KR20110090775A - Polymer composition, cross-linked polymer formed therefrom, electrode for fuel cell comprising the polymer, electrolyte membrane for fuel cell comprising the same, and fuel cell having the same - Google Patents

Abstract

PURPOSE: A polymer composition is provided to obtain a cross-linked polymer composition with enhanced capability of retaining phosphoric acid at a wide range of temperature and to secure long-term durability and enhanced proton conductivity. CONSTITUTION: A polymer composition comprises: a polymer having a first repeating unit represented by chemical formula 1 and a second repeating unit represented by chemical formula 2, and an oxazine-based monomer. In chemical formula 1, Ar is a substituted or unsubstituted C6-C20 arylene group or a substituted or unsubstituted C3-C20 heteroarylene group and m is a number from 0.01 from 1. In chemical formula 2, R1 is a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C6-C20 aryloxy group, a substituted or unsubstituted C3-C20 heteroaryl group, or a substituted or unsubstituted C3-C20 heteroaryloxy group; R2 and R3 are each independently a hydrogen atom, an unsubstituted or substituted C1-C20 alkyl group, an unsubstituted or substituted C1-C20 alkoxy group, an unsubstituted or substituted C6-C20 aryl group, an unsubstituted or substituted C6-C20 aryloxy group, an unsubstituted or substituted C3-C20 heteroaryl group, or an unsubstituted or substituted C3-C20 heteroaryloxy group, or R2 and R3 may be linked to form a C4-C20 carbocyclic group or a C3-C20 heterocyclic group; and n is a number from 0 to 0.99.

Description

Polymer composition, polymer cross-linked body formed therefrom, electrode for fuel cell comprising same, electrolyte membrane for fuel cell, and fuel cell employing the same (Polymer composition, cross-linked polymer formed therefrom, electrode for fuel cell comprising the polymer, electrolyte membrane for fuel cell comprising the same, and fuel cell having the same}

The present invention relates to a polymer composition, a polymer crosslinked body formed therefrom, an electrode for a fuel cell including the same, an electrolyte membrane for a fuel cell including the same, and a fuel cell employing the same.

Fuel cells using polymer electrolyte membranes as polymer electrolytes are expected to be used as power sources for electric vehicles and household distributed power generation systems because of their relatively low operating temperatures and miniaturization. Polymer Electrolyte Membrane A perfluorocarbon sulfonic acid polymer membrane represented by Nafion (registered trademark) is used as the polymer electrolyte membrane used in the fuel cell.

However, in order for this type of polymer electrolyte membrane to express proton conduction, humidification is necessary because water is required. In addition, high temperature operation at a temperature of 100 ° C. or higher is required in order to increase battery system efficiency, but there is a problem in that moisture in the electrolyte membrane is evaporated and depleted, and the function as a solid electrolyte is lost.

In order to solve the problems caused by these conventional techniques, a non-humidified electrolyte membrane capable of operating at a high temperature of 100 ° C. or more while being humidified has been developed. A material such as polybenzimidazole doped with phosphoric acid is disclosed as a constituent material of a non-humidified electrolyte membrane.

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.

In addition, in a fuel cell using polybenzimidazole (PBI), which maintains phosphoric acid, which is a high-temperature, non-humidifying electrolyte, in an electrolyte membrane, impregnation of liquid phosphoric acid in the electrode has been attempted to improve contact between the electrode and the membrane interface. Attempts have been made to increase the loading content of metal catalysts, but there are many room for improvement as satisfactory properties are difficult to obtain in mechanical properties, chemical stability and phosphate retention capacity.

A polymer composition having improved mechanical strength, a polymer crosslinked body formed therefrom, an electrode for a fuel cell and an electrolyte membrane for a fuel cell, and a fuel cell employing the same are provided.

According to an aspect of the present invention, there is provided a polymer composition comprising a first repeating unit of Formula 1 and a second repeating unit of Formula 2, and an oxazine monomer.

 [Formula 1]

이고,In the above formula,

ego,

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

m is 0.01 to 1,

[Formula 2]

In the above formula, R ₁ And R ₃ is independently of each other 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 ₂ And R ₃ are linked to each other to form a C4-C20 carbon ring or a C3-C20 heterocycle,

n is 0 to 0.99.

According to another aspect of the present invention, there is provided a polymer crosslinked product which is a crosslinked product obtained through a crosslinking reaction of the polymer composition.

According to another aspect of the invention there is provided an electrolyte membrane for a fuel cell comprising the above-described polymer composition or the above-described polymer crosslinked product.

According to another aspect of the present invention there is provided a fuel cell electrode comprising the above-described polymer composition or the above-described polymer crosslinked product.

According to another aspect of the invention the cathode, anode and intervening between them

A fuel cell including an electrolyte membrane and at least one selected from the cathode, the anode, and the electrolyte membrane includes the polymer composition or the polymer crosslinked body described above.

As the content of phosphoric acid is improved, a polymer crosslinked product having excellent mechanical properties is provided. By using this compound, the ability to retain phosphoric acid over a wide temperature range is improved, thereby ensuring long-term durability and producing electrodes and electrolyte membranes for fuel cells with improved proton conductivity.

1 shows an IR spectrum of a polymer crosslinked product prepared according to Example 1,
2 shows a change in conductivity according to temperature in a fuel cell according to Preparation Example 1 and Comparative Preparation Example 1,
3 illustrates a voltage change according to current density in the fuel cell according to Preparation Example 1. FIG.

Provided is a polymer comprising a polymer comprising a first repeating unit represented by Formula 1 and a second repeating unit represented by Formula 2, a polymer composition comprising an oxazine monomer, and a crosslinked product obtained through a crosslinking reaction of the composition.

 [Formula 1]

In Formula 1,

이고,

ego,

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

m is 0.01 to 1,

[Formula 2]

R ₁ and R ₂ in Formula 2 are each independently a 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 ₂ To R ₃ are connected to each other to form a C4-C20 carbon ring or a C3-C20 heterocycle,

n is 0 to 0.99. For example, n is 0.01 to 0.99.

In the above formula, m and n are percentages constituting the polymer repeating unit, and when their sum is 1, m is 0.01 to 1 and n is 0 to 0.99. For example, m is 0.1 to 1 and n is 0 to 0.9.

In the formula, m: n may be a mixed molar ratio of the first repeating unit and the second repeating unit.

In the case where both the repeating unit of Formula 1 and the repeating unit of Formula 2 are included, m is 0.1 to 0.9 and n is 0.1 to 0.9.

Ar is at least one selected from the group represented by the following formula (2A).

[Formula 2A]

Examples of the second repeating unit of Chemical Formula 1 include a repeating unit represented by the following Chemical Formula 2B or 2C.

[Formula 2B]

[Formula 2C]

Ar in Formula 2B-2C is an unsubstituted or substituted C6-C20 arylene group or an unsubstituted or substituted C3-C20 heteroarylene group,

m is 0.01-1.

The polymer crosslinked product is obtained by heat-treating a mixture of a polymer, an oxazine monomer and a polyphosphoric acid containing the first repeating unit represented by Formula 1 and the second repeating unit represented by Formula 2.

In the polymer including the first repeating unit of Formula 1 and the repeating unit of Formula 2, the repeating unit of Formula 2 is 0.01 to 99 moles based on 1 mole of the repeating unit of Formula 1.

The mixing ratio (eg, mixing molar ratio) of the first repeating unit of Formula 1 and the second repeating unit of Formula 2 is 0.1: 9.9 to 9.9: 0.1, for example 1: 9 to 9: 1, and for example 8: 2 to 2: 8, 8: 2, 5: 5, or 2: 8.

The polymer may be a homopolymer containing only a repeating unit of Formula 1.

The polymer has a retention capacity of phosphoric acid due to retention of thiazole groups, and as the amount of sulfur introduced increases, the degree of crosslinking increases, thereby improving physical properties such as mechanical strength.

The content of the oxazine monomer is represented by the formula

10 to 1000 parts by weight based on 100 parts by weight of the polymer including the first repeating unit and the second repeating unit of the formula (2).

When the content of the oxazine monomer is in the above range, it is excellent in physical properties such as the mechanical strength of the desired polymer, it is possible to manufacture the electrolyte membrane and electrode for fuel cells that the gas permeability is reduced to reduce fuel penetration.

The crosslinked product of the polymer may have a structure in which a polymer of an oxazine monomer is graft polymerized to a side chain of a polymer including a first repeating unit of Formula 1 and a second repeating unit of Formula 2 to form a graft copolymer. Alternatively, the polymer of the oxazine monomer may have a structure that forms a crosslink in the side chain of the polymer including the first repeating unit of Formula 1 and the second repeating unit of Formula 2.

The polymer crosslinked body obtained by using the polymer including the first repeating unit of Formula 1 and the second repeating unit of Formula 2 and the oxazine monomer may require physical properties required for the fuel cell electrolyte membrane and / or electrolyte membrane including mechanical strength. It has chemical stability. Therefore, the above-mentioned electrolyte membrane has a strong phosphoric acid trapping ability, and the ability to retain phosphoric acid in a wide temperature range is greatly improved, thereby ensuring long-term durability.

The polymer including the first repeating unit of Formula 1 and the second repeating unit of Formula 2 may be a copolymer including the first repeating unit of Formula 1 and the second repeating unit of Formula 2, for example, It may be a block copolymer comprising the first repeating unit of 1 and the second repeating unit of the formula (2). Such a block copolymer has a rigid structure, not only can serve as a support for maintaining the shape of the electrolyte membrane, but also has a high degree of polymerization and improved mechanical strength.

The electrolyte membrane described above can be usefully used for a high temperature unhumidified fuel cell.

The degree of polymerization of the polymer comprising the first repeating unit of Formula 1 and the second repeating unit of Formula 2 is 1 to 900, for example, 10 to 900, and another example, 20 to 900.

The polymer including the first repeating unit of Formula 1 and the second repeating unit of Formula 2 may be a compound represented by the following Formula 3.

(3)

In Formula 3, Ar ₁ is an unsubstituted or substituted C6-C20 arylene group or an unsubstituted or substituted C3-C20 heteroarylene group,

R ₁ To R ₃ is independently hydrogen, an unsubstituted or substituted C1-C20 alkyl group, an unsubstituted or substituted C1-C20 alkoxy group, an unsubstituted or substituted C1-C20 aryl group, unsubstituted or substituted C1-C20 aryloxy group, unsubstituted or substituted C3-C20 heteroaryl group, unsubstituted or substituted C3-C20 heteroaryloxy group, or R ₂ And R ₃ are connected to each other to form a C4-C20 carbon ring or a C3-C20 hetero ring,

m ₁ is 0.01 to 1, n ₁ is 0 to 0.99, k ₁ is a number from 10 to 250,

[Formula 4]

Ar ₂ in Formula 4 is an unsubstituted or substituted C6-C20 arylene group or an unsubstituted or substituted C3-C20 heteroarylene group,

R ₁ To R ₃ is independently hydrogen, an unsubstituted or substituted C1-C20 alkyl group, an unsubstituted or substituted C1-C20 alkoxy group, an unsubstituted or substituted C1-C20 aryl group, unsubstituted or substituted C1-C20 aryloxy group, unsubstituted or substituted C3-C20 heteroaryl group, unsubstituted or substituted C3-C20 heteroaryloxy group, or R ₂ And R ₃ are linked to each other to form a C4-C20 carbon ring or a C3-C20 heterocycle,

m ₂ is 0.01 to 1, n ₂ is 0 to 0.99, and k ₂ is a number from 10 to 250.

The polymer including the first repeating unit of Formula 1 and the second repeating unit of Formula 2 may be a compound represented by the following Formula 11.

[Formula 11]

M ₃ in Formula 11 is 0.01 to 1, for example, 1 or 0.1 to 0.9, n ₃ is 0 to 0.99, for example, 0 or 0.1 to 0.9. k ₃ is a number from 10 to 250.

A method of preparing a polymer including a repeating unit represented by Formula 1 and a repeating unit represented by Formula 2 will be described, for example, a method of preparing a polymer represented by Formula 3 will be described.

Referring to Scheme 1 below, the following compound (A), compound (B) and compound (C) are dissolved in polyphosphoric acid at 60 to 150 ° C., and then heat-treated to synthesize a polymer of Formula 3.

Scheme 1

Formula 3

In compound (A), compound (B), compound (C) and formula 3 of Scheme 1,

Ar ₁ is an unsubstituted or substituted C6-C20 arylene group or an unsubstituted or substituted C3-C20 heteroarylene group,

R ₁ To R ₃ is independently hydrogen, an unsubstituted or substituted C1-C20 alkyl group, an unsubstituted or substituted C1-C20 alkoxy group, an unsubstituted or substituted C1-C20 aryl group, unsubstituted or substituted C1-C20 aryloxy group, unsubstituted or substituted C3-C20 heteroaryl group, unsubstituted or substituted C3-C20 heteroaryloxy group, or R ₂ And R ₃ are linked to each other to form a C4-C20 carbon ring or a C3-C20 heterocycle,

m ₁ is 0.01 to 1, n ₁ is 0 to 0.99, and k ₁ is a number from 10 to 250.

The 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 content of the polyphosphoric acid is 1000 to 4000 parts by weight based on 100 parts by weight of the compound (A).

The heat treatment is carried out in the range of 60 to 250 ℃.

The oxazine monomer is not particularly limited, and for example, one or more selected from compounds represented by the following Chemical Formulas 5 to 10 may be used.

[Chemical Formula 5]

In Formula 5, R ₄ , R ₅ , R ₆ , and R ₇ 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 group , Substituted or unsubstituted C2-C20 heteroaryloxy group, substituted or unsubstituted C4-C20 carbocyclic group, substituted or unsubstituted C4-C20 carbocyclic group, substituted or unsubstituted C2-C20 heterocyclic group , A halogen atom, a hydroxyl group, or a cyano group,

R ₈ 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 6]

R ₈ ′ in Formula 6 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 ₉ 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- ,

[Formula 7]

In Formula 7, 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 ₁₀ and R ₁₁ are connected to each other to form a ring,

The ring is a C6-C10 carbocyclic 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 8]

In Formula 8, 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 ₁₂ R ₁₉ is independently from each other hydrogen, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, a C1-C20 heteroaryl group, a C1-C20 heteroaryloxy group, C4- A C20 cycloalkyl group, a C1-C20 heterocyclic group, a halogen atom, a cyano group, or a hydroxy group,

 [Formula 9]

In Formula 9, R ₂₀ and R ₂₁ are each 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 9A,

[Formula 9A]

In Formula 9 and Formula 9A, R ₂₂ is independently 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 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 10]

In Formula 10, R ₂₃ , R ₂₄ And two or more adjacent groups selected from R ₂₅ are connected to each other and represented by the following Formula 10A,

R ₂₃ and R ₂₄ And the remaining groups not selected from R ₂₅ 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,

R ₂₆ , R ₂₇ and R ₂₈ Two or more adjacent groups selected from each other are linked to each other and represented by the following Chemical Formula 10A,

The remaining group not selected from R ₂₆ , R ₂₇ and R ₂₈ is 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 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 10A]

R ₂₉ in Formula 10A 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 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 ₂₃ , R ₂₄ in Formula 10. And positions adjacent to two or more adjacent groups selected from R ₂₅ and two or more adjacent groups selected from R ₂₆ , R _27, and R ₂₈ , respectively.

R ₂₉ in Formula 10A is one selected from the group represented by Formula 10B.

[Formula 10B]

As an example of the compound represented by the said Formula (5), the compound represented by following formula (12)-60 is mentioned.

[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]

[Formula 56] [Formula 57] [Formula 58]

[Formula 59] [Formula 60]

As an example of the compound represented by the said Formula (6), the compound represented by following formula (61)-65 is mentioned.

[Formula 61] [Formula 62]

[Formula 63] [Formula 64]

O

(65)

R ₈ ′ in Formula 61-65 is 4-tertbutylphenyl group-CH ₂ —CH═CH ₂ , or one selected from the group represented by the following Formula 65A.

[Formula 65A]

 For example, the compound of Formula 6 may be selected from compounds represented by the following Chemical Formulas 66-69.

[Formula 66] [Formula 67]

[Formula 68] [Formula 69]

Examples of the compound represented by Chemical Formula 7 include compounds represented by the following Chemical Formulas 70 to 73.

(70)

In Formula 70, R 'is hydrogen or a C1-C10 alkyl group,

(71)

(72)

(73)

가 하기 화학식 74으로 표시되는 그룹중의 하나이다.In the formula 70 to 73

Is one of the groups represented by the following general formula (74).

≪ EMI ID =

The compound represented by Chemical Formula 7 is selected from, for example, a compound represented by the following Chemical Formulas 75 to 95.

[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 90]

[Formula 91] [Formula 92] [Formula 93]

[Formula 94] [Formula 95]

A ′ of Formula 8 may be one of groups represented by the following Formula 96 or 97.

[Formula 96] [Formula 97]

In Formulas 96 and 97, 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 8 may be a compound represented by the following Formula 98 or 99.

[Formula 98] [Formula 99]

In Formulas 98 and 99, R _{k is} one selected from the group represented by 99A.

[Formula 99A]

상기 화학식 8의 화합물들은 하기 화학식 100 내지 105로 표시되는 화합물중에서 선택된 하나일 수 있다.

The compounds of Formula 8 may be one selected from compounds represented by the following Formulas 100 to 105.

[Formula 100] [Formula 101]

[Formula 102] [Formula 103]

[Formula 104] [Formula 105]

Examples of the compound represented by Formula 9 include a compound represented by the following Formula 106, 107 or 109.

≪ EMI ID =

≪ EMI ID =

In Formulas 106 and 107, R ₁₇ ′ 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 Formula 108,

(108)

[Formula 109]

In Formula 109, R ₁₇ 'is a C6-C10 aryl group,

R ₁₉ ′ is selected from the group represented by the following formula (110).

[Formula 110]

The compound of Formula 9 may be one selected from compounds represented by the following Chemical Formula 111 or 112.

[Formula 111] [Formula 112]

In Formulas 111 and 112, R ₁₉ ′ is selected from the group represented by Formula 111A.

Formula 111A]

The compound of Chemical Formula 9 may be a compound represented by the following Chemical Formulas 113 to 119.

[Formula 113] [Formula 114]

[Formula 115] [Formula 116]

[Formula 117] [Formula 118]

Formula 119

As an example of the compound represented by the said Formula (10), the compound represented by following formula (120)-122 is mentioned.

[Formula 120] [Formula 121]

[Formula 122]

In Formulas 120-122. R _j is one of the groups represented by the following formula 121A.

[Formula 121A]

Specific examples of the compound represented by Formula 10 include compounds represented by the following Formulas 123 to 130.

[Formula 123]

[Formula 124]

[Formula 125]

[Formula 126]

(127)

(128)

≪ EMI ID =

[Formula 130]

Hereinafter, a method for preparing a polymer crosslinked product according to one embodiment of the present invention will be described in detail.

A polymer, an oxazine monomer, and polyphosphoric acid containing the first repeating unit of Formula 1 and the second repeating unit of Formula 2 are mixed.

The mixture is then heat treated.

Polymerization of the oxazine monomer during the heat treatment occurs, the oxazine monomer formed by this polymerization reaction is graft polymerized or crosslinked to the side chain of the polymer containing the repeating unit of Formula 1 and the repeating unit of Formula 2 to form a crosslinked polymer A sieve is obtained. The heat treatment takes place at 60 to 250 ° C. If the heat treatment is in the above range, the mechanical strength of the finally obtained electrolyte membrane is excellent.

The degree of polymerization of the polymer crosslinked body is a number of 1 to 900, for example, 10 to 900, another example, 20 to 900.

Looking at the method for producing an electrolyte membrane by using the polymer crosslinked product is as follows.

First, a mixture of a polymer, an oxazine monomer, and polyphosphoric acid containing a repeating unit of Formula 1 and a second repeating unit of Formula 2 is mixed and stirred. Herein, the content of polyphosphoric acid is 1000 to 4000 parts by weight based on 100 parts by weight of the polymer including the repeating unit of Formula 1 and the second repeating unit of Formula 2.

The mixture is cast on a substrate and heat treated.

The heat treatment temperature is made at 100 to 250 ℃.

The heat treated reaction mixture is impregnated with phosphoric acid at room temperature. Here, as phosphoric acid, ortho-phosphoric acid itself is used or an aqueous solution of phosphoric acid of 5 to 30% by weight is used.

The reaction mixture, which has been heat-treated prior to impregnation with phosphoric acid, is subjected to constant temperature and humidity conditions.

Neglecting may be performed. Upon treatment under such constant temperature and humidity conditions, hydrolysis of polyphosphoric acid occurs.

Looking at the constant temperature and humidity conditions, the temperature is -20 to 30 ℃, relative humidity is adjusted to 5 to 50% RH range.

The temperature is −10 to 15 ° C. and the relative humidity ranges from 5 to 25% RH. Alternatively, the solution may be slowly hydrolyzed at -10 ^o C, 25% RH for at least 48 hours.

When the temperature is in the above range, it is easy to control the hydrolysis rate without lowering the hydrolysis reactivity. And when the relative humidity is in the above range, the physical properties of the finally obtained electrolyte membrane is excellent without lowering the hydrolysis reactivity.

When the resultant obtained by the above process is vacuum dried at room temperature (20 ° C.), an electrolyte membrane for a fuel cell including a polymer crosslinked product can be obtained.

Although the sol-gel method using the above-mentioned polyphosphoric acid may be used in the preparation of the electrolyte membrane, it is also possible to carry out the same procedure as in the preparation method of the electrolyte membrane described in Korean Patent Publication No. 2009-0045655 by the present applicant. .

The fuel cell electrode may include the polymer crosslinked body and the catalyst described above. With such a composition, oxygen permeability can be improved while using air in the cathode, and the wetting ability and thermal stability of phosphoric acid (H ₃ PO ₄ ) in the electrode can be improved. Therefore, a fuel cell employing such an electrode and an electrolyte membrane has advantages in that it can operate under high temperature and no humidification conditions, can enhance thermal stability, and can exhibit improved power generation performance.

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, molybdenum, cobalt and chromium or the catalyst metal It may be a supported catalyst supported on this carbon carrier. For example, one or more catalyst metals selected from the group consisting of platinum (Pt), platinum cobalt (PtCo) and platinum ruthenium (PtRu), or supported catalysts in which the catalyst metal is supported on a carbon-based carrier is used.

The electrode may further include a binder commonly used in manufacturing a fuel cell electrode.

The binder may be at least one selected from the group consisting of poly (vinylidene fluoride), polytetrafluoroethylene, tetrafluoroethylene-hexafluoroethylene copolymer, and perfluoroethylene, and the content of the binder is catalyzed. 0.001 to 0.5 parts by weight based on 1 part by weight.

If the content of the binder is in the above range it can effectively improve the wet state of the electrode.

The fuel cell electrode may be manufactured according to a method using polyphosphoric acid described below, or may be manufactured in the same manner as the method for manufacturing an electrode described in Korean Patent Publication No. 2009-0045655 by the present applicant.

Dispersion is obtained by first dispersing the catalyst in a solvent. In this case, N-methylpyrrolidone (NMP), dimethylacetamide (DMAc) and the like are used as the solvent, and the content thereof is 1 to 10 parts by weight based on 1 part by weight of the catalyst.

A mixture comprising a polymer, an oxazine monomer, a solvent, and a polyphosphoric acid including the first repeating unit of Formula 1 and the repeating unit of Formula 2 is added to the dispersion and stirred.

N-methylpyrrolidone (NMP), dimethylacetamide (DMAc) and the like are used as the solvent.

The mixture may further include a binder commonly used in the manufacture of fuel cell electrodes.

The content of the polyphosphoric acid is 1 to 10 parts by weight based on 100 parts by weight of the polymer including the first repeating unit of Formula 1 and the repeating unit of Formula 2.

The mixture 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 mixture is coated and dried, the solvent is removed and is carried out 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 further comprise one or more proton conductors in which the catalyst layer is selected from phosphoric acid and C1-C20 organic phosphonic acid. Here, the content of the proton conductor is used in an amount of 10 to 1000 parts by weight based on 100 parts by weight of the total weight of the electrode.

The concentration of the acid is not particularly limited, but when phosphoric acid is used, an aqueous solution of 80% by weight of phosphoric acid is used, and the phosphoric acid impregnation time is in the range of 2.5 hours to 14 hours at 80 ° C.

In addition to using phosphoric acid when preparing the polymer of the oxazine monomer in forming the electrolyte membrane and the electrode, it is also possible to undergo a second impregnation process of phosphoric acid separately. The phosphoric acid used at this time may be used 5 to 30% by weight aqueous solution of phosphoric acid.

The fuel cell optimizes the electrolyte membrane forming material and / or the electrode forming material to maximize the cell performance of the battery formed therefrom.

The fuel cell electrolyte membrane and the fuel cell electrode may be manufactured using a polymer composition obtained by mixing the above-described polymer and oxazine monomer.

A method of manufacturing a fuel cell including the fuel cell electrode will be described.

As the electrolyte membrane, an electrolyte membrane commonly used in a fuel cell may be used, or an electrolyte membrane including the above-described oxazine monomer and a polymer crosslinked body including the first repeating unit of Formula 1 and the second repeating unit of Formula 2 may be used. have.

For example, when the polymer is used as the electrolyte membrane, the contact resistance between the electrolyte membrane and the electrode may be reduced, thereby maximizing the cell performance of the fuel cell.

As the electrolyte membrane commonly used in the fuel cell, for example, polybenzimidazole electrolyte membrane, polybenzoxazine-polybenzimidazole copolymer electrolyte membrane, polytetrafluoroethylene (PTFE) porous membrane, etc. Can be used.

Looking at the process of manufacturing an electrode-membrane assembly for a fuel cell is as follows. The term "membrane and electrode assembly" (MEA) refers to a structure in which electrodes formed of a catalyst layer and a diffusion layer are stacked on both sides of an electrolyte membrane.

The MEA may be formed by placing the electrode having the above-described electrode catalyst layer on both sides of the electrolyte membrane obtained according to the above process, and then bonding them at high temperature and high pressure, and bonding the fuel diffusion layer thereto.

At this time, the heating temperature and pressure for the bonding is carried out by pressurizing at a pressure of 0.1 to 3 ton / cm ² , for example, about 1 ton / cm ² in a state heated to the temperature that the electrolyte membrane is softened.

Thereafter, bipolar plates are mounted on the electrode-membrane assemblies, respectively, to complete the fuel cell. Here, the bipolar plate has a fuel supply groove and has a current collector function.

The fuel cell is not particularly limited in use, but is used as a polymer electrolyte membrane fuel cell.

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 the "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, etc. are mentioned.

At least one hydrogen atom 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, C2-C20 Alkoxyalkyl, 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 hetero Or an arylalkyl 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, monohaloalkyl, dihaloalkyl or perhaloalkyl. One polyhaloalkyl is mentioned.

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” as 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" as used in the formula refers to a 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 one or more hydrogen atoms of the alkenyl may be substituted with the same substituent as in the alkyl group described above.

The term “alkynyl” group 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 above 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 the “aryl” include phenyl, naphthyl, tetrahydronaphthyl and the like.

In addition, at least one hydrogen atom of 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” as used in the formula means O-aryl, and examples of the aryloxy group include phenoxy. At least one hydrogen atom of the above-mentioned arylaryl may be substituted with the same substituent as in the alkyl group described above.

The term “heteroaryl” as used in the formula refers to a monocyclic or bicyclic organic compound comprising at least one heteroatom selected from N, O, P or S and wherein the remaining ring atoms are 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” refers to an O-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.

The “carbon ring” group used in the formula refers to a saturated or partially unsaturated non-aromatic monocyclic, bicyclic or tricyclic hydrocarbon group.

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.

“Heterocyclic” as 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, and one or more hydrogen of such heterocyclic groups. The atoms may be substituted as in the case of the alkyl group described above.

The term “heterocyclic oxy” means an —O-heterocycle, wherein at least one hydrogen atom of the heterocyclic oxy group is replaceable as in the case of the alkyl group described above.

The term “sulfonyl” refers to R˝SO ₂ —, where 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 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.

The terms “alkylene” group, “alkenylene” group, “alkynylene” group, “arylene” group and “heteroarylene” group each represent monovalent “alkyl”, “alkenyl”, “alkynyl”, and “aryl” The same definitions apply except that the “group” and “heteroaryl” group are changed to a divalent group.

At least one hydrogen atom of the alkylene group, the alkenylene group, the alkynylene group, the arylene group and the heteroarylene group may be substituted in the same manner as in 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: polymer Crosslinked material  Synthesis and Using the Same Electrolyte membrane  Produce

First, a polymer of Chemical Formula 11 was prepared according to Scheme 2 below.

0.0186 mol of diaminobenzenedithiol, 0.0186 mol of terephthalic acid and 0.0434 mol of diaminobenzoic acid were dissolved in 307 g of polyphosphoric acid at 60 to 150 ° C., and then heat-treated at 150 to 250 ° C. for 12 hours to synthesize a polymer of Formula 11 have.

Scheme 2

 [Formula 11]

In Formula 11, m ₃ is about 2, and n ₃ is about 8.

When the polymerization was completed, the reaction mixture became a highly viscous solution, and orthophosphoric acid was added to the solution and dissolved at 150 ° C. The number average molecular weight of the benzthiazole polymer obtained by this polymerization reaction was about 150,000. This number average molecular weight was measured by gel permeation chromatography.

To the mixture was added 65 parts by weight of a compound represented by the following Chemical Formula 21 (4FPh2AP) and stirred. The content of the compound of Formula 11 to react with the compound represented by Formula 21 was 35 parts by weight.

[Formula 21]

The stirred product was cast on top of a quartz plate, which was placed in an oven at 100 ° C. under a nitrogen gas atmosphere to cure it.

After about 3 hours of slowly raising the temperature to 100 ° C to 220 ° C, the temperature was fixed at 220 ° C for 1 hour, and the temperature was slowly cooled to room temperature in an oven.

The reaction product was placed at −10 ° C. and 25% RH for at least 48 hours, and then slowly hydrolyzed.

The film prepared in about 20% by weight aqueous solution of phosphoric acid was immersed at room temperature for 24 hours to undergo a second hydrolysis process. Then remove the film from the aqueous solution of phosphoric acid

The phosphoric acid on the surface was wiped off and dried in a vacuum oven for at least 24 hours to obtain an electrolyte membrane made of a polymer crosslinked product.

1 shows an IR spectrum of the polymer crosslinked product.

In the electrolyte membrane made of a polymer crosslinked product prepared according to Example 1, physical properties were measured and shown in Table 1 below. The physical properties of Table 1 were measured using UTM (model name: universal testing machine (Lloyd LR-10K)), and the specimens were evaluated by fabricating batches using ASTM standard D638 (Type V specimens).

division Phosphoric Acid
content*
(weight%) Modulus (MPa) The tensile strength
(MPa) Breaking strength
(MPa) Strain Example 1 65.4 91.3 3.50 2.83 16.2 72.8 45.2 3.22 3.04 28.8

Example  2: polymer Crosslinked material  Synthesis and Using the Same Electrolyte membrane  Produce

0.0187 mol of diaminobenzenedithiol and 0.0187 mol of terephthalic acid were dissolved in 82 g of polyphosphoric acid at 60 to 150 ° C., and then heat-treated at 150 to 250 ° C. for 12 hours to synthesize a benzthiazole polymer of Formula 11 (n = 0). Could.

A polymer crosslinked product was synthesized in the same manner as in Example 1 except that the compound of Formula 11 (m ₃ was about 2 and n ₃ = 0) was used instead of the compound of Formula 11, and an electrolyte membrane was prepared using the compound. Prepared.

Comparative example  One: Poly (2,5- benzimidazole ) ( ABPBI ) Electrolyte membrane  Produce

At 150 ° C, DABA was completely dissolved in a polyphosphoric acid (PPA) solvent. When the mixture was stirred to form a uniform solution, the temperature was raised to 220 ° C. and polymerization was performed for 30 minutes to obtain ABPBI.

The ABPBI was impregnated with 85 wt% phosphoric acid at 80 ° C. for at least 4 hours to form an electrolyte membrane. Herein, the phosphoric acid content was about 530 parts by weight based on 100 parts by weight of the electrolyte membrane total weight.

Production example  One: Example  1 of Electrolyte membrane  Fabrication of Fuel Cells Used

In a stirring vessel, 1 g of a catalyst having 50 wt% PtCo supported on carbon and 3 g of a solvent NMP were added and stirred to form a slurry. To the slurry was added 5% by weight of NMP solution of polyvinylidene fluoride was added so that the polyvinylidene fluoride to 0.025g and mixed for 10 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 600 μm.

Coating the cathode catalyst layer forming slurry on top of the carbon paper, it was dried for 1 hour at room temperature, 1 hour at 80 ℃, 30 minutes at 120 ℃ and 15 minutes at 150 ℃ cathode (fuel electrode) Was prepared. The platinum cobalt loading in the finished cathode has a value of 3.0 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 1 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 .

The platinum cobalt loading in the finished cathode according to the above procedure has a value of about 2.33 mg / cm ² and the loading of platinum in the completed anode has a value of 1.4 mg / cm ² .

MEA was produced between the cathode and the anode through the electrolyte membrane of Example 1. 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 for the main gasket and a 20 μm thick Teflon membrane for the sub-gasket were used to overlap the electrode and the electrolyte membrane interface. 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. In this case, since the phosphorus-doped electrolyte is used,

As the performance of the fuel cell is improved, it is aged and finally evaluated until the operating voltage reaches its peak. And the area of the cathode and anode is fixed to 2.8 × 2.8 = 7.84 cm ² and the thickness of the cathode and anode is changed due to the scattering 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.

Production example  2: Example  2 of Electrolyte membrane  Fabrication of Fuel Cells Used

A fuel cell was prepared in the same manner as in Production Example 3, except that the electrolyte membrane obtained in Example 2 was used instead of the electrolyte membrane obtained in Example 1.

Comparative Production Example  One: ABPBI Electrolyte membrane  Fabrication of Fuel Cells Used

A fuel cell was manufactured by the same method as Preparation Example 1, except that the ABPBI electrolyte membrane of Comparative Example 1 was used instead of the electrolyte membrane of Example 1.

In the fuel cell manufactured according to Production Example 1 and Comparative Production Example 1, the change in proton conductivity with temperature is investigated. Proton conductivity was evaluated according to the following method.

The electrolyte membrane is first heated to 180 ° C. in a stainless steel vessel and then stabilized for 30 minutes. Then, after adjusting the temperature to 80 ° C., the conductivity is evaluated with a 4-probe electrode while scanning the temperature. The resistance is measured with a 10 mV (vs. O.C.V) voltage bias in the frequency range of 1 Hz to 1 MHz. The electrode is mainly made of stainless steel and platinum is used as an electrode to evaluate reproducibility. The high temperature stability of the electrolyte membrane is evaluated by measuring the change in conductivity over time at high temperature, and the relative humidity is maintained at 0% using deionized water and dry nitrogen at each temperature.

The proton conductivity evaluation results are shown in FIG. 1.

Referring to FIG. 1, it can be seen that the fuel cell of Example 1 has improved ion conductivity characteristics as compared with that of Comparative Production Example 1.

In the fuel cell manufactured according to Preparation Example 1, the cell voltage characteristics according to the current density were investigated and are shown in FIG. 2.

2, it was found that the cell voltage characteristics of the fuel cell of Preparation Example 1 were excellent. Although described with reference to the preparation examples above, those skilled in the art will understand that various modifications and changes can be made without departing from the spirit and scope of the invention as set forth in the claims below.

Claims (14)

A polymer composition comprising a polymer comprising a first repeating unit of Formula 1 and a second repeating unit of Formula 2, and an oxazine monomer.
[Formula 1]

In Formula 1,

ego,
Ar is an unsubstituted or substituted C6-C20 arylene group or an unsubstituted or substituted C3-C20 heteroarylene group,
m is 0.01 to 1,
(2)

In Formula 2, R ₁ 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, an unsubstituted or substituted C3-C20 heteroaryl group, an unsubstituted or substituted C3-C20 heteroaryloxy group,
R ₂ And R ₃ is independently of each other 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 linked to each other C4-C20 carbon ring or C3-C20 heterocycle Form a flag,
n is 0 to 0.99. The method of claim 1, wherein the content of the oxazine monomer,
10 to 1000 parts by weight based on 100 parts by weight of the polymer including the first repeating unit of Formula 1 and the second repeating unit of Formula 2. The method of claim 1, wherein Ar is in the group represented by the following formula (2A)
At least one polymer composition selected.
[Formula 2A]

The method of claim 1, wherein the polymer,
A polymer composition which is a block copolymer represented by the following formula (3) or (4):
(3)

In Formula 3, Ar ₁ is an unsubstituted or substituted C6-C20 arylene group or an unsubstituted or substituted C3-C20 heteroarylene group,
R ₁ is 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 aryl An oxy group, an unsubstituted or substituted C3-C20 heteroaryl group, an unsubstituted or substituted C3-C20 heteroaryloxy group,
R ₂ And R ₃ is independently of each other 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 linked to each other C4-C20 carbocyclic group or C3-C20 hetero Form a ring,
m ₁ is 0.01 to 1, n ₁ is 0 to 0.99, k ₁ is a number from 10 to 250,
[Chemical Formula 4]

Ar ₂ in Formula 4 is an unsubstituted or substituted C6-C20 arylene group or an unsubstituted or substituted C3-C20 heteroarylene group,
R ₁ is 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 aryl An oxy group, an unsubstituted or substituted C3-C20 heteroaryl group, an unsubstituted or substituted C3-C20 heteroaryloxy group,
R ₂ And R ₃ is independently of each other 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 linked to each other C4-C20 carbocyclic group or C3-C20 hetero Form a ring,
m ₂ is 0.01 to 1, n ₂ is 0 to 0.99, and k ₂ is a number from 10 to 250. The polymer composition of claim 1, wherein the degree of polymerization of the polymer including the first repeating unit of Formula 1 and the second repeating unit of Formula 2 is 1 to 900. According to claim 1, wherein the polymer comprising a first repeating unit of Formula 1 and a second repeating unit of Formula 2,
A polymer composition which is a compound represented by the following formula (11):
(11)

Wherein m ₃ is 0.01 to 1, n ₃ is 0 to 0.99, and k ₃ is a number from 10 to 250. The method of claim 1, wherein the oxazine monomer,
A polymer composition, characterized in that at least one selected from the compounds represented by formulas (5) to (10).
[Chemical Formula 5]

In Formula 5, R ₄ , R ₅ , R ₆ , and R ₇ 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 ₈ 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 6]

R ₈ ′ in Formula 6 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 ₉ 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- ,
[Formula 7]

In Formula 7, 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 ₁₀ and R ₁₁ are connected to each other to form a ring,
The ring is a C6-C10 carbocyclic 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 8]

In Formula 8, 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 ₁₂ R ₁₉ is independently from each other hydrogen, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl group, a C6-C20 aryloxy group, a C1-C20 heteroaryl group, a C1-C20 heteroaryloxy group, C4- A C20 cycloalkyl group, a C1-C20 heterocyclic group, a halogen atom, a cyano group, or a hydroxy group,
[Formula 9]

In Formula 9, R ₂₀ and R ₂₁ are each 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 9A,
[Formula 9A]

In Formulas 9 and 9A, R ₂₂ is independently 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 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 10]

In Formula 10, R ₂₃ , R ₂₄ And two or more adjacent groups selected from R ₂₅ are connected to each other and represented by the following Chemical Formula 2A,
R ₂₃ and R ₂₄ And the remaining groups not selected from R ₂₅ 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 ₂₆ , R _27, and R ₂₈ are connected to each other and represented by the following Formula 10A,
The remaining group not selected from R ₂₆ , R ₂₇ and R ₂₈ is 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 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 10A]

R ₂₉ in Formula 10A 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 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 ₂₃ , R ₂₄ in Formula 10. And positions adjacent to two or more adjacent groups selected from R ₂₅ and two or more adjacent groups selected from R ₂₆ , R _27, and R ₂₈ , respectively. The polymer crosslinked body which is a crosslinked body obtained through the crosslinking reaction of the polymer composition of any one of Claims 1-7. Claim 1 to claim 7, comprising the polymer composition of any one of
Electrolyte membrane for fuel cell. An electrolyte membrane for a fuel cell comprising the polymer crosslinked product of claim 8. Claim 1 to claim 7, comprising the polymer composition of any one of
Fuel cell electrode. A fuel cell electrode comprising the polymer crosslinked product of claim 8. A cathode, an anode and an electrolyte membrane interposed therebetween,
At least one selected from the cathode, the anode and the electrolyte membrane,
The polymer composition according to any one of claims 1 to 7
Fuel cell comprising. A cathode, an anode and an electrolyte membrane interposed therebetween,
At least one selected from the cathode, the anode and the electrolyte membrane,
A fuel cell comprising the polymer crosslinked product of claim 8.

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