KR20170030693A - Crosslinker containing electron withdrawing group for ion exchangable polymer, ion exchangable-crosslinked polymer crosslinked by the crosslinker and use thereof - Google Patents

Abstract

The present invention relates to an ion exchangeable polymer cross-linking agent having an electron withdrawing group, an ion conductive cross-linking polymer cross-linked by the cross-linking agent, and a use of the same. More specifically, without forming an ion exchangeable functional group as a primary or secondary amine cross-linking agent, cross-linking can be performed exclusively; and an electron withdrawing group is included, so a rapid cross-linking reaction is inhibited during membrane production, and thereby a change in the shape of a membrane can be prevented. In particular, dimension stability and mechanical stability caused by cross-linking are improved without affecting the functions, such as water uptake and conductivity, of a membrane. Also, a negative ion exchange functional group can be easily adjusted in the ion exchangeable polymer cross-linking agent.

Description

[0001] The present invention relates to a crosslinking agent for an ion-exchange polymer having an electron-withdrawing group, an ion-conductive crosslinking polymer crosslinked by the crosslinking agent, and a use thereof.

The present invention relates to a crosslinking agent for an ion-exchange polymer having an electron-withdrawing group, an ion-conducting crosslinked polymer crosslinked by the crosslinking agent, and a use thereof.

Worldwide, the value of water resources is increasing due to the deepening of drought phenomena caused by global warming, depletion of groundwater, progress of desertification, population increase, increase of living and industrial water use by industrialization, and the desalination of seawater, And recycling are emerging as new issues. In addition, as interest in the production of ultra pure water for industrial use increases, the demand for clean water that can be eaten and washed increases in living, and research on the development of high efficiency ion removing apparatus is actively carried out.

The evaporation method and the reverse osmosis membrane method are mainly used for evaporation method, reverse osmosis membrane method and ion exchange membrane method. The evaporation method and the reverse osmosis membrane method have operation cost and operational problems due to high energy consumption and the most widely used ion exchange membrane The method has the disadvantage of producing secondary pollutants because it uses excess acid or salt (NaCl) during regeneration.

Concentrated water as such by-product can be used as a good raw material in the reverse electrodialysis process. Reverse electrodialysis is a renewable energy system that produces electricity through the reverse operation of electrodialysis. In other words, when the cation exchange membrane and the anion exchange membrane alternate with each other to create a compartment and alternately flow salt water and agricultural water to each compartment, ion flow is generated through each ion exchange membrane and the current generated through the ion exchange membrane is utilized. The ion exchange membrane, which is the core material of the ion exchange membrane, is the most important material that determines the performance of the system. However, since the ion exchange membrane used is very expensive and the durability is not satisfactory due to the ion selectivity, new materials and technologies Is required.

Electrodialysis using an ion exchange membrane is a process for separating ionic materials dissolved in water by using an electric field formed by a direct current power supplied through an electrode and an electrolyte solution. The ion exchange membrane used here indicates the selective permeability of the corresponding ions by the ionic bonding of the fixed ions in the membrane in the electrolyte solution. In general, ion exchange membranes are required to have high permeability selectivity, low electrical resistance, excellent mechanical strength, and high chemical stability.

A method for producing an ion exchangeable and / or ionically conductive crosslinked polymer by using an existing amine-based crosslinking agent is a method in which a tertiary amine is used as a crosslinking agent and the tertiary amine crosslinking agent is converted into an ammonium ion, . However, this affects the functionality of ion-exchange membranes such as water uptake and conductivity.

An object of the present invention is to provide a crosslinking agent capable of only crosslinking without formation of an ion-exchange functional group and inhibiting a sudden crosslinking reaction at the time of film formation to prevent a change in the shape of the membrane, an ionically conductive crosslinked polymer crosslinked with the crosslinking agent, and a use thereof will be.

A first aspect of the present invention provides a crosslinking agent composition for an ion-exchange crosslinked polymer comprising a compound represented by the following formula (1): < EMI ID =

[Chemical Formula 1]

In Formula 1,

A is an electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) - , or or the electron withdrawing group substituted by at least one of C ₆ aryl or C _{5 -20 -20} heteroaryl;

B ₁ and B ₂ are each independently -NH ₂ , or -NHR;

R is hydrogen, - (CH ₂ ) _z CH ₃ (z is 0 or an integer in the range 1≤z≤100), - (CX ₂ ) _z CX ₃ - (z is 0 or an integer in the range 1≤z≤100, X is a halogen atom), -NH ₂ , -NH (CH ₃ ), -NH- (CH ₂ ) _y -NH ₂ (1 ≦ y ≦ 100, y is an integer), - (C═O) _{(CH 3) 2 H, -CH} 2 (OH), -O-CH 2 -C (CH 3) 2 -CH 2 -OH, - (O-CH 2 -CH 2) p -O-CH 2 -CH ₃ (1? P? 100, p is an integer), -O- (CH ₂ ) ₂ - (O-CH ₂ -CH ₂ ) _x -OH, -OH, -SO ₂ H, , C _{1 -6} alkyl or C _{6 -10} aryl group optionally substituted with a blood rolgi, unsubstituted or halogen, C _{1 -6} alkyl or C _{6 -10} a pyridine group substituted with aryl group, a phenol group or a phenyl group;

m and n are each independently an integer of 1 to 100;

The second aspect of the present invention provides an ionically conductive crosslinked polymer characterized in that the ion conductive polymer is crosslinked through a crosslinking unit represented by the following formula (2)

(2)

In Formula 2,

A is an electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) - , or or the electron withdrawing group substituted by at least one of C ₆ aryl or C _{5 -20 -20} heteroaryl;

B ₁ 'and B ₂ ' are each independently -NH-, or -NR-;

R is hydrogen, - (CH ₂ ) _z CH ₃ (z is 0 or an integer in the range 1≤z≤100), - (CX ₂ ) _z CX ₃ - (z is 0 or an integer in the range 1≤z≤100, X is a halogen atom), -NH ₂ , -NH (CH ₃ ), -NH- (CH ₂ ) _y -NH ₂ (1 ≦ y ≦ 100, y is an integer), - (C═O) _{(CH 3) 2 H, -CH} 2 (OH), -O-CH 2 -C (CH 3) 2 -CH 2 -OH, - (O-CH 2 -CH 2) p -O-CH 2 -CH ₃ (1? P? 100, p is an integer), -O- (CH ₂ ) ₂ - (O-CH ₂ -CH ₂ ) _x -OH, -OH, -SO ₂ H, , C _{1 -6} alkyl or C _{6 -10} aryl group optionally substituted with a blood rolgi, unsubstituted or halogen, C _{1 -6} alkyl or C _{6 -10} a pyridine group substituted with aryl group, a phenol group or a phenyl group;

m and n are each independently an integer of 1 to 100;

A third aspect of the present invention provides a compound comprising a repeating unit represented by the following general formula (3-1), (4-1) or (5-1)

[Formula 3-1]

[Formula 4-1]

[Formula 5-1]

In the above Formulas (3-1), (4-1) and (5-1)

A is an electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) - , or or the electron withdrawing group substituted by at least one of C ₆ aryl or C _{5 -20 -20} heteroaryl;

B ₁ 'and B ₂ ' are each independently -NH-, or -NR-;

_{R, R 1 ", R 2} ", R 3 ", R 4", R 5 ", R 6", R 7 ", R 8", R 9 ", R 10", R 11 ", R 12", R ₁₃ ", R ₁₄ ", R ₁₅ ", R ₁₆ ", R ₁₇ ", R ₁₈ ", D and D 'are each independently hydrogen, - (CH ₂ ) _z CH ₃ - (CX ₂ ) _z CX ₃ - (z is an integer in the range of 0 or 1? Z? 100, X is a halogen atom), -NH ₂ , -NH (CH ₃ ) _{(CH 2) y -NH 2 (} 1≤y≤100, y is an integer), - (C = O) H, -C (CH 3) 2 H, -CH 2 (OH), -O-CH 2 - _{C (CH 3) 2 -CH 2} -OH, - (O-CH 2 -CH 2) p -O-CH 2 -CH 3 (1≤p≤100, p is an integer), -O- (CH _{2) 2 - (O-CH 2 -CH} 2) x -OH, -OH, -SO 2 H, -SH, unsubstituted or halogen, C _{1 -6} the blood rolgi, unsubstituted or substituted by alkyl, C _{6 -10} aryl or a halogen, C _{1 -6} alkyl or C _{6 -10} a pyridine group substituted with aryl group, a phenol group or a phenyl group;

X is a halogen atom;

m, n, q, r and p are each independently an integer of 1 to 100;

0.001? Q / (q + r)? 0.50.

A fourth aspect of the present invention is the method for producing an ionically conductive crosslinked polymer according to the second aspect,

A first step of preparing a halogenated polymer;

A second step of adding a crosslinking agent represented by the following formula (1) to the halogenated polymer to form a crosslinked polymer by a cross-linking reaction between halogenated polymers at some halogen functional sites of the halogenated polymer; And

And a third step of replacing the residual halogen functionality of the crosslinking polymer with an anion exchange functional group, a cation exchange functional group or an amphoteric ion exchange functional group.

[Chemical Formula 1]

In Formula 1,

A is an electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) - , or or the electron withdrawing group substituted by at least one of C ₆ aryl or C _{5 -20 -20} heteroaryl;

B ₁ and B ₂ are each independently -NH ₂ , or -NHR;

R is hydrogen, - (CH ₂ ) _z CH ₃ (z is 0 or an integer in the range 1≤z≤100), - (CX ₂ ) _z CX ₃ - (z is 0 or an integer in the range 1≤z≤100, X is a halogen atom), -NH ₂ , -NH (CH ₃ ), -NH- (CH ₂ ) _y -NH ₂ (1 ≦ y ≦ 100, y is an integer), - (C═O) _{(CH 3) 2 H, -CH} 2 (OH), -O-CH 2 -C (CH 3) 2 -CH 2 -OH, - (O-CH 2 -CH 2) p -O-CH 2 -CH ₃ (1? P? 100, p is an integer), -O- (CH ₂ ) ₂ - (O-CH ₂ -CH ₂ ) _x -OH, -OH, -SO ₂ H, , C _{1 -6} alkyl or C _{6 -10} aryl group optionally substituted with a blood rolgi, unsubstituted or halogen, C _{1 -6} alkyl or C _{6 -10} a pyridine group substituted with aryl group, a phenol group or a phenyl group;

m and n are each independently an integer of 1 to 100;

A fifth aspect of the present invention provides a film comprising the ionically conductive crosslinked polymer according to the second aspect.

Hereinafter, the present invention will be described in detail.

In the present invention, a primary or secondary amine cross-linking agent can be used as the amine-based cross-linking agent to perform crosslinking only without forming an ion-exchange functional group. In particular, it has an advantage that it improves the dimensional stability and mechanical stability due to crosslinking without affecting the functions of membranes such as water uptake and conductivity, and is easy to control the anion exchange function.

FIG. 1 is a schematic view illustrating a process for producing an ion exchangeable and / or ionically conductive crosslinked polymer according to one embodiment of the present invention.

In particular, in the present invention, by using an aromatic primary or secondary amine crosslinking agent having an electron-withdrawing group at the "A" position as a compound represented by the following formula (1), it is possible to suppress the rapid crosslinking reaction during film formation,

[Chemical Formula 1]

Preferably A is an electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) - , or or the substituted with one or more electron withdrawing groups of the C _{6 -20} aryl or C _5-20 heteroaryl group, especially a a - (C = O) - a compound having the ion-exchangeable crosslinked amine as a crosslinking agent for the production of high molecular Can be used.

Specifically, in the examples of the present invention, when an ion-exchange membrane was prepared using various amine-based crosslinking agents and subjected to a screening test, the aromatic and alicyclic amines as crosslinking agents were much longer in retention time than aliphatic groups, ", It was found that the retention time was significantly increased in the case of the electron withdrawing group, and it was confirmed that the effect of preventing the change of the film shape due to the rapid crosslinking reaction during the film formation was confirmed. In addition, when the primary or secondary amine group of -NH ₂ or -NHR is located in the above-mentioned "B ₁ " and "B ₂ ", and the compound represented by the above formula 1 is not a ion exchange functional group Can only act.

The ion exchangeable and / or ionically conductive crosslinked polymer of the present invention can be used for preparing ion exchange membranes. The ion exchangeable and / or ionically conductive crosslinked polymer of the present invention is applicable to water treatment such as reverse electrodialysis (RED), electrodialysis (ED), capacitive deionization (CDI), etc. can do.

Reverse Electrodialysis is a blue energy technology that generates power using the difference in salinity between seawater and fresh water, such as PRO (pressure-retarded osmosis). It is a general energy that generates electricity by supplying electricity. In contrast to the dialysis process, electrodialysis is used to obtain energy while going through the reverse process of desalination. For the efficient process of reverse electrodialysis, the ion exchange membrane is required to have low electrical resistance, high selectivity permeability, durability, high strength, and low production cost.

Electrodialysis is an ion exchange membrane process in which an ionic material is separated using an electric field formed by a direct current power supplied through an electrode and an electrolyte solution. The electrodialysis process is divided into desalting electrodialysis, water-decomposing electrodialysis, and electric deionization depending on the application. The electroplating wastewater process, which is the most widely used field of electrodialysis in the wastewater treatment process, is the recycling of industrial water and the recovery of metal ions. In addition, copper plating process and cyan plating process are applied to plating process. In addition, sodium nitrate concentration, concentration and recovery of sodium sulfide, and electrodialysis are used for concentration and recovery of calcium chloride. Water-splitting electrodialysis (WSED) is a process that uses a bipolar membrane together with a cation / anion exchange membrane. It is a process that introduces a bipolar membrane and is effective for producing acid / base without producing by-products in various chemical and biological processes. Process. Continuous electrodeionization (CEDI) is mainly used for the production of ultrapure water for semiconductor, power generation, food, medical and energy businesses. Electrodeionization process (CEDI) is an alternative to conventional ion exchange resin processes and is a process for the production of ultrapure water and for the removal of ionic substances in the inflow water at low concentrations.

Capacitive deionization (CDI) is based on the principle that ions are adsorbed to the charged electrode surface by electrostatic attraction. When a potential within an overpotential is applied to a polarized electrode, positive and negative charges are charged to the positive and negative electrodes, respectively. When brine is supplied between the charged electrodes, an electrostatic attractive force between the charged electrode and the ions acts to desorb the positive ions on the negative electrode and the negative ions on the positive electrode surface. The ions adsorbed on the electrode surface can be desorbed by shorting the two electrodes or applying a reverse potential.

The cross-linking agent composition according to the present invention can be used as a cross-linking agent in the present invention, such as polypropylene, polyethylene, polyethylene terephthalate, polyethylene naphthalate, polystyrene, polycarbonate, polymethyl methacrylate, polyethersulfone, polyvinylidene fluoride, polyether ketone, A polymer selected from the group consisting of polyester, polyacrylonitrile, polyacrylic acid, polyacrylate, polymethyl methacrylate, polyethyleneimide, cellulose acetate, cellulose triacetate, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, , A polymer selected from the group consisting of polyethylene oxide, polyvinyl acetate, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate and polyethylene naphthalate.

In the present invention, it is possible to provide an ionically conductive crosslinked polymer crosslinked by the crosslinking agent represented by the general formula (1).

As used herein, the term "ionically conductive polymer" refers to a polymer having ionic conductivity, which is a polymer provided as a polymer backbone before crosslinking.

The term "ionically conductive crosslinked polymer" used in the present invention may mean an ion conductive polymer crosslinked by the crosslinking agent represented by the general formula (1). In this case, the crosslinking may occur between the main chain portions of the ion conductive polymer and may occur at the side chain portions connected to the main chain of the ion conductive polymer.

The ion conductive crosslinked polymer according to the present invention is characterized in that the ion conductive polymer is crosslinked through a crosslinking unit represented by the following formula (2).

(2)

In Formula 2,

A is an electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) - , or or the electron withdrawing group substituted by at least one of C ₆ aryl or C _{5 -20 -20} heteroaryl;

B ₁ 'and B ₂ ' are each independently -NH-, or -NR-;

R is hydrogen, - (CH ₂ ) _z CH ₃ (z is 0 or an integer in the range 1≤z≤100), - (CX ₂ ) _z CX ₃ - (z is 0 or an integer in the range 1≤z≤100, X is a halogen atom), -NH ₂ , -NH (CH ₃ ), -NH- (CH ₂ ) _y -NH ₂ (1 ≦ y ≦ 100, y is an integer), - (C═O) _{(CH 3) 2 H, -CH} 2 (OH), -O-CH 2 -C (CH 3) 2 -CH 2 -OH, - (O-CH 2 -CH 2) p -O-CH 2 -CH ₃ (1? P? 100, p is an integer), -O- (CH ₂ ) ₂ - (O-CH ₂ -CH ₂ ) _x -OH, -OH, -SO ₂ H, , C _{1 -6} alkyl or C _{6 -10} aryl group optionally substituted with a blood rolgi, unsubstituted or halogen, C _{1 -6} alkyl or C _{6 -10} a pyridine group substituted with aryl group, a phenol group or a phenyl group;

m and n are each independently an integer of 1 to 100;

The ionically conductive crosslinked polymer according to the present invention may be formed by crosslinking a halogenated polymer at a halogen functional site in the halogenated polymer.

Wherein the ion conductive polymer is selected from the group consisting of polypropylene, polyethylene, polyethylene terephthalate, polyethylene naphthalate, polystyrene, polycarbonate, polymethyl methacrylate, polyether sulfone, polyvinylidene fluoride, polyether ketone, polyphenyl sulfide, , Polyacrylonitrile, polyacrylic acid, polyacrylate, polymethylmethacrylate, polyethyleneimide, cellulose acetate, cellulose triacetate, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, sulfonated polysulfone, polyethylene The main chain may be a polymer selected from the group consisting of oxide, polyvinyl acetate, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and polyethylene naphthalate.

In the present invention, the ion conductive polymer may have an anion-exchangeable functional group, a cation-exchangeable functional group or an amphoteric ion-exchange functional group.

In the present invention, the anion-exchangeable functional group is selected from -NH ₃ E, -NR'H ₂ E, -NR ' ₂ HE, -NR' ₃ E, -PR ' ₃ E or -SR' ₂ E or -C ₅ H ₅ NHE and (R 'is C _{1 -4} alkyl or C _{6 -12} aryl, E is a hydroxide anion, bicarbonate anion, a chloride anion or a sulfate anion Im), a cation-exchange functional groups are -SO ₃ ^-, -COO ^- , -PO ₃ ^{2 -} , -PO ₃ H ^- or -C ₆ H ₄ 0 ^- , and the amphoteric ion-exchange functional group may be betaine or sulfobetaine.

In one embodiment, the ionically conductive crosslinked polymer according to the present invention may have a skeleton containing a repeating unit represented by the following formula (3).

(3)

In Formula 3,

A is an electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) - , or or the electron withdrawing group substituted by at least one of C ₆ aryl or C _{5 -20 -20} heteroaryl;

B ₁ 'and B ₂ ' are each independently -NH-, or -NR-;

_{R, R 1 ", R 2} ", D and D 'are each independently _{hydrogen, - (CH 2) z CH} 3 (z is zero or an integer in the range _{1≤z≤100), - (CX 2) z} CX ₃ - (z is 0 or an integer in the range of ₁ ? Z? 100, X is a halogen atom), -NH ₂ , -NH (CH ₃ ), -NH- (CH ₂ ) _y -NH ₂ , y is an integer), - (C = O) H, -C (CH 3) 2 H, -CH 2 (OH), -O-CH 2 -C (CH 3) 2 -CH 2 -OH, - ( _{O-CH 2 -CH 2) p} -O-CH 2 -CH 3 (1≤p≤100, p is an _{integer), -O- (CH 2) 2} - (O-CH 2 -CH 2) x -OH , -OH, -SO ₂ H, -SH, unsubstituted or halogen, C _1-6 alkyl substituted with a blood or C _6-10 aryl rolgi, unsubstituted or halogen, C _1-6 alkyl or C _6-10 aryl A phenoxy group or a phenyl group;

f is an anion exchange functional group, a cation exchange functional group or an amphoteric ion exchange functional group;

m, n, q, r and p are each independently an integer of 1 to 100;

0.001? Q / (q + r)? 0.50.

The ion-conductive crosslinked polymer having a skeleton containing the repeating unit represented by the above-mentioned formula (3) can be produced by reacting a halogen functional group of a crosslinked polymer having a skeleton containing a repeating unit represented by the following formula (3-1) with an anion- Or by ion exchange with an amphoteric ion-exchange functional group.

[Formula 3-1]

In Formula 3-1,

Wherein A, B ₁ ', B ₂ ', R, R ₁ ", R ₂ ", D, D ', m, n, q, r and p are as defined in Formula 3;

X is a halogen atom.

In another embodiment, the ionically conductive crosslinked polymer according to the present invention may have a skeleton containing a repeating unit represented by the following formula (4).

[Chemical Formula 4]

In this formula,

A is an electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) - , or or the electron withdrawing group substituted by at least one of C ₆ aryl or C _{5 -20 -20} heteroaryl;

B ₁ 'and B ₂ ' are each independently -NH-, or -NR-;

_{R, R 3 ", R 4} ", R 5 ", R 6", R 7 ", R 8", R 9 ", R 10", D and D 'are independently hydrogen, respectively - _z (CH ₂₎ CH ₃ (z is zero or an integer in the range _{1≤z≤100), - (CX 2) z} CX 3 - (z is zero or an integer from 1≤z≤100 range, X is a halogen atom), -NH _{2, -NH (CH 3), -NH- (} CH 2) y -NH 2 (1≤y≤100, y is an integer), - (C = O) H, -C (CH 3) 2 H, -CH 2 (OH), -O-CH ₂ -C (CH ₃ ) ₂ -CH ₂ -OH, - (O-CH ₂ -CH ₂ ) _p -O-CH ₂ -CH _{3 integer), -O- (CH 2) 2} - (O-CH 2 -CH 2) x -OH, -OH, -SO 2 H, -SH, unsubstituted or halogen, C _1-6 alkyl or C _6- substituted with aryl blood rolgi _10, unsubstituted or halogen, C _1-6 alkyl or C _6-10 aryl substituted with a pyridine group, a phenol group or a phenyl group;

f is an anion exchange functional group, a cation exchange functional group or an amphoteric ion exchange functional group;

m, n, q, r and p are each independently an integer of 1 to 100;

0.001? Q / (q + r)? 0.50.

The ionically conductive crosslinked polymer having a skeleton containing the repeating unit represented by the formula (4) can be obtained by reacting a halogen functional group of a crosslinked polymer having a skeleton containing a repeating unit represented by the following formula 4-1 with an anion exchange functional group, Or by ion exchange with an amphoteric ion-exchange functional group.

[Formula 4-1]

In the above formula (4-1)

_{A, B 1 ', B 2} ', R, R 3 ", R 4", R 5 ", R 6", R 7 ", R 8", R 9 ", R 10", D, D ', m , n, q, r and p are as defined in Formula 4 above;

X is a halogen atom.

In another embodiment, the ionically conductive crosslinked polymer according to the present invention may have a skeleton containing a repeating unit represented by the following formula (5).

[Chemical Formula 5]

In Formula 5,

A is an electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) - , or or the electron withdrawing group substituted by at least one of C ₆ aryl or C _{5 -20 -20} heteroaryl;

B ₁ 'and B ₂ ' are each independently -NH-, or -NR-;

_{R, R 11 ", R 12} ", R 13 ", R 14", R 15 ", R 16", R 17 ", R 18", D and D 'are independently hydrogen, and each - (CH _{2) z} CH ₃ (z is zero or an integer in the range _{1≤z≤100), - (CX 2) z} CX 3 - (z is zero or an integer from 1≤z≤100 range, X is a halogen atom), -NH _{2, -NH (CH 3), -NH- (} CH 2) y -NH 2 (1≤y≤100, y is an integer), - (C = O) H, -C (CH 3) 2 H, -CH 2 (OH), -O-CH ₂ -C (CH ₃ ) ₂ -CH ₂ -OH, - (O-CH ₂ -CH ₂ ) _p -O-CH ₂ -CH _{3 integer), -O- (CH 2) 2} - (O-CH 2 -CH 2) x -OH, -OH, -SO 2 H, -SH, unsubstituted or halogen, C _1-6 alkyl or C _6- substituted with aryl blood rolgi _10, unsubstituted or halogen, C _1-6 alkyl or C _6-10 aryl substituted with a pyridine group, a phenol group or a phenyl group;

f is an anion exchange functional group, a cation exchange functional group or an amphoteric ion exchange functional group;

m, n, q, r and p are each independently an integer of 1 to 100;

0.001? Q / (q + r)? 0.50.

The ionically conductive crosslinked polymer having a skeleton containing the repeating unit represented by the above-mentioned formula (5) can be produced by reacting a halogen functional group of a crosslinked polymer having a skeleton containing a repeating unit represented by the following formula (5-1) with an anion exchange functional group, Or by ion exchange with an amphoteric ion-exchange functional group.

[Formula 5-1]

In Formula 5-1,

_{A, B 1 ', B 2} ', R, R 11 ", R 12", R 13 ", R 14", R 15 ", R 16", R 17 ", R 18", D, D ', m , n, q, r, and p are as defined in Formula 5 above;

X is a halogen atom.

In the ion conductive crosslinked polymer according to the present invention, R ₁ "and R ₂ " in each repeating unit; Or R ₃ ", R ₄ ", R ₅ ", R ₆ ", R ₇ ", R ₈ ", R ₉ "and R ₁₀ "; Or R ₁₁ ", R ₁₂ ", R ₁₃ ", R ₁₄ ", R ₁₅ ", R ₁₆ ", R ₁₇ "and R ₁₈ " may be the same or different from each other. Accordingly, in the ionically conductive crosslinked polymer according to the present invention, each repeating unit may be composed of the same repeating units or different repeating units may form a certain block to form a block copolymer, May be randomly connected to form a random copolymer.

In the ion conductive crosslinked polymer according to the present invention, 0.001? Q / (q + r)? 0.50, more preferably 0.01? Q / (q + r)? In the present invention, "q / (q + r)" means the molar ratio of the crosslinking group to 100 moles of the total halogen reactant, and may mean the crosslinking ratio. Here, the ion-exchange functional group is bonded to the block of the repeating unit r not bonded to the crosslinking group.

The ionically conductive crosslinked polymer according to the present invention may have Mn (number-average molecular weight) of 10,000 to 1,000,000 or molecular weight of Mw (weight-average molecular weight) of 10,000 to 10,000,000. When the molecular weight is low, for example, when Mn and Mw are less than 10,000, film formation is difficult, the moisture content is increased, and it is easily decomposed by the attack of radical, so that conductivity and durability may be decreased. On the other hand, when the molecular weight is high, for example, when the Mn is more than 1,000,000 or the Mw is more than 10,000,000, the production of the polymer solution and molding into a film become difficult due to the rapidly increased viscosity, and the film manufacturing process may become impossible.

Since the weight average molecular weight and the viscosity average molecular weight are similar to each other, the intrinsic viscosity of the polymer is measured to predict the molecular weight in the specific examples of the present invention. GPC (gel permeation chromatography) can be used to measure the molecular weight. However, in the case of a polymer substituted with a sulfonic acid group, the molecular weight can be estimated by measuring viscosity since it is difficult to trust data due to interaction between sulfonic acid groups.

In the present invention, the ion conductive polymer preferably has a halogen functional group, and at the halogen functional group position, the compound represented by the general formula (1), that is, the crosslinking agent according to the present invention, The ion-conductive crosslinked polymer according to the present invention can be formed.

As described above, the ion conductive polymer as a main chain of the ion conductive crosslinked polymer according to the present invention may be a random copolymer, a cross-copolymer or a block copolymer. That is, the ion conductive polymer constituting the backbone itself may be various types of polymers such as random copolymers, cross-linked copolymers, and block copolymers. In the functional groups capable of causing a cross-linking reaction in the polymer, Crosslinked by a compound, polymers having various forms such as random copolymers, cross-linked copolymers, and block copolymers can be crosslinked to form ionically-crosslinked polymers (FIG. 1). The functional group capable of causing the crosslinking reaction is preferably a halogen element. Examples of the halogen element include F (fluorine), Cl (chlorine), Br (bromine) and I (iodine). The halogen element is a substituent that is widely introduced for the reaction such as condensation and substitution because it is excellent in reactivity when it is introduced as a substituent to an organic compound due to high electronegativity due to high effective nuclear charge. More preferably, the halogen element may be a chlorine atom.

As described above, the method for producing an ionically conductive crosslinked polymer according to the second aspect,

A first step of preparing a halogenated polymer;

A second step of adding a crosslinking agent represented by the following formula (1) to the halogenated polymer to form a crosslinked polymer by a cross-linking reaction between halogenated polymers at some halogen functional sites of the halogenated polymer; And

And a third step of replacing the residual halogen functionality of the crosslinking polymer with an anion exchange functional group, a cation exchange functional group or an amphoteric ion exchange functional group.

[Chemical Formula 1]

In this formula,

A is an electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) - , or or the electron withdrawing group substituted by at least one of C ₆ aryl or C _{5 -20 -20} heteroaryl;

B ₁ and B ₂ are each independently -NH ₂ , or -NHR;

R is hydrogen, - (CH ₂ ) _z CH ₃ (z is 0 or an integer in the range 1≤z≤100), - (CX ₂ ) _z CX ₃ - (z is 0 or an integer in the range 1≤z≤100, X is a halogen atom), -NH ₂ , -NH (CH ₃ ), -NH- (CH ₂ ) _y -NH ₂ (1 ≦ y ≦ 100, y is an integer), - (C═O) _{(CH 3) 2 H, -CH} 2 (OH), -O-CH 2 -C (CH 3) 2 -CH 2 -OH, - (O-CH 2 -CH 2) p -O-CH 2 -CH ₃ (1? P? 100, p is an integer), -O- (CH ₂ ) ₂ - (O-CH ₂ -CH ₂ ) _x -OH, -OH, -SO ₂ H, , C _{1 -6} alkyl or C _{6 -10} aryl group optionally substituted with a blood rolgi, unsubstituted or halogen, C _{1 -6} alkyl or C _{6 -10} a pyridine group substituted with aryl group, a phenol group or a phenyl group;

m and n are each independently an integer of 1 to 100;

The first step is a step of preparing a polymer to which a halogen functional group is introduced as a reactive functional group capable of causing a crosslinking reaction.

The term " degree of halogenation "used in the present invention is a value obtained by dividing the number of halogen functional groups produced in the whole polymer by the halogenation reaction divided by the total number of repeating units. I. E., The number of halogen functional groups per repeating unit. Similarly, for example, "degree of bromination" is a value obtained by dividing the number of bromine functional groups produced in the entire polymer by the number of all repeating units through the bromination reaction, and "degree of chloromethylation ""Is a value obtained by dividing the number of bromine functional groups produced in the entire polymer by the number of all repeating units through chloromethylation reaction.

In the present invention, the degree of halogenation of the halogenated polymer is 1 to 150% (0.01 to 1.5), such as 10 to 120% (0.1 to 1.2), 10 to 30% (0.1 to 0.3), 30 to 50% (0.3 to 0.5) 80 to 100% (0.8 to 1), and the like.

In the present invention, a halogenated polymer can be used by obtaining a commercially available one, or by directly halogenating a non-halogenated polymer. Also, in the present invention, the halogenated polymer may be prepared by using a monomer as a desired polymer by directly polymerizing and halogenating the monomer.

The halogenation can be carried out using various known methods. For example, the bromination of poly (2,6-dimethyl-1,4-phenylene oxide) (PPO) can be carried out as described in Hsin-I Chang et al. Methyl-brominated PPO synthesis method of Reactive & Functional Polymers, 70, (2010) 944-950 and X. Tongwen, Y. Weihua (Journal of Membrane Science, 190, (2001) 159-166) . The desired degree of bromination can be controlled according to the molar ratio of NBS (N-bromosuccinimide). In addition, chloromethylation of polyphenylsulfone and polysulfone can be carried out by referring to a process for producing an anion conductor-containing solution of Korean Patent No. 10-1284009. The desired degree of chloromethylation can be controlled by the molar ratio of chloromethyl methyl ether.

The reaction temperature, the reaction time, the stirring conditions, and the halogen element used in the halogenation are not particularly limited, but may be appropriately selected depending on the size, performance characteristics, quality and other properties of the resultant ion exchange membrane. The halogen atom is not particularly limited, but includes fluorine, chlorine, bromine and iodine in particular.

The halogenation reaction temperature is selected, for example, preferably in the range of 0 to 300 占 폚, more preferably in the range of 20 to 200 占 폚. The halogenation reaction time can be appropriately selected depending on other conditions, and is preferably 1 to 10 hours. Under stirring conditions at the time of halogenation, a stirring speed in a usual halogenation reaction may be used. The reaction initiator used may be water-soluble or lipophilic and, in normal use, its peroxide or azo initiator may be used. For additives, conventional stabilizers and others may be used. Other reaction conditions are not specifically limited.

In the second step, a cross-linking agent represented by the general formula (1) is added to a halogenated polymer to form a cross-linked polymer by cross-linking reaction between halogenated polymers at a halogen functional site of the halogenated polymer.

In the second step, the film formation can be performed simultaneously with the crosslinking reaction. Specifically, the resin composition obtained by adding the crosslinking agent represented by the general formula (1) to the halogenated polymer can be formed into a molded article in the form of fiber or film by any method such as casting, extrusion, spinning or rolling. The resin composition may further contain various additives such as an antioxidant, a heat stabilizer, a lubricant, a tackifier, a plasticizer, a cross-linking agent, a defoaming agent, and a dispersant, if necessary.

The reaction temperature, the reaction time, and the stirring conditions during the crosslinking in the second step are not specifically limited, but may be appropriately selected depending on the size, performance characteristics, quality and other properties of the resultant ion exchange membrane. The reaction temperature is, for example, preferably selected within the range of -10 to 400 占 폚, more preferably 0 to 200 占 폚. The reaction time can be appropriately selected depending on other conditions, and is preferably within 100 hours. In the stirring condition, the stirring speed in the ordinary crosslinking reaction can be used. Other reaction conditions are not specifically limited.

For example, a resin composition obtained by adding a crosslinking agent represented by the general formula (1) to a halogenated polymer may be molded to prepare an ion exchange membrane. Specifically, the halogenated polymer and the crosslinking agent represented by the formula (1) are dissolved in an organic solvent, the solution is poured into a molding mold such as a silicone mold, and the temperature is elevated from room temperature to 40 to 100 ° C stepwise to cause a crosslinking reaction. A film having a thickness of several to several hundreds of μm, preferably 10 to 200 μm, more preferably 50 to 150 μm, and then desorbing from the molding mold. Examples of the organic solvent include, but are not limited to, saturated chain hydrocarbons such as pentane, (n-) hexane and heptane; Alicyclic hydrocarbons such as cyclohexane; Aromatic hydrocarbons such as benzene, toluene and xylene; Or a general-purpose solvent such as chloroform, dimethylsulfoxide, dimethylacetamide, dimethylformamide, chlorobenzene, N-methyl-2-pyrrolidinone and the like. Among the above-mentioned organic solvents, chloroform and N-methyl-2-pyrrolidinone are more preferable. The above-mentioned solvent is only illustrative, and the scope of the present invention is not limited thereto. Conventional organic solvents may be used as long as they dissolve the polymer and can be evaporated under the drying condition. Specifically, the same organic solvent as that used in the preparation of the polymer may be used.

According to a specific embodiment of the present invention, poly (2,6-dimethyl-1,4-phenylene bromide), chloromethylated polyphenylsulfone or chloromethylated polysulfone as a halogenated polymer are used as crosslinking agents, Minobenzophenone dissolved in a solvent and poured into a silicone mold having a predetermined size, and dried at 60 to 100 ° C., preferably 70 to 90 ° C., for 12 to 36 hours, preferably 18 to 30 hours to obtain a film.

The third step is a step in which the residual halogen functional group of the crosslinkable polymer is substituted with an anion exchange functional group, a cation exchange functional group or an amphoteric ion exchange functional group to impart ionic conductivity.

The ion exchangeable functional group substitution can be carried out by various known substitution methods. For example, in the second step, the crosslinked polymer may be immersed in a solution in which an aqueous solution of a compound having various ion exchangeable functional groups such as trimethylamine is diluted in acetone for a predetermined time, and then immersed in distilled water for a predetermined time.

The present invention can provide a film containing the ionically conductive crosslinked polymer. The membrane may be an ion exchange membrane. Further, the film may be a water treatment film.

The anion which can be exchanged by using the ion exchange membrane comprising the ion conductive crosslinked polymer according to the present invention is an organic anion or an inorganic anion, which means an anion generated by loss of one or more hydrogen ions from an organic acid or an inorganic acid.

As inorganic anions, there may be mentioned, for example, sulfates, phosphonates, borates, cyanides, carbonates, hydrogen carbonates, thiocyanates, thiosulfates, sulfites, hydrogen sulfites, nitrates, cyanates, phosphates, (E.g. molybdate, tungstate, metavanadate, pyrovanadate, hydrogen pyrovanadate, niobate, tantalate, perrhenate, etc.), tetrafluoroaluminate, tetrafluoroborate, hexa Fluorophosphate and tetrachloroaluminate, and Al ₂ Cl ₇ ^- ions.

Organic anions include sulfonates, formates, oxalates, acetates, (meth) acrylates, trifluoroacetates, tropluoromethane sulfonates and bis (trifluoromethanesulfonate) amides, (CF ₃ SO ₂ ) ₃ Cl ^- anion, and the like.

The amine-based crosslinking agent according to the present invention can be crosslinked only without forming an ion-exchange functional group as a primary or secondary amine crosslinking agent, and can inhibit the rapid crosslinking reaction at the time of film formation by preventing electron- it has an advantage that it improves the dimensional stability and mechanical stability due to crosslinking without affecting the function of the membrane such as water uptake and conductivity and is easy to control the anion exchange function. Accordingly, it is possible to produce a polymer membrane having the same or similar ion exchange capacity (IEC) and superior dimensional stability and / or shape stability as compared with conventional ion conductive polymers by using the amine-based crosslinking agent according to the present invention have.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram illustrating a process for producing an ion exchangeable and / or ionically conductive crosslinked polymer according to an embodiment of the present invention. FIG.
2 shows a state of an ion exchange membrane formed by the method of case 4 (a) and case 5 (b) in Example 3 of the present invention.
3 shows a state of an ion exchange membrane formed by the method of case 6 to case 10 (ae) in Example 3 of the present invention.
4 shows a state of an ion exchange membrane formed by the method of case 11 to case 14 (ad) in Example 4 of the present invention.
Fig. 5 shows the state of the ion exchange membrane formed by the method of Example 5 of the present invention without the addition of the crosslinking agent and the case 15 to case 19 (af).

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.

Example  One: Cross-linking  Choice 1

To compare the crosslinking rates of aliphatic and aromatic amine compounds, eight amine compounds shown in Table 1 below were tested.

First, an amine compound was added to a solution prepared by dissolving 1 g of poly (2,6-dimethyl-1,4-phenylene oxide) 30% brominated as a halogenated polymer in 10 ml of dimethylacetamide, and the mixture was stirred at 25 ° C., The gelation time was measured. When 8 kinds of amine compounds were used, all were gelled. The respective gelation times are shown in Table 1 below.

[Table 1]

From Table 1 above, it can be seen that 4,4'-diaminobenzophenone exhibits the longest gelation time. As a result, aromatic amine compounds have slightly longer gelation times than aliphatic amine compounds, and in particular, amine compounds having C = O, which is an electron attractive group between aromatic groups such as 4,4'-diaminobenzophenon, Time. On the other hand, 2,6-diaminopyridine was not soluble in the tested dimethylacetamide solvent, and the gelation time could not be compared with other amine compounds.

Example  2: Cross-linking  Choice 2

In order to compare the crosslinking speeds of 4,4'-diaminobenzophenon and the common amine crosslinking agent showing the longest gelation time in Example 1, four commercially available amine crosslinking agents (Kukdo Chemical Co., Ltd., Korea) and 4,4 ' -diaminobenzophenone. < / RTI >

The crosslinking rate test was carried out in the same manner as in Example 1 except that 4,4'-diaminobenzophenone was added, followed by 30 minutes at 40 ° C, 30 minutes at 60 ° C The gelation time was measured at a temperature elevation maintaining 80 ° C. That is, the cross-linking test was carried out at room temperature under the same conditions as in Example 1, and the cross-linking test was conducted under the temperature increasing condition in which 4,4'-diaminobenzophenone accelerated crosslinking.

All four crosslinking agents were gelated and the respective gelation times are listed in Table 2 below.

[Table 2]

Although the aromatic amine compound has a longer gelation time than that of the aliphatic amine compound in Example 1, the time required for the aromatic amine compound to gelate in the above Table 2 is longer than that of the aromatic amine compound, In the case of 4,4'-diaminobenzophenone having a pulling group, the gelation time was remarkably long. Furthermore, 4,4'-diaminobenzophenone exhibited significantly longer gelation times than conventional amine cross-linking agents even at elevated temperatures at which the crosslinking rate was faster. As a result, 4,4'-diaminobenzophenone was selected as a crosslinking agent capable of prolonging the crosslinking reaction during the longest retention time.

Example  3: Bridged Of poly (2,6-dimethyl-1,4-phenylene oxide)  Manufacturing and Manufacturing of Ion Exchange Membranes

As a result, various bromination degrees and molecular weights were obtained as shown in Table 3 below using poly (2,6-dimethyl-1,4-phenylene oxide) (PPO) as a polymer and 4,4'-diaminobenzophenone selected in Example 2 as a cross- Crosslinking and ion exchange membranes were prepared according to the amount of crosslinking agent added.

[Table 3]

In Table 3, the mol% of the crosslinking agent is expressed on the basis of 1 g of the polymer.

Bromination of PPO is described in Reactive & Functional Polymers, 70, 2010, 944-950; Journal of Membrane Science, 190, 2001, 159-166; And Energy & Environmental Science, 5, 2012, 7888-7892. The degree of bromination desired can be controlled according to the molar ratio of NBS (N-bromosuccinimide). Specifically, the degree of bromination of 30% can be controlled as shown in Table 4, and the degree of bromination of 20% can be controlled as shown in Table 5. [Table 5] ^The degree of bromination was confirmed by ¹ H-NMR.

[Table 4]

[Table 5]

Specifically, when the degree of bromination is 50%, bromination of PPO is carried out as follows, and the degree of bromination can be controlled by controlling the number of moles of NBS (N-bromosuccinimide).

12 g of PPO was dissolved homogeneously in chlorobenzene at a concentration of 8 wt%. Then, 8.9 g of N-bromosuccinimide (NBS) and 0.5 g of 2,2'-azobis-isobutyronitrile (AIBN) were added to the PPO solution. The mixture was reacted at 140 DEG C for 3 hours using a reflux condenser. The reaction product was slowly cooled at room temperature and then precipitated in a 10-fold excess of ethanol. The polymer was filtered, washed with methanol, and the resultant was dissolved in chloroform (100 ml), precipitated in a 10-fold excess of methanol, and filtered.

The PPO bromide synthesized as described above appeared as a yellow or brown powder according to the degree of bromination and was dried in a vacuum oven overnight at 40 ° C.

Crosslinking and film formation were performed as follows.

1 g of the corresponding poly (2,6-dimethyl-1,4-phenylene oxide) bromide was dissolved in 15 ml of a mixed solvent of NMP / chloroform at 25 ° C., and the corresponding amount of 4,4'-diaminobenzophenone was added thereto. Min. Depending on the degree of bromination of the polymer, 0 to 10 ml of chloroform may be added to the solvent. The solution was filled in a 11x11 cm silicon mold and heated from 25 占 폚 to 40 占 폚 for 1 hour, maintained at 40 占 폚 for 2 hours, elevated from 40 占 폚 to 60 占 폚 for 1 hour, maintained at 60 占 폚 for 2 hours, The temperature was raised to 80 캜 for 1 hour and then kept at 80 캜 for 12 hours. Immediately after the cross-linking and film-forming, the ion exchange membrane in a dry state had a thickness of 70 to 100 탆. trimethylamine aqueous solution was diluted in acetone to a concentration of 1M. The ion exchange membrane prepared above was immersed in the solution for 24 hours, and then immersed in distilled water for 24 hours to add -N ⁺ (CH ₃ ) ₃ functional group. The ion exchange membrane can be immersed in a 0.5M NaCl solution for 24 hours to convert it to Cl ^- form.

FIG. 2 shows the state of the ion exchange membrane formed by the methods of case 4 (a) and case 5 (b).

FIG. 3 shows the state of the ion exchange membrane formed by the method of case 6 to case 10 (ae).

Experimental Example  One: Bridged Of poly (2,6-dimethyl-1,4-phenylene oxide)  Performance Analysis of Ion Exchange Membrane

The membrane resistance, ion selectivity, IEC and conductivity of the ion exchange membrane corresponding to case 6 of Example 3 were analyzed. Three samples were taken from case 6 (2.5 mol% cross-linking agent) under the same conditions, and their names were shown as case 6-1, case 6-2, case 6-3, respectively. Commercial anion exchange membrane AMX (Asahi glass Co., Japan) and AMH (Asahi glass Co., Japan) were compared under the same analytical conditions. All membrane resistances, transport number, IEC and conductivity were measured at 25 ℃ and all trimethylammonium anion exchange groups were substituted. All except IEC were measured in Cl ^- ion form. Each analysis condition was as follows.

The membrane resistance was measured by immersing the ion exchange membrane in a 0.5M NaCl aqueous solution for 24 hours at room temperature. A sample was sandwiched between Pt electrodes having a diameter of 0.5 cm, and resistance was measured with a resistance meter (Hioki 3560) under the electrolyte solution using an aqueous 0.5M NaCl solution as an electrolyte solution.

The transport number was measured by immersing the ion exchange membrane in 0.001M NaCl solution at room temperature for 24 hours. A 0.001M, 0.005M NaCl aqueous solution was placed on both sides of the sample, and the potential difference between the two solutions was measured with a resistance meter (Hioki 3560).

IEC was measured after immersing the ion exchange membrane in aqueous 1M NaOH solution at room temperature for 24 hours after changing the Cl ^- ion form to the OH ^- ion form. OH ^- ion forms were each stirred in 0.01 M aqueous HCl solution for 24 hours and acid - base titrated with 0.01 M NaOH aqueous solution.

For conductivity measurement, the ion exchange membranes were aliquoted at a sample size of 1 × 3 cm 2 and used for testing. A sample was placed on the Pt electrode cell and the impedance was measured at 25 ° C and 100% relative humidity using a 4-probe electrochemical impedance spectroscopy (Solatron 1280).

The results of the analysis are shown in Table 6 below.

[Table 6]

The three kinds of samples shown in Table 6 show similar numerical values to those of the commercialized membranes in the transport number and show better values than those of the commercialized membranes in terms of conductivity.

Experimental Example  2: Bridged Of poly (2,6-dimethyl-1,4-phenylene oxide)  Shape stability investigation

(2,6-dimethyl-1,4-phenylene oxide) cross-linked using 2.5 mol% and 5.0 mol% of a crosslinking agent (4,4'-diaminobenzophenone) -1,4-phenylene oxide) was subjected to solubility analysis using various solvents as shown in Table 7 below to investigate the morphological stability of the crosslinked polymer.

Specifically, each of the polymers was formed in the same manner as in Example 3, and was cut into a sample size of 1 x 1 cm 2 and used for the test. Solubility was analyzed by observing changes in membrane morphology after immersing in each solvent for 24 hours at room temperature.

The results are shown in Table 7 below.

[Table 7]

The results of the solubility analysis of Table 7 show that the poly (2,6-dimethyl-1,4-phenylene oxide) which is brominated before crosslinking exhibits solubility in all four solvents, but the crosslinking agent is 2.5 mol% and 5.0 mol% The crosslinked polymer did not dissolve in all four kinds of solvents. In addition, since the rate of change of the width to the weight change rate is small, it can be seen that the crosslinked polymer has shape stability.

Example  4: Bridged Of polyphenylsulfone  Manufacturing and Manufacturing of Ion Exchange Membranes

Using polyphenylsulfone as a polymer and chloromethylating the polyphenylsulfone, 4,4'-diaminobenzophenone selected in Example 2 was used as a crosslinking agent, and crosslinking and ion exchange membranes were prepared according to the amount of various crosslinking agents as shown in Table 8 below. Respectively.

[Table 8]

In Table 8, the mol% of the crosslinking agent is expressed on the basis of 1 g of the polymer.

Specifically, for the chloromethylation of polyphenylsulfone, reference is made to a method for preparing an anionic conductor-containing solution of Korean Patent No. 10-1284009. The desired degree of chloromethylation can be controlled by the molar ratio of chloromethyl methyl ether and can be analyzed by ¹ H-NMR spectroscopy. The chloromethylation degree of the polyphenylsulfone in this example was 0.982.

First, 100 g of polyphenylsulfone (Radel®, Solvay, number average molecular weight = 20,000) was dried in a 100 ° C. vacuum oven for 24 hours, and the dried polyphenylsulfone was placed in a constant temperature water bath for mechanical stirrer, gas inlet, condenser, Was placed in a 1 L four-neck round bottom flask equipped with a stirrer. Subsequently, 425.8 ml of 1,1,2,2-tetrachloroethane (TCE, 1,1,2,2-tetrachloroethane) was sufficiently dissolved so as to obtain 12.8% by weight of polyphenylsulfone to prepare a solution. After completely dissolving at room temperature, the temperature of the constant temperature water bath was set at 40 占 폚. 8.7327 g of catalyst ZnCl ₂ was added to the reactor and stirred for about 30 minutes. Then, 103.0 ml of chloromethyl methyl ether (CMME) was dropped through a dropping funnel. The amount of CMME added was 6 times (6 × (molar ratio)) times the number of moles of CMME reacted per mole of polyphenylsulfone (G / mol) × (molecular weight of chloromethyl methyl ether) (g / mol)}. The inert gas was injected through the gas inlet of the reactor, The resulting reaction product was filtered and then precipitated in an excess amount of methanol, and the precipitated chloromethylated polyphenylsulfone was pulverized by a pulverizer and washed several times with methanol and tertiary distilled water. The chloromethylated polyphenylsulfone thus obtained was dried in a drier at 80 DEG C for 12 hours and vacuum-dried at 80 DEG C for 36 hours.

The cross-linking and membrane formation were then carried out as follows.

First, 1 g of chloromethylated polyphenylsulfone was dissolved in 10 ml of DMAc at 25 ° C, 4,4'-diaminobenzophenone was added as a crosslinking agent of the corresponding amount, and the mixture was stirred for 10 minutes. The solution was filled in a 10x10 cm silicone mold and heated from 25 占 폚 to 40 占 폚 for 1 hour, maintained at 40 占 폚 for 2 hours, elevated from 40 占 폚 to 60 占 폚 for 1 hour, maintained at 60 占 폚 for 2 hours, Lt; 0 > C for 1 hour and then kept at 80 < 0 > C for 12 hours. Immediately after the crosslinking and film-forming, the ion-exchange membrane in a dried state had a thickness of 80 to 110 탆. trimethylamine aqueous solution was diluted in acetone to 1 M concentration. The ion exchange membrane was immersed in the solution for 24 hours, and then immersed in distilled water for 24 hours to add -N ⁺ (CH ₃ ) ₃ functional group. The ion exchange membrane can be immersed in a 0.5M NaCl solution for 24 hours to convert it to Cl ^- form.

FIG. 4 shows the state of the ion exchange membrane formed by the method of case 11 to case 14 (ad).

Experimental Example  3: Bridged Of polyphenylsulfone  Performance Analysis of Ion Exchange Membrane

The analytical values of the crosslinked polyphenylsulfone membrane prepared in the same manner as in Example 4 were examined according to the amount of the crosslinking agent.

For comparison, commercial anion exchange membranes AMX and AMH were compared under the same analytical conditions. All membrane resistances, transport number, IEC and conductivity were measured at 25 ℃ and all trimethylammonium anion exchange groups were substituted. All except IEC were measured in Cl ^- ion form. Each analysis was performed in the same manner as the analysis conditions in Experimental Example 1.

The results of the analysis are shown in Table 9 below.

[Table 9]

From Table 9, it can be seen that as the cross-linking agent increases, the IEC and conductivity decrease but the transport number increases. Compared with commercial membranes AMX and AMH, the polyphenylsulfone crosslinked in terms of conductivity is superior and has similar transport number values.

Experimental Example  4: Bridged Of polyphenylsulfone  Shape stability investigation

The polyphenyl sulfone crosslinked with non-crosslinked polyphenyl sulfone and various crosslinking agents (4,4'-diaminobenzophenone) as shown in Table 10 were subjected to solubility analysis using various solvents as shown in Table 10 below The morphological stability of the crosslinked polymer was investigated.

Specifically, each of the polymers was formed in the same manner as in Example 4 and was cut into a sample size of 1 x 1 cm 2 and used in the test. Solubility was analyzed by observing changes in membrane morphology after immersing in each solvent for 24 hours at room temperature.

The results are shown in Table 10 below.

[Table 10]

Table 10 shows the solubility test results of polyphenylsulfone according to the crosslinking agent content. The non - crosslinked polymer was completely dissolved in 5 kinds of solvents except toluene, but the crosslinked polymer had slight thickness and length change but did not completely dissolve in 6 kinds of solvents. As a result, it can be seen that polyphenylsulfone polymer exhibits low solubility with a shape stability to a solvent when 4,4'-diaminobenzophenone crosslinking agent is used.

Example  5: Bridged Polysulfone  Manufacturing and Manufacturing of Ion Exchange Membranes

Crosslinking and ion exchange membranes were prepared according to various amounts of crosslinking agent as shown in Table 11 using 4,4'-diaminobenzophenone selected in Example 2 as a crosslinking agent using polysulfone as a polymer and chloromethylating the polysulfone as a crosslinking agent.

[Table 11]

In Table 11, the mol% of the crosslinking agent is expressed on the basis of 1 g of the polymer.

Specifically, the chloromethylation for polysulfone was referred to the method for preparing an anionic conductor-containing solution of Korean Patent No. 10-1284009. The desired degree of chloromethylation can be controlled by the molar ratio of chloromethyl methyl ether and can be analyzed by ¹ H-NMR spectroscopy. The degree of chloromethylation of the polysulfone in this example was 1.136.

First, polysulfone ^{(UDEL ® Polysulfone, P-3500} LCD MB, Solvay Advanced Polymers) 100g was the dried in a vacuum oven at 100 ℃ for 24 hours, the dried polysulfone mechanical stirrer, a constant temperature for the gas inlet, condenser and a temperature set And placed in a 1 L four-neck round bottom flask equipped with a water bath. Subsequently, 425.8 ml of 1,1,2,2-tetrachloroethane (TCE, 1,1,2,2-tetrachloroethane) was sufficiently dissolved to make the polysulfone 12.8% by weight to prepare a solution. After completely dissolving at room temperature, the temperature of the constant temperature water bath was set at 40 占 폚. 8.7327 g of catalyst ZnCl ₂ was added to the reactor and stirred for about 30 minutes. Then, 103.0 ml of chloromethyl methyl ether (CMME) was dropped through a dropping funnel. The amount of the CMME added was 6 times (6 × (poly (G / mol) × (molecular weight of chloromethyl methyl ether) (g / mol)} was added dropwise to the reactor. The inert gas was injected through the gas inlet of the reactor and stirred vigorously The precipitated chloromethylated polysulfone was pulverized by a pulverizer and washed several times with methanol and tertiary distilled water, and the washed chloroform The methylated polysulfone was dried in a drier at 80 DEG C for 12 hours and vacuum-dried at 80 DEG C for 36 hours.

The cross-linking and membrane formation were then carried out as follows.

First, 1 g of chloromethylated polysulfone was dissolved in 10 ml of DMAc at 25 ° C, 4,4'-diaminobenzophenone was added as a crosslinking agent of the corresponding amount, and the mixture was stirred for 10 minutes. The solution was filled in a 10x10 cm silicone mold and heated from 25 占 폚 to 40 占 폚 for 1 hour, maintained at 40 占 폚 for 2 hours, elevated from 40 占 폚 to 60 占 폚 for 1 hour, maintained at 60 占 폚 for 2 hours, Lt; 0 > C for 1 hour and then kept at 80 < 0 > C for 12 hours. Immediately after the crosslinking and film-forming, the ion-exchange membrane in a dried state had a thickness of 70 to 110 탆. trimethylamine aqueous solution was diluted in acetone to 1 M concentration. The ion exchange membrane was immersed in the solution for 24 hours, and then immersed in distilled water for 24 hours to add -N ⁺ (CH ₃ ) ₃ functional group. The ion exchange membrane can be immersed in a 0.5M NaCl solution for 24 hours to convert it to Cl ^- form.

FIG. 5 shows the state of the ion exchange membrane formed by the method of the case 15 to case 19 (af) in which no crosslinking agent is added.

Experimental Example  5: Bridged Polysulfone  Performance Analysis of Ion Exchange Membrane

The analytical values of the membrane according to the crosslinking agent content of the crosslinked polysulfone prepared as in Example 5 were examined.

For comparison, commercial anion exchange membranes AMX and AMH were compared under the same analytical conditions. All membrane resistances, transport number, IEC and conductivity were measured at 25 ℃ and all trimethylammonium anion exchange groups were substituted. All except IEC were measured in Cl ^- ion form. Each analysis was performed in the same manner as the analysis conditions in Experimental Example 1.

The results of the analysis are shown in Table 12 below.

[Table 12]

From Table 12, it can be seen that as the content of crosslinking agent increases, the membrane resistance value increases, which is similar to that of commercial AMX (based on 15 mol%). conductivity was decreased as the amount of crosslinking agent increased, but it was higher than that of commercial AMX and AMH by 15 mol%, and showed excellent conductivity more than 2 times as high as 1 mol%. The transport number is similar to AMX and AMH when compared with the 15 mol% sample with the highest amount of cross-linking agent.

Experimental Example  6: Bridged Polysulfone  Shape stability investigation

Crosslinked polysulfone was crosslinked with various amounts of crosslinking agent (4,4'-diaminobenzophenone) as shown in Table 13 below, and solubility analysis was carried out using various solvents as shown in Table 13, The morphological stability of the polymer was investigated.

Specifically, each of the polymers was formed in the same manner as in Example 5 and was cut into a sample size of 1 x 1 cm 2 and used in the test. Solubility was analyzed by observing changes in membrane morphology after immersing in each solvent for 24 hours at room temperature.

The results are shown in Table 13 below.

[Table 13]

Table 13 shows the solubility test and the change in length and thickness according to the crosslinker content based on the polysulfone polymer. The non - crosslinked polysulfone polymer was dissolved in all six solvents, but the crosslinked polymer did not dissolve.

Claims (19)

1. A crosslinking agent composition for an ion-exchange crosslinked polymer comprising a compound represented by the following formula
[Chemical Formula 1]

In this formula,
A is an electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) - , or or the electron withdrawing group substituted by at least one of C ₆ aryl or C _{5 -20 -20} heteroaryl;
B ₁ and B ₂ are each independently -NH ₂ , or -NHR;
R is hydrogen, - (CH ₂ ) _z CH ₃ (z is 0 or an integer in the range 1≤z≤100), - (CX ₂ ) _z CX ₃ - (z is 0 or an integer in the range 1≤z≤100, X is a halogen atom), -NH ₂ , -NH (CH ₃ ), -NH- (CH ₂ ) _y -NH ₂ (1 ≦ y ≦ 100, y is an integer), - (C═O) _{(CH 3) 2 H, -CH} 2 (OH), -O-CH 2 -C (CH 3) 2 -CH 2 -OH, - (O-CH 2 -CH 2) p -O-CH 2 -CH ₃ (1? P? 100, p is an integer), -O- (CH ₂ ) ₂ - (O-CH ₂ -CH ₂ ) _x -OH, -OH, -SO ₂ H, , C _{1 -6} alkyl or C _{6 -10} aryl group optionally substituted with a blood rolgi, unsubstituted or halogen, C _{1 -6} alkyl or C _{6 -10} a pyridine group substituted with aryl group, a phenol group or a phenyl group;
m and n are each independently an integer of 1 to 100;
The crosslinking agent composition according to claim 1, wherein the ion exchangeable crosslinked polymer is for preparing an ion exchange membrane.
The method according to claim 1, further comprising the step of applying a coating composition comprising a polyolefin selected from the group consisting of polypropylene, polyethylene, polyethylene terephthalate, polyethylene naphthalate, polystyrene, polycarbonate, polymethyl methacrylate, polyethersulfone, polyvinylidene fluoride, polyether ketone, A polymer selected from the group consisting of an ester, polyacrylonitrile, polyacrylic acid, polyacrylate, polymethyl methacrylate, polyethyleneimide, cellulose acetate, cellulose triacetate, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, Wherein the cross-linking agent is used for crosslinking a polymer selected from the group consisting of polyethylene oxide, polyvinyl acetate, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate and polyethylene naphthalate.
Wherein the ionically conductive polymer is crosslinked through a crosslinking unit represented by the following formula (2): < EMI ID =
(2)

In this formula,
A is an electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) - , or or the electron withdrawing group substituted by at least one of C ₆ aryl or C _{5 -20 -20} heteroaryl;
B ₁ 'and B ₂ ' are each independently -NH-, or -NR-;
R is hydrogen, - (CH ₂ ) _z CH ₃ (z is 0 or an integer in the range 1≤z≤100), - (CX ₂ ) _z CX ₃ - (z is 0 or an integer in the range 1≤z≤100, X is a halogen atom), -NH ₂ , -NH (CH ₃ ), -NH- (CH ₂ ) _y -NH ₂ (1 ≦ y ≦ 100, y is an integer), - (C═O) _{(CH 3) 2 H, -CH} 2 (OH), -O-CH 2 -C (CH 3) 2 -CH 2 -OH, - (O-CH 2 -CH 2) p -O-CH 2 -CH ₃ (1? P? 100, p is an integer), -O- (CH ₂ ) ₂ - (O-CH ₂ -CH ₂ ) _x -OH, -OH, -SO ₂ H, , C _{1 -6} alkyl or C _{6 -10} aryl group optionally substituted with a blood rolgi, unsubstituted or halogen, C _{1 -6} alkyl or C _{6 -10} a pyridine group substituted with aryl group, a phenol group or a phenyl group;
m and n are each independently an integer of 1 to 100;
5. The ionically conductive crosslinked polymer according to claim 4, wherein the halogenated polymer is bridged at the halogen functional site among the halogenated polymers.
The ion conductive polymer according to claim 4, wherein the ion conductive polymer is selected from the group consisting of polypropylene, polyethylene, polyethylene terephthalate, polyethylene naphthalate, polystyrene, polycarbonate, polymethyl methacrylate, polyethersulfone, polyvinylidene fluoride, polyether ketone, But are not limited to, sulfides, aromatic polyesters, polyacrylonitrile, polyacrylic acid, polyacrylates, polymethylmethacrylate, polyethyleneimide, cellulose acetate, cellulose triacetate, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, Wherein the polysiloxane is selected from the group consisting of polysulfone, polyethylene oxide, polyvinyl acetate, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate and polyethylene naphthalate.
The ionically conductive crosslinked polymer according to claim 4, wherein the ion conductive polymer has an anion-exchangeable functional group, a cation-exchangeable functional group or an amphoteric ion-exchange functional group.
The method of claim 7, wherein the anion-exchange functional group is _{-NH 3 E, -NR'H 2 E,} -NR '2 HE, -NR' 3 E, -PR '3 E , or -SR' or E ₂ -C ₅ NHE H ₅ and (R 'is C _{1 -4} alkyl or C _{6 -12} aryl, E is a hydroxide anion, bicarbonate anion, a chloride anion or a sulfate anion Im), a cation-exchange functional groups are -SO ₃ ^{-, _{-COO -, -PO 3 2 -,}} -PO 3 H - , or -C ₆ H ₄ 0 ^-, and the amphoteric ion-exchange functional groups are betaine or alcohol Phoebe characterized in the ion-conducting crosslinked polymer others.
5. The ionically conductive crosslinked polymer according to claim 4, which has a skeleton containing a repeating unit represented by the following formula (3):
(3)

In Formula 3,
A is an electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) - , or or the electron withdrawing group substituted by at least one of C ₆ aryl or C _{5 -20 -20} heteroaryl;
B ₁ 'and B ₂ ' are each independently -NH-, or -NR-;
_{R, R 1 ", R 2} ", D and D 'are each independently _{hydrogen, - (CH 2) z CH} 3 (z is zero or an integer in the range _{1≤z≤100), - (CX 2) z} CX ₃ - (z is 0 or an integer in the range of ₁ ? Z? 100, X is a halogen atom), -NH ₂ , -NH (CH ₃ ), -NH- (CH ₂ ) _y -NH ₂ , y is an integer), - (C = O) H, -C (CH 3) 2 H, -CH 2 (OH), -O-CH 2 -C (CH 3) 2 -CH 2 -OH, - ( _{O-CH 2 -CH 2) p} -O-CH 2 -CH 3 (1≤p≤100, p is an _{integer), -O- (CH 2) 2} - (O-CH 2 -CH 2) x -OH , -OH, -SO ₂ H, -SH, unsubstituted or halogen, C _{1 -6} alkyl substituted with a blood or C _6-10 aryl rolgi, unsubstituted or halogen, C _{1 -6} alkyl or C _{6 -10} aryl A phenoxy group or a phenyl group;
f is an anion exchange functional group, a cation exchange functional group or an amphoteric ion exchange functional group;
m, n, q, r and p are each independently an integer of 1 to 100;
0.001? Q / (q + r)? 0.50.
The ionically conductive crosslinked polymer according to claim 4, which has a skeleton containing a repeating unit represented by the following formula (4):
[Chemical Formula 4]

In this formula,
A is an electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) - , or or the electron withdrawing group substituted by at least one of C ₆ aryl or C _{5 -20 -20} heteroaryl;
B ₁ 'and B ₂ ' are each independently -NH-, or -NR-;
_{R, R 3 ", R 4} ", R 5 ", R 6", R 7 ", R 8", R 9 ", R 10", D and D 'are independently hydrogen, respectively - _z (CH ₂₎ CH ₃ (z is zero or an integer in the range _{1≤z≤100), - (CX 2) z} CX 3 - (z is zero or an integer from 1≤z≤100 range, X is a halogen atom), -NH _{2, -NH (CH 3), -NH- (} CH 2) y -NH 2 (1≤y≤100, y is an integer), - (C = O) H, -C (CH 3) 2 H, -CH 2 (OH), -O-CH ₂ -C (CH ₃ ) ₂ -CH ₂ -OH, - (O-CH ₂ -CH ₂ ) _p -O-CH ₂ -CH _{3 integer), -O- (CH 2) 2} - (O-CH 2 -CH 2) x -OH, -OH, -SO 2 H, -SH, unsubstituted or halogen, C _{1 -6} alkyl, or C _{6 -} substituted with aryl blood rolgi _10, unsubstituted or halogen, C _{1 -6} alkyl or C _{6 -10} a pyridine group substituted with aryl group, a phenol group or a phenyl group;
f is an anion exchange functional group, a cation exchange functional group or an amphoteric ion exchange functional group;
m, n, q, r and p are each independently an integer of 1 to 100;
0.001? Q / (q + r)? 0.50.
5. The ionically conductive crosslinked polymer according to claim 4, which has a skeleton containing a repeating unit represented by the following formula (5):
[Chemical Formula 5]

In Formula 5,
A is an electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) - , or or the electron withdrawing group substituted by at least one of C ₆ aryl or C _{5 -20 -20} heteroaryl;
B ₁ 'and B ₂ ' are each independently -NH-, or -NR-;
_{R, R 11 ", R 12} ", R 13 ", R 14", R 15 ", R 16", R 17 ", R 18", D and D 'are independently hydrogen, and each - (CH _{2) z} CH ₃ (z is zero or an integer in the range _{1≤z≤100), - (CX 2) z} CX 3 - (z is zero or an integer from 1≤z≤100 range, X is a halogen atom), -NH _{2, -NH (CH 3), -NH- (} CH 2) y -NH 2 (1≤y≤100, y is an integer), - (C = O) H, -C (CH 3) 2 H, -CH 2 (OH), -O-CH ₂ -C (CH ₃ ) ₂ -CH ₂ -OH, - (O-CH ₂ -CH ₂ ) _p -O-CH ₂ -CH _{3 integer), -O- (CH 2) 2} - (O-CH 2 -CH 2) x -OH, -OH, -SO 2 H, -SH, unsubstituted or halogen, C _{1 -6} alkyl, or C _{6 -} substituted with aryl blood rolgi _10, unsubstituted or halogen, C _{1 -6} alkyl or C _{6 -10} a pyridine group substituted with aryl group, a phenol group or a phenyl group;
f is an anion exchange functional group, a cation exchange functional group or an amphoteric ion exchange functional group;
m, n, q, r and p are each independently an integer of 1 to 100;
0.001? Q / (q + r)? 0.50.
Of claim 9 to claim 11 according to any one of claims, wherein the anion-exchange functional group is _{-NH 3 E, -NR'H 2 E,} -NR '2 HE, -NR' 3 E, -PR '3 E or - SR 'E ₂ or -C ₅ H ₅ NHE and (R' is C _{1 -4} alkyl or C _{6 -12} aryl, E is a hydroxide anion, bicarbonate anion, a chloride anion or a sulfate anion Im), cation-exchange functional group is ^{_{-SO 3 -, -COO -, -PO}} 3 2 -, -PO 3 H - , or -C ₆ H ₄ 0 ^-, and the amphoteric ion-exchange functional groups are betaine or alcohol Phoebe ions characterized others Conducting crosslinked polymer.
5. The ionically conductive crosslinked polymer of claim 4, having a molecular weight of Mn (number-average molecular weight) of 10,000 to 1,000,000 or Mw (weight-average molecular weight) of 10,000 to 10,000,000.
The ionically conductive crosslinked polymer according to claim 4, wherein the ion conductive polymer is a random copolymer, a cross-copolymer or a block copolymer.
A compound comprising a repeating unit represented by the following formula (3-1), (4-1) or (5-1)
[Formula 3-1]

[Formula 4-1]

[Formula 5-1]

In this formula,
A is an electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) - , or or the electron withdrawing group substituted by at least one of C ₆ aryl or C _{5 -20 -20} heteroaryl;
B ₁ 'and B ₂ ' are each independently -NH-, or -NR-;
_{R, R 1 ", R 2} ", R 3 ", R 4", R 5 ", R 6", R 7 ", R 8", R 9 ", R 10", R 11 ", R 12", R ₁₃ ", R ₁₄ ", R ₁₅ ", R ₁₆ ", R ₁₇ ", R ₁₈ ", D and D 'are each independently hydrogen, - (CH ₂ ) _z CH ₃ - (CX ₂ ) _z CX ₃ - (z is an integer in the range of 0 or 1? Z? 100, X is a halogen atom), -NH ₂ , -NH (CH ₃ ) _{(CH 2) y -NH 2 (} 1≤y≤100, y is an integer), - (C = O) H, -C (CH 3) 2 H, -CH 2 (OH), -O-CH 2 - _{C (CH 3) 2 -CH 2} -OH, - (O-CH 2 -CH 2) p -O-CH 2 -CH 3 (1≤p≤100, p is an integer), -O- (CH _{2) 2 - (O-CH 2 -CH} 2) x -OH, -OH, -SO 2 H, -SH, unsubstituted or halogen, C _{1 -6} the blood rolgi, unsubstituted or substituted by alkyl, C _{6 -10} aryl or a halogen, C _{1 -6} alkyl or C _{6 -10} a pyridine group substituted with aryl group, a phenol group or a phenyl group;
X is a halogen atom;
m, n, q, r and p are each independently an integer of 1 to 100;
0.001? Q / (q + r)? 0.50.
12. A method for producing an ionically conductive crosslinked polymer according to any one of claims 4 to 11,
A first step of preparing a halogenated polymer;
A second step of adding a crosslinking agent represented by the following formula (1) to the halogenated polymer to form a crosslinked polymer by a cross-linking reaction between halogenated polymers at some halogen functional sites of the halogenated polymer; And
And a third step of replacing the residual halogen functionality of the crosslinking polymer with an anion exchange functional group, a cation exchange functional group or an amphoteric ion exchange functional group.
[Chemical Formula 1]

In this formula,
A is an electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) - , or or the electron withdrawing group substituted by at least one of C ₆ aryl or C _{5 -20 -20} heteroaryl;
B ₁ and B ₂ are each independently -NH ₂ , or -NHR;
R is hydrogen, - (CH ₂ ) _z CH ₃ (z is 0 or an integer in the range 1≤z≤100), - (CX ₂ ) _z CX ₃ - (z is 0 or an integer in the range 1≤z≤100, X is a halogen atom), -NH ₂ , -NH (CH ₃ ), -NH- (CH ₂ ) _y -NH ₂ (1 ≦ y ≦ 100, y is an integer), - (C═O) _{(CH 3) 2 H, -CH} 2 (OH), -O-CH 2 -C (CH 3) 2 -CH 2 -OH, - (O-CH 2 -CH 2) p -O-CH 2 -CH ₃ (1? P? 100, p is an integer), -O- (CH ₂ ) ₂ - (O-CH ₂ -CH ₂ ) _x -OH, -OH, -SO ₂ H, , C _{1 -6} alkyl or C _{6 -10} aryl group optionally substituted with a blood rolgi, unsubstituted or halogen, C _{1 -6} alkyl or C _{6 -10} a pyridine group substituted with aryl group, a phenol group or a phenyl group;
m and n are each independently an integer of 1 to 100;
12. A membrane comprising the ionically conductive crosslinked polymer according to any one of claims 4 to 11.
18. The membrane of claim 17, wherein the membrane is an ion exchange membrane.
18. The membrane of claim 17, wherein the membrane is a water treatment membrane.

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