KR101688625B1 - Ionomer Nanoparticles Dispersion - Google Patents

Ionomer Nanoparticles Dispersion Download PDF

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KR101688625B1
KR101688625B1 KR1020150059996A KR20150059996A KR101688625B1 KR 101688625 B1 KR101688625 B1 KR 101688625B1 KR 1020150059996 A KR1020150059996 A KR 1020150059996A KR 20150059996 A KR20150059996 A KR 20150059996A KR 101688625 B1 KR101688625 B1 KR 101688625B1
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ionomer
dispersion
pressure
solvent
group
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KR1020150059996A
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Korean (ko)
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KR20160128134A (en
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이창현
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단국대학교 천안캠퍼스 산학협력단
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Priority to KR1020150059996A priority Critical patent/KR101688625B1/en
Priority to PCT/KR2016/004141 priority patent/WO2016175502A1/en
Priority to US15/570,334 priority patent/US10717861B2/en
Priority to CN201680038278.5A priority patent/CN107820502B/en
Priority to CN202010488746.7A priority patent/CN111704731B/en
Publication of KR20160128134A publication Critical patent/KR20160128134A/en
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Publication of KR101688625B1 publication Critical patent/KR101688625B1/en

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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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C08L23/0876—Neutralised polymers, i.e. ionomers
    • 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

The present invention relates to a dispersion of ionomeric nanoparticles in which a perfluorinated ionomer having an ion conductive functional group is nano-dispersed in a mixed solvent containing water and an alcohol.
Since the ionomer nanoparticle dispersion according to the present invention has a high content of the azeotropic mixture in the liquid phase, it is easy to remove the solvent, so that the product can be easily molded using the dispersion and the manufacturing cost can be reduced. Perfluorinated ionomers having various salt forms thereof are nano-dispersed with a narrow molecular weight distribution, thereby improving the uniformity of the product.

Description

Ionomer Nanoparticles Dispersion < RTI ID = 0.0 >

The present invention relates to a dispersion of ionomeric nano-particles in which a perfluorocompound ionomer having various ion-conductive functional groups and various salt forms thereof is nano-dispersed in a mixed solvent containing water and an alcohol.

Polymer electrolyte membrane fuel cells (PEMFCs) are based on the polymer electrolyte membrane (PEM), which selectively permeates only hydrogen ions (protons, H + ). The electrochemical catalytic reactions of hydrogen gas -catalytic reaction to generate high-efficiency energy.

Perfluorinated sulfonic acid ionomers (PFSA) such as Nafion manufactured by DuPont are examples of representative materials of the polymer electrolyte membrane and the catalyst binder of the polymer electrolyte fuel cell.

The perfluorinated sulfonated ionomer (PFSA) is known to have a high hydrogen ion conductivity and excellent chemical stability. However, when operated in a dry state, the hydrogen ion conductivity rapidly drops due to the spontaneous evaporation of water and the chemical / Chemical degradation has a fatal weak point. In order to solve this problem, the concept introduced is a pore-filling membrane (PFM) impregnated with a perovskite / partial fluorine / hydrocarbon-based proton ion conductive ionomer on a porous porous support having excellent chemical durability.

For effective PFM preparation, the ionomer should be completely dissolved in the solvent or prepared in a dispersed state. In this case, it is preferable to use water and an alcohol co-solvent instead of an organic solvent in order to achieve environmental problems, ease of molding, and complete removal of the solvent when removing the solvent for film formation.

The perfluorinated sulfonated ionomer used in the production of the polymer electrolyte membrane, the catalyst binder and the PFM is prepared by emulsion polymerization and used as an emulsion state of water and isopropyl alcohol co-solvent phase.

So far, various attempts have been made to prepare dispersions of perfluorinated, partially fluorinated, hydrocarbon-based ionomer nanoparticles. J. Power Sources 2006, 163, 56, Electrochim. Acta. 2007, 52, 4916, Electrochem. Soc. 2007, 154, B739, J. Power Sources 2007, 169, 271, it was not possible to dissolve a partially fluorinated or hydrocarbon solid state ionomer in water or alcohol unless the degree of hydrophilization of the ionomer was increased. Also, when ionomer having high hydrophilicity is used as a polymer electrolyte membrane (PEM) or a catalyst binder, it dissolves / leaks under high temperature and humid conditions during fuel cell operation, causing delamination of the polymer electrolyte membrane (PEM) And the electrochemical performance is rapidly reduced.

On the other hand, when an organic solvent is used instead of water or an alcohol, or when some organic solvent is introduced into a water and an alcohol co-solvent, the introduced organic solvent remains through strong secondary bonding with the ion conductive functional group of the ionomer.

To date, no method has been reported to produce dispersions of hydrocarbon-based and partially fluorinated ionomer nanoparticles that are effectively nano-dispersed in mixed solvents including water and alcohols. (PFSA) ionomer emulsion, which has completely different structure and chemical properties, is used instead of a homo-ionomer for the catalyst binder in the electrode manufacturing process, so that the interface problem between the polymer electrolyte membrane (PEM) and the electrode layer and the short- Causing characteristic problems.

Solid phase perfluorinated sulfonated ionomers (PFSA) also have common solubility problems with water and alcohol solvents or co-solvents. Anal. Chem. As reported in 1982, 54, 1639, an aqueous ionomer solution can be prepared by heating a perfluorinated sulfonated ionomer (PFSA) having a relatively high degree of hydrophilicity (e.g., EW 970) in an aqueous solution, And it was impossible to operate the fuel cell for a long time due to weak hydration stability when the fuel cell electrode layer was introduced.

As a method for solving this problem, a method of producing a perfluorinated sulfonated ionomer (PFSA) emulsion from a fluorine monomer through an aqueous emulsion polymerization as in US 2005/0096442, US 7,071,271 has been developed and used in commercial processes at present . This method is effective for producing a perfluorinated sulfonated ionomer (PFSA) aqueous emulsion having a relatively stable hydrophilicity under water and alcohol co-solvent conditions. However, due to the inherent synthetic characteristics of emulsion polymerization, it has a limitation in obtaining high molecular weight and has a broad molecular weight distribution (PDI). Also, due to limited monomer conditions and synthesis processes for emulsion polymerization, only the perfluorinated sulfonated ionomer (PFSA) in the form of sulfonic acid (-SO 3 H) having thermal stability below 100 ° C can be obtained as a reactant. In addition, due to the difficulty of controlling the co-solvent ratio, it shows the limit of ionomer concentration and viscosity control, revealing the compatibility with the organic electrolyte membrane (PEM) and the organic and inorganic materials introduced for electrode production, ) Indicating difficulty in reforming.

US 2005/0096442 US 7,071,271

J. Power Sources 2006, 163, 56 Electrochim. Acta. 2007, 52, 4916 Electrochem. Soc. 2007, 154, B739 J. Power Sources 2007, 169, 271

SUMMARY OF THE INVENTION The present invention is directed to a homogeneous dispersion of homogenous nanoparticles in which a perfluorinated ionomer having various ion-conducting functional groups and various salt forms thereof is nano-dispersed in a continuous phase containing water and an alcohol having a high content of an azeotropic mixture .

In order to solve the above problems,

A continuous phase comprising water and an alcohol,

Based ionomer nanoparticles dispersed in the continuous phase and insoluble in both water and alcohol,

Wherein the content of the azeotropic mixture in the continuous phase is 20 wt% or more.

The ionomer nanoparticle dispersion according to the present invention has a high content of an azeotropic mixture in a liquid phase and is easy to remove a solvent, so that it is easy to mold a product using the dispersion and the manufacturing cost can be reduced. In addition, the dispersion is nano-dispersed with a narrow molecular weight distribution of perfluorinated ionomers having various ion-conducting functional groups and various salt forms thereof, thereby improving the uniformity of the product.

Also, the ionomer constituting the nanoparticles contained in the dispersion has a high molecular weight, so that the polymer electrolyte membrane prepared using the nanoparticles has increased thermal stability and mechanical strength as compared with membranes prepared using a commercial ionomer emulsion.

In addition, since perfluorinated ionomers having various types of salts having high heat resistance (-SO 3 - M + ; eg, M = Li + , Na + , K + etc.) are uniformly nano-dispersed in the dispersion, When a polymer electrolyte membrane is prepared, a salt form (eg, -SO 3 - Na + ) is used to avoid thermal decomposition occurring when a commercial dispersion is used, which is limited to ionomers having a sulfonic acid group (-SO 3 - H + It is possible to omit the conversion step (NaCl solution treatment), the step of removing excessively introduced salt, and the three step step of drying step, thereby shortening the overall manufacturing process and reducing the manufacturing cost.

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

The present invention provides a homogeneous dispersion of homogeneous nanoparticles in which perfluorinated ionomer nanoparticles having various ion-conducting functional groups and various salt forms thereof having a very low solubility in a continuous phase containing water and alcohol are uniformly dispersed .

Overpayment Ionomer  Nanoparticle

In the present invention, an ionomer refers to an ion conductive polymer having a fixed ion (mainly an anion) attached to a side chain of a polymer through a covalent bond.

Preferably, the ionomer has at least one ion-conducting functional group selected from the group consisting of a sulfonic acid, a sulfonic acid salt, a carboxylic acid, a carboxylic acid salt, and a fluorosulfonyl.

At this time, the sulfonic acid salt may be selected from the group consisting of lithium sulfonate, sodium sulfonate, potassium sulfonate, magnesium sulfonate, calcium sulfonate, ammonium sulfonate, and alkylammonium sulfonate.

The carboxylic acid salt may be at least one selected from the group consisting of lithium carboxylate, sodium carboxylate, potassium carboxylate, and alkylammonium carboxylate.

Preferred examples of the perfluorinated ionomer include poly (perfluorosulfonic acid), poly (perfluorocarboxylic acid), copolymers of tetrafluoroethylene and fluorovinyl ether containing a sulfonic acid group, and combinations thereof, Flemion, Ashiflex, 3M Ionomer, Dow Ionomer, Solvay Ionomer, Sumitomo 3M Ionomer, and mixtures thereof.

The ionomer nanoparticles preferably have an average particle size of 0.01 nm to 600 nm, and the content of the ionomer nanoparticles is preferably 0.01 to 30% by weight of the total dispersion.

The ionomer constituting the nanoparticles of the present invention has a polydispersity index (Mw / Mn, PDI) of 1.0 to 2.5. In the dispersion of the present invention, when the molecular weight distribution of the ionomer is less than 1.0, it is difficult to achieve because it is less than the theoretical limit that can be achieved through well-controlled polymer synthesis, and when it exceeds 2.5, mechanical properties are deteriorated.

The nanoparticles of the present invention can be used in the form of nanoparticles of TiO 2 , SiO 2 , Al 2 O 3 , ZrO 2 , tetraethoxysilane (TEOS), montmorillonite, mordenite, zirconium phosphate (ZrP) And one kind of additive selected from the group consisting of stearic acid, silico tungstic acid, phosphomolybdic acid, silicomolybdic acid, fluorinated aliphatic hydrocarbons including hydrophilic functional groups, and mixtures thereof.

The aliphatic hydrocarbon of the fluorinated aliphatic hydrocarbon containing hydrophilic functional groups may include linear or branched C4 to C30 alkyl groups or linear or branched C4 to C30 alkylene oxides.

The fluorinated aliphatic hydrocarbons containing the hydrophilic functional group may be substituted at one end by -H, -NH 4 + , -SO 3 H, -SO 3 NH 4 , -P (O) (ONH 4 ) ONH 4 ) 2, and combinations thereof, and has an amphiphilic structure having both hydrophobicity and hydrophilicity simultaneously.

The fluorinated aliphatic hydrocarbons containing such a hydrophilic functional group may be used directly or may be purchased commercially. As an example, the use of one member selected from the group consisting of Zonyl (Zonyl ®) system, 3M's nobek (Novec ®) system or mixtures thereof Company Du Pont. Specifically, the Zonyl-based dispersion agent, Zonyl ® TBS (RfCH 2 CH 2 SO 3 X (X = H or NH 4), Rf = F ( CF 2 CF 2) 3-8), Zonyl ® FSN (RfCH 2 CH the 2 O (CH 2 CH 2 0 ) xH)), Zonyl ® FSP (RfCH 2 CH 2 O) P (O) (ONH 4) 2 or the like can be used. Novec dispersants include Novec ® 4200 (Ammonium Fluoroalkylsulfonamide), Novec ® 4300 (Ammonium Fluoroalkylsulfonate), Novec ® 4430 (polymeric fluorochemical active) and Novec ® 4432 (polymeric fluorochemical actives).

Wherein the content of the additive is 0.001 to 15% by weight in the total dispersion.

The ionomer forming the nanoparticles has a number average molecular weight of 70,000 Da to 500,000 Da, and the viscosity of the electrolyte composition is 10 cP To 250 cP. It is possible to secure further improved mechanical properties in such a molecular weight range. When the number average molecular weight is less than 70,000 Da, the mechanical strength is weak and it is not suitable for polymer application. When the number average molecular weight exceeds 500,000 Da, the correlation between molecular weight and mechanical strength is more than the equilibrium condition. , The effect of increasing the molecular weight is weak and it is not economical.

Continuous phase

The continuous phase contains water and alcohol as the remainder excluding the nanoparticles in the whole dispersion. In this case, the volume ratio of water to alcohol is preferably from 17:83 to 75:25.

The alcohol can be used for an alcohol containing at least one hydroxyl group in the main chain having 1 to 10 carbon atoms. More preferably, an alcohol having at least one hydroxyl group bonded to the main chain having 1 to 7 carbon atoms can be used, but the present invention is not limited thereto.

Examples of the solvent include alcohols such as methanol, ethanol, 1-propanol, isopropyl alcohol, butanol, isobutanol, 2-butanol, tert-butanol, n- pentanol, isopentyl alcohol, Methylene-1-pentane, 2-methyl-1-pentanol, 2-methyl-1-pentanol, 2-methyl- Methyl-2-pentanol, 2-methyl-3-pentanol, 2-methyl-3-pentanol, 3-methyl Dimethyl-1-butanol, 2,3-dimethyl-1-butanol, 2-ethyl- Butanol, 1-butanol, 1-heptanol, 2-heptanol, 3-heptanol and 4-heptanol and mixtures thereof.

The continuous phase may further contain an organic solvent in addition to water and alcohol.

Preferred examples of the solvent include acetone, ethyl carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate, fluoroethylene carbonate, dimethylacetamide, dimethylsulfoxide, dimethylformamide, N-methylpyrrolidone, One species selected from the group is available. The content of the organic solvent may be 0.01 to 40% by weight of the total dispersion.

In the present invention, an azeotropic mixture of an alcohol or an alcohol-organic solvent and water is formed to lower the boiling point of the entire mixed solvent.

As used herein, the term 'azeotropic mixture' refers to a solution in which the composition ratio of the solution and the vapor is the same when boiling without changing the composition ratio at a constant temperature such as a pure liquid in a liquid having a specific composition ratio. The equilibrium temperature, which is the boiling point of the azeotropic mixture, is called the azeotropic point. The azeotropic state in which the ratio of the solution and the vapor are the same is changed by the pressure. The azeotropic point is the minimum value on the boiling point curve showing the relationship between the component ratio and the boiling point. It shows the maximum value.

The dispersion of the present invention has a high content of azeotropic mixture in the continuous phase. Preferably 20 wt.% Or more, more preferably 25 wt.% To 50 wt.% Of the continuous phase. When the content of the azeotropic mixture in the continuous phase is within the above range, the efficiency of removing the continuous phase, that is, the solvent, can be maximized. If the content of the azeotrope in the continuous phase is less than the above range, the evaporation rate of the solvent from the co-solvent is not faster than the evaporation rate from the general mixed solvent, which is not economically advantageous. Conversely, There is no meaning because it can not be done.

The ionomer nanoparticle dispersion of the present invention, as described above,

Preparing a mixed solvent of water and alcohol,

Adding the mixed solvent and the perfluorinated ionomer to the reactor, and reacting the mixture solvent in a supercritical condition to form ionomer nanoparticles

Lt; / RTI >

Each step will be described in detail below.

First, a mixed solvent of water and alcohol is prepared.

The alcohol is as described above.

In this case, the mixed solvent may further contain, in addition to water and alcohol, acetone, ethyl carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate, fluoroethylene carbonate, dimethylacetamide, dimethylsulfoxide, And an organic solvent selected from the group consisting of water, an organic solvent, a water-soluble organic solvent, a water-soluble organic solvent, and a mixture thereof.

Next, the mixed solvent and the perfluorinated ionomer are placed in the reactor, and the reaction is carried out under supercritical conditions to form ionomer nanoparticles.

The supercritical conditions include, but are not limited to, a temperature of at least 100 < 0 > C and a pressure of 20 psig. Preferably a temperature of 100 to 300 캜 and a pressure of 20 to 2000 psig.

In the present invention, the temperature and the pressure can be suitably adjusted according to the desired ionomer nanoparticle size and distribution.

When the temperature is less than 100 ° C or the reaction pressure is less than 20 psig, the size of the ionomer nanoparticles produced increases and the particle size distribution becomes wider. On the other hand, when the temperature exceeds 300 ° C or the pressure exceeds 2000 psig The economical efficiency is low because the high temperature and high pressure must be maintained.

In the present invention, the reaction time for producing the ionomer nanoparticles is 5 minutes to 24 hours. When the reaction time is less than the above range, the nanoparticles are large and the particle size distribution is widened. When the reaction time exceeds the above range, economical efficiency is low.

Under such supercritical conditions, the mixed solvent introduced into the reactor becomes a supercritical fluid state. Supercritical fluids are incompressible fluids that are at temperatures and pressures above the critical point and exhibit unique characteristics that are not present in conventional organic solvents. That is, supercritical fluids have excellent physical properties such as high density close to liquid, low viscosity close to gas, high diffusion coefficient, and very low surface tension. This supercritical fluid permeates between the ionomer chains to weaken the ionomer intermolecular / intramolecular interaction forces to form nanoparticles. In addition, the vapor alcohol content increases gradually while repeating evaporation and condensation of water and alcohol co-solvent at supercritical conditions. As a result, the composition becomes close to the azeotropic mixture composition at a constant temperature and a constant pressure, and the content of the azeotropic mixture in the condensation after the completion of the reaction is absolutely increased.

At this time, the perfluorinated ionomer to be fed into the reactor can be any shape, for example, a film, a plate, a pellet, a powder or a fiber.

After the supercritical condition is maintained for a predetermined time, the reaction is terminated when the pressure returns to the normal pressure. That is, at the conclusion of the reaction, various ion-conductive functional groups having very low solubility in a continuous phase including water and alcohol without any recovery step and the like, and fungi having uniformly dispersed perfluorocarbon ionomer nanoparticles having various salt forms thereof A homogeneous nanoparticle dispersion can be obtained.

The above-described dispersion of the present invention has the following advantages.

1. High average molecular weight and narrow molecular weight distribution of ionomers

Compared to commercial ionomer dispersions prepared by emulsion polymerization, ionomers have a higher molecular weight and a narrower molecular weight distribution.

2. Increasing the azeotropic mixture and viscosity

Due to the high molecular weight of the ionomer, it exhibits a high viscosity in the same composition. Also, the content of the azeotropic mixture in the continuous phase is high, so that the boiling point of the continuous phase is lowered and the solvent is easily removed.

3. Increased thermal stability, chemical stability and mechanical strength

Due to the increase in molecular weight and the increase in intermolecular or intramolecular hydrogen bonding force and van der Waals force, thermal stability, chemical stability and mechanical strength are increased compared with polymer electrolyte membranes prepared using commercial ionomer dispersions in the production of polymer electrolyte membranes.

4. Process shortening in manufacturing reinforced composite membrane and pure membrane

The commercial ionomer dispersion has a proton-type sulfonic acid (-SO 3 - H + ) group having EW = 1100 as a functional group, and when the membrane is formed by using the polymer, the solvent evaporates at a temperature lower than the glass transition temperature of the polymer, Mechanical strength is very low. Therefore, heat treatment at 200 ° C or higher must be performed to solve this problem. However, the proton-type sulfonic acid group is pyrolyzed at 100 ° C, and hydrogen ion conductivity is drastically reduced when heat treatment is performed after film formation. Therefore, in the membrane production process, the proton-type sulfonic acid is converted into a salt form (e.g., -SO 3 - Na + ) which is maintained at 300 ° C with heat resistance, a step of removing excessive salts, A further three-step process is required. However, if the various salt forms of the present invention are used in the ionomeric nanoparticle dispersion having an ion-conductive functional group, the above-mentioned additional step can be omitted.

5. Improved hydrogen ion conductivity

Since the dispersion of the present invention contains ionomer nanoparticles having various EW values, the ionomer having a low EW value can be used for the dispersion of a commercial ionomer, while the dispersion of the present invention has an EW value (e.g., 1100) of an ionomer. Can be improved.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided to further understand the present invention, and the present invention is not limited by the examples.

(Example 1)

5% by weight of dry Nafion 112 membrane having a water / isopropyl alcohol co-solvent (volume ratio of 25:75) and sulfonic acid (-SO 3 - H + ) as an ion conductive functional group was added in a high- And subjected to a supercritical reaction at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 2)

10% by weight of dry Nafion 112 membrane having a water / isopropyl alcohol co-solvent (volume ratio of 25:75) and sulfonic acid (-SO 3 - H + ) as an ion conductive functional group was added to the high- And subjected to a supercritical reaction at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 3)

20% by weight of dry Nafion 112 membrane having a water / isopropyl alcohol co-solvent (volume ratio of 57:43) and sulfonic acid (-SO 3 - H + ) as an ion conductive functional group was added to the high- And subjected to a supercritical reaction at 160 DEG C under a pressure of 500 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 4)

20% by weight of dry Nafion 112 membrane having a water / isopropyl alcohol co-solvent (volume ratio of 57:43) and sulfonic acid (-SO 3 - H + ) as an ion conductive functional group was added to the high- And subjected to a supercritical reaction at 160 DEG C under a pressure of 500 psig for 120 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 5)

20% by weight of dry Nafion 112 membrane having a water / isopropyl alcohol co-solvent (volume ratio of 57:43) and sulfonic acid (-SO 3 - H + ) as an ion conductive functional group was added to the high- And subjected to a supercritical reaction at 200 ° C under a pressure of 1900 psig for 1 day. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 6)

In a high-temperature and high-pressure reactor, a dry Nafion 112 membrane having a sulfonic acid sodium salt (-SO 3 - Na + ) as a water / isopropyl alcohol co-solvent (volume ratio 75:25) %, And subjected to a supercritical reaction at 120 ° C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 7)

A dry Nafion 112 powder having a sulfonic acid sodium salt (-SO 3 - Na + ) as a water / isopropyl alcohol co-solvent (volume ratio 75:25) and an ion conductive functional group of 1.5 wt% %, And subjected to a supercritical reaction at 120 ° C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 8)

Total 100% by weight of sodium acid in water / isopropyl alcohol co-solvent (volume ratio 50: 50) and the ion-conducting functional group such that the salt in the high-temperature high-pressure reactor (-SO 3 - Na +) dry Nafion 112 membrane having a weight of 1.5 %, And subjected to a supercritical reaction at 120 ° C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 9)

In a high-temperature and high-pressure reactor, 1.5 parts by weight of dry Nafion 112 membrane having a water / isopropyl alcohol co-solvent (volume ratio 17:83) and sulfonic acid sodium salt (-SO 3 - Na + %, And subjected to a supercritical reaction at 120 ° C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 10)

In a high-temperature and high-pressure reactor, a dry Nafion 112 powder having a form of sodium sulfonate (-SO 3 - Na + ) with a water / isopropyl alcohol co-solvent (50:50 by volume) and an ion- 1.5% by weight, and the mixture was subjected to a supercritical reaction at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 11)

1.5% by weight of dry Nafion 112 pellets having a water / isopropyl alcohol co-solvent (volume ratio 17:83) and a sulfonic acid sodium salt (-SO 3 - Na + ) as a conductive functional group, , And the supercritical reaction was carried out at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 12)

In a high temperature and high pressure reactor, dry Nafion 112 fibers (having a diameter of 17: 83) and sodium sulfonate (-SO 3 - Na + ) as an ion conductive functional group, having a water / isopropyl alcohol co- : 1 mm) 1.5% by weight, and the mixture was subjected to a supercritical reaction at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 13)

A dry Nafion 112 fiber (diameter: 0.5) having a water / isopropyl alcohol co-solvent (volume ratio 17:83) and sulfonic acid (-SO 3 - H + mm) 20% by weight, and the mixture was subjected to a supercritical reaction at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 14)

A dry Nafion 112 membrane having a water / isopentyl alcohol co-solvent (volume ratio 57:43) and sulfonic acid (-SO 3 - H + ) as an ion conductive functional group so that the total amount of the water / 20% by weight, and the mixture was subjected to a supercritical reaction at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 15)

A dry Nafion 112 membrane having a water / isopropyl alcohol / acetone co-solvent (60:20:20 by volume) and sulfonic acid (-SO 3 - H + ) as an ion conductive functional group was added in a high- 20% by weight, and the mixture was subjected to a supercritical reaction at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 16)

A dry Nafion 112 membrane having a water / isopropyl alcohol co-solvent (volume ratio of 57:43) and sulfonic acid (-SO 3 - H + ) as an ion conductive functional group so that the total amount of 100 wt% 20 wt% and Al 2 O 3 5 % By weight, and subjected to a supercritical reaction at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 17)

20% by weight of a dry Nafion 112 membrane having a water / isopropyl alcohol co-solvent (volume ratio 57:43) and sulfonic acid (-SO 3 - H + ) as an ion conductive functional group so as to make the total 100% 6 wt% of Zonyl TBS and 3 wt% of silica (Aerosil 812, hydrophobic silica) were added and subjected to a supercritical reaction at 120 캜 under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 18)

A high-temperature and high-pressure reactor, a total of 100% by weight is such that the water / isopropyl alcohol co-solvent (volume ratio 25: 75), ion-conducting functional group in the sulfonic acid (-SO 3 - H +) dry Nafion 112 membrane having a 5% by weight, Zonyl 12 weight% of silica (Aerosil 812, hydrophobic silica) and 3 weight% of silica (FSP ([F (CF 2 CF 2 ) 3-8 CH 2 CH 2 O] P (O) (ONH 4 ) 2 , density 1.15 g / , And the supercritical reaction was carried out at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 19)

5 wt% of a dry state plasmionic membrane having a water / 1-pentanol co-solvent (volume ratio of 25:75) and a carboxylic acid (-COO - H + ) as an ion conductive functional group was contained in a high- Was added, and supercritical reaction was carried out at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 20)

A dry Nafion 112 membrane having a water / 1-heptanol co-solvent (volume ratio 57:43) and sulfonic acid (-SO 3 - H + ) as an ion conductive functional group was added to the high- 20% by weight, and the mixture was subjected to a supercritical reaction at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 21)

5% by weight of a dry state polymer membrane having a water / isopropyl alcohol co-solvent (25:75 by volume) and a carboxylic acid (-COO - H + ) as an ion conductive functional group was added to a high temperature and high pressure reactor in an amount of 100% Supercritical reaction was carried out at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 22)

20% by weight of a dry state polymer membrane having a water / isopropyl alcohol co-solvent (volume ratio 57:43) and a carboxylic acid (-COO - H + ) as an ion conductive functional group was added in a high temperature and high pressure reactor, Supercritical reaction was carried out at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 23)

1.5% by weight of a dry state polymer membrane having a water / isopropyl alcohol co-solvent (volume ratio 75:25) and sodium carboxylate sodium salt (-COO - Na + ) as an ion conductive functional group was added in a high- And subjected to a supercritical reaction at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 24)

1.5% by weight of a dry state of plamion powder having a water / isopropyl alcohol co-solvent (75:25 by volume) and sodium carboxylate (-COO - Na + ) as an ion conductive functional group was added to a high- And subjected to a supercritical reaction at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 25)

1.5% by weight of a dry state polymer membrane having a water / isopropyl alcohol co-solvent (50:50 by volume) and sodium carboxylate sodium salt (-COO - Na + ) as an ion conductive functional group was added in a high- And subjected to a supercritical reaction at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 26)

1.5% by weight of a dry state polymer membrane having a water / isopropyl alcohol co-solvent (volume ratio 17:83) and sodium carboxylate (-COO - Na + ) as an ion conductive functional group was added to a high temperature and high pressure reactor in an amount of 100% And subjected to a supercritical reaction at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 27)

1.5% by weight of a dry state of a plamion powder having a water / isopropyl alcohol co-solvent (50:50 by volume) and sodium carboxylate (-COO - Na + ) as an ion conductive functional group was added in a high-temperature and high- And subjected to a supercritical reaction at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 28)

20% by weight of dry state polymeric pellets having a water / isopropyl alcohol co-solvent (volume ratio 57:43) and an ion conductive functional group sodium carboxylate (-COO - Na + ) were added in a high-temperature and high- And subjected to a supercritical reaction at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 29)

Total 100% by weight carboxylic acid sodium salt with water / isopropyl alcohol co-solvent (volume ratio 17:83) and the ion-conducting functional group such that in the high-temperature high-pressure reactor-player lukewarm fibers having dry (-COO Na +) (diameter: 2 mm) 1.5% by weight, and the mixture was subjected to a supercritical reaction at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 30)

(Diameter: 0.1 mm) having a water / isopropyl alcohol co-solvent (volume ratio 57:43) and carboxylic acid (-COO - H + ) as an ion conductive functional group so that the total amount of 100% 20% by weight, and the mixture was subjected to a supercritical reaction at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 31)

20% by weight of a dry state polymer membrane having a water / isopentyl alcohol co-solvent (volume ratio of 57:43) and a carboxylic acid (-COO - H + ) as an ion conductive functional group was added in a high-temperature and high- Supercritical reaction was carried out at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 32)

20 parts by weight of a dry state polymer membrane having a water / isopropyl alcohol / acetone copolymer (volume ratio of 40:20:40) and carboxylic acid (-COO - H + ) as an ion conductive functional group so that the total amount of 100 weight% %, And subjected to a supercritical reaction at 120 ° C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 33)

A high-temperature and high-pressure reactor, a total of 100% by weight is such that the water / isopropyl alcohol co-solvent (volume ratio 57:43), ion-conducting functional groups in the carboxylic acid (-COO - H +) Al 2 and play the warm film 20% by weight of the dry state with a O 3 in 0.1% by weight, and subjected to a supercritical reaction at 120 ° C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 34)

20% by weight of a dry state polymeric membrane having a water / isopropyl alcohol co-solvent (volume ratio of 57:43) and carboxylic acid (-COO - H + ) as an ion conductive functional group, 1% by weight of silica and 0.2% by weight of silica (Aerosil 812, hydrophobic silica) were added and subjected to a supercritical reaction at 120 캜 under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 35)

5% by weight of a dry state polymer membrane having a water / isopropyl alcohol co-solvent (volume ratio of 25:75) and an ion-conductive functional group of carboxylic acid (-COO - H + ) so that the total amount of 100% 3 wt% of silica (Aerosil 812, hydrophobic silica) and 10 wt% of silica (FSP ([F (CF 2 CF 2 ) 3-8 CH 2 CH 2 O] P (O) (ONH 4 ) 2 , density 1.15 g / , And the supercritical reaction was carried out at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 36)

20% by weight of a dry state polymer membrane having a water / 1-heptanol co-solvent (volume ratio of 57:43) and a carboxylic acid (-COO - H + ) as an ion conductive functional group was added to a high temperature and high pressure reactor in an amount of 100% , And subjected to supercritical reaction at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 37)

In total 100% by weight of the water / isopropyl alcohol co-solvent (volume ratio 25: 75) and the ion-conducting functional group to be in the high-temperature high-pressure reactor, acid-ammonium salt (-SO 3 - NH 4 +) in dry Nafion 112 membrane having a 5 % By weight, and subjected to a supercritical reaction at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure .

(Example 38)

In a high-temperature and high-pressure reactor, a dry Nafion 112 (having a volume ratio of 57:43) and a sulfonic acid-triethylamine salt (-SO 3 - TEA + ) as an ion conductive functional group 20% by weight of the membrane was added, and supercritical reaction was carried out at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 39)

In a high-temperature and high-pressure reactor, a dry Nafion 112 (having a volume ratio of 75:25) and a sulfonic acid-diethylamine salt (-SO 3 - DEA + ) as an ion conductive functional group 1.5% by weight of the membrane was added, and supercritical reaction was carried out at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 40)

1.5% by weight of a dry Nafion 117 membrane having a fluorosulfonyl group as an ion conductive functional group and a water / isopropyl alcohol co-solvent (volume ratio 50:50) were added in a high-temperature and high-pressure reactor so that the total amount was 100% Supercritical reaction was carried out under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 41)

1.5% by weight of a dry Nafion 115 membrane having a fluorosulfonyl group as an ion conductive functional group and a water / isopropyl alcohol co-solvent (volume ratio 50:50) were added in a high-temperature and high-pressure reactor in an amount of 100% Supercritical reaction was carried out under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 42)

20% by weight of dry Nafion 112 pellets having a water / isopropyl alcohol co-solvent (volume ratio of 57:43) and a fluorosulfonyl group as an ion conductive functional group were added in a high-temperature and high-pressure reactor so that the total amount was 100% Supercritical reaction was carried out under psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 43)

In a high-temperature and high-pressure reactor, a dry Nafion 112 membrane having a form of a sulfonic acid lithium salt (-SO 3 - Li + ) with a water / isopropyl alcohol co-solvent (volume ratio of 25:75) 5% by weight, and subjected to a supercritical reaction at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 44)

In a high-temperature and high-pressure reactor, a dry Nafion 112 membrane with a water / isopropyl alcohol co-solvent (volume ratio of 25:75) and a potassium sulfonate salt (-SO 3 - K + 5% by weight, and subjected to a supercritical reaction at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Example 45)

In a high-temperature and high-pressure reactor, a water / isopropyl alcohol co-solvent (25:75 by volume) and a dry state having a form of calcium sulfonate (- (SO 3 - ) 2 Ca 2+ ) 5% by weight of Nafion 112 membrane was added, and supercritical reaction was carried out at 120 DEG C under a pressure of 200 psig for 20 minutes. The reaction was then terminated when the pressure returned to atmospheric pressure.

(Comparative Example 1)

A commercially available ionomer dispersion (trade name: Nafion D521) was selected in the same solvent composition and ionomer content as in Example 1 above.

(Comparative Example 2)

A commercial ionomer dispersion (trade name: Nafion D1021) having the same solvent composition and ionomer content as in Example 2 was selected.

(Comparative Example 3)

A commercial ionomer dispersion (trade name: Nafion D2021) having the same solvent composition and ionomer content as in Example 2 was selected.

(Experimental Example)

The physical properties of the ionomer dispersions of Examples 1 to 45 and Comparative Examples 1 to 3 were measured as follows.

One. Continuous phase  The content of azeotropic mixture

The ionomer dispersion was measured by thermogravimetric analysis (TGA) using an SDT 2960 instrument (TA instrument, New Castle, DE, USA). For this, the substrate was heated from room temperature to 150 ° C in a nitrogen atmosphere at a rate of 5 ° C / min. When the co-solvent is known to have a mixed weight ratio, the solvent is evaporated at the boiling point of the azeotropic mixture in addition to the boiling point of the respective component solvent. At this time, the reduction in mass due to the evaporation of the component solvent is discontinuous. If the content is subtracted from the content of the solvent in the mixed solvent, the content of the azeotropic mixture can be obtained. The results are shown in Table 1.

division Azeotropic mixture content [wt.%] Example 1 28.82 Example 2 28.81 Example 3 47.72 Example 4 48.03 Example 5 48.23 Example 6 20.38 Example 7 20.34 Example 8 44.89 Example 9 20.21 Example 10 44.92 Example 11 20.19 Example 12 20.23 Example 13 20.22 Example 14 37.87 Example 15 32.73 Example 16 47.71 Example 17 47.74 Example 18 28.80 Example 19 20.92 Example 20 37.81 Example 21 28.80 Example 22 47.21 Example 23 20.35 Example 24 20.37 Example 25 44.91 Example 26 20.17 Example 27 44.90 Example 28 47.71 Example 29 20.22 Example 30 47.69 Example 31 37.86 Example 32 20.01 Example 33 47.68 Example 34 47.69 Example 35 28.79 Example 36 47.72 Example 37 28.78 Example 38 47.71 Example 39 20.36 Example 40 44.92 Example 41 44.93 Example 42 47.71 Example 43 28.79 Example 44 28.80 Example 45 28.81 Comparative Example 1 13.7 Comparative Example 2 14.1 Comparative Example 3 17.8

2. Viscosity of the dispersion

The viscosity was obtained by measuring the measured shear rate and shear stress by spinning the spinning needle into the ionomer dispersion using Haake RheoStress 1 (Thermo Scientific Inc., USA). The measured viscosity is shown in Table 2 as a result obtained when the shear rate is 70 / sec.

division Viscosity [cP] Example 1 88.6 Example 2 143.3 Example 3 220.26 Example 4 211.18 Example 5 206.9 Example 6 11.12 Example 7 10.9 Example 8 15.83 Example 9 20.12 Example 10 12.0 Example 11 21.2 Example 12 20.81 Example 13 19.1 Example 14 230.89 Example 15 225.7 Example 16 229.21 Example 17 231.42 Example 18 92.53 Example 19 89.88 Example 20 231.11 Example 21 90.22 Example 22 240 Example 23 10.83 Example 24 9.9 Example 25 11.09 Example 26 22.43 Example 27 11.11 Example 28 213.03 Example 29 21.44 Example 30 209.98 Example 31 226.14 Example 32 228.08 Example 33 230.03 Example 34 231.94 Example 35 90 Example 36 228.61 Example 37 93.33 Example 38 219.23 Example 39 10.28 Example 40 13 Example 41 11.99 Example 42 222.21 Example 43 93.62 Example 44 95 Example 45 93.42 Comparative Example 1 9.2 Comparative Example 2 11.6 Comparative Example 3 163.8

3. Molecular weight and molecular weight distribution

Ionomer dispersion, and then dissolved in N-methylpyrrolidone containing 0.05 M LiCl, and then measured using a gel permeation chromatograph (GPC) method. The results are shown in Table 3.

division Molecular weight [Da] Molecular Weight Distribution [PDI] Example 1 93,000 2.14 Example 2 93,500 2.21 Example 3 91,700 2.16 Example 4 92,000 2.11 Example 5 92,700 2.17 Example 6 93,500 2.13 Example 7 93,000 2.2 Example 8 93,000 2.19 Example 9 93,700 2.17 Example 10 93,500 2.15 Example 11 92,700 2.15 Example 12 91,800 2.16 Example 13 92,500 2.13 Example 14 90,700 2.15 Example 15 91,500 2.14 Example 16 93,000 2.15 Example 17 93,700 2.23 Example 18 94,500 2.16 Example 19 297,700 2.22 Example 20 94,500 2.17 Example 21 389,500 2.23 Example 22 396,500 2.25 Example 23 397,000 2.19 Example 24 391,700 2.18 Example 25 392,000 2.25 Example 26 393,500 2.26 Example 27 390,000 2.24 Example 28 389,500 2.21 Example 29 388,700 2.25 Example 30 386,500 2.24 Example 31 390,000 2.23 Example 32 384,700 2.27 Example 33 395,000 2.2 Example 34 394,700 2.19 Example 35 395,500 2.24 Example 36 470,000 2.21 Example 37 92,700 2.15 Example 38 93,700 2.11 Example 39 92,500 2.11 Example 40 95,000 2.15 Example 41 94,700 2.09 Example 42 93,500 2.11 Example 43 93,000 2.14 Example 44 92,500 2.14 Example 45 92,700 2.11 Comparative Example 1 63,000 2.94 Comparative Example 2 64,000 2.91 Comparative Example 3 66,000 2.93

4. Ionomeric  Average particle size

The average particle size of the ionomer in the ionomer dispersion was measured using a dynamic light scattering apparatus (Zetasizer, Model HAS 300, Malvern, Worcestershire, UK) and the results are shown in Table 4.

division Average particle size [nm] Example 1 11 Example 2 3 Example 3 0.09 Example 4 0.07 Example 5 0.05 Example 6 43 Example 7 31 Example 8 68 Example 9 83 Example 10 94 Example 11 80 Example 12 96 Example 13 93 Example 14 0.9 Example 15 49 Example 16 209 Example 17 230 Example 18 280 Example 19 241 Example 20 0.1 Example 21 270 Example 22 300 Example 23 325 Example 24 330 Example 25 378 Example 26 490 Example 27 351 Example 28 327 Example 29 468 Example 30 330 Example 31 329 Example 32 512 Example 33 328 Example 34 331 Example 35 337 Example 36 137 Example 37 198 Example 38 23 Example 39 86 Example 40 80 Example 41 64 Example 42 69 Example 43 21 Example 44 47 Example 45 134 Comparative Example 1 17 Comparative Example 2 11 Comparative Example 3 6

5. Dispersion safety

Shear rate and shear stress were measured by spinning the spinning needle in the ionomer dispersion using Haake RheoStress 1 (Thermo Scientific Inc., USA), and the shear rate and shear stress (Shear stress / (shear rate - shear stress)). The results are shown in Table 5.

division Dispersion stability Example 1 1.098 Example 2 1.089 Example 3 1.077 Example 4 1.076 Example 5 1.079 Example 6 1.097 Example 7 1.098 Example 8 1.099 Example 9 1.096 Example 10 1.096 Example 11 1.099 Example 12 1.097 Example 13 1.099 Example 14 1.078 Example 15 1.079 Example 16 1.076 Example 17 1.076 Example 18 1.089 Example 19 1.087 Example 20 1.077 Example 21 1.088 Example 22 1.077 Example 23 1.099 Example 24 1.099 Example 25 1.098 Example 26 1.096 Example 27 1.095 Example 28 1.078 Example 29 1.099 Example 30 1.079 Example 31 1.076 Example 32 1.077 Example 33 1.079 Example 34 1.077 Example 35 1.098 Example 36 1.074 Example 37 1.095 Example 38 1.076 Example 39 1.101 Example 40 1.121 Example 41 1.099 Example 42 1.073 Example 43 1.099 Example 44 1.097 Example 45 1.096 Comparative Example 1 1.027 Comparative Example 2 1.012 Comparative Example 3 1.031

6. Ionic conducting functional groups and polymers Main chain  Pyrolysis temperature

Ionomer dispersion, and then measured by thermogravimetric analysis (TGA) using an SDT2960 instrument (TA instrument, New Castle, DE, USA). Prior to the measurement, the sample was treated in a nitrogen atmosphere at 90 캜 for 10 minutes to remove water contained in the sample, and then the temperature was lowered to 50 캜 and then heated to 600 캜 at a rate of 10 캜 / min. The ion conductive functional group was firstly decomposed before the main chain was decomposed, and the temperature at which decomposition started was measured as T d . The results are shown in Table 6.

division The thermal decomposition temperature (T d ) of the ion- Example 1 137 Example 2 138 Example 3 144 Example 4 140 Example 5 143 Example 6 360 Example 7 368 Example 8 364 Example 9 369 Example 10 362 Example 11 363 Example 12 360 Example 13 361 Example 14 142 Example 15 140 Example 16 145 Example 17 141 Example 18 143 Example 19 201 Example 20 141 Example 21 206 Example 22 204 Example 23 300 Example 24 304 Example 25 301 Example 26 305 Example 27 302 Example 28 307 Example 29 300 Example 30 302 Example 31 207 Example 32 203 Example 33 202 Example 34 209 Example 35 208 Example 36 201 Example 37 386 Example 38 207 Example 39 206 Example 40 356 Example 41 351 Example 42 352 Example 43 330 Example 44 379 Example 45 399 Comparative Example 1 103 Comparative Example 2 101 Comparative Example 3 106

7. Chemical stability under radical conditions

After membrane formation using the ionomer dispersion, Fenton reagent (containing 2 ppm FeSO 4) , which simulates the radical generation conditions 3 wt.% H 2 O 2 , 80 ° C.) for 7 hours and then the mechanical strength of the sample was measured on the basis of ASTM D882 using an Instron mechanical testing machine (INSTRON 1708, Boston, Mass., USA). At this time, the crosshead speed was 5 mm < -1 >, and the measurement temperature was 25 deg. The results are shown in Table 7.

division Tensile Strength [MPa] Elongation [%] Example 1 27.8 231.4 Example 2 28.1 228.1 Example 3 29.2 227.9 Example 4 29.3 231.1 Example 5 29.7 231.2 Example 6 26.1 235.1 Example 7 25.6 234.1 Example 8 25.4 236.5 Example 9 24.9 228.9 Example 10 25.1 229.7 Example 11 25.4 229.8 Example 12 25.8 228.9 Example 13 24.9 229.9 Example 14 29.3 231.9 Example 15 29.1 232.0 Example 16 29.1 231.0 Example 17 28.5 230.8 Example 18 27.6 229.8 Example 19 26.1 230.1 Example 20 28.5 229.7 Example 21 27.1 231.1 Example 22 29.1 228.9 Example 23 24.3 229.8 Example 24 25.7 229.6 Example 25 25.3 232.0 Example 26 25.8 231.1 Example 27 25.4 229.4 Example 28 29.5 232.0 Example 29 24.9 231.5 Example 30 28.7 229.9 Example 31 29.1 229.8 Example 32 29.2 228.9 Example 33 28.4 233.0 Example 34 28.9 231.7 Example 35 26.8 231.6 Example 36 28.7 231.4 Example 37 26.8 232.1 Example 38 29.1 229.9 Example 39 24.1 228.9 Example 40 25.8 229.4 Example 41 29.2 228.9 Example 42 27.8 231.2 Example 43 26.5 231.9 Example 44 24.5 231.8 Example 45 25.1 231.8 Comparative Example 1 19.5 199.1 Comparative Example 2 19.8 215.3 Comparative Example 3 21.1 222.1

8. Mechanical strength

The ionomer dispersion was used to form a film and then measured on the basis of ASTM D882 using an Instron mechanical testing machine (INSTRON 1708, Boston, Mass., USA). At this time, the crosshead speed was 5 mm < -1 >, and the measurement temperature was 25 deg. The results are shown in Table 8.

division Tensile Strength [MPa] Elongation [%] Example 1 35 266.1 Example 2 38 270.2 Example 3 38 265.8 Example 4 37 265.9 Example 5 35 259.1 Example 6 39 275.8 Example 7 35 274.9 Example 8 36 274.1 Example 9 34 274.5 Example 10 34 269.2 Example 11 37 267.5 Example 12 39 269.4 Example 13 38 274.1 Example 14 34 275 Example 15 31 269.9 Example 16 37 273.5 Example 17 41 280.1 Example 18 43 280 Example 19 31 279.6 Example 20 33 278.6 Example 21 30 279.3 Example 22 32 274.5 Example 23 33 278.1 Example 24 33 274.9 Example 25 30 280.1 Example 26 31 276.8 Example 27 31 279.1 Example 28 32 278.5 Example 29 33 278.8 Example 30 31 279.1 Example 31 34 281.1 Example 32 30 276.9 Example 33 36 278.8 Example 34 42 281.2 Example 35 42 282.5 Example 36 31 278.1 Example 37 34 283.8 Example 38 36 271.9 Example 39 39 280.1 Example 40 37 279.9 Example 41 38 279.8 Example 42 38 279.9 Example 43 37 278.2 Example 44 36 278.9 Example 45 38 278.1 Comparative Example 1 26 246.8 Comparative Example 2 28 253.1 Comparative Example 3 30 260.1

9. Hydrogen ion conductivity

(1 * 4 cm < 2 >) of a certain size was placed in a 30 [deg.] C resistance measuring cell containing ultrapure water, and an impedance meter was used to measure resistance R ) was measured. The measured resistance was obtained by calculating in [S / cm] = 1 [cm] / ( R [] * S [cm 2 ]). Here, S and I represent the distance between the cross-section where the current flows and the electrode where the voltage drop occurs.

division Hydrogen ion conductivity 30 ° C Ultrapure water [S / cm] Example 1 0.109 Example 2 0.112 Example 3 0.113 Example 4 0.113 Example 5 0.112 Example 6 0.0981 Example 7 0.099 Example 8 0.0987 Example 9 0.0983 Example 10 0.0991 Example 11 0.0988 Example 12 0.098 Example 13 0.0989 Example 14 0.118 Example 15 0.121 Example 16 0.116 Example 17 0.113 Example 18 0.115 Example 19 0.108 Example 20 0.117 Example 21 0.107 Example 22 0.108 Example 23 0.095 Example 24 0.096 Example 25 0.1 Example 26 0.099 Example 27 0.098 Example 28 0.098 Example 29 0.097 Example 30 0.094 Example 31 0.11 Example 32 0.108 Example 33 0.111 Example 34 0.118 Example 35 0.12 Example 36 0.118 Example 37 0.099 Example 38 0.098 Example 39 0.099 Example 40 0.12 Example 41 0.119 Example 42 0.12 Example 43 0.09 Example 44 0.091 Example 45 0.093 Comparative Example 1 0.097 Comparative Example 2 0.108 Comparative Example 3 0.101

Claims (19)

A continuous phase comprising water and alcohol having a volume ratio of 17:83 to 75:25,
Based ionomer nanoparticles dispersed in the continuous phase and insoluble in both water and alcohol,
The content of the azeotrope in the continuous phase is 20% by weight to 50% by weight, and the content of the azeotrope in the continuous phase is determined by thermogravimetric analysis using the mass of the corresponding solvent Wherein the reduced content is obtained by subtracting the reduced content from the total content of the corresponding solvent in the continuous phase. delete The ionomer nano-particle dispersion according to claim 1, wherein the ionomer has at least one ion-conductive functional group selected from the group consisting of a sulfonic acid, a sulfonic acid salt, a carboxylic acid, a carboxylic acid salt and a fluorosulfonyl. 4. The method of claim 3, wherein the sulfonate salt is
Wherein the ionomer nanoparticle dispersion is one selected from the group consisting of a lithium salt of a sulfonic acid, a sodium sulfonate, a potassium sulfonate, a magnesium sulfonate, a calcium sulfonate, an ammonium sulfonate, and an alkyl sulfonate. 4. The method of claim 3, wherein the carboxylic acid salt is selected from the group consisting of
Wherein the ionomer nanoparticle dispersion is one selected from the group consisting of a lithium salt of a carboxylic acid, a sodium carboxylate, a potassium carboxylate, and an alkylammonium carboxylate. delete The method of claim 1, wherein the alcohol is selected from the group consisting of
But are not limited to, methanol, ethanol, 1-propanol, isopropyl alcohol, butanol, isobutanol, Methyl propyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl propyl ketone, methyl propyl ketone, methyl propyl ketone, methyl isopropyl ketone, Methyl-2-pentanol, 4-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl- Butanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 2-ethyl- Butanol, 1-heptanol, 2-heptanol, 3-heptanol and 4-heptanol and mixtures thereof. 2. The method of claim 1,
Wherein the solvent is selected from the group consisting of acetone, ethyl carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate, fluoroethylene carbonate, dimethylacetamide, dimethylsulfoxide, dimethylformamide, Wherein the ionomer nanoparticle dispersion comprises one kind of organic solvent. 9. The method of claim 8, wherein the organic solvent comprises
Wherein the dispersion is contained in an amount of 0.01 to 40% by weight in the dispersion. The method of claim 1, wherein the perfluorinated ionomer is
A dispersion of ionomer nanoparticles wherein the ionomer nanoparticle dispersion is one selected from the group consisting of poly (perfluorosulfonic acid), poly (perfluorocarboxylic acid), copolymer of tetrafluoroethylene and fluorovinyl ether containing sulfonic acid group, and combinations thereof. The method of claim 10, wherein the perfluorinated ionomer
Wherein the ionomer nanoparticle dispersion is one selected from the group consisting of Nafion, Plemion, Ashiflex, 3M ionomer, Dow ionomer, Solvay ionomer, Sumitomo 3M ionomer, and mixtures thereof. The method of claim 1, wherein the nanoparticles
Wherein the average particle size is from 0.01 nm to 600 nm. The method of claim 1, wherein the nanoparticles
Wherein the dispersion is contained in an amount of 0.01 to 30% by weight in the dispersion. The ionomer nanoparticle dispersion according to claim 1, wherein the ionomer has a polydispersity index of 1.0 to 2.5. The method of claim 1, wherein the nanoparticles
TiO 2, SiO 2, Al 2 O 3, ZrO 2, tetraethoxysilane (TEOS), montmorillonite (montmorillonite), moden night (mordenite), zirconium phosphate (ZrP), phosphine poteong stick acid, silicotungstic tongue stick to Wherein the ionomer nanoparticle dispersion further comprises one additive selected from the group consisting of an acid, a phosphomolybdic acid, a silicomolybdic acid, a fluorinated aliphatic hydrocarbon including a hydrophilic functional group, and a mixture thereof. 16. The method of claim 15, wherein the fluorinated aliphatic hydrocarbon comprising the hydrophilic functional group is
A linear or branched C4 to C30 alkyl group, or a linear or branched C4 to C30 alkylene oxide partially or entirely substituted with a fluorine atom. 16. The method of claim 15, wherein the fluorinated aliphatic hydrocarbon comprising the hydrophilic functional group is
F (CF 2 CF 2) 3 ~ 8 CH 2 CH 2 SO 3 H would nanoparticle dispersion of the ionomer. The method according to claim 1, wherein the number average molecular weight of the ionomer is
70,000 Da to 500,000 Da. The method of claim 1, wherein the viscosity of the dispersion is
Lt; RTI ID = 0.0 > cP < / RTI > to 250 cP.
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