CN100567370C - Polybenzoxazine-based compound, the fuel cell that comprises its dielectric film and adopt this dielectric film - Google Patents
Polybenzoxazine-based compound, the fuel cell that comprises its dielectric film and adopt this dielectric film Download PDFInfo
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- CN100567370C CN100567370C CNB2006101280397A CN200610128039A CN100567370C CN 100567370 C CN100567370 C CN 100567370C CN B2006101280397 A CNB2006101280397 A CN B2006101280397A CN 200610128039 A CN200610128039 A CN 200610128039A CN 100567370 C CN100567370 C CN 100567370C
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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Abstract
The crosslinked body of polybenzoxazine-based compound is provided, and its polymerisate by first simple function group benzoxazine-Ji monomer or second polyfunctional group benzoxazine-Ji monomer and crosslinkable compound constitutes; The dielectric film that comprises crosslinked body; The method for preparing dielectric film; And employing comprises the fuel cell of the dielectric film of crosslinked body.The crosslinked body of polybenzoxazine-based compound has the strong acid capture ability because of benzoxazine-based compound, and because crosslinked and have a high mechanical property.In addition, also eliminated the solvability of crosslinked body in polyphosphoric acid, thereby crosslinked body chemically is being very stable.The dielectric film that comprises crosslinked body has phosphoric acid complementary capabilities and machinery and chemical stability under the excellent high temperature.Particularly, even increasing such as the pickup of proton carriers such as phosphoric acid when improving proton conductive, dielectric film still has excellent machinery and chemical stability.Therefore, this dielectric film can be used for high temperature and non-humidified fuel cell.
Description
Technical field
The present invention relates to polybenzoxazine-based compound, the dielectric film that comprises it, and the fuel cell of this dielectric film of employing, more specifically, the present invention relates to new polybenzoxazine-based compound, the dielectric film that is used for high temperature and non-humidified fuel cell, and adopt the fuel cell of this dielectric film.
Background technology
In the conventional ion conductor, ion moves by applying voltage.Ionophore is widely used in electrochemical appliance such as fuel cell, the electrochemical sensor etc.
For example, aspect generating efficiency, system efficiency and parts weather resistance, fuel cell needs such proton conductor, and this proton conductor is that 100～300 ℃ and zero humidity or relative humidity are lower than 50% low humidity condition and have proton conductive steady in a long-term in working temperature.
In the exploitation of conventional solid polymer type fuel battery, considered above-mentioned requirements.Yet, comprise the solid polymer type fuel battery of perfluoro sulfonic acid membrane as dielectric film, working temperature be 100～300 ℃ and relative humidity be 50% or lower condition under still can not generate electricity fully.
The conventional oil battery comprises: the fuel cell that adopts the dielectric film that contains the proton conductive agent, adopt the fuel cell of silicon-dioxide diffusion barrier, adopt the fuel cell of inorganic-organic hybrid films, adopt the fuel cell of phosphate-doped graft copolymer membrane, and adopt the fuel cell of ionic liquid composite membrane.
In addition, the solid polymer dielectric film that is formed by the polybenzimidazole (PBI) that has wherein mixed such as strong acid such as phosphoric acid is disclosed among the US 5525436.In this dielectric film, ionic conductivity increases by phosphate-doped, but the phosphate-doped mechanical property of dielectric film that causes worsens.Especially, be doped with PBI shortage physical strength and chemical stability at high temperature, and the liquid complementary capabilities of phosphoric acid descends such as strong acid such as phosphoric acid.
Summary of the invention
The invention provides polybenzoxazine-based compound, it has excellent sour capture ability, machinery and chemical stability and the phosphoric acid complementary capabilities under the high temperature; The dielectric film that comprises it; And the method for this dielectric film of preparation.
The present invention also provides fuel cell, and this fuel cell has excellent fuel efficiency and generating efficiency by adopting above-mentioned dielectric film.
According to an aspect of the present invention, provide the crosslinked body of polybenzoxazine-based compound, it is to be made of the second benzoxazine-Ji monomer shown in first benzoxazine-Ji monomer shown in the following formula 1 or the following formula 2 and the polymerisate of crosslinkable compound:
In the formula
R
1Be hydrogen, replace or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
4-C
20Cycloalkyl replaces or unsubstituted C
2-C
20Heterocyclic radical, halogen atom, hydroxyl, perhaps cyano group; And R
2For replacing or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
7-C
20Arylalkyl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
2-C
20Heteroarylalkyl replaces or unsubstituted C
4-C
20Carbocylic radical replaces or unsubstituted C
4-C
20The carbocyclic ring alkyl replaces or unsubstituted C
2-C
20Heterocyclic radical perhaps replaces or unsubstituted C
2-C
20Heterocyclylalkyl;
In the formula
R
2For replacing or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
7-C
20Arylalkyl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
2-C
20Heteroarylalkyl replaces or unsubstituted C
4-C
20Carbocylic radical replaces or unsubstituted C
4-C
20The carbocyclic ring alkyl replaces or unsubstituted C
2-C
20Heterocyclic radical perhaps replaces or unsubstituted C
2-C
20Heterocyclylalkyl; And R
3For replacing or unsubstituted C
1-C
20Alkylidene group replaces or unsubstituted C
1-C
20Alkylene group replaces or unsubstituted C
1-C
20Alkynylene replaces or unsubstituted C
6-C
20Arylidene replaces or unsubstituted C
2-C
20Inferior heteroaryl ,-C (=O)-, perhaps-SO
2-.
According to a further aspect in the invention, provide the crosslinked body of polybenzoxazine-based compound, it is to be made of the monomeric polymerisate of second benzoxazine-Ji shown in first benzoxazine-Ji monomer shown in the following formula 1 or the following formula 2:
In the formula
R
1Be hydrogen, replace or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
4-C
20Cycloalkyl replaces or unsubstituted C
2-C
20Heterocyclic radical, halogen atom, hydroxyl, perhaps cyano group; And R
2For replacing or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
7-C
20Arylalkyl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
2-C
20Heteroarylalkyl replaces or unsubstituted C
4-C
20Carbocylic radical replaces or unsubstituted C
4-C
20The carbocyclic ring alkyl replaces or unsubstituted C
2-C
20Heterocyclic radical perhaps replaces or unsubstituted C
2-C
20Heterocyclylalkyl;
In the formula
R
2For replacing or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
7-C
20Arylalkyl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
2-C
20Heteroarylalkyl replaces or unsubstituted C
4-C
20Carbocylic radical replaces or unsubstituted C
4-C
20The carbocyclic ring alkyl replaces or unsubstituted C
2-C
20Heterocyclic radical perhaps replaces or unsubstituted C
2-C
20Heterocyclylalkyl; And R
3For replacing or unsubstituted C
1-C
20Alkylidene group replaces or unsubstituted C
1-C
20Alkylene group replaces or unsubstituted C
1-C
20Alkynylene replaces or unsubstituted C
6-C
20Arylidene replaces or unsubstituted C
2-C
20Inferior heteroaryl ,-C (=O)-, perhaps-SO
2-.
The dielectric film of the crosslinked body that comprises above-mentioned benzoxazine-based compound is provided according to a further aspect in the invention.
According to a further aspect in the invention, the method of the dielectric film for preparing the crosslinked body that comprises polybenzoxazine-based compound is provided, this crosslinked body is to be made of the second benzoxazine-Ji monomer shown in first benzoxazine-Ji monomer shown in the following formula 1 or the following formula 2 and the polymerisate of crosslinkable compound, and this method comprises: second benzoxazine of hybrid 1 first benzoxazine-Ji monomer or formula 2-Ji monomer and crosslinkable compound; And the mixture of curing gained, then products therefrom is immersed in the proton conductor:
In the formula
R
1Be hydrogen, replace or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
4-C
20Cycloalkyl replaces or unsubstituted C
2-C
20Heterocyclic radical, halogen atom, hydroxyl, perhaps cyano group; And R
2For replacing or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
7-C
20Arylalkyl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
2-C
20Heteroarylalkyl replaces or unsubstituted C
4-C
20Carbocylic radical replaces or unsubstituted C
4-C
20The carbocyclic ring alkyl replaces or unsubstituted C
2-C
20Heterocyclic radical perhaps replaces or unsubstituted C
2-C
20Heterocyclylalkyl;
In the formula
R
2For replacing or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
7-C
20Arylalkyl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
2-C
20Heteroarylalkyl replaces or unsubstituted C
4-C
20Carbocylic radical replaces or unsubstituted C
4-C
20The carbocyclic ring alkyl replaces or unsubstituted C
2-C
20Heterocyclic radical perhaps replaces or unsubstituted C
2-C
20Heterocyclylalkyl; And R
3For replacing or unsubstituted C
1-C
20Alkylidene group replaces or unsubstituted C
1-C
20Alkylene group replaces or unsubstituted C
1-C
20Alkynylene replaces or unsubstituted C
6-C
20Arylidene replaces or unsubstituted C
2-C
20Inferior heteroaryl ,-C (=O)-, perhaps-SO
2-.
According to a further aspect in the invention, provide preparation to comprise the dielectric film method of the crosslinked body of polybenzoxazine-based compound, this crosslinked body is to be made of the second benzoxazine-Ji monomer shown in first benzoxazine-Ji monomer shown in the following formula 1 or the following formula 2 and the polymerisate of crosslinkable compound, and this method comprises: second benzoxazine of hybrid 1 first benzoxazine-Ji monomer or formula 2-Ji monomer and crosslinkable compound; And utilize gained mixture film forming on support, and solidify products therefrom then, then the solidified product is immersed in the proton conductor:
In the formula
R
1Be hydrogen, replace or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
4-C
20Cycloalkyl replaces or unsubstituted C
2-C
20Heterocyclic radical, halogen atom, hydroxyl, perhaps cyano group; And R
2For replacing or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
7-C
20Arylalkyl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
2-C
20Heteroarylalkyl replaces or unsubstituted C
4-C
20Carbocylic radical replaces or unsubstituted C
4-C
20The carbocyclic ring alkyl replaces or unsubstituted C
2-C
20Heterocyclic radical perhaps replaces or unsubstituted C
2-C
20Heterocyclylalkyl;
In the formula
R
2For replacing or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
7-C
20Arylalkyl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
2-C
20Heteroarylalkyl replaces or unsubstituted C
4-C
20Carbocylic radical replaces or unsubstituted C
4-C
20The carbocyclic ring alkyl replaces or unsubstituted C
2-C
20Heterocyclic radical perhaps replaces or unsubstituted C
2-C
20Heterocyclylalkyl; And R
3For replacing or unsubstituted C
1-C
20Alkylidene group replaces or unsubstituted C
1-C
20Alkylene group replaces or unsubstituted C
1-C
20Alkynylene replaces or unsubstituted C
6-C
20Arylidene replaces or unsubstituted C
2-C
20Inferior heteroaryl ,-C (=O)-, perhaps-SO
2-.
Described film forming can be carried out on support by banded curtain coating (tape casting) gained mixture.As selection, described film forming also can be carried out on support by curtain coating gained mixture.
This method comprises that also separation cured product and support are to remove support.
Described proton conductor can be phosphoric acid and C
1-C
10At least a in the alkylphosphonic acid carboxylic acid; And the amount of this proton conductor is counted 100～1000 weight parts by the crosslinked body of the polybenzoxazine-based compound of 100 weight parts.
The fuel cell of the dielectric film that adopts the crosslinked body that comprises above-mentioned polybenzoxazine-based compound is provided according to a further aspect in the invention.
Description of drawings
By the reference accompanying drawing in detail its exemplary is described in detail, above-mentioned and other feature and advantage of the present invention can be clearer, in the accompanying drawings:
Figure 1A and Figure 1B illustrate the curing reaction of benzoxazine-Ji monomer and polybenzimidazole according to embodiments of the present invention;
Fig. 1 C and Fig. 1 D illustrate the reaction mechanism of other embodiment benzoxazine-Ji monomer and polybenzimidazole according to the present invention;
Fig. 2 to Fig. 4 is the graphic representation of the ionic conductivity of dielectric film according to embodiments of the present invention;
Fig. 5 to Fig. 7 is the battery performance graphic representation of fuel cell according to embodiments of the present invention;
Fig. 8 is the graphic representation of the battery performance～time of fuel cell according to embodiments of the present invention;
Fig. 9 to Figure 11 is that Polybenzoxazine is monomeric according to embodiments of the present invention
1The graphic representation of H-NMR data;
Figure 12 is the graphic representation of the ionic conductivity of dielectric film according to embodiments of the present invention;
Figure 13 to Figure 15 is the graphic representation of the battery performance of fuel cell according to embodiments of the present invention;
Figure 16 is a benzoxazine monomer according to embodiments of the present invention, polybenzimidazole, and nucleus magnetic resonance (NMR) spectrum of the crosslinked body of benzoxazine-based compound;
Figure 17 is the DOSY-NMR spectrum of the mixture of benzoxazine and polybenzimidazole; And
Figure 18 is the NMR spectrum through heat treated benzoxazine-polybenzimidazole mixture.
Embodiment
The present invention hereinafter more fully is described with reference to the accompanying drawings, has wherein provided exemplary of the present invention.
According to embodiment of the present invention, a kind of dielectric film is provided, it has excellent machinery and chemical stability, even also be like this when maximum or bigger such as the pickup of proton carriers such as phosphoric acid, this dielectric film is to utilize the crosslinked system of benzoxazine-based compound to be equipped with, and described benzoxazine-based compound is that the first benzoxazine-Ji monomer of formula 1 below polymerization or the polyfunctional group second benzoxazine-Ji monomer and the crosslinkable compound of following formula 2 form:
In the formula
R
1Be hydrogen, replace or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
4-C
20Cycloalkyl replaces or unsubstituted C
2-C
20Heterocyclic radical, halogen atom, hydroxyl, perhaps cyano group; And R
2For replacing or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
7-C
20Arylalkyl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
2-C
20Heteroarylalkyl replaces or unsubstituted C
4-C
20Carbocylic radical replaces or unsubstituted C
4-C
20The carbocyclic ring alkyl replaces or unsubstituted C
2-C
20Heterocyclic radical perhaps replaces or unsubstituted C
2-C
20Heterocyclylalkyl;
In the formula
R
2For replacing or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
7-C
20Arylalkyl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
2-C
20Heteroarylalkyl replaces or unsubstituted C
4-C
20Carbocylic radical replaces or unsubstituted C
4-C
20The carbocyclic ring alkyl replaces or unsubstituted C
2-C
20Heterocyclic radical perhaps replaces or unsubstituted C
2-C
20Heterocyclylalkyl; And R
3For replacing or unsubstituted C
1-C
20Alkylidene group replaces or unsubstituted C
1-C
20Alkylene group replaces or unsubstituted C
1-C
20Alkynylene replaces or unsubstituted C
6-C
20Arylidene replaces or unsubstituted C
2-C
20Inferior heteroaryl ,-C (=O)-, perhaps-SO
2-.
According to another embodiment of the present invention, a kind of dielectric film is provided, it has excellent machinery and chemical stability, even also be like this when maximum or bigger such as the pickup of proton carriers such as phosphoric acid, this dielectric film is to utilize the crosslinked system of benzoxazine-based compound to be equipped with, and described benzoxazine-based compound is to form by polyfunctional group second benzoxazine of first benzoxazine of formula above the polymerization 1-Ji monomer or top formula 2-Ji monomer.
The R of top formula 1
1Can be preferably the tertiary butyl.
The R of top formula 1 and formula 2
2Can be phenyl ,-CH
2-CH=CH
2, the group shown in various below perhaps:
R when formula 2
3For-C (CH
3)
2-,-C (CF
3)
2-,-C (=O)-,-SO
2-,-CH
2-,-C (CCl
3)-,-CH (CH
3)-, perhaps-CH (CF
3)-time, formula 2 is for containing two functional group's benzoxazine-based compounds of two benzoxazine rings.R when formula 2
3During for the group shown in the following formula, formula 2 is for containing the trifunctional benzoxazine-based compound of three benzoxazine rings:
For instance, first benzoxazine of formula 1-Ji monomer can for formula 3 to the compound shown in the formula 12:
For instance, second benzoxazine of formula 2-Ji monomer can for formula 13 to the compound shown in the formula 17:
In the formula
R
1For-C (CH
3)
2-,-C (CF
3)
2-,-C (=O)-,-SO
2-,-CH
2-,-C (CCl
3)-,-CH (CH
3)-,-CH (CF
3)-, perhaps
And R
2Be phenyl ,-CH
2-CH=CH
2, the group shown in various below perhaps:
The crosslinkable compound of current embodiment can be any compound that can be monomer crosslinked with benzoxazine-Ji according to the present invention.
For example, crosslinkable compound can comprise and is selected from least a in polybenzimidazole, polybenzothiozole, polybenzoxazole and the polyimide, but be not limited to these.
The method of the crosslinked body of synthetic polybenzoxazine-based compound now will be described, the polymerisate of second benzoxazine of first benzoxazine that this crosslinked body is top formula 1-Ji monomer or top formula 2-Ji monomer and crosslinkable compound.
With the first benzoxazine-Ji monomer of top formula 1 or second benzoxazine of top formula 2-Ji monomer ratio of mixture in accordance with regulations, with crosslinkable compound.Here, by the first benzoxazine-Ji monomer of the formula 1 of 100 weight parts or the second benzoxazine-Ji monomer of formula 2, the amount of crosslinkable compound can be 5～95 weight parts.
When the amount of crosslinkable compound during less than 5 weight parts, phosphoric acid can not flood, thereby reduces proton conductive.When the amount of crosslinkable compound during greater than 95 weight parts, crosslinked body is dissolved in the polyphosphoric acid, thereby causes gas-permeable.
When solidifying the gained mixture, can obtain the crosslinked body of polybenzoxazine-based compound by the reaction that is cross-linked with each other shown in Figure 1A or Figure 1B.In other words, by the reaction that is cross-linked with each other of gained mixture, can obtain the crosslinked body of polybenzoxazine-based compound.That is, utilize the thermal-ring-opening polymerization method, first or second benzoxazine-Ji monomer and crosslinkable compound such as polybenzimidazole polymerization (curing), form polymeric matrix.The thermal-ring-opening polymerization method is undertaken by attemperation progressively.Reaction times should be at least 1 hour, so that polymeric matrix has reticulated structure.
Fig. 1 C and Fig. 1 D have described the reaction mechanism of first benzoxazine of other embodiment-Ji monomer and polybenzimidazole according to the present invention respectively, and the reaction mechanism of second benzoxazine-Ji monomer and polybenzimidazole.
With reference to Fig. 1 C and Fig. 1 D, the oxazine ring of first and second benzoxazines-Ji monomer is owing to heating is opened, and then products therefrom combines (n is 100～10000 number) with the ortho position of the phenyl ring of polybenzimidazole.Therefore, the be cross-linked with each other reaction identical with the direction of growth shown in Fig. 1 C and Fig. 1 D takes place.
Curing reaction temperature can be according to the type of first benzoxazine-Ji monomer, second benzoxazine-Ji monomer and crosslinkable compound etc. and different, but can be 50～250 ℃.If curing reaction temperature is lower than 50 ℃, curing reaction can not take place.If curing reaction temperature is higher than 250 ℃, then obtain the side reaction thing.
The curing reaction time is depended on curing reaction temperature, and can be at least 1 hour in the said temperature scope.Especially, the curing reaction time can be 8～20 hours.
The chemistry and the physical properties of the crosslinked body of polybenzoxazine-based compound now will be described, the polymerisate of second benzoxazine of first benzoxazine that this crosslinked body is a formula 1-Ji monomer or formula 2-Ji monomer and crosslinkable compound.
Crosslinked body according to polybenzoxazine-based compound of the present invention has thermoset, so this crosslinked body is insoluble to any organic solvent, acid or alkali.Thereby molecular weight can not utilize gel permeation chromatography (GPC) to measure, and this method is the ordinary method that obtains the information of relevant polymericular weight.
As mentioned above, the crosslinked body of the polybenzoxazine-based compound that is generated by first or second benzoxazine monomer by polymerization is a thermosetting resin.Therefore, in case implement polymerization, crosslinked body just no longer is dissolved in any organic solvent.And this crosslinked body does not resemble has glass transition temperature other polymkeric substance.Thereby this crosslinked body can not utilize ordinary method analysis.In addition, even thermosetting resin and thermoplastic resin form multipolymer, the gross properties of this multipolymer also is similar to thermosetting resin.Thereby, can not utilize the multipolymer between ordinary method checking first or second benzoxazine-Ji monomer and the polybenzimidazole to form.
So, form in order to verify described multipolymer, implement following experiment.
As mentioned above, the polymeric reaction product of thermosetting resin has solubility problem, thereby can not analyze it.So, analyze the initial product of polyreaction, with check first or second benzoxazine-Ji monomer and polybenzimidazole between form chemical bond.That is in order to check the formation of chemical bond, making seldom during initial polymerization, first or the second benzoxazine-Ji monomer of part combines with polybenzimidazole.When the overall aggregation property of polybenzimidazole does not change, be considered as first or second benzoxazine-Ji monomer and polybenzimidazole formed multipolymer.
Figure 16 is benzoxazine-Ji monomer (A), polybenzimidazole (B), and nucleus magnetic resonance (NMR) spectrum of the crosslinked body (C) of benzoxazine-based compound, the crosslinked body (C) of described benzoxazine-based compound is by with regulation mixed benzoxazine-Ji monomer and polybenzimidazole, then the gained mixture is prepared 100 ℃ of following heating 30 minutes.As shown in figure 16, benzoxazine-Ji monomer and polybenzimidazole are confirmed by the peak position of each component except that the coordinative solvent peak.That is to say that in NMR spectrographic Figure 16 of diagram polybenzimidazole, (A) the representative benzoxazine on-(a) to (d) of Ji monomer proton peak is different from each position of (B).Therefore, can confirm the existence of benzoxazine-Ji monomer and polybenzimidazole, even they are blended in (C) of Figure 16.
Particularly, (a) on (A) is current embodiment and the phenyl bonded tertiary butyl (C (CH benzoxazine-Ji monomer it (t-BuPh-a) according to the present invention among Figure 16
3)
3) the peak.Even a spot of (C (CH
3)
3), also can detect, because (C (CH
3)
3) have a integrated value corresponding to 9 hydrogen atoms.Therefore, this peak is used to analyze benzoxazine-Ji monomer and combines with polybenzimidazole.
Diffusion ordering NMR spectrum (DOSY-NMR) is NMR measuring method recently, and it can be by being dissolved in the hydrokinetics volume difference (or spread coefficient) of each component in the solution, with the spectral classification of each component.Utilize DOSY-NMR, analyzing polymers at an easy rate is because DOSY-NMR can classify the solution in the polymkeric substance, need not special pre-treatment (reference: B.Antalek, Concepts in Magnetic Resonance, 14 (4), 225-258 (2002), S.Viel, D.Capitani, L.Mannina, A.Segre, Biomacromolecules, 4,1843-1847 (2003), D.A.Jayawickrama, C.K.Larive, E.F.Macord, D.C.Roe, Magn.Reson.Chem., 36,755-760 (1998), K.Nishinari, K.Kohyama, P.A.Williams, G.O.Phillips, W.Burchard, K.Ogino, Macromolecules, 24,5590-5593 (1991), C.M.Leon, V.Gorkom, T.M.Hancewicz, J.Magn.Reson., 130,125-130 (1998), A.Chen, D.Wu, C.S.Johnson, Jr., J.Am.Chem.Soc.117,7965-7970 (1995).
Utilize DOSY-NMR, can confirm the formation of the benzoxazine-PBI multipolymer of current embodiment according to the present invention.Figure 17 is the DOSY-NMR of the mixture of benzoxazine and polybenzimidazole during the initial polymerization reaction.According to the DOSY-NMR principle, the molecule of similar size or appear at by the molecule that combination reaction is connected with each other on the same line of NMR spectrum Y-axle.As shown in Figure 17, has very little molecular dimension by each peak of establishing such as water, DMSO, DMAc equal solvent by (a) expression.Therefore, the value of these peaks on the Y-axle is-9.0～-9.2.Be positioned at by the benzoxazine-Ji monomer before the reaction shown in (b) on the same line (e) of pact-9.5～-9.6.Therefore, utilize DOSY-NMR, can the type and the size of molecule be classified by the peak on the one-dimensional NMR spectrum shown in Figure 16.
On the one hand, the peak (c) that comes from PBI is positioned at pact-10.6, and this is much smaller than benzoxazine-Ji monomer.According to the DOSY-NMR principle, the value on the Y-axle is corresponding to spread coefficient, and along with the increase of molecular dimension, the value on the Y-axle increases along negative direction.Therefore, has bigger negative value as the polybenzimidazole of the polymkeric substance benzoxazine as individual molecule more preceding than reaction.The monomeric proton peak corresponding to the tertiary butyl of benzoxazine-Ji (being marked with asterisk) is positioned on the line identical with polybenzimidazole (long and short dash line d).This shows that benzoxazine and polybenzimidazole combine, and forms the multipolymer of the current embodiment according to the present invention.
Figure 18 shows and adopts gradient intensity is that 98% PFG technology obtains
1The comparison of the normal spectrum of H-NMR spectrum and process heat treated benzoxazine-PBI mixture is to prove conclusively the DOSY spectral results once more.Because disappear, so in (A) of Figure 18, do not demonstrate peak corresponding to benzoxazine-Ji monomer and solvent by the peak of establishing less than the molecule of polybenzimidazole.Yet, although they are very little, but still can utilize among (A) of Figure 18 corresponding to the peak of polybenzimidazole (being marked in (a)), conclusive evidence is corresponding to the proton peak (marking with asterisk) of the tertiary butyl.Compare with Figure 18 (B), the tertiary butyl shown in Figure 18 (A) not only is formed among (B) of Figure 18 with the amount that can discern during initial reaction, and because moves 0.2ppm with the reaction of polybenzimidazole to high field orientation.This chemical shift in the NMR spectrum is the typical phenomenon that takes place in the chemical reaction process.In addition, only when benzoxazine-Ji monomer is present in around the polybenzimidazole, this phenomenon can not take place.Therefore, utilize aforesaid method, can prove conclusively Polybenzoxazine-common-polybenzimidazole (PBOA-co-PBI), i.e. multipolymer of benzoxazine and polybenzimidazole.
Fig. 9 to Figure 11 is that the Polybenzoxazine of the current embodiment of the present invention is monomeric
1The H-NMR data plot.
Above-mentioned polymerisate can be used in the dielectric film of fuel cell.There are two kinds to prepare the method for dielectric film according to embodiments of the present invention.Here, utilize polybenzimidazole as crosslinkable compound.
According to first method, with the first benzoxazine-Ji monomer of above-mentioned formula 1 or second benzoxazine-Ji monomer and the crosslinkable compound such as the polybenzimidazole blend of above-mentioned formula 2.With products therefrom 50～250 ℃, preferably solidify down at 80～220 ℃.Then with proton conductor such as acid dipping in the solidified product, to form dielectric film.
According to second method, the first benzoxazine-Ji monomer of above-mentioned formula 1 or the second benzoxazine-Ji monomer of above-mentioned formula 2 are mixed with crosslinkable compound such as polybenzimidazole, and with gained mixture film forming on support.Then products therefrom is solidified, and be immersed in the proton conductor.This film can utilize banded curtain coating (tape casting) method or conventional coating method to form.For example, Chang Gui coating method can utilize scraper curtain coating gained mixture on support to carry out.Here, scraper can have the gap of 250～500 μ m.
When adopting in the film process when utilizing the casting method of scraper, can also be after solidifying products therefrom and flood separating of enforcement film and support before the cured product.The separation of described film can be carried out in distilled water under 60～80 ℃.
Can use can the supporting electrolyte film any support.The example of support comprises substrate of glass, polyimide film etc.When adopting banded casting method, before solidifying gains, film is separated with support such as polyethylene terephthalate, film is placed in the baking oven is cured then.Therefore, need not the removal of support.
In addition, when adopting banded casting method, can filter the gained mixture.
So, by the heat treatment for solidification products therefrom, then the solidified product is immersed in such as in the proton conductors such as acid, to form dielectric film.
The example of described proton conductor can be phosphoric acid, C
1-C
10Alkylphosphonic acid carboxylic acid etc., but be not limited to these.C
1-C
10The example of alkylphosphonic acid carboxylic acid comprises ethyl phosphonic acid etc.
By the crosslinkable compound of 100 weight parts, the amount of proton conductor can be 100～1000 weight parts.Density to proton conductor does not have concrete restriction, but when using phosphoric acid, preferably uses the phosphate aqueous solution of 85wt%.Dipping time under 80 ℃ in phosphoric acid can be 2.5～14 hours.
When only using first or second benzoxazine-when the Ji monomer prepares dielectric film, should adopting condition same as described above, just do not use crosslinkable compound such as polybenzimidazole etc.
Described dielectric film can be used as the hydrogen ion conducting film of fuel cell.It is as follows to utilize this hydrogen ion conducting film to prepare the method for membrane electrode assembly (MEA).Used herein term " MEA " is meant that the electrode layer that comprises catalyst layer and diffusion layer is combined in the structure of dielectric film both sides.
In MEA, the arrangement of electrodes with catalyst layer is in each side of dielectric film according to embodiments of the present invention.Then, can be by under High Temperature High Pressure, electrode being combined on the dielectric film; Perhaps the metal catalyst that causes electrochemical catalysis reaction by coating makes fuel diffusion layer be combined on the metal catalyst on dielectric film then, forms MEA.
Here, the bonded temperature can be enough to softening dielectric film, and pressure can be 0.1～3ton/cm
2, for example be 1ton/cm
2
For the preparation fuel cell, bipolar plates is attached on the MEA.Bipolar plates has the groove that is used to provide fuel, and plays current collector.
When preparation MEA, catalyzer can be independent platinum, perhaps platinum and the alloy or the compound that are selected from following at least a metal: gold, palladium, rhodium, iridium, ruthenium, tin, molybdenum, cobalt, and chromium.
In application facet fuel cell is not had concrete restriction, but be preferably used as polymer dielectric film fuel cell (PEMFC).
Now, the monomeric Preparation Method of first benzoxazine-Ji of above-mentioned formula 1 is described with reference to following reacting flow chart:
[reaction process 1]
In the formula, R
1And R
2As described above.
R in the reaction process 1
1Can be the tertiary butyl, R
2Can be phenyl ,-CH
2-CH=CH
2, the group shown in various below perhaps:
With reference to reaction process 1, phenolic compound (A), p-formaldehyde and sulfonamide derivatives (B) are mixed.This mixture is heated under solvent-free or utilize solvent to reflux.Thereby the process that products therefrom stands to excite gradually obtains the benzoxazine-Ji monomer of formula 1.
The example of solvent comprises 1,4-dioxane, chloroform, methylene dichloride, toluene, THF etc.In addition, during refluxing, regulating and controlling temperature is 50～90 ℃, particularly about 80 ℃.
The specific examples of sulfonamide derivatives (B) is R wherein
2As following compound shown in various:
Now, the monomeric preparation method of second benzoxazine-Ji of above-mentioned formula 2 is described with reference to following reaction process 2:
[reaction process 2]
In the formula, R
2And R
3As mentioned above, particularly, R
3Can be-C (CH
3)
2-,-C (CF
3)
2-,-C (=O)-,-SO
2-,-CH
2-,-C (CCl
3)-,-CH (CH
3)-,-CH (CF
3)-, perhaps
R
2Can be phenyl ,-CH
2-CH=CH
2, the group shown in various below perhaps:
With reference to reaction process 2, phenolic compound (A), p-formaldehyde and sulfonamide derivatives (B) are mixed.This mixture is heated under solvent-free or utilize solvent to reflux.Thereby the process that products therefrom stands to excite gradually obtains the benzoxazine-Ji monomer of formula 2.
The example of solvent comprises 1,4-dioxane, chloroform, methylene dichloride, toluene, THF etc.In addition, during refluxing, regulating and controlling temperature is 50～90 ℃, particularly about 80 ℃.
The specific examples of sulfonamide derivatives (B) as mentioned above.
Now with the substituting group that is adopted in formula 1 and the formula 2.
Unsubstituted C
1-C
20The specific examples of alkyl can be methyl, ethyl, propyl group, isobutyl-, sec-butyl, amyl group, isopentyl, hexyl etc.At least one hydrogen atom in this alkyl can be by halogen atom, the C that is replaced by halogen atom
1-C
20Alkyl (CCF for example
3, CHCF
2, CH
2F, CCl
3Deng), hydroxyl, nitro, cyano group, amino, amidino groups, hydrazine, hydrazone, carboxyl or its alkali, sulfonic group or its alkali, phosphoric acid or its alkali, C
1-C
20Alkyl, C
2-C
20Alkenyl, C
2-C
20Alkynyl, C
1-C
20Assorted alkyl, C
6-C
20Aryl, C
6-C
20Arylalkyl, C
6-C
20Heteroaryl, perhaps C
6-C
20Heteroarylalkyl replaces.
Unsubstituted C
2-C
20The specific examples of alkenyl comprises vinyl, allyl group etc.In addition, at least one hydrogen atom in this alkenyl can be replaced by the substituting group identical with abovementioned alkyl.
Unsubstituted C
1-C
20The specific examples of alkynyl comprises acetylene etc.In addition, at least one hydrogen atom in this alkynyl can be replaced by the substituting group identical with abovementioned alkyl.
Unsubstituted C
1-C
20The specific examples of alkylidene group comprises methylene radical, ethylidene, propylidene, isobutylidene, inferior sec-butyl, pentylidene, isopentylidene, hexylidene etc.In addition, at least one hydrogen atom in this alkylidene group can be replaced by the substituting group identical with abovementioned alkyl.
Unsubstituted C
1-C
20The specific examples of alkylene group comprises aryl etc.In addition, at least one hydrogen atom in this alkylene group can be replaced by the substituting group identical with abovementioned alkyl.
Unsubstituted C
1-C
20The specific examples of alkynylene comprises ethynylene etc.In addition, at least one hydrogen atom in this alkynylene can be replaced by the substituting group identical with abovementioned alkyl.
Aryl can use separately or with at least two types be used in combination, and for comprising the C of at least one ring
6-C
20The carbocyclic ring aromatic series.These rings can link together or condense together by the method for dangling.Aryl comprises the aromaticity group, as phenyl, naphthyl and tetralyl.Aryl can have substituting group, as haloalkyl, nitro, cyano group and low-grade alkyl amino.In addition, at least one hydrogen atom in this aryl can be replaced by the substituting group identical with abovementioned alkyl.
Arylidene can use separately, and also can at least two types be used in combination and can be for comprising the C of at least one ring
6-C
20The carbocyclic ring aromatic series.These rings can link together or condense together by the method for dangling.Arylidene comprises the aromaticity group, as phenylene, naphthylidene and tetrahydrochysene naphthylidene.Arylidene can have substituting group, as haloalkyl, nitro, cyano group, alkoxyl group and low-grade alkyl amino.In addition, at least one hydrogen atom in this arylidene can be replaced by the substituting group identical with abovementioned alkyl.
Arylalkyl is the substituting group that a plurality of hydrogen atoms of wherein above-mentioned aryl are replaced by the group such as low alkyl group, methyl, ethyl and propyl group.The example comprises phenmethyl, styroyl etc.In addition, at least one hydrogen atom in this arylalkyl can be replaced by the substituting group identical with abovementioned alkyl.
Heteroaryl comprises 1,2 or 3 heteroatoms that is selected from N, O, P, S.In addition, heteroaryl has the monovalence single ring architecture that contains 5～30 annular atomses, and wherein Yu Xia annular atoms is a carbon, perhaps is acyclic aromaticity divalence organic compound.In addition, at least one hydrogen atom in this heteroaryl can be replaced by the substituting group identical with abovementioned alkyl.
Inferior heteroaryl comprises 1,2 or 3 heteroatoms that is selected from N, O, P, S.In addition, inferior heteroaryl has the monovalence single ring architecture that contains 1～20 carbon atom, and wherein Yu Xia annular atoms is a carbon, perhaps is acyclic aromaticity divalence organic compound.In addition, at least one hydrogen atom in this inferior heteroaryl can be replaced by the substituting group identical with abovementioned alkyl.
Heteroarylalkyl is the substituting group that replaced by alkyl of a plurality of hydrogen atoms in the heteroaryl wherein.In addition, at least one hydrogen atom in this heteroarylalkyl can be replaced by the substituting group identical with abovementioned alkyl.
Carbon ring group is the cyclic group that comprises 5～10 carbon atoms, as cyclohexyl.In addition, at least one hydrogen atom in the carbon ring group can be replaced by the substituting group identical with abovementioned alkyl.
The carbocyclic ring alkyl is the substituting group that replaced by alkyl of a plurality of hydrogen atoms in the carbon ring group wherein.In addition, at least one hydrogen atom in the carbocyclic ring alkyl can be replaced by the substituting group identical with abovementioned alkyl.
Heterocyclic radical is to comprise the cyclic group that forms such as heteroatomic atoms such as nitrogen, sulphur, phosphorus, oxygen by 5～10.In addition, at least one hydrogen atom in this heterocyclic radical can be replaced by the substituting group identical with abovementioned alkyl.
Heterocyclylalkyl is the substituting group that replaced by alkyl of a plurality of hydrogen atoms in the Heterocyclylalkyl wherein.In addition, at least one hydrogen atom in this Heterocyclylalkyl can be replaced by the substituting group identical with abovementioned alkyl.
Now illustrate in greater detail the present invention with reference to the following examples.The following examples only are used for explanation, rather than to the restriction of scope of the present invention.
Synthesis example 1
The monomeric preparation of the benzoxazine-Ji of formula 3
The phenol of 1mol, the p-formaldehyde of 2.2mol and the aniline of 1.1mol are mixed, and this mixture was stirred 1 hour down at 110 ℃, make crude product.
This crude product is cleaned twice in the 1N NaOH aqueous solution, in distilled water, clean once then.The crude product that utilizes dried over mgso to clean then.Then, filter products therefrom, therefrom remove then and desolvate.Next, with products therefrom vacuum-drying, obtain the benzoxazine-Ji monomer (yield=95%) of formula 3.
Synthesis example 2
The Polybenzoxazine-based monomeric preparation of formula 4
The tert.-butyl phenol of 1mol, the p-formaldehyde of 2.2mol and the aniline of 1.1mol are mixed, and under the situation of not using any solvent, this mixture was stirred 1 hour down at 110 ℃, make crude product.
This crude product is cleaned twice in the 1N NaOH aqueous solution, in distilled water, clean once then.The crude product that utilizes dried over mgso to clean then.Then, filter products therefrom, therefrom remove then and desolvate.Next, with products therefrom vacuum-drying, obtain the benzoxazine-Ji monomer (yield=95%) of formula 4.
Synthesis example 3
The Polybenzoxazine-based monomeric preparation of formula 5
The tert.-butyl phenol of 1mol, the p-formaldehyde of 2.2mol and the 3-aminopropyl imidazoles of 1.1mol are mixed, and under the situation of not using any solvent, this mixture was stirred 1 hour down at 110 ℃, make crude product.
This crude product is cleaned twice in the 1N NaOH aqueous solution, in distilled water, clean once then.The crude product that utilizes dried over mgso to clean then.Then, filter products therefrom, therefrom remove then and desolvate.Next, with products therefrom vacuum-drying, obtain the benzoxazine-Ji monomer (yield=95%) of formula 5.
Synthesis example 4
The benzoxazine of formula 13-Ji monomer (R
2
=phenyl) preparation
The dihydroxyphenyl propane (BP) of 1mol, the p-formaldehyde of 4.4mol and the aniline of 2.2mol are mixed, and this mixture was stirred 1 hour down at 110 ℃, make crude product.
This crude product is cleaned twice in the 1N NaOH aqueous solution, in distilled water, clean once then.The crude product that utilizes dried over mgso to clean then.Then, filter products therefrom, therefrom remove then and desolvate.Next, with products therefrom vacuum-drying, obtain the benzoxazine-Ji monomer (R of formula 13
2=aniline) (yield=95%).
Synthesis example 5
Polybenzoxazine-based monomer (the R of formula 14
2
=phenyl) preparation
With 4,4 of 1mol '-hexafluoroisopropyli,ene biphenol (4,4 '-HFIDPH), the aniline of the p-formaldehyde of 4.4mol and 2.2mol mixes, and this mixture was stirred 1 hour down at 110 ℃, make crude product.
This crude product is cleaned twice in the 1N NaOH aqueous solution, in distilled water, clean once then.The crude product that utilizes dried over mgso to clean then.Then, filter products therefrom, therefrom remove then and desolvate.Next, with products therefrom vacuum-drying, obtain the benzoxazine-Ji monomer (yield=96%) of formula 14.
Synthesis example 6
Polybenzoxazine-based monomer (the R of formula 15
2
=1-imidazolyl propyl group) preparation
The p-formaldehyde of 4,4 of 1mol '-dihydroxy benaophenonel, 2.2mol and the 3-aminopropyl imidazoles of 1.1mol are mixed, and under the situation of not using any solvent, this mixture was stirred 1 hour down at 110 ℃, make crude product with melted state.
This crude product is cleaned twice in the 1N NaOH aqueous solution, in distilled water, clean once then.The crude product that utilizes dried over mgso to clean then.Then, filter products therefrom, therefrom remove then and desolvate.Next, with products therefrom vacuum-drying, obtain the benzoxazine-Ji monomer (yield=80%) of formula 15.
Synthesis example 7
Polybenzoxazine-based monomer (the R of formula 16
2
=1-imidazolyl propyl group) preparation
The bisphenol S (BS) of 1mol, the p-formaldehyde of 4.4mol and 1-(3-aminopropyl) imidazoles of 2.2mol are mixed, and under the situation of not using any solvent, this mixture was stirred 1 hour down at 110 ℃, make crude product with melted state.
This crude product is cleaned twice in the 1N NaOH aqueous solution, in distilled water, clean once then.The crude product that utilizes dried over mgso to clean then.Then, filter products therefrom, therefrom remove then and desolvate.Next, with products therefrom vacuum-drying, obtain the benzoxazine-Ji monomer (yield=98%) of formula 16.
Synthesis example 8
Polybenzoxazine-based monomer (the R of formula 17
2
=allyl group) preparation
With 1,1 of 1mol, the p-formaldehyde of 1-three (4-hydroxy phenyl) ethane, 6.6mol and the allyl amine of 3.3mol mix, and with melted state this mixture are stirred 1 hour down at 110 ℃ under the situation of not using any solvent, make crude product.
This crude product is cleaned twice in the 1N NaOH aqueous solution, in distilled water, clean once then.The crude product that utilizes dried over mgso to clean then.Then, filter products therefrom, therefrom remove then and desolvate.Next, with products therefrom vacuum-drying, obtain the benzoxazine-Ji monomer (yield=95%) of formula 17.
Dielectric film and adopt the preparation of its fuel cell
The benzoxazine monomer of the formula 3 that 65 weight parts are prepared in synthesis example 1 and the polybenzimidazole blend of 35 weight parts.Products therefrom is heated to 220 ℃ with 20 ℃/hour speed.Under 220 ℃, the product of heating is solidified, thus the crosslinked body of synthetic polybenzoxazine-based compound.
With the crosslinked body of described polybenzoxazine-based compound under 80 ℃ in the phosphoric acid of 85wt% dipping 2 hours 30 minutes, make dielectric film.Here, by the dielectric film of 100 weight parts, the amount of phosphoric acid is about 500 weight parts.
The dielectric film that the crosslinked body by polybenzoxazine-based compound that is impregnated with phosphoric acid is formed is placed between the electrode, obtains membrane electrode assembly (MEA).Can use following three types electrode.
At first, first electrode is used as negative electrode and anode.This first electrode prepares by following method: by mixing polybenzimidazole, poly(vinylidene fluoride) and platinum, preparation is used to form the slurry of catalyst layer; And utilize scraping strip coating machine, at the slurry that scribbles this formation catalyst layer of coating on the carbon paper of microporous layers.The platinum heap(ed) capacity of first electrode is 1.0～2.0mg/cm
2This first electrode need not dipping and can use.In the present invention, the PBI electrode is represented first electrode.
Secondly, use the electrode (E-TEK manufacturing) of phosphoric acid type fuel cell as negative electrode and anode.The platinum heap(ed) capacity of the electrode of phosphoric acid type fuel cell is 2.0mg/cm
2By the electrode of the phosphoric acid type fuel cell of 100 weight parts, the electrode of phosphoric acid type fuel cell under 110 ℃ and vacuum in the phosphoric acid of 110 weight parts dipping 1 hour, under 110 ℃ and normal pressure, flooded once more 10 hours then.
Once more, use described first electrode as anode, and use second electrode as negative electrode.This second electrode preparation is as follows: by mixing platinum-cobalt-base alloy and poly(vinylidene fluoride), preparation is used to form the slurry of catalyst layer; And utilize scraper, at the slurry that scribbles this formation catalyst layer of coating on the carbon paper of microporous layers.The platinum heap(ed) capacity of second electrode is 2.2～3.5mg/cm
2This second electrode need not dipping and can use.
Dielectric film and adopt the preparation of its fuel cell
Prepare dielectric film and adopt its fuel cell by the mode identical, only be to use the benzoxazine monomer of the formula 4 of preparation in synthesis example 2 to replace the benzoxazine monomer of formula 3 with embodiment 1.
Dielectric film and adopt the preparation of its fuel cell
Prepare dielectric film and adopt its fuel cell by the mode identical, only be to use the benzoxazine monomer of the formula 5 of preparation in synthesis example 3 to replace the benzoxazine monomer of formula 3 with embodiment 1.
Dielectric film and adopt the preparation of its fuel cell
The benzoxazine monomer of the formula 13 that 65 weight parts are prepared in synthesis example 4 and the benzoxazine-Ji monomer blend of 35 weight parts.Products therefrom is heated to 220 ℃ with 20 ℃/hour speed.Under 220 ℃, the product that is heated is solidified, with the crosslinked body of synthetic polybenzoxazine-based compound.
Under 80 ℃, the crosslinked body of this polybenzoxazine-based compound was flooded in 85wt% phosphoric acid 2 hours 30 minutes, make dielectric film.Here, by the dielectric film of 100 weight parts, the amount of described phosphoric acid is about 500 weight parts.
As electrode, can use following three types electrode.
At first, first electrode is used as negative electrode and anode.This first electrode prepares by following method: by mixing polybenzimidazole, poly(vinylidene fluoride) and platinum, preparation is used to form the slurry of catalyst layer; And utilize scraping strip coating machine, at the slurry that scribbles this formation catalyst layer of coating on the carbon paper of microporous layers.The platinum heap(ed) capacity of first electrode is 1.0～2.0mg/cm
2This first electrode need not dipping and can use.In the present invention, the PBI electrode is represented first electrode.
Secondly, use the electrode (E-TEK manufacturing) of phosphoric acid type fuel cell as negative electrode and anode.The platinum heap(ed) capacity of the electrode of phosphoric acid type fuel cell is 2.0mg/cm
2By the electrode of the phosphoric acid type fuel cell of 100 weight parts, the electrode of phosphoric acid type fuel cell under 110 ℃ and vacuum in the phosphoric acid of 110 weight parts dipping 1 hour, under 110 ℃ and normal pressure, flooded once more 10 hours then.
Once more, use described first electrode as anode, and use second electrode as negative electrode.This second electrode preparation is as follows: by mixing platinum-cobalt-base alloy and poly(vinylidene fluoride), preparation is used to form the slurry of catalyst layer; And utilize scraper, at the slurry that scribbles this formation catalyst layer of coating on the carbon paper of microporous layers.The platinum heap(ed) capacity of second electrode is 2.2～3.5mg/cm
2This second electrode need not dipping and can use.
Dielectric film and adopt the preparation of its fuel cell
Prepare dielectric film and adopt its fuel cell by the mode identical, just be used in the benzoxazine monomer of the benzoxazine monomer formula 13 of the formula 14 of preparation in the synthesis example 5 with embodiment 4.
Dielectric film and adopt the preparation of its fuel cell
Prepare dielectric film and adopt its fuel cell by the mode identical with embodiment 4, the benzoxazine monomer that just is used in the formula 15 of preparation in the synthesis example 6 replaces the benzoxazine monomer of formula 13.
Dielectric film and adopt the preparation of its fuel cell
Prepare dielectric film and adopt its fuel cell by the mode identical with embodiment 4, the benzoxazine monomer that just is used in the formula 16 of preparation in the synthesis example 7 replaces the benzoxazine monomer of formula 13.
Dielectric film and adopt the preparation of its fuel cell
Prepare dielectric film and adopt its fuel cell by the mode identical with embodiment 4, the benzoxazine monomer that just is used in the formula 17 of preparation in the synthesis example 8 replaces the benzoxazine monomer of formula 13.
Comparative Examples 1
Utilize PBI CELAZOLE (Celanese Corp. manufacturing) preparation polybenzimidazole membrane, and at room temperature this polybenzimidazole membrane was flooded 4 hours in 85wt% phosphoric acid.
Be placed between a pair of first electrode of preparation among the embodiment 1 preparation MEA by the polybenzimidazole membrane that this be impregnated in the 85wt% phosphoric acid.
Comparative Examples 2
Utilize PBI CELAZOLE (Celanese Corp. manufacturing) preparation polybenzimidazole membrane, and at room temperature this polybenzimidazole membrane was flooded 4 hours in 85wt% phosphoric acid.
Be placed between the electrode (E-TEK manufacturing) of a pair of phosphoric acid type fuel cell among the embodiment 1 preparation MEA by the polybenzimidazole membrane that this be impregnated in the 85wt% phosphoric acid.
Measure the ionic conductivity under the high temperature in time, derive from the dielectric film stability at high temperature of embodiment 1～3 with analysis.In embodiment 1～3, use the stainless steel metal electrode.
Ionic conductivity is measured as follows.
Under the frequency of 1Hz to 1MHz, apply 10mV (with respect to O.C.V.) bias voltage, simultaneously measuring resistance.At first use stainless steel metal as electrode, and estimate the reproducibility of dielectric film, use platinum then as electrode.
Fig. 2 to Fig. 4 is respectively the graphic representation of ionic conductivity of the dielectric film of embodiment 1～3.
With reference to Fig. 2 to Fig. 4, adopt with respect to the polybenzimidazole amount be 15～85 weight parts benzoxazine-based compound by with the crosslinked body of embodiment 1 same way as preparation, have the proton conductive higher than pure polybenzimidazole.When the amount of benzoxazine-based compound was 85 weight parts, the crosslinked body of gained had the highest proton conductive, and these at least 10 times to proton conductive PBI-H preferably
3PO
4Dielectric film.Utilize the benzoxazine-based compound of 65 weight parts and the polybenzimidazole of 35 weight parts, can processing machinery intensity and the crosslinked body of the equal ideal of electroconductibility.
SYRI PBI among Fig. 2 is the pure polybenzimidazole that does not contain benzoxazine-based compound.15PBXZN-85PBI is the polymer dielectric of the polybenzimidazole preparation of the benzoxazine-Ji monomer that utilizes 15 weight parts and 85 weight parts.75PBXZN-25PBI is the polymer dielectric of the polybenzimidazole preparation of the benzoxazine-Ji monomer that utilizes 75 weight parts and 25 weight parts.Use phenol-aniline as the benzoxazine-based compound among Fig. 2, use tert.-butyl phenol-aniline, and use tert.-butyl phenol amino-imidazoles as the benzoxazine among Fig. 4-Ji monomer as the benzoxazine among Fig. 3-Ji monomer.
Analyze in embodiment 2～4 and Comparative Examples 1～2 fuel cell performance of preparation, way is the initial performance of estimating fuel battery, and with 0.2A/cm
2The estimating fuel battery once more of working after 16 hours.In embodiment 2～4, use the electrode (E-TEK manufacturing) of a pair of described electrode and a pair of phosphoric acid type fuel cell.
Here, by performance being analyzed with respect to the current density measuring voltage.In addition, by the alternating-current impedance of measuring under 1kHz resistance is analyzed.The fuel cell performance analysis is not providing hydrogen fuel and air, and keeping fuel temperature simultaneously is to carry out under 150 ℃ the situation.When using in the fuel cell when comprising as the polybenzimidazole electrode of the PtCo catalyzer among the embodiment 4 or air electrode, the current-voltage performance is at 100ccm (cm
3Measure under/hydrogen flow min) and the air flow quantity of 200ccm.When the electrode that uses E-TEK to make in the fuel cell, the current-voltage performance is measured under the air flow quantity of the hydrogen flow of 100ccm and 300ccm.
Fig. 5 to Fig. 7 is respectively the graphic representation of the battery performance of the fuel cell of preparation in embodiment 1 and Comparative Examples 1 and 2.In embodiment 1, use the electrode (E-TEK manufacturing) of a pair of described electrode and a pair of phosphoric acid type fuel cell.
With reference to Fig. 5 to Fig. 7, with employing PBI-H
3PO
4The fuel cell of dielectric film is compared, and adopts and utilizes tert.-butyl phenol-aniline to have excellent MEA performance as the fuel cell of the polymer dielectric film of benzoxazine-based compound preparation.Compare with the fuel cell that adopts PBI-phosphoric acid electrolyte film, adopt the fuel cell of the polymer dielectric film that uses tert.-butyl phenol amino-imidazoles to have similar MEA performance.When the fuel cell that utilizes employing to impregnated in the E-TEK electrode in the polyphosphoric acid (105wt% phosphoric acid) was analyzed the MEA performance, adopting use tert.-butyl phenol-aniline and tert.-butyl phenol amino-imidazoles all was excellent as the current-voltage performance of the polymer dielectric film of benzoxazine-based compound.The MEA performance of PBI-phosphoric acid is low to be because of gas-permeable (gas permeation), and it is because the polyphosphoric acid dissolving polybenzimidazole in the electrode causes.Because the E-TEK electrode is handled through repellency, thereby suppress phosphoric acid and migrate to electrode, the result, excessive phosphoric acid remains in the dielectric film.Along with the rising of temperature, excessive phosphoric acid is transformed into polyphosphoric acid and dissolves the PBI film.
Utilization impregnated in the E-TEK electrode in the polyphosphoric acid, can analyze the chemical stability of dielectric film.Therefore, the polymer dielectric film that comprises the crosslinked body of polybenzoxazine-based compound has excellent chemical stability in polyphosphoric acid.
Reference among Fig. 5 and Fig. 6 (PBI dielectric film/PBI electrode) is to adopt the PBI electrode and the MEA of the PBI-phosphoric acid electrolyte film of preparation in Comparative Examples 1.In addition, another among Fig. 5 and Fig. 6 is the MEA of preparation in Comparative Examples 2 with reference to (PBI dielectric film/E-TEK electrode).In Fig. 5, t-BuPh-a/PBI electrode (disclosed method #1) is the electrode of preparation in embodiment 2.In Fig. 6, t-BuPh-AIMDZ/PBI electrode (disclosed method #1) is the electrode of preparation in embodiment 3.
In Fig. 7, be the MEA of preparation in Comparative Examples 2 with reference to (PBI dielectric film/E-TEK electrode).T-BuPh-AIMDZ/E-TEK electrode (disclosed method #2) is to be used among the embodiment 3 polymer dielectric film of preparation and platinum heap(ed) capacity that E-TEK makes is 2mg/cm
2The electrode that is used for phosphoric acid type fuel cell as the MEA of hydrogen and air electrode.T-BuPh-a/E-TEK electrode (disclosed method #2) is used in the polymer dielectric of preparation among the embodiment 2 and the platinum heap(ed) capacity of E-TEK manufacturing is 2mg/cm
2The electrode that is used for phosphoric acid type fuel cell as the MEA of hydrogen and air electrode.
Fig. 8 is the graphic representation of the battery performance of the fuel cell of preparation in embodiment 4 with respect to the time.
With reference to Fig. 8, by comprise platinum-cobalt catalyst in air electrode, fuel cell is at 150mV or more have improved battery performance under the high-voltage.In addition, open circuit potential increases continuously 3 natural rear stabilizations.In other words, not observing the electromotive force that causes because of gas-permeable at least in 150 hours reduces.Therefore, the crosslinked body that comprises Polybenzoxazine has excellent chemical stability.In addition, this fuel cell is at high temperature, non-humidified, 0.3A/cm
2And have very excellent performance under the 0.7V equally.
Figure 10 is the graphic representation of the ionic conductivity of the dielectric film of preparation in embodiment 4～8.Here, in embodiment 4～8, use the stainless steel metal electrode.
With reference to Figure 12, to compare with the polybenzimidazole dielectric film, the dielectric film that comprises the crosslinked body of polybenzoxazine-based compound has higher proton conductive.
In Figure 12, when BP-a is to use dihydroxyphenyl propane-aniline, 04,4-HFIDPH-a is to use 4,4 '-during hexafluoroisopropyli,ene biphenol-aniline, △ 4, and 4O-a is to use 4,4 '-during dihydroxy benaophenonel-aniline, ◇ 4,4O-aa is to use 4,4 '-during dihydroxy benaophenonel-arylamines, ● when BS-aa is to use bisphenol S-allyl amine, when ■ BP-aa is to use dihydroxyphenyl propane-allyl amine, ● 4,4-HFIDPH-aa is to use 4,4 '-during hexafluoroisopropyli,ene biphenol-allyl amine, ▲ 4,4O-AIMDZ is to use 4,4 '-4,4 '-during dihydroxy benaophenonel-1-(3-aminopropyl) imidazoles, ◆ when BS-AIMDZ is to use bisphenol S-1-(3-aminopropyl) imidazoles, and ■ THPE-a is when being to use (1,1,1-three (4-cyano-phenyl) ethane (THPE)-aniline).
Analyze the fuel cell performance of preparation in embodiment 5～8 and Comparative Examples 1～2, way is the initial performance of estimating fuel battery, and at 0.3A/cm
2Under the estimating fuel battery once more of working after 16 hours.Here, performance is to analyze with respect to the voltage of current density by measuring.In addition, resistance is to analyze by the alternating-current impedance of measuring under the 1kHz.The fuel cell performance analysis need not to provide hydrogen fuel and air, and keeping fuel temperature simultaneously is to carry out under 150 ℃ the condition.When adopting the polybenzimidazole electrode in the fuel cell or comprise air electrode as the PtCo catalyzer among the embodiment 4, the current-voltage performance is at 100ccm (cm
3/ minute) the hydrogen flow and the air flow quantity of 200ccm under measure.
Figure 13 to Figure 15 is the graphic representation of the battery performance of the fuel cell of preparation in embodiment 5 and Comparative Examples 1 and 2.In Figure 13 and Figure 14, use a pair of first electrode; And in Figure 15, use first electrode as anode and use second electrode as negative electrode.
With reference to Figure 13 and Figure 14, compare with the PBI electrode that is made as reference, utilize the 44-HFIDPh-a monomer to have identical or more excellent battery performance with the electrode of 44-HFIDPh-aa BOA monomer preparation.Figure 15 is the battery performance of fuel cell with respect to the graphic representation of working hour, and this fuel cell is to utilize polybenzimidazole and cross-linking compounds as monomeric 44HFIDPh-a, particularly utilizes PtCo to form in air electrode.
With reference to Figure 13 to Figure 15, compare with the fuel cell of preparation in Comparative Examples 1 and 2, the fuel cell of preparation has excellent performance in embodiment 5.
The fuel cell of preparation is at 0.3A/cm in embodiment 5
2Have very excellent performance down, the operating voltage of 0.67V reaches 330 hours.In addition, the fuel cell of preparation also has excellent weather resistance in embodiment 5, without any pressure drop (voltage drop).
The crosslinked body of polybenzoxazine-based compound has the strong acid capture ability with respect to benzoxazine-based compound and because of the high-mechanical property due to crosslinked.In addition, this crosslinked body solvability in polyphosphoric acid is eliminated, thereby this crosslinked body chemically is being very stable.The dielectric film that comprises crosslinked body has excellent high temperature phosphoric acid complementary capabilities and machinery and chemical stability.The crosslinked body of polybenzoxazine-based compound can utilize simple polymerization process to obtain, and this polymerization process utilization heating replaces utilizing polymerization starter or linking agent.In addition, also need not extra linking agent, thereby can produce in large quantity.Moreover the raw materials cost during synthesizing cross-linked body is reasonable, thereby expense is rational.
The dielectric film that comprises the crosslinked body of polybenzoxazine-based compound of the present invention can be applicable in the non-humidified fuel cell of high temperature.
Although provide and illustrated the present invention particularly with reference to its exemplary, but those of ordinary skill in the art is to be understood that, under the situation that does not break away from defined design of the present invention and scope in the following claims, can on form and content, make various changes to it.
Claims (28)
1. dielectric film, the crosslinked body that comprises polybenzoxazine-based compound, this crosslinked body are to be made of second benzoxazine-Ji monomer shown in first benzoxazine-Ji monomer shown in the following formula 1 or the following formula 2 and the polymerisate that is selected from least a crosslinkable compound of polybenzimidazole, polybenzothiozole, polybenzoxazole and polyimide:
In the formula
R
1Be hydrogen, replace or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
4-C
20Cycloalkyl replaces or unsubstituted C
2-C
20Heterocyclic radical, halogen atom, hydroxyl, perhaps cyano group; And
R
2For replacing or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
7-C
20Arylalkyl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
2-C
20Heteroarylalkyl replaces or unsubstituted C
4-C
20Carbocylic radical, or replacement or unsubstituted C
2-C
20Heterocyclic radical;
In the formula
R
2For replacing or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
7-C
20Arylalkyl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
2-C
20Heteroarylalkyl replaces or unsubstituted C
4-C
20Carbocylic radical, or replacement or unsubstituted C
2-C
20Heterocyclic radical; And
R
3For replacing or unsubstituted C
1-C
20Alkylidene group replaces or unsubstituted C
1-C
20Alkylene group replaces or unsubstituted C
1-C
20Alkynylene replaces or unsubstituted C
6-C
20Arylidene replaces or unsubstituted C
2-C
20Inferior heteroaryl ,-C (=O)-, perhaps-SO
2-,
Wherein said substituting group is a halogen atom, the C that is replaced by halogen atom
1-C
20Alkyl, hydroxyl, nitro, cyano group, amino, amidino groups, hydrazine, hydrazone, carboxyl or its alkali, sulfonic group or its alkali, phosphoric acid or its alkali, C
1-C
20Alkyl, C
2-C
20Alkenyl, C
2-C
20Alkynyl, C
1-C
20Assorted alkyl, C
6-C
20Aryl, C
6-C
20Arylalkyl, C
6-C
20Heteroaryl, perhaps C
6-C
20Heteroarylalkyl.
2. according to the dielectric film of claim 1, the R of its Chinese style 1
1Be C
1-C
10Alkyl, allyl group, C
6-C
20Aryl, the tertiary butyl, C-C
10Alkenyl, perhaps C
1-C
10Alkynyl.
3. according to the dielectric film of claim 1, the R of its Chinese style 1 and formula 2
2Be phenyl ,-CH
2-CH=CH
2, the group shown in various below perhaps:
4. according to the dielectric film of claim 1, the R of its Chinese style 2
3For-C (CH
3)
2-,-C (CF
3)
2-,-C (=O)-,-SO
2-,-CH
2-,-CH (CH
3)-,-CH (CF
3)-, perhaps
5. according to the dielectric film of claim 1, its Chinese style 1 is represented by following formula 3 to formula 12:
6. according to the dielectric film of claim 1, its Chinese style 2 is selected from following formula 13 to formula 17:
In the formula,
R
2Be phenyl ,-CH
2-CH=CH
2, the group shown in various below perhaps:
7. according to the dielectric film of claim 1, wherein by the first benzoxazine-Ji monomer or the second benzoxazine-Ji monomer of 100 weight parts, the amount of described crosslinkable compound is 5～95 weight parts.
8. according to each dielectric film of claim 1-7, also comprise proton conductor.
9. dielectric film according to Claim 8, wherein this proton conductor is for being selected from phosphoric acid and C
1-C
10At least a in the alkylphosphonic acid carboxylic acid; Reach the crosslinked body by the polybenzoxazine-based compound of 100 weight parts, the amount of described proton conductor is 100～1000 weight parts.
10. method for preparing dielectric film, this dielectric film comprises the crosslinked body of polybenzoxazine-based compound, this crosslinked body is to be made of the second benzoxazine-Ji monomer shown in first benzoxazine-Ji monomer shown in the following formula 1 or the following formula 2 and the polymerisate of crosslinkable compound, and this method comprises:
Second benzoxazine of hybrid 1 first benzoxazine-Ji monomer or formula 2-Ji monomer and the crosslinkable compound that is selected from polybenzimidazole, polybenzothiozole, polybenzoxazole and polyimide; And
Solidify the mixture of gained, then products therefrom be immersed in the proton conductor:
In the formula
R
1Be hydrogen, replace or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
4-C
20Cycloalkyl replaces or unsubstituted C
2-C
20Heterocyclic radical, halogen atom, hydroxyl, perhaps cyano group; And
R
2For replacing or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
7-C
20Arylalkyl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
2-C
20Heteroarylalkyl replaces or unsubstituted C
4-C
20Carbocylic radical, or replacement or unsubstituted C
2-C
20Heterocyclic radical;
In the formula
R
2For replacing or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
7-C
20Arylalkyl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
2-C
20Heteroarylalkyl replaces or unsubstituted C
4-C
20Carbocylic radical, or replacement or unsubstituted C
2-C
20Heterocyclic radical; And
R
3For replacing or unsubstituted C
1-C
20Alkylidene group replaces or unsubstituted C
1-C
20Alkylene group replaces or unsubstituted C
1-C
20Alkynylene replaces or unsubstituted C
6-C
20Arylidene replaces or unsubstituted C
2-C
20Inferior heteroaryl ,-C (=O)-, perhaps-SO
2-,
Wherein said substituting group is a halogen atom, the C that is replaced by halogen atom
1-C
20Alkyl, hydroxyl, nitro, cyano group, amino, amidino groups, hydrazine, hydrazone, carboxyl or its alkali, sulfonic group or its alkali, phosphoric acid or its alkali, C
1-C
20Alkyl, C
2-C
20Alkenyl, C
2-C
20Alkynyl, C
1-C
20Assorted alkyl, C
6-C
20Aryl, C
6-C
20Arylalkyl, C
6-C
20Heteroaryl, perhaps C
6-C
20Heteroarylalkyl.
11. according to the method for claim 10, wherein by first or the second benzoxazine-Ji monomer of 100 weight parts, the amount of described crosslinkable compound is 5～95 weight parts.
12. according to the method for claim 10, wherein being solidificated under 50～250 ℃ of gained mixture carried out.
13. according to the method for claim 10, wherein by the crosslinkable compound of 100 weight parts, the amount of described proton conductor is 100～1000 weight parts.
14. according to the method for claim 10, wherein said proton conductor is for being selected from phosphoric acid and C
1-C
10At least a in the alkylphosphonic acid carboxylic acid; Reach the crosslinked body by the polybenzoxazine-based compound of 100 weight parts, the amount of described proton conductor is 100～1000 weight parts.
15. according to each method of claim 10-14, also be included in and solidify before the gains, utilize gained mixture film forming step on support.
16. according to the method for claim 15, wherein said film forming is undertaken by banded curtain coating gained mixture on support.
17. according to the method for claim 15, wherein said film forming is undertaken by curtain coating gained mixture on support.
18., also comprise the solidified product is separated to remove support with support according to the method for claim 15.
19. a fuel cell, it adopts according to each dielectric film in the claim 1～9.
20. a dielectric film comprises the crosslinked body of polybenzoxazine-based compound, this crosslinked body is to be made of the monomeric polymerisate of second benzoxazine-Ji shown in first benzoxazine-Ji monomer shown in the following formula 1 or the following formula 2:
In the formula
R
1Be hydrogen, replace or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
4-C
20Cycloalkyl replaces or unsubstituted C
2-C
20Heterocyclic radical, halogen atom, hydroxyl, perhaps cyano group; And
R
2For replacing or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
7-C
20Arylalkyl, power generation or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
2-C
20Heteroarylalkyl replaces or unsubstituted C
4-C
20Carbocylic radical, or replacement or unsubstituted C
2-C
20Heterocyclic radical;
In the formula
R
2For replacing or unsubstituted C
1-C
20Alkyl replaces or unsubstituted C
1-C
20Alkenyl replaces or unsubstituted C
1-C
20Alkynyl replaces or unsubstituted C
6-C
20Aryl replaces or unsubstituted C
7-C
20Arylalkyl replaces or unsubstituted C
2-C
20Heteroaryl replaces or unsubstituted C
2-C
20Heteroarylalkyl replaces or unsubstituted C
4-C
20Carbocylic radical, or replacement or unsubstituted C
2-C
20Heterocyclic radical; And
R
3For replacing or unsubstituted C
1-C
20Alkylidene group replaces or unsubstituted C
1-C
20Alkylene group replaces or unsubstituted C
1-C
20Alkynylene replaces or unsubstituted C
6-C
20Arylidene replaces or unsubstituted C
2-C
20Inferior heteroaryl ,-C (=O)-, perhaps-SO
2-,
Wherein said substituting group is a halogen atom, the C that is replaced by halogen atom
1-C
20Alkyl, hydroxyl, nitro, cyano group, amino, amidino groups, hydrazine, hydrazone, carboxyl or its alkali, sulfonic group or its alkali, phosphoric acid or its alkali, C
1-C
20Alkyl, C
2-C
20Alkenyl, C
2-C
20Alkynyl, C
1-C
20Assorted alkyl, C
6-C
20Aryl, C
6-C
20Arylalkyl, C
6-C
20Heteroaryl, perhaps C
6-C
20Heteroarylalkyl.
21. according to the dielectric film of claim 20, the R of its Chinese style 1
1Be C
1-C
10Alkyl, aryl, C
6-C
20Aryl, the tertiary butyl, C-C
10Alkenyl, perhaps C
1-C
10Alkynyl.
22. according to the dielectric film of claim 20, the R of its Chinese style 1 and formula 2
2Be phenyl ,-CH
2-CH=CH
2, the group shown in various below perhaps:
23. according to the dielectric film of claim 20, the R of its Chinese style 2
3For-C (CH
3)
2-,-C (CF
3)
2-,-C (=O)-,-SO
2-,-CH
2-,-CH (CH
3)-,-CH (CF
3)-, perhaps
24. according to the dielectric film of claim 20, its Chinese style 1 is represented by following formula 3 to formula 12:
25. according to the dielectric film of claim 20, its Chinese style 2 is selected from following formula 13 to formula 17:
In the formula
R
2Be phenyl ,-CH
2-CH=CH
2, the group shown in various below perhaps:
26., also comprise proton conductor according to each dielectric film among the claim 20-25.
27. according to the dielectric film of claim 26, wherein said proton conductor is for being selected from phosphoric acid and C
1-C
10At least a in the alkylphosphonic acid carboxylic acid; Reach the crosslinked body by the polybenzoxazine-based compound of 100 weight parts, the amount of described proton conductor is 100～1000 weight parts.
28. a fuel cell, it adopts according to each dielectric film among the claim 20-27.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR81994/05 | 2005-09-03 | ||
| KR81995/05 | 2005-09-03 | ||
| KR1020050081994A KR100818253B1 (en) | 2005-09-03 | 2005-09-03 | Polybenzoxazines, an electrolyte membrane comprising the same and fuel cell employing the electrolyte membrane |
Related Child Applications (1)
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| CN2009102077312A Division CN101684180B (en) | 2005-09-03 | 2006-09-04 | Polybenzoxazine-based compound, electrolyte membrane including the same, and fuel cell employing the electrolyte membrane |
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Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1760110B1 (en) | 2005-09-03 | 2011-11-02 | Samsung SDI Co., Ltd. | Polybenzoxazine-based compound, electrolyte membrane including the same, and fuel cell employing the electrolyte membrane |
| KR100818255B1 (en) | 2006-05-29 | 2008-04-02 | 삼성에스디아이 주식회사 | Polybenzoxazines, an electrolyte membrane comprising the same and fuel cell employing the electrolyte membrane |
| KR100745741B1 (en) | 2006-08-22 | 2007-08-02 | 삼성에스디아이 주식회사 | Membrane and electrode assembly for fuel cell and fuel cell employing the same |
| EP2433947B1 (en) | 2007-09-11 | 2014-05-07 | Samsung Electronics Co., Ltd. | Phosphorous containing benzoxazine-based monomer |
| EP2036910B1 (en) | 2007-09-11 | 2012-06-27 | Samsung Electronics Co., Ltd. | Benzoxazine-based monomer, polymer thereof, electrode for fuel cell including the same, electrolyte membrane for fuel cell includind the same, and fuel cell using the same |
| KR101366808B1 (en) | 2007-10-11 | 2014-02-25 | 삼성전자주식회사 | Polybenzimidazole-base complex, crosslinked material of polybenzoxazines formed thereof, and fuel cell using the same |
| EP2058321B1 (en) | 2007-11-02 | 2014-01-08 | Samsung Electronics Co., Ltd. | Phosphorous containing monomer, polymer thereof, electrode for fuel cell including the polymer, electrolyte membrane for fuel cell including the polymer, and fuel cell using the electrode |
| EP2055706B1 (en) | 2007-11-02 | 2011-08-24 | Samsung Electronics Co., Ltd. | Electrode and electrolyte membrane for fuel cell including a naphthoxazine based polymer and fuel cell using the electrode |
| KR101537311B1 (en) * | 2007-11-02 | 2015-07-17 | 삼성전자주식회사 | Electrolyte Membrane for fuel cell and fuel cell using the same |
| EP2062891B1 (en) | 2007-11-06 | 2012-08-08 | Samsung Electronics Co., Ltd. | Benzoxazine-based monomer, polymer thereof, electrode for fuel cell including the polymer, electrolyte membrane for fuel cell including the polymer, and fuel cell using the electrode |
| CN101265322B (en) * | 2008-05-08 | 2010-04-21 | 山东大学 | Preparation method of cyano-containing benzoxazine resin |
| KR101124506B1 (en) * | 2009-04-24 | 2012-03-16 | 서울대학교산학협력단 | Cross-linked polyazole,method of preparing the polyazole, electrode for fuel cell including the corss-linked polyazole, electrolyte membrane for fuel cell including the cross-linked polyazole, method of manufacturing the electrolyte membrane, and fuel cell including the cross-linked polyazole |
| WO2011057804A1 (en) * | 2009-11-14 | 2011-05-19 | Basf Se | Method for mechanically stabilizing nitrogen-containing polymers |
| US9112232B2 (en) | 2010-02-05 | 2015-08-18 | Samsung Electronics Co., Ltd. | Composition, polymer thereof, electrode and electrolyte membrane for fuel cell, and fuel cell including the same |
| US9368803B2 (en) | 2010-03-03 | 2016-06-14 | Samsung Electronics Co., Ltd. | Composition, method of preparing the composition, electrode including the composition, and fuel cell including the electrode |
| KR101747863B1 (en) * | 2010-03-03 | 2017-06-16 | 삼성전자주식회사 | Polybenzthiazole-based compound composition, preparing method thereof, electrode using the composition, and fuel cell employing the same |
| WO2011151775A1 (en) * | 2010-05-31 | 2011-12-08 | Basf Se | Mechanically stabilized polyazoles |
| CN104080842A (en) * | 2010-05-31 | 2014-10-01 | 巴斯夫欧洲公司 | Mechanically stabilized polyazoles |
| CN102432560B (en) * | 2011-09-13 | 2014-11-12 | 华南理工大学 | Preparation method for benzoxazine intermediate and synthetic resin of intermediate |
| CN102618032A (en) * | 2012-03-15 | 2012-08-01 | 浙江理工大学 | Full-biology-base composite material |
| CN103694192B (en) * | 2013-12-26 | 2015-06-17 | 上海交通大学 | Benzoxazine compound with photo-initiation performance, preparation method and application of benzoxazine compound |
| KR101537310B1 (en) * | 2014-10-24 | 2015-07-16 | 삼성전자주식회사 | Electrolyte Membrane for fuel cell and fuel cell using the same |
| CN105199102A (en) * | 2015-07-09 | 2015-12-30 | 华东理工大学 | Novel thermosetting ultraviolet stabilizer and preparation method thereof |
| CN110760045A (en) * | 2019-10-08 | 2020-02-07 | 华东理工大学 | Novel benzoxazine resin with ultraviolet absorption function and one-step preparation method thereof |
| CN110828897B (en) * | 2019-11-25 | 2023-02-28 | 中国科学院青岛生物能源与过程研究所 | Heat stress type thermal runaway prevention electrolyte and application thereof in secondary battery |
| CN116515110A (en) * | 2023-04-20 | 2023-08-01 | 佛山科学技术学院 | Modified polybenzimidazole and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5525436A (en) | 1994-11-01 | 1996-06-11 | Case Western Reserve University | Proton conducting polymers used as membranes |
| US6620905B1 (en) | 2002-02-23 | 2003-09-16 | National Starch And Chemical Investment Holding Corporation | Curable compositions containing benzoxazine |
| US7157509B2 (en) | 2003-06-27 | 2007-01-02 | Henkel Corporation | Curable compositions |
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2005
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| CN1923874A (en) | 2007-03-07 |
| KR20070025626A (en) | 2007-03-08 |
| KR100818253B1 (en) | 2008-04-01 |
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