KR20110100155A - Polybenzthiazole-based compound composition, preparing method thereof, electrode using the composition, and fuel cell employing the same - Google Patents

Abstract

Disclosed are a composition in which a polyoxazine compound is uniformly dispersed, a manufacturing method thereof, an electrode using the same, and a fuel cell employing the same.

Description

Polybenzoxazine compound composition, a method of manufacturing the same, an electrode using the same and a fuel cell employing the electrode {Polybenzthiazole-based compound composition, preparing method etc, electrode using the composition, and fuel cell employing the same}

A composition, a method of manufacturing the same, an electrode using the same, and a fuel cell employing the electrode are provided.

In a phosphoric acid fuel cell operating at high temperature (150-200 ° C.), phosphoric acid, which is liquid, is used as an electrolyte, but a problem arises in that the liquid phosphoric acid is present in a large amount in the electrode, thereby inhibiting gas diffusion. Therefore, an electrode catalyst layer capable of mixing polytetrafluoroethylene (PTFE), which is a water repellent material, with the electrode catalyst and preventing the pores in the electrode from being blocked by phosphoric acid is used.

High temperature humidified polyelectrolyte fuel cell (PEMFC) is operated at a temperature of 150-200 ℃. In order to operate at such temperatures for extended periods of time, the material of the electrode must also have a long life.

The binder used to form the electrode plays an important role in phosphate distribution and structure formation in the electrode and plays an important role in maintaining the electrode's performance during operation. As the binder of the electrode, a water-repellent polymer such as polytetrafluoroethelin (PTFE) is used.

However, binders known to date have a lot of room for improvement since they do not reach satisfactory levels of phosphate resistance and heat resistance.

A composition having excellent dispersibility, a manufacturing method thereof, an electrode using the composition, and a fuel cell employing the composition are provided.

According to one aspect of the invention there is provided a composition comprising a polyoxazine compound particles and a dispersion medium in which the polyoxazine compound particles are dispersed.

Preparing an acid solution of the oxazine monomer by mixing an oxazine monomer with an acid according to another aspect of the present invention;

Thermally treating the acid solution of the oxazine monomer to polymerize it;

Separating the polyoxazine-based compound from the polymerization product; And

Provided is a method for preparing the composition, comprising the step of dispersing the polyoxazine compound in a dispersion medium.

Support according to another aspect of the present invention; There is provided an electrode including a catalyst layer formed on the support and containing a coating product of the composition described above, and a fuel cell employing the same.

The composition according to the embodiment of the present invention is a polyoxazine-based compound particles having a small average particle diameter are evenly dispersed in the dispersion medium, which can be uniformly dispersed in the electrode catalyst layer, and using this, the phosphoric acid retention, high temperature and acid The electrode with improved durability can be manufactured.

1 is an average particle diameter analysis photograph of a polybenzoxazine compound obtained in Example 1,
2 is a thermogravimetric analysis graph of the polybenzoxazine compound prepared according to Examples 1, 3, and 4;
3 is a result of analyzing the platinum catalyst area used for the cathode reaction in the fuel cell prepared according to Production Example 1, Comparative Production Example 1-2,
4 is a view showing the cell voltage characteristics according to the current density in the fuel cell manufactured according to Production Example 1, Comparative Production Example 1-2,
FIG. 5 is a view showing cell voltage characteristics according to current densities in fuel cells manufactured according to Production Example 2-4 and Comparative Production Example 1. FIG.

Provided is a polyoxazine compound composition comprising polyoxazine compound particles and a dispersion medium in which the polyoxazine compound particles are dispersed.

The "polyoxazine-based compound particles are dispersed" means that the polyoxazine-based compound particles are present in a state in which they are not dissolved in the dispersion medium. As such, when the polyoxazine-based compound particles are present in a dispersed state without being dissolved in a dispersion medium, various dispersion mediums can be used.

The dispersion medium may be an organic compound having a density of 0.5 to 2.0 mg / cm ³ as a solvent for dispersing the polyoxazine compound particles.

If the density of the dispersion medium is within the above range, the dispersibility of the polyoxazine compound particles is excellent.

As the dispersion medium, one or more selected from the group consisting of alcohol, water, acid and a hydrocarbon solvent may be used.

Examples of the hydrocarbon solvent include N-Methyl-Pyrrolidine, dimethyl acetamide, toluene, benzene, xylene, and the like. Examples of the alcohol include methanol, ethanol, isopropanol, butanol, and the like. There is this.

Phosphoric acid-based material is used as the acid.

Examples of the phosphoric acid material include polyphosphoric acid, phosphonic acid (H ₃ PO ₃ ), organic phosphonic acid, orthophosphoric acid (H ₃ PO ₄ ), pyrophosphoric acid (H ₄ P ₂ 0 ₇ ), triphosphate (H ₅ P ₃ O _10), there may be mentioned meta-phosphoric acid or a derivative thereof and the like.

The concentration of acid may be at least 80%, 90%, 95% or 98% by weight. For example, the concentration of acid is 80-98% by weight.

The content of the polyoxazine-based compound particles in the polyoxazine-based compound composition is 1 to 80% by weight based on the total weight of the polyoxazine-based compound composition.

The composition can be used for forming a composition for forming an electrode catalyst layer, for example, a fuel cell electrode catalyst layer.

It looks at the manufacturing process of the composition.

The polyoxazine compound is formed by polymerizing an oxazine monomer, and has acid resistance and heat resistance. By the way, the polyoxazine compound is not easy to process into a powder having a large particle size because of its large strength. An acid catalysis process is used to obtain a polymer dispersed in a small particle size in the process of forming a polymer to form a polyoxazine compound from an oxazine monomer.

First, an acid solution of an oxazine monomer is prepared by dissolving an oxazine monomer in an acid.

Dissolving the oxazine monomer in an acid is made at 50 to 100 ℃. When the acid dissolution of the oxazine monomer is performed at the above temperature, the solubility of the oxazine monomer is increased to increase the yield of the polymerization reaction.

Subsequently, the acid solution of this oxazine monomer is heat-treated to perform a polymerization reaction.

The acid solution consists of acid and water.

Phosphoric acid-based material may be used as the acid.

The phosphoric acid-based material may be polyphosphoric acid, phosphonic acid (H ₃ PO ₃ ), organic phosphonic acid, orthophosphoric acid (H ₃ PO ₄ ), pyrophosphoric acid (H ₄ P ₂ 0 ₇ ), triphosphate (H ₅ P ₃ O ₁₀ ), metaphosphoric acid or derivatives thereof, and the like.

Polyphosphoric acid is, for example, conventional polyphosphoric acid available from Riedel-de Haen. The polyphosphate H _{n +2} P _n O _{3n +1} (n> 1) is generally calculated at a concentration of at least 85%, P ₂ O ₅ (by acidimetry).

The concentration of acid may be at least 80%, 90%, 95% or 98% by weight. For example, the concentration of acid is 80-98% by weight.

The acid content is 1000 to 100,000 parts by weight, for example 6,000 to 20,000 parts by weight, based on 100 parts by weight of the oxazine monomer. When the acid content is in the above range, the reactivity of the polymerization reaction of the oxazine monomer is excellent.

The heat treatment takes place at 150 to 250 ° C, for example 150-200 ° C. When the heat treatment temperature is within the above range, the particle size of the polyoxazine-based compound contained in the finally obtained polyoxazine-based compound composition is small and the yield is excellent.

The polymerization product is worked up to separate a polyoxazine compound.

The work-up process is, for example, a process in which water is added to the polymerization product and centrifuged using a centrifuge to remove acid components to separate solids.

By adding water to the separated polybenzoxazine compound, a polyoxazine compound composition can be obtained.

The composition comprises 1 to 80% by weight of the polyoxazine compound, the average particle diameter of the polyoxazine compound is 0.5 to 10㎛.

When the content of the polyoxazine compound in the above-described composition is in the above range, the dispersibility is excellent. In the polyoxazine-based compound composition described above, when the polyoxazine-based compound has the aforementioned particle size range, dispersibility in the electrode catalyst layer is excellent.

The polyoxazine-based compound is excellent in heat resistance at a temperature of up to 300 ° C, and does not dissolve in an acid such as phosphoric acid at a temperature of about 150 to 200 ° C, about 180 ° C. And it has excellent acid holding ability such as phosphoric acid. In addition, when the electrode is formed using a conventional oxazine monomer, it is possible to prevent the problem that the unreacted oxazine monomer is present as impurities in the electrode, the performance of the electrode is reduced.

The composition obtained according to the above process can be used as a binder of the electrode for fuel cells.

The oxazine monomer is not particularly limited, and for example, one or more selected from compounds represented by the following Chemical Formulas 1 to 6 may be used.

[Formula 1]

In Formula 1, R ₁ , R ₂ , R ₃ , and R ₄ are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C2-C20 alkenyl group, substituted or unsubstituted C2-C20 alkynyl group, substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C6-C20 aryloxy group, substituted or unsubstituted C2-C20 heteroaryl Groups, substituted or unsubstituted C2-C20 heteroaryloxy groups, substituted or unsubstituted C4-C20 carbocyclic groups, substituted or unsubstituted C4-C20 carbocyclic groups, substituted or unsubstituted C2-C20 heterocycles A group, a halogen atom, a hydroxyl group, or a cyano group,

R ₅ is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, Substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C6-C20 aryloxy group, substituted or unsubstituted C7-C20 arylalkyl group, substituted or unsubstituted C2-C20 heteroaryl group, Substituted or unsubstituted C2-C20 heteroaryloxy group, substituted or unsubstituted C2-C20 heteroarylalkyl group, substituted or unsubstituted C4-C20 carbocyclic group, substituted or unsubstituted C4-C20 carbon A cyclic alkyl group, a substituted or unsubstituted C2-C20 heterocyclic group, or a substituted or unsubstituted C2-C20 heterocyclic alkyl group,

[Formula 2]

R ₅ ′ in Formula 2 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2 -C20 alkynyl group, substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C6-C20 aryloxy group, substituted or unsubstituted C7-C20 arylalkyl group, substituted or unsubstituted C2- C20 heteroaryl group, substituted or unsubstituted C2-C20 heteroaryloxy group, substituted or unsubstituted C2-C20 heteroarylalkyl group, substituted or unsubstituted C4-C20 carbocyclic group, substituted or unsubstituted C4-C20 carbocyclic alkyl group, substituted or unsubstituted C2-C20 heterocyclic group, or substituted or unsubstituted C2-C20 heterocyclic alkyl group,

R ₆ is a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C2-C20 alkenylene group, a substituted or unsubstituted C2-C20 alkynylene group, a substituted or unsubstituted C6-C20 arylene group, a substituted Or an unsubstituted C2-C20 heteroarylene group, -C (= 0)-, -SO2-,

(3)

In Formula 3, A, B, C, D, and E are all carbon, or one or two selected from A, B, C, D, and E are nitrogen (N), and the rest are carbon (C),

R ₇ And R ₈ are connected to each other to form a ring,

The ring is a C6-C10 cycloalkyl group, a C3-C10 heteroaryl group, a fused C3-C10 heteroaryl group, a C3-C10 heterocyclic group or a fused C3-C10 heterocyclic group,

[Formula 4]

In Formula 4, A 'is a substituted or unsubstituted C1-C20 heterocyclic group, a substituted or unsubstituted C4-C20 cycloalkyl group, or a substituted or unsubstituted C1-C20 alkyl group,

R ₉ R ₁₆ is independently of each other hydrogen, C1-C20 alkyl group, C1-C20 alkoxy group, C6-C20 aryl group, C6-C20 aryloxy group, C1-C20 heteroaryl group, C1-C20 heteroaryloxy group, C4- A C20 cycloalkyl group, a C1-C20 heterocyclic group, a halogen atom, a cyano group, or a hydroxy group,

 [Chemical Formula 5]

In Formula 5, R ₁₇ And R ₁₈ is independently a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, or a group represented by the following Formula 5A,

[Formula 5A]

In Formulas 5 and 5A,

R ₁₉ and R ₁₉ ′ independently of one another are hydrogen, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, a halogenated C6-C20 aryl group, a halogenated C6-C20 aryl Oxy group, C1-C20 heteroaryl group, C1-C20 heteroaryloxy group, halogenated C1-C20 heteroaryl group, halogenated C1-C20 heteroaryloxy group, C4-C20 cycloalkyl group, halogenated C4-C20 cycloalkyl group , C1-C20 heterocyclic group, or halogenated C1-C20 heterocyclic group,

[Formula 6]

In Formula 6, R ₂₀ , R ₂₁ And two or more adjacent groups selected from R ₂₂ are connected to each other and represented by the following Chemical Formula 6A,

R ₂₀ and R ₂₁ And the remaining groups not selected from R ₂₂ are hydrogen, C 1 -C 20 alkyl group, C 1 -C 20 alkoxy group, C 6 -C 20 aryl group, C 6 -C 20 aryloxy group, halogenated C 6 -C 20 aryl group, halogenated C 6 -C 20 aryl Oxy group, C1-C20 heteroaryl group, C1-C20 heteroaryloxy group, halogenated C1-C20 heteroaryl group, halogenated C1-C20 heteroaryloxy group, C4-C20 carbocyclic group, halogenated C4-C20 carbon A cyclic group, a C1-C20 heterocyclic group, or a halogenated C1-C20 heterocyclic group,

Two or more adjacent groups selected from R ₂₃ , R _24, and R ₂₅ are connected to each other and represented by the following Chemical Formula 6A,

The remaining group not selected from R ₂₃ , R _24, and R ₂₅ may be a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, a halogenated C6-C20 aryl group, or a halogenated group. C6-C20 aryloxy group, C1-C20 heteroaryl group, C1-C20 heteroaryloxy group, halogenated C1-C20 heteroaryl group, halogenated C1-C20 heteroaryloxy group, C4-C20 carbocyclic group, halogenated C4-C20 carbocyclic group, C1-C20 heterocyclic group, or halogenated C1-C20 heterocyclic group

 [Formula 6A]

R ₁ ′ in Formula 6A is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2 -C20 alkynyl group, substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C6-C20 aryloxy group, substituted or unsubstituted C7-C20 arylalkyl group, substituted or unsubstituted C2- C20 heteroaryl group, substituted or unsubstituted C2-C20 heteroaryloxy group, substituted or unsubstituted C2-C20 heteroarylalkyl group, substituted or unsubstituted C4-C20 carbocyclic group, substituted or unsubstituted C4-C20 carbocyclic alkyl group, substituted or unsubstituted C2-C20 heterocyclic group, or substituted or unsubstituted C2-C20 heterocyclic alkyl group,

* Is R ₂₀ , R ₂₁ in Chemical Formula 6 And positions adjacent to two or more adjacent groups selected from R ₂₂ and two or more adjacent groups selected from R ₂₃ , R _24, and R ₂₅ , respectively.

R ₁ ′ in Formula 6A is one selected from the group represented by the following structural formula.

As an example of the compound represented by the said Formula (1), the compound represented by following formula (7)-55 is mentioned.

[Formula 7] [Formula 8] [Formula 9]

[Formula 10] [Formula 11] [Formula 12]

[Formula 13] [Formula 14] [Formula 15]

[Formula 16] [Formula 17] [Formula 18]

[Formula 19] [Formula 20]

[Formula 21] [Formula 22]

[Formula 23] [Formula 24] [Formula 25]

[Formula 26] [Formula 27] [Formula 28]

[Formula 29] [Formula 30] [Formula 31]

[Formula 32] [Formula 33] [Formula 34]

[Formula 35] [Formula 36] [Formula 37]

[Formula 38] [Formula 39] [Formula 40]

[Formula 41] [Formula 42] [Formula 43] [Formula 44]

[Formula 45] [Formula 46] [Formula 47] [Formula 48]

[Formula 49] [Formula 50] [Formula 51]

[Formula 52] [Formula 53]

[Formula 54] [Formula 55]

As an example of the compound represented by the said Formula (2), the compound represented by following formula (56)-60 is mentioned.

[Formula 56] [Formula 57]

[Formula 58] [Formula 59]

[Formula 60]

R ₂ in Formula 56-60 is selected from the group represented by 4-tertbutylphenyl group -CH ₂ -CH = CH ₂ , or the following Formula 61.

(61)

 For example, the compound of Formula 2 may be selected from compounds represented by the following Formulas 62, 63, 64, 65, and 66.

   [Formula 62] [Formula 63]

[Formula 64] [Formula 65]

[Formula 66]

Examples of the compound represented by Chemical Formula 3 include compounds represented by the following Chemical Formulas 67 to 70.

(67)

In Formula 67, R 'is hydrogen or a C1-C10 alkyl group,

(68)

[Formula 69]

(70)

가 하기 화학식 71으로 표시되는 그룹중의 하나이다.In Chemical Formulas 67 to 70

Is one of the groups represented by the following general formula (71).

(71)

Examples of the compound represented by Formula 3 are selected from the compounds represented by the following Formulas 72 to 94.

[Formula 72] [Formula 73]

[Formula 74] [Formula 75]

[Formula 76] [Formula 77]

[Formula 78] [Formula 79]

 [Formula 80] [Formula 81]

[Formula 82] [Formula 83] [Formula 84]

[Formula 85] [Formula 86] [Formula 87]

[Formula 88] [Formula 89]

[Formula 89A] [Formula 90]

[Formula 91] [Formula 92]

[Formula 93] [Formula 94]

In the compound represented by Chemical Formula 4, A 'may be one of groups represented by the following Chemical Formula 95 or 96.

[Formula 95] [Formula 96]

In Formulas 95 and 96, R _k represents hydrogen, C1-C20 alkyl group, C1-C20 alkoxy group, C6-C20 aryl group, C6-C20 aryloxy group, halogenated C6-C20 aryl group, halogenated C6-C20 aryl jade C1-C20 heteroaryl group, C1-C20 heteroaryloxy group, halogenated C1-C20 heteroaryl group, halogenated C1-C20 heteroaryloxy group, C4-C20 carbon ring, halogenated C4-C20 carbon ring Group, C1-C20 heterocyclic group, or halogenated C1-C20 heterocyclic group.

The compound of Formula 4 may be a compound represented by the following Formula 97 or 98.

[Formula 97] [Formula 98]

In Formulas 97 and 98, R _{k is} one selected from the group _represented by Formula 99 below.

[Formula 99]

Examples of the compound of Formula 4 may include one selected from compounds represented by the following Formulas 100 to 105.

[Formula 100] [Formula 101]

[Formula 102] [Formula 103]

[Formula 104] [Formula 105]

≪ EMI ID =

Examples of the compound represented by Formula 5 include a compound represented by the following Formula 107, 108 or 110.

≪ EMI ID =

(108)

R ₁₇ ′ in Formulas 107 and 108 is a C1-C10 alkyl group, a C1-C10 alkoxy group, a C6-C10 aryl group, or a C6-C10 aryloxy group,

R ₁₉ ′ is selected from the group represented by the following formula (109),

[Formula 109]

[Formula 110]

In Formula 110, R ₁₇ ′ is a C6-C10 aryl group.

R ₁₉ ′ is selected from the group represented by the following formula (111).

[Formula 111]

The compound of Formula 5 may be a compound represented by the following Formula 112 to 116, 117 or 118.

[Formula 112] [Formula 113]

[Formula 114] [Formula 115]

[Formula 116] [Formula 117]

[Formula 118]

As an example of the compound represented by the said General formula (6), the compound represented by following formula (119)-121 can be mentioned.

[Formula 119] [Formula 120]

[Formula 121]

In Formulas 119 to 121. R _j is one of the groups represented by the following Chemical Formula 122.

[Formula 122]

Specific examples of the compound represented by Chemical Formula 6 include compounds represented by the following Chemical Formulas 123 to 130.

[Formula 123]

[Formula 124]

[Formula 125]

[Formula 126]

(127)

(128)

≪ EMI ID =

[Formula 130]

As the polyoxazine-based compound contained in the composition, the compound of formula 16 (4FPh2AP), the compound of formula 28 (3,4-FPh4FA), the compound of formula 66, the compound of formula 62 (HF-a) , At least one selected from a compound of formula 89 (3HP2AP) and a compound of formula 116 (PPO).

[Formula 16] [Formula 28]

 [Formula 66]

[Formula 62]

(89)

[Formula 116]

According to one embodiment of the present invention, there is provided an electrode having a catalyst layer containing a coating product of the composition described above.

The term "coating product of the composition" refers to a product obtained by coating the polyoxazine-based compound composition or a product obtained by coating and heat-treatment, wherein only the dispersion medium contained in the polyoxazine-based compound composition according to the coating and / or heat treatment temperature It may refer to the removed state, that is, the polyoxazine-based compound itself, or may represent a cured product of the polyoxazine-based compound.

Hereinafter, a process of manufacturing an electrode using the composition will be described.

The electrode can be used, for example, as an electrode for fuel cells.

The catalyst, the composition described above, and the solvent are mixed to prepare a composition for forming an electrode catalyst layer.

As the solvent, N-methylpyrrolidone, N, N-dimethylacetamide, water, an acid, etc. are used, and at least one content selected from the compound represented by Formula 1 and the compound represented by Formula 2 is 0.001 to 0.5 parts by weight based on 1 part by weight of catalyst, for example 0.001 to 0.1 parts by weight. When at least one content selected from the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 is within the above range, the binding force of the electrode catalyst layer to the support is excellent.

As the catalyst, platinum (Pt) alone or an alloy or mixture of at least one metal and platinum selected from the group consisting of gold, palladium, rhodium, iridium, ruthenium, tin, molybdenium, cobalt and chromium is used. Alternatively, the catalyst may include one or more alloys or mixtures of platinum and platinum selected from the group consisting of platinum (Pt) alone or gold, palladium, rhodium, iridium, ruthenium, tin, molybdenium, cobalt, and chromium on a carbon-based carrier. It may be a supported supported catalyst.

The electrode catalyst layer forming composition is coated and dried on a support to form a catalyst layer to form an electrode for a fuel cell.

The content of the polyoxazine compound of the composition is 0.001 to 20 parts by weight based on 1 part by weight of the catalyst.

When the content of the polyoxazine compound is in the above range, the binding force of the electrode catalyst layer to the support is excellent.

The coating solution is coated on the surface of the carbon support to complete the electrode. It is easy to coat the carbon support on the glass substrate here. And the coating method is not particularly limited. Coating using a doctor blade, bar coating, screen printing, or the like can be used.

After the coating solution is coated and dried, the solvent is removed in a temperature range of 20 to 150 ° C. And the drying time depends on the drying temperature, it is carried out in the range of 10 to 60 minutes.

The electrode may be further subjected to acid impregnation.

In addition, the composition for forming an electrode catalyst layer may further include a crosslinkable compound.

The crosslinkable compound may be used as long as the compound has a functional group capable of crosslinking with at least one selected from the compound represented by Formula 1 and the compound represented by Formula 2.

The crosslinkable compound may be used as long as it is a nitrogen-containing aromatic compound. Specifically, a nitrogen-containing aromatic compound of five membered cycles and a six membered cycle such as polypyrimidine may be used. Nitrogen-containing aromatic compounds and the like can be used.

Examples of the crosslinkable compound include at least one polymer selected from polyazole-based materials, polyimides, and polyoxazoles.

The content of the crosslinkable compound is 10 to 500 parts by weight based on 100 parts by weight of the polyoxazine compound. When the content of the crosslinkable compound is in the above range, the additional phosphoric acid impregnation force of the polyazole is added to the heat resistance of the polyoxazine compound.

When the polyazole-based material is used as the crosslinkable compound, the final product is obtained by graft copolymer obtained by graft polymerization of at least one polymer selected from the compound represented by Formula 1 and the compound represented by Formula 2 with the polyazole-based material. Can be formed.

The term "polymerization reaction product of at least one selected from a compound represented by Formula 1 and a compound represented by Formula 2 with a polyazole-based material '' is used as a meaning including the structure described above.

The polyazole-based material refers to a polymer in which the repeating unit in the polymer includes at least one aryl ring having at least one nitrogen element.

The aryl ring may have a structure in which a 5- or 6-membered ring having 1 to 3 nitrogen atoms is fused to another ring, for example, another aryl ring or heteroaryl ring. In this connection the nitrogen atoms are substitutable by oxygen, phosphorus and / or sulfur atoms. Representative examples of the aryl ring are phenyl, naphthyl, hexahydroindyl, indanyl, or tetrahydronaphthyl.

The polyazole-based material has at least one amino group in the repeating unit as described above. In this regard, the amino group may be present as a primary amino group, secondary amino group or tertiary amino group as part of an aryl ring or as a substituent part of an aryl unit.

The term "amino group" refers to a case where a nitrogen atom is covalently bonded to at least one carbon or heteroatom. Amino groups include, for example, -NH ₂ and substituted moieties.

The term "alkylamino group" includes alkylamino in which nitrogen is bound to at least one additional alkyl group, and "arylamino" and "diarylamino" groups in which at least one or two or more nitrogens are independently selected from aryl groups.

Polyazole-based materials and processes for the preparation of polymer films containing them are known from US 2005 / 256296A.

According to one embodiment of the present invention, the polyazole-based material is a polyazole-based material including an azole unit represented by the following Chemical Formulas 131 to 144.

[Formula 131]

[Formula 132]

[Formula 133]

[Formula 134]

[Formula 135]

[Formula 136]

[Formula 137]

[Formula 138]

[Formula 139]

[Formula 140]

Formula 141

[Formula 142]

[Formula 143]

[Formula 144]

In Formulas 131 to 144, Ar ⁰ is the same as or different from each other, and a monocyclic or polycyclic divalent C6-C20 aryl group or C2-C20 heteroaryl group,

Ar is the same as or different from each other, and each of them is a monovalent or polycyclic tetravalent C6-C20 aryl group or C2-C20 heteroaryl group,

Ar ¹ is the same as or different from each other, and each of them is a monocyclic or polycyclic divalent C6-C20 aryl group or C2-C20 heteroaryl group,

Ar ² is the same as or different from each other, each of which is a monocyclic or polycyclic divalent or trivalent C6-C20 aryl group or C2-C20 heteroaryl group,

Ar ³ is the same as or different from each other, is a monocyclic or polycyclic trivalent C6-C20 aryl group or C2-C20 heteroaryl group,

Ar ⁴ is the same as or different from each other, each of which is a monocyclic or polycyclic trivalent C6-C20 aryl group or C2-C20 heteroaryl group,

Ar ⁵ is the same as or different from each other, and each of them is a monovalent or polycyclic tetravalent C6-C20 aryl group or C2-C20 heteroaryl group,

Ar ⁶ is the same as or different from each other, is a monocyclic or polycyclic divalent C6-C20 aryl group or C2-C20 heteroaryl group,

Ar ⁷ is the same as or different from each other, is a monocyclic or polycyclic divalent C6-C20 aryl group or C2-C20 heteroaryl group,

Ar ⁸ is the same as or different from each other, is a monocyclic or polycyclic trivalent C6-C20 aryl group or C2-C20 heteroaryl group,

Ar ⁹ is the same as or different from each other, and is a monocyclic or polycyclic divalent, trivalent or tetravalent C6-C20 aryl group or C2-C20 heteroaryl group,

Ar ¹⁰ is the same as or different from each other, and is a monocyclic or polycyclic divalent or trivalent C6-C20 aryl group or C2-C20 heteroaryl group,

Ar ¹¹ is the same as or different from each other, is a monocyclic or polycyclic divalent C6-C20 aryl group or C2-C20 heteroaryl group,

X ₃ to X ₁₁ are the same or different and are oxygen, sulfur or —N (R ′), wherein R ′ is hydrogen, C 1 -C 20 alkyl group, C 1 -C 20 alkoxy group, C 6 -C 20 aryl group,

R ₉ is the same or different and represents hydrogen, a C1-C20 alkyl group or a C6-C20 aryl group,

n ₀ , n ₄ N ₁₆ and m ₂ are each independently an integer of 10 or more, for example, 100 to 100,000 as an integer of 100 or more.

The aryl or heteroaryl group is, for example, benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, quinoline, pyridine, bipyridine, pyridazine, pyrimidine , Pyrazine, triazine, tetraazine, pyrrole, pyrazole, anthracene, benzopyrrole, benzotriazole, benzooxathiazole, benzooxadiazole, benzopyridine, benzopyrazine, benzopyrazidine, benzopyrimidine, benzotri Azine, indolizine, quinolysine, pyridopyridine, imidazopyrimidine, pyrazinopyrimidine, carbazole, aziridine, phenazine, benzoquinoline, phenoxazine, phenothiazine, acridizin, benzoproperi Dine, phenanthroline or phenanthrene, which may have a substituent.

Ar ⁰ , Ar ¹ , Ar ⁴ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ , Ar ¹⁰ , Ar ¹¹ may have all possible substitution patterns. For example, when Ar ⁰ , Ar ¹ , Ar ⁴ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ , Ar ¹⁰ and Ar ¹¹ are phenylene, Ar ⁰ , Ar ¹ , Ar ⁴ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ , Ar ¹⁰ and Ar ¹¹ are orthophenylene, metaphenylene or paraphenylene.

The alkyl group is, for example, a C1-C4 short-chain alkyl group such as methyl, ethyl, n-propyl, i-propyl and t-butyl groups, and the aryl group is, for example, a phenyl or naphthyl group.

The substituent is a halogen atom such as fluorine, an amino group, a hydroxyl group, or a short chain alkyl group such as methyl or ethyl.

Specific examples of the polyazole-based material include polyimidazole, polybenzothiazole, polybenzoxazole, polyoxadiazole, polyquinoxaline, polythiadiazole, polypyridine, polypyrimidine or polytetraazaprene. Can be.

The polyazole-based material may be a copolymer or blend including at least two units of Formulas 131 to 144. The polyazole-based material is a block copolymer (diblock, triblock), random copolymer, periodic copolymer or alternating polymer comprising at least two units of Formulas 131 to 144.

Polyazole-based materials containing only units of Formulas 131 and / or 132 are used.

Examples of the polyazole-based material include polymers represented by the following Chemical Formulas 145 to 171.

[Formula 145]

Formula 146

[Formula 147]

[Formula 148]

[Formula 149]

[Formula 150]

[Formula 151]

[Formula 152]

[Formula 153]

Formula 154

[Formula 155]

[Formula 156]

[Formula 157]

[Formula 158]

[Formula 159]

[Formula 160]

[Formula 161]

[Formula 162]

[Formula 163]

Formula 164

Formula 165

Formula 166

Formula 167

Formula 168

[Formula 169]

[Formula 170]

[Formula 171]

In Formulas 145 to 171, l, n ₁₇ to n ₄₃ and m ₃ to m ₇ are each an integer of 10 or more, for example, an integer of 100 or more,

z represents a chemical bond or is-(CH ₂ ) _S- , -C (= 0)-, -SO _2- , -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2- , and s is 1 It is an integer of -5.

As the polyazole-based material, a compound having a compound of Formula 172 (m-PBI) or a compound of Formula 173 (p-PBI) may be used.

 [Formula 172]

In Formula 172, n ₁ is an integer of 10 or more,

[Formula 173]

In Formula 173, n ₂ is an integer of 10 or more.

 The number average molecular weight of the polymer represented by Chemical Formula 172 or 173 is 1 million or less.

As the polyazole-based material, it is also possible to use a benzimidazole-based polymer represented by the following general formula (174).

[Formula 174]

In Formula 174, R ₂₆ And R ₂₇ independently of one another is hydrogen, an unsubstituted or substituted C1-C20 alkyl group, an unsubstituted or substituted C1-C20 alkoxy group, an unsubstituted or substituted C6-C20 aryl group, unsubstituted or substituted C6-C20 aryloxy group, unsubstituted or substituted C3-C20 heteroaryl group, unsubstituted or substituted C3-C20 heteroaryloxy group, or R ₂₆ And R ₂₇ connected to each other to form a C4-C20 carbon ring or a C3-C20 heterocycle,

Ar ¹² is an unsubstituted or substituted C6-C20 arylene group or an unsubstituted or substituted C3-C20 heteroarylene group,

R ₂₈ To R ₃₀ each represent a mono- or polysubstituted substituent,

Hydrogen, unsubstituted or substituted C1-C20 alkyl group, unsubstituted or substituted C1-C20 alkoxy group, unsubstituted or substituted C6-C20 aryl group, unsubstituted or substituted C6-C20 aryloxy group, Unsubstituted or substituted C3-C20 heteroaryl group, or unsubstituted or substituted C3-C20 heteroaryloxy group,

L represents a linker,

m ₁ is 0.01 to 1,

a ₁ is 0 or 1,

n ₃ is 0 to 0.99,

k is a number from 10 to 250.

The benzimidazole-based polymer may be a compound represented by Formula 175 or Formula 176.

[Formula 175]

K ₁ in Formula 175 is a number from 10 to 300 as a degree of polymerization.

Formula 176

M ₈ in Formula 176 is 0.01 to 1, according to one embodiment, 1 or 0.1 to 0.9, n ₄₄ is 0 to 0.99, for example, 0 or 0.1 to 0.9,

k ₂ is a number from 10 to 250.

The electrode for a fuel cell obtained by the above process is combined with an electrolyte membrane to form a membrane electrode assembly.

The membrane electrode assembly is put in a fuel cell and charged with air and hydrogen fuel, and then operated. The operating temperature of the fuel cell is for example at 150 to 180 ° C.

The electrolyte membrane can be used as long as it is an electrolyte membrane commonly used in fuel cells. For example, a polybenzimidazole electrolyte membrane, a polybenzoxazine-polybenzimidazole copolymer electrolyte membrane, a PTFE porous membrane, or the like can be used. Alternatively, an electrolyte membrane using a polymerization reaction product of at least one oxazine monomer selected from the compound of Formula 1 and the compound of Formula 2 may be used in the same manner as the electrode.

The electrolyte membrane may be further impregnated with a proton conductor.

As the proton conductor, polyphosphoric acid, phosphonic acid (H ₃ PO ₃ ), orthophosphoric acid (H ₃ PO ₄ ), pyrophosphoric acid (H ₄ P ₂ 0 ₇ ), triphosphate (H ₅ P ₃ O ₁₀ ), meta Phosphoric acid or derivatives thereof are exemplified. The concentration of the proton conductor may be at least 80 wt%, 90 wt%, 95 wt%, 98 wt%.

The process of preparing an electrolyte membrane using the polymerization reaction product of one or two kinds of oxazine monomers can be prepared according to the method described in Korean Patent Laid-Open No. 2009-0045655.

Looking at the definition of the substituent used in the formula as follows.

The term alkyl as used in the formula refers to a fully saturated branched or unbranched (or straight or linear) hydrocarbon.

Non-limiting examples of such alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl, iso-amyl, n-hexyl, 3- Methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, n-heptyl, and the like.

One or more hydrogen atoms of the alkyl may be a halogen atom, a C1-C20 alkyl group substituted with a halogen atom (e.g., CCF ₃ , CHCF ₂ , CH ₂ F, CCl _3, etc.), alkoxy of C1-C20, alkoxyalkyl of C2-C20 , Hydroxy group, nitro group, cyano group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonyl group, sulfamoyl group, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, or C1-C20 Alkyl group, C2-C20 alkenyl group, C2-C20 alkynyl group, C1-C20 heteroalkyl group, C6-C20 aryl group, C6-C20 arylalkyl group, C6-C20 heteroaryl group, C7-C20 heteroarylalkyl group , A C6-C20 heteroaryloxy group, a C6-C20 heteroaryloxyalkyl group, or a C6-C20 heteroarylalkyl group.

The term halogen atom includes fluorine, bromine, chlorine, iodine and the like.

The term C1-C20 alkyl group substituted with a halogen atom refers to a C1-C20 alkyl group substituted with one or more halo groups and includes, but is not limited to, polyhalo-containing monohaloalkyl, dihaloalkyl or perhaloalkyl. Haloalkyl.

Monohaloalkyl is the case with one iodine, bromine, chlorine or fluorine in the alkyl group, dihaloalkyl and polyhaloalkyl represent an alkyl group having two or more identical or different halo atoms.

The term alkoxy used in the formula represents alkyl-O-, wherein alkyl is as described above. Non-limiting examples of the alkoxy include methoxy, ethoxy, propoxy, 2-propoxy, butoxy, tert-butoxy, pentyloxy, hexyloxy, cyclopropoxy, cyclohexyloxy and the like. At least one hydrogen atom of the alkoxy group may be substituted with the same substituent as in the alkyl group described above.

The term alkoxyalkyl used in the formula refers to the case where the alkyl group is substituted by the alkoxy described above. At least one hydrogen atom of the alkoxyalkyl may be substituted with the same substituent as in the alkyl group described above. As such, the term alkoxyalkyl includes substituted alkoxyalkyl moieties.

The term alkenyl group used in the formula refers to a branched or unbranched hydrocarbon having at least one carbon-carbon double bond. Non-limiting examples of alkenyl groups include vinyl, allyl, butenyl, isopropenyl, isobutenyl, and the like, and at least one hydrogen atom of the alkenyl may be substituted with the same substituent as in the alkyl group described above. .

The term alkynyl group as used in the formula refers to a branched or unbranched hydrocarbon having at least one carbon-carbon triple bond. Non-limiting examples of the alkynyl include ethynyl, butynyl, isobutynyl, isopropynyl and the like.

One or more hydrogen atoms of the alkynyl may be substituted with the same substituent as in the alkyl group described above.

The term aryl as used in the formula is used alone or in combination to mean an aromatic hydrocarbon comprising one or more rings.

The term aryl also includes groups in which an aromatic ring is fused to one or more cycloalkyl rings.

Non-limiting examples of such aryls include phenyl, naphthyl, tetrahydronaphthyl and the like.

At least one hydrogen atom in the aryl group may be substituted with the same substituent as in the alkyl group described above.

The term arylalkyl means alkyl substituted with aryl. Examples of arylalkyl include benzyl or phenyl-CH ₂ CH _2- .

The term aryloxy used in the formula means -0-aryl, and examples of the aryloxy group include phenoxy and the like. At least one hydrogen atom of the aryloxy group may be substituted with the same substituent as in the alkyl group described above.

As used herein, the term heteroaryl group refers to a monocyclic or bicyclic organic compound containing at least one heteroatom selected from N, O, P or S, and the remaining ring atoms being carbon. The heteroaryl group may include, for example, 1-5 heteroatoms, and may include 5-10 ring members.

The S or N may be oxidized to have various oxidation states.

Monocyclic heteroaryl groups are thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1, 2,5-oxadiazolyl, 1,3,4-oxadiazolyl group, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1 , 3,4-thiadiazolyl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazole- 5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, 1,2,4-triazol-3-yl, 1,2,4-triazole- 5-yl, 1,2,3-triazol-4-yl, 1,2,3-triazol-5-yl, tetrazolyl, pyrid-2-yl, pyrid-3-yl, 2-pyrazine -2 days, pyrazin-4-yl, pyrazin-5-yl, 2-pyrimidin-2-yl, 4-pyrimidin-2-yl, or 5-pyrimidin-2-yl.

The term heteroaryl includes when the heteroaromatic ring is fused to one or more aryl, cycloaliphatic, or heterocycle.

Examples of bicyclic heteroaryl include indolyl, isoindolyl, indazolyl, indolizinyl, purinyl, quinolizinyl, and quinoli Quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, phthalazinyl, naphthyridinyl, quinazolinyl, quinaxalinyl, phenaxalinyl Phenanthridinyl, phenathrolinyl, phenazinyl, phenazinyl, phenothiazinyl, phenoxazinyl, benzoisoquinolinyl, benzisoqinolinyl, thieno [2,3-b] Furanyl (thieno [2,3-b] furanyl), furo [3,2-b] -pyranyl, 5H-pyrido [2,3-d]- o-oxazinyl (5H-pyrido [2,3-d] -o-oxazinyl), 1H-pyrazolo [4,3-d] -oxazolyl (1H-pyrazolo [4,3-d] -oxazolyl), 4H-imidazo [4,5-d] thiazolyl (4H-imidazo [4,5-d] thiazolyl), pyrazino [2,3-d] pyridazinyl , Imidazo [2 , 1-b] thiazolyl (imidazo [2,1-b] thiazolyl), imidazo [1,2-b] [1,2,4] triazinyl (imidazo [1,2-b] [1,2 , 4] triazinyl), 7-benzo [b] thienyl, benzooxazolyl (7-benzo [b] thienyl, benzoxazolyl), benzimidazolyl, benzothiazolyl, benzooxazinyl ), Benzoxazinyl, 1H-pyrrolo [1,2-b] [2] benzazinyl (1H-pyrrolo [1,2-b] [2] benzazapinyl), benzofuryl, benzo Benzothiophenyl, benzotriazolyl, pyrrolo [2,3-b] pyridinyl, pyrrolo [3,2-c] pyridinyl 3,2-c] pyridinyl), pyrrolo [3,2-b] pyridinyl, imidazo [4,5-b] pyridinyl (imidazo [4,5- b] pyridinyl), imidazo [4,5-c] pyridinyl, pyrazolo [4,3-d] pyridinyl Pyrazolo [4,3-c] pyridinyl, pyrazolo [3,4-c] pyridinyl, pyrazolo [4,3-c] pyridinyl 3,4-d] pyri Pyrazolo [3,4-d] pyridinyl, pyrazolo [3,4-b] pyridinyl, imidazo [1,2-a] pyridinyl (imidazo [ 1,2-a] pyridinyl), pyrazolo [1,5-a] pyridinyl, pyrrolo [1,2-b] pyridolo [1,2 -b] pyridazinyl), imidazo [1,2-c] pyrimidinyl, pyrido [3,2-d] pyrimidinyl (3,2-d) ] pyrimidinyl, pyrido [4,3-d] pyrimidinyl, pyrido [3,4-d] pyrimidinyl Pyrido [2,3-d] pyrimidinyl, pyrido [2,3-b] pyrazinyl, pyrido [3,4-b] pyrazinyl (pyrido [3,4-b] pyrazinyl), pyrimido [5,4-d] pyrimidinyl (pyrimido [5,4-d] pyrimidinyl), pyrazino [2, 3-b] pyrazinyl (pyrazino [2,3-b] pyrazinyl), or pyrimido [4,5-d] pyrimidinyl (pyrimido [4,5-d] pyrimidinyl).

At least one hydrogen atom of the heteroaryl may be substituted with the same substituent as in the alkyl group described above.

The term heteroarylalkyl means alkyl substituted with heteroaryl.

The term heteroaryloxy means a -0-heteroaryl moiety. At least one hydrogen atom of the heteroaryloxy may be substituted with the same substituent as in the alkyl group described above.

The term heteroaryloxyalkyl means alkyl substituted with heteroaryloxy. At least one hydrogen atom of the heteroaryloxyalkyl may be substituted with the same substituent as in the alkyl group described above.

Carbocyclic groups used in the formula refer to saturated or partially unsaturated non-aromatic monocyclic, bicyclic or tricyclic hydrocarbon groups.

Examples of such monocyclic hydrocarbons include cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl and the like.

Examples of the bicyclic hydrocarbons include carbonyl, decahydronaphthyl, bicyclo [2.1.1] hexyl, and bicyclo [2.1.1] heptyl. [2.2.1] heptyl), bicyclo [2.2.1] heptenyl, or bicyclo [2.2.2] octyl.

Examples of the tricyclic hydrocarbons include adamantly and the like.

At least one hydrogen atom in the carbon ring may be substituted with the same substituent as in the alkyl group described above.

The carbon ring group used in the formula refers to a ring group consisting of 5 to 10 atoms containing heteroatoms such as nitrogen, sulfur, phosphorus, oxygen, and the like, and specific examples thereof include pyridyl and the like. Substitutable as in the case of the above-described alkyl group.

The term heterocyclic oxy means —0-heterocycle, wherein at least one hydrogen atom of the heterocyclic oxy group is substitutable as in the case of the alkyl group described above.

The term sulfonyl means R'-SO _2- , wherein R 'is hydrogen, alkyl, aryl, heteroaryl, aryl-alkyl, heteroaryl-alkyl, alkoxy, aryloxy, cycloalkyl or heterocyclic group.

The term sulfamoyl group is H ₂ NS (O ₂ )-, alkyl-NHS (O ₂ )-, (alkyl) ₂ NS (O ₂ ) -aryl- NHS (O ₂ )-, alkyl- (aryl) -NS ( O ₂₎ -, (aryl) ₂ NS (O) _2, heteroaryl, -NHS (O ₂₎ -, _{(aryl-alkyl) - NHS (O 2) -} , or (heteroaryl-alkyl) -NHS (O ₂ )-.

At least one hydrogen atom of the sulfamoyl may be substituted as in the case of the alkyl group described above.

The term amino group refers to the case where a nitrogen atom is covalently bonded to at least one carbon or heteroatom. Amino groups include, for example, -NH ₂ and substituted moieties.

The term alkylamino group includes alkylamino in which nitrogen is bonded to at least one additional alkyl group, arylamino and diarylamino groups in which at least one or more than one nitrogen is bonded to an independently selected aryl group.

The terms alkylene group, alkenylene group, alkynylene group, arylene group and heteroarylene group are the same except that the monovalent alkyl, alkenyl, alkynyl, aryl and heteroaryl groups are each changed to a divalent group. Is defined.

At least one hydrogen atom of the alkylene group, alkenylene group, alkynylene group, arylene group and heteroarylene group may be substituted as in the case of the alkyl group described above.

Hereinafter, the following examples will be described, but are not meant to be limited only to the following examples.

Example  1: Compound of Formula 16 (4 FPh2AP ) Polybenzoxazine system  Preparation of Compound Composition

200 g of 85% by weight of phosphoric acid was added to 2 g of the compound of Formula 16 (4FPh2AP) and mixed at 80 ° C for 1 hour to obtain a phosphoric acid solution of 4FPh2AP, which was then thermally treated at 160 ° C to conduct a polymerization reaction.

The polymerization reaction product was centrifuged to remove phosphoric acid, which was washed with water, and water was added to obtain a polybenzoxazine compound composition comprising about 3.4 wt% of polybenzoxazine compound particles.

The particle size of the polybenzoxazine-based compound particles contained in the polybenzoxazine-based compound composition obtained in Example 1 was investigated using an optical microscope, and the results are shown in FIG. 1.

Referring to Figure 1 it can be seen that the particle size of the polybenzoxazine compound particles is about 1㎛.

Example  2: a compound of formula 62 ( HF with -a) Polybenzoxazine system  Preparation of Compound Composition

200 g of 85% by weight of phosphoric acid was added to 1 g of the compound of Formula 62, and the mixture was mixed at 80 ° C. for 1 hour to obtain a phosphoric acid solution of HF-a. Was carried out.

The polymerization reaction product was centrifuged to remove phosphoric acid, which was washed with water, and water was added to obtain a composition containing about 3.4% by weight of polybenzoxazine compound particles. It was found that the particle diameter of the polybenzoxazine compound particles contained in the composition was about 1 μm.

Example  3: of formula 28 Compound (3,4-DPh4FA)  Used Polybenzoxazine system  Preparation of Compound Composition

200 g of 85% by weight of phosphoric acid was added to 2 g of the compound of the formula (3,4-DPh4FA) and mixed at 80 ° C. for 1 hour to obtain a phosphoric acid solution of 3,4-DPh4FA, which was then heat-treated at 160 ° C. for 3 hours. The polymerization reaction was carried out.

The polymerization reaction product was centrifuged to remove phosphoric acid, which was washed with water, and water was added to obtain a composition containing about 3.4% by weight of polybenzoxazine compound particles. It was found that the particle diameter of the polybenzoxazine compound particles contained in the composition was about 1 μm.

Example  4: of formula 89 Compound (3HP2AP)  Used Polybenzoxazine system  Preparation of Compound Composition

200 g of 85% by weight of phosphoric acid was added to 2 g of the compound of Formula 89 (3HP2AP), and the mixture was mixed at 80 ° C for 1 hour to obtain a phosphoric acid solution of 3HP2AP.

The polymerization reaction product was centrifuged to remove phosphoric acid, which was washed with water, and water was added to obtain a polybenzoxazine compound composition containing about 3.4% by weight of polybenzoxazine compound particles.

In the polybenzoxazine-based compounds prepared according to Examples 1, 3, and 4, their thermogravimetric characteristics were investigated using a thermogravimetric analyzer, and the results are shown in FIG. 2.

Referring to Figure 2, it was found that the polybenzoxazine-based compounds prepared according to Examples 1, 3 and 4 are excellent in thermal stability up to 300 ° C.

Production example  1: Manufacture of fuel cell

By using the polybenzoxazine-based compound composition obtained in Example 1 to obtain a 2% by weight of the polybenzoxazine-based compound composition, 0.5g, 2% by weight of the polybenzoxazine-based compound composition 1g and N- 4 g of methylpyrrolidone was mixed to prepare a composition for forming an electrode catalyst layer.

Coating the cathode catalyst layer-forming composition on the carbon paper, and dried for 1 hour at room temperature, 1 hour at 80 ℃, 30 minutes at 120 ℃ and 15 minutes at 150 ℃ to prepare a cathode. . Pt loading in the finished cathode has a value of 1.57 mg / cm ² .

As an anode, an electrode obtained according to the following procedure was used.

To the stirring vessel was added 2 g of a catalyst loaded with 50 wt% Pt to carbon and 9 g of solvent NMP, which was stirred for 2 minutes using a high speed stirrer. Subsequently, a solution in which 0.05 g of polyvinylidene fluoride was dissolved in 0.95 g of NMP was added to the mixture, followed by further stirring for 2 minutes to prepare a slurry for forming an anode catalyst layer. This was produced by coating with a bar coater on a carbon paper (carbon paper) coated with a microporous layer (microporous layer). The platinum loading of the finished anode has a value of 0.9 mg / cm ² .

Separately, 50 parts by weight of the compound (PPO) represented by Formula 115 and 50 parts by weight of polybenzimidazole (m-PBI) represented by Formula 172 were blended, and then a curing reaction was performed at 80 to 220 ° C.

[Formula 115]

[Formula 172]

In Formula 172, n ₁ is 130. Subsequently, 85 wt% phosphoric acid was impregnated at 80 ° C. for at least 4 hours to form an electrolyte membrane. The phosphoric acid content was about 500 parts by weight based on 100 parts by weight of the total electrolyte membrane weight.

MEA was produced between the cathode and the anode via the electrolyte membrane. Here and the cathode and anode were used without phosphate impregnation.

In order to prevent gas permeation between the cathode and the anode, a 200 μm thick Teflon membrane (polytetrafluoroethylene membrane) for the main gasket and a 20 μm thick Teflon membrane for the sub-gasket were used at the interface between the electrode and the electrolyte membrane. And the pressure applied to the MEA was adjusted using a torque wrench, and assembled in increments up to 1, 2, 3 N-m Torque.

Hydrogen (flow rate: 100 ccm) was flowed through the anode and air (250 ccm) was flown through the anode on conditions not humidifying the electrolyte membrane at a temperature of 150 ° C., and the battery characteristics were measured. At this time, since the electrolyte is doped with phosphoric acid, the performance of the fuel cell is improved as time passes, and the final evaluation is performed after aging until the operating voltage reaches the highest point. The area of the cathode and the anode was fixed at 2.8 × 2.8 = 7.84 cm ² , and the thicknesses of the cathode and the anode were about 430 μm and 390 μm, respectively.

Production example  2-4: Manufacture of Fuel Cell

Except for using the polybenzoxazine compound composition obtained in Example 2-4 instead of the polybenzoxazine compound composition obtained in Example 1, it was carried out in the same manner as in Production Example 1.

Comparative Production Example  1: Manufacture of fuel cell

Production Example, except that 0.01 g of polyvinylidene fluoride was used instead of 0.5 g of polybenzoxazine compound composition as a binder when preparing the cathode and anode, and the amount of Pt loading in the finished finished cathode was 1.51 mg / cm ² . A fuel cell was fabricated in the same manner as in Example 1.

Comparative Production Example  2: Manufacture of fuel cell

2 g of Pt / C and 9 g of solvent NMP were added to the stirring vessel, which was stirred for 2 minutes using a high speed stirrer. A solution in which 0.05 g of 4FPh2AP was dissolved in 0.5 g of NMP was added thereto, followed by further stirring for 2 minutes.

Subsequently, a solution in which 0.05 g of polyvinylidene fluoride was dissolved in 0.95 g of NMP was added to the mixture, followed by further stirring for 2 minutes to prepare a slurry for forming a cathode catalyst layer.

The carbon paper was cut into 4 × 7 cm ² , fixed on a glass plate, coated with a doctor blade, and the gap spacing was adjusted to 850 μm.

The cathode was coated with a slurry for forming the cathode catalyst layer on the carbon paper, and dried at room temperature for 1 hour, dried at 80 ° C for 1 hour, dried at 120 ° C for 30 minutes, and dried at 150 ° C for 15 minutes. . Pt loading in the finished cathode has a value of 2.28 mg / cm ² .

As an anode, an electrode obtained according to the following procedure was used.

2 g of Pt and 9 g of solvent NMP were added to the stirring vessel, which was stirred for 2 minutes using a high speed stirrer. Subsequently, a solution in which 0.05 g of polyvinylidene fluoride was dissolved in 0.95 g of NMP was added to the mixture, followed by further stirring for 2 minutes to prepare a slurry for forming an anode catalyst layer. This was produced by coating with a bar coater on a carbon paper (carbon paper) coated with a microporous layer (microporous layer). The platinum loading of the finished anode has a value of 1.4 mg / cm ² .

Separately, 50 parts by weight of the compound (PPO) represented by Formula 115 and 50 parts by weight of polybenzimidazole (m-PBI) represented by Formula 172 were blended, and then a curing reaction was performed at 80 to 220 ° C.

[Formula 115]

[Formula 172]

In Formula 172, n ₁ is 130. Subsequently, 85 wt% phosphoric acid was impregnated to form an electrolyte membrane. The phosphoric acid content was about 500 parts by weight based on 100 parts by weight of the total electrolyte membrane weight.

MEA was produced between the cathode and the anode via the electrolyte membrane. Here and the cathode and anode were used without phosphate impregnation.

In order to prevent gas permeation between the cathode and the anode, a 200 μm thick Teflon membrane (polytetrafluoroethylene membrane) for the main gasket and a 20 μm thick Teflon membrane for the sub-gasket were used at the interface between the electrode and the electrolyte membrane. And the pressure applied to the MEA was adjusted using a torque wrench, and assembled in increments up to 1, 2, 3 N-m Torque.

Hydrogen (flow rate: 100 ccm) was flowed through the anode and air (250 ccm) was flown through the anode on conditions not humidifying the electrolyte membrane at a temperature of 150 ° C., and the battery characteristics were measured. At this time, since the electrolyte is doped with phosphoric acid, the performance of the fuel cell is improved as time passes, and the final evaluation is performed after aging until the operating voltage reaches the highest point. And the area of the anode and cathode is fixed to 2.8 × 2.8 = 7.84 cm ² and the thickness of the cathode and the anode is changed due to the dispersion of carbon paper, the thickness of the electrode of the cathode is about 430㎛ and the thickness of the anode is about 390 [Mu] m.

In the fuel cell manufactured according to Preparation Example 1, Comparative Preparation Example 1-2, the platinum catalyst used for the cathode reaction was investigated and the results are shown in FIG. The platinum catalyst area used for the cathode reaction here is evaluated by the method of cyclic voltametry of the cathode. When hydrogen is purged at the anode and nitrogen is purged at the cathode, a hydrogen desorption peak is generated between 0.08V and 0.4V when the cathode is scanned from 0.08V to 1V. The total area of the cycle formed by these peaks is proportional to the platinum area and in this way the platinum / phosphate contact area can be calculated.

Platinum utilization can be obtained by comparing the platinum / phosphate contact area calculated as described above with the amount of catalyst platinum used in the cathode.

In Production Example 1, the platinum utilization rate was 26%, in Comparative Production Example 1, the platinum utilization rate was 22%, and in Comparative Production Example 2, the platinum utilization rate was 22%. It was found that the utilization rate of platinum is higher than the cathode of 1-2.

In the fuel cell manufactured according to Production Example 1 and Comparative Production Example 1-2, the cell voltage characteristics were evaluated according to the current density, and the results are shown in FIG. 4.

Referring to FIG. 4, it can be seen that the fuel cell of Preparation Example 1 has improved cell voltage characteristics as compared with the case of Comparative Preparation Examples 1-2.

In the fuel cell manufactured according to Production Example 2-4 and Comparative Production Example 1, the cell voltage characteristics were evaluated according to the current density, and the results are shown in FIG. 5.

Referring to FIG. 5, it can be seen that the fuel cell of Preparation Example 2-4 is superior in cell voltage to the fuel cell of Comparative Preparation Example 1.

Claims (16)

A composition comprising polyoxazine compound particles and a dispersion medium in which the polyoxazine compound particles are dispersed. According to claim 1, wherein the content of the polyoxazine-based compound particles,
1 to 80% by weight, based on the total weight of the composition. The method of claim 1, wherein the dispersion medium,
At least one composition selected from the group consisting of alcohols, water, acids and hydrocarbon-based solvents. The particle size of the polyoxazine compound particles according to claim 1,
0.5-10 μm. Mixing an oxazine monomer with an acid to prepare an acid solution of the oxazine monomer;
Thermally treating the acid solution of the oxazine monomer to polymerize it;
Separating the polyoxazine-based compound from the polymerization product; And
The method of claim 1, further comprising dispersing the polyoxazine compound in a dispersion medium. The method of claim 5, wherein the acid,
A process for preparing a composition that is a phosphoric acid material. The acid solution of the oxazine monomers according to claim 5,
A method for producing a composition containing 1,000 to 100,000 parts by weight of acid based on 100 parts by weight of oxazine monomer. The method of claim 5, wherein the heat treatment is performed at a temperature of 150 to 250 ° C. 7. The method of claim 5, wherein the step of separating the polyoxazine-based compound from the polymerization product,
Centrifuging by adding water to the polymerization product; And
Separating the solid from the centrifuged product. The method of claim 5, wherein the mixing step of the oxazine monomer and acid (acid),
Process for the preparation of the composition carried out at a temperature of 50 to 100 ℃. The method of claim 5, wherein the oxazine monomer,
A method for preparing a composition which is at least one selected from compounds represented by formulas (1) to (6).
[Formula 1]

In Formula 5, R ₁ , R ₂ , R ₃ , and R ₄ are each independently hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C2-C20 alkenyl group, substituted or unsubstituted C2-C20 alkynyl group, substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C6-C20 aryloxy group, substituted or unsubstituted C2-C20 heteroaryl Groups, substituted or unsubstituted C2-C20 heteroaryloxy groups, substituted or unsubstituted C4-C20 carbocyclic groups, substituted or unsubstituted C4-C20 carbocyclic groups, substituted or unsubstituted C2-C20 heterocycles A group, a halogen atom, a hydroxyl group, or a cyano group,
R ₅ is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, Substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C6-C20 aryloxy group, substituted or unsubstituted C7-C20 arylalkyl group, substituted or unsubstituted C2-C20 heteroaryl group, Substituted or unsubstituted C2-C20 heteroaryloxy group, substituted or unsubstituted C2-C20 heteroarylalkyl group, substituted or unsubstituted C4-C20 carbocyclic group, substituted or unsubstituted C4-C20 carbon A cyclic alkyl group, a substituted or unsubstituted C2-C20 heterocyclic group, or a substituted or unsubstituted C2-C20 heterocyclic alkyl group,
(2)

R ₅ ′ in Formula 2 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2 -C20 alkynyl group, substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C6-C20 aryloxy group, substituted or unsubstituted C7-C20 arylalkyl group, substituted or unsubstituted C2- C20 heteroaryl group, substituted or unsubstituted C2-C20 heteroaryloxy group, substituted or unsubstituted C2-C20 heteroarylalkyl group, substituted or unsubstituted C4-C20 carbocyclic group, substituted or unsubstituted C4-C20 carbocyclic alkyl group, substituted or unsubstituted C2-C20 heterocyclic group, or substituted or unsubstituted C2-C20 heterocyclic alkyl group,
R ₆ is a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C2-C20 alkenylene group, a substituted or unsubstituted C2-C20 alkynylene group, a substituted or unsubstituted C6-C20 arylene group, a substituted Or an unsubstituted C2-C20 heteroarylene group, -C (= 0)-, -SO _2- ,
(3)

In Formula 3, A, B, C, D, and E are all carbon, or one or two selected from A, B, C, D, and E are nitrogen (N), and the rest are carbon (C),
R ₇ And R ₈ are connected to each other to form a ring,
The ring is a C6-C10 cycloalkyl group, a C3-C10 heteroaryl group, a fused C3-C10 heteroaryl group, a C3-C10 heterocyclic group or a fused C3-C10 heterocyclic group,
[Chemical Formula 4]

In Formula 4, A 'is a substituted or unsubstituted C1-C20 heterocyclic group, a substituted or unsubstituted C4-C20 cycloalkyl group, or a substituted or unsubstituted C1-C20 alkyl group,
R ₉ R ₁₆ is independently of each other hydrogen, C1-C20 alkyl group, C1-C20 alkoxy group, C6-C20 aryl group, C6-C20 aryloxy group, C1-C20 heteroaryl group, C1-C20 heteroaryloxy group, C4- A C20 cycloalkyl group, a C1-C20 heterocyclic group, a halogen atom, a cyano group, or a hydroxy group,
[Chemical Formula 5]

In Formula 5, R ₁₇ And R ₁₈ is independently a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, or a group represented by the following Formula 5A,
[Formula 5A]

In Formulas 5 and 5A,
R ₁₉ and R _{19 ′} independently of one another are hydrogen, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, a halogenated C6-C20 aryl group, a halogenated C6-C20 aryl Oxy group, C1-C20 heteroaryl group, C1-C20 heteroaryloxy group, halogenated C1-C20 heteroaryl group, halogenated C1-C20 heteroaryloxy group, C4-C20 cycloalkyl group, halogenated C4-C20 cycloalkyl group , C1-C20 heterocyclic group, or halogenated C1-C20 heterocyclic group,
[Formula 6]

In Formula 6, R ₂₀ , R ₂₁ And two or more adjacent groups selected from R ₂₂ are connected to each other and represented by the following Chemical Formula 6A,
R ₂₀ and R ₂₁ And the remaining groups not selected from R ₂₂ are hydrogen, C 1 -C 20 alkyl group, C 1 -C 20 alkoxy group, C 6 -C 20 aryl group, C 6 -C 20 aryloxy group, halogenated C 6 -C 20 aryl group, halogenated C 6 -C 20 aryl Oxy group, C1-C20 heteroaryl group, C1-C20 heteroaryloxy group, halogenated C1-C20 heteroaryl group, halogenated C1-C20 heteroaryloxy group, C4-C20 carbocyclic group, halogenated C4-C20 carbon A cyclic group, a C1-C20 heterocyclic group, or a halogenated C1-C20 heterocyclic group,
Two or more adjacent groups selected from R ₂₃ , R _24, and R ₂₅ are connected to each other and represented by the following Chemical Formula 2A,
The remaining group not selected from R ₂₃ , R _24, and R ₂₅ may be a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, a halogenated C6-C20 aryl group, or a halogenated group. C6-C20 aryloxy group, C1-C20 heteroaryl group, C1-C20 heteroaryloxy group, halogenated C1-C20 heteroaryl group, halogenated C1-C20 heteroaryloxy group, C4-C20 carbocyclic group, halogenated C4-C20 carbocyclic group, C1-C20 heterocyclic group, or halogenated C1-C20 heterocyclic group
[Formula 6A]

In Formula 6A, R ₁ 'is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C6-C20 aryloxy group, substituted or unsubstituted C7-C20 arylalkyl group, substituted or unsubstituted C2 -C20 heteroaryl group, substituted or unsubstituted C2-C20 heteroaryloxy group, substituted or unsubstituted C2-C20 heteroarylalkyl group, substituted or unsubstituted C4-C20 carbocyclic group, substituted or unsubstituted A substituted C4-C20 carbocyclic alkyl group, a substituted or unsubstituted C2-C20 heterocyclic group, or a substituted or unsubstituted C2-C20 heterocyclic alkyl group,
* Is R ₂₀ , R ₂₁ in Chemical Formula 6 And positions adjacent to two or more adjacent groups selected from R ₂₂ and two or more adjacent groups selected from R ₂₃ , R _24, and R ₂₅ , respectively. The method of claim 5, wherein the oxazine monomer,
A compound of formula 16 (4FPh2AP), a compound of formula 28 (3,4-FPh4FA), a compound of formula 66, a compound of formula 62 (HF-a), a compound of formula 89 (3HP2AP), and a formula 116. A process for the preparation of at least one composition selected from compounds of 116 (PPO).
[Formula 16] [Formula 28]

[Formula 66]

[Formula 62]

[Formula 89]

[Formula 116]

Support; An electrode comprising a catalyst layer formed on said support and containing a coating product of the composition of any one of claims 1-4. The electrode of claim 13, wherein the composition further comprises a crosslinkable compound. The method of claim 13, wherein the catalyst layer further comprises a catalyst,
The content of the polyoxazine-based compound in the catalyst layer is 0.001 to 20 parts by weight based on 1 part by weight of the catalyst. A fuel cell comprising the electrode of claim 13.

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