KR101705563B1 - Ion-exchange membrane for water treatment and manufacturing method the same - Google Patents
Ion-exchange membrane for water treatment and manufacturing method the same Download PDFInfo
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- KR101705563B1 KR101705563B1 KR1020150059816A KR20150059816A KR101705563B1 KR 101705563 B1 KR101705563 B1 KR 101705563B1 KR 1020150059816 A KR1020150059816 A KR 1020150059816A KR 20150059816 A KR20150059816 A KR 20150059816A KR 101705563 B1 KR101705563 B1 KR 101705563B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
An embodiment of the present invention relates to a porous support comprising a polyolefin matrix (base material), a nanoparticle inorganic filler dispersed in the polyolefin matrix, and paraffin oil; And an anion conductor adsorbed on the porous support. The present invention also provides an ion exchange membrane for water treatment using the porous support.
Description
The present invention relates to an ion exchange membrane for water treatment, and more particularly, to an ion exchange membrane for ED (Electrodialysis) and RED (reverse electrodialysis) and a method for producing the same.
The ion exchange membrane is capable of selectively separating cations and anions in the aqueous solution, and can be used for a wide variety of applications such as fuel cells, electrodialysis, electrodialysis for water decomposition for acid and base recovery, diffusion dialysis for recovering acid and metal species from acid waste, In recent years, the application range of the ion exchange membrane has been expanded as a high performance ion exchange membrane is developed.
Ion exchange membranes must have high selectivity, low permeability of solvents and non-ionic solutes, low resistance to diffusion of selected permeate ions, high mechanical strength and chemical resistance. Such an ion exchange membrane is required to have excellent mechanical strength and durability. Methods commonly used to meet such demands include a method of producing a hybrid composite membrane by adding an inorganic substance, a hot pressing method of hot pressing the catalyst mixture, and a method of adding a hardening agent.
In the hybrid composite membrane manufacturing method, if the swelling phenomenon of the membrane is continued, there is a gap between the inorganic substance and the polymer membrane of the membrane, so that a proper ion exchange ability can not be exhibited. The hot press method in which the catalyst mixture is heated and pressed has a disadvantage in that the catalyst layer is dissolved over time. Also, the method of adding a curing agent also has a disadvantage that the curing agent is dissolved over time. It has been required to develop an ion exchange membrane having high durability and excellent mechanical properties due to the above-mentioned problems.
Currently, commercialized ion exchange membranes used in fuel cell membranes, electrode membranes, etc. are sulfonated polystyrene, Nafion TM (hereinafter referred to as "Nafion") manufactured by Du Pont, and the like. However, when sulfonated polystyrene is dried, it is broken due to increase of brittleness, which makes it difficult to form into a thin film or a composite film, and has a disadvantage that mechanical stability is poor when it is processed into an electrode. In order to improve such disadvantages, there is a method of controlling the sulfonation ratio of polystyrene or a method of increasing the thickness of the membrane. At this time, the membrane resistance is increased and the ion exchange ability of the membrane is remarkably decreased, When the system is manufactured, the volume is increased and the space is limited. In addition, Nafion has been used as an ion exchange membrane due to its high conductivity and chemical stability as a fluorine-based material. However, Nafion is very expensive due to the fluorine compound contained therein and has a disadvantage that its use at a high temperature is limited. In fact, expensive ion-exchange membranes such as Nafion have a great effect on the actual battery operation and are pointed out as a cause of increasing the manufacturing cost of the battery. The unit price of perfluorosulfonic acid ion exchange membrane such as Nafion TM is about 1 million won / m 2 , which is one of the problems to be solved.
A variety of studies have been conducted on non-fluorine ion exchange membranes that are inexpensive and cost effective. Especially, sulfonated polyarylene ether sulfone (SPES), sulfonated polyetherether ketone (SPEEK), polybenzimidazole (PBI), sulfonated polysulfone (SPSf) Studies on the polymers of the family have been extensively conducted.
Non-fluorinated polymeric materials have been tested for the possibility of new materials by controlling various factors such as introduction of various functional groups, arrangement of polymer chains, and control of molecular weight. However, most of the materials have limited limitations in practical applications due to their low chemical / physical stability compared to their excellent electrical performance. Therefore, various methods have been proposed to improve the performance of the polymer material. However, the results of these efforts show low ion selectivity and low durability.
Disclosure of Invention Technical Problem [8] The present invention provides an ion exchange membrane using a porous support capable of reducing mechanical properties and cost, and a method for producing the same.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not intended to limit the invention to the precise form disclosed. There will be.
According to an aspect of the present invention, there is provided a method of manufacturing a polyolefin substrate, the method comprising: providing a porous support including a polyolefin matrix, a nanoparticle inorganic filler dispersed in the polyolefin matrix, and paraffin oil; And an anion conductor impregnated in the porous support. The present invention also provides an ion exchange membrane for water treatment using the porous support.
In an embodiment of the present invention, the polyolefin matrix may be ultra-high molecular weight polyethylene having a molecular weight of from 1,000,000 to 5,000,000 or high molecular weight polyethylene having a molecular weight of from 30,000 to 700,000, or a mixture thereof.
In an embodiment of the present invention, the porous support may have an air permeability of less than 10 to 150 seconds, a porosity of 40 to 80%, and a pore diameter of 0.1 to 50 탆.
In an embodiment of the present invention, the nanoparticle inorganic filler is selected from the group consisting of silica (SiO 2 ), titanium dioxide (TiO 2 ), alumina (Al 2 O 3 ), barium titanate (BaTiO 2 ), zeolite Inorganic phosphorus filler having a size of 10 nm to 600 nm composed of at least one inorganic material selected from borate, bismuth, calcium carbonate (CaCO 3 ), and the like.
In an embodiment of the present invention, the nanoparticle inorganic filler may be contained in an amount of 10 to 50% by weight based on the total weight of the ion exchange membrane composition for water treatment.
In an embodiment of the present invention,
[Chemical Formula 1]
Having the structure of Formula 1,
Y is -, -CO-, -SO 2 - or -O-, Z and D are to be equal to or different from each other -, -O- or -S-, C is -, -C (CH 3) 2 - Or -C (CF 3 ) 2 -, R 1 is H or -CH 2 N + R 2 R 3 R 4 and R 2 , R 3 , R 4 are the same or different and are -CH 3 , -CH 2 CH 3 , - (CH 2 ) 2 CH 3 , -CH 2 NH 2 , - (CH 2 ) 2 NH 2 Or - (CH 2 ) 3 NH (CH 3 ) Cl, x and y are arbitrary repeating units, and x / (x + y) can be 0.001 to 1.
In an embodiment of the present invention, the anion conductor is selected from the group consisting of aminated PAES (polyarylene ether sulfone), aminated PEK (polyether ketone), aminated PEEK (polyether ether ketone), aminated PS (polysulfone), aminated PES PPO (polyphenylene oxide), aminated PPS (polyphenylene sulfide), or a mixture of two or more of them.
A method of manufacturing an ion exchange membrane for water treatment according to an embodiment of the present invention comprises: i) preparing a polyolefin matrix and nanoparticle inorganic filler (S100); ii) mixing the polyolefin matrix and the nanoparticle inorganic filler with paraffin oil (S200); iii) a step of removing fine bubbles by vacuum defoaming (S300); iv) a melt-kneading and discharging step (S400) at 150 to 300 캜; v) forming a porous support on a casting roll at a temperature of 50 to 100 캜 in the melt-kneaded discharge product produced in the discharging step (S500); vi) biaxially stretching and fixing the porous support (S600); vii) removing the paraffin oil by immersing the porous support in a solvent (S700); viii) immersing the porous support in an anionic conductor solution or applying an anionic conductor solution to the porous support (S800); ix) impregnating the porous support with an anion conductor (S900).
In an embodiment of the present invention, in the nanoparticle inorganic filler and polyolefin matrix preparation step (S100), the nanoparticle inorganic filler is spherical nanosilica having a size of 10 nm to 600 nm and may be an ethylene surface-treated.
In an embodiment of the present invention, in the step (S100) of preparing the nanoparticle inorganic filler and the polyolefin base material, the polyolefin base material may be an ultrahigh molecular weight polyethylene having a molecular weight of 1,100,000 to 1,800,000 or a high molecular weight polyethylene having a molecular weight of 30,000 to 400,000, Lt; / RTI >
In the embodiment of the present invention, the biaxial stretching step (S600) of the porous support may be 60 to 100% stretching in both the transverse direction and the longitudinal direction at a temperature of 100 to 200 캜.
In an embodiment of the present invention, after the porous support is immersed in a solvent to remove paraffin oil (S700), the porous support is shrunk by 5 to 20% in each of the transverse and longitudinal directions and shrunk by 3 to 10% And a second stretching step (S710) of holding and heat setting the wafer.
In an embodiment of the present invention, the tensile strength of the prepared porous support may be 1000 to 2000 kgf / cm 2.
In an embodiment of the present invention, in the step of immersing the porous support in an anionic conductor solution or applying an anionic conductor solution to the porous support (S800)
The anion conductor solution may contain,
[Chemical Formula 1]
Having the structure of Formula 1,
Y is -, -CO-, -SO 2 - or -O-, Z and D are to be equal to or different from each other -, -O- or -S-, C is -, -C (CH 3) 2 - Or -C (CF 3 ) 2 -, R 1 is H or -CH 2 N + R 2 R 3 R 4 and R 2 , R 3 , R 4 are the same or different and are -CH 3 , -CH 2 CH 3 , - (CH 2 ) 2 CH 3 , -CH 2 NH 2 , - (CH 2 ) 2 NH 2 Or - (CH 2 ) 3 NH (CH 3 ) Cl, x and y are arbitrary repeating units, and x / (x + y) can be 0.001 to 1.
In an embodiment of the present invention, in the step of immersing the porous support in an anionic conductor solution or applying an anionic conductor solution to the porous support (S800)
The anion conductor solution may contain,
i) 4,4'-dichlorodiphenylsulfone, 4,4'-biphenol, K 2 CO 3 and NMP, and toluene are charged, and a monomer dissolving step (S810 ); ii) raising the temperature to 150 to 180 캜, refluxing with toluene for 3 to 6 hours to remove water as a reaction product (S820); iii) further increasing the temperature to 190 to 250 캜 to completely remove residual toluene from the dean-stark trap and reacting for 20 to 48 hours (S830); iv) diluting and filtering the reaction solution, pouring into water to precipitate and filter in the form of swollen fiber (S840); v) chloromethylating the copolymer by dissolving in 1,1,2,2-tetrachloroethane and drying (S850); and vi) amination of the chloromethylated polyarylene ether sulfone copolymer by dissolving it in dimethylacetamide (DMAc) at room temperature (S860).
In an embodiment of the present invention, the degree of amination of the copolymer obtained may be from 20 to 50%.
According to the embodiment of the present invention, physical strength can be ensured by biaxial stretching at a rate lower than the micropores formed on the polyolefin matrix and the stretching magnification of a conventional 100% PE resin film.
In addition, according to the embodiment of the present invention, the manufacturing cost is lower than that of a conventional perfluorosulfonic acid ion exchange membrane such as Nafion.
In addition, according to the embodiment of the present invention, the physical / chemical properties are relatively excellent because the inorganic filler is composed of a polyolefin-based organic / inorganic composite membrane which is inexpensive and uniformly dispersed in inorganic filler such as nanosilica particles. As a result, it has high mechanical strength (tensile strength, puncture strength) and acid resistance and refractory properties and maintains high effect even in long term stability. Also, the ion exchange effect by the anion conductor adsorbed on the porous support and the movement of the ions through the micropores can be freely controlled, and the pore size can be controlled to block the specific ions at a physical size, so that a high selective permeability can be expected.
It should be understood that the effects of the present invention are not limited to the above effects and include all effects that can be deduced from the detailed description of the present invention or the configuration of the invention described in the claims.
1 is a photograph of the porous support prepared in Comparative Example 1, in the method of producing a polymer electrolyte membrane.
2 is a photograph of an electrolyte membrane produced by an embodiment of the present invention.
3 is a SEM photograph of a porous support prepared according to an embodiment of the present invention.
4 is a more enlarged SEM image of a porous support made according to an embodiment of the present invention.
5 is a cross-sectional SEM photograph of a porous support prepared according to an embodiment of the present invention.
6 is a flowchart showing a method of manufacturing an ion exchange membrane according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.
Throughout the specification, when a part is referred to as being "connected" (connected, connected, coupled) with another part, it is not only the case where it is "directly connected" "Is included. Also, when an element is referred to as "comprising ", it means that it can include other elements, not excluding other elements unless specifically stated otherwise.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprises" or "having" and the like refer to the presence of stated features, integers, steps, operations, elements, components, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
The ion exchange membrane for water treatment according to one embodiment includes a polyolefin matrix (base material), a porous support including a nanoparticle inorganic filler dispersed in the polyolefin matrix, and an anion conductor adsorbed to the porous support. The ion exchange membrane may be formed to have a thickness of 10 to 100 mu m. Such an ion exchange membrane for water treatment can be applied, for example, as an ion exchange membrane for ED (Electrodialysis) and RED (Reverse Electrolysis), and has a low manufacturing cost and excellent mechanical properties and chemical stability.
Preferably, the porous support is prepared by biaxial stretching and has an air permeability of less than 70 to 180 seconds, a porosity of 40 to 80%, and a pore diameter of 0.1 to 50 占 퐉. The diameter of the pores may be adjusted to the size of the ions for which selective permeation is required.
The polyolefin membrane, which is the base material of the porous support, is selected from among high density polyethylene (HDPE), ultra high molecular weight polyethylene (UHMWPE), polypropylene (PP), and polymethylpentene In particular, the polyolefin membrane, which is the base material of the porous support, can be made of ultra high molecular weight polyethylene (UHMWPE) in an amount of 5-50% of the total weight of the porous support, high density polyethylene HDPE) in an amount of 5-20% based on the total weight and 5-20% based on the total weight of polypropylene.
In this case, the ultra high molecular weight polyethylene (UHMWPE) has a molecular weight of 100-500,000 and a dispersion degree (dispersion) of 3-6, and high density polyethylene (HDPE) has a weight average molecular weight of 30-70,000 Molecular weight and a degree of dispersion (degree of dispersion) of from 3 to 6, and the polypropylene preferably has a molecular weight of from 10 to 20,000 in weight average molecular weight and a degree of dispersion (dispersity) of from 3 to 6.
When the ultrahigh molecular weight polyethylene (UHMWPE) or the high density polyethylene resin and the polypropylene resin are melt-kneaded in the extruder (Mixing at Melt State), a small amount of compatibilizer can be added. For example, a plasticizer, a processing agent, or an antioxidant may be added. In particular, a plasticizer or a processability-improving agent may be added to each of high-density polyethylene, polypropylene, and polymethylpentene resin to improve compatibility It is preferable that it is composed of an ethylene oligomer-based material.
Nanoparticles, inorganic filler can be applied to a silica (SiO 2), TiO 2, Al 2 O 3, zeolite (zeolite), AlOOH, BaTiO2, talc (Talk), Al (OH) 3, CaCO 3 at least one selected from and , Preferably 10 nm to 6 탆, and hydrophilized surface-treated nanomaterials, and more preferably the spherical particle size is 50 nm-1 탆. The addition ratio of the surface-treated nanoparticle inorganic filler is preferably 10 to 50% by weight based on the total weight of the entire porous support. If the inorganic filler is added in an amount of 50% or more based on the total weight of the nanoparticle, the mechanical strength of the porous support decreases. If less than 10% of the inorganic filler is added, the inorganic filler does not work.
Hydrophobic surface treatment Nanoparticle silica (SiO 2 ) has various sizes and shapes depending on the production process. In the present invention, as shown in the SEM image, the spherical type is most suitable. According to such a sol-gel synthesis method, it is possible to produce nano-sized particles having a small average particle size and a narrow particle size distribution.
In addition, it is preferable that silica (SiO 2 ) is coated with hydrophobic (linear hydrocarbon) molecules on its surface. Since the silica itself has a hydrophilic property, it can be seen that a nanoparticle spherical type silica coated with a straight chain hydrocarbon molecule is suitable for improving compatibility with a polyolefin resin originally hydrophobic.
That is, the nanoparticle inorganic filler is spherical nanosilica having a size of 10 nm to 600 nm and preferably has an ethylene surface treatment. At this time, the nanoparticle inorganic filler is preferably contained in an amount of 10 to 50 wt% based on the total weight of the ion exchange membrane for water treatment. Nanoparticle inorganic filler has relatively good physical / chemical properties and thus has high mechanical strength (tensile strength, puncture strength) and acid resistance and fire resistance, so that it can maintain high effect even in long term operation .
The anionic conductor may have the following chemical structure.
Wherein A and A 'are one selected from -S-, -SO 2 -, -NH-, -C (CH 3 ) 2 - and -C = O-, B is -O-, -SO 2 - , -C = O-, or a -C (CF 3) 2, X is preferably a sodium or potassium, and k = n + mk, n / (n + m) is 0.001 to 1.
The polymer represented by the general formula (1) has an intrinsic viscosity of not less than 0.1 as measured on NMP (N-methyl-α-pyrrolidinone) and is present in the range of not less than 0.8 and not more than 2.5 as measured on NMP Can be used.
In one embodiment, the anionic conductor solution may be one comprising 10 to 30% by weight of the polymer having an anion-exchange group represented by the general formula (1) in the whole solution.
The anion conductors include, for example, aminated polyarylene ether (PAES), aminated polyether ketone (PEK), aminated polyether ether ketone (PEEK), aminated polyether sulfone (PES), aminated polyether sulfone (PPE) polyphenylene sulfide) or a mixture of two or more of them may be applied.
6 is a flowchart illustrating a method of manufacturing an ion exchange membrane for water treatment according to an embodiment of the present invention.
Referring to FIG. 6, a method for preparing an ion exchange membrane for water treatment includes preparing a polyolefin matrix and a nanoparticle inorganic filler (S100), mixing the polyolefin matrix and nanoparticle inorganic filler with a paraffin oil (S200); A step of removing fine bubbles by vacuum defoaming (S300); A melt-kneading and discharging step (S400) at 150-300 占 폚; (S500) forming a melt-kneaded discharge product from a casting roll at 50-100 DEG C as a porous support; Biaxially stretching the porous support (S600); Immersing the porous support in a solvent to remove paraffin oil (S700); (S800) of immersing the porous support in an anionic conductor solution or by impregnating the porous support with an anionic conductor by applying an anionic conductor solution to the base sheet.
In the polyolefin matrix and nanoparticle inorganic filler preparing step (S100), the nanoparticle inorganic filler is spherical nanosilica having a size of 10 nm to 600 nm and the surface is preferably treated with ethylene.
In the step (S100) of preparing the polyolefin matrix and the nanoparticle inorganic filler, the polyolefin matrix is preferably an ultra-high molecular weight polyethylene having a molecular weight of 1,100,000 to 1,800,000, a high molecular weight polyethylene having a molecular weight of 30,000,000 or a mixture thereof.
In addition, it is preferable that the step of biaxially stretching the porous support (S600) is 80-150% stretching in both the transverse direction and the longitudinal direction at a temperature of 100-200 占 폚.
In order to obtain higher mechanical properties, the porous support is immersed in a solvent to remove paraffin oil (S700). After the stretching, 5-20% stretching is performed in each of the transverse and longitudinal directions, followed by 3-10% shrinkage after 20-120 seconds And a second elongating step (s710) for heat setting (heat setting).
The step S800 of immersing the porous support in the anion conductor solution or applying the anion conductor solution to the porous support may include an anion conductor solution such as aminated PAES, aminated PEK, aminated PEEK, polyether ether ketone, , aminated PS (polysulfone), aminated PES (polyether sulfone), aminated PPO (polyphenylene oxide) and aminated PPS (polyphenylene sulfide), and the mixture is stirred at 80 to 150 ° C. for 30 minutes to 2 hours (S810); Raising the temperature to 150 to 180 캜, refluxing with toluene for 3 to 6 hours to remove water as a reaction product (S820); Further increasing the temperature to 190 to 250 캜 to completely remove residual toluene from the dean-stark trap and reacting for 20 to 48 hours (S830); The reaction solution is diluted and filtered, and then poured into water to precipitate and filter in the form of swollen fiber (S840); 1,1,2,2-tetrachloroethane to chloromethylate the copolymer (S850); And (S860) amination of the chloromethylated polyarylene ether sulfone copolymer by dissolving it in dimethylacetamide (DMAc) at room temperature.
The degree of amination of the porous support prepared in this way is 20 to 50%, and the tensile strength is 1000 to 2000 kgf / cm < 2 >.
The method for producing the thus-configured ion exchange membrane will be described in more detail with reference to the following examples.
[Example]
1. Example
1-1. Porous support fabrication
Spherical nano silica having an average particle diameter of 20% by weight and a kinematic viscosity of 40 cSt (based on 40 ° C) 65% of liquid paraffin oil, 20% by weight of ultra high molecular weight polyethylene (Mw = 1.5 million), high molecular weight polyethylene By weight).
Hydrocarbon surface treated nanosilica particles were mixed in liquid paraffin oil at a ratio of 10 to 50% and the nanosilica particles were uniformly dispersed using a high speed mixing mixer.
After the vacuum defoaming process, microbubbles formed during the mixing process were removed. Kneaded and discharged at a temperature of 190 to 230 캜 using a twin screw extruder equipped with a T-die having a width of 350 mm. At this time, the feed content was controlled so that the inorganic filler content was 51.4% based on the weight of the final porous support.
The melt-kneaded material extruded through the T-die was cooled and solidified at room temperature through a casting roll at 60 DEG C, and the thickness of the sheet was adjusted to 1 to 2 mm.
Next, the extruded porous support was stretched to 100% in the transverse direction and 100% in the transverse direction using a biaxial stretching machine heated to 120 ° C to produce a film.
Thereafter, the stretched film was immersed in methylene chloride at 40 DEG C for 1 hour to remove the liquid paraffin oil.
The residue was then dried at room temperature to remove residual solvent. Thereafter, the film was stretched 5% in the transverse direction through a biaxial stretching machine and shrunk 5% in the transverse direction, stretched 10% in the longitudinal direction, shrunk 5%, and held for 30 seconds.
1-2. Preparation of Aminate Polyarylene Ether Sulfone Copolymer
A gas inlet, a thermometer, a Dean-Stark trap, a condenser and a stirrer were installed in a 100 ml round-bottom flask equipped with a stirrer, and air and impurities were removed for a few minutes in a nitrogen atmosphere. Then, 4,4'-dichlorodiphenylsulfone , 3.7242 g of 4'-biphenol (hereinafter referred to as "BP"), 3.9301 g of disulfonated dichlorodiphenylsulfone, 3.1787 g of K2CO3 and 44.4 ml of NMP, 22.2 ml of toluene (2 P / And the monomer was dissolved while stirring at 80 DEG C or higher for 1 hour.
Thereafter, the temperature of the reaction solution was raised to 160 ° C., refluxed with toluene for 4 hours to remove water as a reaction product, and then the temperature was raised to 190 ° C. to completely remove the residual toluene from the Dean-Stark trap, . When the reaction was completed, the reaction solution was diluted with NMP and filtered, and then poured into water to precipitate in the form of swollen fiber and filtered. Thereafter, the obtained reaction product was dried in a vacuum dryer at 120 캜 for 24 hours to obtain a polymer polymer.
100 g of the obtained polymer was placed in a mechanical stirrer, a gas inlet, a condenser and a thermostatic chamber for temperature setting, and then put into a 1 L four-necked flask. Thereafter, the polymer was sufficiently dissolved so as to be 12.8 wt% (wt.%) Based on 425.8 mL of 1,1,2,2-tetracyloethane (TEC, 1,1,2,2-tetrachloroethane). 8.233 g of the reaction catalyst ZnCl 2 was added to the constant temperature water bath at 40 ° C, stirred for 30 minutes, and 103.0 mL of chloromethyl methyl ether (CMME) was added thereto through a dropping funnel.
The amount of the chloromethylmelyl ether added was calculated by multiplying the mole number of CMME reacted per unit molar amount by 5 times.
The reaction was stirred for 4 hours while inert gas was injected through the gas inlet. The reaction product was filtered and precipitated in an excess amount of methanol. The precipitated chloromethylated polyethylene sulfone was pulverized and washed several times with ethanol and deionized water.
The washed chloromethylated polyethylene sulfone was dried in a vacuum oven at 90 DEG C for at least 12 hours.
200 g of the prepared chloromethylated polyether sulfone was placed in a 2 L 4 flask equipped with a mechanical stirrer and dissolved in 1489.4 ml of dimethylacetamide (DMAc, N, N-dimethylacetamide) at 12.5 wt% (wt.%). When 366 mL of trimethylamine was added dropwise to the reactor using a dropping funnel, the amount of the input was 4 times or more the molar amount of trimethylamine (TMEA) reacted per mol of the chloromethylated polyether sulfone repeating unit, and the reaction was carried out for 12 hours to obtain an anion conductor solution .
1-3. The prepared aminated polyarylene ether sulfone (APAES) copolymer solution was applied to a porous support and then uniformly impregnated through a reduction / pressure process to prepare an electrolyte membrane.
2. Comparative Example 1
The commercialized Neosepta (trade name) cation exchange membrane (CMX) was washed with deionized water and the electrolyte membrane was evaluated using the method described above.
3. Comparative Example 2
The commercially available Neosepta (trade name) anion exchange membrane (AMX) was washed with deionized water and the electrolyte membrane was evaluated using the measurement method described above.
4. Comparative Example 3
The ion conductor prepared in the examples was uniformly impregnated with the ion conductor in the same manner as in the example of the embodiment, except for the silica particles, to prepare an electrolyte membrane.
[Test Measurement Method]
1. Ventilation
Prepare the sample at 30mm * 30mm and measure the time that 100ml air passes through TOYOSEIKI airflow meter.
2. Tensile strength
The porous support sample is cut in the MD and TD directions to conform to the specimen shape of the ASTM D standard. Bite the specimen to a jig on a universal tensile testing machine (UTM), and pull it at a constant speed to measure the stress (N) applied until fracture occurs.
(탆)
(Permeability)
(sec)
Break Strength
(kgf / cm²)
3. Porosity (%)
The porous support sample film is cut into a predetermined size, and the weight is measured with an electronic scale. Density is measured using a density gradient method in the absence of pores (eg after cooling after melting). Then, the theoretical weight of the film weight and the cut size is calculated by the measured density value, and then the porosity is calculated.
4. Puncture Strength
Prepare a porous support sample of 100 mm * 50 mm. Measure the force at the time when the porous support sample is pierced by applying force with a stick by using a KATOTECH Co.'s pendulum strength meter.
5. Measurement of water absorption rate
In order to measure the water absorption rate of the electrolyte membrane prepared in the Examples and Comparative Examples, the electrolyte membrane was washed several times with deionized water, and the washed polymer electrolyte membrane was immersed in deionized water for 24 hours, And the weight was measured (W wet ). Subsequently, the same membrane was again dried in a vacuum dryer at 120 ° C for 24 hours and then weighed again (W dry ). The water absorption rate was calculated by the following formula (1).
[Equation 1]
Water uptake (%) = [(W wet -W dry ) / W dry ] x 100
6. Measurement of dimensional stability
The dimensional stability was measured in the same manner as the water absorption rate measurement method, but instead of weighing, the area change of the membrane was measured and then calculated by the following equation (2).
&Quot; (2) "
Dimensional change ratio (%) = [(membrane area wet-membrane area dry) / membrane area dry] x 100
7. Ion conductivity measurement
The ionic conductivity of the nanocomposite electrolyte membranes prepared in Examples and Comparative Examples was measured using a measuring instrument (VSP-300 Impedance / Gain-Phase analyzer, Neoscience Co., Ltd.). At this time, the impedance spectrum was recorded from 10 MHz to 10 Hz, and the ion conductivity was calculated by the following equation (3).
&Quot; (3) "
Ion conductivity (S / cm); ? = (1 / R) x (L / A)
(Where R is the measurement resistance (?), L is the length (cm) between the measurement electrodes, and A is the cross-sectional area (cm 2) of the electrolyte membrane produced.
(meq./g)
(탆)
(mS / cm)
(W cm 2 )
No.
8. Molecular weight measurement
In order to measure the molecular weight of polyethylene, it was dissolved in 1,2,4-trichlorobenzene for at least 8 hours and flowed at a rate of 0.92 ml / min.
Gel Permeation Chromatography (GPC) was performed using CPCV 2000 from Waters.
Number-average molecular weight (Mn)
Weight-average molecular weight (Mw)
Hi: The detector signal height at the baseline of the retention volume (Vi)
Mi; The molecular weight of the polymer fraction at the retention volume (Vi)
n: number of data
As shown in Table 2, the water-treating ion exchange membrane according to the present invention showed excellent physical properties having a high ion conductivity (6.343 mS / cm) even at a low film thickness (1.198 W cm 2).
That is, the ion exchange membrane for water treatment according to the embodiment of the present invention is less expensive than the fluorine ion exchange membrane such as the conventional Nafion. In addition, the physical and chemical properties are relatively excellent because they are composed of a polyolefin-based organic / inorganic composite membrane in which inorganic pellets such as nano-silica particles are uniformly dispersed while being inexpensive. With such a constitution, it has high mechanical strength (tensile strength, puncture strength) and acid resistance and refractory characteristics, and maintains high effect even in long term stability. Also, the ion exchange effect by the anion conductor adsorbed on the porous support and the movement of the ions through the micropores can be freely controlled, and the pore size can be controlled to block the specific ions at a physical size, so that a high selective permeability can be expected.
It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.
The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.
Claims (16)
A porous support comprising a polyolefin matrix (base material), a nanoparticle inorganic filler dispersed in the polyolefin matrix, and paraffin oil;
An anionic conductor impregnated in the porous support;
Lt; / RTI >
Wherein the nanoparticle inorganic filler is spherical and nanoparticle silica (SiO 2 ) is coated on the surface thereof with hydrophobic chain hydrocarbon molecules.
Wherein the polyolefin matrix is an ultrahigh molecular weight polyethylene having a molecular weight of from 1,000,000 to 5,000,000 or a high molecular weight polyethylene having a molecular weight of from 30,000 to 700,000, or a mixture thereof.
Wherein the porous support has an air permeability of less than 10 to 150 seconds, a porosity of 40 to 80%, and a pore diameter of 0.1 to 50 占 퐉.
Wherein the nanoparticle inorganic filler is contained in an amount of 10 to 50% by weight based on the total weight of the ion exchange membrane composition for water treatment.
[Chemical Formula 1]
Having the structure of Formula 1,
Y is -, -CO-, -SO 2 - or -O-, Z and D are to be equal to or different from each other -, -O- or -S-, C is -, -C (CH 3) 2 - Or -C (CF 3 ) 2 -, R 1 is H or -CH 2 N + R 2 R 3 R 4 and R 2 , R 3 , R 4 are the same or different and are -CH 3 , -CH 2 CH 3 , - (CH 2 ) 2 CH 3 , -CH 2 NH 2 , - (CH 2 ) 2 NH 2 Or (CH 2 ) 3 NH (CH 3 ) Cl, x and y are arbitrary repeating units, and x / (x + y) is 0.001 to 1. The ion exchange membrane for water treatment using the porous support .
The anion conductor may be selected from the group consisting of aminated PAES (polyarylene ether sulfone), aminated polyether ketone (PEK), aminated polyether ether ketone (PEEK), aminated polyether sulfone (PES), aminated polyether sulfone (PPE) polyphenylene sulfide) or a mixture of two or more thereof.
I) preparing a polyolefin matrix and nanoparticle inorganic filler;
Ii) mixing the polyolefin matrix and the nanoparticle inorganic filler with paraffin oil;
Iii) a step of removing microbubbles by vacuum degassing;
Iv) melt-kneading and discharging at 150 to 300 캜;
(V) forming a porous support on the casting roll at a temperature of 50 to 100 캜 by using the melt-kneaded discharge product produced in the discharging step;
(Vi) biaxially stretching the porous support;
(D) immersing the porous support in a solvent to remove paraffin oil;
(D) immersing the porous support in an anionic conductor solution or impregnating the porous support with an anionic conductor by applying an anionic conductor solution to the porous support;
Lt; / RTI >
Wherein the nanoparticle inorganic filler is a spherical nanoparticle silica (SiO 2 ) coated with a hydrophobic chain hydrocarbon molecule on the surface of the nanoparticle inorganic filler in the step (i).
Wherein the polyolefin matrix is an ultrahigh molecular weight polyethylene having a molecular weight of 1,100,000 to 1,800,000 or a high molecular weight polyethylene having a molecular weight of 3,000,000 to 4,000,000 or a mixture thereof.
Wherein the step (vi) comprises stretching 60 to 100% in both the transverse direction and the longitudinal direction at a temperature of 100 to 200 ° C.
Further comprising a second stretching step of stretching 5 to 20% in each of the transverse and longitudinal directions after the step (iii) and then shrinking 3 to 10% after holding for 20 to 120 seconds to heat set A method for manufacturing an ion exchange membrane for water treatment using a porous support.
Wherein the porous support has a tensile strength of 1000 to 2000 kgf / cm < 2 >.
In the step (e)
The anion conductor solution may contain,
[Chemical Formula 1]
Having the structure of Formula 1,
Y is -, -CO-, -SO 2 - or -O-, Z and D are to be equal to or different from each other -, -O- or -S-, C is -, -C (CH 3) 2 - Or -C (CF 3 ) 2 -, R 1 is H or -CH 2 N + R 2 R 3 R 4 and R 2 , R 3 , R 4 are the same or different and are -CH 3 , -CH 2 CH 3 , - (CH 2 ) 2 CH 3 , -CH 2 NH 2 , - (CH 2 ) 2 NH 2 Or (CH 2 ) 3 NH (CH 3 ) Cl, x and y are arbitrary repeating units, and x / (x + y) is 0.001 to 1. The ion exchange membrane for water treatment using the porous support ≪ / RTI >
In the step (e)
The anion conductor solution may contain,
1) 4,4'-dichlorodiphenylsulfone, 4,4'-biphenol, disulfonated dichlorodiphenylsulfone, K 2 CO 3 and NMP, and toluene are charged and heated at 80 to 150 ° C. for 30 minutes to 2 hours Stirring monomer dissolving step;
2) raising the temperature to 150 to 180 캜 and refluxing with toluene for 3 to 6 hours to remove water as a reaction product;
3) further increasing the temperature to 190 to 250 캜 to completely remove residual toluene from the dean-stark trap and reacting for 20 to 48 hours;
4) The reaction solution is diluted and filtered, then poured into water to precipitate in the form of swollen fiber and filtrate;
5) dissolving in 1,1,2,2-tetrachloroethane to chloromethylate the copolymer and drying;
6) Aminating the chloromethylated polyarylene ether sulfone copolymer by dissolving it in dimethylacetamide (DMAc) at room temperature;
Wherein the porous support comprises a porous support.
Wherein the degree of amination of the copolymer obtained in the step 6) is 20 to 50%.
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| KR102028535B1 (en) | 2017-03-31 | 2019-10-04 | 코오롱인더스트리 주식회사 | Ion exchanging membrane, method for manufacturing the same and energy storage system comprising the same |
| CN108752681B (en) * | 2018-04-10 | 2020-09-25 | 衢州蓝然新材料有限公司 | Polyethylene/polystyrene composite film roll with mesh cloth support and manufacturing method thereof |
| JP7020654B2 (en) * | 2019-03-08 | 2022-02-16 | ダブリュー－スコープ コリア カンパニー，リミテッド | Anion exchange membrane and its manufacturing method |
| KR102241065B1 (en) * | 2019-03-08 | 2021-04-19 | 더블유스코프코리아 주식회사 | An anion-exchange membrane and a method for manufacturing the same |
| KR102260082B1 (en) * | 2019-06-04 | 2021-06-03 | 경상국립대학교산학협력단 | Anion-exchange composite membrane, preparation method thereof and fuel cell comprising the same |
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| JP2003132909A (en) | 2001-10-29 | 2003-05-09 | Tokuyama Corp | Ion exchange resin film |
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| KR101144975B1 (en) | 2010-04-21 | 2012-05-11 | 충남대학교산학협력단 | Ion exchange membrane comprising copolymer containing ion exchange group |
| KR101284009B1 (en) * | 2010-11-26 | 2013-07-15 | 한국화학연구원 | Manufacturing Method of Capacitive Deionization Electrode |
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