KR101609649B1 - Inorganic fiber reinforced organic-inorganic hybrid ion exchange membrane with high dimensional stability and high thermal resistance and method for manufacturing the same - Google Patents

Abstract

The present invention relates to an inorganic fiber-reinforced organic-inorganic hybrid ion exchange membrane having a high water-solubility stability and a high heat resistance, and more particularly, to an inorganic fiber-reinforced organic-inorganic hybrid ion exchange membrane having high oxidation stability and high heat resistance, Inorganic hybrid inorganic-fiber-reinforced ion-exchange membrane and a method for producing the inorganic-fiber-reinforced organic-inorganic hybrid ion-exchange membrane.
The ion exchange membrane according to the present invention is composed of siloxane bonds stable to oxidation or composed of siloxane bonds and saturated hydrocarbons, and thus has excellent oxidation stability and heat resistance. According to the present invention, by implementing a composite ion exchange membrane using inorganic fibers having a low thermal expansion coefficient, dimensional stability can be remarkably improved. Therefore, the ion exchange membrane according to the present invention can be used in various temperature ranges

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inorganic fiber-reinforced organic-inorganic hybrid ion-exchange membrane having a high water-solubility stability and a high heat resistance, and a method for producing the same. 2. Description of the Related Art Inorganic-

The present invention relates to an inorganic fiber-reinforced organic-inorganic hybrid ion exchange membrane having a high water-solubility stability and a high heat resistance and a method for producing the same. More particularly, the present invention relates to an inorganic- Inorganic hybrid inorganic-fiber-reinforced ion exchange membrane having high stability and high heat resistance, which can be used in various temperature ranges, and a method for producing 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. Such ion exchange membranes can be used in various temperature ranges (room temperature to 200 ° C) depending on their applications.

The ion exchange membrane has been studied as a fluorine ion exchange membrane / a nonfluorine ion exchange membrane / a composite ion exchange membrane depending largely on the type of backbone constituting the ion exchange membrane.

Nafion, a fluorine-based ion exchange membrane, is a commercial ion exchange membrane developed by DuPont due to a problem of oxidation stability of a non-fluorine ion exchange membrane. Due to its high oxidation stability and high ion conductivity, . However, Nafion has a disadvantage in that it has a limitation of gauss swelling characteristics and thus the application temperature (80 캜), and its application is restricted due to its high price.

Accordingly, recently, a composite type ion exchange membrane research is proceeding in the direction of improving the above characteristics by adding a siloxane inorganic filler to Nafion. Ion exchange membranes have been proposed for the first time in 1992 as a backbone of siloxane polymer as another research topic of ion exchange membranes. However, they are rarely applied because of low mechanical strength. The siloxane bond constituting the siloxane polymer is pyrolyzed at 350 ° C or higher, and the siloxane polymer has higher thermal stability than the general hydrocarbon polymer except for the polymer such as polyimide. Therefore, it is necessary to study the siloxane complex type ion exchange membrane which is excellent in oxidation stability and dimensional stability.

Korean Patent Publication No. 10-2012-0074365

The present invention provides an inorganic fiber-reinforced organic-inorganic hybrid ion exchange membrane having excellent dimensional stability and oxidation stability, high water-solubility stability and high heat resistance, and a process for producing the same.

The present invention relates to a method for preparing an organosilane composition, which comprises: (a) mixing an organosilane modified with an amine group represented by the following formula (1), an organosilane having an ion exchange characteristic represented by the following formula (2) Performing a sol-gel process on the mixture prepared according to step (a) to prepare an organic-inorganic hybrid resin (step b); And a step (c) of polymerizing an amine group and an epoxy after impregnating the inorganic fiber with an epoxy added to the resin, wherein the epoxy is an epoxy monomer, an epoxy oligomer, an alicyclic epoxy monomer, and an alicyclic epoxy monomer Inorganic hybrid ion exchange membrane having a high water-solubility stability and a high heat resistance, characterized in that it comprises at least one selected from the group consisting of an epoxy oligomer and an epoxy oligomer.

[Chemical Formula 1]

(Wherein R ¹ is an organic functional group in which the amine group is modified, R ² and R ³ are each independently a linear or branched alkyl group having 1 to 7 carbon atoms, and n is an integer of 0 to 2)

(2)

(In the general formula 2 R ⁴ is having the ion-exchange properties _{^{-NH 3 +, -NRH 2 +,}} -NRR'H +, -NRR'R "+, -PRR'R" + and -SRR 'the group consisting of ⁺ (Wherein R, R 'and R "are each independently a linear or branched alkyl group having 1 to 20 carbon atoms), R ⁵ and R ⁶ are each independently an organic functional group having an ion- Straight or branched chain alkyl having 1 to 7 carbon atoms, and n is an integer between 0 and 2.)

In the step c, a monomer or oligomer having both an epoxy group or an amine group capable of polymerization with an epoxy and an ion-exchange group may be further added.

Also, the present invention relates to a method for preparing an organosilane composition, which comprises mixing organosilane modified with an amine group represented by the formula (1) and water and adjusting the pH (step a '); Performing a sol-gel process on the mixture prepared according to step a) to prepare an organic-inorganic hybrid resin (step b '); And a step of adding a monomer or oligomer having both an epoxy group or an amine group and an ion exchange group capable of polymerizing with the epoxy to the resin and then impregnating the inorganic fiber with an amine group and performing an epoxy polymerization reaction (step c ' ), Wherein the epoxy comprises at least one member selected from the group consisting of an epoxy monomer, an epoxy oligomer, an alicyclic epoxy monomer, and an alicyclic epoxy oligomer. The inorganic fiber reinforced with high temperature stability and high heat resistance The present invention also provides a method for producing an organic-inorganic hybrid ion exchange membrane.

The organosilane having an amine group represented by the formula (1)

(3-aminopropyltriethoxysilane), 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3-aminopropyldiethoxymethylsilane (3 3-aminopropylmethyldiethoxysilane, trimethoxy [3- (methylamino) propyl] silane, trimethoxy [3- 3-aminopropylmethyldiethoxysilane, 3-aminopropyldiisopropylethoxysilane, trimethoxy [3- (methylamino) propyl] silane, , 3-aminopropyldimethylethoxys (3-aminopropyldimethylethoxys aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-3- [(amino (polypropyleneoxy)] aminopropyltri Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) , (Aminoethylamino) -3-isobutyldimethylmethoxysilane, (3-trimethoxysilylpropyl) diethylenetriamine, and (n- But are not limited to, n-butylaminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, Methoxy silane (N-phenylaminopropyltrimethoxysilane), 4-aminobutyltriethoxy Aminobutyltriethoxysilane, m-aminophenyltrimethoxysilane, p-aminophenyltrimethoxysilane, aminophenyltrimethoxysilane, 11-aminoundecylsilane, Aminoundecyltriethoxysilane, 3- (m-aminophenoxy) propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, Aminopropyltriethoxysilane, N- (6-aminohexyl) aminomethyltriethoxysilane, N- (6-aminohexyl) amino Aminomethyltrimethoxysilane, N- (2-aminoethyl) -11-aminoundecyltrimethoxysilane, N- (2-aminoethyl) Ethylamino methyl) phenethyltrimethoxysilane, N- (2-aminoethyl) -3-amino (2-aminoethyl) -3-aminoisobutylmethyldimethoxysilane, cyclohexylaminomethyl triethoxysilane, cyclohexylaminomethyltrimethoxysilane, cyclohexylaminomethyltrimethoxysilane, and the like. ) trimethoxysilane, N-ethylaminoisobutylmethyldiethoxysilane, (phenylaminomethyl) methyldimethoxysilane, N-phenylaminomethyltriethoxysilane (N- phenylaminomethyltriethoxysilane) and N-methylaminopropylmethyldimethoxysilane, and more preferably at least one selected from the group consisting of N- (2-aminoethyl) -3-aminopropylmethyldi Methoxy silane.

The organosilane having an ion-exchangeable organic functional group represented by the general formula (2)

N-trimethoxysilylpropyl-N, N, N-trimethylammonium chloride, trimethyl [3- (triethoxysilyl) propyl] ammonium chloride - (triethoxysilyl) propyl] ammonium chloride, octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, N, N-predecyl- 3-trimethoxysilylpropyl) ammonium chloride, tetradecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride (N, N-diethyl- 3-trimethoxysilylpropyl) ammonium chloride, N- (trimethoxysilylethyl) benzyl-N, N, N-trimethylammonium chloride, N- Methoxysilylpropyl) isothiouronium chloride (N- (trimethoxysilylpropyl) isothiouronium chloride) It can include one or more selected from the group eojin and may be more preferably N- trimethoxysilylpropyl -N, N, N- trimethylammonium chloride.

In the production of an anion exchange membrane, the pH of the step a and the step a 'can be adjusted to more than 7.

In the step a and the step a ', a catalyst may be further added.

The catalyst may include at least one member selected from the group consisting of an acid, a base, an acid base ion-exchange resin and an amine. The acid may include at least one selected from the group consisting of 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 and perchloric acid.

The base may include at least one selected from the group consisting of ammonia, sodium hydroxide, imidazole, ammonium perchlorate, potassium hydroxide, barium hydroxide and strontium hydroxide. The acid base ion exchange resin may include at least one selected from the group consisting of a hydrogen form and a chloride form. The amines may include at least one member selected from the group consisting of triethylamine, trimethylamine, n-butylamine, di-n-butylamine and tri-n-butylamine.

The hydrogen foam may be an Amberlite IRC76 hydrogen form, and the chloride foam may be an Amberlite IRA-400 chloride form.

The amount of the catalyst to be added is not particularly limited, and it is preferable to add the catalyst until the pH of the mixture is adjusted to more than 7 (when an anion exchange membrane is manufactured).

The sol-gel process may be performed by a method commonly used in the art.

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

[Reaction Scheme 1]

The sol-gel process is sufficient for stirring for 4 to 168 hours at room temperature. The sol-gel process is carried out at 0 to 100 ° C., preferably 60 to 80 ° C. for 4 to 24 hours to accelerate the reaction rate and complete the hydrolysis- The hydrolysis-condensation reaction can be induced to form the organic-inorganic hybrid resin. When the reaction time of the sol-gel process is 4 hours or more, the hydrolysis-condensation reaction proceeds sufficiently and the Si-O-Si bond can be sufficiently formed. When the reaction time exceeds 168 hours, the hydrolysis- (gel) oxidation occurs and the organic-inorganic hybrid ion exchange resin can not be obtained.

Also, in the organic-inorganic hybrid resin prepared through the sol-gel process, the by-product alcohol and water remaining after the reaction are present, which can be removed under reduced pressure and N ₂ purging at 0-100 ° C , Preferably in the case of alcohol, at a reduced pressure of -0.1 MPa at 30 to 60 ° C for 1 hour or more, and in the case of water at 60 to 100 ° C for 1 hour or more.

The resin synthesized by the sol-gel process may be in the form of an oligomer.

The backbone of the epoxy added in the step c and the step c 'may be a hydrocarbon type system consisting of a carbon-carbon single bond or a siloxane system composed of a siloxane bond.

The epoxy added in the step c and the step c '

Hydrogenated BPA Type Epoxy Resin, Tri-Functional Epoxy Resin, Polyaliphatic Epoxy Resin, 1,3-butadiene dyes, 1,3-butadiene diepoxide, 1,4-butanediol diglycidyl ether, butyl glycidyl ether, tertiary-butylglycidyl Tert-butyl glycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,2,7,8-diepoxy octane (1,2,7,8- 8-diepoxyoctane, diglycidyl 1,2-cyclohexanedicarboxylate, 1,2-epoxybutane, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexanecarboxylate, Bis (3,4-epoxycyclohexylmethyl) adipate, 1,2-epoxydodecane, 1,2-epoxyhexane, glycidyl 2,2,3 , 3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl ether (glycidyl 2,2,3,3,4,4,5,5 , 6,6,7,7,8,8,9,9-hexadecafluorononyl ether, glycidyl hexadecyl ether, glycidyl 1,1,2,2-tetrafluoroethyl ether ( glycidyl 1,1,2,2-tetrafluoroethyl ether, neopentyl glycol diglycidyl ether, epoxycyclohexylethyl terminated polydimethylsiloxane, epoxypropoxypropyltrimethoxysilane, Epoxypropoxypropyl terminated polydimethylsiloxane, epoxypropoxypropyl terminated polyphenylmethylsiloxane, (epoxypropoxypropyl) dimethoxysilyl terminate, and the like. (Epoxypropoxypropyl) dimethoxysilyl terminated polydimethylsiloxane, mono- (2,3-epoxy) propyl ether terminated polydimethylsiloxane, mono- (2,3-epoxy) propylether terminated polydimethylsiloxane, Glycidoxypropyldimethylsiloxy) phenylsilane, PSS- [2- (3,4-epoxycyclohexyl) ethyl] -heptaisobutylsubstilide (PSS- [2- 3,4-epoxycyclohexyl) ethyl] -heptaisobutyl), tris [(epoxypropoxypropyl) dimethylsilyloxy] -POSS), PSS- (3-glycidyl) (3-glycidyl) propoxy-heptaisobutyl), 1,3-bis [2- (3,4-epoxycyclohexyl) ethyl] tetramethyldisiloxane -bis [2- (3,4-epoxycyclohexyl) ethyl] tetramethyldisiloxane, 1,5-bis (glycidoxypropyl) -3-phenyl-1,1,3,5,5-pentamethyltrisiloxane , 5-bis (glycidoxypropyl) -3-phenyl-1,1,3,5,5-pentamethyltrisiloxane and 1,3-bis (glycidoxypropyl) tetramethyldisiloxane ), More preferably a hydrogenated bisphenol-A type epoxy resin, or 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane Carboxylate.

Hydrogenated BPA Type Epoxy Resin, Tri-Functional Epoxy Resin and Polyaliphatic Epoxy Resin may be purchased from Kukdo Chemical Co., Ltd. The hydrogenated bisphenol-A type epoxy resin, the hydrogenated bisphenol-A type epoxy resin, the tri-functional epoxy resin and the polyaliphatic epoxy resin may be purchased from Kukdo Chemical Co., The product number is as follows. Hydrogenated BPA Type Epoxy Resin (ST-3000, Kukdo Chemical), Tri-Functional Epoxy Resin (YH-300, Kukdo Chemical), Polyaliphatic Epoxy Resin Epoxy Resin, PG-207P, 1,4BDGE, 1,6HDGE, BGE, LGE, Neokukdo-P, Neokukdo-E, PP-101, PG-202.

The monomer or oligomer which simultaneously has an epoxy group or an amine group capable of polymerization with the epoxy and an ion-exchange group is preferably selected from the group consisting of glycidyltrimethylammonium chloride, (2-carbamoyloxyethyl) trimethylammonium chloride ) trimethylammonium chloride and (hydrazinecarbonylmethyl) trimethylammonium chloride. The glycidyltrimethylammonium chloride may be more preferably at least one selected from the group consisting of trimethylammonium chloride, trimethylammonium chloride and hydrazinecarbonylmethyl trimethylammonium chloride.

The inorganic fibers may include at least one selected from the group consisting of glass fibers and carbon fibers.

The glass fiber may include at least one selected from the group consisting of glass cloth, glass fabric, glass nonwoven fabric and glass mesh, and the carbon fiber is selected from the group consisting of carbon cloth, carbon cloth, carbon nonwoven fabric and carbon mesh And may include one or more.

The polymerization reaction of the amine group and the epoxy may be performed by thermal curing.

The thermosetting may be performed at 20 to 180 ° C for 1 minute to 72 hours.

If the thermosetting is carried out at less than 20 캜, the epoxy-amine polymerization reaction may not take place sufficiently, and when the thermosetting is performed at a temperature exceeding 180 캜, the ion exchange ability of the organic functional group of the ion- .

In the step of adding epoxy to the resin of step c and step c ', a curing catalyst may be further added. The curing catalyst may be a thermosetting catalyst for promoting thermosetting.

The thermosetting catalyst may be selected from the group consisting of amine series such as tris (dimethylaminomethyl) phenol, dimethylaminomethylphenol and benzyldimethylamine, imidazole series such as 1-methylimidazole and 2-phenylimidazole, Phosphorus-containing compounds such as phosphorus-containing heat, such as phosphine, triphenylphosphate, trioctylphosphine, tri-tert-butylphosphine and tert-butylphosphonium methane sufonate, aluminum acetylacetonate (Alacac), platinum-cyclovinylmethylsiloxane complex, (Dibutylsulfide) rhodium trichloride, 3-methyl-2-butenyltetramethylsulfonium hexafluoroantimonate, and the like, and preferably tris (dimethylaminomethyl) phenol can be used But is not limited thereto.

The thermosetting may be added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the 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-

In addition, a solvent may be added to facilitate the epoxy polymerization reaction and to control the viscosity. As the solvent for the epoxy polymerization reaction, benzyl alcohol having a phenol group, nonylphenol and the like can be used, and benzyl alcohol can be preferably used, but not always limited thereto.

The inorganic fiber-reinforced organic-inorganic hybrid ion exchange membrane having a high water-solubility and a high heat resistance prepared by the above-mentioned method is characterized in that an organic-inorganic hybrid resin having a siloxane bond and a hydrocarbon-based or siloxane- (Or alicyclic epoxy) monomers or oligomers, it is composed of siloxane bonds stable to oxidation or composed of siloxane bonds and saturated hydrocarbons. Therefore, it can have excellent heat resistance as compared with a hydrocarbon-based ion exchange membrane having an unsaturated hydrocarbon backbone. In addition, it has been realized as a composite ion exchange membrane using inorganic fibers with low thermal expansion coefficient, and has greatly improved dimensional stability, which is advantageous to use in various temperature ranges.

The present invention also relates to an inorganic fiber-reinforced organic-inorganic hybrid ion exchange membrane having a high water-solubility stability and a high heat resistance, which is prepared by impregnating and curing an inorganic fiber with an oil-in-inorganic hybrid resin containing an epoxy in an oligomer form, An organosilane modified with an amine group represented by the formula (1) and an organosilane modified with an organofunctional group represented by the formula (2), wherein the epoxy comprises an epoxy monomer, an epoxy oligomer, an alicyclic epoxy monomer And an alicyclic epoxy oligomer. The inorganic fiber-reinforced organic-inorganic hybrid ion exchange membrane has a high water-solubility stability and a high heat resistance.

The oligomer-type organic-inorganic hybrid resin may further include a monomer or an oligomer having an epoxy group or an amine group capable of polymerizing with an epoxy and an ion-exchange group at the same time.

The present invention also relates to an epoxy resin composition comprising an epoxy and an oligomer-type organic-inorganic hybrid resin containing an epoxy or amine group capable of polymerizing with epoxy and an ion-exchange group simultaneously modified with an inorganic fiber, An inorganic fiber-reinforced organic-inorganic hybrid ion exchange membrane having water stability and high heat resistance, wherein the oligomer comprises an organosilane modified with an amine group represented by Formula 1, wherein the epoxy is an epoxy monomer, an epoxy oligomer, An inorganic fiber-reinforced organic-inorganic hybrid ion exchange membrane having a high water-solubility stability and high heat resistance, characterized by containing at least one selected from the group consisting of an epoxy-based monomer and an alicyclic epoxy oligomer.

An organosilane modified with an amine group represented by Formula 1, an organosilane having an ion-exchangeable organic functional group represented by Formula 2, an epoxy or an epoxy group capable of polymerizing with an epoxy, and an ion exchanger are simultaneously modified The details of the monomer or oligomer, the inorganic fiber, the glass fiber, the carbon fiber, etc. are the same as those described above and therefore will not be described here.

The present invention also relates to a method for preparing an organosilane composition, which comprises mixing an organosilane having an epoxy group represented by the formula (3), an organosilane having an ion exchange property represented by the following formula (4) ); Performing a sol-gel process on the mixture prepared according to step d) to prepare a oil-inorganic hybrid resin (step e); And a step (f) of impregnating the inorganic fiber with a monomer or oligomer modified with an organic functional group participating in the epoxy polymerization reaction to the resin, followed by performing a polymerization reaction of the epoxy (step f) Inorganic hybrid ion exchange membrane having a high water-solubility stability and a high heat resistance, characterized in that the organic functional group-modified monomer or oligomer containing at least one selected from the group consisting of an epoxy group, a mercapto group and a hydroxyl group is contained. to provide.

(3)

(Wherein R ⁷ is an epoxy functional group and R ⁸ and R ⁹ are each independently a linear or branched alkyl having 1 to 7 carbon atoms and n is an integer between 0 and 2)

[Chemical Formula 4]

(In the general formula 4 R ¹⁰ is -SO ₃ having ion exchange properties _{^{-, -COO -, -PO 3 2-}} , -PO 3 H - , or -C ₆ H ₄ O ^- and the organic functional group formula, R ¹¹ Is a linear or branched alkyl having 1 to 7 carbon atoms, R ¹² is a linear or branched alkyl having 1 to 7 carbon atoms or H (hydrogen), and n is an integer between 0 and 2.)

In the step f,

A monomer or oligomer having both an epoxy group or a mercapto group or a hydroxyl group capable of undergoing a polymerization reaction with an epoxy and an ion exchange group may be further added.

The present invention also relates to a process for preparing an organosilane composition, which comprises mixing an organosilane having an epoxy group represented by the following formula (3) and water and adjusting the pH (step d '); Performing a sol-gel process on the mixture prepared according to the step d 'to prepare an organic-inorganic hybrid resin (step e'); And a monomer or oligomer modified with an organic functional group participating in the epoxy polymerization reaction and a monomer or oligomer having both an epoxy group or a mercapto group capable of polymerizing with epoxy or a hydroxyl group and an ion exchange group are added to the resin, Inorganic hybrid ion exchange membrane having a high water-solubility stability and a high heat resistance, characterized by comprising a step (f ') of carrying out a polymerization reaction of a post-epoxy. The organic functional group-modified monomer or oligomer participating in the epoxy polymerization reaction may include at least one selected from an epoxy group, a mercapto group and a hydroxyl group.

The epoxy group-modified organosilane represented by the above formula (3) can be synthesized by reacting (3-glycidyloxypropyl) methyldimethoxysilane, (3-glycidyloxypropyl) diethoxy (3-Glycidyloxypropyl) methyldiethoxysilane, (3-Glycidyloxypropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyldiethoxymethylsilane 2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane), and more preferably, at least one selected from the group consisting of (3-glycidyloxypropyl) dimethoxymethylsilane May be

The organosilane having an ion-exchangeable organic functional group represented by Formula 4 may be 3- (trihydroxysilyl) -1-propane sulfonic acid, sodium 3- (Trimethoxysilyl) propane-1-sulfonate and sodium 3- (dimethoxy (methyl) silyl) propane-1-sulfonate (sodium 3- (dimethoxymethylsilyl) ) propane-1-sulfonate), and more preferably 3- (trihydroxysilyl) -1-propanesulfonic acid.

In preparing the cation exchange membrane, the pH of step d and step d 'may be adjusted to less than 7.

In the step d and the step d ', a catalyst may be further mixed. The addition amount of the catalyst is not particularly limited, and in the case of the cation exchange membrane, it is preferable to add until the pH of the mixture of step d and step d 'is adjusted to less than 7. The catalyst that can be mixed in step d, step d 'is substantially the same as the catalyst added in step a, step a'. Therefore, the details are the same as those described above, and therefore, detailed description thereof will be omitted here. Since the sol-gel process is also the same as that described above, the detailed description is omitted. The resin synthesized by the sol-gel process may be in the form of an oligomer.

The backbone of the organic functional group-modified monomer or oligomer participating in the epoxy polymerization reaction added in the step f and the step f 'may be a hydrocarbon system composed of a carbon-carbon single bond or a siloxane system composed of a siloxane bond.

The organic functional group-modified monomer or oligomer participating in the epoxy polymerization reaction added in step f and step f '

Hydrogenated BPA Type Epoxy Resin, Tri-Functional Epoxy Resin, Polyaliphatic Epoxy Resin, 1,3-butadiene dyes, 1,3-butadiene diepoxide, 1,4-butanediol diglycidyl ether, butyl glycidyl ether, tertiary-butylglycidyl Tert-butyl glycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,2,7,8-diepoxy octane (1,2,7,8- 8-diepoxyoctane, diglycidyl 1,2-cyclohexanedicarboxylate, 1,2-epoxybutane, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexanecarboxylate, Bis (3,4-epoxycyclohexylmethyl) adipate, 1,2-epoxydodecane, 1,2-epoxyhexane, glycidyl 2,2,3 , 3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl ether (glycidyl 2,2,3,3,4,4,5,5 , 6,6,7,7,8,8,9,9-hexadecafluorononyl ether, glycidyl hexadecyl ether, glycidyl 1,1,2,2-tetrafluoroethyl ether ( glycidyl 1,1,2,2-tetrafluoroethyl ether, neopentyl glycol diglycidyl ether, epoxycyclohexylethyl terminated polydimethylsiloxane, epoxypropoxypropyltrimethoxysilane, Epoxypropoxypropyl terminated polydimethylsiloxane, epoxypropoxypropyl terminated polyphenylmethylsiloxane, (epoxypropoxypropyl) dimethoxysilyl terminate, and the like. (Epoxypropoxypropyl) dimethoxysilyl terminated polydimethylsiloxane, mono- (2,3-epoxy) propyl ether terminated polydimethylsiloxane, mono- (2,3-epoxy) propylether terminated polydimethylsiloxane, Glycidoxypropyldimethylsiloxy) phenylsilane, PSS- [2- (3,4-epoxycyclohexyl) ethyl] -heptaisobutylsubstilide (PSS- [2- 3,4-epoxycyclohexyl) ethyl] -heptaisobutyl), tris [(epoxypropoxypropyl) dimethylsilyloxy] -POSS), PSS- (3-glycidyl) (3-glycidyl) propoxy-heptaisobutyl), 1,3-bis [2- (3,4-epoxycyclohexyl) ethyl] tetramethyldisiloxane -bis [2- (3,4-epoxycyclohexyl) ethyl] tetramethyldisiloxane, 1,5-bis (glycidoxypropyl) -3-phenyl-1,1,3,5,5-pentamethyltrisiloxane 1,3-bis (glycidoxypropyl) -3-phenyl-1,1,3,5,5-pentamethyltrisiloxane, 1,3-bis (glycidoxypropyl) tetramethyldisiloxane, (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and tris [3-mercaptopropionate), trimethylolpropane, (3-mercaptopropionyloxy) ethyl] isocyanurate), and more preferably at least one selected from the group consisting of hydrogenated bisphenol Epoxy-type epoxy resin, or 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate.

The monomer or oligomer having an epoxy group or a mercapto group or a hydroxyl group capable of polymerizing with epoxy and having an ion-exchange group added at the step f 'or step f,

Sodium 3-mercapto-1-propanesulfonate, 3-hydroxy-1-propanesulfonic acid sodium salt, formaldehyde, - formaldehyde-sodium bisulfite adduct, and more preferably may be sodium 3-mercapto-1-propanesulfonate.

In the step of adding the epoxy to the resin of step f, step f ', a curing catalyst may be further added. The curing catalyst may be a thermosetting catalyst. The polymerization of the epoxy may be carried out by a heat curing method. Curing catalyst, thermosetting method, inorganic fiber, glass fiber, carbon fiber and the like are the same as those described above and therefore will not be described here.

The inorganic fiber-reinforced organic-inorganic hybrid ion exchange membrane having a high water-solubility and a high heat resistance produced by the above-mentioned method is characterized in that an organic-inorganic hybrid resin having a siloxane bond and a hydrocarbon-based or backbone- ) It is composed of siloxane bonds stable to oxidation, or composed of siloxane bonds and saturated hydrocarbons since they are prepared by epoxy polymerization between monomers or oligomers. Therefore, it can have excellent heat resistance as compared with a hydrocarbon-based ion exchange membrane having an unsaturated hydrocarbon backbone. In addition, it has been realized as a composite ion exchange membrane using inorganic fibers with low thermal expansion coefficient, and has greatly improved dimensional stability, which is advantageous to use in various temperature ranges.

The present invention also relates to an inorganic fiber-reinforced oil having high temperature stability and high heat resistance, which is prepared by impregnating and curing an inorganic fiber with an organic-inorganic hybrid resin containing an organic functional group-modified monomer or oligomer participating in an epoxy polymerization reaction Inorganic hybrid resin comprises an organosilane modified with an epoxy group represented by the formula (3) and an organosilane modified with an organic functional group having an ion exchange characteristic represented by the formula (4) Inorganic hybrid inorganic-fiber-reinforced organic-inorganic hybrid ion exchange resin having high temperature stability and high heat resistance, characterized in that at least one of an epoxy group, a mercapto group and a hydroxyl group is contained in the monomer or oligomer modified with an organic functional group participating in the epoxy polymerization reaction. Lt; / RTI > The organic-inorganic hybrid resin may be in an oligomer form.

The organic-inorganic hybrid resin may further include a monomer or oligomer having an epoxy group, a mercapto group or a hydroxyl group capable of polymerization reaction with an epoxy, and an ion exchange group.

 The present invention also relates to an organic-inorganic hybrid resin comprising an organic functional group-modified monomer or oligomer participating in an epoxy polymerization reaction and a monomer or oligomer having both an epoxy group or a mercapto group capable of polymerizing with epoxy or a hydroxyl group and an ion- Inorganic hybrid inorganic-fiber-reinforced ion-exchange hybrid membrane having a high water-solubility stability and a high heat resistance, which is obtained by impregnating and curing an inorganic fiber with an inorganic-base material, wherein the organic-inorganic hybrid resin is an organosilane Characterized in that the monomer or oligomer modified with an organic functional group participating in the epoxy polymerization reaction comprises at least one selected from an epoxy group, a mercapto group and a hydroxyl group. Fiber-reinforced oil-inorganic hybrid Ion exchange membrane.

The organic-inorganic hybrid resin may be in an oligomer form.

An organosilane modified with an epoxy group represented by the formula (3), an organosilane modified with an organic functional group represented by the formula (4), an organic functional group-modified monomer or oligomer participating in an epoxy polymerization reaction, The content of a monomer or oligomer, an inorganic fiber, a glass fiber, a carbon fiber and the like which have a reactive epoxy group or mercapto group or a hydroxyl group and an ion exchange group at the same time are the same as those described above.

The ion exchange membrane according to the present invention is composed of siloxane bonds stable to oxidation or composed of siloxane bonds and saturated hydrocarbons, and thus has excellent oxidation stability and heat resistance. Further, according to the present invention, by implementing a composite ion exchange membrane using inorganic fibers having a low thermal expansion coefficient, dimensional stability can be remarkably improved. Therefore, the ion exchange membrane according to the present invention can be used in various temperature ranges.

According to the present invention, the free volume of the ion exchange membrane can be easily controlled by introducing a monomer or an oligomer having an epoxy or the like having various chain lengths, thereby easily controlling the ion exchange capacity of the ion exchange membrane .

According to the process for producing an ion exchange membrane according to the present invention, since -OH or -O- group is generated after the polymerization reaction caused by the epoxy polymerization reaction, the adhesion to other materials is excellent, It is easy to manufacture the exchange membrane.

Since the ion exchange membrane according to the present invention is a composite form of an inorganic fiber having a low coefficient of thermal expansion (CTE) and a monomer or oligomer including an oligomer type resin, an epoxy, etc., the ion exchange membrane has a low thermal expansion coefficient, .

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

≪ Example 1 >

10.32 g (0.05 mol) of N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (TCI) was added to a 100 ml one-necked flask , And then 9.01 g (0.5 mol) of water was added thereto and mixed to prepare a mixture of pH 13. The prehydrolysis process was performed at room temperature for 2 hours. After the prehydrolysis process, the mixture was stirred at 80 DEG C for 24 hours under reflux. After 24 hours sol-gel process, the resin obtained was filtered off with methanol and water as by-products at 80 ° C under reduced pressure, and then filtered through a glassy filter to obtain an amine hybrid resin. Hydrogenated bisphenol-A type epoxy liquid resin (ST-3000, Kukdo Chemical Co., Ltd.) and glycidyltrimethylammonium chloride (Aldrich) monomer were added to the resin obtained through the above process 71: 115: 75 weight ratio, and the mixture was stirred at room temperature with a paste mixer (thinky) for 3 minutes and defoamed for 1 minute. The stirred resin was impregnated in a glass cloth (E-glass) having a thickness of 50 탆 and thermally cured at 150 캜 for 2 hours. Thereafter, a glass fiber reinforced ammonium-amine-epoxy hybrid ion exchange membrane having a thickness of 60 탆 .

≪ Example 2 >

10.32 g (0.05 mol) of N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (TCI) was added to a 100 ml one-necked flask , And 9.01 g (0.5 mol) of water were added to the mixture to prepare a mixture of pH 13, and a prehydrolysis process was performed at room temperature for 2 hours. After the prehydrolysis process, the mixture was stirred at 80 DEG C for 24 hours under reflux. After 24 hours sol-gel process, the resin obtained was filtered off with methanol and water as by-products at 80 ° C under reduced pressure, and then filtered through a glassy filter to obtain an amine hybrid resin. Hydrogenated bisphenol-A type epoxy liquid resin (ST-3000, Kukdo Chemical Co., Ltd.) and glycidyltrimethylammonium chloride (Aldrich) monomer were added to the resin obtained through the above process (Dimethylaminomethyl) phenol was added as a polymerization catalyst at a weight ratio of 5 wt% based on the total resin to lower the epoxy polymerization reaction temperature, and the mixture was stirred at room temperature with a paste mixer (thinky) Stirring for 3 minutes and defoaming for 1 minute. The stirred resin was impregnated in a glass cloth (E-glass) having a thickness of 50 탆 and thermally cured at 120 캜 for 2 hours. Thereafter, a glass fiber reinforced ammonium-amine-epoxy hybrid ion exchange membrane having a thickness of 60 탆 .

≪ Example 3 >

10.32 g (0.05 mol) of N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (TCI) was added to a 100 ml one-necked flask , And 9.01 g (0.5 mol) of water were added to the mixture to prepare a mixture of pH 13, and a prehydrolysis process was performed at room temperature for 2 hours. After the prehydrolysis process, the mixture was stirred at 80 DEG C for 24 hours under reflux. After 24 hours sol-gel process, the resin obtained was filtered off with methanol and water as by-products at 80 ° C under reduced pressure, and then filtered through a glassy filter to obtain an amine hybrid resin. To the resin obtained through the above process, hydrogenated 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Aldrich) monomer and glycidyltrimethylammonium chloride (dimethylaminomethyl) phenol was added as a polymerization catalyst at a weight ratio of 5 wt% to the total resin in order to lower the temperature of the epoxy polymerization reaction, followed by addition of glycidyltrimethylammonium chloride (Aldrich) monomer at a weight ratio of 71: 63: The mixture was stirred at room temperature with a paste mixer (thinky) for 3 minutes and defoamed for 1 minute. The stirred resin was impregnated in a glass cloth (E-glass) having a thickness of 50 탆 and thermally cured at 120 캜 for 2 hours. Thereafter, a glass fiber reinforced ammonium-amine-epoxy hybrid ion exchange membrane having a thickness of 60 탆 .

<Example 4>

N-trimethoxysilylpropyl-N, N-trimethylammonium chloride, 50% in methanol, Gelest): N- (2-aminoethyl) -3 -Aminopropylmethyldimethoxysilane (TCI) was added to a 100 ml 1-necked flask at a rate of 2.58 g: 18.57 g (0.01 mol: 0.09 mol) After stirring for a minute, 9.01 g (0.5 mol) of water having a HCl 1N concentration was added and further mixed to prepare a mixture having a pH of 10.5, and a prehydrolysis process was performed at room temperature for 2 hours. After the prehydrolysis process, the mixture was stirred at 80 DEG C for 24 hours under reflux. After 24 hours sol-gel process, the resin obtained was filtered off with methanol and water as by-products at 80 ° C under reduced pressure, and then filtered through a glassy filter to obtain an amine hybrid resin. A hydrogenated bisphenol-A type epoxy liquid resin (Hydrogenated bisphenol-A type epoxy liquid resin, ST-3000, Kukdo Chemical Co., Ltd.) was added to the resin obtained through the above process at a weight ratio of 175: 230, Followed by stirring for 3 minutes and degassing for 1 minute. The stirred resin was impregnated in a glass cloth (E-glass) having a thickness of 50 탆 and thermally cured at 150 캜 for 2 hours. Thereafter, a glass fiber reinforced ammonium-amine-epoxy hybrid ion exchange membrane having a thickness of 60 탆 .

&Lt; Example 5 >

6.223 g (0.01 mol) of 3- (trihydroxysilyl) -1-propane sulfonic acid (30-35% in water Gelest) was dissolved in 100 ml of 1 neck, (3-glycidyloxypropyl) methyldimethoxysilane ((3-glycidyloxypropyl) methyldimethoxysilane (3-glycidyloxypropyl)) was added to the flask, and 1 g of NaOH (0.09 mol) of HCl 0.1N) was added to the mixture to prepare a slightly acidic mixture, and prehydrolysis was carried out at room temperature for 2 hours. The process was carried out. After the prehydrolysis process, the mixture was stirred at 80 DEG C for 24 hours under reflux. After 24 hours of sol-gel process, the resin obtained was filtered off with methanol using a glassy filter at 30 ° C under reduced pressure to obtain a sulfonic-epoxy hybrid resin. The resin obtained through the above process was added with hydrogenated bisphenol-A type epoxy liquid resin (ST-3000, Kukdo Chemical Co., Ltd.) and sodium 3-mercapto-1-propane sulfonate mercapto-1-propanesulfonate, Aldrich) monomers were added at a weight ratio of 168: 115: 178, and then benzyldimethylamine was added to the premix mixture in an amount of 5 wt% to further promote the epoxy polymerization reaction. Then, the mixture was stirred at room temperature with a paste mixer (thinky) for 3 minutes and defoamed for 1 minute. After agitated resin was impregnated into a glass cloth (E-glass) having a thickness of 50 탆, heat treatment was performed at 100 캜 for 1 hour to remove water in the resin, followed by thermal curing at 150 캜 for 2 hours, A glass fiber reinforced sulphonic-mercapto-epoxy hybrid ion exchange membrane having a thickness of 60 mu m was obtained.

&Lt; Example 6 >

(0.05 mol) of (3-glycidyloxypropyl) methyldimethoxysilane (Aldrich) were added and stirred for 15 minutes. Then, 0.901 g (0.05 mol) were added and mixed to make a slightly acidic mixture, and a prehydrolysis process was performed at room temperature for 2 hours. After the prehydrolysis process, the mixture was stirred at 80 DEG C for 24 hours under reflux. After 24 hours of sol-gel process, the resin obtained was filtered off with methanol using a glassy filter at 30 ° C under reduced pressure to obtain a sulfonic-epoxy hybrid resin. Epoxycyclohexylmethyl 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Aldrich) monomer and sodium 3-mercapto-1- (3-mercaptohexanecarboxylate) Sodium 3-mercapto-1-propanesulfonate (Aldrich) monomer was added at a weight ratio of 78: 63: 178, and then benzyldimethylamine was added to the premix mixture in an amount of 5 wt% to further promote the epoxy polymerization reaction. Then, the mixture was stirred at room temperature with a paste mixer (thinky) for 3 minutes and defoamed for 1 minute. After agitated resin was impregnated into a glass cloth (E-glass) having a thickness of 50 탆, heat treatment was performed at 100 캜 for 1 hour to remove water in the resin, followed by thermal curing at 150 캜 for 2 hours, A glass fiber reinforced sulphonic-mercapto-epoxy hybrid ion exchange membrane having a thickness of 60 mu m was obtained.

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. Analysis of glass transition temperature and storage modulus

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 inorganic fiber-impregnated organic-inorganic hybrid ion exchange membrane was measured using a dynamic mechanical analyzer (TA, DMA 2980). Before the measurement, the inorganic fiber-impregnated oil-inorganic hybrid ion exchange membrane was subjected to heat treatment at 100 ° C for 2 hours under vacuum to remove moisture. 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 2. Coefficient of thermal expansion

The thermal expansion coefficients of the inorganic fiber impregnated U-inorganic hybrid ion exchange membranes were analyzed using a thermomechanical analyzer (TMA, Seiko, EXTAR series TMA / SS 6100). Before the measurement, the inorganic fiber-impregnated oil-inorganic hybrid ion exchange membrane was subjected to heat treatment at 100 ° C for 2 hours under vacuum to remove moisture. The measurement conditions were a temperature range of -75 to 200 ° C and a rate of temperature increase of 5 ° C / min. The coefficient of thermal expansion of the glass transition temperature (-25 to 25 ° C) and the glass transition temperature (150 to 170 ° C) expansion was calculated from the TMA graph. To confirm the dimensional stability, the TMA measurement was performed twice with the same sample to compare the first and second values.

The thermomechanical characteristics of the inorganic fiber impregnated organic-inorganic hybrid ion exchange membrane are shown in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Glass transition temperature (캜) 54 50 63 48 51 61 Storage
modulus
(MPa) glassy state 16800 17000 17800 16500 15900 18000 rubbery state 11000 10800 11900 10900 10500 11500 Coefficient of thermal expansion
(ppm / ° C, -25 to 25 ° C) Primary measurement 21.0 22.0 19.8 20.7 22.0 19.5 Secondary measurement 23.0 21.0 19.4 20.2 21.2 19.3 Coefficient of thermal expansion
(ppm / DEG C, 150 to 170 DEG C) Primary measurement 12.4 11.5 14.5 10.5 11.3 14.2 Secondary measurement 10.3 12.3 15.4 9.8 10.7 14.7

The glass transition temperature of the organic-inorganic hybrid ion exchange membrane synthesized by the methods of Examples 1 to 6 is about 50 to 60 ° C and the storage modulus of the organic-inorganic hybrid ion exchange membrane of the prior art KR 2012-0125665 the storage modulus of the glassy state and the rubbery state before and after the glass transition temperature as compared with the modulus of the glass transition temperature was remarkably increased due to the strengthening effect of the inorganic fiber glass fiber. In the case of the prior art KR 2012-0125665 glass-fiber-impregnated, organic-inorganic hybrid ion exchange membrane, the difference in the thermal expansion coefficient after the glass transition temperature is about 100 ppm / It can be seen that the difference in thermal expansion coefficient between the hybrid ion exchange membrane and that before and after the glass transition temperature hardly varies. In addition, it is seen that the thermal expansion coefficient does not differ even in the repeated measurement of the same sample. Thus, it can be seen that the inorganic fiber-reinforced organic-inorganic hybrid ion exchange membrane has excellent dimensional stability.

The inorganic fiber-reinforced organic-inorganic hybrid ion exchange membranes prepared by the methods of Examples 1 to 6 are composed of siloxane bonds stable to oxidation or composed of siloxane bonds and saturated hydrocarbons, and thus are excellent in oxidation stability and heat resistance. Furthermore, by implementing a composite ion exchange membrane employing inorganic fibers having a low thermal expansion coefficient, dimensional stability can be remarkably improved. Therefore, inorganic fiber-reinforced organic-inorganic hybrid ion exchange membranes can be used in various temperature ranges.

Claims (52)

(A) mixing an organosilane having an amine group represented by the following formula (1), an organosilane having an ion-exchange characteristic represented by the following formula (2), and water;
Performing a sol-gel process on the mixture prepared according to step (a) to prepare an organic-inorganic hybrid resin (step b); And
(C) a step of adding an epoxy to the resin, impregnating the inorganic fiber with the epoxy resin, and carrying out a polymerization reaction of an amine group and an epoxy (step c)
Wherein the epoxy comprises at least one member selected from the group consisting of an epoxy monomer, an epoxy oligomer, an alicyclic epoxy monomer, and an alicyclic epoxy oligomer. The inorganic fiber-reinforced organic-inorganic hybrid ion Exchange membrane manufacturing method.
[Chemical Formula 1]

(Wherein R ¹ is an organic functional group in which the amine group is modified, R ² and R ³ are each independently a linear or branched alkyl group having 1 to 7 carbon atoms, and n is an integer of 0 to 2)
(2)

(In the general formula 2 R ⁴ is having the ion-exchange properties _{^{-NH 3 +, -NRH 2 +,}} -NRR'H +, -NRR'R "+, -PRR'R" + and -SRR 'the group consisting of ⁺ (Wherein R, R 'and R "are each independently a linear or branched alkyl group having 1 to 20 carbon atoms), R ⁵ and R ⁶ are each independently an organic functional group having an ion- Straight or branched chain alkyl having 1 to 7 carbon atoms, and n is an integer between 0 and 2.)
The method according to claim 1,
In the step (c), an inorganic fiber-reinforced organic-inorganic hybrid ion exchange membrane having a high water-solubility stability and a high heat resistance, which further comprises a monomer or oligomer having both an epoxy group or an amine group capable of polymerization with an epoxy and an ion- Way.
Mixing an organosilane modified with an amine group represented by the following formula (1) and water, and adjusting the pH (step a);
Performing a sol-gel process on the mixture prepared according to step (a) to prepare an organic-inorganic hybrid resin (step b); And
(C) a step of adding a monomer or an oligomer having both an epoxy group or an amine group and an ion exchange group capable of polymerizing with epoxy to the resin, then impregnating the inorganic fiber with an amine group and an epoxy, Including,
Wherein the epoxy comprises at least one member selected from the group consisting of an epoxy monomer, an epoxy oligomer, an alicyclic epoxy monomer, and an alicyclic epoxy oligomer. The inorganic fiber-reinforced organic-inorganic hybrid ion Exchange membrane manufacturing method.
[Chemical Formula 1]

(Wherein R ¹ is an organic functional group in which the amine group is modified, R ² and R ³ are each independently a linear or branched alkyl group having 1 to 7 carbon atoms, and n is an integer of 0 to 2)
The method according to claim 1 or 3,
The organosilane having an amine group represented by the formula (1)
(3-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- Aminopropyldimethoxysilane, trimethoxy [3- (methylamino) propyl] silane, trimethoxy [3- (phenylamino) , 3-aminopropylmethyldiethoxysilane, 3-aminopropyldiisopropylethoxysilane, 3-aminopropyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-3- [(amino (polypropyleneoxy)] aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, Methylmethoxysilane, (3-trimethoxysilylpropyl) diethylenetriamine, n-butylaminopropyltrimethoxysilane, N-ethylamino Aminopropyltrimethoxysilane, isopropyltrimethoxysilane, isobutyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 4-aminobutyltriethoxysilane, m- Aminophenoxy) propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- Aminomethyltrimethoxysilane, N- (6-aminopentyl) aminomethyltriethoxysilane, N- (6-aminohexyl) aminomethyltrimethoxysilane, N- (Aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl) -3-aminoisobutylmethyldimethoxysilane, (cyclohexylaminomethyl) triethoxysilane, (cyclohexylamino Methyl) trimethoxysilane, N-ethylaminoisobutylmethyldiethoxysilane, (phenylaminomethyl) methyldimethoxysilane Is an inorganic fiber reinforced oil having high temperature stability and high heat resistance, characterized by containing at least one member selected from the group consisting of N-phenylaminomethyltriethoxysilane and N-methylaminopropylmethyldimethoxysilane. - Method for manufacturing an inorganic hybrid ion exchange membrane.
The method according to claim 1,
The organosilane having an ion-exchangeable organic functional group represented by the general formula (2)
N, N, N-trimethylammonium chloride, trimethyl [3- (triethoxysilyl) propyl] ammonium chloride, octadecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride, N , N-decyl-N-methyl-N- (3-trimethoxysilylpropyl) ammonium chloride, tetradecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride, N- And at least one member selected from the group consisting of N, N, N, N-trimethylammonium chloride and N- (trimethoxysilylpropyl) isothiouronium chloride. Method for fabricating a fiber - reinforced oil - and - inorganic hybrid ion exchange membrane.
The method according to claim 1 or 3,
Inorganic hybrid inorganic-fiber-reinforced organic-inorganic hybrid-type ion exchange membrane having a high water-solubility stability and a high heat resistance.
The method of claim 6,
Wherein the catalyst comprises at least one member selected from the group consisting of an acid, a base, an acid base ion-exchange resin and an amine,
The acid includes at least one selected from the group consisting of acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, chlorosulfonic acid, para-toluic acid, trichloroacetic acid, polyphosphoric acid, philophosphoric acid,
Wherein the base comprises at least one selected from the group consisting of ammonia, sodium hydroxide, imidazole, ammonium perchlorate, potassium hydroxide, barium hydroxide and strontium hydroxide,
The acid base ion exchange resin includes at least one selected from the group consisting of hydrogen form and chloride form,
Characterized in that the amines include at least one member selected from the group consisting of triethylamine, trimethylamine, n-butylamine, di-n-butylamine and tri-n-butylamine. Inorganic hybrid inorganic-fiber reinforced organic-inorganic hybrid ion exchange membrane.
The method according to claim 1 or 3,
Wherein the resin synthesized by the sol-gel process is in the form of an oligomer. The method for producing an inorganic fiber-reinforced organic-inorganic hybrid ion exchange membrane according to claim 1,
The method according to claim 1 or 3,
The inorganic fiber-reinforced organic-inorganic hybrid ion exchange membrane having a high water-solubility stability and a high heat resistance, characterized in that the backbone of the epoxy added in the step (c) is a hydrocarbon-based or siloxane- Gt;
The method according to claim 1 or 3,
The epoxy added in step c)
Hydrogenated bisphenol-A type epoxy resins, 3-functional epoxy resins, polyalipathic epoxy resins, 1,3-butadienediepoxide, 1,4-butanediol glycidyl ether, butylglycidyl Ether, tertiary-butyl glycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,2,7,8-diepoxy octane, diglycidyl 1,2-cyclohexanedicarboxyl Epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 1,2-epoxydodecane, 1,3-epoxycyclohexylmethacrylate, 1,2-epoxyhexane, glycidyl 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl ether, glycidyl Epoxycyclohexyl ethyl trimellitate, polydimethylsiloxane, epoxycyclohexylmethyldimethylsiloxane, epoxycyclohexylmethyldimethylsiloxane, epoxycyclohexylmethyldimethylsiloxane, epoxycyclohexylmethyldimethylsiloxane, (Epoxypropoxy) dimethoxysilyl terminated polydimethylsiloxane, mono- (2,3-epoxy) propoxylated polydimethylsiloxane, epoxypropoxypropyl terminated polydimethylsiloxane, (Glycidoxypropyldimethylsiloxy) phenylsilane, PSS- [2- (3,4-epoxycyclohexyl) ethyl] -heptaisobutyl substistide, tris [(Epoxypropoxy) dimethylsilyloxy] -POSS, PSS- (3-glycidyl) propoxy-heptathobutyl substistide, 1,3-bis [2- (3,4- Hexyl) ethyl] tetramethyldisiloxane, 1,5-bis (glycidoxypropyl) -3-phenyl-1,1,3,5,5-pentamethyltrisiloxane and 1,3- ) &Lt; / RTI &gt; tetramethyldisiloxane. &Lt; RTI ID = 0.0 &gt; Inorganic fiber-reinforced and having a heat-resistant organic-inorganic hybrid method for producing an ion exchange membrane.
The method according to claim 2 or 3,
The monomer or oligomer having both an epoxy group or an amine group capable of undergoing a polymerization reaction with the epoxy and an ion-
(2-carbamoyloxyethyl) trimethylammonium chloride, and (hydrazinecarbonylmethyl) trimethylammonium chloride. 2. The method of claim 1, wherein the at least one compound is selected from the group consisting of glycidyltrimethylammonium chloride, (EN) METHOD FOR PREPARING INORGANIC FIBER - REINFORCED WATER - INORGANIC HYBRID ION EXCHANGE MEMBRANE WITH RESISTANCE.
The method according to claim 1 or 3,
Inorganic hy- droxy-enriched inorganic ion-exchange membrane having a high temperature stability and high heat resistance, wherein a thermosetting catalyst is further added in the step of adding epoxy to the resin of step (c).
The method of claim 12,
The thermoset catalyst may be selected from the group consisting of tris (dimethylaminomethyl) phenol, dimethylaminomethylphenol, benzyldimethylamine, 1-methylimidazole, 2-phenylimidazole, triphenylphosphine, triphenylphosphate, Phosphine, tri-tert-butylphosphine, tert-butylphosphonium methanesulfonate, aluminum acetylacetonate (Alacac), platinum-cyclovinylmethylsiloxane complex, tris (dibutylsulfide) rhodium trichloride and 3- -Butenyltetramethylenesulfonium hexafluoroantimonate salt having a high water-solubility and a high heat resistance, characterized in that the inorganic fiber-reinforced organic-inorganic-inorganic hybrid ion exchange membrane comprises at least one member selected from the group consisting of polytetrafluoroethylene-butenyltetramethylenesulfonium hexafluoroantimonate salts.
The method according to claim 1 or 3,
Wherein the inorganic fibers comprise at least one member selected from the group consisting of glass fibers and carbon fibers, and having high stability and high heat resistance.
15. The method of claim 14,
Wherein the glass fiber comprises at least one selected from the group consisting of glass cloth, glass fabric, glass nonwoven fabric, and glass mesh, and the carbon fiber is at least one selected from the group consisting of carbon cloth, carbon cloth, carbon non- Inorganic hybrid inorganic-fiber reinforced organic-inorganic hybrid ion-exchange membrane having a high water-solubility stability and a high heat resistance.
The method according to claim 1 or 3,
Wherein the polymerization of the amine group and the epoxy is carried out by a thermal curing process, and the inorganic fiber-reinforced organic-inorganic hybrid ion exchange membrane having high temperature stability and high heat resistance.
18. The method of claim 16,
Wherein the thermosetting is performed at 20 to 180 ° C for 1 minute to 72 hours. The method for producing an inorganic fiber-reinforced organic-inorganic hybrid ion exchange membrane according to claim 1,
An inorganic fiber-reinforced organic-inorganic hybrid ion exchange membrane produced by impregnating and curing an inorganic fiber with an organic-inorganic hybrid ion exchange resin in the form of an oligomer containing an epoxy and having high stability and high heat resistance,
Wherein the oligomer comprises an organosilane modified with an amine group represented by the following general formula (1) and an organosilane having an organofunctional group having an ion-exchange property represented by the following general formula (2)
Wherein the epoxy comprises at least one member selected from the group consisting of an epoxy monomer, an epoxy oligomer, an alicyclic epoxy monomer, and an alicyclic epoxy oligomer. The inorganic fiber-reinforced organic-inorganic hybrid ion Exchange membrane.
[Chemical Formula 1]

(Wherein R ¹ is an organic functional group in which the amine group is modified, R ² and R ³ are each independently a linear or branched alkyl group having 1 to 7 carbon atoms, and n is an integer of 0 to 2)
(2)

(In the general formula 2 R ⁴ is having the ion-exchange properties _{^{-NH 3 +, -NRH 2 +,}} -NRR'H +, -NRR'R "+, -PRR'R" + and -SRR 'the group consisting of ⁺ (Wherein R, R 'and R "are each independently a linear or branched alkyl group having 1 to 20 carbon atoms), R ⁵ and R ⁶ are each independently an organic functional group having an ion- Straight or branched chain alkyl having 1 to 7 carbon atoms, and n is an integer between 0 and 2.)
19. The method of claim 18,
Wherein the oligomer-type organic-inorganic hybrid resin further comprises a monomer or oligomer having both an epoxy group or an amine group capable of polymerization with an epoxy and an ion-exchange group, Inorganic hybrid ion exchange membrane.
An inorganic or organic hybrid resin having an epoxy group and an epoxy group capable of polymerization reaction with an epoxy and a monomer or oligomer having both an amine group and an ion exchange group simultaneously and impregnated with an inorganic fiber and cured, As the fiber-reinforced oil-and-inorganic hybrid ion exchange membrane,
Wherein the organic-inorganic hybrid resin comprises an organosilane modified with an amine group represented by the following formula (1)
Wherein the epoxy comprises at least one member selected from the group consisting of an epoxy monomer, an epoxy oligomer, an alicyclic epoxy monomer, and an alicyclic epoxy oligomer. The inorganic fiber-reinforced organic-inorganic hybrid ion Exchange membrane.
[Chemical Formula 1]

(Wherein R ¹ is an organic functional group in which the amine group is modified, R ² and R ³ are each independently a linear or branched alkyl group having 1 to 7 carbon atoms, and n is an integer of 0 to 2)
The method according to claim 18 or 20,
The organosilane having an amine group represented by the formula (1)
(3-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- Aminopropyldimethoxysilane, trimethoxy [3- (methylamino) propyl] silane, trimethoxy [3- (phenylamino) , 3-aminopropylmethyldiethoxysilane, 3-aminopropyldiisopropylethoxysilane, 3-aminopropyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-3- [(amino (polypropyleneoxy)] aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, Methylmethoxysilane, (3-trimethoxysilylpropyl) diethylenetriamine, n-butylaminopropyltrimethoxysilane, N-ethylamino Aminopropyltrimethoxysilane, isopropyltrimethoxysilane, isobutyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 4-aminobutyltriethoxysilane, m- Aminophenoxy) propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- Aminomethyltrimethoxysilane, N- (6-aminopentyl) aminomethyltriethoxysilane, N- (6-aminohexyl) aminomethyltrimethoxysilane, N- (Aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl) -3-aminoisobutylmethyldimethoxysilane, (cyclohexylaminomethyl) triethoxysilane, (cyclohexylamino Methyl) trimethoxysilane, N-ethylaminoisobutylmethyldiethoxysilane, (phenylaminomethyl) methyldimethoxysilane Is an inorganic fiber reinforced oil having high temperature stability and high heat resistance, characterized by containing at least one member selected from the group consisting of N-phenylaminomethyltriethoxysilane and N-methylaminopropylmethyldimethoxysilane. - Inorganic hybrid ion exchange membrane.
19. The method of claim 18,
The organosilane having an ion-exchangeable organic functional group represented by the general formula (2)
N, N, N-trimethylammonium chloride, trimethyl [3- (triethoxysilyl) propyl] ammonium chloride, octadecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride, N , N-decyl-N-methyl-N- (3-trimethoxysilylpropyl) ammonium chloride, tetradecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride, N- And at least one member selected from the group consisting of N, N, N, N-trimethylammonium chloride and N- (trimethoxysilylpropyl) isothiouronium chloride. Fiber reinforced oil - inorganic hybrid ion exchange membrane.
The method according to claim 18 or 20,
The epoxy,
Hydrogenated bisphenol-A type epoxy resins, 3-functional epoxy resins, polyalipathic epoxy resins, 1,3-butadienediepoxide, 1,4-butanediol glycidyl ether, butylglycidyl Ether, tertiary-butyl glycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,2,7,8-diepoxy octane, diglycidyl 1,2-cyclohexanedicarboxyl Epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 1,2-epoxydodecane, 1,3-epoxycyclohexylmethacrylate, 1,2-epoxyhexane, glycidyl 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl ether, glycidyl Epoxycyclohexyl ethyl trimethyl polydimethyl siloxane, epoxycyclohexyl phthalate, glycidyl 1,1,2,2-tetrafluoroethyl ether, neopentyl glycol diglycidyl ether, epoxycyclohexylethyl terminated polydimethylsiloxane, (Epoxypropoxy) dimethoxysilyl terminated polydimethylsiloxane, mono- (2,3-epoxy) propoxylated polydimethylsiloxane, epoxypropoxypropyl terminated polydimethylsiloxane, (Glycidoxypropyldimethylsiloxy) phenylsilane, PSS- [2- (3,4-epoxycyclohexyl) ethyl] -heptaisobutyl substistide, tris [(Epoxypropoxy) dimethylsilyloxy] -POSS, PSS- (3-glycidyl) propoxy-heptathobutyl substistide, 1,3-bis [2- (3,4- Hexyl) ethyl] tetramethyldisiloxane, 1,5-bis (glycidoxypropyl) -3-phenyl-1,1,3,5,5-pentamethyltrisiloxane and 1,3- ) Tetramethyldisiloxane. &Lt; Desc / Clms Page number 14 &gt;&lt; RTI ID = 0.0 &gt; An inorganic fiber-reinforced organic-inorganic hybrid ion exchange membrane having high heat resistance.
The method according to claim 19 or 20,
The monomer or oligomer having both an epoxy group or an amine group capable of undergoing a polymerization reaction with the epoxy and an ion-
(2-carbamoyloxyethyl) trimethylammonium chloride, and (hydrazinecarbonylmethyl) trimethylammonium chloride. 2. The method of claim 1, wherein the at least one compound is selected from the group consisting of glycidyltrimethylammonium chloride, An inorganic fiber-reinforced oil-and-inorganic hybrid ion exchange membrane having heat resistance.
The method according to claim 18 or 20,
The inorganic fiber-reinforced organic-inorganic-inorganic hybrid ion exchange membrane according to claim 1, wherein the inorganic fibers include at least one selected from the group consisting of glass fibers and carbon fibers.
26. The method of claim 25,
Wherein the glass fiber comprises at least one selected from the group consisting of glass cloth, glass fabric, glass nonwoven fabric, and glass mesh, and the carbon fiber is at least one selected from the group consisting of carbon cloth, carbon cloth, carbon non- Inorganic hybrid inorganic-fiber-reinforced organic-inorganic hybrid ion exchange membrane having a high water-solubility stability and a high heat resistance.
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