fuel cell reactor according to the present invention exhibits a low internal resistance of 333.4 Ω compared to the comparative microbial fuel cell 1 (361.7 Ω) and the comparative microbial fuel cell 2 (351.5 Ω).

From the above results, it can be confirmed that the microbial fuel cell according to the present invention exhibits significantly higher output compared to a commercial membrane.

From the above description, those skilled in the art to which the present invention pertains will understand that the present invention may be implemented in other specific forms without changing the technical spirit or essential characteristics thereof. In this regard, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

Claims (9)

A polymer based on partially crosslinked polyphenylene oxide (poly(phenylene oxide), PPO), characterized in that represented by the following [Formula 1];
[Formula 1]

In the above [Formula 1],
wherein a and b are 1 to 30,
Wherein m, n and l are 1 to 100,
wherein x is 1 to 100,000,000. (A1) N-bromosuccinimide (NBS) and 2,2′-azobis (2) on poly(2,6-dimethylphenylene oxide) -Methylpropionitrile) (2,2'-azobis(2-methylpropionitrile), AIBN) was added to prepare a first polymer represented by the following [Formula 2];
(A2) preparing a second polymer represented by the following [Formula 3] by adding N,N-dimethyl-1-hexadecylamine (DMHDA) to the first polymer step; and
(A3) N,N,N',N'-tetramethyl-1,6-hexanediamine (N,N,N',N'-tetramethyl-1,6-hexanediamine, TMHDA) to the second polymer Partially cross-linked polyphenylene oxide, characterized in that it comprises; preparing a polymer based on partially cross-linked polyphenylene oxide (poly (phenylene oxide), PPO) represented by the following [Formula 1] by adding A method for producing a polymer based on;
[Formula 1]

[Formula 2]

[Formula 3]

In the above [Formula 1],
wherein a and b are 1 to 30,
Wherein m, n and l are 1 to 100,
wherein x is 1 to 100,000,000. 3. The method of claim 2,
The step (A1) is
(A1a) dissolving poly(2,6-dimethylphenylene oxide) in a first solvent;
(A1b) preparing a mixture by adding NBS and AIBN to the dissolved poly(2,6-dimethylphenylene oxide); and
(A1c) adding a first solvent to the mixture to obtain a first polymer represented by the above [Formula 2] as a precipitate; manufacturing method. 4. The method of claim 3,
The first solvent of step (A1) is 1 selected from the group consisting of alcohol, glycerin, butylene glycol, propylene glycol, methyl acetate, ethyl acetate, acetone, benzene, hexane, diethyl ether, chloroform, chlorobenzene and dichloromethane A method for producing a polymer based on partially cross-linked polyphenylene oxide, characterized in that more than one species. 3. The method of claim 2,
The step (A2) is
(A2a) dissolving the first polymer in methylpyrrolidone (N-methyl-2-pyrrolidone, NMP);
(A2b) adding DMHDA to the dissolved first polymer to prepare a mixture; and
(A2c) adding a second solvent to the mixture to obtain a second polymer represented by [Formula 3]; Method for producing a polymer based on partially crosslinked polyphenylene oxide, characterized in that it consists of . 6. The method of claim 5,
The second solvent of step (A2) is 1 selected from the group consisting of alcohol, glycerin, butylene glycol, propylene glycol, methyl acetate, ethyl acetate, acetone, benzene, hexane, diethyl ether, chloroform, chlorobenzene and dichloromethane A method for producing a polymer based on partially crosslinked polyphenylene oxide, characterized in that more than one species. An anion exchange membrane comprising a polymer based on partially crosslinked polyphenylene oxide (PPO) represented by the following [Formula 1];
[Formula 1]

In the above [Formula 1],
wherein a and b are 1 to 30,
Wherein m, n and l are 1 to 100,
wherein x is 1 to 100,000,000. 8. The method of claim 7,
The anion exchange membrane is an anion exchange membrane, characterized in that the transparent membrane having a thickness of 150 to 350 ㎛. (B1) heating a polymer based on partially crosslinked polyphenylene oxide (poly(phenylene oxide), PPO) represented by the following [Formula 1];
(B2) N,N,N′,N′-tetramethyl-1,6-hexanediamine (N,N,N′,N′-tetramethyl-1,6-hexanediamine, TMHDA) in the heated polymer adding to prepare a membrane; and
(B3) manufacturing an anion exchange membrane by washing and drying the immersed membrane;
[Formula 1]

In the above [Formula 1],
wherein a and b are 1 to 30,
Wherein m, n and l are 1 to 100,
wherein x is 1 to 100,000,000.

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