CN1703443A - Polyarylene ether compound containing sulfonic acid group, composition containing same, and method for manufacturing those - Google Patents

Polyarylene ether compound containing sulfonic acid group, composition containing same, and method for manufacturing those Download PDF

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CN1703443A
CN1703443A CNA2003801009963A CN200380100996A CN1703443A CN 1703443 A CN1703443 A CN 1703443A CN A2003801009963 A CNA2003801009963 A CN A2003801009963A CN 200380100996 A CN200380100996 A CN 200380100996A CN 1703443 A CN1703443 A CN 1703443A
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sulfonic
polymkeric substance
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坂口佳充
北村幸太
永原重德
山下全广
中尾淳子
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Toyobo Co Ltd
Toyo Textile Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

A polyarylene ether compound is characterized by containing a polymer component represented by the general formulae (1) and (2). (1) (2) In the above formulae, Ar represents a divalent aromatic group, Y represents a sulfonic group or a ketone group, X represents H or a monovalent cation species, and Ar' represents a divalent aromatic group.

Description

Contain sulfonic poly (arylene ether) based compound, contain its composition and method of making the same
Technical field
The present invention relates to can be as the sulfonic poly (arylene ether) based compound that contains of polyelectrolyte membrane.
Background technology
The electrochemical appliance example that adopts polymer solid electrolyte to replace liquid electrolyte to use as ionophore can be enumerated water electrolyzer and fuel cell.The polymeric membrane that uses in these devices, must be as cationic exchange membrane on proton conductivity, and abundant stable on chemistry, calorifics, electrochemistry and mechanics.Therefore, as this film that can life-time service, use with " the Na Off イ オ Application (registered trademark) " of E.I.Du Pont Company's preparation perfluorocarbon sulfonate film as typical example always.Yet in case Na Off イ オ Application film is being turned round above under 100 ℃ of conditions, outside the water ratio of membrane removal sharply reduced, film is significantly deliquescing also.Therefore, in the fuel cell that acts as a fuel with methyl alcohol of expectation in the future, the performance that methyl alcohol sees through in film will reduce, and can not give full play to performance.And as doing near the fuel cell that fuel turn round 80 ℃ with hydrogen of main research now, the cost of film is too high, it is said that this will become the obstacle of establishment fuel cell technology.
In order to overcome this shortcoming, studied in free-floride system contains the polymkeric substance of aromatic nucleus and imported sulfonic various polyelectrolyte membranes.Skeleton as polymkeric substance, consider thermotolerance and chemical stability, can enumerate aromatic polyether based compounds such as poly (arylene ether) ketone and poly (arylene ether) sulfone class as promising structure, that has reported has poly (arylene ether) sulfone sulfonated material (for example referring to " membrane science impurity " (Journal of Memberane Science), (オ ラ Application ダ) 1993 83 volumes 211-220 page or leaf), with polyether-ether-ketone sulfonated material (for example opening flat 6-93114 communique, 15-17 page or leaf) and sulfonated polystyrene etc. referring to the spy.
Though wherein also reported and contained 4,4 '-biphenyl is as monomeric sulfonation poly (arylene ether) (for example referring to the open WO00/24796 communique of international monopoly), but in the hot and humid problem that has swelling polymer down, particularly in the high composition of sulphonation rate, this tendency is more remarkable.And utilize the sulfonation reaction of these polymkeric substance on aromatic ring, to import sulfonic group, the tendency that breaks away from easily because of being heated is generally arranged, as the method for improving this shortcoming, reported to adopt and imported under the situation of sulfonic monomer-polymer the sulfonation poly (arylene ether) sulfone based compound that thermostability is high (for example referring to No. 2002/0091225 Instructions Page 1-2 of U.S. Patent Publication) on the electrophilic aromatic ring.In this case, because monomeric reactivity is low, the problem (for example referring to " ACSPolymer Preprints ", the U.S., 2000 41 (2) volumes, 1388-1389 page or leaf) that polymerization for a long time obtains polymkeric substance appears.Adopt 4 though put down in writing, wherein still there is the hot and humid problem of swelling polymer down in other monomers that 4 '-bis-phenol is used as copolymerization, and particularly this tendency becomes more remarkable in the composition that sulphonation rate increases.
Disclosure of an invention
The object of the invention be to utilize polymerizability good simultaneously can be as the importing of polyelectrolyte membrane sulfonic poly (arylene ether) based compound, obtain the macromolecular material that dimensional stability, processibility, ionic conductivity under thermotolerance, the high temperature is all good, be specially adapted to ion-conductive membranes.
The invention provides a kind of polyarylene ether compound, it is characterized in that, contain polymkeric substance constituent by general formula (1) and general formula (2) expression.
Figure A20038010099600111
Figure A20038010099600112
Ar represents divalent aryl in the formula, and Y represents sulfonic group or ketone group, and X represents H or monovalent cation kind, and Ar ' represents divalent aryl.
One of them preferably contains-the Ph-Ph-group at least for described Ar and Ar ', remove to combine in the sulfonic skeleton structure ,-O-Ar-O-unit or-O-Ar '-O-unit or these unit sums account in polymer architecture more than the 52 weight %.
Polyarylene ether compound of the present invention preferably contains the polymkeric substance constituent by general formula (3) and general formula (4) expression.
Figure A20038010099600122
X wherein 2Expression H or monovalent cation kind.
Polyarylene ether compound of the present invention preferably also contains the polymkeric substance constituent by general formula (5) and general formula (6) expression.
Figure A20038010099600124
Wherein in formula (5) and (6), n 1, n 2And n 3The sulfonic group of representing each aromatic ring is in conjunction with number, n 1, n 2And n 3Independently be 0～2 integer separately, n 2+ n 3It is 1～4 integer.X 3Be from-CN ,-COOY ,-COONR 2In one or more groups of selecting, Y represents hydrogen, atoms metal, various ammonium, R represents one or more groups of selecting from hydrogen and alkyl.Z 1And Z 2Be one or more functional groups that select rudimentary carbonyl, nitro, amino, hydroxyl and the halogen atom of the rudimentary carboxyl of the lower alkoxy of the low alkyl group from 1～6 carbon atom, 1～6 carbon atom, 1～6 carbon atom, 1～6 carbon atom.R1 and r2 represent Z1 and Z2 on each aromatic ring separately in conjunction with number, r 1And r 2Independently be 0～4 integer separately, n 2+ r 1≤ 4, n 3+ r 2≤ 4.
Polyarylene ether compound of the present invention preferably also contains the polymkeric substance constituent that general formula (7) is represented.
Figure A20038010099600125
Wherein in formula (7), n 4And n 5Represent the sulfonic of each aromatic ring, n in conjunction with number 4And n 5Independently be 0～2 integer separately, n 4+ n 5It is 1～4 integer.
Polyarylene ether compound of the present invention, sulfonic group content is in 0.3～3.5meq/g scope, and sulfonic group content preferably is in 0.2～6.0meq/g scope.
The present invention also provides a kind of polyarylene ether compound, it is characterized in that it being that (poly (arylene ether) O-Ph-Ph-O-) is that polymer has imported sulfonic structure to containing the above dioxy diphenylene of 52 weight % unit in the polymer architecture.
Polyarylene ether compound of the present invention preferably contains the polymkeric substance constituent by general formula (3) and general formula (4) expression.
Figure A20038010099600131
Figure A20038010099600132
Wherein X2 represents H or monovalent cation kind.
Polyarylene ether compound of the present invention preferably also contains the polymkeric substance constituent by general formula (5) and general formula (6) expression.
Figure A20038010099600133
Wherein in formula (5) and (6), n 1, n 2And n 3The sulfonic group of representing each aromatic ring is in conjunction with number, n 1, n 2And n 3Independently be 0～2 integer separately, n 2+ n 3It is 1～4 integer.X 3Be from-CN ,-COOY ,-COONR 2In one or more groups of selecting, Y represents hydrogen, atoms metal, various ammonium, R represents one or more groups of selecting from hydrogen and alkyl.Z 1And Z 2Be one or more functional groups that select rudimentary carbonyl, nitro, amino, hydroxyl and the halogen atom of the rudimentary carboxyl of the lower alkoxy of the low alkyl group from 1～6 carbon atom, 1～6 carbon atom, 1～6 carbon atom, 1～6 carbon atom.r 1And r 2Represent Z on each aromatic ring 1And Z 2Separately in conjunction with number, r 1And r 2Be independently to be 0～4 integer separately, n 2+ r 1≤ 4, n 3+ r 2≤ 4.
Polyarylene ether compound of the present invention preferably also contains the polymkeric substance constituent that general formula (7) is represented.
Figure A20038010099600141
Wherein in formula (7), n 4And n 5The sulfonic group of representing each aromatic ring is in conjunction with number, n 4And n 5Independently be 0～2 integer separately, n 4+ n 5It is 1～4 integer.
Sulfonic group content preferably is in 0.2～6.0meq/g scope.
The preparation method of polyarylene ether compound of the present invention is characterized in that, preferably by containing by the compound of general formula (13) and (14) expression and bis-phenol based compound as monomeric aromatic nucleophilie nuclear substituting reaction polymerization.
Y wherein 2Expression sulfonic group or ketone group, X 6Expression monovalent cation kind, Z 4Expression elemental chlorine or fluorine.
The preparation method of polyarylene ether compound of the present invention is characterized in that, preferably by containing by the compound of general formula (13) and (14) expression and bis-phenol based compound as monomeric aromatic nucleophilie nuclear substituting reaction polymerization.
Y wherein 2Expression sulfonic group or ketone group, X 6Expression monovalent cation kind, Z 4Expression elemental chlorine or fluorine.
The present invention also provides a kind of composition, it is characterized in that, contains the above-mentioned polyarylene ether compound of 50～100 weight %.
The present invention also provides a kind of composition, it is characterized in that, contains to comprise by the polybenzimidazole based compound of polymkeric substance constituent shown in the general formula (8) and above-mentioned polyarylene ether compound.
M in the formula 1The integer of expression 1 to 4, R 1Expression can form the tetravalence aromatics combining unit of imidazole ring, R 2Expression divalent aromatic combining unit, R 1And R 2Both can be the monocycle of aromatic ring, also can be the conjugant or the condensed ring of a plurality of aromatic rings, stable substituting group can also be arranged, Z 3Expression sulfonic group and/or phosphonate group, its part also can form the salt structure.
Composition of the present invention, wherein said polybenzimidazole based compound are preferably with (9): (10)=n 6: (1-n 6) mol ratio contains the polymkeric substance constituent by general formula (9) and (10) expression.
Figure A20038010099600153
Figure A20038010099600154
M in the formula 2The integer of expression 1 to 4, Ar " expression divalent aromatic combining unit, X 4Be from-O-,-SO 2-,-C (CH 3) 2-,-C (CF 3) 2-and-more than one groups of selecting among the OphO-, Ph represents divalent aromatic combining unit, 0.2≤n 6≤ 1.0.
Composition of the present invention, wherein said polybenzimidazole based compound are preferably with (11): (12)=n 7: (1-n 7) mol ratio contains the polymkeric substance constituent by general formula (11) and (12) expression.
Figure A20038010099600161
Figure A20038010099600162
M in the formula 3The integer of expression 1 to 4, Ar represents aromatics combining unit, X 5Be from-O-,-SO 2-,-S-,-CH 2-and-more than one groups of selecting among the OphO-, Ph represents divalent aromatic combining unit, n 7Be in 0.2～1.0 scope.
Composition of the present invention, the amount of contained sulfonic acid and/or phosphine carboxylic is preferably 0.5～4.0 equivalent/kilogram in wherein said poly (arylene ether) based compound and/or the polybenzimidazole based compound.
The present invention also provides a kind of ion-conductive membranes, it is characterized in that, contains above-mentioned compound.
Ion-conductive membranes of the present invention, wherein the methyl alcohol of 5M methanol aqueous solution is to the penetration speed of mean thickness 50 micron membranes, preferably is in 7 mmoles/square metre below second under 25 ℃.
The preparation method of ion-conductive membranes of the present invention wherein preferably includes cast and contains the solution of polyarylene ether compound and solvent, make cast thickness be in the operation in 10～1000 micrometer ranges and will pour into a mould after solution exsiccant operation.
The present invention also provides a species complex, it is characterized in that, comprises above-mentioned ion-conductive membranes and electrode.
The present invention also provides a kind of fuel cell, it is characterized in that, contains above-mentioned complex body.
Fuel cell of the present invention wherein preferably adopts methyl alcohol to act as a fuel.
The present invention also provides a kind of tackiness agent, it is characterized in that, contains above-mentioned polyarylene ether compound.
Description of drawings
Fig. 1 is illustrated in S-DCDPS: DCBN=44: the infrared spectra record diagram of the sulfonation poly (arylene ether) that obtains under 56 the condition.
Fig. 2 is illustrated in S-DCDPS: DCBN=38: the infrared spectra record diagram of the sulfonation poly (arylene ether) that obtains under 62 the condition.
Fig. 3 is illustrated in S-DCDPS: DCBN=38: the TGA record diagram of the sulfonation poly (arylene ether) that obtains under 62 the condition.
Fig. 4 is the record diagram of the infrared spectra of the sulfonated aromatic polyethers mesentery that obtains of expression embodiment 7.
Fig. 5 is illustrated in S-DCDPS: DCBN=38: the graphic representation of the power generation characteristics of sulfonation poly (arylene ether) that obtains under 62 the condition and Na Off イ オ Application 112 (registered trademarks).
Embodiment
The present invention is used in the poly (arylene ether) based compound that imports sulfonic acid on the aromatic ring, provide dimensional stability, thermotolerance, processibility and ionic conductivity under a kind of high temperature all good, be particularly suitable for the macromolecular material used as ion-conductive membranes, the feature that contains sulfonic poly (arylene ether) based compound of the present invention is, even dimensional change and stripping are also few under special hot conditions.That is to say, as on the Electron Affinities aromatic ring, importing sulfonic monomer, by adopting 3,3 '-disulfo-4,4 '-DCBP base sulfone derivatives synthesizes poly (arylene ether), even provide a kind of sulfonic group at high temperature also to be difficult to the polymkeric substance that breaks away from, simultaneously by with 3,3 '-disulfo-4,4 '-DCBP base sulfone derivatives uses two halogen benzonitriles together, also has following feature: promptly use 3,3 '-disulfo-4,4 '-DCBP base sulfone derivatives also can obtain the polyarylene ether compound of high-polymerization degree at short notice.
The present invention imports on aromatic ring in the poly (arylene ether) based compound of sulfonic acid, by import the dioxy diphenylene structural unit more than the specified quantitative in polymer architecture, can achieve the above object.
Imported sulfonic aromatic polyether compound, generally need import many sulfonic groups in order to make it ionic conductivity occur, but sulfonic importing, the swelling of polymkeric substance also increases when improving ionic conductivity, and the battery that acts as a fuel turns round under hot conditions and goes wrong easily.The present invention imports the dioxy diphenylene structural unit more than the specified quantitative for realizing high ionic conductivity in polymkeric substance, import and to suppress swelling even improve sulfonic group in order to produce high ionic conductivity, particularly at high temperature thereby can see the clearer and more definite feature of its dimensional stability general than also.And processibility also shows well.
The present invention also provides a kind of sulfonic poly (arylene ether) based compound that contains, and contains the composition of polybenzimidazole based compound simultaneously.Like this, can in easy film-forming process, be shaped, can also obtain simultaneously a kind ofly not only suppressing hot and humid film expansion down, but also show the polyelectrolyte membrane of high ionic conductivity.Below describe the present invention in detail.
(poly (arylene ether) based compound)
Of the present inventionly contain sulfonic poly (arylene ether) based compound, it is characterized in that, comprise constituent by following general formula (1) and general formula (2) expression.
Figure A20038010099600181
Wherein, Ar represents divalent aryl in the formula, and Y represents sulfonic group or ketone group, X 1Expression H or monovalent cation kind, Ar ' represents divalent aryl.
And contain in the sulfonic poly (arylene ether) based compound structural unit beyond also can containing shown in above-mentioned general formula (1) and the general formula (2) of the present invention.At this moment, the structural unit beyond shown in above-mentioned general formula (1) or the general formula (2) preferably accounts for below the 50 weight % that imported sulfonic poly (arylene ether) based compound of the present invention.It is accounted for below the 50 weight %, the characteristic that contains sulfonic poly (arylene ether) based compound of the present invention is fully activated.
Of the present inventionly containing sulfonic poly (arylene ether) based compound, is to contain the above dioxy diphenylene of 52 weight % (O-Ph-Ph-O-) unit, and then import the compound that sulfonic structure is a feature in polymer architecture.Poly (arylene ether) based compound of the present invention, in the polymer that mainly constitutes by aromatic ring, comprise ehter bond as aromatic ring unit ways of connecting, except that ehter bond, also can have direct combination, form ketone, the general combination that adopts during aromatic(based)polymer such as sulfone, sulfide, various alkylidene group, imide, acid amides, ester, urethane.The repeating unit that ehter bond is suitable with the main composition composition preferably has more than one, and is preferred especially more than two.Aromatic ring is not only the hydro carbons aromatic ring, also can comprise heterocycle etc.And can constitute polymkeric substance with aromatic ring in some aliphatics unit.Also can there be alkyl such as alkyl, alkoxyl group, aryl, aryloxy the aromatic ring unit, and halogen atom, nitro, cyano group, amino, haloalkyl, carboxyl, sulfonic group, hydroxyl etc. are substituting group arbitrarily.
Of the present inventionly contain sulfonic poly (arylene ether) based compound, this aromatic-polyether that contains the above dioxy diphenylene of 52 weight % unit (each unitary molecular weight is equivalent to 184.19) in the polymer architecture is that polymer has and imported sulfonic structure.That is to say, in the skeleton structure except that combining sulfonic group, be for the polymer for containing unitary this aromatic-polyether of the above dioxy diphenylene of 52 weight %, has to have imported sulfonic structure.By dioxy diphenylene unit is in more than the 52 weight %, even for obtaining the sulfonic group that sufficient ionic conductivity imports necessary amount, it is little also can to demonstrate the swelling that causes because of humidity, particularly the characteristic of excellent size stability at high temperature.The diphenylene unit is in more than the 54 weight %.In case the diphenylene unit is lower than 52 weight %, under similarity condition, import under the sulfonic situation, the dimensional change that causes because of swelling under hot and humid condition will increase.Wherein what is called has imported sulfonic group, both can directly import on polymer ring, also can import by the substituting group of aromatic ring.
Contain sulfonic poly (arylene ether) based compound as of the present invention, especially preferably comprise the constituent shown in following general formula (3) and the general formula (4).Because by having the diphenylene structure, make excellent size stability under the hot and humid condition, simultaneously the cause that also increases of the obdurability of film.
Figure A20038010099600191
Wherein X2 represents H or monovalent cation kind.
Polyarylene ether compound of the present invention also contains the compound that has by following general formula (5) and (6) expression in case of necessity together as constituent.
Figure A20038010099600193
Figure A20038010099600194
Wherein in formula (5) and (6), n 1, n 2And n 3The sulfonic group of representing each aromatic ring is in conjunction with number, n 1, n 2And n 3Independently be 0～2 integer separately, n 2+ n 3It is 1～4 integer.That is to say, also can import two with interior sulfonic group in the structural unit of formula (5) expression.On the other hand, must import at least one sulfonic group in the structural unit of formula (6) expression, suitable with aromatic ring in addition sulfonic importing number must be in two.Import more than three under the sulfonic situation when being equivalent to aromatic ring, when high temperature, can produce the problem that water tolerance is reduced because of water is moistening.In the structural unit of formula (5) expression, X 3Be from-CN ,-COOY 1,-COONR 2In one or more groups of selecting, Y 1Expression hydrogen, atoms metal, various ammonium, R are represented one or more groups of selecting from hydrogen and alkyl.That is to say, in the structural unit of formula (5) expression, can also be except that sulfonic group in conjunction with cyano group, carboxyl, amide group and derivative thereof.Wherein preferred at least a portion contains cyano group.And to separately binding site there is no particular restriction, but as phenylene preferably to phenylene or metaphenylene.In addition as the structural unit of formula (5) expression, preferred 1-cyano group-2,6-phenylene.
In the structural unit of formula (6) expression, Z 1And Z 2Be independent respectively one or more functional groups that from rudimentary carbonyl, nitro, amino, hydroxyl and the halogen atom of the rudimentary carboxyl of the lower alkoxy of the low alkyl group of 1～6 carbon atom, 1～6 carbon atom, 1～6 carbon atom, 1～6 carbon atom, select, r 1And r 2Independent respectively each aromatic ring Z of expression 1And Z 2In conjunction with number, r 1And r 2Independently be 0～4 integer separately, n 2+ r 1≤ 4, n 3+ r 2≤ 4.That is to say, in the structural unit of formula (6) expression, except that sulfonic group, can also add one or more functional groups that select rudimentary carbonyl, nitro, amino, hydroxyl and the halogen atom of the rudimentary carboxyl of the lower alkoxy of the low alkyl group from 1～6 carbon atom, 1～6 carbon atom, 1～6 carbon atom, 1～6 carbon atom.
Poly (arylene ether) based compound of the present invention can also contain the structural unit by following general formula (7) expression in case of necessity.
Figure A20038010099600201
Wherein, n 4And n 5The sulfonic group of representing each aromatic ring is in conjunction with number, n 4And n 5Independently be 0～2 integer separately, n 4+ n 5It is 1～4 integer.That is to say, in the structural unit of formula (7) expression, preferably import at least one sulfonic group, the sulfonic importing number of each aromatic ring is in two.This is because do not import under the sulfonic situation, is unfavorable for occurring the cause of abundant ionic conductivity, in case and the sulfonic importing number of each aromatic ring reach more than three, will be because the imbibition of water produce the problem of water tolerance reduction when high temperature.
(sulfonic group)
The sulfonic group that contains sulfonic poly (arylene ether) based compound of the present invention both can directly import on aromatic ring, also can import via the substituting group of aromatic ring.Sulfonic group except that the acid type of proton is followed in existence, also can exist with metal-salt, amine salt, various salt form.
Of the present invention containing in the sulfonic poly (arylene ether) based compound, when containing the constituent of being represented by above-mentioned general formula (1) and (2), sulfonic group content preferably is in 0.3～3.5meq/g scope.Be lower than under the situation of 0.3meq/g, when using as ion-conductive membranes, ionic conductivity often can not fully show, and under the situation greater than 3.5meq/g, under hot and humid condition the swelling of ion-conductive membranes excessive, the tendency that is unsuitable for using is arranged.
And among the present invention, in the skeleton structure except that the sulfonic group that in the poly (arylene ether) based compound, combines, containing under the unitary situation of the above dioxy diphenylene of 52 weight %, sulfonic group content preferably imports in 0.2～6.0meq/g scope.Be lower than under the situation of 0.2meq/g, sufficient ionic conductivity can not occur, and in case above 6.0meq/g, water tolerance just there is the tendency of reduction.Wherein preferably be in 1.0～3.0meq/g scope, more preferably be in 1.5～2.3meq/g scope.
Wherein sulfonic group content can adopt the volumetry experiment to obtain.
(method for making of polymkeric substance constituent and polymkeric substance)
Poly (arylene ether) based compound of the present invention can be with the nucleophilic aromatic substitution reaction of activatory dihalogenated aromatic compounds and aromatic dihydroxy compound, and perhaps the nucleophilic aromatic substitution reaction of halogenated aromatic oxy-compound synthesizes.In at least a monomer, import sulfonic group in advance, perhaps with after the polymerization of aromatic-polyether form with the reaction of suitable sulphonating agent, can in polymkeric substance, import sulfonic group." activation " of wherein said activation dihalogenated aromatic compounds is meant that the existence because of electron-withdrawing group is increased the reactivity worth of nucleophilic aromatic substitution reaction.
There is no particular restriction for the structure of the activation dihalogenated aromatic compounds that can use in nucleophilic aromatic substitution reaction, can enumerate 4,4 '-dichloro diphenyl sulfone, 4,4 '-difluorodiphenyl sulfone, 4,4 '-dichloro diphenylketone, 4,4 '-difluoro benzophenone, 2,6-dichlorobenzonitrile, 2,6-fluorine two cyanobenzenes, 2,4-dichlorobenzonitrile, 2,4-difluorobenzonitrile, 2,5-dichlorobenzonitrile, 2,5-difluorobenzonitrile etc.As importing the monomer that the cyano group phenylene is used, preferably use 2, the 6-dichlorobenzonitrile.And in the activation dihalogenated aromatic compounds, do not contain under the unitary situation of xenyl, especially preferably use the low dihalogenated aromatic compounds of molecular weight.Though these activation dihalogenated aromatic compounds can be used separately, also can most dihalogenated aromatic compounds and usefulness.
Among the present invention, the aromatic dihydroxy compound of using as nucleophilic aromatic substitution reaction, can enumerate 4,4 '-bis-phenol, two (4-hydroxy phenyl) sulfone, 1, two (4-hydroxy phenyl) ethane of 1-, 2, two (4-hydroxy phenyl) propane of 2-, two (4-hydroxy phenyl) methane, 2, two (4-hydroxy phenyl) butane of 2-, 3, two (4-hydroxy phenyl) pentanes of 3-, 2, two (the 4-hydroxyls-3 of 2-, the 5-3,5-dimethylphenyl) propane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl) methane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl) methane, two (4-hydroxy phenyl) phenylmethane, two (4-hydroxy phenyl) ditan, two (4-hydroxyphenoxies)-4,4 '-biphenyl, 4,4 '-two (4-hydroxy phenyl) diphenyl ether, 9,9 '-two (4-hydroxy phenyl) fluorenes, 9,9 '-two (3-methyl-4-hydroxy phenyl) fluorenes, 2, two (4-hydroxy phenyl) HFC-236fa of 2-, quinhydrones, Resorcinol etc.In addition, also can use and to make the various aromatic diols that adopt in the polymerization of poly (arylene ether) based compound by nucleophilic aromatic substitution reaction.These aromatic diols both can use separately, also can multiple aromatic diol and usefulness.In order in poly (arylene ether) based compound of the present invention, to import the diphenylene unit, special preferred use 4,4 '-bis-phenol.
And among the present invention, there is no particular restriction for the halogenated aromatic oxy-compound of using in the nucleophilic aromatic substitution reaction, can enumerate 4-hydroxyl-4 '-chloro benzophenone, 4-hydroxyl-4 '-fluoro benzophenone, 4-hydroxyl-4 '-chloro sulfobenzide, 4-hydroxyl-4 '-fluoro sulfobenzide, 4-chloro-4 '-(p-hydroxybenzene) sulfobenzide, 4-fluoro-4 '-(p-hydroxybenzene) benzophenone etc.These can also use with two or more form of mixtures except that can using separately.In addition, in the reaction of activation dihalogenated aromatic compounds and aromatic dihydroxy compound, also can make these halogenated aromatic oxy-compound react the synthesis of aromatic polyether compound jointly.
Contain in the sulfonic poly (arylene ether) based compound of the present invention, pass through nucleophilic aromatic substitution reaction, under the situation that contains sulfonic monomer polymerization, though can import sulfonic group in the monomer arbitrarily, preferably synthetic by the nucleophilic aromatic substitution reaction that contains the compound of representing by following general formula (13) and general formula (14) as monomer especially.
Figure A20038010099600221
Y wherein 2Expression sulfonic group or ketone group, X 6Expression monovalent cation kind, Z 4Expression elemental chlorine or fluorine.
Specific examples as the compound of representing by general formula (13), can enumerate 3,3 '-disulfo-4,4 '-dichloro-sulfobenzide, 3,3 '-disulfo-4,4 '-two fluoro sulfobenzides, 3,3 '-disulfo-4,4 '-dichloro-benzophenone, 3,3 '-disulfo-4, the salt that 4 '-two fluoro benzophenone and these sulfonic groups and monovalent cation form.As monovalent cation, can be sodium, potassium and other metal ions and various amine, without limits to it.And conduct can enumerate 2,6-dichlorobenzene formonitrile HCN, 2,6-phenyl-difluoride formonitrile HCN, 2,4-dichlorobenzene formonitrile HCN, 2,4-phenyl-difluoride formonitrile HCN, 2,5-dichlorobenzene formonitrile HCN and 2,5-phenyl-difluoride formonitrile HCN by the specific examples of the compound of general formula (14) expression.
In above-mentioned nucleophilic aromatic substitution reaction, can be as monomer with the compound of representing by above-mentioned general formula (13), (14) also with various activatory two fluoro aromatic substance and dichloro-aromatic substance.As these examples for compounds, though can enumerate 4,4 '-dichloro-sulfobenzide, 4,4 '-two fluoro sulfobenzides, 4,4 '-benzophenone of dichloro, 4,4 '-two fluoro benzophenone etc., but be not limited to these compounds, also can use in nucleophilic aromatic substitution reaction, to have active other aromatics dihalo compounds, aromatics dinitro compound, aromatics dicyano compound etc.
And by the Ar in the constituent of above-mentioned general formula (1) expression with by the Ar ' in the constituent of above-mentioned general formula (1) expression, generally be in the polymerization of aromatics nucleophilic substitution, carried out the structure that the aromatic diol monomer component of nucleophilic aromatic substitution reaction imports with compound by above-mentioned general formula (13), (14) expression.As the monomeric example of this aromatic diol, can enumerate 4,4 '-bis-phenol, two (4-hydroxy phenyl) sulfone, 1, two (4-hydroxy phenyl) ethane of 1-, 2, two (4-hydroxy phenyl) propane of 2-, two (4-hydroxy phenyl) methane, 2, two (4-hydroxy phenyl) butane of 2-, 3, two (4-hydroxy phenyl) pentanes of 3-, 2, two (the 4-hydroxyls-3 of 2-, the 5-3,5-dimethylphenyl) propane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl) methane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl) methane, two (4-hydroxy phenyl) phenylmethane,-two (4-hydroxy phenyl) ditan, 9, two (4-hydroxy phenyl) fluorenes of 9-, 9, two (3-methyl-4-hydroxy phenyl) fluorenes of 9-, 2, two (4-hydroxy phenyl) HFC-236fa of 2-, quinhydrones, Resorcinol etc., but other various aromatic diols that utilize nucleophilic aromatic substitution reaction to make to use in the polymerization of poly (arylene ether) based compound also can be used.These aromatic diols both can use separately, also can most aromatic diols and usefulness.
Utilize nucleophilic aromatic substitution reaction to make of the present invention containing under the sulfonic poly (arylene ether) based compound polymeric situation, can be in the presence of basic cpd, make to contain and react with the aromatic diol class and obtain polymer by the activation two fluoro aromatic substance of above-mentioned general formula (13) and general formula (14) expression compound and/or dichloro-aromatic substance.Though polymerization can be carried out in 0～350 ℃ of temperature range, preferably carries out under 50～250 ℃ of temperature.Be lower than under 0 ℃ the situation, the tendency that can not fully react is arranged, polymkeric substance has the tendency that begins to produce decomposition under 350 ℃ the situation and be higher than.Though reaction also can be carried out under solvent-free, preferably carries out in solvent.As the solvent that can use, can enumerate N-N-methyl-2-2-pyrrolidone N-, N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, dimethyl sulfoxide (DMSO), sulfobenzide, tetramethylene sulfone etc., but be not limited to these solvents, also can use those that in nucleophilic aromatic substitution reaction, use as stable solvent.These organic solvents can use separately or two or more and usefulness.
As basic cpd, can enumerate sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus etc., so long as can make the aromatic diol class form active phenoxy group structure, can use and unrestricted.In nucleophilic aromatic substitution reaction, often generate water as by product.This moment is irrelevant with polymer solvent, can adopt toluene etc. as the azeotrope that coexists in the reaction system, and water is removed from system.As the method that water is removed, also can use water-absorbing materials such as molecular sieve from system.In solvent, carry out under the situation of aromatics nucleophilic reaction, preferably add monomer and make the polymer concentration that obtains reach 5～50 weight %.Be lower than under the situation of 5 weight %, be difficult to improve the polymerization degree, and surpass under the situation of 50 weight %, reaction system viscosity becomes too high, the aftertreatment difficulty of reactant.Behind the polymer reaction, evaporation removes and desolvates from reaction solution, obtains required polymkeric substance in case of necessity behind the debris.And, polymkeric substance is precipitated with solid form by in reaction soln being added the low solvent of polymer dissolution degree, behind the filtering-depositing thereby can access polymkeric substance.
Poly (arylene ether) based compound of the present invention also can adopt the aromatics electrophilic substitution reaction of known " reaction of Knut Fridell Kerafyrm thatch " synthetic.As being subjected to the aromatic monomer that parent's electricity is attacked this moment, can use phenyl ether, 1,4-two phenoxy group benzene, 1,3-two phenoxy group benzene, 4,4 '-two phenoxy group biphenyl, 3,3 '-two phenoxy group biphenyl, two (4-phenyl phenoxy groups)-1,4-biphenyl, two (4-phenyl phenoxy groups)-4,4 '-biphenyl, 4-phenoxy group biphenyl, two (4-phenyl phenoxy group) ether, two (3-phenyl phenoxy group) ether, 4,4 '-two (4-Phenoxyphenyl) phenyl ether, 4,4 '-two phenoxy group benzophenone, 1, two (the 4-phenyl benzoin) benzene of 4-, 1, two (the 4-phenyl benzoin) benzene of 3-, two [4-(4-phenoxy group benzoin) phenyl] ether, two [4-(3-phenoxy group benzoin) phenyl] ether, biphenyl, terphenyl, join general those that in this reaction, use such as four benzene, and can be used in combination.Wherein, for example as 4,4 '-two (4-phenyl phenoxy group) phenyl ether is such, preferably with structure contain dioxy diphenylene structure as main component.
Monomer as electrophilic is attacked can use the aromatic dicarboxylic acid acyl chlorides.As the example, can use p-phthaloyl chloride, m-phthaloyl chloride, 2,6-naphthalene dimethyl chloride, 1,5-naphthalene dimethyl chloride, 4,4 '-biphenyl dimethyl chloride, phenyl ether-3,3 '-dicarboxylic acid, phenyl ether-4,4 '-dicarboxylic acid, benzophenone-4, the general material that uses in this reaction such as 4 '-dicarboxylic acid also can be used in combination.But also can and with 4-phenoxy group Benzoyl chloride etc. from the condensed type monomer polymerization.
There is no particular restriction for above-mentioned aromatics electrophilic substitution reaction condition, for example can use Knut Fridell-Kerafyrm thatch reaction of making catalyzer with aluminum chloride.Solvent as this moment can use 1, and 2-ethylene dichloride, methylene dichloride, sym.-tetrachloroethane, chloroform etc. contain halohydrocarbon, oil of mirbane, dithiocarbonic anhydride etc.Can also use other solvents such as hydrogen fluoride/boron trifluoride in addition, and other catalyst systems such as zinc chloride, aluminum bromide, iron trichloride, titanium tetrachloride.And can be with the aromatic dicarboxylate as monomer, with dehydration polycondensations such as Tripyrophosphoric acid.
Among the present invention, when employing does not import the synthetic poly (arylene ether) based compound of sulfonic monomer to the monomer that forms dioxy diphenylene structure, by the poly (arylene ether) based compound that obtains is carried out sulfonation reaction, also can generate sulfonation poly (arylene ether) based compound of the present invention.At this moment, preferably contain simultaneously with the compound of following general formula (15) expression as monomer and with the compound of following general formula (16) expression as monomer, obtain polymkeric substance by nucleophilic aromatic substitution reaction, with the polymkeric substance sulfonation that obtains.
In the formula (15), X 7Expression elemental chlorine or fluorine.
In nucleophilic aromatic substitution reaction and aromatics electrophilic substitution reaction, the poly (arylene ether) based compound there not to be sulfonic form to obtain in the whichever reaction can both obtain containing sulfonic poly (arylene ether) based compound by carrying out sulfonation reaction.And in above-mentioned general formula (6), contain n by making 2, n 3Being 0 the unitary poly (arylene ether) based compound of formation carries out sulfonation reaction and can obtain.For preparation contains the operable sulphonating agent of sulfonic poly (arylene ether) based compound, there is no particular restriction, for example can use the vitriol oil and oleum (for example to be disclosed in " Solid State Ionics " 106, in 219 pages (1998)), chlorsulfonic acid (for example is disclosed in " J.Polym.Sci.Polym.Chem. " 22, in 295 pages (1984)), the anhydrous slufuric acid complex compound (for example is disclosed in " J.Polym.Sci.Polym.Chem. " 22, among 721 pages (1984) and " J.Polym.Sci.Polym.Chem. " 23,1231 pages (1985)) etc.
And except this well-known sulphonating agent, can also use the sulphonating agent on the patent gazette No. 2884189, promptly 1,3,5-Three methyl Benzene-2-sulfonic acid, 1-2, the 4-disulfonic acid, 1,2,4-Three methyl Benzene-5-sulfonic acid, 1-3-sulfonic acid, 1,2,3-Three methyl Benzene-4-sulfonic acid, 1,2,3,4-tetramethyl-benzene-5-sulfonic acid, 1,2,3,5-tetramethyl-benzene-4-sulfonic acid, 1,2,4,5-tetramethyl-benzene-3-sulfonic acid, 1,2,4,5-tetramethyl-benzene-3,6-disulfonic acid, 1,2,3,4,5-pentamethylbenzene-6-sulfonic acid, 1,3,5-triethylbenzene-2-sulfonic acid, 1-ethyl-3,5-dimethyl benzene-4-sulfonic acid, 1-ethyl-3,4-dimethyl benzene-6-sulfonic acid, 1-ethyl-2,5-dimethyl benzene-3-sulfonic acid, 1,2,3,4-tetraethylbenzene-5-sulfonic acid, 1,2,4,5-tetraethylbenzene-3-sulfonic acid, 1,2,3,4,5-pentaethyl benzene-6-sulfonic acid, 1,3,5-triisopropylbenzene-2-sulfonic acid, 1-propyl group-3,5-dimethyl benzene-4-sulfonic acid etc.
In the above-mentioned sulphonating agent, particularly preferably in the compound that is replaced by low alkyl group on the ortho position of sulfonic group both sides, for example 1,3,5-Three methyl Benzene-2-sulfonic acid, 1-3-sulfonic acid, 1,2,3,5-tetramethyl-benzene-4-sulfonic acid, 1,2,3,4,5-pentamethylbenzene-6-sulfonic acid, 1-2,4-disulfonic acid, 1,3,5-triethylbenzene-2-sulfonic acid etc.1-2-sulfonic acid preferably.
Wherein in that preparation is of the present invention when containing sulfonic arylene ether based compound, preferably with respect to 100 weight part poly (arylene ether) based compounds, in 30～50000 weight part scopes, add these sulphonating agents, more preferably in 50～10000 weight part scopes, add.The addition of sulphonating agent is lower than under the situation of 30 weight parts, the tendency that exists sulfonation reaction fully not carry out, and the addition of sulphonating agent surpasses under the situation of 50000 weight parts, reacted sulphonating agent is handled needs the many work of cost.
And for preparing the organic solvent that sulfonic poly (arylene ether) based compound is used that contains of the present invention, there is no particular restriction, so long as can dissolve poly (arylene ether) based compound and/or sulphonating agent, and to sulfonation reaction do not have past of harmful effect known those, can use.As specific examples, can enumerate chloroform, methylene dichloride, 1, halogenated aliphatic hydrocarbon classes such as 2-ethylene dichloride, trichloroethane, tetrachloroethane, trieline, zellon, halogenated aromatic such as dichlorobenzene, trichlorobenzene hydro carbons, nitro-compound such as Nitromethane 99Min., oil of mirbane, alkyl benzenes such as Three methyl Benzene, tributyl benzene, tetramethyl-benzene, pentamethylbenzene, heterocycles such as tetramethylene sulfone, straight chain, side chain or annular aliphatic hydro carbons such as octane, decane, hexanaphthene.
These solvents can use a kind of or with two or more mixing, though its usage quantity can suitably be selected according to the kind of poly (arylene ether) based compound and sulphonating agent, preferably are in usually in 100～2000 weight part scopes with respect to 100 weight part sulphonating agents.Quantity of solvent is lower than under the situation of 100 weight parts, is difficult to carry out the sulfonation reaction of homogeneous, and quantity of solvent surpasses under the situation of 2000 weight parts, a large amount of work of manipulation requires such as recovery cost of the separating of reaction back solvent and sulphonating agent, solvent.
Sulfonic import volume can be controlled by the poly (arylene ether) based compound being set sulfonation conditions such as sulphonating agent, temperature of reaction, reaction times in case of necessity.Preferably be in-20～150 ℃ in temperature of reaction, the reaction times is in 0.1～100 hour and carries out sulfonation reaction in the scope.When temperature of reaction was lower than-20 ℃, the speed of response of sulfonation reaction slowed down, and temperature of reaction is in case above 150 ℃, will produce restive sulfonated problem.And, preferably under inert gas atmospheres such as nitrogen, argon gas, carry out sulfonation reaction in order to obtain the sulfonic poly (arylene ether) based compound that contains of the present invention.Because will prevent the oxidized deterioration of the polymkeric substance that obtains like this.
(polymkeric substance logarithm viscosity)
And, of the present inventionly containing sulfonic poly (arylene ether) based compound, the polymkeric substance logarithm viscosity that adopts method described later to measure preferably is in more than 0.1.Logarithm viscosity is in case less than 0.1, become fragile easily when forming ion-conductive membranes.The reduction reduced viscosity more preferably is in more than 0.3.On the other hand, in case the reduction reduced viscosity surpasses 5, that processibility is gone wrong is bad because of the dissolving difficulty of polymkeric substance etc.Wherein measure the solvent that logarithm viscosity is used, generally can use N-Methyl pyrrolidone, N,N-dimethylacetamide isopolarity organic solvent, under the situation that solvability is low in these solvents, also can measure with the vitriol oil.
(composition)
Of the present inventionly contain sulfonic poly (arylene ether) based compound, use though can be used as monomer, preferably and the polybenzimidazole based compound be mixed together use.And of the present inventionly contain sulfonic poly (arylene ether) based compound, also can use with other combination of polymers.As these polymkeric substance, for example can enumerate polyethylene terephthalate, polyester such as polybutylene terephthalate PEN, nylon 6, nylon 6,6, nylon 6,10, nylon 12 etc. are polyamide-based, polymethylmethacrylate, the ester class of polymethyl acrylic acid, polymethyl acrylate, acrylate resins such as polyacrylic ester class, the polyacrylic resin, polymethyl acrylic acid is a resin, polyethylene, polypropylene, with the various polyolefine that contain polystyrene or diene polymer, polyurethane series resin, rhodia, cellulose-based resin such as ethyl cellulose, polyarylester, polyaramide, polycarbonate, polyphenylene sulfide, polyphenylene oxide, polysulfones, polyethersulfone, polyether-ether-ketone, polyetherimide, polyimide, polyamidoimide, polybenzimidazole, polybenzoxazole, aromatic polymers such as polybenzothiozole, Resins, epoxy, phenolic resin, thermosetting resins such as lacquer resins benzoxazine colophony etc. are not particularly limited.The composition of alkaline polymers such as above-mentioned polybenzimidazole based compound and polyvinylpyridine can be described as particularly preferred a kind of combination for the stability that improves polymer sizes.
Among the present invention, particularly with poly (arylene ether) based compound of the present invention, the composition that also contains polybenzimidazole based compound with acidic-group, use this combination can access not only on weather resistance, and on processibility and ionic conductivity etc., can both show the novel materials of advantageous property.Owing to have this good character, so the solid polyelectrolyte membrane material that the above-mentioned composition among the present invention can be used as fuel well.
Poly (arylene ether) based compound of the present invention preferably contains in composition is all and is lower than 100 weight % more than the 50 weight %.More preferably contain and be lower than 100 weight % more than the 70 weight %.The content that contains sulfonic poly (arylene ether) based compound of the present invention, be lower than under the situation of 50 weight %, the ion-conductive membranes that contains this resin combination can not obtain good ionic conductivity because of sulfonic group concentration is low, and forms the trend that discontinuous phase has the degree of excursion reduction that makes conducting ion because of containing sulfonic unit.
In order to obtain containing the composition of poly (arylene ether) based compound of the present invention and polybenzimidazole based compound, can be by polybenzimidazole based compound and poly (arylene ether) based compound blended mode of the present invention be obtained.And, this mixed polymer composition, can adopt with polymeric solution, isolating polymkeric substance and again any means such as the extruding of dissolved polymers solution, spinning, calendering, cast be configured as fiber or film.In these forming processes, preferably be shaped with the solution that is dissolved in the appropriate solvent.As the dissolved solvent, can be from N, N-N,N-DIMETHYLACETAMIDE, N, aprotic polar solvents such as dinethylformamide, dimethyl sulfoxide (DMSO), N-N-methyl-2-2-pyrrolidone N-, hexamethylphosphoramide, with suitably selection in the strong acid such as Tripyrophosphoric acid, methylsulfonic acid, sulfuric acid, trifluoroacetic acid, but be not limited to these.In these solvents, especially preferably from organic solvent, be shaped.These solvents also can mix use with several within the bounds of possibility.And, can also use lewis acidic materials such as in organic solvent, having added lithiumbromide, lithium chloride, aluminum chloride as solvent as improving deliquescent means.Polymer concentration in the solution preferably is in 0.1～50 weight % scope.Cross low then plasticity and worsen, too high then processibility worsens.
Composition wherein of the present invention can also contain for example various additives such as antioxidant, thermo-stabilizer, lubricant, tackiness imparting agent, softening agent, viscosity modifier, static inhibitor, antiseptic-germicide, defoamer, dispersion agent, stopper in case of necessity.
＜polybenzimidazole based compound 〉
Of the present inventionly contain sulfonic poly (arylene ether) based compound, it is characterized in that, contain structure by following general formula (8) expression.
Figure A20038010099600291
M in the formula (8) 1The integer of expression 1 to 4, R 1Expression can form the tetravalence aromatics combining unit of imidazole ring, R 2Expression divalent aromatic unit, R 1And R 2Both can all be the monocycle of aromatic ring, also can be the conjugant or the condensed ring of a plurality of aromatic rings, also stable substituting group can be arranged.Z 3Expression sulfonic group and/or phosphonate group, its part also can form the salt structure.
For the synthetic route that contains the polybenzimidazole based compound of acidic-group of the present invention that contains structure shown in the above-mentioned formula (8), be not particularly limited, usually can be by making more than one compounds of selecting in the aromatic series tetraamine that from compound, can form imidazole ring and the derivative thereof, synthetic with the method for more than one compounds reactions of from aromatic binary carboxylic acid and derivative thereof, selecting.At this moment, in the di-carboxylic acid that uses, use under the situation of the di-carboxylic acid that contains sulfonic group and phosphonate group or its salt, can in the polybenzimidazole that obtains, import sulfonic group or phosphonate group.The di-carboxylic acid that contains sulfonic group or phosphonate group though can be used in combination its more than one, also can use the di-carboxylic acid that contains the sulfonic group di-carboxylic acid and contain phosphonate group simultaneously.
Wherein in the present invention, itself be that the benzoglyoxaline of polybenzimidazole based compound integrant binds and closes the unit, has the combining unit of the aromatic binary carboxylic acid of sulfonic group and/or phosphonate group, both do not had sulfonic group also not have aromatic binary carboxylic acid combining unit and other combining units of phosphonate group, the preferably mode combination by random polymerization and/or alternating polymerization.And these polymerization methodses be not limited to a kind of, also can two or more polymerized forms and be stored in the same compound.
Contain in containing of the constituent shown in the above-mentioned formula (8) of the sulfonic polybenzimidazole based compound, especially preferably with n 6: (1-n 6) mol ratio contains structure is represented shown in following formula (9) and (10) combining unit as constituent.
Figure A20038010099600301
Figure A20038010099600302
In formula (9) and (10), m 2The integer of expression 1 to 4, Ar " expression divalent aromatic combining unit, X 4Be from-O-,-SO 2-,-C (CH 3) 2-,-C (CF 3) 2-and-more than one groups of selecting among the OphO-, Ph represents the divalent aromatic combining unit.And mol ratio satisfies formula: 0.2≤n 6≤ 1.0.
In above-mentioned formula (9) and (10), m 2In case greater than 5, the water tolerance of the polymkeric substance that obtains just has the trend of deterioration, and mol ratio n 6In case, the tendency that can not show abundant ionic conductivity is just arranged less than 0.2.
There is no particular restriction as the specific examples that can form the aromatic series tetramine that contains sulfonic polybenzimidazole based compound that contains constituent shown in the above-mentioned formula (8), for example can enumerate 1,2,4,5-tetramino benzene, 3,3 '-diaminobenzidine, 3,3 ', 4,4 '-tetramino phenyl ether, 3,3 ', 4,4 '-tetramino diphenylsulfide, 3,3 ', 4,4 '-tetramino sulfobenzide, 2, two (3, the 4-diamino-phenyl) propane of 2-, two (3, the 4-diamino-phenyl) methane, 2,2-two (3, the 4-diamino-phenyl) HFC-236fa, 1, two (3, the 4-diamino phenoxy) benzene of 4-etc. and derivative thereof.In these materials, especially preferably can form 3,3 ' of the combining unit shown in the formula (10), 4,4 '-tetramino sulfobenzide, 3,3 ', 4,4 '-tetramino phenyl ether, 2, two (3, the 4-diamino-phenyl) propane, 2 of 2-, 2-two (3, the 4-diamino-phenyl) HFC-236fa, 1, two (3, the 4-diamino phenoxy) benzene and the derivatives thereof of 4-.
As the specific examples of these aromatic series tetraamine derivatives, can enumerate and hydrochloric acid, sulfuric acid.The salt that acid such as phosphoric acid forms.And these compounds both can use separately, also can use majority simultaneously.In addition, these compounds also can contain known antioxidants such as tindichloride and phosphorons acid compound in case of necessity.
Can form the sulfonic di-carboxylic acid that contains of formula (8) structure, can select to contain in the aromatic binary carboxylic acid one to four sulfonic di-carboxylic acid, as specific examples, for example can enumerate 2,5-dicarboxyl Phenylsulfonic acid, 3,5-dicarboxyl Phenylsulfonic acid, 2,5-dicarboxyl-1,4-benzene disulfonic acid, 4,6-dicarboxyl-1,3-benzene disulfonic acid, 2,2 '-disulfo-4,4 '-diphenyl dicarboxylic acid, 3,3 '-disulfo-4,4 '-biphenyl dicarboxylic acid etc. contain sulfonic di-carboxylic acid and derivative thereof.As derivative, can enumerate an alkali metal salts such as sodium, potassium, ammonium salt and alkylammonium salt etc.Be not particularly limited for containing sulfonic di-carboxylic acid structure.M in the above-mentioned formula (8) 1, select from 1 to 4 the integer.m 1In case be in more than 5, not preferred because the water tolerance of polymkeric substance produces the tendency that reduces.
Contain sulfonic di-carboxylic acid, not only can it is independent, and can also import with the form that does not contain sulfonic di-carboxylic acid copolymerization.As can be with containing the di-carboxylic acid that sulfonic di-carboxylic acid uses, can use terephthalic acid, m-phthalic acid, naphthalic acid, phenyl ether dioctyl phthalate, sulfobenzide dioctyl phthalate, biphenyl dicarboxylic acid, terphenyl dioctyl phthalate, 2, the general di-carboxylic acid that two (4-carboxyl phenyl) HFC-236fa of 2-etc. are reported as polyester raw material, but wherein be not limited to illustrative these materials.
Though there is no particular restriction for the purity that contains sulfonic di-carboxylic acid, preferred more than 98%, more preferably more than 99%.Containing the polybenzimidazole that sulfonic di-carboxylic acid is a polymerizable raw material, with use the situation that does not contain sulfonic di-carboxylic acid under compare, can see the tendency that the polymerization degree reduces, thus preferably use purity high as far as possible contain sulfonic di-carboxylic acid.Use under the situation that does not contain the sulfonic group di-carboxylic acid with containing sulfonic di-carboxylic acid, make and contain sulfonic di-carboxylic acid and account for 20 moles of whole di-carboxylic acid more than the %, can make the sulfonic acid effect clear and definite.For making the sulfonic acid effect produce significantly, it is accounted for more than 50 moles.Be lower than under the situation of 20 moles of % when containing sulfonic di-carboxylic acid content, have the electric conductivity of polybenzimidazole based compound to reduce, be not suitable as the tendency of solid polymer electrolyte material.
The sulfonic polybenzimidazole based compound that contains as containing constituent shown in the above-mentioned formula (8) is characterized in that, with n 7: (1-n 7) mol ratio contains structural unit by the expression of following formula (11) and formula (12) as constituent.
Figure A20038010099600311
In formula (11) and the formula (12), m 3The integer of expression 1 to 4, Ar represents aromatics combining unit, X 5Be from-O-,-SO 2-,-S-,-CH 2-and-more than one groups of selecting among the OphO-, Ph represents the divalent aromatic combining unit.And mol ratio satisfies 0.2≤n 7≤ 1.0.
In above-mentioned formula (11), (12), m 3In case greater than 5, the water tolerance of the polymkeric substance that obtains just has the tendency of deterioration, and mol ratio n 7Less than the tendency that can not fully show ionic conductivity was just arranged in 0.2 o'clock.
The specific examples that can form the aromatics tetramine that contains sulfonic polybenzimidazole shown in the above-mentioned formula (8) is not particularly limited, and for example can enumerate 1,2,4,5-tetramino benzene, 3,3 '-diaminobenzidine, 3,3 ', 4,4 '-tetramino phenyl ether, 3,3 ', 4,4 '-tetramino diphenyl sulfide, 3,3 ', 4,4 '-tetramino sulfobenzide, 2,2-two (3, the 4-diamino-phenyl) propane, two (3, the 4-diamino-phenyl) methane, 2, two (3, the 4-diamino-phenyl) HFC-236fa, 1 of 2-, two (3, the 4-diamino phenoxy) benzene of 4-etc. and derivative thereof.In these materials, especially preferably can form above-mentioned formula (9) expression combining unit 3,3 ', 4,4 '-tetramino diphenyl ether, 3,3 ', 4,4 '-tetramino sulfobenzide, 3,3 ', 4,4 '-tetramino diphenyl sulfide, two (3, the 4-diamino-phenyl) methane, 1, two (3, the 4-diamino phenoxy) benzene and the derivatives thereof of 4-.
The specific examples of these aromatic tetraamines derivatives can be enumerated the salt of acid such as hydrochloric acid, sulfuric acid, phosphoric acid etc.And these compounds both can use separately, also can use multiple simultaneously.In addition, these compounds can also contain known antioxidants such as tindichloride and phosphorons acid compound where necessary.
As synthetic aromatic binary carboxylic acid and derivative thereof that use, that have phosphonate group when having sulfonic polybenzimidazole based compound shown in the above-mentioned formula (11), be not particularly limited, can suitably use the compound that 1 to 4 phosphonate group is arranged in the aromatic binary carboxylic acid skeleton.As specific examples, can enumerate 2,5-dicarboxyl phenyl-phosphonic acid, 3,5-dicarboxyl phenyl-phosphonic acid, 2,5-'-diphosphono terephthalic acid etc. has the aromatic binary carboxylic acid and the derivative thereof of phosphonate group.In a single day 5 above phosphonate groups are arranged in the aromatic binary carboxylic acid skeleton, the water tolerance of polymkeric substance just has the tendency of reduction, thereby bad.
Wherein, can enumerate an alkali metal salt and ammonium salt, alkylammonium salts etc. such as sodium, potassium as phosphonate derivative with aromatic binary carboxylic acid of these phosphonate groups.And these compounds can use separately, perhaps use multiple simultaneously.In addition, these compounds can also contain known antioxidants such as tindichloride and phosphorons acid compound where necessary.
And the structure that contains the aromatic binary carboxylic acid of phosphonate group is not limited to these, but the aromatic binary carboxylic acid with phosphonate group of preferred phenyl-phosphonic acid fundamental mode shown in it.
Though the purity of the aromatic binary carboxylic acid of using for synthetic polybenzimidazole based compound among the present invention with phosphonate group is not particularly limited, preferred more than 97%, more preferably more than 98%.With the aromatic binary carboxylic acid that contains phosphonate group is the polybenzimidazole based compound of polymerizable raw material, there is not the aromatic binary carboxylic acid of sulfonic group and phosphonate group to do to compare under the situation of raw material with employing, can see the tendency that the polymerization degree reduces, so preferably use the high as far as possible aromatic binary carboxylic acid that contains phosphonate group of purity.That is to say that be lower than when the purity of aromatic binary carboxylic acid under 97% the situation, the polymerization degree of the polybenzimidazole based compound that obtains reduces, have and be unsuitable for the tendency used as solid polymer electrolyte material.
Though containing the aromatic binary carboxylic acid of above-mentioned phosphonate group can be only with its independent use, but also can be used for the polybenzimidazole based compound that synthetic the present invention has phosphonate group by carrying out copolyreaction with the aromatic binary carboxylic acid that does not contain sulfonic group and phosphonate group.As being not particularly limited with the aromatic binary carboxylic acid that does not contain sulfonic group and phosphonate group that the aromatic binary carboxylic acid that contains the phosphonate group base uses, for example can use terephthalic acid, m-phthalic acid, naphthalic acid, phenyl ether dioctyl phthalate, sulfobenzide dioctyl phthalate, biphenyl dicarboxylic acid, terphenyl dioctyl phthalate, 2, the general aromatic binary carboxylic acid that two (4-carboxyl phenyl) HFC-236fa of 2-etc. are reported as polyester raw material.
Though and these these compounds can use separately, also can use multiple simultaneously.These compounds can also contain known antioxidants such as tindichloride and phosphorons acid compound in case of necessity in addition.
In polybenzimidazole based compound of the present invention synthetic, with the aromatic binary carboxylic acid that phosphonate group is arranged, use under the situation of the aromatic binary carboxylic acid that does not contain sulfonic group and phosphonate group, the aromatic binary carboxylic acid that contains phosphonate group is all being accounted under 20 moles of situations more than the % in the aromatic binary carboxylic acids, can make the polybenzimidazole based compound among the present invention more obvious because of the excellent results that has phosphonate group and produce.And, the aromatic binary carboxylic acid content proportioning with phosphonate group must be accounted for more than 50 moles for making polybenzimidazole based compound among the present invention because of the effect that has phosphonate group and produce is remarkable.When the aromatic binary carboxylic acid content that contains phosphonate group is lower than under the situation of 20 moles of %, polybenzimidazole based compound of the present invention has electric conductivity to be reduced, and is not suitable as the tendency of solid polymer electrolyte material.
Wherein, have above-mentioned sulfonic aromatic binary carboxylic acid and aromatic binary carboxylic acid with phosphonate group, though they can use separately, carry out copolyreaction by making the two, also can be used for the polybenzimidazole based compound that synthetic the present invention has sulfonic group and/or phosphonate group.
And this moment, have sulfonic aromatic binary carboxylic acid and aromatic binary carboxylic acid with phosphonate group, use though can only it be mixed, but, also can synthesize the polybenzimidazole based compound with sulfonic group and/or phosphonate group of the present invention by carrying out copolyreaction with the aromatic binary carboxylic acid that does not contain sulfonic group and phosphonate group.
More than one compounds that employing is selected from above-mentioned aromatic series tetraamine and derivative thereof, with more than one compounds of from aromatic binary carboxylic acid and derivative thereof, selecting, synthetic method with polybenzimidazole based compound of sulfonic group and/or phosphonate group, there is no particular restriction, for example can be according to J.F.Wolfe work " polymer science and engineering complete works " second edition, 11 volumes, 601 pages (1998) are gone up record the sort of with Tripyrophosphoric acid as solvent dewater, the method for cyclopolymerization is synthetic.Replace Tripyrophosphoric acid but also can adopt, carry out the synthetic method with same mechanism with methylsulfonic acid/five phosphorus oxide mixed solvents.Wherein, for the synthetic high polybenzimidazole based compound of thermostability, more preferably use general widely used Tripyrophosphoric acid polymerization.
In addition, in order to obtain polybenzimidazole based compound of the present invention, for example can adopt in suitable organic solvent or with the form of mixing raw material monomer melt, in advance synthetic precursor polymer with polyamide structure etc., make its cyclisation through suitable thermal treatment then, convert thereof into the method for purpose polybenzimidazole structure etc.
And the reaction times during synthetic polybenzimidazole based compound of the present invention, because optimum reacting time is relevant with the combination of each starting monomer, so generally can not stipulate, but as past report under the long-time situation of reacting, in the system that contains starting monomers such as aromatic binary carboxylic acid with sulfonic group and/or phosphonate group, the thermostability of the polybenzimidazole based compound that obtains is reduced, so preferably in the scope that can obtain effect of the present invention, will shorten in the reaction times in this case.By such shortening reaction times, can under the high state of thermostability, obtain having the polybenzimidazole based compound of sulfonic group and/or phosphonate group.
And the temperature of reaction of polybenzimidazole based compound of the present invention when synthetic, generally can not stipulate because of optimum reacting time is relevant with the combination of each starting monomer, when but Bao Gao such high temperature reacts down in the past, in the system that contains starting monomers such as aromatic binary carboxylic acid with sulfonic group and/or phosphonate group, often can not control the import volume of sulfonic group in the polybenzimidazole based compound that obtains and/or phosphonate group, preferably in the scope that can obtain effect of the present invention, temperature of reaction be reduced in this case.By such reduction temperature of reaction, can be controlled at the import volume of sulfonic group in the many polybenzimidazole based compounds of acidic-group amount and/or phosphonate group, can obtain this compound with the high state of thermostability.
And after polybenzimidazole based compound of the present invention is synthetic, the starting monomer that constitutes repeating unit is by under the multiple situation about forming, when between this repeating unit with random copolymerization and/or alternating copolymerization in conjunction with the time, as the material of polyelectrolyte membrane have exhibit stabilization can feature.Wherein, for polybenzimidazole based compound of the present invention is synthetic with random copolymerization and/or alternating copolymerization polymerized form, the preferred employing from the polymerization initial stage just realizes that according to the equivalent ratio method of the whole raw material monomers of adding carries out polymerization.
Though wherein also can be not with random copolymerization or alternating copolymerization, and with the synthetic polybenzimidazole based compound of block polymerization method, but preferably carry out polymerization this moment in the following ways, the i.e. oligopolymer of synthetic first composition under the reinforced condition of the raw material monomer of the equivalent cooperation ratio that staggers, and then add raw material monomer and also comprise second composition and adjust proportioning equivalent is coincide.
Among the present invention, have the molecular weight of the polybenzimidazole based compound of sulfonic group and/or phosphonate group, though be not particularly limited, preferred more than 1000, more preferably more than 3000.And this molecular weight preferably is in below 1000000, more preferably is in below 200000.This molecular weight is less than under 1000 the situation, reduces the shaping thing that is difficult to obtain having with the polybenzimidazole based compound good character because of viscosity.And this molecular weight is in case above 1000000, be difficult to make the polybenzimidazole based compound to be shaped because of viscosity rises.And, have the molecular weight of the polybenzimidazole based compound of sulfonic group and/or phosphonate group among the present invention, in fact can be used in the logarithm viscosity evaluation of measuring in the vitriol oil.So this logarithm viscosity preferably is in more than 0.25, especially preferably is in more than 0.40.And this logarithm viscosity preferably is in below 10, more preferably is in below 8.This logarithm viscosity is lower than under 0.25 the situation, because of the low shaping thing that can not obtain having good character with the polybenzimidazole based compound of viscosity.And this logarithm viscosity is in case above 10, will be difficult to make the polybenzimidazole based compound to be shaped because of viscosity rises.
The composition of being made up of alkaline polymers such as poly (arylene ether) based compound and polybenzimidazole of report so far, under the interaction of soda acid between polymkeric substance, generation precipitates when polymer dissolution.Therefore, interpolation amine compound etc. makes the acidic polymer salify, makes two kinds of polymer dissolution in same solvent.Therefore, for example after being configured as ion-conductive membranes, must carry out the operation that acid treatment makes desalination in order to give proton-conducting.The polybenzimidazole that contains acidic-group among the present invention is owing to have acidic-group in the alkaline polymer chain, so it is characterized in that not and can precipitate because of the polymkeric substance salify that contains acidic-group with adding.Therefore, two kinds of polymkeric substance former state homogeneous can be dissolved in the same solvent, after the formation particle conductive membranes, have the advantage of direct demonstration proton-conducting.
The method that obtains molding from solution can adopt known method.For example by heating, drying under reduced pressure, can with impregnating in the polymkeric substance non-solvent of the solvent of dissolve polymer, remove desolvate after, can obtain containing the molding of the polybenzimidazole of sulfonic group and/or phosphonate group.Solvent is under the situation of organic solvent, and preferred heating or the drying under reduced pressure of adopting is except that desolvating.Solvent is under the situation of strong acid, preferably the method for flooding at water, methyl alcohol, acetone etc.
Making poly (arylene ether) based compound of the present invention and the preferred method that the film that contains sulfonic poly (arylene ether) based compound is shaped, is the method with solution casting.From the solution of cast, remove to desolvate in the manner described above and can obtain film.Removing of solvent is from the preferred desiccating method of the homogeneity of film.And since the decomposition of polymkeric substance and solvent and rotten, drying under reduced pressure under the preferred alap temperature.The substrate of cast can adopt sheet glass and polyfluortetraethylene plate etc.Under the high situation of soltion viscosity,, can pour into a mould easily in case at high temperature pour into a mould because of soltion viscosity reduces with substrate and solution heating.Though the sample path length during cast is not particularly limited, be preferably 10～1000 microns.In case cross the thin shape that just can not keep film, the blocked up film heterogeneity that then makes easily.More preferably be in 100～500 micrometer ranges.The method of control solution casting thickness can adopt known method.For example can utilize spreader, cutter to be coated with coating such as device certain thickness, perhaps with bezel etc. make the cast area certain and under the amount of solution and concentration control thickness.The solution of cast is removed the film that can access homogeneous under the situation of speed adjusting solvent.For example under Jia Re the situation, in the initial period, form low temperature velocity of evaporation is descended.And under the situation of in non-solvents such as water, flooding, in advance solution is placed appropriate time in air He in the rare gas element, can adjust the setting rate of polymkeric substance.Though film of the present invention can be made any thickness as required, preferably approach as far as possible from ionic conductivity.Specifically, preferably be in below 200 microns, more preferably be in below 50 microns, preferably be in below 20 microns.
(preparation of molding)
Sulfonic poly (arylene ether) based compound and the composition thereof of containing of the present invention can adopt any means such as extruding, spinning, calendering or cast to make moldinies such as fiber or film.The wherein preferred solution that is dissolved in the appropriate solvent that adopts is shaped.As this solvent, can be from N, suitably select in aprotic polar solvent such as dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), N-N-methyl-2-2-pyrrolidone N-, hexamethylphosphoramide and the alcohols such as methyl alcohol, ethanol and do not have a special restriction.These solvents also can use several within the bounds of possibility.Compound concentration in the solution preferably is in 0.1～50 weight % scope.Compound concentration in the solution just is difficult to obtain good shaping thing in case be lower than 0.1 weight %, if surpass the tendency that 50 weight % then have processibility to worsen.From solution, obtain the method for molding, can adopt known method to carry out.For example, by heating, drying under reduced pressure, can with impregnating in the compound non-solvent of the solvent of dissolved compound, remove and can obtain molding after desolvating.Solvent is under the situation of organic solvent, and preferred heating or the drying under reduced pressure of adopting distills except that desolvating.This moment as required, also can with other compound compound forms under be configured as different shapes such as fibrous, membranaceous, granular, sheet, bar-shaped, tubulose, spherical, bulk.Under the situation of solubility behavior similar compounds combination, preferred from the angle that can well be shaped.Though the sulfonic group in the molding that obtains so also comprises and the salifiable form of positively charged ion, also can convert thereof into the free sulfonic group by acid treatment as required.
(ion-conductive membranes)
With sulfonic poly (arylene ether) based compound and the composition thereof of containing of the present invention, also can prepare ion-conductive membranes.The method of formation ion-conductive membranes is the solution casting method preferably, can obtain ion-conductive membranes except that desolvating like that from cast solution according to above-mentioned.Remove from the preferred employing desiccating method of the homogeneity of ion-conductive membranes and to desolvate.And for fear of the decomposition of compound and solvent and rotten, also can be under alap temperature drying under reduced pressure.Under the high situation of soltion viscosity,, will reduce in addition, can pour into a mould easily in case at high temperature pour into a mould soltion viscosity with substrate and solution heating.Though there is no particular restriction for the sample path length during for cast, preferred 10～1000 microns.More preferably 100～500 microns.Sample path length is in case thinly just have a tendency that can not keep the ion-conductive membranes shape than 10 microns, and in a single day the trend of the inhomogenous polyelectrolyte membrane of easy formation just arranged than 1000 micron thickness.The method of control solution casting thickness can adopt known method.For example can be coated with device etc. and be applied to certain thickness with spreader, cutter, perhaps with bezel etc. make the cast area certain and under the quantity of solution and concentration control thickness.The solution of cast is removed the film that can access homogeneous under the situation of speed adjusting solvent.For example under the situation of heating, form low temperature in the initial period velocity of evaporation is descended.And under the situation of in non-solvents such as water, flooding, in advance solution is placed appropriate time etc. in air and in the rare gas element, can adjust the setting rate of polymkeric substance.
And sulfonation poly (arylene ether) based compound of the present invention, perhaps can form the sulfonated polyarylene ether compound precursor of the present invention that has the dioxy diphenylene based compound structure of unsulfonated still at least of sulfonation poly (arylene ether) based compound of the present invention or contain the combination of this precursor by sulfonation reaction, be shaped as membranaceous after, while keeping the film shape to carry out under the situation of sulfonation reaction, can make ion-conductive membranes of the present invention.Sulphonating agent as this moment can use above-mentioned various sulphonating agents.In addition also can be with for example opening the sort of gaseous state put down in writing in clear 63-291920 and the special public table 2002-543224 communique or vaporific sulphonating agent sulfonation the spy.
Though ion-conductive membranes of the present invention can be made any thickness as required, preferably approach as far as possible from ionic conductivity.Specifically, preferably be in 5～200 micrometer ranges, more preferably be in 5～50 micrometer ranges, preferably be in 5～20 micrometer ranges.The thickness of ion-conductive membranes is in case thinner than 5 microns, it is difficult that the processing of ion-conductive membranes will become, and the tendency that produces short circuit is arranged under the situation of making fuel cell, and in case above 200 microns, the resistance of ion-conductive membranes will increase, and the power generation characteristics of fuel cell just has the tendency of reduction.Under the situation about using as ion-conductive membranes,, also can make it be transformed into free sulfonic acid by suitable acid treatment though that the sulfonic group in the China ink also comprises is salifiable.In this case, under the heating or under not heating the film that obtains being carried out dip treating in the aqueous solution such as sulfuric acid, hydrochloric acid, also be effective.And the ionic conductance of ion-conductive membranes, preferably be in 1.0 * 10 -3More than the S/cm.Work as ionic conductance, preferably be in 1.0 * 10 -3Under the situation more than the S/cm, in the fuel cell that uses this ion-conductive membranes, can obtain good output, and be lower than 1.0 * 10 -3Under the situation of S/cm, the output of fuel cell has the trend of reduction.
Ion-conductive membranes of the present invention is characterized in that also can being used for the direct methanol fuel cell that acts as a fuel with methyl alcohol.Make mean thickness and be 50 microns film, preferably at the film that is in the following numerical value of 7 mmoles/square metre second with the 5M methanol solution 25 ℃ of methyl alcohol penetrate speed of measuring down.More preferably penetration speed was in below 74 mmoles/square metre second, and preferred especially penetration speed was in below 71 mmoles/square metre second.Because will show good especially power generation characteristics when showing this methanol permeability.Wherein, the thickness penetration speed of the different methyl alcohol trend that generally just has difference to increase in a single day.Therefore, though in the evaluation of methanol permeability, the sample of making 50 microns of mean thicknesss has been done evaluation, when the battery that in fact acts as a fuel uses with ion-conductive membranes, special restriction should not arranged for thickness.In fact the film that so-called mean thickness is 50 microns is meant that mean thickness is in 48 microns to 52 micrometer ranges.
(complex body)
Ion-conductive membranes drought films by the invention described above is set etc. can access the complex body of ion-conductive membranes of the present invention or film etc. and electrode.As the preparation method of this species complex, the known method of can adopting is over carried out, and for example has to be coated with tackiness agent with the method for ion-conductive membranes and electrode sticking or with ion-conductive membranes and the hot pressed method of electrode on electrode surface.Wherein preferred on electrode surface coating with the tackiness agent that contains sulfonic poly (arylene ether) based compound or its resin combination as main component of the present invention, with the method for its adhesion.It is believed that this is because the tackiness of ion-conductive membranes and electrode improves, and the ionic conductivity of ion-conductive membranes is damaged the cause that reduces.
(fuel cell)
Use the conjugant of above-mentioned ion-conductive membranes or film etc. and electrode, also can make fuel cell.Ion-conductive membranes of the present invention or film etc., because thermotolerance, processibility and ionic conductivity are all good, so can turn round under the withstand high temperatures, preparation can provide the fuel cell with good output easily.
[embodiment]
Below specify the present invention with embodiment, but the present invention is not subjected to the restriction of these embodiment.Wherein various mensuration are as follows.
Soltion viscosity: polymer powder is dissolved in the N-Methyl pyrrolidone to 0.5g/dl concentration, (ウ ベ ロ-デ) the type viscometer carries out viscosimetric analysis with black Baird in 30 ℃ thermostatic bath, with logarithm viscosity (ln[ta/tb]/c) carried out estimating (ta: the second number that sample solution falls, tb: the second number that solvent falls, c: polymer concentration).
TGA: the thermogravimetric with Shimadzu Seisakusho Ltd.'s preparation measures devise a stratagem (TGA-50), has carried out measuring (kept 30 minutes at 150 ℃ in the way, fully remove moisture content) with 10 ℃ of/minute heat-up rates in argon gas atmosphere.
The mensuration of ionic conductivity: platinum line (0.2 millimeter of diameter) is pressed on the surface of short volume shape sample with homemade probe (tetrafluoroethylene system), sample is remained on climatic chamber (the Na ガ ノ of Co., Ltd. science machinery production institute of 80 ℃ of 95% relative humidity, LH-20-01) in, utilize 1250 frequency response analyzers of SOLARTRON company to measure impedance between the platinum line.Pole distance is changed down measure, utilizes following formula, calculate the electric conductivity that to contact between film and platinum line after the impedance elimination by pole distance and the slope of mapping from the impedance measuring value of C-C curve estimation.
Wide [the cm] * thickness of electric conductivity [S/cm]=1/ film [cm] * impedance interpolar slope [Ω/cm]
The measuring method of dioxy diphenylene amount in the polymer backbone structure: the fashionable monomer addition of polymer poly though can calculate dioxy diphenylene amount in the skeleton structure by it, also can be measured the dioxy diphenylene amount of obtaining by H-NMR than under the clear and definite situation.At this moment, structured data such as the sulfonic acid base unit weight of obtaining from loading capacity (IEC) and infrared spectra also can be with for referencial use.
H-NMR measures: use the Gemini-200NMR optical splitter of Varian company, measure under DMSO-d6 solution and 80 ℃.
Methyl alcohol penetrate speed: the liquid fuel penetration speed of ion-exchange membrane, measure with the penetration speed form of methyl alcohol in order to following method.The ion-exchange membrane (mean thickness being in the film that 48 microns to 52 microns film is decided to be 50 microns of mean thicknesss) that will flood 24 hours 50 microns of mean thicknesss in 5M (mol) methanol aqueous solution of adjusting under 25 ℃ is clamped in the H type battery, inject the methanol aqueous solution of 100 milliliters of 5M in a side of battery, inject 100 milliliters of ultrapure waters (18M Ω cm) in another battery, stir the battery of both sides down on one side at 25 ℃, it is spread on one side by ion-exchange membrane in ultrapure water, calculate (area of ion-exchange is 2.0 square centimeters) after the amount with gas Chromatographic Determination diffusion methyl alcohol.
Loading capacity (IEC): the example weight at weighing dry night under nitrogen atmosphere, after the aqueous sodium hydroxide solution stir process, obtain with the aqueous hydrochloric acid back titration.
Generating is estimated: the carbon that supports the Pt/Ru catalyzer (TEC61E54 of Tianzhonggui Metal Industrial Co., Ltd) go up add a small amount of ultrapure water and Virahol moistening after, the 20% Na Off イ オ Application solution (numbering: SE-20192), make to support that weight ratio reaches 2.5: 1 between Pt/Ru catalyzer and Na Off イ オ Application that adds E.I.Du Pont Company's preparation.Then, under agitation prepared anode catalyzer thickener.Utilize silk screen print method this catalyzer thickener to be coated on the carbon paper TGPH-060 of the eastern レ Co., Ltd. preparation that forms gas diffusion layers, reach 2 milligrams/square centimeter after making platinum adhesion amount drying, made and be attached with the carbon paper of anode with electrode catalyst layer.And the carbon that supports the Pt catalyzer (TEC10V40E of Tianzhonggui Metal Industrial Co., Ltd) go up to add a small amount of ultrapure water and Virahol moistening after, the 20% Na Off イ オ Application solution (numbering: SE-20192) that adds E.I.Du Pont Company's preparation, make that weight ratio reaches 2.5: 1 between the carbon that supports the Pt catalyzer and Na Off イ オ Application, prepared the catalyst for cathode thickener under stirring.This catalyzer thickener is coated on the carbon paper TGPH-060 through eastern レ Co., Ltd. preparation of hydrophobic treatment, reaches 1 milligram/square centimeter after making platinum adhesion amount drying, made and be attached with the carbon paper of negative electrode with electrode catalyst layer.Membrane sample is clamped between above-mentioned two kinds of carbon papers that have an electrode catalyst layer, electrode catalyst layer is contacted with membrane sample, by means of pressure sintering under 130 ℃ with 8MPa hot pressing 3 minutes, make film-electrode bond.This conjugant is assembled in electrochemistry Co., Ltd. estimates among the fuel cell FC25-02SP of usefulness, utilize fuel cell power generation trier (Co., Ltd.'s Dongyang technology preparation) to carry out power generation test.Generating is under 40 ℃, Yi Bian anode and negative electrode are supplied with the 2 mol methanol aqueous solutions (1.5 ml/min) of adjusting to 40 ℃ and high purity oxygen gas (80 ml/min) Yi Bian carry out respectively.
(embodiment 1)
Measure 5.2335 gram (0.01065 moles) 3,3 '-disulfo-4,4 '-dichloro diphenyl sulfone disodium salt (simple number: S-DCDPS), 2.3323 the gram (0.013559 mole) 2.6-dichlorobenzonitriles (suspension points: DCBN), 4.5086 the gram (0.02421 moles) 4,4 '-bis-phenol, 3.8484 gram (0.02784 mole) salt of wormwood and 2.61 mol sieve place 100 milliliters of four-hole boiling flasks, feed nitrogen.Add 35 milliliters of NMP, after stirring one hour under 150 ℃, make temperature of reaction rise to 195～200 ℃, continue reaction and making the viscosity of system rise to purpose numerical value (5 hours).After placing cooling, remove settled molecular sieve, make it in water, be precipitated as strip.The polymkeric substance that obtains washed in ebullient water after 1 hour, drying.The logarithm viscosity of polymkeric substance is 1.24.
With 1 the gram polymer dissolution in 5 milliliters of NMP, on the sheet glass of hot plate, be poured into about 200 micron thickness, the distillation remove NMP to form membranaceous after, in water the dipping one night more than.The film that obtains is handled 1 hour except that after desalting with boiled water in dilute sulphuric acid (300 milliliters in 6 milliliters of the vitriol oils and water), removed the disacidify composition in 1 hour with boiling pure water again.The IR spectrogram that obtains film is shown in Fig. 1.After measuring the ionic conductivity of this film, show the numerical value of 0.17S/cm.It is that the temperature that reduces of 3% weight (with 200 ℃ example weights as benchmark) is 389 ℃ that the thermogravimetric of this film measures definite value.
(embodiment 2)
Except with 3,3 '-disulfo-4,4 '-dichloro diphenyl sulfone disodium salt (simple number: S-DCDPS) be decided to be 3.9251 the gram (0.00799 mole) and with the 2.6-dichlorobenzonitrile (suspension points: DCBN) be decided to be 2.7904 the gram (0.01622 mole) in addition, carry out polymerization similarly to Example 1, obtained polymkeric substance.The logarithm viscosity of polymkeric substance is 1.58.
To adjust the polymers soln of concentration, be cast on the sheet glass on the hot plate and adjust thickness, distillation remove NMP to form membranaceous after, dipping is more than one night in water.Be adjusted to mean thickness and be 50 microns film.The film that obtains is handled 1 hour except that after desalting in dilute sulphuric acid (300 milliliters in 6 milliliters of the vitriol oils and water), removed the disacidify composition in 1 hour with the pure water dipping again.After measuring the ionic conductivity of this film, show the numerical value of 0.11S/cm.It is that the temperature that reduces of 3% weight (with the example weight under 200 ℃ as benchmark) is 389 ℃ that the thermogravimetric of this film measures definite value.The penetration speed of methyl alcohol is 3.92 mmoles/square metre second.Even the film that obtains was flooded 5 hours in ebullient water, it is good that the form of film still keeps.
(embodiment 3)
In embodiment 2, synthesized polymkeric substance changing under the condition of S-DCDPS and the ratio of DCBN, and carried out same evaluation.The results are shown in the table 1.And Fig. 2 and Fig. 3 show and use S-DCDPS: DCBN=38: the IR spectrum of the polymeric film that 62 (mol ratios) obtain and TGA record diagram.
Table 1
Monomer ratio (mol ratio) Reaction times (hour) Logarithm viscosity (dl/g) Electric conductivity (S/cm) 3% decrement temperature (℃) Methyl alcohol penetrate speed (mmol/m 2??·sec)
??S-DCDPS ? ??DCBN ?
??22 ??78 ??3 ??1.37 ??0.03 ??379 ??2.27
??23 ??77 ??6 ??1.00 ??0.04 ??367 ??2.60
??28 ??72 ??6 ??1.09 ??0.07 ??385 ??3.87
??38 ??62 ??5 ??0.77 ??0.14 ??380 ??5.68
??50 ??50 ??9 ??1.15 ??0.22 ??369 ??8.45
??60 ??40 ??6 ??0.99 ??0.27 ??382 ??10.5
??70 ??30 ??11 ??1.10 ??0.36 ??351 ??12.0
??80 ??20 ??9 ??0.84 ??0.45 ??324 ??14.5
(embodiment 4)
In embodiment 3, the ratio of S-DCDPS and DCBN is modified to S-DCDPS: DCBN=48: carried out same evaluation under the condition of 52 (mol ratios). DOD 4,4 base unit weight in this polymer backbone structure is 54.3 weight %.The logarithm viscosity of polymkeric substance is 0.92.The IEC that the film of making obtains through titration is 2.19meq/g, and ionic conductance is 0.28S/cm, and the temperature that 3% weight reduces is 381 ℃.Though this film has been placed 4 hours under 130 ℃ of saturated vapo(u)r atmospheric conditions, but still kept the film form.
(reference examples 1)
After not synthesized polymkeric substance under the condition with DCBN among the embodiment 1, the polymkeric substance that obtains becomes water miscible, can not carry out the evaluation of ion-conductive membranes.
(reference examples 2)
After not synthesized polymkeric substance under the condition with S-DCDPS among the embodiment 1, be under 2.5 hours, obtained logarithm viscosity and be 2.76 polymkeric substance in the reaction times.The ionic conductivity of film is in to be measured below the lower limit.
(reference examples 3)
With 4 of 3,8934 grams (0.013559 mole), after 4 '-dichloro diphenyl sulfone replaced DCBN polymerization among the embodiment 1, obtain logarithm viscosity and be 0.70 polymkeric substance needed 16 hours.
(reference examples 4)
Among the embodiment 3, with 11.872 gram (0.02417 mole) S-DCDPS, 8.482 gram (0.02954 moles) 4,4 '-dichloro diphenyl sulfone (suspension points: DCDPS), 10.000 the gram (0.05370 moles) 4,4 '-bis-phenol and 8.536 gram (0.06176 mole) salt of wormwood, NMP100ml has carried out same evaluation.DOD 4,4 base unit weight in this polymer backbone structure is 46.0 weight %.Polymeric logarithm viscosity was 0.71 in 11 hours.The IEC that the film of making obtains through titration is 1.69meq/g, and ionic conductance is 0.19S/cm, and the temperature that 3% weight reduces is 372 ℃.This film is found the film fusion after having placed 4 hours under 130 ℃ of saturated vapo(u)r atmospheric conditions, the form collapse.
(embodiment 5)
In comparative example 4,, carried out same evaluation with 10.025 gram (0.02041 mole) S-DCDPS, 1.851 gram (0.00644 mole) DCDPS and 4.619 gram (0.02685 mole) DCBN.DOD 4,4 base unit weight in this polymer backbone structure is 53.7 weight %.Polymeric logarithm viscosity was 0.62 in 7 hours.The IEC that the film of making obtains through titration is 1.73meq/g, and ionic conductance is 0.16S/cm, and the temperature that 3% weight reduces is 372 ℃.Though this film was placed 4 hours under 130 ℃ of saturated vapo(u)r atmospheric conditions, did not find the film fusion.
(embodiment 6)
Measure 14.029 gram (0.08156 mole) DCBN, 15.1873 gram (0.08156 moles) 4,4 '-bis-phenol and 12.963 gram (0.09379 mole) salt of wormwood place 300 milliliters of four-hole boiling flasks, feed nitrogen.Add 110 milliliters of NMP, after stirring one hour under 150 ℃, make temperature of reaction rise to 195～200 ℃, continue reaction and making the viscosity of system rise to purpose numerical value (about 2 hours).After placing cooling, make the polymkeric substance that obtains in water, be precipitated as strip.The polymkeric substance that obtains washed in ebullient water after 1 hour, drying.The logarithm viscosity of polymkeric substance is 1.65.The DOD 4,4 base unit weight of this polymkeric substance is 64.6 weight %.With 1 gram polymkeric substance with 20 milliliters of vitriol oils 65 ℃ of following heated and stirred 7 hours.Polymers soln is injected water reclaim polymkeric substance, be washed with water to neutral after drying repeatedly.The receipts amount of the polymkeric substance that obtains is 1.1 grams.The IEC that obtains through titration is 1.61meq/g.Though this sample was placed 4 hours under 130 ℃ of saturated vapo(u)r atmospheric conditions, has not been found that the molten form of film has any variation.
(embodiment 7)
Measure 14.332 grams (0.02917, mole) S-DCDPS, 6.387 gram (0.03713 mole) DCBN, 12.3468 gram (0.06631 moles) 4,4 '-biphenyl and 10.5387 gram (0.07625 mole) salt of wormwood place 300 milliliters of four-hole boiling flasks, feed nitrogen.Add 110 milliliters of NMP, after stirring 1 hour under 150 ℃, make temperature of reaction rise to 195～200 ℃, continue reaction and making the viscosity of system rise to purpose numerical value (about 6 hours).After placing cooling, make the polymkeric substance that obtains in water, be precipitated as strip.The polymkeric substance that obtains washed in ebullient water after 1 hour, drying.The logarithm viscosity of polymkeric substance is 1.06.With 1 the gram polymer dissolution in 5 milliliters of NMP, be cast in about 200 micron thickness on the glass substrate on the hot plate, the distillation remove NMP to form membranaceous after, in water the dipping one night more than.The film that obtains at room temperature flooded 90 minutes in the vitriol oil.Removed the disacidify composition in 1 hour with boiling pure water, after the drying, the IEC that this film obtains through titration is 2.43meq/g.The numerical value that ionic conductivity is measured the back demonstration is 0.36S/cm.It is 331 ℃ that 3% weight that the flow measurement of this film thermogravimetric obtains reduces temperature (with the weight of 200 ℃ of following samples as benchmark).The IR spectrum of this film is shown in Fig. 4.
(embodiment 8)
In the polymerization of embodiment 7, DCBN is decided to be 9.237 grams (0.05370 mole), 4,4 '-bis-phenol is decided to be that 10.000 gram (0.05370 mole), salt of wormwood are decided to be 8.536 grams (0.06176 mole), NMP is decided to be 100 milliliters, reacts equally.The logarithm viscosity of 3 hours polymerization post polymerization things is 2.76.To in the vitriol oil, flood 63 hours under the 1 gram polymkeric substance room temperature.Removed the disacidify composition in 1 hour with boiling pure water, after the drying, the IEC that this film obtains through titration is 1.90meq/g.
(embodiment 9)
With the polymkeric substance that embodiment 8 obtains, made film similarly to Example 7.The film that obtains has at room temperature been flooded in the vitriol oil 90 hours.Removed the disacidify composition in 1 hour with boiling pure water, after the drying, the IEC that obtains through titration is 1.17meq/g, and the mensuration ionic conductivity is 0.011S/cm.
(reference examples 5)
The ionic conductivity of the vitriol oil dipping cephacoria that embodiment 9 obtains is in to be measured below the lower limit.
(embodiment 10)
In aggregation container, measure 1.500 grams (5.389 * 10 -3The mole) 3,3 ', 4,4 '-tetramino sulfobenzide (suspension points: TAS), 1.445 the gram (5.389 * 10 -3Mole) 2,5-dicarboxyl benzene sulfonic acid sodium salt (suspension points: STA, purity 99%), 20.48 gram Tripyrophosphoric acid (five phosphorus oxide content 75%) and 16.41 grams, five phosphorus oxide.Feed nitrogen, on oil bath slowly stir on one side, be warming up to 100 ℃ on one side.After keeping 1 hour under 100 ℃, be warming up to 150 ℃ of polymerizations 1 hour, be warming up to 200 ℃ of polymerizations 4 hours.Polymerization stops the back and places cooling, adds entry and takes out polymkeric substance, and the water repetitive scrubbing is to pH test paper neutrality in the family expenses mixing machine.The polymkeric substance that obtains spends the night at 80 ℃ of following drying under reduced pressure.The logarithm viscosity of polymkeric substance is 1.71.The polybenzimidazole polymer that will contain this acidic-group is called TTS100.
Measure 5.9472 gram (0.01211 mole) S-DCDPS, 2.0824 gram (0.01211 mole) DCBN, 4.5086 gram (0.02421 moles) 4 in 100 milliliters of four-hole boiling flasks, 4 '-bis-phenol and 3.8484 gram (0.02784 mole) salt of wormwood feed nitrogen.Add 35 milliliters of NMP, after stirring 1 hour under 150 ℃, make temperature of reaction rise to 195～200 ℃, continue reaction and making the viscosity of system rise to purpose numerical value (about 5 hours).After placing cooling, make it in water, be precipitated as strip.After the polymkeric substance that obtains is cleaned with water retting repeatedly, drying.The logarithm viscosity of polymkeric substance is 1.24.This polymkeric substance is called S-DCDPS: DCBN=1: 1 polymkeric substance.
Be heated to 170 ℃ in oil bath 3 gram TTS100 are dissolved among 15 milliliters of NMP, make 3 gram S-DCDPS: DCBN=1 under the room temperature: 1 polymer dissolution is mixed the solution that obtains homogeneous with two kinds of solution under the room temperature in 9 milliliters of NMP.Making this solution on sheet glass, be cast to about 500 micron thickness on the hot plate, NMP is evaporated.After film peeled off from sheet glass, after dipping spends the night in water, handle 1 hour with 70 ℃ of 1M aqueous sulfuric acids after, ionic conductivity mensuration film is made in washing repeatedly.Ionic conduction degree under 80 ℃ of 95% relative humidity is 0.004S/cm.The penetration speed of methyl alcohol is 1.15 mmoles/square metre second.To be cut into 1 centimetre of this film of quadrate and in 100 ℃ of hot water, flood after 1 hour, not find the variation of film shape.Film is carried out thermogravimetric flow measurement result is, it is 372 ℃ that 3% weight reduces temperature (with the example weight under 200 ℃ as benchmark). the IEC that titration is obtained is 2.18.
(embodiment 11)
Similarly to Example 10, synthesized S-DCDPS: DCBN=38: 62 polymkeric substance (the logarithm viscosity of the polymkeric substance that obtains is 1.31), when membrane prepare,, 1 gram TTS100 restrains among the NMP except being dissolved in 10, restrain S-DCDPS: DCBN=38 with 4: 62 polymer dissolution has been carried out same evaluation with embodiment 10 beyond 10 restrain among the NMP.Ionic conduction degree under 80 ℃ of 95% relative humidity is 0.034S/cm.The penetration speed of methyl alcohol is 2.62 mmoles/square metre second.To be cut into 1 centimetre of this film of quadrate and in 100 ℃ of hot water, flood after 1 hour, not find the variation of film shape.Film is carried out thermogravimetric flow measurement result is, it is 357 ℃ that 3% weight reduces temperature (with the example weight under 200 ℃ as benchmark).The IEC that titration is obtained is 1.81.
(embodiment 12)
Similarly to Example 10, synthesized S-DCDPS: DCBN=70: 30 polymkeric substance (the logarithm viscosity of the polymkeric substance that obtains is 1.02), when membrane prepare,, 1 gram TTS100 restrains among the NMP except being dissolved in 10, restrain S-DCDPS: DCBN=70 with 4: 30 polymer dissolution has been carried out same evaluation with embodiment 10 beyond 10 restrain among the NMP.Ionic conduction degree under 80 ℃ of 95% relative humidity is 0.16S/cm.To be cut into 1 centimetre of this film of quadrate and in 100 ℃ of hot water, flood after 1 hour, not find the variation of film shape.Film is carried out thermogravimetric flow measurement result is, it is 376 ℃ that 3% weight reduces temperature (with the example weight under 200 ℃ as benchmark). the IEC that titration is obtained is 2.60.
(reference examples 6)
Only use embodiment 12 synthetic S-DCDPS: DCBN=70: 30 polymer manufacture film, the ionic conduction degree under 80 ℃ of 95% relative humidity is 0.38S/cm.But after will being cut into 1 centimetre of this film of quadrate and in 100 ℃ of hot water, flooding, the remarkable swelling of film, shape collapse.
(reference examples 7)
In embodiment 12, only do not synthesized polybenzimidazole with TASz with STA.The logarithm viscosity that obtains polymkeric substance is 2.33.Made the S-DCDPS that forms similarly to Example 10 with this polymkeric substance: DCBN=70: the composition of 30 polymkeric substance is also estimated.But in this case, mix when the nmp solution, in order to find with the sedimentary behavior of sulfonic group polymer complex form, must be with S-DCDPS: DCBN=70: 30 polymkeric substance triethylamineization be made homogeneous solution, removes amine salt after the membranization and makes the purpose compound.And the ionic conduction degree under 80 ℃ of 95% relative humidity shows the low numerical value that reaches 0.009S/cm.
(embodiment 13)
8.98 gram (0.01773 mole) 4,4 '-two (4-Phenoxyphenyl) phenyl ether and 3.60 gram (0.01773 mole) m-phthaloyl chlorides are dissolved in 200 milliliters of ethylene dichloride, and the cooling back adds 6.15 gram (0.0461 mole) aluminum chloride in ice bath.Stir after 1 hour, remove ice bath and at room temperature proceed polymerization in 17 hours.Reactant injects methyl alcohol and takes out polymkeric substance, and continue with behind the hot water repetitive scrubbing back in dilute hydrochloric acid, drying.The logarithm viscosity that the polymkeric substance that obtains is measured in the vitriol oil is 1.01.The DOD 4,4 base unit weight of this polymer backbone structure is 57.9 weight %.
1 gram polymer dissolution in 20 milliliters of vitriol oils, was stirred 5 hours under the room temperature.Polymers soln is injected water reclaim polymkeric substance, repetitive scrubbing to washing lotion is neutral after drying.The receipts amount of the polymkeric substance that obtains is 1.0 grams.With 500 milligrams of sulfonated polymers stirring and dissolving in 2.5 milliliters of NMP, be to be poured on the heated glass plate on the hot plate 200 micron thickness under the room temperature, distillation has obtained film with water retting after removing and desolvating.Film carried out 1 hour dip treating in 100 ℃ of dilute sulphuric acids after, in 100 ℃ of pure water, carry out 1 hour dip treating again.Loading capacity is 2.02meq/g.Ionic conduction degree under 80 ℃ of 98% relative humidity is 0.19S/cm.The logarithm viscosity of measuring in nmp solution is 1.67.In the mensuration of TGA, be that to reduce temperature be 346 ℃ for 3% weight of benchmark with the weight under 200 ℃.Methyl alcohol penetrate speed is 6.81 mmoles/square metre second.To be cut into 1 centimetre of this film of quadrate and in 100 ℃ of hot water, flood after 1 hour, not find the variation of film shape.
(embodiment 14)
Restrain (0.01065 moles) 3 with 6.2992 among the embodiment 1,3 '-disulfo-4,4 '-dichloro-benzophenone disodium salt conductor S-DCDPS has carried out polymerization in 20 hours.The logarithm viscosity that obtains polymkeric substance is 0.67.After the ionic conductivity of the film of Zhi Zuoing is measured similarly to Example 1, show 0.14S/cm numerical value.It is 358 ℃ that this film 3% weight in the thermogravimetric flow measurement reduces temperature (making benchmark with 200 ℃ of following example weights measures)
(embodiment 15)
Synthesized S-DCDPS: DCBN=55 similarly to Example 3: 45 polymkeric substance.Made film similarly to Example 3, dipping is after 3 hours under the room temperature in the vitriol oil with the film that obtains, and the film that washing obtains has been kept original shape.Loading capacity is 3.15meq/g.The ionic conductivity of this film is 0.56S/cm under 80 ℃ of 95% relative humidity after measuring, and shows the value of 0.02S/cm in 50% relative humidity condition.3% weight minimizing temperature (is benchmark with the weight under 200 ℃) is 361 ℃ in the thermogravimetric flow measurement of this film.Methyl alcohol penetrate speed is 9.97 mmoles/square metre second.Even the film that obtains was flooded 5 hours in ebullient water, has also kept the film shape well.
(embodiment 16)
Synthesized S-DCDPS: DCBN=80 similarly to Example 15: 20 polymkeric substance.Dipping is after 1 hour under the room temperature in the vitriol oil with the film that obtains, and the loading capacity of the polymkeric substance that washing obtains is 3.37meq/g.The polymkeric substance that use obtains replaces S-DCDPS: DCBN=38 among the embodiment 11: 62 polymkeric substance, made composite membrane with TTS100.The ionic conduction degree of the film that obtains under 80 ℃ of 95% relative humidity is 0.21S/cm.Methyl alcohol penetrate speed is 11.5 mmoles/square metre second.To be cut into 1 centimetre of this film of quadrate and in 100 ℃ of hot water, flood 1 hour, but not find the film change of shape.3% weight minimizing temperature (is benchmark with the weight under 200 ℃) is 371 ℃ in the thermogravimetric flow measurement of film.
(embodiment 17)
S-DCDPS among the embodiment 11: DCBN=38: 62 polymkeric substance, the polymkeric substance that obtains with embodiment 13 replaces, and has carried out same evaluation.Ionic conduction degree under 80 ℃ of 95% relative humidity is 0.051S/cm.Methyl alcohol penetrate speed is 3.03 mmoles/square metre second.To be cut into 1 centimetre of this film of quadrate and in 100 ℃ of hot water, flood 1 hour, but not find the film change of shape.3% weight minimizing temperature (is benchmark with the weight under 200 ℃) is 366 ℃ in the thermogravimetric flow measurement of film.The IEC that titration is obtained is 1.39.
(embodiment 18)
Except using 5.5199 gram dihydroxyphenyl propane conductors 4, beyond 4 '-bis-phenol, carried out polymerization similarly to Example 2, obtained polymkeric substance.The logarithm viscosity of polymkeric substance is 1.31.Measure the numerical value that shows 0.14S/cm to making film forming ionic conductivity.3% weight minimizing temperature is 362 ℃ in the thermogravimetric flow measurement of this film.Methyl alcohol penetrate speed is 6.61 mmoles/square metre second.Even the film that obtains flooded 5 hours, also keep the shape of film well in ebullient water.
(embodiment 19)
Among the embodiment 11 2, the 6-dichlorobenzonitrile has synthesized polymkeric substance with the 2,4 difluorobenzene formonitrile HCN replacement of equimolar amount.The logarithm viscosity of polymkeric substance is 0.61.Measure the numerical value that shows 0.11S/cm to making film forming ionic conductivity.3% weight minimizing temperature is 371 ℃ in the thermogravimetric flow measurement of this film.Methyl alcohol penetrate speed is 4.24 mmoles/square metre second.Even the film that obtains flooded 5 hours, also kept the shape of film well in ebullient hot water.
(embodiment 20)
Among the embodiment 3 in order to S-DCDPS: DCBN=38: the polymkeric substance that 62 (mol ratios) obtain has been made film, and has carried out generating and estimated.What obtain the results are shown in Fig. 5.After using same evaluation of Na Off イ オ Application 112 (registered trademark) film of E.I.Du Pont Company's preparation, find to show good power generation characteristics through contrast.
Should be known in the each point that above disclosed embodiment and embodiment are not limited to enumerate.Though scope of the present invention should comprise not explanation in the above, but is illustrated by protection scope of the present invention, with protection domain equalization and the whole changes that are within its scope.
Need to prove and " abovely, following " include end points among the present invention.

Claims (39)

1. a polyarylene ether compound is characterized in that, contains the polymkeric substance constituent by general formula (1) and general formula (2) expression,
Figure A2003801009960002C1
Ar represents divalent aryl in the formula, and Y represents sulfonic group or ketone group, X 1Expression H or monovalent cation kind, Ar ' represents divalent aryl.
2. polyarylene ether compound according to claim 1 is characterized in that, one of them contains-the Ph-Ph-group at least for described Ar and Ar '.
3. polyarylene ether compound according to claim 1 is characterized in that, in removing the sulfonic skeleton structure that combines ,-O-Ar-O-unit or-O-Ar '-O-unit or its sum of the two account in polymer architecture more than the 52 weight %.
4. polyarylene ether compound according to claim 2 is characterized in that, contains the polymkeric substance constituent by general formula (3) and general formula (4) expression,
Figure A2003801009960002C2
X wherein 2Expression H or monovalent cation kind.
5. polyarylene ether compound according to claim 1 is characterized in that, also contains the polymkeric substance constituent by general formula (5) and general formula (6) expression,
Wherein in formula (5) and (6), n 1, n 2And n 3The sulfonic group of representing each aromatic ring is in conjunction with number, n 1, n 2And n 3Independently be 0～2 integer separately, n 2+ n 3It is 1～4 integer.X 3Be from-CN ,-COOY ,-COONR 2In one or more groups of selecting, Y represents hydrogen, atoms metal, various ammonium, R represents one or more groups of selecting from hydrogen and alkyl; Z 1And Z 2Be one or more functional groups that select rudimentary carbonyl, nitro, amino, hydroxyl and the halogen atom of the rudimentary carboxyl of the lower alkoxy of the low alkyl group from 1～6 carbon atom, 1～6 carbon atom, 1～6 carbon atom, 1～6 carbon atom; r 1And r 2Represent Z on each aromatic ring 1And Z 2Separately in conjunction with number, r 1And r 2Be independently to be 0～4 integer separately, n 2+ r 1≤ 4, n 3+ r 2≤ 4.
6. polyarylene ether compound according to claim 5 is characterized in that, also contains the polymkeric substance constituent of general formula (7) expression,
Figure A2003801009960003C2
Wherein in formula (7), n 4And n 5Represent the sulfonic of each aromatic ring, n in conjunction with number 4And n 5Independently be 0～2 integer separately, n 4+ n 5It is 1～4 integer.
7. polyarylene ether compound according to claim 1 is characterized in that sulfonic group content is in 0.3～3.5meq/g scope.
8. polyarylene ether compound according to claim 5 is characterized in that sulfonic group content is in 0.2～6.0meq/g scope.
9. a polyarylene ether compound is characterized in that, is that (poly (arylene ether) O-Ph-Ph-O-) is to have imported sulfonic structure in the polymer to containing the above dioxy diphenylene of 52 weight % unit in the polymer architecture.
10. polyarylene ether compound according to claim 9 is characterized in that, contains the polymkeric substance constituent by general formula (3) and general formula (4) expression,
X wherein 2Expression H or monovalent cation kind.
11. polyarylene ether compound according to claim 9 is characterized in that, also contains the polymkeric substance constituent by general formula (5) and general formula (6) expression,
Figure A2003801009960004C2
Wherein in formula (5) and (6), n 1, n 2And n 3The sulfonic group of representing each aromatic ring is in conjunction with number, n 1, n 2And n 3Independently be 0～2 integer separately, n 2+ n 3Be 1～4 integer, X 3Be from-CN ,-COOY ,-COONR 2In one or more groups of selecting, Y represents hydrogen, atoms metal, various ammonium, R represents one or more groups of selecting, Z from hydrogen and alkyl 1And Z 2Be one or more functional groups that select rudimentary carbonyl, nitro, amino, hydroxyl and the halogen atom of the rudimentary carboxyl of the lower alkoxy of the low alkyl group from 1～6 carbon atom, 1～6 carbon atom, 1～6 carbon atom, 1～6 carbon atom, r 1And r 2Represent Z on each aromatic ring 1And Z 2Separately in conjunction with number, r 1And r 2Be independently to be 0～4 integer separately, n 2+ r 1≤ 4, n 3+ r 2≤ 4.
12. polyarylene ether compound according to claim 11 is characterized in that, also contains the polymkeric substance constituent of general formula (7) expression,
Figure A2003801009960005C1
Wherein in formula (7), n 4And n 5The sulfonic group of representing each aromatic ring is in conjunction with number, n 4And n 5Independently be 0～2 integer separately, n 4+ n 5It is 1～4 integer.
13. polyarylene ether compound according to claim 9 is characterized in that sulfonic group content is in 0.2～6.0meq/g scope.
14. the preparation method of the described polyarylene ether compound of claim 1 is characterized in that, by containing polymerization as monomer by the aromatic nucleophilie nuclear substituting reaction of the compound of general formula (13) and (14) expression and bis-phenol based compound,
Figure A2003801009960005C2
Y wherein 2Expression sulfonic group or ketone group, X 6Expression monovalent cation kind, Z 4Expression elemental chlorine or fluorine.
15. the preparation method of the described polyarylene ether compound of claim 9 is characterized in that, by contain the polymerization by the aromatic nucleophilie nuclear substituting reaction of the compound of general formula (13) and (14) expression and bis-phenol based compound as monomer.
Figure A2003801009960005C3
Y wherein 2Expression sulfonic group or ketone group, X 6Expression monovalent cation kind, Z 4Expression elemental chlorine or fluorine.
16. a composition is characterized in that, contains the described polyarylene ether compound of 50～100 weight % claims 1.
17. a composition is characterized in that, contains the described polyarylene ether compound of 50～100 weight % claims 9.
18. a composition is characterized in that, contains: comprise polybenzimidazole based compound and the described polyarylene ether compound of claim 1 by the polymkeric substance constituent of general formula (8) expression,
M in the formula 1The integer of expression 1 to 4, R 1Expression can form the tetravalence aromatics combining unit of imidazole ring, R 2Expression divalent aromatic combining unit, R 1And R 2All both can be the monocycle of aromatic ring, also can be the conjugant or the condensed ring of a plurality of aromatic rings, also stable substituting group, Z can be arranged 3Expression sulfonic group and/or phosphonate group, its part also can form the salt structure.
19. a composition is characterized in that, contains: comprise polybenzimidazole based compound and the described polyarylene ether compound of claim 9 by the polymkeric substance constituent of general formula (8) expression,
Figure A2003801009960006C2
M in the formula 1The integer of expression 1 to 4, R 1Expression can form the tetravalence aromatics combining unit of imidazole ring, R 2Expression divalent aromatic combining unit, R 1And R 2All both can be the monocycle of aromatic ring, also can be the conjugant or the condensed ring of a plurality of aromatic rings, also stable substituting group, Z can be arranged 3Expression sulfonic group and/or phosphonate group, its part also can form the salt structure.
20. composition according to claim 18 is characterized in that, described polybenzimidazole based compound is with (9): (10)=n 6: (1-n 6) mol ratio contains the polymkeric substance constituent by general formula (9) and (10) expression,
M in the formula 2The integer of expression 1 to 4, Ar " expression divalent aromatic combining unit, X 4Be from-O-,-SO 2-,-C (CH 3) 2-,-C (CF 3) 2-and-more than one groups of selecting among the OphO-, Ph represents divalent aromatic combining unit, 0.2≤n 6≤ 1.0.
21. composition according to claim 19 is characterized in that, described polybenzimidazole based compound is with (9): (10)=n 6: (1-n 6) mol ratio contains the polymkeric substance constituent by general formula (9) and (10) expression,
M in the formula 2The integer of expression 1 to 4, Ar " expression divalent aromatic combining unit, X 4Be from-O-,-SO 2-,-C (CH 3) 2-,-C (CF 3) 2-and-more than one groups of selecting among the OphO-, Ph represents divalent aromatic combining unit, 0.2≤n 6≤ 1.0.
22. composition according to claim 18 is characterized in that, described polybenzimidazole based compound is with (11): (12)=n 7: (1-n 7) mol ratio contains the polymkeric substance constituent by general formula (11) and (12) expression,
M in the formula 3The integer of expression 1 to 4, Ar represents aromatics combining unit, X 5Be from-O-,-SO 2-,-S-,-CH 2-and-more than one groups of selecting among the OphO-, Ph represents divalent aromatic combining unit, n 7Be in 0-2～1.0 scopes.
23. composition according to claim 19 is characterized in that, described polybenzimidazole based compound is with (11): (12)=n 7: (1-n 7) mol ratio contains the polymkeric substance constituent by general formula (11) and (12) expression,
M in the formula 3The integer of expression 1 to 4, Ar represents aromatics combining unit, X 5Be from-O-,-SO 2-,-S-,-CH 2-and-more than one groups of selecting among the OphO-, Ph represents divalent aromatic combining unit, n 7Be in 0.2～1.0 scope.
24. composition according to claim 16 is characterized in that, the amount of contained sulfonic acid and/or phosphine carboxylic is 0.5～4.0 equivalent/kilogram in described polyarylene ether compound and/or the polybenzimidazole based compound.
25. composition according to claim 17 is characterized in that, the amount of contained sulfonic acid and/or phosphine carboxylic is 0.5～4.0 equivalent/kilogram in described polyarylene ether compound and/or the polybenzimidazole based compound.
26. an ion-conductive membranes is characterized in that, contains the described compound of claim 1.
27. an ion-conductive membranes is characterized in that, contains the described compound of claim 9.
28. ion-conductive membranes according to claim 26 is characterized in that, the methyl alcohol of 5M methanol aqueous solution is to the penetration speed of mean thickness 50 micron membranes, is 7 mmoles/square metre below second under 25 ℃.
29. ion-conductive membranes according to claim 27 is characterized in that, the methyl alcohol of 5M methanol aqueous solution is to the penetration speed of mean thickness 50 micron membranes, is in 7 mmoles/square metre below second under 25 ℃.
30. the preparation method of ion-conductive membranes according to claim 26, it is characterized in that, comprise that cast contains the solution of described compound of claim 1 and solvent, make cast thickness be in the operation in 10～1000 micrometer ranges and will pour into a mould after solution exsiccant operation.
31. the preparation method of ion-conductive membranes according to claim 27, it is characterized in that, comprise that cast contains the solution of described compound of claim 9 and solvent, make cast thickness be in the operation in 10～1000 micrometer ranges and will pour into a mould after solution exsiccant operation.
32. a species complex is characterized in that, comprises described ion-conductive membranes of claim 26 and electrode.
33. a species complex is characterized in that, comprises described ion-conductive membranes of claim 27 and electrode.
34. a fuel cell is characterized in that, contains the described complex body of claim 32.
35. a fuel cell is characterized in that, contains the described complex body of claim 33.
36. fuel cell according to claim 34 is characterized in that, uses methyl alcohol to act as a fuel.
37. fuel cell according to claim 35 is characterized in that, uses methyl alcohol to act as a fuel.
38. a tackiness agent is characterized in that, contains the described compound of claim 1.
39. a tackiness agent is characterized in that, contains the described compound of claim 9.
CNB2003801009963A 2002-10-08 2003-10-07 Polyarylene ether compound containing sulfonic acid group, composition containing same, and method for manufacturing those Expired - Fee Related CN1292015C (en)

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