KR20140133748A - Ion-conducting polymer comprising controlled sulfonated poly(phenyl sulfone) and use thereof - Google Patents

Abstract

The present invention relates to an ionic conducting polymer characterized by comprising: a block copolymer including a hydrophilic block and a hydrophobic block, wherein the hydrophilic block includes sulfonated polyphenyl sulfone structure including sulfonic acid groups, and the hydrophobic block includes benzene rings bonded by ether bonds of the increased number; a block copolymer including repeating units having the hydrophobic bond and the hydrophilic block including or not including capping units on both linked ends; a method to manufacture the block copolymer; an ionic conductor including the ionic conducting polymer or block copolymer; and a battery including an electrolyte membrane or a separator formed from a resin composition including the ionic conductive polymer or block copolymer. The ionic conducting polymer of the present invention is a block copolymer which includes the hydrophobic block including benzene rings bonded by ether bond to provide flexibility while including hydrophilic block including polyphenyl sulfone structure including sulfonic acid groups to maintain strength and dimensional stability.

Description

[0001] The present invention relates to an ion-conducting polymer comprising a polyphenylsulfone structure substituted with a controlled number of sulfonic acid groups, and to an ion-

The present invention relates to an ion conductive polymer comprising a hydrophilic block and a block copolymer comprising a hydrophobic block, wherein the hydrophilic block comprises a sulfonated poly (phenyl sulfone) structure containing a sulfonic acid group, An ionic conducting polymer comprising a benzene ring linked by an increased number of ether bonds; A block copolymer comprising a repeating unit in which a hydrophilic block having hydrophilic blocks, each hydrophilic block containing or not including capping units at both ends thereof, is connected independently; A method for producing the block copolymer; An ion conductor comprising the ion conductive polymer or block copolymer; An electrolyte membrane formed from a resin composition containing the ion conductive polymer or a block copolymer, or a battery having a separation membrane.

Fuel cells are energy conversion devices that convert the chemical energy of fuels directly into electric energy, and have been developed as a next generation energy source with high energy efficiency and eco-friendly characteristics with less pollutant emissions. Proton exchange membrane fuel cells (PEMFCs) containing polymer electrolyte membranes have advantages such as low operating temperature, elimination of leakage problems due to the use of solid electrolytes, and fast operation, Devices.

In general, an electrolyte membrane used in a polymer electrolyte fuel cell can be divided into a perfluorinated polymer electrolyte and a hydrocarbon polymer electrolyte. The fluorinated polymer electrolyte is chemically stable due to a strong binding force between carbon-fluorine (CF) and a shielding effect which is a characteristic of a fluorine atom, and has excellent mechanical properties. Particularly, And has been commercialized as a polymer membrane of an electrolyte type fuel cell. Nafion (perfluorinated sulfonic acid polymer), a product of Du Pont, USA, is a typical example of a commercially available hydrogen ion exchange membrane, and has been most commercially used since it has excellent ionic conductivity, chemical stability and ion selectivity. However, the fluorinated polymer electrolyte membrane has a low utilization rate for industrial use due to its high price compared to the excellent performance, a disadvantage that the methanol permeability (methanol crossover) of methanol through the polymer membrane is high and the efficiency of the polymer membrane is decreased And therefore, researches on hydrocarbon ion exchange membranes that can be competitive in terms of price have been actively conducted.

Since the polymer electrolyte membrane used in the fuel cell must be stable under the conditions required for driving the fuel cell, the usable polymer is very limited by aromatic polyether (APE) and the like. Hydrolysis, oxidation, and reduction reactions during the operation of a fuel cell cause degradation of the polymer membrane, thereby deteriorating the performance of the fuel cell. Accordingly, polyetherketone and polyethersulfone-based polyaryleneether polymers have been studied for their application to fuel cells due to their excellent chemical stability and mechanical properties.

The polymer sulfonation methods disclosed in the prior art have the disadvantage that when the degree of sulfonation (DS) (degree of sulfonation) is increased in order to realize hydrogen ion conductivity similar to that of commercialized Nafion (Dupont), the water content And the methanol content is excessively increased to dissolve the electrolyte membrane in methanol, thereby remarkably deteriorating the mechanical integrity of the electrolyte membrane, failing to satisfy the physical properties of the electrolyte membrane required for driving the fuel cell.

Accordingly, the present inventors have made intensive researches to prepare an ion conductive polymer which has flexibility to control the content of a substituent introduced into a hydrophilic block and which does not lose its chemical durability while being flexible enough to form a film. As a result, In order to overcome the difficulty of membrane formation due to the chemical structure, it is overcome by increasing the content of flexible ether bond in hydrophobic block. Furthermore, it has been confirmed that the polymer can prevent the chemical durability from deteriorating by containing a reactive ether bond at a position separated from the sulfonic acid group.

DISCLOSURE OF THE INVENTION The object of the present invention is to provide a polyphenylsulfone-containing polyphenylene sulfone-based polyphenylene sulfide having a structure in which an ionic conductor having a rigid structure The present invention provides a polymer having sufficient flexibility by using a hydrophobic block containing a benzene ring linked with a flexible ether group in the production of a block copolymer by collecting a hydrophilic block containing a sulfone structure.

The present invention relates to an ion conductive polymer comprising a hydrophilic block and a block copolymer comprising a hydrophobic block, wherein the hydrophilic block comprises a sulfonated poly (phenyl sulfone) structure containing a sulfonic acid group, Is represented by the following general formula (1): < EMI ID = 1.0 >

[Chemical Formula 1]

In Formula 1,

A 'is an electron withdrawing group such as - (SO ₂ ) -, - (C═O) -, -CF ₂ -, -C (CF ₃ ) ₂ - or - (P═O)

p is 1 or 2,

q may be an integer of 1 or more.

In this case, the hydrophilic block may be represented by any one of the following formulas (2) to (4).

(2)

(3)

[Chemical Formula 4]

In the above Chemical Formulas 2 to 4,

a and b are each independently an integer of 1 to 4,

M is a ^{cation, H +, Li +, Na} +, K +, NR 4 + or PR ₄ ^+,

A is an electron withdrawing group, - (SO ₂ ) -, - (C═O) -, -CF ₂ -, -C (CF ₃ ) ₂ - or -

l is an integer of 0 to 2,

m is an integer of 1 or more.

The present invention also provides a block copolymer comprising a hydrophilic block and a hydrophobic block comprising a repeating unit represented by any one of the following formulas (5) to (7):

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the above formulas 5 to 7,

a, b, A, A ', M, l, m, p and q are as defined in claim 1 or 3, y is an integer of 1 or more, E and E' Or a molecule comprising at least one benzene ring as a capping unit and containing a hydroxy or fluorine group as a reactive functional group at the terminal.

And when E or E 'is a capping unit, it may be connected to the hydrophobic unit polymer and the hydrophilic unit polymer through a terminal hydroxyl group or a fluorine group, respectively.

Further, the present invention provides a method for producing the block copolymer, comprising the steps of: preparing a precursor of a hydrophilic unit polymer represented by the following formula (13) to (15), which contains a sulfide group; Preparing a hydrophobic unit polymer represented by the following formula (1); Mixing a precursor of the hydrophilic unit polymer with a hydrophobic unit polymer to form a block copolymer by a condensation reaction; And oxidizing the sulfide group of the precursor of the hydrophilic unit polymer to a sulfone group.

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

Further, the present invention provides an ion conductor comprising the ion conductive block copolymer of the present invention.

The ion conductor may be a molded body formed from a resin composition containing the ion conductive block copolymer of the present invention. The molded article may be an electrolyte membrane, a separator membrane or a water treatment membrane.

The present invention also provides a battery having an electrolyte membrane or separator formed from a resin composition comprising the block copolymer of the present invention.

Hereinafter, the present invention will be described in detail.

In view of the fact that ionic conductors containing a conventional polyphenylsulfone structure are liable to be very easily broken down in the form of a film due to its rigid chemical structure, the present invention has a structure in which a polyphenylsulfone structure containing a sulfonic acid group And a hydrophobic block containing a benzene ring linked by a flexible ether group when the hydrophilic block is assembled into a block copolymer in the form of a block copolymer.

In addition, the ion conductive polymer comprising the hydrophilic and hydrophobic block according to the present invention is characterized in that the solubility is increased by increasing the content of the benzene ring linked to the hydrophobic block through the ether group, and the flexibility of the membrane is improved. Surprisingly, although the polymer of the present invention contains an increased number of ether bonds, the ether bond is contained in the hydrophobic block and is isolated from the sulfonic acid group, so that the water absorption rate and dimensional stability deterioration , Chemical durability reduction, and the like.

The sulfonic acid group (-SO ₃ H) is introduced to impart hydrogen ion (proton, H ⁺ ) conductivity to the polymer electrolyte membrane. Alkali metal salts of sulfonic acids may be used for the same purpose. The "alkali metal salt" may be a cation of an alkaline metal such as Na ⁺ , K ⁺ , or Li ⁺ in place of a proton (H ⁺ ) of sulfonic acid.

In the present invention, the hydrophilic block includes a polyphenylsulfone structure containing a sulfonic acid group. For example, benzene rings are linked to somewhat rigid sulfone groups, imparting strength and increasing chemical stability. However, such a sulfonated structure has a disadvantage in that it is brittle due to its rigid chemical structure when it is prepared into a membrane form.

Accordingly, the present invention may include a hydrophobic block comprising a plurality of benzene rings linked by an ether linkage. It contains an ether bond having a relatively flexible structure in the hydrophobic block, and sufficient flexibility can be ensured by increasing the content of the ether bond. That is, the polymer according to the present invention can be prepared in the form of a block copolymer in which rigid hydrophilic blocks are collected and separated into flexible hydrophobic blocks, thereby ensuring flexibility while ensuring sufficient durability under conditions of high temperature and high acidity, Which is easy to manufacture. On the other hand, by forming a dense and densely and locally substituted sulfonated structure of the sulfonic acid group, an effective phase separation of the hydrophilic domain and the hydrophobic domain can be induced.

In a specific embodiment of the present invention, in order to confirm the effect of the increased content of ether linkage introduced into the hydrophobic block, as a comparative example, a block copolymer containing a block of the same hydrophilic structure and containing a low content of ether linkage in the hydrophobic block And a block copolymer having an ether bond introduced into a hydrophilic block were prepared and used. As a result, it was confirmed that the block copolymer containing an increased amount of ether bond in the hydrophobic block according to the present invention had the same or higher chemical durability with increased flexibility as compared with the block copolymer containing a lower content of ether bond (Fig. 1 and Table 3). On the other hand, when the ether bond was introduced into the hydrophilic block, the chemical durability was drastically decreased and the oxidation stability was low.

The hydrophilic block according to the present invention can be prepared by reacting a monomer having a sulfonic acid group represented by the following formula (8) with a monomer having a sulfide group represented by the formula (9) or (10). A compound containing a sulfur atom (S) is a good nucleophile having a high nucleophilicity and can cause a nucleophilic substitution reaction with a halogen-containing compound as a reactor. As a result, a compound having a sulfido group Can be provided.

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

Wherein a, b and A are each as defined for formulas 2 to 4, X is halogen and l is 1 or 2.

For example, a nucleophilic substitution reaction of a compound represented by the formula (9) or (10) with a sulfide group can be carried out at a position substituted with halogens at both terminals of a monomer having a sulfonic acid group represented by the formula (8) A phenyl group connected with the sulfide group or a compound substituted with a sulfur atom is formed. The compound thus prepared can be converted into a sulfone group by forming a block copolymer by a polymerization reaction and then oxidizing it as a precursor of the hydrophilic block according to the present invention.

The hydrophobic block according to the present invention can be prepared from the monomers represented by the following general formulas (11) and (12). The compound represented by the following general formula (11) includes a halogen as a reactive group at both ends and a compound represented by the general formula (12) as a hydroxyl group, and the substitution reaction can be carried out by the difference in reactivity in the nucleophilic reaction between the hydroxyl group and the halogen have. That is, the hydroxy group is substituted with a halogen, which is a good leaving group, and the compound represented by the general formula (12) forms an ether bond at both ends of the compound represented by the general formula (11) to form a hydrophobic block.

(11)

[Chemical Formula 12]

Wherein A 'and p are as defined for formula (1), and X is halogen.

The polymer according to the present invention may further include a capping unit containing a hydroxyl group or a halogen as a reactive functional group at both ends of the hydrophilic block or the hydrophobic block, respectively. The capping unit blocks a highly reactive sulfide group exposed at both ends of the hydrophilic unit polymer precursor forming the hydrophilic block or both ends of the hydrophobic unit polymer so that the hydrophilic unit polymer precursor forms a disulfide bond with high mutual reactivity Can be introduced to suppress hypertrophy. The disulfide bond is highly reactive and can reduce the chemical durability. The dimerization or massification of the hydrophilic block through the disulfide bond expands the hydrophilic block having a rigid chemical structure and is liable to be fragile when it is made into a film . Also, dimerization or multimerization of the hydrophobic block through the disulfide bond can extend the hydrophobic block containing the highly reactive ether bond to reduce stability.

,

,

,

,

,

,

또는

일 수 있고, 이때 상기 X는 단일결합, -CF₂- 또는 -C(CF₃)₂-일 수 있으나, 이에 제한되지 않는다.The capping unit may be a molecule in which a series of phenyl groups are directly or indirectly connected. The molecule may be introduced at the terminal of the hydrophilic block through the reactive substituent by substituting a hydroxyl group or a halogen at both terminals. Preferably, the capping unit comprises

,

,

,

,

,

,

or

, Where X may be a single bond, -CF ₂ - or -C (CF ₃ ) ₂ -, but is not limited thereto.

Preferably, the block copolymer according to the present invention is a block copolymer comprising a hydrophilic block and a hydrophobic block containing a repeating unit represented by any one of formulas (5) to (7), specifically, a hydrophobic block represented by formula And a hydrophilic block represented by any one of formulas (2) to (4), wherein the hydrophilic block further comprises a capping unit.

이고 상기 X는 단일결합이며; E'은 단일결합일 수 있다.In one embodiment of the block copolymer represented by any one of formulas (5) to (7), a and b are 1; M is H ⁺ , Na ⁺ or K ⁺ ; A is - (SO ₂₎ -; l is an integer from 0 to 2; p is 1 or 2; E is

And X is a single bond; E 'may be a single bond.

The block copolymer according to the present invention preferably has an ion exchange capacity (IEC) of 1.0 to 3.0 meq / g, and the hydrophilic block and the hydrophobic block each have a number average molecular weight ranging from 2,000 to 50,000 Da. For example, when the ion exchange capacity is less than 1.0 meq / g, the ion conductivity is too low to be utilized. When the ion exchange capacity is more than 3.0 meq / g, the polymer swells excessively due to water and can not act as an actual separator. When the molecular weight of the hydrophilic block and the hydrophobic block is less than 2,000 Da, the fine phase separation effect between the hydrophilic region and the hydrophobic region hardly occurs. Therefore, the hydrophobic block and the hydrophobic block do not exhibit the properties as a block copolymer. The polymer is excessively swollen in water and can not act as an actual separation membrane.

Preferably, the molecular weight of the polymer according to the present invention may be Mn (number-average molecular weight) of 10,000 to 1,000,000 or molecular weight of Mw (weight-average molecular weight) of 10,000 to 10,000,000 . More preferably from 10,000 to 300,000, or from 10,000 to 2,000,000. When the molecular weight is low, for example, when it is 10,000 or less, film formation is difficult, the moisture content is increased, and it is easily decomposed by the attack of radical, so that conductivity and durability may be decreased. On the other hand, in the case where the molecular weight is high, for example, 1,000,000 or more, the rapidly increasing viscosity may make the preparation of the polymer solution and molding into a film difficult, making the film production process impossible.

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

A method for preparing a block copolymer according to the present invention comprises: a first step of preparing a precursor of a hydrophilic unit polymer containing a sulfide group; A second step of preparing a hydrophobic unit polymer containing a phenyl group linked by an ether bond; A third step of mixing a precursor of the hydrophilic unit polymer with a hydrophobic unit polymer to form a block copolymer by a condensation reaction; And a fourth step of oxidizing the sulfide group of the precursor of the hydrophilic unit polymer to a sulfone group. In this case, the precursor of the hydrophilic unit polymer may be represented by any one of the following formulas (13) to (15), and the hydrophobic unit polymer may be represented by the formula (1).

[Chemical Formula 1]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

In the above formulas (1) and (13) to (15)

a, b, A, A ', M, l, m, p and q are as defined for formulas 5 to 7, respectively.

The method of producing the block copolymer according to the present invention does not require post-treatment for sulfonation using 1) a hydrophilic block having a sulfonic acid group introduced therein, 2) The copolymer is converted into a sulfonic acid group by oxidizing it.

First, as described above, the process according to the present invention does not require a post-treatment process for sulfonation since a polymer is prepared using a sulfonate-introduced reactant. That is, the ratio of the sulfonic acid group introduced into the hydrophilic block can be easily controlled by preparing the polymer using the reactant in which the number of introduced sulfonic acid groups is controlled. Therefore, it is possible to overcome the disadvantage that the sulfonic acid group is randomly introduced into the polymer backbone by post-treatment sulfonation, and its distribution, position and number are difficult to control.

Further, in forming the hydrophilic block, the sulfide group has a high reactivity capable of achieving excellent polymerization degree, and is advantageous in that it can be converted into a sulfone group to exclude the electron-donating group and include only a high electron-withdrawing group. That is, it is easy to form and control the molecular weight when preparing the hydrophilic block through the nucleophilic substitution reaction. By oxidizing the sulfide bond formed from the nucleophile through the oxidation reaction to the sulfone group of the electron donor, it is possible to improve the chemical durability of the copolymer and the ion The conductivity can be improved.

The precursor of the hydrophilic unit polymer and / or the hydrophobic unit polymer can be purchased and used by synthesizing or selling using a method known in the art. When the above compounds are synthesized, they can be prepared using a nucleophilic substitution reaction, but the synthesis method is not limited thereto.

Preferably, the first to third steps may be performed by a nucleophilic substitution reaction, respectively. The term "nucleophilic substitution" of the present invention refers to a reaction in which a nucleophile is bonded to a site where a leaving group is bonded to a substrate to remove a leaving group. The reaction is a reaction that is common in organic chemistry and may occur at the center of a saturated aliphatic carbon, a saturated aromatic or other unsaturated carbon. The "nucleophile" is an atom or molecule having a non-covalent electron pair that does not participate in a chemical bond, and attacks the substrate through the non-covalent electron pair to form a new bond. At this time, the leaving group bonded on the substrate is separated from the substrate with its bonding electron pair. A good or better nucleophile can form a bond through the electron pair to a reactor having an excellent ability to provide the non-covalent electron pair, and a good nucleophile has a good electron donor electron donor, that is, a good Lewis base. A good or better leaving group, on the other hand, refers to a reactor that is capable of accepting the binding electron pair, which can be separated from the substrate itself with a binding pair of electrons, or can be readily separated from the substrate for attack of the nucleophile Have the ability. An example of a representative good leaving group is a conjugate base of strong acid that accepts a bond electron with hydrogen and easily releases a proton. The coupling of the nucleophile and the separation of the leaving group may occur at the same time or may occur sequentially in such a manner that the leaving group is separated and then the nucleophile is bonded. The kind of the reaction can be determined depending on the type of the nucleophile and the leaving group, the relative reactivity thereof, and the kind of other substituent bonded to the position where the reaction on the substrate takes place. In addition, reaction conditions such as solvent, temperature, and reaction medium (solvent) also affect reaction mechanism and product.

When the reactivity of the reactants and intermediates used in the present invention is compared with the reactivity of the thiol group, the hydroxyl group and the halogen such as chlorine and fluorine, the ability of the halogen to be separated from the substrate with a shared electron pair This can serve as an excellent good release. Thus, the halogen can be easily substituted by a thiol group or a hydroxyl group, so that it can be easily substituted by a molecule containing it as a reactor, in which a sulfide or an ether bond can be formed. On the other hand, in the nucleophilicity, the thiol group can act as the most excellent nucleophile. Thus, a molecule containing a thiol group as a reactor at both ends can be bonded to form a sulfide bond with a molecule containing a hydroxyl group or a halogen as a reactor. At this time, the hydroxyl group or the halogen may be separated from the substrate as a leaving group, respectively.

Preferably, the nucleophilic reaction can be found in DMAc (N, N -Dimethylacetamide), DMSO (dimethyl sulfoxide) for the production of the hydrophilic polymer precursor of the unit (the first step) or a hydrophobic polymer units (step 2), DMF (N, A dipolar aprotic solvent such as N- dimethylformamide, NMP (1-methyl-2-pyrrolidone) or sulfolane and a solvent such as toluene or cyclohexane at a volume ratio of 1.3: 1 to 2: , And can be carried out using potassium carbonate or cesium carbonate (Ce ₂ CO ₃ ) as a catalyst. And may further be carried out with calcium carbonate as an auxiliary catalyst for promoting the reaction. The reaction product may be added to the mixed solvent, heated to 130 to 170 캜 and dissolved by stirring for 1.5 to 2.5 hours. And then refluxing for about 3 to 5 hours to remove water as a by-product of the reaction. Then slowly raising the temperature to 160 to 200 캜 and reacting for 3 to 48 hours while maintaining the temperature.

Preferably, the production process according to the present invention may further comprise the step of bonding the capping unit to the precursor of the hydrophilic unit polymer or to the end of the hydrophobic unit polymer before the condensation reaction. The introduction of the capping unit is accomplished by reaction with a capping agent having a hydroxy group or a halogen substituted at both ends. The introduction of the capping unit may be performed once, or may be repeated twice or more with different kinds of capping agents. Can be achieved. For example, a capping agent such as 1,4-dihydroxybenzene or 4,4'-biphenol, which contains a hydroxyl group at both terminals, is firstly introduced A capping agent containing a halogen such as perfluorobenzene or decafluorobiphenyl can be further introduced. Non-limiting examples of the capping agent include 1,4-dihydroxybenzene, 4,4'-biphenol, perfluorobenzene, decafluorobiphenyl, difluorobis (perfluorophenyl ) methane, 6,6 '- (perfluoropropane-2,2-diyl) bis (1,2,3,4,5-pentafluorobenzene) -diyl) bis (1,2,3,4,5-pentafluorobenzene)), or a combination thereof.

The fourth step of oxidizing the sulfide group to a sulfone group can be carried out using any method known in the art without limitation. The oxidizing step may be performed on the polymer itself, or may be carried out after molding into a membrane. For example, a dried powder-form copolymer may be dispersed in acetic acid, sulfuric acid may be added, and hydrogen peroxide may be added to the reaction solution, followed by reaction with stirring. In this case, a process of converting a sulfonic acid group into an alkali metal salt form may be further performed to form a solution having a low viscosity in order to facilitate processing such as molding. Preferably in the form of a potassium salt, by reacting with a K ₂ CO ₃ solution.

As described above, the precursor of the hydrophilic unit polymer according to the present invention includes a phenyl group linked with a sulfide group. Accordingly, when the compound is prepared by synthesis, it can be prepared as a compound having a thiol group at both terminals according to convenience of the reaction. The thiol groups are highly reactive and can bond to each other to form disulfide bonds to form an undesired polymer. Thus, when the precursor of the hydrophilic unit polymer contains a thiol group at both ends, it further includes a step of binding a capping unit containing a hydroxyl group or a halogen at the terminal, which is relatively stable and can participate in the nucleophilic reaction according to reaction conditions . The capping unit may be introduced through one or more reactions. The capping unit may be selected so as to have a reactive group at both ends thereof which is easy to bond with the hydrophobic block.

The hydrophobic unit polymer according to the present invention includes a phenyl group linked by an ether bond. Therefore, when the hydrophobic unit polymer is produced by synthesis, it can be prepared as a compound having a hydroxy group at both terminals according to convenience of the reaction. Accordingly, the capping unit may be selected to include other end-reactive groups at the end to easily react with the hydroxyl group of the hydrophobic unit polymer, but the present invention is not limited thereto.

The ion conductive polymer or block copolymer according to the present invention provides an ion conductor comprising a sulfonic acid group or an alkali metal salt thereof.

The molded article can be formed from the resin composition containing the ion conductive polymer or block copolymer according to the present invention. Non-limiting examples of the molded body include an electrolyte membrane, a separation membrane, or a water treatment membrane.

The resin composition of the present invention may further contain various additives such as an antioxidant, a heat stabilizer, a lubricant, a tackifier, a plasticizer, a crosslinking agent, a defoaming agent, and a dispersant.

The resin composition comprising the ion conductive polymer or block copolymer according to the present invention can be extruded and molded into a molded product such as fiber or film by any method such as spinning, rolling or casting.

For example, the resin composition containing the ion conductive polymer or block copolymer of the present invention can be molded to produce an electrolyte membrane. Specifically, the block copolymer is dissolved in a solvent such as N-methylpyrrolidone (NMP), dimethylformamide, dimethylsulfoxide or dimethylacetamide, and the solution is poured into a plate such as a glass plate, To obtain a film having a thickness of several to several hundreds of μm, preferably 10 to 120 μm, more preferably 50 to 100 μm, and then desorbing from the plate. The above-mentioned solvent is only illustrative, and the scope of the present invention is not limited thereto. Conventional organic solvents may be used as long as they dissolve the polymer and can be evaporated under the drying condition. Specifically, the same organic solvent as that used in the preparation of the polymer may be used.

According to a specific embodiment of the present invention, the prepared polymer is dissolved in DMAc and / or DMSO and poured onto a glass plate and dried at 60 to 100 ° C, preferably 70 to 90 ° C for 12 to 36 hours, preferably 18 to 30 hours So that a film can be obtained. The drying can be performed using a halogen lamp in a nitrogen atmosphere. The obtained membrane may be washed with a sulfuric acid solution and distilled water in turn to convert it into a proton-type polymer membrane.

The molded article according to the present invention, that is, the ion conductive polymer or block copolymer according to the present invention The polymer membrane can be used as an electrolyte membrane or separator for a battery.

The present invention provides a battery having an electrolyte membrane formed from a resin composition containing the ion conductive polymer or block copolymer.

The electrolyte membrane formed from the resin composition comprising the ion conductive polymer or block copolymer according to the present invention has high hydrogen ion conductivity, mechanical strength, and excellent chemical stability, and thus can be used as a hydrogen ion electrolyte membrane. In particular, The present invention can be used as an ion exchange membrane in a proton exchange membrane fuel cell aka polymer electrolyte membrane fuel cell (PEMFC), a direct methanol fuel cell (DMFC), or a redox flow battery.

The ion conductive polymer of the present invention comprises a hydrophilic block containing a benzene ring linked by an ether bond, thereby imparting flexibility, and including a hydrophilic block containing a polyphenylsulfone structure including a sulfonic acid group, so that a block capable of maintaining strength and dimensional stability As the copolymer, the ion conductive polymer has improved solubility and flexibility in the production of a film containing the ion conductive polymer, while adversely affecting the deterioration of water absorption rate or dimensional stability and chemical durability, which can generally be caused by an increase in the ratio of ether bonds It is possible to provide a polymer film which has excellent physical properties and can be easily formed into a film. Also, since it exhibits excellent ion exchange ability, it can provide an electrolyte membrane for a polymer fuel cell having excellent chemical stability while exhibiting improved conductivity and excellent physical properties.

1 is a graph showing the results of measurement of glass transition temperature through DSC analysis.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are for further illustrating the present invention, and the scope of the present invention is not limited to these examples.

Example  1: a hydrophilic unit polymer precursor The sulfonic acid group  Included Polyphenylsulfide  Preparation of derivatives

The hydrophilic unit polymer according to the present invention may have a different molecular weight depending on the molar ratio of the monomers to be produced. Thus, the target molecular weight is set and the amount of reactant used is determined accordingly. In the present invention, the target molecular weight was set to 10 kg / mol and the synthesis was carried out.

1.1. TBBT (4,4'- thiobisbenzenethiol ) -Based hydrophilic unit polymer precursor ( TBBT - philic )

A four-necked flask was equipped with a condenser, a mechanical stirrer, and a Dean-Stark trap, and purged sufficiently with argon gas. A solution of 3.3798 g (0.0135 mol) of 4,4'-thiobisbenzenethiol (TBBT), 4,4'-difluorodiphenyl sulfone containing 6.6201 g (0.0144 mol) 4,4'-difluorodiphenyl sulfone; SDFDPS) of anhydrous _{K 2 CO 3 (anhydrous potassium carbonate} ; 2.2386 g, 0.0162 mol) and _{CaCO 3 (calcium carbonate; 1.6212 g} , 0.0162 mol) and dimethylacetamide (with dimethylacetamide; DMAc) And a mixed solvent of toluene (v / v = 1.6 / 1). The temperature was raised to 150 ° C and the monomer was dissolved while stirring for 2 hours, and then toluene was refluxed for 4 hours to remove water as a reaction byproduct. Thereafter, the temperature was raised to 175 캜 for 1 hour and reacted for 18 hours to prepare a TBBT-based hydrophilic unit polymer precursor (TBBT-philic).

1.2. Li ₂ S Based hydrophilic unit polymer precursor ( Li ₂ S - philic )

A three-necked flask was equipped with a condenser and a mechanical stirrer and sufficiently purged with argon gas. 0.8735 g (0.0190 mol) of Li ₂ S (lithium sulfide) and 9.1264 g (0.0199 mol) were mixed and the temperature was raised and SDFDPS of DMAc was added to the 160 ℃ for 3 hours to react for 18 hours Li ₂ S- based To prepare a hydrophilic unit polymer precursor (Li ₂ S-philic).

1.3. BDT ( benzene -1,4-dithiol) -based hydrophilic unit polymer precursor ( BDT -philic

The four-necked flask was equipped with a condenser, a mechanical stirrer and a Deanstock trap, and sufficiently purged with argon gas. 2.2611 g (0.0158 mol) of benzene-1,4-dithiol (BDT) and 7.7388 g (0.0168 mol) of SDFDPS were mixed with anhydrous K ₂ CO ₃ (2.6365 g, 0.0190 mol) The mixture was stirred and heated to 150 ° C with a mixture of DMAc and toluene (v / v = 1.6 / 1). The monomer was dissolved by stirring for 2 hours and toluene was refluxed for 4 hours to remove water as a byproduct. The BDT-based hydrophilic unit polymer precursor (BDT-philic) was then prepared by heating at 175 ° C for 1 hour and reacting for 18 hours.

Example  2: at the end of the hydrophilic unit polymer precursor Capping  Introduction of unit

In order to improve the stability of the polyphenylsulfide derivative, which is the hydrophilic unit polymer precursor produced in Example 1, and to improve the reactivity to the condensation reaction with the hydrophobic unit polymer, a capping unit containing a hydroxy or halogen at the terminal thereof is referred to as the hydrophilic unit Was introduced into both ends of the polymer precursor.

2.1. TBBT -Based hydrophilic units at the ends of the polymer precursor Capping  Introduction of unit

After the temperature of the reaction mixture solution of Example 1.1 was lowered to 80 占 폚, 0.5586 g (0.00300 mol) of 4,4'-biphenol (BP) was added and slowly heated to 175 占 폚 And allowed to react for 3 hours. After filtration to remove the by-products formed by K ₂ CO ₃ , it was precipitated in isopropyl alcohol (IPA). The precipitate was repeatedly washed, filtered and purified, and then dried under reduced pressure at 80 DEG C for 24 hours.

Decafluorobiphenyl (DFBP) was introduced at the terminal of the hydrophilic unit polymer precursor into which BP was introduced at the terminal for further improving the reactivity to the condensation reaction.

Specifically, 0.5528 g of K ₂ CO ₃ was added to 10 g of the hydrophilic unit polymer precursor prepared by introducing purified BP and dried and purified, followed by the addition of a mixed solvent v (v) of dimethylacetamide (DMAc) and cyclohexane / v = 1.6 / 1). The temperature was adjusted to 80 ° C and the monomer was dissolved while stirring for 1 hour. Cyclohexane was refluxed for 4 hours to remove water as a reaction by-product. After the temperature of the solution was lowered to room temperature, DFBP (2.004 g, 0.00600 mol) was added and the temperature was gradually raised to 80 ° C and reacted for 4 hours. After filtration to remove the by-products produced by K ₂ CO ₃ , it was precipitated in isopropyl alcohol. The precipitate was repeatedly washed, filtered and purified, and then dried under reduced pressure at 80 DEG C for 24 hours to obtain a TBBT-based hydrophilic unit polymer precursor (capped TBBT-philic) having capping units introduced at both ends.

2.2. Li ₂ S -Based hydrophilic units at the ends of the polymer precursor Capping  Introduction of unit

The embodiment 1.2 the reaction Raise the BP, anhydrous K ₂ CO ₃ (0.8707 g) and the temperature was added to toluene of 0.5586 g (0.00300 mol) and then lowering the temperature of the mixed solution to 80 ℃ to 150 ℃ toluene for 4 hours To remove water as a by-product of the reaction. Thereafter, the temperature was raised to 150 DEG C for one hour and reacted for 3 hours. After filtration to remove the by-products produced by K ₂ CO ₃ , it was precipitated in isopropyl alcohol. The precipitate was repeatedly washed, filtered and purified, and then dried under reduced pressure at 80 DEG C for 24 hours.

In the condensation reaction Decafluorobiphenyl (DFBP) was introduced at the end of the hydrophilic unit polymer precursor into which BP was introduced at the terminal for further improving the reactivity. The introduction of the DFBP was obtained to that according to Example 2.1 is performed as a capping unit in both ends it introduced Li ₂ S- based hydrophilic units of the polymer precursor (capped Li ₂ S-philic) above.

2.3. BDT -Based hydrophilic units at the ends of the polymer precursor Capping  Introduction of unit

After the temperature of the reaction mixture solution of Example 1.3 was lowered to 80 ° C, 0.5586 g of BP was added and the temperature was gradually raised to 175 ° C for 3 hours. After filtration to remove the by-products formed by K ₂ CO ₃ , it was precipitated in isopropyl alcohol (IPA). The precipitate was repeatedly washed, filtered and purified, and then dried under reduced pressure at 80 DEG C for 24 hours.

Decafluorobiphenyl (DFBP) was introduced at the terminal of the hydrophilic unit polymer precursor into which BP was introduced at the terminal for further improving the reactivity to the condensation reaction. The introduction of the DFBP was carried out as in Example 2.1 described above to obtain a BDT-based hydrophilic unit polymer precursor (capped BDT-philic) with capping units introduced at both ends.

Example  3: linked with ether as hydrophobic unit polymer Polyphenyl  Preparation of derivatives

The molecular weight of the hydrophobic unit polymer can also be adjusted according to the molar ratio of the monomers to be produced. Thus, the target molecular weight is set and the amount of reactant used is determined accordingly. In the present invention, the target molecular weight was set to 6 kg / mol and the synthesis was carried out.

Specifically, a four-necked flask was equipped with a condenser, a mechanical stirrer, and a Dean-Stark trap, and sufficiently purged with argon gas. 4.6012 g (0.0213 mol) of 4,4'-dihydroxydiphenyl ether (DHDPE), 5.6988 g (0.0198 mol) of 4,4'-dichlorodiphenyl sulfone (4,4'-dihydroxydiphenyl ether -dichlorodiphenyl sulfone (DCDPS) was reacted with K ₂ CO ₃ (3.5278 g, 0.0255 mol) in a mixed solvent of dimethylacetamide and toluene (v / v = 1.6 / 1). After the temperature was raised to 150 ° C and the monomer was dissolved while stirring for 2 hours, toluene was refluxed for 4 hours to remove water as a reaction by-product. Thereafter, the mixture was heated at 175 DEG C for 1 hour and reacted for 18 hours to prepare a polyphenyl ether derivative. When the reaction was completed, the temperature was lowered to room temperature and then poured into distilled water to precipitate the product. The precipitate was repeatedly washed, filtered and purified, and then dried under reduced pressure at 80 DEG C for 24 hours.

Example  4: hydrophilic unit polymer precursor and hydrophobic unit polymer Condensation

4.1. TBBT -Based hydrophilic unit polymer precursor

The hydrophilic unit polymer precursor (capped TBBT-philic) containing the capping unit at both ends prepared according to Examples 1.1 and 2.1 was condensed with the hydrophobic unit polymer prepared according to Example 3 to obtain an ion conductive block copolymer Precursor.

Specifically, a four-necked flask was equipped with a condenser, a mechanical stirrer, and a Dean-Stark trap, and sufficiently purged with argon gas. The polyphenyl ether derivative prepared in Example 3 and K ₂ CO ₃ (3.5278 g, 0.0255 mol) were added thereto, and a mixed solvent of dimethyl acetamide and cyclohexane (v / v = 1.6 / 1) The compounds were dissolved while stirring for 1 hour. When the dissolution was completed, the temperature of the mixed solution was raised to 135 ° C, and cyclohexane was refluxed for 4 hours to remove water as a reaction by-product. After the temperature of the solution was lowered to room temperature, a hydrophilic unit polymer precursor containing a capping unit was added to both ends prepared in Examples 1.1 and 2.1, and the temperature was gradually raised to 80 ° C until the viscosity increased The reaction was maintained. After the reaction was completed, the temperature was cooled to room temperature and poured into distilled water to precipitate a block copolymer containing polyphenyl sulfide in the hydrophilic block in the reaction mixture solution in the form of a swollen fiber. The precipitate was repeatedly washed and filtered to give the purified copolymer. Thereafter, it was dried under reduced pressure at 120 DEG C for 24 hours.

4.2. Li ₂ S -Based hydrophilic unit polymer precursor

The hydrophilic unit polymer precursor (capped Li ₂ S-philic) containing capping units at both ends, prepared according to Examples 1.2 and 2.2, and the hydrophobic unit polymer prepared according to Example 3 were condensed to form ion conductive block air To prepare a precursor of the coalescence. Specific reaction conditions are as described in Example 4.1 above.

4.3. BDT -Based hydrophilic unit polymer precursor

The hydrophilic unit polymer precursor (capped BDT-philic) containing the capping unit at both ends prepared according to Examples 1.3 and 2.3 was condensed with the hydrophobic unit polymer prepared according to Example 3 to prepare an ion conductive block copolymer Precursor. Specific reaction conditions are as described in Example 4.1 above.

Example  5: Oxidation reaction The sulfonic acid group  Included Polyphenylsulfone  Preparation of an ion conductive block copolymer containing a derivative in a hydrophilic unit polymer

5.1. Hydrophilic unit polymer TBBT -base Polyphenylsulfone  Preparation of ion-conducting block copolymer containing

The block copolymer containing TBBT-based polyphenylsulfide was oxidized to the hydrophilic block prepared in Example 4.1 to prepare a TBBT-based polyphenylsulfone-containing block copolymer as an ion conductive block copolymer. The oxidation reaction can be achieved in two forms. One is to perform the oxidation reaction using the block copolymer itself, and the other is to perform the oxidation reaction on the film produced after molding the block copolymer into a film form. In the present invention, the former was selected. Specifically, the dried powdery copolymer (2 g) obtained in Example 4.1 was dispersed in acetic acid (40 ml) and sulfuric acid (3 ml) was added. 30% hydrogen peroxide (2.6 ml) was slowly added to the reaction solution, followed by reaction at room temperature for 2 days with stirring. When the reaction was completed, the reaction solution was filtered to separate the product. The separated product can be converted into a potassium salt form by converting the substituted sulfonic acid group into a potassium salt solution so as to form a solution having a low viscosity when reacted with a K ₂ CO ₃ solution so as to facilitate processing.

5.2. Hydrophilic unit polymer Li ₂ S -base Polyphenylsulfone  Preparation of ion-conducting block copolymer containing

The exemplary oxidation of a block copolymer including a Li ₂ S- based polyphenylene sulfide in a hydrophilic block produced in Example 4.2 to prepare a block copolymer comprising an ion conductive block copolymer Li ₂ S- based polyphenyl sulfone. The oxidation reaction was carried out in the same manner as described in Example 5.1.

5.3. Hydrophilic unit polymer BDT -base Polyphenylsulfone  Preparation of ion-conducting block copolymer containing

The block copolymer containing BDT-based polyphenylsulfide was oxidized to the hydrophilic block prepared in Example 4.3 to prepare a block copolymer containing BDT-based polyphenylsulfone as an ion conductive block copolymer. The oxidation reaction was carried out in the same manner as described in Example 5.1.

Example  6: Preparation of polymer membrane using ion conductive block copolymer

The hydrophilic block prepared in Examples 5.1 to 5.2 contained a plurality of aryl groups connected with a sulfonic group containing at least one aryl group substituted with a sulfonic acid and an ion conductive block copolymer (0.35 g) containing a phenyl group linked to the hydrophobic block via an ether bond, Was dissolved in a mixed solvent of 5 ml of DMAc and the same volume of DMSO and filtered through a 0.5 [mu] m filter to prepare a copolymer solution. The solution was poured onto a glass plate and dried for 12 hours or more under a nitrogen atmosphere at 80 ° C to completely remove the solvent, thereby preparing a polymer electrolyte membrane. The polymer membranes prepared from the block copolymers containing the hydrophilic blocks synthesized from the double TBBTs were used as the experimental group 1 and the polymer membranes prepared from the block copolymers containing the hydrophilic blocks synthesized from Li ₂ S were used as the experimental group 2, Lt; / RTI >

Comparative Example  One: The sulfonic acid group  Included The sulfide group  Included TBBT - Preparation of Polymeric Membrane Using Ionic Conducting Polymers Contained in Hydrophilic Unit - based Polymers

As Comparative Example 1, a TBBT-based block copolymer without conversion of sulfide to sulfonic acid through the oxidation reaction according to Example 5.1, that is, the copolymer synthesized by Example 4.1, was used. The copolymer was molded into a polymer membrane according to the method described in Example 6 and used in the physical properties test together with the experimental group.

Comparative Example  2: The sulfonic acid group  Included The sulfide group  Included Li ₂ S -Based Hydrophilic Unit Polymers and Preparation of Polymeric Membranes Using the Ionic Conducting Polymers

As Comparative Example 2, a Li ₂ S-based block copolymer without conversion of sulfide to sulfone through the oxidation reaction according to Example 5.2, that is, the copolymer synthesized by Example 4.2, was used. The copolymer was molded into a polymer membrane according to the method described in Example 6 and used in the physical properties test together with the experimental group.

Comparative Example  3: The ether content in the hydrophobic block Reduced  The hydrophilic block contains Sulfide And a polymer membrane using the same

For comparison with a block copolymer having an increased ether content in the hydrophobic block according to the present invention, a block copolymer containing the same hydrophilic block as the copolymer of Example 4.1 but having reduced ether bond number in the hydrophobic block was prepared, Respectively. The specific production method of Comparative Example 3 is as follows.

First, a four-necked flask was equipped with a condenser, a mechanical stirrer, and a Dean Stark trap, and sufficiently purified by argon gas. BP (biphenol; 4.4730 g, 0.0240 mol), 4,4'- difluoro Lodi sulfone (4,4'-difluorodiphenyl sulfone; DFDPS, 5.5270 g, 0.0217 mol) and _{K 2 CO 3 (3.9840 g,} 0.0288 mol) And the mixture was stirred at 150 ° C for 2 hours to dissolve the compounds. The toluene was refluxed for 4 hours to remove water as a by-product of the reaction. Thereafter, the temperature was raised to 175 DEG C for one hour and reacted for 18 hours. After the reaction was completed, the temperature was lowered to room temperature and poured into distilled water to precipitate the synthesized oligomer in the reaction mixture solution. The precipitate was repeatedly washed and filtered to give a purified oligomer. Thereafter, it was dried under reduced pressure at 80 DEG C for 24 hours to obtain a hydrophobic oligomer with reduced ether content.

The four-necked flask was equipped with a condenser, a mechanical stirrer and a Deanstock trap, and sufficiently purged with argon gas. The prepared hydrophobic oligomer and K ₂ CO ₃ were added and the mixture was dissolved with stirring at 80 ° C for one hour by adding a mixed solvent of DMAc and cyclohexane (v / v = 1.6 / 1). When completely dissolved, the temperature of the mixed solution was raised to 135 ° C and cyclohexane was refluxed for 4 hours to remove the by-product water. After the temperature of the solution was lowered to room temperature, the TBBT-based hydrophilic unit polymer precursor prepared according to Examples 1.1, 1.2, and 4.1 was added and the temperature was gradually raised to 80 DEG C to maintain the reaction until the viscosity increased. When the reaction was completed, the temperature was cooled to room temperature and poured into distilled water to precipitate the block copolymer in the form of swollen fiber in the reaction mixture. The precipitate was repeatedly washed and filtered to give the purified copolymer. Thereafter, it was dried under reduced pressure at 120 DEG C for 24 hours. The polymer membrane was prepared using the block copolymer containing the sulfide group before the above-obtained additional oxidation process, and used as Comparative Example 3.

Comparative Example  4: The ether content in the hydrophobic block Reduced  The hydrophilic block contains Polyphenyl Copolymer containing sulfone structure and production of polymer membrane using the same

The polymer of Comparative Example 3 was oxidized to convert the sulfide group contained in the hydrophilic block to a sulfone group. The polymer membrane was prepared using the block copolymer and used as Comparative Example 4.

Comparative Example  5: Copolymer Containing Ether Group in Hydrophilic Block and Preparation of Polymeric Membrane Using It

In order to confirm the effect of the distribution of the ether groups, a copolymer having an ether group introduced into the hydrophilic block was prepared. To this end, a hydrophilic oligomer was synthesized in the same manner as in Example 1.1 using biphenol instead of TBBT. The prepared hydrophilic oligomer was subjected to the reaction described in Example 2.1 to introduce capping units at both ends. The hydrophilic block having capping units introduced at both ends was condensed with the BP-based hydrophobic polymer prepared by the method described in Comparative Example 3 to prepare a copolymer having an ether group introduced into the hydrophilic block, which was used as Comparative Example 5 Respectively.

Experimental Example  1: An ion conductive polymer containing Electrolyte membrane  Check property

The physical properties of the polymer membrane prepared in Example 6 and Comparative Example 1 were measured. Specifically, conductivity, dimensional change and water absorption rate were measured.

First, the proton conductivity was measured at 100% relative humidity at 25 ° C and 80 ° C using an AC impedance analyzer (Solatron 1280, Impedance / gain phase analyzer). Four prove conductivity cells were measured in the in-phase direction in the range of 0.1 to 20 kHz. The temperature was maintained for 30 minutes in the thermo-hygrostat chamber before measurement, and the conductivity was calculated by the following equation.

Where I is the distance between the electrodes, R is the impedance of the film, and S is the surface area over which the protons move.

Next, the degree of dimensional change was measured. In order to measure the degree of dimensional change, the prepared membrane was immersed in distilled water for 24 hours, the volume (Vwet) of the wet membrane was measured, and the wet membrane was vacuum dried again at 120 ° C for 24 hours to measure the volume (Vdry). These measured values were substituted into the following equations to calculate the degree of dimensional change.

Finally, water uptake (WU) was measured. The water absorption rate was calculated by measuring the mass (Wwet) of the wet film and the mass (Wdry) of the dried film using the following equation.

The molecular weight was measured by measuring intrinsic viscosity. In order to measure the intrinsic viscosity, the prepared polymer was dissolved in NMP and the viscosity of the solution prepared at a concentration of 0.5 g / dl was measured in a 25 ° C. thermostat using a Ube load viscometer.

The results thus obtained are summarized in Table 1 below.

As shown in Table 1, the polymer membranes (experimental groups 1 and 2) prepared using the ion conductive polymer according to the present invention had a similar skeleton used as a comparative example, but did not undergo an oxidation process and contained a sulfide group instead of a sulfone group (Comparative Examples 1 and 2). The polymer membranes prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were found to have equivalent ion conductivity. In addition, although the content of the ether group of the flexible property was increased, the dimensional change and the water absorption rate were rather reduced (Experimental Example 1 to Comparative Example 4). This indicates that when the polymer membrane including the ion conductive polymer according to the present invention is used as an electrolyte membrane of a fuel cell, the swelling in the longitudinal direction can be suppressed and thus the membrane can be advantageously used for durability.

Experimental Example  2: Solubility and Flexibility of Copolymer to Organic Solvent by Ether Group Content

The solubilities of the copolymers prepared according to the Preparation Examples and Comparative Examples in various organic solvents were measured and reported in Table 2 below. The polymers containing ether groups (Experiments 1 and 2) in the hydrophobic block according to the present invention had significantly improved solubility compared to the polymer composed of hydrophobic blocks containing relatively low content of ether groups (Comparative Example 4) Respectively.

The glass transition temperature was also measured by DSC analysis to confirm the change in flexibility of the copolymer with increasing ether group content. Film type sample while heating at a rate of 10 ° C / minute. In particular, FIG. 1 shows the results of measuring the glass transition temperature of experimental group 1 and comparative example 4, which are polymers containing the same hydrophilic block and changing only the ether content of the hydrophobic block. As a result, it was confirmed that Experimental Group 1 containing a higher content of ether groups in the hydrophobic block exhibited lower glass transition temperature than Comparative Example 4, indicating that the polymer having increased ether content in the hydrophobic block according to the present invention exhibited higher flexibility .

Experimental Example  3: Ether group  Chemical durability according to content and distribution

Oxidation stability tests were performed on Fenton reagents to confirm the chemical durability of the prepared copolymers. In order to confirm not only the content of the ether groups but also the chemical durability according to the distribution, it was confirmed that the copolymer of Comparative Example 4 containing a lower content of ether group in the hydrophobic block than the copolymer of the present invention and the hydrophilic block had an ether group The same experiment was performed on the copolymer of Comparative Example 5. Specifically, the weight (W1) of the vacuum dried film was measured and then immersed in a Fenton reagent (3 wt% hydrogen peroxide solution containing 2 ppm of FeSO ₄ catalyst), and the weight change and film cracking time were measured in a thermostatic chamber at 80 ° C . The weight change value was calculated as the percentage of the weight after the reaction (W2 / W1 × 100) with respect to the pre-reaction weight after the film was taken out from the Fenton reagent and dried in a vacuum oven for 24 hours after measuring the weight (W2). The film cracking time was measured by measuring the time from the start of the film cracking in the Fenton reagent. The results are shown in Table 3 below.

As shown in Table 3, the copolymers according to the present invention (Experimental Groups 1 and 2) were found to have equivalent or higher oxidation stability than Comparative Example 4, even though they contain higher reactive ether groups. On the other hand, the block copolymer of Comparative Example 5 containing a hydrophilic block ether group has a markedly reduced oxidation stability due to the fact that the reactive ether group is adhered to the sulfonic acid group introduced for imparting hydrophilicity to the chemical stability, All disassembled. That is, in order to improve the flexibility, the block copolymer according to the present invention introduces the ether group into the hydrophobic block separated from the sulfonic acid group, thereby improving the flexibility without accompanied by reduction of the oxidation stability.

Claims (19)

An ion conductive polymer comprising a block copolymer comprising a hydrophilic block and a hydrophobic block,
Wherein the hydrophilic block comprises a sulfonated poly (phenyl sulfone) structure comprising a sulfonic acid group,
Wherein the hydrophobic block is represented by the following formula (I): < EMI ID =
[Chemical Formula 1]

In Formula 1,
A 'is an electron withdrawing group such as - (SO ₂ ) -, - (C═O) -, -CF ₂ -, -C (CF ₃ ) ₂ - or - (P═O)
p is 1 or 2,
q is an integer of 1 or more.
The method according to claim 1,
Wherein the hydrophilic block is selected from the group consisting of the following formulas (2) to (4):
(2)

(3)

[Chemical Formula 4]

In the above Chemical Formulas 2 to 4,
a and b are each independently an integer of 1 to 4,
M is a ^{cation, H +, Li +, Na} +, K +, NR 4 + or PR ₄ ^+,
A is an electron withdrawing group, - (SO ₂ ) -, - (C═O) -, -CF ₂ -, -C (CF ₃ ) ₂ - or -
l is an integer of 0 to 2,
m is an integer of 1 or more.
The method according to claim 1,
Wherein the hydrophilic block or the hydrophobic block further comprises capping units E and E 'each independently containing a hydroxyl group or a halogen as a reactive functional group at both terminals.
The method of claim 3,
The capping units E and E 'are each independently

,

,

,

,

,

,

And

And X is a single bond, -CF ₂ - or -C (CF ₃ ) ₂ -.
A block copolymer comprising a hydrophilic block and a hydrophobic block comprising a repeating unit represented by any one of the following formulas (5) to (7):
[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the above formulas 5 to 7,
and E and E 'are each independently a single bond or a capping unit, and the fourth, fifth, sixth, seventh, eighth, Lt; / RTI >
y is an integer of 1 or more,
E or E 'is a capping unit, is connected to the hydrophobic unit polymer via a terminal hydroxy group or a fluorine group.
6. The method of claim 5,
The capping units E and E 'are each independently 1,4-dihydroxybenzene, 4,4'-biphenol, perfluorobenzene, decafluorobiphenyl, difluorobisperfluorophenylmethane, 6 , 6 '- (perfluoropropane-2,2-diyl) bis (1,2,3,4,5-pentafluorobenzene), and combinations thereof.
6. The method of claim 5,
Wherein the hydrophilic block is prepared from a monomer having a sulfonic acid group represented by the following formula (8) and a monomer containing a sulfide group represented by the following formula (9) or (10)
[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

Wherein a, b and A are each as defined in claim 2, X is a hydroxy group or halogen, and l is 1 or 2.
6. The method of claim 5,
Wherein the hydrophobic block is prepared from the monomers represented by formulas (11) and (12):
(11)

[Chemical Formula 12]

Wherein A 'and p are as defined in claim 1, and X is halogen.
6. The method of claim 5,
a and b are 1,
M is H ⁺ , Na ⁺ or K ⁺
A is - (SO ₂₎ -,
l is an integer of 0 to 2,
p is 1 or 2,
E is

And X is a single bond and E 'is a single bond.
6. The method of claim 5,
Wherein the block copolymer has a number-average molecular weight (Mn) of 10,000 to 1,000,000 or a weight-average molecular weight (Mw) of 10,000 to 10,000,000.
A method for producing a block copolymer according to claim 5,
Preparing a precursor of a hydrophilic unit polymer represented by the following formula (13) containing a sulfide group;
Preparing a hydrophobic unit polymer represented by the following formula (1);
Mixing a precursor of the hydrophilic unit polymer with a hydrophobic unit polymer to form a block copolymer by a condensation reaction; And
And oxidizing the sulfide group of the precursor of the hydrophilic unit polymer to a sulfone group.
[Chemical Formula 1]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

In the above formulas (1) and (13) to (15)
a, b, A, A ', M, l, m, p and q are each as defined in claim 5.
12. The method of claim 11,
Further comprising the step of binding the capping unit E to the precursor of the hydrophilic unit polymer prior to the condensation reaction or coupling the capping unit E 'to the hydrophobic unit polymer.
13. The method of claim 12,
The capping units E and E 'are each independently selected from the group consisting of 1,4-dihydroxybenzene, 4,4'-biphenol, perfluorobenzene, decafluorobiphenyl, difluorobisperfluorophenylmethane, Is reacted with a capping agent selected from the group consisting of 6,6 '- (perfluoropropane-2,2-diyl) bis (1,2,3,4,5-pentafluorobenzene) Way.
14. The method of claim 13,
Wherein the reaction with the capping agent is performed with one kind of capping agent or with two or more kinds of capping agents through two or more reactions.
An ion conductor comprising the ion conductive polymer according to any one of claims 1 to 4 or the block copolymer according to any one of claims 5 to 10.
16. The method of claim 15,
Wherein the ion conductor is a molding formed of a resin composition comprising an ion conductive polymer or a block copolymer.
17. The method of claim 16,
Wherein the molded body is an electrolyte membrane, a separation membrane, or a water treatment membrane.
A battery comprising an ionic conductive polymer according to any one of claims 1 to 4 or an electrolyte membrane or separator formed from a resin composition comprising the block copolymer according to any one of claims 5 to 10.
19. The method of claim 18,
A proton exchange membrane fuel cell, a direct methanol fuel cell, or a redox flow cell.

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