KR101532306B1 - Ion-conducting polymer comprising phenyl pendant substituted with at least two sulfonated aromatic groups - Google Patents

Abstract

The present invention relates to a polymer comprising a phenylpentane substituted with two or more sulfonated aromatic groups, a method for producing the polymer, an ion conductor including the polymer, a molded article formed from the resin composition containing the polymer, and a resin containing the polymer To a battery having an electrolyte membrane formed from a composition.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a polymeric ion conductor comprising a phenyl-pendant substituted with at least two sulfonated aromatic groups,

The present invention relates to a polymer comprising a phenylpentane substituted with two or more sulfonated aromatic groups, a method for producing the polymer, an ion conductor including the polymer, a molded article formed from the resin composition containing the polymer, and a resin containing the polymer To a battery having an electrolyte membrane formed from a composition.

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. Therefore, polyetherketone and polyethersulfone-based polyaryleneether polymers have been studied for application to fuel cells due to their excellent chemical stability and mechanical properties.

U.S. Patent No. 4,625,000 discloses a post-sulfonation process of a polyethersufone with a polymer electrolyte membrane. The post-treatment sulfonation method disclosed in the above document uses a strong acid such as sulfuric acid as a sulfonating agent and randomly introduces a sulfonic acid group (-SO ₃ H) into the polymer skeleton, so that the distribution of sulfonic acid groups, It is difficult to control the position, number, and the like.

In addition, European Patent No. 1,113,517 A2 discloses a block copolymer polyelectrolyte membrane composed of a block having a sulfonic acid group and a block having no sulfonic acid group. There is a problem such that the chemical bond of the aliphatic polymer is decomposed during the sulfonation process because the block copolymer composed of the aliphatic block and the aromatic block is sulfonated using sulfuric acid which is a strong acid, It was difficult to control the position and number of sulfonic acid groups in the polymer skeleton.

On the other hand, Japanese Patent Application Laid-Open No. 2003-147074 discloses a method of introducing a sulfonic acid group into a fluorene of a polymer by using a chlorosulfonic acid (HSO ₃ Cl) or a sulfuric acid as a copolymer containing a fluorene compound Method. In this method, a sulfone group is randomly introduced into a ring constituting a fluorene compound.

The polymer sulfonation methods proposed in the above-mentioned prior arts have the disadvantages that when the sulfonate group content (sulfonation degree: 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 are excessively increased to dissolve the electrolyte membrane in methanol, and the mechanical densities of the electrolyte membranes are remarkably decreased, failing to satisfy the physical properties of the electrolyte membrane required for fuel cell operation.

The present inventors have introduced a polymer capable of inducing effective phase separation of a hydrophilic domain and a hydrophobic domain by introducing a multiphenyl pendant and substituting a sulfonic acid group at a terminal thereof to form a sulfonated structure densely and locally And further to provide a polymer capable of enhancing the chemical stability against various radicals by constituting the polymer backbone with a carbon-carbon bond without a weak ether bond (-O-). When such a polymer is used, it is possible to provide an electrolyte membrane for a fuel cell which exhibits high ionic conductivity and at the same time has excellent chemical stability.

The present invention provides a polymer having a backbone comprising at least one phenylene repeating unit represented by the following formula (1) and at least one phenylene repeating unit represented by the following formula (2)

[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,

A ₁ and A ₂ is a single bond, each independently, - (C = O) - , - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) - ego;

B is _{-O-, -S-, - (SO 2} ) -, - (C = O) -, -NH- or -NR ₃₃ -, and wherein R ₃₃ is C1 ~ C6 alkyl group;

At least two or all of R ₁ to R ₅ are a sulfonated phenyl, a sulfonated pyridinyl or a sulfonated naphthalenyl which is substituted with a sulfonic acid group or an alkali metal salt thereof, and R ₁ To R ₅ each independently represent a hydrogen atom (-H), a halogen atom (-X), a sulfonic acid group (-SO ₃ H), a phosphoric acid group (-PO ₃ H ₂ ), an acetic acid group (-CO ₂ H) (-NO ₂ ), a perfluoroalkyl group, a perfluoroalkylaryl group optionally containing one or more oxygen, nitrogen or sulfur atoms in its chain, a perfluoroaryl group and an -O-perfluoroaryl group, or one Or an aryl group substituted with at least one halogen, a sulfonic acid group, a phosphoric acid group, an acetic acid group or a nitro group, and the perfluoro group may include a substituent selected from the group consisting of sulfonic acid, phosphoric acid, acetic acid and nitro, , The phosphoric acid group and the acetic acid group are alkaline May be in the form of a metal salt;

R ₆ to R ₁₀ are each independently a hydrogen atom, at least one fluorine atom (F) (except when all are fluorine), an aryl group, a perfluoroalkyl group, optionally one or more oxygen atoms in the chain, nitrogen And / or a perfluoroalkylaryl group including a sulfur atom, a perfluoroaryl group, and an -O-perfluoroaryl group;

R ₁₁ to R ₁₄ each independently may include a substituent selected from the group consisting of a hydrogen atom, a halogen atom, a sulfonic acid group, a phosphoric acid group, an acetic acid group and a nitro group, and the sulfonic acid group, phosphoric acid group and acetic acid group may be in the form of an alkali metal salt ;

a, b, c and d are each independently an integer of 0 or more and 10 or less.

The present invention also provides a method for producing a polymer, which comprises reacting a dihalobenzene containing an aryl group substituted with a reactive halogen element connected to an side chain represented by the following Reaction Scheme 1 by an electron-attracting group and a reactive halogen element Which is substituted with a reactive halogen element from a mixture of dihalobenzenes containing an aryl group which is not substituted with a halogen atom, and benzene having an aryl group in an unsubstituted aryl group on the side chain, by a colon coupling reaction step; A second step of replacing a halogen element substituted with an aryl group bonded to the side chain of the benzene skeleton by a nucleophilic substitution reaction represented by the following Reaction Scheme 2 with a polyphenyl pendant; And a third step of treating the polymer substituted with the polyphenyl pendant represented by the following reaction formula 3 with a sulfonating agent, a nitrifying agent, a phosphorylating agent, or a halogenating agent, and post-treating the polymer.

[Reaction Scheme 1]

[Reaction Scheme 2]

[Reaction Scheme 3]

Further, the present invention provides an ion conductor comprising the polymer.

Furthermore, the present invention provides a molded article formed from the resin composition containing the polymer.

The present invention also provides a battery having an electrolyte membrane formed from a resin composition containing a polymer.

Hereinafter, the present invention will be described in detail.

The present invention is characterized in that a polymer having a skeleton containing two or more phenylene repeating units includes a polyphenyl pendant in which one type of phenylene repeating unit is substituted with two or more sulfonated aromatic groups at the terminal .

According to the present invention, "multiphenyl pendant" may be a substituent comprising a plurality of phenyl groups. For example, a phenyl ring containing one or more substituted or unsubstituted phenyl, naphthalene or heteroatom in one phenyl ring may be a further substituted bulky substituent.

A sulfuric 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 instead of a sulfonic acid proton.

On the other hand, the aromatic rings formed on the side chains have higher sulfonation reactivity than the aromatic rings forming the main chain skeleton. Therefore, the phenyl group at the end of the side chain among the phenylene repeating units has five substitution sites, so that up to five sulfonic acid groups or their alkali metal salts can be introduced. Rather than directly introducing a sulfonic acid group or its alkali metal salt into the phenyl group at the side chain terminal, a phenyl group, a pyridinyl group or a naphthalenyl group may be introduced at a desired position among five substitution positions of the phenyl group at the side chain terminal group the position, the number and the like of the sulfonic acid group or the alkali metal salt thereof can be easily controlled by introducing a sulfonic acid group or an alkali metal salt thereof into a phenyl group, a pyridinyl group or a naphthalenyl group by substituting two or more naphthalenyl groups. When a phenyl, pyridinyl or naphthalenyl group is further introduced at a desired position (s) among the five substitution positions of the phenyl group at the side chain terminal, the steric hindrance is reduced during the sulfonation reaction, And the control of the introduction position and number of the alkali metal salt or its alkali metal salt becomes easy.

For example, the present invention can introduce a multi-phenyl pendant, which is a large-sized substituent, into a post-treatment sulphonate, and substitute a sulfonic acid group or an alkali metal salt at the end thereof to densely cluster a plurality of sulfonic acid groups. Accordingly, the polymer of the present invention can induce effective phase separation of a hydrophilic domain and a hydrophobic domain by forming a sulphonated structure in which a sulfonic acid group is densely and locally substituted at the terminal of one phenylene repeating unit.

Further, in order to form a hydrophilic repeating unit having a dense sulfonic acid group by a nucleophilic substitution reaction, a phenyl functional group in which a sulfonated phenyl, a sulfonated pyridinyl or a sulfonated naphthalenyl group, which is sulfonated, A hydrophilic repeating unit having a plurality of sulfonic acid groups in the side chain can be formed without damaging the main chain skeleton.

As described above, instead of directly introducing a sulfonic acid group into the phenyl group located at the end of the side chain, introduction of a polyphenyl pendant as a substituent and sulfonation can increase the fluidity of the hydrophilic part composed of the sulfonic acid group to more effectively form a hydrophilic channel, It can induce phase separation. In addition, the degree of sulfonation may be controlled by adjusting the number of the multiple phenylpendants introduced. On the other hand, since the sulfonic acid group is located far away from the polymer backbone structure, the possibility of decomposing the backbone of the polymer backbone can be reduced.

,

,

(이때, M=수소원자 또는 알칼리금속(Li, Na, K, Rb, Cs or Fr))등이 있다.
In the present invention, preferred examples of a sulfonated phenyl group, a sulfonated pyridinyl group or a sulfonated naphthalenyl group substituted with a sulfonic acid group or an alkali metal salt thereof include

,

,

(Where M = a hydrogen atom or an alkali metal (Li, Na, K, Rb, Cs or Fr)).

On the other hand, since the sulfonic acid group and the alkali metal salt thereof are hydrophilic, when the sulfonic acid group is introduced in a large amount, the water resistance of the polymer electrolyte membrane deteriorates and the mechanical strength and the degree of integration of the polymer electrolyte membrane are lowered due to the increase in water content, It may be difficult to satisfy the physical properties of the electrolyte membrane. Accordingly, since the polymer of the present invention contains the hydrophobic monomer represented by the above formula (2) in the skeleton, it can provide an increased mechanical strength and can effectively control the ion exchange rate.

Also, it is possible to provide a polymer capable of increasing the chemical stability against various radicals by constituting the back bone of the polymer as a carbon-carbon bond without a weak ether bond (-O-) as shown in the following formula (3) . When such a polymer is used, it is possible to provide an electrolyte membrane for a fuel cell which exhibits high ionic conductivity and at the same time has excellent chemical stability.

(3)

In Formula _{3 A 1, A 2, B} , R 1 to R _5, R ₆ to R _10, a, b, c and d are the same as defined for formula 1 and 2, m, n and p are Each independently an integer of 1 or more.

The fact that the skeleton of the polymer comprises at least one repeating unit represented by the formula (1) and at least one repeating unit represented by the formula (2) contributes to decrease the pKa of the polymer according to the present invention, as compared with the standard polymer according to the prior art. This decrease in pKa is due to the increase in acidity due to the substituted sulfonic acid groups, and thus the modified polymer can be used as a film in battery devices operating at high temperatures.

The polymer of the present invention may be symmetrically substituted with a sulfonated phenyl, sulfonated pyridinyl or sulfonated naphthalenyl group substituted with a sulfonic acid group or its alkali metal salt in R ₁ to R ₅ have. For example, the position of the combination selected from the group consisting of (R ₁ and R ₅ ), (R ₂ and R ₄ ), (R ₁ , R ₃ and R ₅ ) and (R ₁ , R ₂ , R ₄ and R ₅ ) May be substituted with a sulfonated phenyl group, a sulfonated pyridinyl group or a sulfonated naphthalenyl group substituted with a sulfonic acid group or an alkali metal salt thereof.

"Halogen" is an atom selected from fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).

"Alkyl" is a saturated linear or branched structure of from 1 to 20 carbon atoms, or a saturated cyclic structure consisting of from 3 to 20 carbon atoms. For example, methyl, ethyl, n-propyl, i-propyl (isopropyl), n-butyl, i-butyl, t-butyl, n-dodecyl, cyclopropyl or cyclohexyl groups do. And may contain one or more heteroatoms selected from oxygen, sulfur and / or nitrogen in the cyclic structure.

"Aryl" means a functional group or substituent derived from an aromatic ring compound. The cyclic compound may be composed of only carbon atoms and may include one or more hetero atoms selected from oxygen, sulfur and / or nitrogen. For example, the carbon-only aryl group includes phenyl, naphthyl, anthracenyl and the like. Examples of the aryl group containing a hetero atom include thienyl, indolyl, Pyridinyl, and the like. The heteroatom-containing aryl may be heteroaryl, but in the present invention, it is aryl.

The terms "perfluoroalkyl", "perfluoroaryl", "-O-perfluoroaryl", and "perfluoroalkylaryl" Means alkyl, aryl and -O-aryl in which each of the hydrogen atoms thereof is replaced by a fluorine atom (F).

The phenylene groups in the polymer backbone according to the present invention may be orthogonal (1,2-phenylene), meta (1,3-phenylene), or para (1,4-phenylene). And may be para-form.

On the other hand, X and Y connected to each other via the benzene ring may be located in ortho, meta or para to each other.

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.

In the polymer according to the present invention, the repeating units may be random, alternating, or sequential. The repeating units may be block copolymers. When sufficiently limited, the molar ratio of each repeating unit can be varied variously.

The polymer according to the present invention may be a polymer formed by using a polymer represented by the general formula (3) in which the repeating units are bonded at a certain ratio as repeating units.

(3)

Preferably, the ratio of m to n in Formula 3 may be 1: 2 to 1:30, more preferably 1: 5 to 1:15, but is not limited thereto. For example, the polymer of the present invention can be obtained by polymerizing a polymer in which 1 to 30, preferably 5 to 15, hydrophobic repeating units represented by the general formula (2) are bonded to one hydrophilic repeating unit containing multiple phenylpentene represented by the general formula And may be a polymer formed by repeating units.

Preferably, the polymer according to the present invention is a polymer wherein A ₁ is - (C = O) -, - (SO ₂ ) -, -CF ₂ - or - (C (CF ₃ ) ₂ ) -; B is -O-, -S-, - (SO ₂ ) - or - (C = O) -; A ₂ is - (C = O) -; And R ₁ to R _{5 may} all be a sulfonated phenyl group, a sulfonated pyridinyl group or a sulfonated naphthalenyl group substituted with a sulfonic acid group. In this case, a, b, c and d may each be 1.

Table 1 shows the phenylene repeat units of formula (1) according to embodiments of the present invention.

The polymer of the present invention may be a polymer having a skeleton of formula (10) further comprising at least one phenylene repeating unit represented by the following formula (8) or (9).

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the formula (10), T is a unit represented by the formula (8) or (9)

Wherein A ₁ , A ₂ , B and R ₁ to R ₁₅ are the same as in formulas (1) and (2)

Donor or electron - J is a single bond or an electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) Is -O-, -S-, -NH- or -NR ₃₄ -, wherein R ₃₄ is a C 1 to C 6 alkyl group,

R ₁₆ to R ₂₇ each independently may be a hydrogen atom, a fluorine atom, a cyanide (CN), a perfluoroalkyl group (C _n F _{2n + 1} )

m, n and l are each independently an integer of 1 or more.

Specifically, the polymer of the present invention may be a compound represented by the following formula (11).

(11)

Preferably, the ratio of n + 1 to m in Formula 11 may be 1: 2 to 1:30, more preferably 1: 5 to 1:15, and the ratio of n: l may be 10: 1 to 1: 10, but is not limited thereto.

The method for producing a polymer according to the present invention is characterized by substituting a dihalobenzene having an aryl group substituted with a reactive halogen element connected to an side chain represented by the following Reaction Scheme 1 by a reactive halogen element and a reactive halogen element connected to the side chain through an electron- A first step of preparing a polymer having a skeleton composed of benzene having an aryl group on its side chain substituted with a reactive halogen element by a colon coupling reaction from a mixture of dihalobenzenes containing an unsubstituted aryl group; A second step of replacing a halogen element substituted with an aryl group bonded to the side chain of the benzene skeleton by a nucleophilic substitution reaction represented by the following Reaction Scheme 2 with a polyphenyl pendant; And a third step of treating the polymer substituted with the polyphenyl pendant represented by the following Reaction Scheme 3 with a sulfonating agent, a nitrifying agent, a phosphorylating agent, or a halogenating agent, followed by post-treatment.

[Reaction Scheme 1]

[Reaction Scheme 2]

[Reaction Scheme 3]

A ₁ and A ₂ each independently represent - (C═O) -, - (SO ₂ ) -, -CF ₂ - or -C (CF ₃ ) ₂ - as an electron withdrawing group,

R ₁ to R ₅ And R < ₁₁ > to R < ₁₄ >

Wherein R ₂₈ to R ₃₂ correspond to R ₁ to R ₅ , respectively,

When n is an integer of 1 to 5,

When R _n is a sulfonated substituent, R _{n +27} is the corresponding unsulfonated substituent,

When R _n is a non-sulfonated substituent, R _{n +27} is the same substituent as R _n ,

a, b, c and d are each independently an integer of 0 or more and 10 or less.

The first step represented by the above-mentioned Reaction Scheme 1 is a step of reacting a dihalobenzene containing an aryl group substituted with a reactive halogen element connected to the side chain through an electron withdrawing group by a " colon coupling reaction " A step of reacting a dihalobenzene containing an aryl group not substituted with a reactive halogen element connected to an electron withdrawing group with a metal to be reduced with a catalyst to prepare a polyphenylene polymer linked with a carbon- to be. As the metal to be reduced, zinc (Zn), magnesium (Mg), manganese (Mn), aluminum (Al) or calcium (Ca) may be used. As the catalyst, 2,2'- -bipyridine) or triphenylphosphine (PPh _3, triphenylphosphine; TPP) of _{NiBr 2, NiCl 2, Ni (} PPh 3) 2 Cl 2, Br 2, (acac) 2 · H 2 O, (OOCCH 3) · 4H ₂ O, I ₂ .6H ₂ O or other halide salts (F <Cl <Br <I). The above reaction can be used to form a polymer based on a carbon-carbon single bond. It can impart high mechanical strength and chemical stability to conventional polyphenylene based polymers that form a skeleton through an ester and / or ketone.

The second step represented by the above reaction scheme 2 is a process wherein the aryl group substituted or unsubstituted with a halogen atom is bonded to the side chain prepared in the first step by using a benzene in which a single bond or an electron withdrawing group- Reacting the polymer linked by a single bond with a nucleophilic molecule comprising a multiple phenylpentane to introduce a multiple phenylpentane into the site of the halogen located on the side chain of the benzene skeleton. This step is carried out by a nucleophilic substitution reaction. As the nucleophilic molecule, ROH, RSH, RSO ₃ H, or RCO ₂ H can be used. As the catalyst for each reaction, sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, or SOCl ₂ ; And pyridine. The R group of the nucleophilic molecule may comprise a bulky diphenylpentane that is characteristic of the present invention. As a result of the reaction, a bulky multi-phenyl pendant linked with a -O-, -S-, - (SO ₂ ) - or - (C = O) - bond is attached to a part of the side chain of the skeleton linked by a carbon- The introduced polymer can be obtained.

The third step represented by the above reaction scheme 3 is a step of post-treating the polymer having the side chain of the bulky multi-phenylpentane obtained in the second step to introduce a plurality of substituents into the phenyl group of the side chain. The third step is carried out by sulfonation, nitration, phosphorylation or halogenation, which is carried out in order to add hydrophilicity to the polymer of the present invention.

The sulfonation can be carried out using SO ₃ and H ₂ SO ₄ , chlorosulfonic acid (HSO ₃ Cl) or trimethylsilylchlorosulfonic acid [(CH ₃ ) ₃ SiSO ₃ Cl] in the product of the second step . As a result of the sulfonation, a sulfonic acid group (-SO ₃ H) can be introduced into the phenyl group substituted on the side chain.

하에 NO₂ ⁺BF4^-와 반응시키거나, CH₂Cl₂ 하에 NO₂ ⁺CF₃SO₃ ^-와 반응시켜 수행할 수 있다. 상기 니트로화의 결과로 측쇄에 치환된 페닐기에 니트로기(-NO₂)를 도입할 수 있다.Nitration is carried out by reacting the product of the second step with HNO ₃ under H ₂ SO ₄ , Ac ₂ O or H ₂ O conditions,

By reacting with NO ₂ ⁺ BF 4 ^- under CH ₂ Cl ₂ or by reacting with NO ₂ ⁺ CF ₃ SO ₃ ^- under CH ₂ Cl ₂ . As a result of the nitration, a nitro group (-NO ₂ ) may be introduced into the phenyl group substituted on the side chain.

Phosphorylation can be carried out by reacting the product of the third step with H ₃ PO ₄ by adding pyridine and benzene. As a result of the phosphorylation, a phosphoric acid group (-PO ₃ H) can be introduced into the phenyl group substituted on the side chain.

The halogenation can be carried out by reacting the product of the third step with halogen molecules (X ₂ , X = F, Cl, Br or I) by adding CCl ₄ , Fe, H ₂ O or HOAc. As a result of the halogenation, a halogen group (-X) can be introduced into a phenyl group substituted on the side chain.

By using the sulfonating agent to selectively sulfonate the ends of the polyphenyl pendant substituted on the side chain, the hydrophilic repeating units dense and densely formed in the sulfonate group formed ion conduction channels to form an electrolyte membrane containing the polymer of the present invention Hydrogen ion conductivity can be provided.

At this time, the hydrophobic repeating unit represented by the formula (1) and the hydrophobic repeating unit represented by the formula (2) linked by the carbon-carbon bond may provide mechanical strength.

Therefore, since the polymer of the present invention has the hydrogen ion conductivity provided by the hydrophilic repeating unit and the mechanical strength provided by the hydrophobic repeating unit connected by the carbon-carbon bond, it is possible to provide an electrolyte membrane that satisfies the properties required for battery operation have.

The polymer according to the present invention can be used as an ion conductor by a sulfonic acid group or its alkali metal salt.

The molded article can be formed from the resin composition containing the polymer according to the present invention.

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 polymer according to the present invention can be extruded and formed into a molded article in the form of fiber or film by any method such as spinning, rolling or casting.

For example, an electrolyte membrane can be produced by molding a resin composition containing the polymer of the present invention. Specifically, the polymer is dissolved in a solvent such as N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide or dimethylacetamide, the solution is poured into a plate such as a glass plate, and the polymer attached is dried, Preferably 10 to 120 탆, more preferably 50 to 100 탆 thick, and then desorbed 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.

The present invention provides a battery having an electrolyte membrane formed from a resin composition containing the polymer.

Since the electrolyte membrane formed from the resin composition containing the polymer according to the present invention has high hydrogen ion conductivity, mechanical strength and excellent chemical stability, it can be used as a hydrogen ion electrolyte membrane, and can be used as a proton exchange membrane fuel cell membrane fuel cell aka polymer electrolyte membrane fuel cell (PEMFC), direct methanol fuel cell (DMFC) or redox flow battery.

The hydrophilic repeating unit comprising the sulfonated polyphenyl pendant and the polymer comprising the hydrophobic repeating unit of the present invention provide increased hydrogen ion conductivity due to the dense and dense hydrophilic sulfonic acid group and increase the mechanical strength due to the hydrophobic repeating unit . Unlike the case where the conventional repeating units are connected by a ketone or an ester bond, the repeating units of the present invention are connected to each other by a carbon-carbon bond to provide excellent chemical stability. Therefore, the electrolyte membrane produced by molding the resin composition containing the polymer of the present invention has high hydrogen ion conductivity, mechanical strength, and chemical stability, and thus can be utilized as an ion exchange membrane for a fuel cell driven at a high temperature.

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.

Manufacturing example  One: PBPSPP -115 (m = 1, n = 15)

1.1. Fried - Craft Acylation  reaction( Friedel - Craft acylation )

&Lt; 4 & Fluoro -2,5- Dichlorobenzophenone ( M1 ) Manufacturing>

13.4 g (139 mmol) of fluorobenzene and 9.3 g (69.7 mmol) of anhydrous aluminum chloride were mixed with 20 ml of nitromethane in a round bottom flask and cooled to 0 占 폚. 14.6 g (69.7 mmol) of 2,5-dichlorobenzoyl chloride was slowly added thereto, the temperature was raised to room temperature, and the mixture was stirred for 24 hours while maintaining the temperature. The reaction was mixed with dilute aqueous hydrochloric acid solution and filtered to collect the precipitate. The color was removed with activated charcoal and recrystallized from a n-hexane / ethyl acetate (4: 1) solution. Yield 72.5%.

<2,5- Dichlorobenzophenone ( M2 ) Manufacturing>

To a round bottom flask was added 25 g (119.3 mmol) of 2,5-dichlorobenzoyl chloride and 18.1 g (238.6 mmol) of benzene in 30 ml of nitromethan and cooled to 0 占 폚. After 15.9 g (119.3 mmol) of anhydrous aluminum chloride was added to the mixture, the temperature was raised to room temperature and the mixture was stirred for 24 hours. The reaction was mixed with dilute aqueous hydrochloric acid solution and filtered to collect the precipitate. The color was removed by activated charcoal and recrystallized from n-hexane / ethyl acetate (8: 1) solution. Yield 71.3%.

1.2. Colon coupling reaction ( Colon coupling reaction )On by Sulfonation  The unit copolymer before reaction P1 (m = 1, n = 15)

To the reactor was added 0.324 g (1.484 mmol, 7 mol% of monomer) of triphenylphosphine, 10.388 mmol (50 mol% of monomer) and 5.822 g (89.04 mmol of monomer, 4.2 eq) of nickel bromide , And 13 ml of DMAc (dimethylacetamide) was added thereto, followed by heating to 80 ° C. Stirring was continued for about 30 minutes, and M1 (0.36 g, 1.3 mmol) and M2 (5 g, 19.9 mmol) dissolved in 40 ml of DMAc were added. The mixture was stirred while maintaining the temperature for 8 hours, and then the temperature was lowered to room temperature and then mixed with 10% hydrochloric acid / methanol solution to remove zinc. After filtration, the solid obtained by boiling in methanol was obtained by vacuum drying. Yield 91.4%.

1.3. Nucleophilic  Substitution reaction Nucleophilic substitution reaction )On by Multiple phenyl  pendant( 멀티 닐 pendant Introduction - P2 (m = 1, n = 15) Production

4 g of P1 (m = 1, n = 15) was dissolved in a mixed solvent of 100 ml of DMAc and 30 ml of toluene. K ₂ CO ₃ 0.2 g (1.5 mmol) and hexaphenylbenzene alcohol 0.83 g (1.5 mmol) Lt; 0 &gt; C for 3 hours. The temperature was further raised to 175 DEG C and the toluene was removed using a Dean-Stark trap, followed by further stirring for 24 hours. After the temperature was lowered to room temperature, K ₂ CO ₃ and salts were removed by filtration, and then methanol was added to obtain a precipitate. The precipitate was filtered off with methanol and vacuum dried. Yield 86.4%.

1.4. after Sulfonation  By reaction PBPSPP -115 (m = 1, n = 15)

To a solution of 4.54 g (39 mmol) of chlorosulfonic acid in 150 ml of dichloromethane, 3 g of P2, which was completely dissolved in dichloromethane, was slowly added at room temperature. After stirring for 24 hours, the resulting precipitate was filtered and washed several times with distilled water and hot distilled water. After washing with 0.3 wt% K ₂ CO ₃ aqueous solution for 2 hours, it was washed again with distilled water and vacuum dried. Yield 86.4%.

Manufacturing example  2: PBPSPP -112 (m = 1, n = 12)

2.1. Colon coupling reaction ( Colon coupling reaction )On by Sulfonation  The unit copolymer before reaction P1 (m = 1, n = 12)

Monomers M1 and M2 were prepared by the method described in 1.1 of Preparation Example 1, 1.1. 0.46 g of M1 (1.7 mmol) and 5.0 g of M2 (19.9 mmol) were reacted in the same manner as described in Preparation Example 1.2 to give P1 (m = 1, n = 12). Yield 90.7%.

2.2. Nucleophilic  Substitution reaction Nucleophilic substitution reaction )On by Multipage Neil Pendant ( 멀티 닐 pendant Introduction - P2 (m = 1, n = 12) Production

4 g of P1 (m = 1, n = 12) obtained in Preparation Example 2.1 was reacted with 1.10 g of hexaphenylbenzene alcohol (2.0 mmol) according to the method described in Preparation Example 1.3 to give P2 (m = 1, n = 12). Yield 88.4%.

2.3. after Sulfonation  By reaction PBPSPP -112 (m = 1, n = 12)

PBPSPP-112 (m = 1) was obtained by reacting 3 g of P2 (m = 1, n = 12) obtained in Preparation Example 2.2 and 4.92 g (42 mmol) of chlorosulfonic acid by the method described in Production Example 1.4. , n = 12). Yield 85.8%.

Manufacturing example  3: PBPSPP -110 (m = 1, n = 10)

3.1. Colon coupling reaction ( Colon coupling reaction )On by Sulfonation  The unit copolymer before reaction P1 (m = 1, n = 10)

Monomers M1 and M2 were prepared by the method described in 1.1 of Preparation Example 1, 1.1. 0.54 g of M1 (1.99 mmol) and 5.0 g of M2 (19.9 mmol) were reacted by the method described in Preparation Example 1.2 to give P1 (m = 1, n = 10). Yield 90.7%.

3.2. Nucleophilic  Substitution reaction Nucleophilic substitution reaction )On by Multiple phenyl  pendant( 멀티 닐 pendant Introduction - P2 (m = 1, n = 10) Production

4 g of P1 (m = 1, n = 10) obtained in Preparation Example 3.1 was reacted with 1.32 g of hexaphenylbenzene alcohol (2.34 mmol) according to the method described in Preparation Example 1.3 to give P2 (m = 1, n = 10). Yield 88.9%.

3.3. after Sulfonation  By reaction PBPSPP -110 (m = 1, n = 10)

(M = 1, n = 10) obtained in Production Example 3.2 and 3-chlorosulfonic acid (5.38 g, 42 mmol) , n = 10). Yield 82.7%.

Manufacturing example  4: PBPSPP -108 (m = 1, n = 8)

4.1. Colon coupling reaction ( Colon coupling reaction )On by Sulfonation  The unit copolymer before reaction P1 (m = 1, n = 8)

Monomers M1 and M2 were prepared by the method described in 1.1 of Preparation Example 1, 1.1. 0.67 g of M1 (2.49 mmol) and 5.0 g of M2 (19.9 mmol) were reacted in the same manner as described in Preparation Example 1.2 to give P1 (m = 1, n = 8). Yield 88.4%.

4.2. Nucleophilic  Substitution reaction Nucleophilic substitution reaction )On by Multiple phenyl  pendant( 멀티 닐 pendant Introduction - P2 (m = 1, n = 8)

4 g of P1 (m = 1, n = 8) obtained in Preparation Example 4.1 was reacted with 1.65 g of hexaphenylbenzene alcohol (2.99 mmol) according to the method described in Preparation Example 1.3 to give P2 (m = 1, n = 8). Yield 86.7%.

4.3. after Sulfonation  By reaction PBPSPP -108 (m = 1, n = 8)

PBPSPP-108 (m = 1) was obtained by reacting 3 g of P2 (m = 1, n = 8) obtained in Preparation Example 4.2 and 5.92 g (52 mmol) of chlorosulfonic acid by the method described in Production Example 1.4. , n = 8). Yield 80.2%.

Manufacturing example  5: PBPSPP -107 (m = 1, n = 7)

5.1. Colon coupling reaction ( Colon coupling reaction )On by Sulfonation  The unit copolymer before reaction P1 (m = 1, n = 7)

Monomers M1 and M2 were prepared by the method described in 1.1 of Preparation Example 1, 1.1. 0.77 g of M1 (2.84 mmol) and 5.0 g of M2 (19.9 mmol) were reacted in the same manner as described in Preparation Example 1.2 to give P1 (m = 1, n = 7). Yield 87.4%.

5.2. Nucleophilic  Substitution reaction Nucleophilic substitution reaction )On by Multiple phenyl  pendant( 멀티 닐 pendant Introduction - P2 (m = 1, n = 7)

4 g of P1 (m = 1, n = 7) obtained in Preparation 5.1 was reacted with 1.88 g of hexaphenylbenzene alcohol (3.41 mmol) according to the method described in Preparation Example 1.3 to give P2 (m = 1, n = 7). Yield 88.7%.

5.3. after Sulfonation  By reaction PBPSPP -107 (m = 1, n = 7)

3 g of P2 (m = 1, n = 7) obtained in Production Example 5.2 and 6.37 g (56 mmol) of chlorosulfonic acid were reacted by the method described in Production Example 1.4 to obtain PBPSPP-107 , n = 7). Yield 82.7%.

Manufacturing example  6: PBPDPP -108 (m = 1, n = 8)

2.1. Fried - Craft Acylation  reaction( Friedel - Craft acylation )

4'-fluoro-2,5-dichlorobenzophenone (M1) and 2,5-dichlorobenzophenone (M2) were prepared according to the method described in 1.1 of Preparation Example 1 above.

2.2. Colon coupling reaction ( Colon coupling reaction )On by Sulfonation  Before reaction, the unit copolymer ( P1 ' ; m = 1, n = 8)

0.351 g (1.572 mmol) of nickel (II) bromide, 2.912 g (10.587 mmol) of triphenylphosphine and 5.968 g (90.14 mmol) of zinc were added to the reactor and 15 ml of DMAc (dimethylacetamide) . Stirring was continued for about 30 minutes, and M1 (0.69 g, 2.5 mmol) and M2 (5 g, 19.9 mmol) dissolved in 40 ml of DMAc were added. The mixture was stirred while maintaining the temperature for 8 hours, and then the temperature was lowered to room temperature and then mixed with 10% hydrochloric acid / methanol solution to remove zinc. After filtration, the solid obtained by boiling in methanol was obtained by vacuum drying. Yield 92.8%.

2 .3. Nucleophilic  Substitution reaction Nucleophilic substitution reaction )On by Multipage Neil Pendant ( 멀티 닐 pendant Introduction - P2 ' (m = 1, n = 8)

4 g of P1 'was dissolved in a mixed solvent of 100 ml of DMAc and 30 ml of toluene, and 0.2 g (1.5 mmol) of K ₂ CO ₃ and 0.63 g (2.5 mmol) of 2,6-diphenylphenol were added thereto. Lt; / RTI &gt; The temperature was further raised to 175 DEG C and the toluene was removed using a Dean-Stark trap, followed by further stirring for 24 hours. After the temperature was lowered to room temperature, K ₂ CO ₃ and salts were removed by filtration, and then methanol was added to obtain a precipitate. The precipitate was filtered off with methanol and vacuum dried. Yield 88.7%.

2.4. after Sulfonation  By reaction PBPDPP -108 (m = 1, n = 8)

To a solution of 2.28 g (20 mmol) of chlorosulfonic acid in 150 ml of dichloromethane, 3 g of P2 ', completely dissolved in dichloromethane, was slowly added at room temperature. After stirring for 24 hours, the resulting precipitate was filtered and washed several times with distilled water and hot distilled water. After washing with 0.3 wt% K ₂ CO ₃ aqueous solution for 2 hours, it was washed again with distilled water and vacuum dried. Yield 87.7%.

Example  One: Electrolyte membrane  Produce

0.5 g of the polymer prepared in the above Preparation Example was dissolved in 10 ml of DMSO, and then the insoluble polymer was removed using a 5 μm syringe filter. The filtered polymer solution was poured into a 8 cm x 8 cm silicon mold provided on a glass plate and dried at 80 ° C for 24 hours. The dried polymer film was further dried in a 160 [deg.] C vacuum oven for 24 hours to completely remove the inner, unremoved solvent. After drying, it was treated with 1.5 M sulfuric acid aqueous solution for 24 hours and immersed in distilled water for at least 24 hours to remove residual acid.

Example  2: Electrolyte membrane  Check property

The electrolyte membranes of various compositions were prepared by varying the m and n values by controlling the amounts of the reactants using the reaction of the above preparation examples, and the physical properties were measured. PBPSPP-107 (m = 1, n = 7), PBPSPP-108 (m = 1, n = 8), PBPSPP-110 (m = 1, n = 10) represented by the general formula PDPSPP-mn, such as PDPSPP-108 (m = 1, n = 15) represented by the general formula of the formula (5) and PBPSPP-112 (m = 1, n = 12) = 8) was used as a test group, and GS (Formula 6) and GPS (Formula 7) having the following formulas were used as a comparative test group to measure conductivity, dimensional change and water uptake.

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 2 below.

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

Claims (19)

A polymer having a skeleton containing at least one phenylene repeating unit represented by the following formula (1) and at least one phenylene repeating unit represented by the following formula (2)
[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,
A ₁ and A ₂ is a single bond, each independently, - (C = O) - , - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) - ego;
B is -O-, -S-, - (SO ₂ ) -, - (C = O) -, -NH- or -NR ₁₅ -, wherein R ₁₅ is a C 1 to C 6 alkyl group;
At least two or all of R ₁ to R ₅ are a sulfonated phenyl, a sulfonated pyridinyl or a sulfonated naphthalenyl which is substituted with a sulfonic acid group or an alkali metal salt thereof, and R ₁ To R ₅ each independently represent a hydrogen atom (-H), a halogen atom (-X), a sulfonic acid group (-SO ₃ H), a phosphoric acid group (-PO ₃ H ₂ ), an acetic acid group (-CO ₂ H) (-NO ₂ ), a perfluoroalkyl group, a perfluoroalkylaryl group optionally containing one or more oxygen, nitrogen or sulfur atoms in its chain, a perfluoroaryl group and an -O-perfluoroaryl group, or one Or an aryl group substituted with at least one halogen, a sulfonic acid group, a phosphoric acid group, an acetic acid group or a nitro group, and the perfluoro group may include a substituent selected from the group consisting of sulfonic acid, phosphoric acid, acetic acid and nitro, , The phosphoric acid group and the acetic acid group are alkaline May be in the form of a metal salt;
R ₆ to R ₁₀ are each independently a hydrogen atom, at least one fluorine atom (F) (except when all are fluorine), an aryl group, a perfluoroalkyl group, optionally one or more oxygen atoms in the chain, nitrogen And / or a perfluoroalkylaryl group including a sulfur atom, a perfluoroaryl group, and an -O-perfluoroaryl group;
R ₁₁ to R ₁₄ each independently may include a substituent selected from the group consisting of a hydrogen atom, a halogen atom, a sulfonic acid group, a phosphoric acid group, an acetic acid group and a nitro group, and the sulfonic acid group, phosphoric acid group and acetic acid group may be in the form of an alkali metal salt ;
a, b, c and d are each independently an integer of 0 or more and 10 or less.
The method according to claim 1,
Wherein the positions substituted with a sulfonated phenyl, sulfonated pyridinyl or sulfonated naphthalenyl group substituted with a sulfonic acid group or an alkali metal salt thereof in R ₁ to R ₅ are symmetrical.
3. The method of claim 2,
The position of the combination selected from the group consisting of (R ₁ and R ₅ ), (R ₂ and R ₄ ), (R ₁ , R ₃ and R ₅ ) and (R ₁ , R ₂ , R ₄ and R ₅ ) A sulfonated phenyl, a sulfonated pyridinyl, or a sulfonated naphthalenyl group substituted with an alkyl group or an alkali metal salt thereof.
Wherein the polymer has a number average molecular weight (Mw) of 10,000 to 1,000,000 or a molecular weight of Mw (weight-average molecular weight) of 10,000 to 10,000,000.
The method according to claim 1,
Wherein the phenylene groups of the backbone are linked to each other at para positions.
The method according to claim 1,
Wherein the polymer is a random, alternating, block, or sequential polymer.
The method according to claim 1,
A polymer having a skeleton containing a repeating unit represented by the following formula (3):
(3)

In Formula 3,
_{A 1, A 2, B,} R 1 to R _5, R ₆ to R _10, a, b, c and d are as respectively defined in claim 1, m, n and p are each independently one or more It is an integer.
8. The method of claim 7,
Wherein the ratio of m to n in Formula 3 is 1: 1 to 1:30.
9. The method according to any one of claims 1 to 8,
A ₁ is - (C = O) -, - (SO ₂ ) -, -CF ₂ - or - (C (CF ₃ ) ₂ ) -;
B is -O-, -S-, - (SO ₂ ) - or - (C = O) -;
A ₂ is - (C = O) -; And
Wherein all of R ₁ to R ₅ are a sulfonated phenyl group, a sulfonated pyridinyl group or a sulfonated naphthalenyl group substituted with a sulfonic acid group or an alkali metal salt thereof.
9. The method according to any one of claims 1 to 8,
A polymer having a skeleton of formula (10) further comprising at least one phenylene repeating unit represented by the following formula (8) or (9):
[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the formula (10), T is a unit represented by the formula (8) or (9)
Wherein A ₁ , A ₂ , B and R ₁ to R ₁₀ are the same as those in formulas (1) and (2)
Donor or electron - J is a single bond or an electron withdrawing group - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) Is -O-, -S-, -NH- or -NR ₃₄ -, wherein R ₃₄ is a C 1 to C 6 alkyl group,
R ₁₆ to R ₂₇ are each independently a hydrogen atom, a fluorine atom, a cyanide (CN), a perfluoroalkyl group (C _n F _{2n + 1} )
m, n and l are each independently an integer of 1 or more.
11. The method of claim 10,
Is a compound represented by the following formula (11): &lt; EMI ID =
(11)

12. The method of claim 11,
Wherein the ratio of n + 1 to m in Formula 11 is 1: 2 to 1:30.
The method for producing a polymer according to any one of claims 1 to 8,
A dihalobenzene containing an aryl group substituted with a reactive halogen element connected to an side chain represented by the following Reaction Scheme 1 and a dihalobenzene containing an aryl group not substituted with a reactive halogen element connected to the side chain through an electron withdrawing group A first step of preparing a polymer having a skeleton composed of benzene having an aryl group on its side chain substituted with a reactive halogen element by a colon coupling reaction from the mixture;
A second step of replacing a halogen element substituted with an aryl group bonded to the side chain of the benzene skeleton by a nucleophilic substitution reaction represented by the following Reaction Scheme 2 with a polyphenyl pendant; And
A third step of treating the polymer substituted with the polyphenyl pendant represented by the following Reaction Scheme 3 with a sulfonating agent, a nitrifying agent, a phosphorylating agent, or a halogenating agent, and post-treating the polymer;
[Reaction Scheme 1]

[Reaction Scheme 2]

[Reaction Scheme 3]

R ₁ to R ₅ and R ₁₁ to R ₁₄ are the same as those in formula (1)
Wherein R ₂₈ to R ₃₂ correspond to R ₁ to R ₅ , respectively,
When n is an integer of 1 to 5,
When R _n is a sulfonated substituent, R _{n + 27} is the corresponding unsulfonated substituent,
When R _n is a non-sulfonated substituent, R _{n + 27} is the same substituent as R _n ,
a, b, c and d are each independently an integer of 0 or more and 10 or less.
14. The method of claim 13,
Wherein the sulfonating agent is chlorosulfonic acid (HSO ₃ Cl) or trimethylsilyl chlorosulfonic acid [(CH ₃ ) ₃ SiSO ₃ Cl].
An ion conductor comprising the polymer according to any one of claims 1 to 8.
A molded article formed from the resin composition comprising the polymer according to any one of claims 1 to 8.
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