KR101442530B1 - Method for manufacturing organic-inorganic hybrid ion exchange resin and method for manufacturing ion exchange membrane using the same - Google Patents

Abstract

The present invention relates to a process for producing an organic-inorganic hybrid ion-exchange resin and a process for producing a organic-inorganic hybrid ion-exchange membrane using the same, and more particularly, to a process for producing an organic-inorganic hybrid ion- And a method for producing a hybrid organic-inorganic hybrid ion-exchange membrane using the same.
Since the ion exchange resin according to the present invention is composed of oligomers having various molecular weight distributions with a molecular weight of 5,000 or less, it is possible to reduce the problem that shrinkage may occur because there is little reduction in the free volume that can occur during the preparation of the ion exchange membrane. Also, the ion exchange membrane according to the present invention has a small thermal expansion coefficient difference before and after the glass transition temperature, and is superior in thermal mechanical properties to the conventional ion exchange membrane. In addition, according to the present invention, the flexibility of the ion exchange membrane can be controlled by selectively using an organosilane having two or three Si-O-Si bonds.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for producing an organic-inorganic hybrid ion-exchange resin, and a method for manufacturing an ion-exchange membrane using the same. BACKGROUND ART [0002]

The present invention relates to a process for producing an organic-inorganic hybrid ion-exchange resin and a process for producing a organic-inorganic hybrid ion-exchange membrane using the same, and more particularly, to a process for producing an organic-inorganic hybrid ion- And a method for producing a hybrid organic-inorganic hybrid ion-exchange membrane using the same.

The ion exchange resin is a synthetic resin having ion exchange ability. In 1935, BA Adams and FL Homes in the UK found that a resin that condensed polyvalent phenol and formaldehyde and a resin that condensed m-phenylenediamine and formaldehyde exchanged ions. It was found that this resin can remove various ions in the water, and then it started to be systematically studied and industrialized in Germany and the United States. During World War II, it was used in water purification, copper and ammonia recovery in artificial dog factory, and in the United States, it was used to classify fission product, uranium element, and trace element. In addition, purification of various materials (amino acids, antibiotics, etc.) was facilitated by the ion exchange resin, and the ion exchange membrane was developed and became more important in terms of electrochemistry. Currently, ion exchange membranes are widely used in fields such as fuel cells, redox flow cells, electrodialysis, desalination, ultrapure water and wastewater treatment. However, ion exchange membranes can be used in various temperature ranges (from room temperature to 200 ° C) depending on their applications, but researches on ion exchange membranes that can be used stably in various temperature ranges are lacking. Therefore, it is necessary to study general purpose ion exchange membranes with excellent mechanical strength and durability with little change in mechanical properties at various temperature ranges.

Korean Patent Publication No. 10-2012-0074365

The present invention provides an oil-inorganic hybrid ion exchange resin capable of improving thermomechanical characteristics and a oil-inorganic hybrid ion exchange membrane using the same, and a method for manufacturing the same.

According to an embodiment of the present invention, there is provided a process for producing a silane coupling agent, comprising: mixing an organosilane represented by the following formula (1) and an organosilane represented by the following formula (2); And performing a sol-gel process on the mixture. The present invention also provides a method for producing an organic-inorganic hybrid ion-exchange resin.

Wherein R ¹ is a thermally polymerizable and photopolymerizable organic functional group, R ² and R ³ are straight or branched (C 1 -C 7) alkyl, and n is an integer of 0 to 1.

(In the general formula 2 R ⁴ is -SO ₃ having ion exchange properties _{^{-, -COO -, -PO 3 2-}} , -PO 3 H -, -C 6 H 4 O -, -NH 3 +, -NRH 2 ⁺ , -NR ₂ H ⁺ , -NR ₃ ⁺ , -PR ₃ ⁺ and -SR ₂ ⁺ , and R ⁵ and R ⁶ are linear or branched (C1 To C7) alkyl; and n is an integer of 0 to 1.)

According to one embodiment of the present invention, there is provided a method for producing an ion exchange resin, comprising the steps of: And a step of thermally polymerizing or photopolymerizing the ion-exchange resin.

According to one embodiment of the present invention, there is provided a process for producing an organic-inorganic hybrid ion-exchange resin comprising organosilane containing a polymerizable organic functional group and organosilane containing an ion-exchangeable organic functional group and comprising oligomers having a molecular weight of 5,000 or less .

According to one embodiment of the present invention, there is provided a process for producing an ion-exchange resin, which comprises thermally polymerizing or photopolymerizing an ion-exchange resin composed of an organosilane containing a polymerizable organic functional group and an organosilane containing an organic functional group having ion- It is possible to provide the produced oil-inorganic hybrid ion exchange membrane.

Since the ion exchange resin according to the present invention is composed of oligomers having various molecular weight distributions with a molecular weight of less than 5,000, there is little decrease in the free volume that can occur during the preparation of the ion exchange membrane, . Also, the ion exchange membrane according to the present invention has a small thermal expansion coefficient difference before and after the glass transition temperature, and is superior in thermal mechanical properties to the conventional ion exchange membrane.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. The objects, features and advantages of the present invention will be easily understood by the following examples and experimental examples. The present invention is not limited to the embodiments and experimental examples described here, but may be embodied in other forms. The embodiments and examples disclosed herein are provided to enable those skilled in the art to fully understand the spirit of the present invention. Therefore, the present invention should not be limited by the following examples and experimental examples.

According to an embodiment of the present invention, there is provided a method for manufacturing a U-inorganic hybrid ion exchange resin comprising the steps of: (S1) mixing an organosilane represented by the following formula (1) and an organosilane represented by the following formula (2); And (S2) subjecting the mixture to a sol-gel process.

 [Chemical Formula 1]

Wherein R ¹ is a thermally polymerizable and photopolymerizable organic functional group, R ² and R ³ are straight or branched (C 1 -C 7) alkyl, and n is an integer of 0 to 1.

(2)

(In the general formula 2 R ⁴ is -SO ₃ having ion exchange properties _{^{-, -COO -, -PO 3 2-}} , -PO 3 H -, -C 6 H 4 O -, -NH 3 +, -NRH 2 ⁺ , -NR ₂ H ⁺ , -NR ₃ ⁺ , -PR ₃ ⁺ and -SR ₂ ⁺ , and R ⁵ and R ⁶ are linear or branched (C1 To C7) alkyl; and n is an integer of 0 to 1.)

The mixture according to the step (S1) may contain 50 mol% (based on 100 mol% as a whole) of the organosilane having n = 1 in the chemical formula 1 and the chemical formula 2.

When the amount of the organosilane having n = 0 in the formula (1) and the formula (2) is more than 50 mol% (based on 100mol% of the total), the flexibility of the finally prepared organic-inorganic hybrid ion exchange membrane Cracks may occur when using the prepared ion exchange membranes.

The organosilane represented by the formula (1) is preferably selected from the group consisting of diethoxy (3-glycidyloxypropyl) methylsilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, dimethoxymethylvinylsilane, diethoxymethyl Vinylsilane, 3-mercaptopropyl (dimethoxy) methylsilane, 3- (2-aminoethylamino) propyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, Methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, Glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, aryltrimethoxysilane, aryl Vinyltripropoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltrimethoxysilane, N- (3-acryloxy-2- hydroxypropyl) -3-aminopropyltripropoxysilane, 3- Acryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, , 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, N- (aminoethyl-3-aminopropyl) trimethoxysilane, N- Propyl) triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (3-mercaptopropyl) At least one member selected from the group consisting of trimethoxysilane, trimethoxysilane, trimethoxysilane, trimethoxysilane, (3-mercaptopropyl) triethoxysilane, (acryloxymethyl) phenethyltrimethoxysilane and allyloxydecyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane or 3-glycidyloxypropyl (dimethoxy) methylsilane.

The organosilane represented by the general formula (2) is preferably selected from the group consisting of sodium 4- (2- (3- (dimethoxy (methyl) silyl) propylthio) ethylbenzenesulfonate, sodium 3- (trimethoxysilyl) propane- (Trimethoxysilyl) propyl] ammonium chloride, trimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, trimethyl [3- (Methoxyethyl) -3-trimethoxysilylpropylammonium chloride, N, N-predecyl-N-methyl-N- (3-trimethoxysilylpropyl) ammonium chloride, octadecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride, tetradecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride, 3- Silyl) propyl chloroformate, N-trimethoxysilylpropyl- N, N, N-tri-n-butylammonium chloride, Silyl-2-propynyl) triphenylphosphonium chloride and 3-trihydroxysilylpropylmethylphosphonate sodium salt, and preferably at least one selected from the group consisting of sodium 4- (2- (3 - (dimethoxy (methyl) silyl) propylthio) ethyl) benzenesulfonate or trimethyl [3- (trimethoxysilyl) propyl] ammonium chloride.

In general, the sol-gel process is performed as shown below. When water is added to the silane having an alkoxy (-OR) group and subjected to a hydrolysis-condensation reaction, a Si-O-Si bond is formed. (R is a straight or branched chain alkyl)

[Reaction Scheme 1]

According to one embodiment of the present invention, water is added to the organosilane to proceed the hydrolysis-condensation reaction in order to prepare the oil-inorganic hybrid ion exchange resin using the sol-gel process. Since Si-O-Si bonds are formed by this reaction, an acid or base catalyst may be preferably added to promote the reaction. Usable catalysts include acidic catalysts such as acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, chlorosulfonic acid, para-toluic acid, trichloroacetic acid, polyphosphoric acid, pyrophosphoric acid, iodic acid, tartaric acid, perchloric acid, Base catalysts such as butylamine, di-n-butylamine, tri-n-butylamine, imidazole, ammonium perchlorate, potassium hydroxide, barium hydroxide, strontium hydroxide and the like, Amberlite® IRC76 hydrogen form, Amberlite® An ion exchange resin such as IRA-400 chloride form may be used. Preferably, sodium hydroxide or hydrochloric acid may be used, but the present invention is not limited thereto. The addition amount of the catalyst is not particularly limited, and it is sufficient to add 0.0001 to 10 parts by weight based on 100 parts by weight of the organosilane.

The sol-gel process is sufficient for stirring for about 6 to 72 hours at room temperature. The sol-gel process is carried out at a temperature of 0 to 100 ^° C, preferably 80 ^° C for 24 hours to accelerate the reaction rate and proceed the complete hydrolysis- Decomposition-condensation reaction can be induced to form an organic-inorganic hybrid ion-exchange resin. If the reaction time of the sol-gel process is less than 6 hours, the hydrolysis-condensation reaction does not proceed and the Si-O-Si bond is not formed. When the reaction time exceeds 72 hours, the hydrolysis-condensation reaction proceeds excessively, An inorganic hybrid ion exchange resin can not be obtained.

Also, in the organic-inorganic hybrid ion exchange resin prepared through the sol-gel process, the alcohol as a by-product and the water remaining after the reaction are present, which is decomposed under N ₂ purging at 0 ^° C to 100 ^° C , Preferably at 80 ^° C for 1 hour under reduced pressure of -0.1 MPa or for 12 hours under N ₂ purging and stirring at 80 ^° C.

The organic-inorganic hybrid ion exchange resin is preferably composed of oligomers having a molecular weight of 5,000 or less. According to one embodiment of the present invention, since oligomers having various molecular weight distributions of 5,000 or less are gathered to form an ion exchange resin, the degree of decrease in the free volume that can be generated in the process of preparing an ion exchange membrane is much smaller than that of a monomer-based material. Therefore, it has an advantage that shrinkage does not occur well. Since the inorganic part (Si-O-Si bond) of the oligomers in the organic-inorganic hybrid ion exchange membrane serves as a crosslinking point for restricting the movement of the organic part according to the temperature rise, the organic-inorganic hybrid ion exchange resin Inorganic hybrid ion exchange membranes made of oligomers constituting the polymer electrolyte membrane have a high crosslinking density and a small difference in the thermal expansion coefficient before and after the glass transition temperature and thus are superior in thermal mechanical properties to those of conventional ion exchange membranes.

According to another aspect of the present invention, there is provided a method of manufacturing an organic-inorganic hybrid ion exchange membrane, comprising: preparing an ion exchange resin by the above-described method; And thermally or photopolymerizing the ion exchange resin.

Wherein the thermal polymerization or the photopolymerization step comprises the steps of: adding and stirring a thermal or photopolymerization catalyst to the ion exchange resin; And coating the stirred ion-exchange resin on a film, followed by thermal polymerization or photopolymerization.

The thermal polymerization catalyst may be selected from the group consisting of amine series such as benzyldimethylamine, imidazole series such as 1-methylimidazole and 2-phenylimidazole, triphenylphosphine, triphenylphosphate, trioctylphosphine, (Alacac), a platinum-cyclocylvinylmethylsiloxane complex, tris (dibutylsulfide) rhodium trichloride, 3-methyl-cyclopentylmethylsiloxane complexes such as tert-butylphosphonium methosulphonate, 2-butenyltetramethylenesulfonium hexafluoroantimonate, and 2-butenyltetramethylenesulfonium hexafluoroantimonate salts. Of these, 3-methyl-2-butenyltetramethylsulfonium hexafluoroantimonate salts can be used. It is not.

Wherein the photopolymerization catalyst is selected from the group consisting of triarylsulfonium hexafluoroantimonate salts, 2,2-dimethoxy-2-phenylacetophenone, benzophenone, 2-hydroxy- Diethylthioxanthene-9-one, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, and the like, and preferably triarylsulfonium hexafluoroantimonate salts can be used, But is not limited to.

The thermal polymerization or photopolymerization catalyst may be added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the ion exchange resin. When the amount is less than 0.1 part by weight, the polymerization reaction does not occur efficiently and the crosslinking density is low. When the amount is more than 10 parts by weight, the specific gravity of the catalyst is large, so that the characteristics of the oil-

The coating may be performed by a method selected from the group consisting of bar coating, slit die coating, spray coating and spin coating.

The thermal polymerization step may be carried out at a temperature of 50 to 250 DEG C for 1 to 24 hours. When the heat polymerization temperature is higher than 250 ° C, the bonding chain of the organic part of the organic-inorganic hybrid ion exchange membrane may be destroyed. If the temperature is lower than 50 ° C, thermal polymerization may not occur.

The photopolymerization step may be performed for 1 minute to 30 minutes using a light source with a wavelength of 248 to 365 nm, and further heat treatment may be performed for 1 to 6 hours at a temperature of 50 to 250 DEG C after the photopolymerization step. If the photopolymerization time is more than 30 minutes, oxidation of the organic part of the organic-inorganic hybrid ion exchange membrane may occur and the performance of the ion exchange membrane may be deteriorated. If the polymerization time is less than 1 minute, the photopolymerization may not occur.

According to one embodiment of the present invention, there is provided a U-inorganic hybrid ion exchange resin comprising an organosilane containing a polymerizable organic functional group and an organosilane containing an ion-exchangeable organic functional group and oligomers having a molecular weight of 5,000 or less .

The organosilane containing the polymerizable organic functional group is preferably selected from the group consisting of diethoxy (3-glycidyloxypropyl) methylsilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, dimethoxymethylvinylsilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldimethoxymethylsilane, 3-mercaptopropyl (dimethoxy) methylsilane, 3- ) Methyldimethoxysilane, allyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl ) Ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, aryltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, vinyltriethoxysilane, N- Hydroxypropyl) -3-aminopropyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) , 3-acryloxypropylmethylbis (trimethoxy) silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, 3-methacryloxy Methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, N- (aminoethyl-3-aminopropyl) trimethoxysilane, N- (2-amino Ethyl-3-aminopropyl) triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (3- (Acryloxymethyl) phenethyltrimethoxysilane, and allyloxydecyltrimethoxysilane may be selected from the group consisting of (methacryloxypropyl) trimethoxysilane, (3-mercaptopropyl) triethoxysilane, And preferably 3-glycidoxypropyltrimethoxysilane or 3-glycidyloxypropyl (dimethoxy) methylsilane.

The organosilane containing the organic functional group of the ion exchange property is preferably selected from the group consisting of sodium 4- (2- (3- (dimethoxy (methyl) silyl) propylthio) ethylbenzenesulfonate, sodium 3- (trimethoxysilyl) (Trimethoxy silyl) propane-1-sulfonate, trimethyl [3- (triethoxysilyl) propyl] ammonium chloride, trimethyl [3- (trimethoxysilyl) Propyl] ammonium chloride, (2-N-benzylaminoethyl) -3-aminopropyltrimethoxysilane, bis (methoxyethyl) -3- trimethoxysilylpropylammonium chloride, (3-trimethoxysilylpropyl) ammonium chloride, octadecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride, tetradecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride, 3- (Trimethoxysilyl) propyl chloroformate, N-trimethoxysilylpropyl-N, N, N-tri-n- Triphenylphosphonium chloride and 3-trihydroxysilylpropylmethylphosphonate sodium salt, and preferably at least one member selected from the group consisting of sodium (3-trimethoxysilyl-2-propynyl) Propylthio) ethyl) benzenesulfonate or trimethyl [3- (trimethoxysilyl) propyl] ammonium chloride.

According to one embodiment of the present invention, there is provided a process for producing an organic-inorganic hybrid ion exchange resin composed of oligomers having a molecular weight of 5,000 or less and containing an organosilane containing an organosilane containing a polymerizable organic functional group and an organosilane containing an ion- Inorganic hybrid ion exchange membranes prepared by polymerization or photopolymerization can be provided.

The organosilane containing the polymerizable organic functional group is preferably selected from the group consisting of diethoxy (3-glycidyloxypropyl) methylsilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, dimethoxymethylvinylsilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldimethoxymethylsilane, 3-mercaptopropyl (dimethoxy) methylsilane, 3- ) Methyldimethoxysilane, allyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl ) Ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, aryltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, vinyltriethoxysilane, N- Hydroxypropyl) -3-aminopropyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) , 3-acryloxypropylmethylbis (trimethoxy) silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, 3-methacryloxy Methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, N- (aminoethyl-3-aminopropyl) trimethoxysilane, N- (2-amino Ethyl-3-aminopropyl) triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (3- (Acryloxymethyl) phenethyltrimethoxysilane, and allyloxydecyltrimethoxysilane may be selected from the group consisting of (methacryloxypropyl) trimethoxysilane, (3-mercaptopropyl) triethoxysilane, And preferably 3-glycidoxypropyltrimethoxysilane or 3-glycidyloxypropyl (dimethoxy) methylsilane.

The organosilane containing the organic functional group of the ion exchange property is preferably selected from the group consisting of sodium 4- (2- (3- (dimethoxy (methyl) silyl) propylthio) ethylbenzenesulfonate, sodium 3- (trimethoxysilyl) (Trimethoxy silyl) propane-1-sulfonate, trimethyl [3- (triethoxysilyl) propyl] ammonium chloride, trimethyl [3- (trimethoxysilyl) Propyl] ammonium chloride, (2-N-benzylaminoethyl) -3-aminopropyltrimethoxysilane, bis (methoxyethyl) -3- trimethoxysilylpropylammonium chloride, (3-trimethoxysilylpropyl) ammonium chloride, octadecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride, tetradecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride, 3- (Trimethoxysilyl) propyl chloroformate, N-trimethoxysilylpropyl-N, N, N-tri-n-butylammonium At least one member selected from the group consisting of chloride, (3-trimethoxysilyl-2-propynyl) triphenylphosphonium chloride and 3-trihydroxysilylpropylmethylphosphonate sodium salt may be selected and preferably sodium Propylthio) ethyl) benzenesulfonate or trimethyl [3- (trimethoxysilyl) propyl] ammonium chloride.

Hereinafter, the present invention will be described in more detail by way of Examples and Experimental Examples, but the present invention is not limited to these Examples.

Example  One

(Methyl) silyl) propylthio) ethyl) benzenesulfonate): A solution of sodium 4- (2- (3- (dimethoxy 3-Glycidyloxypropyltrimethoxysilane (Aldrich) was mixed at a ratio of 23.2 g: 9.4 g (0.06 mol: 0.04 mol), and the mixture was placed in a 100 ml 1-necked flask. Then, 2.7 g of water having a concentration of 0.1 N of NaOH was added to the mixture, prehydrolysis was performed at room temperature for 6 hours, and then the mixture was stirred at 80 캜 for 24 hours under reflux. The resin obtained after 24 hours of sol-gel reaction was placed in a 100 ml 2-necked flask and reacted at 80 ° C for 12 hours under N ₂ purging and stirring to remove water and methanol as byproducts. The obtained resin was filtered using a glassy filter, and finally a sulfonate-epoxy oligomer resin was obtained. Next, 4 parts by weight of 3-methyl-2-butenyltetramethylenesulfonium hexafluoroantimonate salt (3-methyl-2-butenyltetramethylenesulfonium hexafluoroantimonate salt, CP77, ADEKA) as a thermal polymerization catalyst was added to the resin And stirred for 3 hours. The stirred resin was bar coated on a Kepton film, heat-cured at 120 ° C for 2 hours, and then the Kepton film was removed to obtain a polymerized sulfonate-epoxy hybrid ion exchange membrane.

Example  2

Trimethyl [3- (trimethoxysilyl) propyl] ammonium Chloride, TCI): 3-glycidyloxypropyl (dimethoxy) methylsilane (3-glycidyloxypropyl dimethoxy) methylsilane, Aldrich) were mixed at a ratio of 10.31 g: 13.22 g (0.04 mol: 0.06 mol) and placed in a 100 ml 1-neck flask. Thereafter, 2.7 g of water having a HCl 0.1N concentration was added to the mixture, prehydrolysis was carried out at room temperature for 6 hours, and then the mixture was refluxed at 80 DEG C for 24 hours. The resin obtained after 24 hours of sol-gel reaction was placed in a 100 ml 2-neck flask and reacted by addition of N ₂ purging and stirring at 80 ° C for 12 hours while removing by-products water and methanol. The obtained resin was filtered using a glassy filter, and finally an ammonium-epoxy oligomer resin was obtained. Then, 4 parts by weight of triarylsulfonium hexafluoroantimonate salts (Aldrich) as a photopolymerization catalyst was added to the resin, and the mixture was stirred for 3 hours. The stirred resin was bar coated on a Kepton film, exposed to ultraviolet light of 365 nm for 3 minutes, light cured, and further heat-treated for 120 hours for 2 hours. The Kepton film was removed to obtain a polymerized ammonium-epoxy hybrid ion exchange membrane.

Test Example

The physical properties of the samples obtained in the above Examples were evaluated by the following methods, and the results are shown in Table 1.

Test Example  1. Molecular weight analysis

The molecular weight of the organic-inorganic hybrid ion exchange resin was analyzed using Gel Permeation Chromatography (GPC, Polymer Laboratories, PL-GPC220).

Test Example  2. Glass transition temperature and storage modulus ( storage modulus ) analysis

The storage modulus of the glassy state and the rubbery state before and after the glass transition temperature and the glass transition temperature of the organic-inorganic hybrid ion exchange membrane was measured using a dynamic mechanical analyzer (TA, DMA 2980) Respectively. The measurement conditions include a temperature range of -70 to 200 DEG C, a temperature increase rate of 5 DEG C / min. An offset of 0.01 N and a frequency of 1 Hz were used.

Test Example  3. Thermal expansion coefficient

The thermal expansion coefficients of the organic-inorganic hybrid ion exchange membranes were analyzed using a thermomechanical analyzer (TMA, Seiko, EXTAR series TMA / SS 6100). As the measurement conditions, a temperature range of -120 to 200 ° C and a temperature increase rate of 5 ° C / min were used. The coefficient of thermal expansion of glass transition temperature (-75 to -50 ° C) and glass transition temperature (150 to 170 ° C) Thermal expansion was calculated from the TMA graph.

The molecular weight of the organic-inorganic hybrid ion exchange resin and the thermomechanical characteristics of the organic-inorganic hybrid ion exchange membrane are shown in Table 1 below.

Example 1 Example 2 M _n 1190 1020 M _w 1879 1705 PDI 1.579 1.672 Glass transition temperature 65 ℃ 70 ℃ Storage
modulus glassy state 4058 MPa 3950MPa rubbery state 345 MPa 378 MPa Thermal expansion coefficient (-75 to -50 ° C) 90.1 ppm / ° C 95.1 ppm / ° C Thermal expansion coefficient (150 ~ 170 ℃) 190.4 ppm / ° C 198.4 ppm / ° C

As shown in Table 1, the organic-inorganic hybrid ion exchange resin synthesized by the methods of Examples 1 and 2 has a polydispersity index (PDI) of 1 or more and a number average molecular weight (M _n ) of 5,000 or less and M _w (weight average molecular weight) and oligomers with various molecular weight distributions. The glass transition temperature of the organic-inorganic hybrid ion-exchange membrane synthesized by the methods of Examples 1 and 2 was about 70 ° C and the glass transition temperature was the storage elastic modulus of the glassy state and the rubbery state before and after the temperature storage modulus) is about 1 order difference. Also, the difference in thermal expansion coefficient before and after the glass transition temperature is about 100 ppm / 캜. Polystyrene, a backbone constituting the conventional polymer ion exchange membrane, has a glass transition temperature of about 100 ° C higher than that of the oil-inorganic hybrid ion exchange membrane. However, in the glassy state and the glassy state before and after the glass transition temperature, The difference of the storage modulus of the rubbery state is about 2 orders and the difference of the thermal expansion coefficient before and after the glass transition temperature is several hundred ppm /

The organic-inorganic hybrid ion exchange membranes synthesized by the methods of Examples 1 and 2 are fabricated from a oil-inorganic hybrid ion exchange resin in which oligomers having various molecular weight distributions of 5,000 or less are gathered. The inorganic part (Si-O-Si bond) of the oligomers in the organic-inorganic hybrid ion exchange membrane serves as a crosslinking point for restricting the movement of the organic part according to the temperature rise, and the organic-inorganic hybrid ion exchange membrane has cross- (crosslinking density) and the difference of the thermal expansion coefficient before and after the glass transition temperature are small, and it has excellent thermomechanical characteristics compared with the conventional ion exchange membrane.

Claims (21)

(S1) mixing an organosilane represented by the following formula (1) and an organosilane represented by the following formula (2); And
(S2) subjecting the mixture to a sol-gel process.
[Chemical Formula 1]

Wherein R ¹ is a thermally polymerizable and photopolymerizable organic functional group, R ² and R ³ are straight or branched (C 1 -C 7) alkyl, and n is an integer of 0 to 1.
(2)

(In the general formula 2 R ⁴ is -SO ₃ having ion exchange properties _{^{-, -COO -, -PO 3 2-}} , -PO 3 H -, -C 6 H 4 O -, -NH 3 +, -NRH 2 ⁺ , -NR ₂ H ⁺ , -NR ₃ ⁺ , -PR ₃ ⁺ and -SR ₂ ⁺ , and R ⁵ and R ⁶ are linear or branched (C1 To C7) alkyl; and n is an integer of 0 to 1.) The method according to claim 1,
The organosilane represented by the formula (1) is preferably selected from the group consisting of diethoxy (3-glycidyloxypropyl) methylsilane), 3-glycidyloxypropyl (dimethoxy) methylsilane, dimethoxymethylvinylsilane, diethoxy 3-aminopropyldimethoxymethylsilane, 3-mercaptopropyl (dimethoxy) methylsilane, 3- (2-aminoethylamino) Methyldimethoxysilane, allyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyl triethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, aryl trimethoxysilane, aryl Vinyltripropoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltrimethoxysilane, N- (3-acryloxy-2- hydroxypropyl) -3-aminopropyltripropoxysilane, 3- Acryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, , 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, N- (aminoethyl-3-aminopropyl) trimethoxysilane, N- Propyl) triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (3-mercaptopropyl) Characterized in that at least one member selected from the group consisting of methoxysilane, (3-mercaptopropyl) triethoxysilane, (acryloxymethyl) phenethyltrimethoxysilane and allyloxydecyltrimethoxysilane is selected. - Method for manufacturing inorganic hybrid ion exchange resin. The method according to claim 1,
The organosilane represented by the general formula (2) is preferably selected from the group consisting of sodium 4- (2- (3- (dimethoxy (methyl) silyl) propylthio) ethylbenzenesulfonate, sodium 3- (trimethoxysilyl) propane- (Trimethoxysilyl) propyl] ammonium chloride, trimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, trimethyl [3- (Methoxyethyl) -3-trimethoxysilylpropylammonium chloride, N, N-predecyl-N-methyl-N- (3-trimethoxysilylpropyl) ammonium chloride, octadecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride, tetradecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride, 3- Silyl) propyl chloroformate, N-trimethoxysilylpropyl-N, N, N-tri-n-butylammonium chloride, Inorganic hybrid ion exchange resin characterized in that at least one selected from the group consisting of sodium chloride, potassium chloride, sodium chloride, potassium chloride, sodium chloride, potassium chloride, . The method according to claim 1,
Wherein the mixture according to step (S1) comprises at least 50 mol% of the organosilane having n = 2 in the formula (1) and the formula (2) based on 100 mol% of the total mixture. The method according to claim 1,
The sol-gel process may be carried out in the presence of a base such as acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, chlorosulfonic acid, para-toluic acid, trichloroacetic acid, polyphosphoric acid, philophosphoric acid, iodic acid, tartaric acid, perchloric acid, ammonia, , At least one catalyst selected from the group consisting of di-n-butylamine, tri-n-butylamine, imidazole, ammonium perchlorate, potassium hydroxide, barium hydroxide, strontium hydroxide and acid base ion- Wherein the method comprises the steps of: The method according to claim 1,
Wherein the organic-inorganic hybrid ion exchange resin is composed of oligomers having a molecular weight of 5,000 or less. A process for producing an ion exchange resin according to any one of claims 1 to 6, And
And heat-polymerizing or photopolymerizing the ion-exchange resin. 8. The method of claim 7,
The thermal polymerization or the photopolymerization step may comprise:
Adding a thermal or photopolymerization catalyst to the ion exchange resin and stirring; And
Coating the agitated ion-exchange resin on a film, and then thermally polymerizing and photopolymerizing the organic-inorganic hybrid ion-exchange membrane. 9. The method of claim 8,
The thermal polymerization catalyst is selected from the group consisting of imidazole series such as benzyldimethylamine, 1-methylimidazole and 2-phenylimidazole, triphenylphosphine, triphenylphosphine, trioctylphosphine, tert-butylphosphonium methane sufonate, aluminum acetylacetonate, platinum-cyclovinylmethylsiloxane complex, tris (dibutylsulfide) rhodium trichloride and 3-methyl-2-butenyltetramethylenesulfonium hexafluoroantimony Lt; RTI ID = 0.0 > (I) < / RTI > salt. 9. The method of claim 8,
The photopolymerization catalyst may be selected from the group consisting of arylsulfonium hexafluoroantimonium salts, 2,2-dimethoxy-2-phenylacetophenone, benzophenone, 2-hydroxy-2-phenylacetophenone, Thioguan-9-one, and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide. The method for producing an organic-inorganic hybrid ion-exchange membrane according to claim 1, 9. The method of claim 8,
Wherein the thermal polymerization and the photopolymerization catalyst are added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the ion exchange resin. 9. The method of claim 8,
Wherein the coating is carried out by a method selected from the group consisting of bar coating, slit die coating, spray coating and spin coating. 8. The method of claim 7,
Wherein the thermal polymerization is performed at 50 to 250 DEG C for 1 to 24 hours. 8. The method of claim 7,
Wherein the photopolymerization step comprises photopolymerization for 1 minute to 30 minutes using a light source having a wavelength of 248 to 365 nm. 8. The method of claim 7,
Wherein the photopolymerization step further comprises a step of light-curing the mixture using a light source having a wavelength of 248 to 365 nm for 1 minute to 30 minutes, and then heat-treating the mixture at 50 to 250 ° C for 1 to 6 hours. Gt; An organic-inorganic hybrid ion-exchange resin comprising oligomers having a molecular weight of 5,000 or less,
Wherein the oligomer comprises an organosilane containing an organofunctional group capable of polymerization and an organosilane containing an organofunctional group having an ion exchange property,
The organosilane containing the polymerizable organic functional group is represented by the following general formula (1)
Wherein the organosilane containing the organic functional group of the ion exchange characteristic is represented by the following formula (2).
[Chemical Formula 1]

Wherein R ¹ is a thermally polymerizable and photopolymerizable organic functional group, R ² and R ³ are straight or branched (C 1 -C 7) alkyl, and n is an integer of 0 to 1.
(2)

(In the general formula 2 R ⁴ is -SO ₃ having ion exchange properties _{^{-, -COO -, -PO 3 2-}} , -PO 3 H -, -C 6 H 4 O -, -NH 3 +, -NRH 2 ⁺ , -NR ₂ H ⁺ , -NR ₃ ⁺ , -PR ₃ ⁺ and -SR ₂ ⁺ , and R ⁵ and R ⁶ are linear or branched (C1 To C7) alkyl; and n is an integer of 0 to 1.) 17. The method of claim 16,
The organosilane containing the polymerizable organic functional group is preferably selected from the group consisting of diethoxy (3-glycidyloxypropyl) methylsilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, dimethoxymethylvinylsilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldimethoxymethylsilane, 3-mercaptopropyl (dimethoxy) methylsilane, 3- ) Methyldimethoxysilane, allyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl ) Ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, aryltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, vinyltriethoxysilane, N- Hydroxypropyl) -3-aminopropyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) , 3-acryloxypropylmethylbis (trimethoxy) silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, 3-methacryloxy Methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, N- (aminoethyl-3-aminopropyl) trimethoxysilane, N- (2-amino Ethyl-3-aminopropyl) triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (3- (Acryloxymethyl) phenetyltrimethoxysilane, and allyloxydecyltrimethoxysilane is selected from the group consisting of (methacryloxypropyl) trimethoxysilane, (3-mercaptopropyl) triethoxysilane, Featuring an organic-inorganic hybrid ion exchange resin. 17. The method of claim 16,
The organosilane containing the organic functional group of the ion exchange property is preferably selected from the group consisting of sodium 4- (2- (3- (dimethoxy (methyl) silyl) propylthio) ethylbenzenesulfonate, sodium 3- (trimethoxysilyl) (Trimethoxy silyl) propane-1-sulfonate, trimethyl [3- (triethoxysilyl) propyl] ammonium chloride, trimethyl [3- (trimethoxysilyl) Propyl] ammonium chloride, (2-N-benzylaminoethyl) -3-aminopropyltrimethoxysilane, bis (methoxyethyl) -3- trimethoxysilylpropylammonium chloride, (3-trimethoxysilylpropyl) ammonium chloride, octadecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride, tetradecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride, 3- (Trimethoxysilyl) propyl chloroformate, N-trimethoxysilylpropyl-N, N, N-tri-n- (3-trimethoxysilyl-2-propynyl) triphenylphosphonium chloride, and 3-trihydroxysilylpropylmethylphosphonate sodium salt. Inorganic hybrid ion exchange resin. An organic-inorganic hybrid ion exchange membrane produced by thermally polymerizing or photopolymerizing an organic-inorganic hybrid ion-exchange resin comprising oligomers having a molecular weight of 5,000 or less,
Wherein the oligomer is an oligomer comprising an organosilane containing an organofunctional group capable of polymerization and an organosilane containing an organofunctional group having ion exchange properties
Yu - Inorganic Hybrid Ion Exchange Membrane. 20. The method of claim 19,
The organosilane containing the polymerizable organic functional group is preferably selected from the group consisting of diethoxy (3-glycidyloxypropyl) methylsilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, dimethoxymethylvinylsilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldimethoxymethylsilane, 3-mercaptopropyl (dimethoxy) methylsilane, 3- ) Methyldimethoxysilane, allyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl ) Ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, aryltriethoxysilane, 3-aminopropyltriethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, vinyltriethoxysilane, N- Hydroxypropyl) -3-aminopropyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) , 3-acryloxypropylmethylbis (trimethoxy) silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, 3-methacryloxy Methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, N- (aminoethyl-3-aminopropyl) trimethoxysilane, N- (2-amino Ethyl-3-aminopropyl) triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (3- (Acryloxymethyl) phenetyltrimethoxysilane, and allyloxydecyltrimethoxysilane is selected from the group consisting of (meth) acryloxypropyltrimethoxysilane, (mercaptopropyl) trimethoxysilane, (3-mercaptopropyl) triethoxysilane, Wherein the ion-exchange membrane is an ion exchange membrane. 20. The method of claim 19,
The organosilane containing the organic functional group of the ion exchange property is preferably selected from the group consisting of sodium 4- (2- (3- (dimethoxy (methyl) silyl) propylthio) ethylbenzenesulfonate, sodium 3- (trimethoxysilyl) (Trimethoxy silyl) propane-1-sulfonate, trimethyl [3- (triethoxysilyl) propyl] ammonium chloride, trimethyl [3- (trimethoxysilyl) Propyl] ammonium chloride, (2-N-benzylaminoethyl) -3-aminopropyltrimethoxysilane, bis (methoxyethyl) -3- trimethoxysilylpropylammonium chloride, (3-trimethoxysilylpropyl) ammonium chloride, octadecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride, tetradecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride, 3- (Trimethoxysilyl) propyl chloroformate, N-trimethoxysilylpropyl-N, N, N-tri-n- (3-trimethoxysilyl-2-propynyl) triphenylphosphonium chloride, and 3-trihydroxysilylpropylmethylphosphonate sodium salt. Inorganic hybrid ion exchange membrane.