CN101218281A - Sulfonic acid group-containing polymer, method for producing same, resin composition containing such sulfonic acid group-containing polymer, polymer electrolyte membrane, polymer electrolyte membrane/ - Google Patents

Sulfonic acid group-containing polymer, method for producing same, resin composition containing such sulfonic acid group-containing polymer, polymer electrolyte membrane, polymer electrolyte membrane/ Download PDF

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CN101218281A
CN101218281A CNA2006800207570A CN200680020757A CN101218281A CN 101218281 A CN101218281 A CN 101218281A CN A2006800207570 A CNA2006800207570 A CN A2006800207570A CN 200680020757 A CN200680020757 A CN 200680020757A CN 101218281 A CN101218281 A CN 101218281A
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chemical formula
polymkeric substance
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sulfonic group
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CN101218281B (en
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北村幸太
坂口佳充
山口裕树
山下全广
佐佐井孝介
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Toyobo Co Ltd
Toyo Textile Co Ltd
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Toyo Textile Co Ltd
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Priority claimed from PCT/JP2006/311272 external-priority patent/WO2006132207A1/en
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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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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
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Abstract

Disclosed are a sulfonic acid group-containing polymer having excellent ion conductivity and durability, a method for producing such a sulfonic acid group-containing polymer, a resin composition containing such a sulfonic acid group-containing polymer, a polymer electrolyte membrane, a polymer electrolyte membrane/electrode assembly, and a fuel cell. A first embodiment of the sulfonic acid group-containing polymer contains a constitutional unit represented by the chemical formula (1) below in a molecular chain. [Chemical formula 1] (1) (In the chemical formula (1), X represents a hydrogen or a monovalent cation species; Y represents a sulfonic group or a ketone group; and n represents an arbitrary integer not less than 2.

Description

Contain sulfonic group polymkeric substance and manufacture method thereof, contain this resin combination that contains the sulfonic group polymkeric substance, polymer dielectric film, polymer dielectric film/assembly of electrode, fuel cell
Technical field
The present invention relates to containing sulfonic group polymkeric substance and manufacture method thereof, containing this resin combination that contains the sulfonic group polymkeric substance, polyelectrolyte membrane, polyelectrolyte membrane/assembly of electrode, fuel cell of a kind of novel texture.
Background technology
In recent years, the new generation technology of efficiency and environment excellence enjoys to be gazed at, and with the example of polymer solid electrolyte as the electrochemical appliance of ion-conducting material, is carrying out the exploitation of water electrolyzer and fuel cell as replacing liquid electrolyte.Use has the polymer electrolyte fuel cell of polymer solid electrolyte, owing to have the energy density height and compare with the fuel cell of other modes that thereby operating temperature is low start, stop features such as easy, therefore, carrying out as electromobile and disperseing the exploitation of the supply unit of generating etc.The bonding resin of using as the polyelectrolyte membrane that is used for above-mentioned water electrolyzer and fuel cell and film/assembly of electrode, requirement has the good proton conductivity as cationic exchange membrane, and have the fuel that the hydrogen that prevents fuel etc. sees through and see through prevention property, on chemistry, heat, electrochemistry and mechanics, have sufficient stability.Therefore, as material that can life-time service, mainly uses " Nafion (registered trademark) " made with du pont company as typical example, importing has sulfonic perfluoro sulfonic acid membrane.But when running perfluoro sulfonic acid membrane under the condition more than 100 ℃, outside the water ratio of membrane removal sharply descended, film was also significantly softening.In addition,, cause the reduction of power generation performance by the methyl alcohol penetrate in the film, can not bring into play sufficient fuel battery performance being in the fuel cell of fuel with methyl alcohol.And point out, even about 80 ℃, be in the fuel cell of fuels run with hydrogen, the too high obstacle of establishing fuel cell technology that also becomes of the cost of film.With perfluorinated sulfonic resin as the above-mentioned bonding same problem of also being pointed out to exist during with resin.In addition, using perfluorinated sulfonic acid in fuel cell is that fluorine such as ion-exchange membrane is the situation of ion-exchange membrane as polyelectrolyte membrane, also has according to operating condition is different to cause deleterious fluoric acid to sneak in the gas of discharging and environment caused problem such as bigger load when discarded.
In order to overcome this shortcoming, studying various is to import in the aromatic ring polymkeric substance sulfonic polyelectrolyte membrane is arranged containing non-fluorine.As polymer backbone, when considering thermotolerance and chemical stability, report has the structure that can adopt poly (arylene ether) ketone and poly (arylene ether) sulfone class etc. to be hopeful to make the polyarylene ether compound, and the structure that the sulfonation of poly (arylene ether) sulfone is formed (for example, with reference to membrane science magazine (Journal of Membrane Science) (Holland) 1993,83 volumes, P.211-220 (non-patent literature 1)), structure (for example, opening flat 6-93114 communique (patent documentation 1)) that the polyether-ether-ketone sulfonation is formed etc. with reference to the spy.These are to make sulphonating agent reaction and import sulfonic structure in polymkeric substance.On the other hand, also report has by use has the monomeric polymerization that sulfonation forms and directly obtains the method (for example, with reference to No. 2002/0091225 specification sheets of U.S. Patent Application Publication (patent documentation 2), internationally disclose No. 2003/095509 specification sheets (patent documentation 3), internationally disclose that No. 2004/033534 specification sheets (patent documentation 4), spy are shown 2004-509224 communique (patent documentation 5), the spy opens 2004-149779 communique (patent documentation 6)) of sulfonated polymer.For example, in patent documentation 2 and patent documentation 5, as the hydrocarbon system ion-exchange membrane, motion has the polymkeric substance that importing sulfonic group isoiony group forms in thermally stable polymers such as polyimide and polysulfones.
But,, also wish to demonstrate excellent more ionic conductivity even in these aromatic hydrocarbons mesenterys.In addition, when bonding when making as dielectric film/assembly of electrode used resin,, wish that the connectivity of itself and polyelectrolyte membrane is stronger in order to improve weather resistance.
In the hydrocarbon system ion-exchange membrane, be the identical ionic conductivity of ion-exchange membrane generally, need to import more ionic group in order to manifest with perfluorinated sulfonic acid.But when the amount of ionic group increased, the swelling property that is caused by water became big, becomes the reason of problems such as dimensional change and physical property reduction when moisture absorption.Therefore, for example patent documentation 4 and patent documentation 6 are disclosed such, the structure of improvement polymkeric substance, and motion has the hydrocarbon system ion-exchange membrane of further inhibition swelling property.
But when dwindling swelling property, often physical durability reduces sometimes.Sometimes produce following problem: for example, when being used for the polyelectrolyte membrane of fuel cell and the connectivity of electrode catalyst layer reduce, polyelectrolyte membrane and electrode catalyst layer in polyelectrolyte membrane/assembly of electrode are peeled off, the weather resistance reduction.
In addition, in the fuel cell that uses hydrogen to act as a fuel, generate free radical, and cause the decomposition of ion-exchange membrane by side reaction.Because the hydrocarbon system ion-exchange membrane is that the anti-free radical of ion-exchange membrane is poor than perfluorinated sulfonic acid, so add the hindered amine based compound, the hindered phenol based compound, organo phosphorous compounds, organosulfur compounds etc. (are for example opened 2003-183526 communique (patent documentation 7) with reference to the spy as free-radical scavengers, the spy opens 2003-201403 communique (patent documentation 8), the spy opens 2003-151346 communique (patent documentation 9), the spy opens 2004-047396 communique (patent documentation 10)), or use ionic exchange resin (for example to open 2003-238678 communique (patent documentation 11) with reference to the spy as ionic group with phosphonate group, the spy opens 2003-282096 communique (patent documentation 12), the spy opens 2004-175997 communique (patent documentation 13)), improve anti-free radical thus.
But the free-radical scavengers major part is low-molecular-weight, and exists and to ooze out from ion-exchange membrane and problem such as stripping.In addition, by the ion-exchange membrane that phosphonic ion exchange resin constitutes that has, exist ionic conductivity to hang down such problem as ionic group.
As mentioned above, present present situation is to make ionic conductivity and weather resistance isostatic polymer solid electrolyte film well in the time of can't obtaining being used for fuel cell.
Patent documentation 1: the spy opens flat 6-93114 communique
Patent documentation 2: No. 2002/0091225 specification sheets of U.S. Patent Application Publication
Patent documentation 3: the international specification sheets that discloses No. 2003/095509
Patent documentation 4: the international specification sheets that discloses No. 2004/033534
Patent documentation 5: special table 2004-509224 communique
Patent documentation 6: the spy opens the 2004-149779 communique
Patent documentation 7: the spy opens the 2003-183526 communique
Patent documentation 8: the spy opens the 2003-201403 communique
Patent documentation 9: the spy opens the 2003-151346 communique
Patent documentation 10: the spy opens the 2004-047396 communique
Patent documentation 11: the spy opens the 2003-238678 communique
Patent documentation 12: the spy opens the 2003-282096 communique
Patent documentation 13: the spy opens the 2004-175997 communique
Non-patent literature 1: membrane science magazine (Journal of Membrane Science) (Holland) 1993,83 volumes, P.211-220
Summary of the invention
The objective of the invention is to, obtain having polyelectrolyte membrane/assembly of electrode, fuel cell that this polyelectrolyte membrane is arranged the containing the sulfonic group polymkeric substance, contain this polyelectrolyte membrane that contains the sulfonic group polymkeric substance of excellent ionic conductivity and weather resistance, resin combination, use.
The present invention relates to a kind of sulfonic group polymkeric substance that contains, it contains the constituent that following Chemical formula 1 is represented at molecular chain.
Figure S2006800207570D00041
(in Chemical formula 1, X represents the positively charged ion kind of hydrogen or 1 valency, and Y represents sulfo group or ketone group, and n represents the arbitrary integer more than 2.)
The above-mentioned sulfonic group polymkeric substance that contains preferably also contains the constituent that following Chemical formula 2 is represented.
Figure S2006800207570D00042
(in Chemical formula 2, n represents the arbitrary integer more than 2.)
The above-mentioned sulfonic group content that contains in the sulfonic group polymkeric substance is preferably in the scope of 0.3～5.0meq/g.
Above-mentionedly contain the terminal dihydroxy compound that the sulfonic group polymkeric substance is 3 expressions of following chemical formula, preferably by using composition to obtain as the part of monomer component by the different a plurality of compositions of n constitute and average group becomes the scope of 1＜n≤10.
Figure S2006800207570D00051
(in chemical formula 3, n represents the arbitrary integer more than 0.)
The invention still further relates to a kind of sulfonic group polymkeric substance that contains, its structure with following chemical formula 4～7 expressions is as necessary repeating unit.
Figure S2006800207570D00052
(in chemical formula 4～7, X represents-S (=O) 2-group or C (=O)-and group, Y represents the positively charged ion of H or 1 valency, Z 1, Z 2, Z 4, Z 5In independent respectively expression O or the S atom any, Z 3, Z 6Respectively independent expression O atom, S atom ,-C (CH 3) 2-group ,-C (CF 3) 2-group ,-CH 2In-group, the cyclohexyl any.)
In the present invention, the Ar in the preferred chemical formula 4～7 1And Ar 2It is the group more than a kind that is selected from the structure of following chemical formula 8～11 expressions.
Figure S2006800207570D00061
In the present invention, the Z in the preferred chemical formula 4～7 1, Z 2, Z 4, Z 5It all is the O atom.
In the present invention, the Z in the preferred chemical formula 4～7 3And Z 6It all is the S atom.
In the present invention, the X in the preferred chemical formula 4～7 be-S (=O) 2-group.
In the present invention, the Ar in the preferred chemical formula 4～7 1And Ar 2Be to be selected from following chemical formula
10 and the structure of Chemical formula 11 expression in the group more than a kind.
Figure S2006800207570D00062
In the present invention, the structure that preferably has 4～7 expressions of above-mentioned chemical formula satisfies following mathematical expression 1～3 as the sulfonic group polymkeric substance that contains of necessary repeating unit.
0.9≤(n1+n2+n3+n4)/(n1+n2+n3+n4+n5)≤1.0 (mathematical expression 1)
0.05≤(n1+n2)/(n1+n2+n3+n4)≤0.7 (mathematical expression 2)
0.01≤(n2+n4)/(n1+n2+n3+n4)≤0.95 (mathematical expression 3)
(in the mathematical expression, n1～n4 represents to contain the repeating unit mole % separately of chemical formula 4～7 expressions in the sulfonic group polymer molecule, and n5 represents to contain the mole % of other repeating units in the sulfonic group polymer molecule.)
The invention still further relates to a kind of sulfonic group polymkeric substance that contains, it has the structure of following Chemical formula 12 expressions.
Figure S2006800207570D00071
(in Chemical formula 12, X represents-S (=O) 2-group or C (=O)-and group, Y represents the positively charged ion of H or 1 valency, Z 1, Z 2And Z 3Any of independent respectively expression O or S atom.Ar 1Represent 2 yuan of organic groups, Ar 2, Ar 3And Ar 4Expression does not contain 2 yuan of organic groups of ionic group, Ar respectively 5Represent 3 yuan of organic groups.N, m, o represent the positive number more than 1 respectively.The part of surrounding in [] is represented minimum repeating unit, and each repeating unit is bonding randomly, and same repeating unit is bonding continuously.)
The invention still further relates to a kind of sulfonic group polymkeric substance that contains, it has the structure of following Chemical formula 13 expressions.
Figure S2006800207570D00081
(in Chemical formula 13, X represents-S (=O) 2-group or C (=O)-and group, Y represents the positively charged ion of H or 1 valency, Z 5, Z 6And Z 7In independent respectively expression O or the S atom any.Ar 6Represent any in the structure of following Chemical formula 1 4～16 expressions, Ar 7Represent any in the structure of following Chemical formula 1 7～24 expressions, Ar 8Represent any in the structure of following chemical formula 8～11 expressions, Ar 9Represent 3 yuan of organic groups.N ', n ", m ', m " represent the integer more than 1, o ', o respectively " represent o ' and o respectively " any be not 0 the integer more than 0.The part of surrounding in [] is represented minimum repeating unit, and each repeating unit is bonding randomly, and same repeating unit is bonding continuously.)
Figure S2006800207570D00091
(in Chemical formula 17 and Chemical formula 18, the integer of p ' expression 2～50.)
Figure S2006800207570D00101
In the present invention, the Ar in the preferred Chemical formula 13 7It is the structure of any expression in the following Chemical formula 1 7～20.
In the present invention, the Ar in the preferred Chemical formula 13 7It is the structure of following Chemical formula 19 or 20 expressions.
Figure S2006800207570D00103
In the present invention, the Ar in the preferred Chemical formula 13 9It is phenyl.
In the present invention, the Z in the preferred Chemical formula 13 7It is the O atom.
In the present invention, n ', the n in the preferred Chemical formula 13 ", m ', m ", o ', o " satisfy following mathematical expression 4～7.
0.05≤(n '+n ")/(n '+n "+m '+m ")≤0.8 (mathematical expression 4)
0.001≤(o '+o ")/(n '+n "+m '+m "+o '+o ")≤0.1 (mathematical expression 5)
0.01≤(n '/n ")≤100 (mathematical expressions 6)
0.01≤(m '/m ")≤100 (mathematical expressions 7)
Contain in the sulfonic group polymkeric substance of the present invention, preferably its second-order transition temperature is in 130 ℃～270 ℃ the scope.
Contain in the sulfonic group polymkeric substance of the present invention, more preferably its second-order transition temperature is in 130 ℃～220 ℃ the scope.
The invention still further relates to a kind of manufacture method that contains the sulfonic group polymkeric substance, it is the method that contains the sulfonic group polymkeric substance that is used to obtain to contain the constituent that above-mentioned Chemical formula 1 represents, wherein, contain compound that the sulfonic group polymkeric substance uses 3 expressions of following chemical formula at least a kind, and obtain by the polymerization that utilizes aromatic nucleophilie nuclear substituting reaction as monomer component.
Figure S2006800207570D00111
(in chemical formula 3, n represents the arbitrary integer more than 2.)
The invention still further relates to a kind of above-mentioned resin combination that contains the sulfonic group polymkeric substance that contains.
In above-mentioned resin combination, the content that preferably contains the sulfonic group polymkeric substance is 50～100 quality %.
The invention still further relates to a kind of polyelectrolyte membrane that contains above-mentioned resin combination.
The invention still further relates to a kind of above-mentioned polyelectrolyte membrane that contains the sulfonic group polymkeric substance that contains.
The invention still further relates to a kind of manufacture method of polyelectrolyte membrane, it is a method of making above-mentioned polyelectrolyte membrane, and it comprises: the solution that will contain sulfonic group polymkeric substance and solvent is cast so that casting thickness is the operation of the scope of 10～1500 μ m; Good solution carries out the exsiccant operation to make casting.
The invention still further relates to a kind of use the polyelectrolyte membrane/assembly of electrode of above-mentioned polyelectrolyte membrane is arranged.
The invention still further relates to a kind of use the fuel cell of above-mentioned polyelectrolyte membrane/assembly of electrode is arranged.
The invention still further relates to a kind of above-mentioned fuel cell that uses methyl alcohol to act as a fuel.
The invention still further relates to and a kind of the above-mentioned sulfonic group polymkeric substance that contains is used for the polyelectrolyte membrane/assembly of electrode of electrode catalyst layer and uses the fuel cell that this polyelectrolyte membrane/assembly of electrode is arranged.
The invention still further relates to a kind of polyelectrolyte membrane, it contains structure with 4～7 expressions of following chemical formula and contains the sulfonic group polymkeric substance as necessary repeating unit, wherein, the described sulfonic group polymkeric substance that contains satisfies following mathematical expression 1,8 and 9, and described polyelectrolyte membrane is used for direct methanol fuel cell.
Figure S2006800207570D00121
(in chemical formula 4～7, X represents-S (=O) 2-group or C (=O)-and group, Y represents the positively charged ion of H or 1 valency, Z 1, Z 2, Z 4, Z 5In independent respectively expression O or the S atom any, Z 3, Z 6Respectively independent expression O atom, S atom ,-C (CH 3) 2-group ,-C (CF 3) 2-group ,-CH 2In-group, the cyclohexyl any.)
0.9≤(n1+n2+n3+n4)/(n1+n2+n3+n4+n5)≤1.0 (mathematical expression 1)
0.05≤(n1+n2)/(n1+n2+n3+n4)≤0.5 (mathematical expression 8)
0.05≤(n2+n4)/(n1+n2+n3+n4)≤0.95 (mathematical expression 9)
(in the mathematical expression, n1～n4 represents the above-mentioned repeating unit mole % separately that contains above-mentioned chemical formula 4～7 expressions in the sulfonic group polymer molecule, and n5 represents the above-mentioned mole % that contains other repeating units in the sulfonic group polymer molecule.)
The invention still further relates to a kind of polyelectrolyte membrane, it contains structure with 4～7 expressions of following chemical formula and contains the sulfonic group polymkeric substance as necessary repeating unit, wherein, the described sulfonic group polymkeric substance that contains satisfies following mathematical expression 1,10 and 11, and it is the polymer electrolyte fuel cell of fuel that described polyelectrolyte membrane is used for hydrogen.
Figure S2006800207570D00131
(in chemical formula 4～7, X represents-S (=O) 2-group or C (=O)-and group, Y represents the positively charged ion of H or 1 valency, Z 1, Z 2, Z 4, Z 5In independent respectively expression O or the S atom any, Z 3, Z 6Respectively independent expression O atom, S atom ,-C (CH 3) 2-group ,-C (CF 3) 2-group ,-CH 2In-group, the cyclohexyl any.)
0.9≤(n1+n2+n3+n4)/(n1+n2+n3+n4+n5)≤1.0 (mathematical expression 1)
0.3≤(n1+n2)/(n1+n2+n3+n4)≤0.7 (mathematical expression 10)
0.01≤(n2+n4)/(n1+n2+n3+n4)≤0.25 (mathematical expression 11)
(in the mathematical expression, n1～n4 represents the above-mentioned repeating unit mole % separately that contains above-mentioned chemical formula 4～7 expressions in the sulfonic group polymer molecule, and n5 represents the above-mentioned mole % that contains other repeating units in the sulfonic group polymer molecule.)
The invention still further relates to a kind of polyelectrolyte membrane, what it contained structure with 3 expressions of following Chemical formula 1 contains the sulfonic group polymkeric substance, wherein, n '+n in the above-mentioned Chemical formula 13 "+m '+m "+o '+o " satisfy following mathematical expression 5,12 and 13, described polyelectrolyte membrane is used for direct methanol fuel cell.
Figure S2006800207570D00151
(in Chemical formula 13, X represents-S (=O) 2-group or C (=O)-and group, Y represents the positively charged ion of H or 1 valency, Z 5, Z 6And Z 7In independent respectively expression O or the S atom any.Ar 6Represent any in the structure of following Chemical formula 1 4～16 expressions, Ar 7Represent any in the structure of following Chemical formula 1 7～24 expressions, Ar 8Represent any in the structure of following chemical formula 8～11 expressions, Ar 9Represent 3 yuan of organic groups.N ', n ", m ', m " represent the integer more than 1, o ', o respectively " represent o ' and o respectively " any be not 0 the integer more than 0.The part of surrounding in [] is represented minimum repeating unit, and each repeating unit is bonding randomly, and same repeating unit is bonding continuously.)
Figure S2006800207570D00161
(in Chemical formula 17 and Chemical formula 18, the integer of p ' expression 2～50.)
Figure S2006800207570D00171
0.001≤(o '+o ")/(n '+n "+m '+m "+o '+o ")≤0.1 (mathematical expression 5)
0.05≤(n '+n "+o ')/(n '+n "+m '+m "+o '+o ")≤0.5 (mathematical expression 12)
0.05≤(n "+m ")/(n '+n "+m '+m ")≤0.95 (mathematical expression 13)
The invention still further relates to a kind of polyelectrolyte membrane, what it contained structure with 3 expressions of following Chemical formula 1 contains the sulfonic group polymkeric substance, wherein, n '+n in the above-mentioned Chemical formula 13 "+m '+m "+o '+o " satisfy following mathematical expression 5,14 and 15, it is the polymer electrolyte fuel cell of fuel that described polyelectrolyte membrane is used for hydrogen.
Figure S2006800207570D00181
(in Chemical formula 13, X represents-S (=O) 2-group or C (=O)-and group, Y represents the positively charged ion of H or 1 valency, Z 5, Z 6And Z 7In independent respectively expression O or the S atom any.Ar 6Represent any in the structure of following Chemical formula 1 4～16 expressions, Ar 7Represent any in the structure of following Chemical formula 1 7～24 expressions, Ar 8Represent any in the structure of following chemical formula 8～11 expressions, Ar 9Represent 3 yuan of organic groups.N ', n ", m ', m " represent the integer more than 1, o ', o respectively " represent o ' and o respectively " any be not 0 the integer more than 0.The part of surrounding in [] is represented minimum repeating unit, and each repeating unit is bonding randomly, and same repeating unit is bonding continuously.)
Figure S2006800207570D00191
(in Chemical formula 17 and Chemical formula 18, the integer of p ' expression 2～50.)
Figure S2006800207570D00201
0.001≤(o '+o ")/(n '+n "+m '+m "+o '+o ")≤0.1 (mathematical expression 5)
0.3≤(n '+n "+o ')/(n '+n "+m '+m "+o '+o ")≤0.7 (mathematical expression 14)
0.01≤(n "+m ")/(n '+n "+m '+m ")≤0.25 (mathematical expression 15)
The invention still further relates to a kind of manufacture method of polyelectrolyte membrane, it is that to make the method for the above-mentioned polyelectrolyte membrane that is used for direct methanol fuel cell and make above-mentioned being used for hydrogen be the method for polyelectrolyte membrane of high molecular fuel battery of fuel, and it comprises: will contain that the above-mentioned solution that contains sulfonic group polymkeric substance and solvent is cast so that casting thickness is the operation of the scope of 10～1500 μ m; Good solution carries out the exsiccant operation to make casting.
The invention still further relates to a kind of polyelectrolyte membrane/assembly of electrode, it uses above-mentioned polyelectrolyte membrane or above-mentioned being used for the polyelectrolyte membrane of hydrogen as the high molecular fuel battery of fuel that is used for direct methanol fuel cell.
The invention still further relates to a kind of use the fuel cell of this polyelectrolyte membrane/assembly of electrode is arranged.
The invention still further relates to a kind of this fuel cell that uses methyl alcohol to act as a fuel.
The sulfonic group polymkeric substance that contains of the present invention is the macromolecular material that can have ionic conductivity and the remarkable performance of weather resistance with respect to employed polymer electrolyte in fuel cell etc.By using this to contain the sulfonic group polymkeric substance, can obtain the polyelectrolyte membrane of ionic conductivity and excellent in te pins of durability and polyelectrolyte membrane/assembly of electrode, the fuel cell that use has this polyelectrolyte membrane.
Description of drawings
Fig. 1 is expression by the film that containing of obtaining in embodiment 1A, sulfonic group poly (arylene ether) based compound constituted 1The HNMR wave spectrum reaches the figure by the structural formula of this wave spectrum ownership.
Fig. 2 is expression by the film that containing of obtaining in embodiment 2A, sulfonic group poly (arylene ether) based compound constituted 1The HNMR wave spectrum reaches the figure by the structural formula of this wave spectrum ownership.
Fig. 3 be expression use VARIAN corporate system GEMINI-200, in deuterated dimethyl sulfoxide, measure under the room temperature by the embodiment 1B synthetic polymkeric substance among the present invention 1The figure of H-NMR wave spectrum.
Fig. 4 be expression use VARIAN corporate system GEMINI-200, in deuterated dimethyl sulfoxide, measure under the room temperature by the embodiment 2B synthetic polymkeric substance among the present invention 1The figure of H-NMR wave spectrum.
Fig. 5 be expression use VARIAN corporate system GEMINI-200, in deuterated dimethyl sulfoxide, measure under the room temperature by the embodiment 3B synthetic polymkeric substance among the present invention 1The figure of H-NMR wave spectrum.
Fig. 6 be expression use VARIAN corporate system GEMINI-200, in deuterated dimethyl sulfoxide, measure under the room temperature by the embodiment 4B synthetic polymkeric substance among the present invention 1The figure of H-NMR wave spectrum.
Fig. 7 be expression use Rheogel E-4000 (Toki Sangyo Co., Ltd.'s manufacturings), to the figure of the dynamic visco-elastic property of the polyelectrolyte membrane mensuration that obtains by the embodiment 1B among the present invention.
Fig. 8 be expression use VARIAN corporate system GEMINI-200, in deuterated dimethyl sulfoxide, measure under the room temperature by the embodiment 2C synthetic polymkeric substance among the present invention 1The figure of H-NMR wave spectrum.
Fig. 9 be expression use VARIAN corporate system GEMINI-200, in deuterated dimethyl sulfoxide, measure under the room temperature by the embodiment 3C synthetic polymkeric substance among the present invention 1The figure of H-NMR wave spectrum.
Embodiment
The present invention relates to a kind of sulfonic specific sulfonic group polymkeric substance that contains that on aromatic nucleus, imported, and relate to a kind of ionic conductivity, thermotolerance, processibility, dimensional stability and excellent in te pins of durability, particularly as the effective polyelectrolyte membrane of ion-conductive membranes.The sulfonic group polymkeric substance that contains of the present invention contains the structural unit that following Chemical formula 1 is represented at molecular chain.
Figure S2006800207570D00221
(at this, Y represents sulfo group or ketone group, and X represents the positively charged ion kind of hydrogen or 1 valency, and n represents the integer arbitrarily more than 2.)
In Chemical formula 1,1 valency positively charged ion kind among the X can be enumerated: salt of 1 valency metal-salt such as sodium, potassium, ammonium salt etc. and organo-alkali compound etc.The structure of above-mentioned Chemical formula 1 can be by 3,3 '-disulfo-4,4 '-dihalo diphenyl sulfone, 3,3 '-disulfo-4,4 '-dihalo benzophenone or their derivative and contain the terminal hydroxyl phenylene ether oligomer and utilize aromatic nucleophilie nuclear substituting reaction to form.At this, at the structure division that is made of phenylene ether oligomer, the n in the above-mentioned Chemical formula 1 is with the integer representation arbitrarily more than 2.For the sulfonic group polymkeric substance that contains of the present invention, as the structural unit that Chemical formula 1 is represented, can only contain by n is the single structural unit that specific single number constitutes, and in addition, also can contain n and be a plurality of structural units of different a plurality of numbers.In addition, the sulfonic group polymkeric substance that contains of the present invention, as long as contain structural unit that Chemical formula 1 represents, be that n is the structural unit of the integer more than 2, also can contain the diphenyl ether unit and the two phenoxy group benzene unit of the situation of the n=0 that is equivalent in the structure that Chemical formula 1 represents and n=1.
In order to make the sulfonic group that contains abundant amount in the molecular chain that contains the sulfonic group polymkeric substance of the present invention effectively, the structural unit that preferred Chemical formula 1 is represented is below 10 as the average n that forms.Need to prove that the average composition in this specification sheets is meant that n is the number average bonding numbers of different a plurality of bondings when counting, can determine by NMR etc.
Of the present inventionly contain the sulfonic group polymkeric substance contains above-mentioned Chemical formula 1 in polymer chain structure, but also the structure that can only be represented by above-mentioned Chemical formula 1 constitutes, in addition, constituent as beyond the structural unit of the structure of being represented by above-mentioned Chemical formula 1 for example also can have aromatic dihydroxy compound and aromatic series dihalo compound more than a kind with the form of multipolymer.In any case, contain in the sulfonic group polymkeric substance because the structural unit that above-mentioned Chemical formula 1 is represented is present in, thereby the ionic conductivity of this compound, thermotolerance, processibility and dimensional stability are good.In the present invention, by containing the structural unit that n is the above-mentioned Chemical formula 1 of the integer more than 2, the flexibility that can contain the molecular chain of sulfonic group polymkeric substance in raising, manifest in the such characteristic of excellent in workability when particularly in fuel cell applications, making polyelectrolyte membrane/assembly of electrode, improve the connectivity of polyelectrolyte membrane and electrode, and improve the weather resistance of polyelectrolyte membrane/assembly of electrode, therefore, in containing the sulfonic group polymkeric substance, the content of the structural unit that above-mentioned Chemical formula 1 is represented is preferably more than the 10 quality %, more preferably more than the 20 quality %.
As mentioned above, contain in the sulfonic group polymkeric substance, importantly in polymer chain, contain the structural unit that above-mentioned Chemical formula 1 is represented, therefore, the method for the structure that imports above-mentioned Chemical formula 1 is not particularly limited of the present invention.As general method, can contain 4 of sulfonic group or sulfonic group derivative by what can obtain above-mentioned Chemical formula 1,4 '-dihalo benzophenone and/or 4,4 '-dihalo diphenyl sulfone and contain the terminal hydroxyl phenylene ether oligomer and synthesize as the aromatic nucleophilie nuclear substituting reaction of at least a portion of monomer component.
Contain 4 of sulfonic group or sulfonic group derivative, 4 '-dihalo benzophenone and/or 4, the concrete example of 4 '-dihalo diphenyl sulfone can be enumerated: 3, and 3 '-disulfo-4,4 '-dichloro diphenyl sulfone, 3,3 '-disulfo-4,4 '-difluorodiphenyl sulfone, 3,3 '-disulfo-4,4 '-dichloro benzophenone, 3,3 '-disulfo-4, the salt of 4 '-difluoro benzophenone and these sulfonic groups and 1 valency positively charged ion kind etc.1 valency positively charged ion kind can be enumerated sodium, potassium and other metal object kinds and various amines etc., but is not restricted to these.
In addition, the sulfonic group polymkeric substance that contains of the present invention also contains the structural unit that following Chemical formula 2 is represented preferably when containing the structure that above-mentioned Chemical formula 1 represents.
Figure S2006800207570D00241
(in Chemical formula 2, n represents the integer arbitrarily more than 2.)
For the sulfonic group polymkeric substance that contains of the present invention, as the structural unit that Chemical formula 2 is represented, can only contain by n is the single structural unit that specific single number constitutes, and in addition, also can contain n and be a plurality of structural units of different a plurality of numbers.
Because phenylene ether oligomer shared ratio in the structural unit that Chemical formula 2 is represented is compared bigger with the structural unit that Chemical formula 1 is represented, therefore, of the present inventionly contain the situation that the sulfonic group polymkeric substance contains the structural unit that Chemical formula 2 represents, show and to give better flexibility such effect to the molecular chain of this compound.Need to prove, of the present invention when containing the sulfonic group polymkeric substance and containing the structural unit that above-mentioned Chemical formula 1 and Chemical formula 2 represent simultaneously, as long as this total content that contains the structural unit that Chemical formula 1 is represented in overall texture unit of sulfonic group polymkeric substance structural unit and Chemical formula 2 represent is more than the 40 quality %, be preferred then, more preferably more than the 60 quality % from the viewpoint that contains the sulfonic group polymkeric substance that obtains the flexibility excellence.
To being not particularly limited in the method that contains the structural unit that the above-mentioned Chemical formula 2 of importing is represented in the sulfonic group polymkeric substance of the present invention.As general method, can enumerate by can obtaining 2 of structural unit that above-mentioned Chemical formula 2 represents 6-phenyl-dihalide formonitrile HCN and contain the terminal hydroxyl phenylene ether oligomer and come synthetic method etc. as the aromatic nucleophilie nuclear substituting reaction of at least a portion of monomer component.
2, the example of 6-phenyl-dihalide formonitrile HCN can be enumerated: 2, and 6-dichlorobenzonitrile, 2,6-difluorobenzonitrile etc.
Be used for obtaining the aromatic nucleophilie nuclear substituting reaction that contains the sulfonic group polymkeric substance of the present invention, as the above-mentioned terminal hydroxyl phenylene ether oligomer that contains of the structural unit that can obtain above-mentioned Chemical formula 1 and 2 expressions, can use the oligopolymer of for example following chemical formula 3 expressions.
Figure S2006800207570D00251
(in chemical formula 3, n represents the integer arbitrarily more than 2.)
As chemical formula 3 expression contain the terminal hydroxyl phenylene ether oligomer, can use n is the single composition of single number, also can use the different a plurality of mixture of ingredients of number of n.When the different a plurality of composition of the number that contains n, preferably use the average group that contains the terminal hydroxyl phenylene ether oligomer of chemical formula 3 expressions to become the composition of scope of 1＜n≤10 as the part of monomer component.In addition, more preferably use average group to become the composition of scope of 2≤n≤10 as the part of monomer component.Its reason is, when the n that becomes as average group is 1 when following, there is the second-order transition temperature rising of the polymkeric substance that obtains and acts as a fuel the tendency of battery with the processibility reduction of material, when the n that becomes as average group greater than 10 the time, manifest the second-order transition temperature step-down and the inadequate tendency of thermotolerance during as fuel cell material.Need to prove, chemical formula 3 expression contain the situation that the terminal hydroxyl phenylene ether oligomer contains the different a plurality of compositions of n, the average composition of this oligopolymer can be determined by NMR etc., in addition, the rate that exists of the composition that n is different can be determined by GPC etc.
Be used for obtaining the aromatic nucleophilie nuclear substituting reaction that contains the sulfonic group polymkeric substance of the present invention, can using sensitization difluoro aromatics and dichloro aromatics as the monomer component that is used to obtain Chemical formula 1 and 2 structures of representing structure in addition.But concrete illustration for example: decafluorobiphenyl, ten fluorine phenyl ether, ten fluorine benzophenone, 2,4-dichlorobenzonitrile, 2,4-difluorobenzonitrile, 4,4 '-dichloro benzophenone, 4,4 '-dichloro diphenyl sulfone, 4,4 '-difluoro benzophenone, 4, compounds such as 4 '-difluorodiphenyl sulfone, but be not restricted to these, also can use in aromatic nucleophilie nuclear substituting reaction, to have active other aromatic series dihalo compounds, aromatic dinitro compound, aromatic series dicyano compound etc.In addition, these compounds can use separately, and the mixture that also can be used as more than 2 kinds uses.
In addition, be used to obtain the monomer component of the structure beyond the structure that Chemical formula 1 and Chemical formula 2 represent, also can use the aromatic diol composition.Specifically for example can enumerate: 4,4 '-'-biphenyl diphenol, two (4-hydroxyphenyl) sulfone, 1,1-two (4-hydroxyphenyl) ethane, 2,2-two (4-hydroxyphenyl) propane, two (4-hydroxyphenyl) methane, 2,2-two (4-hydroxyphenyl) butane, 3,3-two (4-hydroxyphenyl) pentane, 2,2-two (4-hydroxyl-3, 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-hydroxyphenyl) phenylmethane, two (4-hydroxyphenyl) ditan, 9,9-two (4-hydroxyphenyl) fluorenes, 9,9-two (3-methyl-4-hydroxyphenyl) fluorenes, 9,9-two (3-phenyl-4-hydroxyphenyl) fluorenes, 2,2-two (4-hydroxyphenyl) HFC-236fa, Resorcinol, Resorcinol, 1, the 4-dihydroxy naphthlene, 1, the 8-dihydroxy naphthlene, 1, the 5-dihydroxy naphthlene, 1, the 6-dihydroxy naphthlene, 1, the 7-dihydroxy naphthlene, 2, the 6-dihydroxy naphthlene, 2, the 7-dihydroxy naphthlene, two (4-hydroxyphenyl) ketone, two (4-hydroxyphenyl) ether, two (4-hydroxyphenyl) thioether, two (4-hydroxyphenoxies)-1,4-benzene, two (4-hydroxyphenoxies)-1,3-benzene etc. also can use the various aromatic diols of polymeric that can be used in the poly (arylene ether) based compound that utilizes aromatic nucleophilie nuclear substituting reaction in addition.In addition, in these aromatic diols, also can the bonding methyl, substituting group such as halogen, cyano group, sulfonic group and salt compound thereof.Substituent kind is not particularly limited, and preferred every aromatic nucleus is 0～2.And, also can use can with the diphenylsulfide-4 of the same reaction of aromatic diol, 4 '-two mercaptan etc.These aromatic diols etc. can use separately, and the mixture that also can be used as more than 2 kinds uses.
In the polymerization that contains the sulfonic group polymkeric substance of the present invention, also can add the halogenated aromatic oxy-compound and carry out polymerization as the reactive monomer composition.The halogenated aromatic oxy-compound that use this moment also is not particularly limited, and for example can enumerate as an example: 4-hydroxyl-4 '-chlorobenzophenone, 4-hydroxyl-4 '-fluorine benzophenone, 4-hydroxyl-4 '-chloro-diphenyl sulfone, 4-hydroxyl-4 '-fluorine sulfobenzide, 4-chloro-4 '-(to hydroxyphenyl) sulfobenzide, 4-fluoro-4 '-(to hydroxyphenyl) benzophenone etc.These can use separately, and the mixture that also can be used as more than 2 kinds uses.
In addition, as in the molecular chain that contains the sulfonic group polymkeric substance among the present invention, be main chain, side chain, the end group of polymkeric substance, also can contain and utilize heat and/or light to carry out crosslinked composition.The heat cross-linking composition can illustration: vinyl, ethynyl, ethynylene etc. contain reactive unsaturated link(age) group etc., but are not limited to these, so long as get final product by the heat cross-linking composition that utilizes heat to react can to form new key between polymer chain.The photocrosslinking reaction composition can be enumerated: functional groups such as benzophenone base, α-diketo, acyloin base, acyloin ether, benzyl alkyl ketal group, phenacyl, multinuclear benzoquinones class, thioxanthene ketone group, acyl group phosphino-, ethene unsaturated group.Wherein, preferred benzophenone base etc. utilizes light can produce the group of free radical and the combination of the group that can react with the free radical of the aromatic group with alkyl such as methyl and ethyls.When using the ethene unsaturated group, preferably add Photoepolymerizationinitiater initiaters such as benzophenone, α-two ketone, acyloin class, acyloin ethers, benzyl alkyl ketal class, acetophenones, multinuclear benzoquinones class, thioxanthene ketone, acylphosphanes class.
When importing crosslinkable groups endways, can be by containing the functionality end-capped agent that the fashionable adding of sulfonic group polymer poly can obtain containing the end structure of crosslinkable groups and import this crosslinkable groups of the present invention.The example of one functionality end-capped agent specifically can be enumerated: 3-fluorine propylene, 3-fluoro-1-propine, 4-fluoro-1-butylene, 4-fluoro-ethyl acetylene, 3-fluorine tetrahydrobenzene, 4-fluorobenzene ethene, 3-fluorobenzene ethene, 2-fluorobenzene ethene, 4-fluorine acetylenylbenzene, 3-fluorine acetylenylbenzene, α-fluoro-4-ethynyl toluene, 4-fluorine Stilbene, 4-(phenylacetylene base) fluorobenzene, 3-(phenylacetylene base) fluorobenzene, chlorallylene, 3-chloro-1-propyne, 4-chloro-1-butylene, 4-chloro-ethyl acetylene, 3-chlorine tetrahydrobenzene, 4-chloro-vinylbenzene, 3-chloro-vinylbenzene, 2-chloro-vinylbenzene, 4-chloro-Phenylacetylene, 3-chloro-Phenylacetylene, α-chloro-4-ethynyl toluene, 4-chloro-Stilbene, 4-(phenylacetylene base) chlorobenzene, 3-(phenylacetylene base) chlorobenzene, 3-hydroxyl propylene, 3-hydroxyl-1-propine, 4-hydroxyl-1-butylene, 4-hydroxyl-ethyl acetylene, 4-hydroxyl-vinylbenzene, 3-hydroxyl-vinylbenzene, 2-hydroxyl-vinylbenzene, 4-hydroxyl-acetylenylbenzene, 3-ethynyl phenol, 4-ethynyl benzylalcohol, 4-hydroxyl Stilbene, 4-(phenylacetylene base) phenol, 3-(phenylacetylene base) phenol, the 4-chlorobenzophenone, 4-fluorine benzophenone, the 4-dihydroxy benaophenonel, the 4-methylphenol, the 3-methylphenol, the 2-methylphenol, the 4-ethylphenol, the 3-ethylphenol, the 4-propylphenol, the 4-butylphenol, the 4-amyl phenol, 4-benzylphenol etc.These end-capped agent can be used separately, but also can be mixed with two or more.
In addition, containing the monomeric concrete example of crosslinkable groups can enumerate: 1-butylene-3, the 4-glycol, 3,5-dihydroxy-benzene ethene, 3,5-dihydroxyl Stilbene, ethyl acetylene-3, the 4-glycol, 1-butylene-3, the 4-glycol, oneself is-2 years old, 4-diine-1, the 6-glycol, 2-ethynyl Resorcinol, 2-(phenylacetylene base) Resorcinol, 5-ethynyl Resorcinol, 2-butylene-1, the 4-glycol, 4,4 '-dihydroxyl Stilbene, 1, the 4-butyleneglycol, 1,2-two (4-hydroxyphenyl) acetylene, 1,2-two (3-hydroxyphenyl) acetylene, 3,3-difluoro propylene, 3,3-difluoro propine, 3,3, the 3-trifluoropropyne, 3,4-two fluoro-1-butylene, 1, the 4-difluoro-2-butene, 3,4-two fluoro-ethyl acetylene, 1,4-two fluoro-2-butyne, 1,6-two fluoro-own-2, the 4-diine, 3,4-difluoro vinylbenzene, 2,6-difluoro vinylbenzene, 2,5-difluoro acetylenylbenzene, 3,5-difluoro acetylenylbenzene, α, α-two fluoro-4-ethynyl toluene, α, α, α-three fluoro-4-ethynyl toluene, 2,4-difluoro Stilbene, 4,4 '-difluoro Stilbene, 1,2-two (4-fluorophenyl) acetylene, 3,4-difluoro (phenylacetylene base) benzene, 3, the 3-dichloropropylene, 3,3-two propargyl chlorides, 3,3,3-three propargyl chlorides, 3,4-two chloro-1-butylene, 1,4-two chloro-2-butylene, 3,4-two chloro-ethyl acetylene, 1,4-two chloro-2-butyne, 3, the 4-dichlorostyrene, 2, the 6-dichlorostyrene, 2,4-difluorophenyl acetic acid (acid of シ Na ミ Star Network), 2,5-sym-dichloroethylene base benzene, 3,5-sym-dichloroethylene base benzene, α, α-two chloro-4-ethynyl toluene, α, α, α-three chloro-4-ethynyl toluene, 2,4-dichloro Stilbene, 4,4 '-dichloro Stilbene, 1,2-two (4-chloro-phenyl-) acetylene, 3,4-dichloro (phenylacetylene base) benzene, 4,4 '-dihydroxy benaophenonel, 4,4 '-dichloro benzophenone, 4,4 '-difluoro benzophenone, the 4-chlorobenzophenone, 4-fluorine benzophenone, the 4-dihydroxy benaophenonel, 1,1-two (4-hydroxyphenyl) ethane, 2,2-two (4-hydroxyphenyl) propane, two (4-hydroxyphenyl) methane, 2,2-two (4-hydroxyphenyl) butane, 3,3-two (4-hydroxyphenyl) pentane, 2,2-two (4-hydroxyl-3,5-3,5-dimethylphenyl) propane, two (4-hydroxyl-3,5-3,5-dimethylphenyl) methane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl) methane, two (4-hydroxyphenyl) phenylmethane, 4-benzyl Resorcinol, 2,5-dimethyl Resorcinol, 4-ethyl resorcinol etc.Contain the crosslinkable groups monomer by adding these when the polymerization of poly (arylene ether) based compound of the present invention, can be in the inner crosslinkable groups that imports of molecular chain.
The sulfonic group polymkeric substance that contains of the present invention is characterised in that all structures with following chemical formula 4～7 expressions are as necessary repeating unit.
Figure S2006800207570D00291
(in chemical formula 4～7, X represents-S (=O) 2-group or C (=O)-and group, Y represents the positively charged ion of H or 1 valency, Z 1, Z 2, Z 4, Z 5In independent respectively expression O or the S atom any, Z 3, Z 6Respectively independent expression O atom, S atom ,-C (CH 3) 2-group ,-C (CF 3) 2-group ,-CH 2In-group, the cyclohexyl any.)
The repeating unit of chemical formula 4～7 expressions can be distinguished randomly bonding, also can the continuous bonding of same repeating unit.In addition, this moment all kinds repeating unit bonding continuously, also can the continuous bonding of only a part of kind.
X represents-S (=O) 2-group or C (=O)-group, when its be-S (=O) 2During-group, the solvability in solvent improves, and is therefore preferred.In addition, when its be C (=O)-during group, can give the polymkeric substance photocrosslinking reaction, therefore preferred.
Y represents the positively charged ion of H or 1 valency, and when being used as the proton exchange membrane of fuel cell, preferred Y is a hydrogen.In addition, in processing such as dissolving, moulding, system film, be that hydrogen is compared with Y, Y is under the cationic situation of 1 valency, its sulfonic thermostability raises, and is therefore preferred.The cationic example of 1 valency can be enumerated: alkalimetal ion such as Na, K, L and ammonium ion, quaternary amine etc., alkalimetal ions such as preferred Na, K, Li.Become the sulfonic group of an alkali metal salt,, can convert sulfonic group to by in strong acid such as sulfuric acid, hydrochloric acid, perchloric acid or its aqueous solution, polymkeric substance being handled.Have sulfonic polymkeric substance and demonstrate high ionic conductivity, can be used as proton exchange resins and proton exchange membrane.Wherein, proton exchange membrane can when using polymkeric substance of the present invention, can obtain having the fuel cell of excellent performance as the ionogen of polymer electrolyte fuel cell.
In chemical formula 4～7, Z 1, Z 2, Z 4, Z 5In independent respectively expression O or the S atom any worked as Z 1, Z 2, Z 4, Z 5All be the O atomic time, monomeric cost and toxicity do not raise, and are not easy to take place painted etc., therefore preferred in the polymerization.Compare for the situation of O atom with it, it is that S atomic time scale resistance raises.Z 3, Z 6Respectively independent expression O atom, S atom ,-C (CH 3) 2-group ,-C (CF 3) 2-group ,-CH 2In-group, the cyclohexyl any.Wherein, preferred O atom, S atom ,-C (CH 3) 2-group ,-C (CF 3) 2-group, cyclohexyl, more preferably O atom and S atom.
In chemical formula 4～7, Z 1～Z 6In Z at least 3And Z 6All be that the S atom is preferred aspect scale resistance, and more preferably Z 2And Z 5Be the S atom.Further preferably it all is the S atom.
Ar in chemical formula 6 and the chemical formula 7 1And Ar 2, be preferably aromatic group with electron-withdrawing group.The example of electron-withdrawing group can be enumerated: perfluoroalkyls such as sulfo group, carbonyl, alkylsulfonyl, phosphino-, cyano group, trifluoromethyl, nitro, halogen etc., preferred cyano group, sulfo group, carbonyl.And, Ar 1And Ar 2Be preferably more than one the group in the structure that is selected from 8～11 expressions of following chemical formula.
Figure S2006800207570D00301
When it was the structure of chemical formula 8, the solvability in solvent raise, and is therefore preferred.In addition, when it is the structure of chemical formula 9, can give the polymkeric substance photocrosslinking reaction, therefore preferred.In addition, when it was the structure of Chemical formula 10 or 11, the swelling property of polymkeric substance diminished, and is therefore preferred.In chemical formula 8～11, preferred Chemical formula 10 or 11 structure, the most preferably structure of Chemical formula 11.
Have of the present invention the contain sulfonic group polymkeric substance of the structure of chemical formula 4～7 expression by use as necessary repeating unit, can obtain that swelling property is little, physical durability and with the polyelectrolyte membrane of the connectivity excellence of electrode catalyst layer etc.
The repeating structure that chemical formula 4～7 in the molecule is represented respectively and the mol ratio of other repeating structures preferably satisfy mathematical expression 1～3.
0.9≤(n1+n2+n3+n4)/(n1+n2+n3+n4+n5)≤1.0 (mathematical expression 1)
0.05≤(n1+n2)/(n1+n2+n3+n4)≤0.7 (mathematical expression 2)
0.01≤(n2+n4)/(n1+n2+n3+n4)≤0.95 (mathematical expression 3)
(in the mathematical expression, n1～n4 represents to contain the repeating unit mole % separately of chemical formula 4～7 expressions in the sulfonic group polymer molecule, and n5 represents to contain the mole % of other repeating units in the sulfonic group polymer molecule.)
Above-mentioned other repeating structures are not particularly limited, and for example, when it is when containing such repeating structure such as phosphonate group or phosphate, scale resistance improves and preferred.In addition, when it is when containing alkyl such as methyl and allyl group, ethynyl, maleinamide etc. and having the repeating structure of group of bridging property, can gives crosslinked polymer and improve the weather resistance of polyelectrolyte membrane and intensity etc., therefore preferred.
The repeating unit that contains chemical formula 4～7 expressions in the sulfonic group polymkeric substance of the present invention is represented with mathematical expression 1 with respect to the preferable range that always repeats unitary ratio.(n1+n2+n3+n4)/(n1+n2+n3+n4+n5) be preferably 0.9～1.0 scope, more preferably 0.95～1.0 scope, more preferably 0.96～1.0 scope.Contain the situation of structure other repeating units in addition of chemical formula 4～7 expressions, other repeating units are with respect to always repeating unitary ratio 0.001～0.04 scope more preferably.
The preferable range that contains sulfonic repeating unit in the repeating unit of chemical formula 4～7 expressions is represented with mathematical expression 2, (n1+n2)/(n1+n2+n3+n4) is preferably 0.05～0.7 scope.As (n1+n2)/when (n1+n2+n3+n4) being lower than 0.05, the tendency that is difficult to obtain sufficient ionic conductivity is arranged, when it is higher than 0.7, there is swelling property significantly to become big or becomes water-soluble and be difficult to tendency as polyelectrolyte membrane.
To the structure of chemical formula 5 in the repeating unit of chemical formula 4～7 expressions and chemical formula 7 expressions, the preferable range of the ratio of its total is represented with mathematical expression 3.(n2+n4)/(n1+n2+n3+n4) be preferably 0.01～0.95 scope.When (n2+n4)/(n1+n2+n3+n4) less than 0.01 the time, the tendency that is difficult to be improved fully effect is arranged, when its greater than 0.95 the time, have the swelling property of film to become big tendency.
The sulfonic group polymkeric substance that contains of the present invention can be used for ion exchange resin and ion-exchange membrane, moisture-absorption resin, hygroscopic mem-brane, moisture permeable membrane, electrolytic film etc., is preferably used as the polyelectrolyte membrane that works as ion-exchange membrane especially.And, used the polyelectrolyte membrane that contains the sulfonic group polymkeric substance of the present invention, can be used as proton exchange membrane by sulfonic group is set at sulfonic acid type, be particularly suitable for ionic exchange film for fuel cell.In addition, of the present invention contain the sulfonic group polymkeric substance with ion-exchange membrane etc. with electrode, when catalyzer engages, also be suitable for use as caking agent.
With polyelectrolyte membrane of the present invention during as the proton exchange membrane of the direct methanol fuel cell of directly using methanol aqueous solution to act as a fuel, the structure of preferred chemical formula 4～7 expressions satisfies following mathematical expression 1,8 and 9.
0.9≤(n1+n2+n3+n4)/(n1+n2+n3+n4+n5)≤1.0 (mathematical expression 1)
0.05≤(n1+n2)/(n1+n2+n3+n4)≤0.5 (mathematical expression 8)
0.05≤(n2+n4)/(n1+n2+n3+n4)≤0.95 (mathematical expression 9)
(in the above-mentioned formula, n1～n4 represents to contain the repeating unit mole % separately of above-mentioned chemical formula 4～7 expressions in the sulfonic group polymer molecule, and n5 represents to contain the mole % of other repeating units in the sulfonic group polymer molecule.)
In mathematical expression 1, (n1+n2+n3+n4)/(n1+n2+n3+n4+n5) be preferably 0.9～1.0 scope, more preferably 0.95～1.0 scope, more preferably 0.96～1.0 scope.Contain the situation of structure other repeating units in addition of chemical formula 4～7 expressions, other repeating units are with respect to always repeating unitary ratio 0.001～0.04 scope more preferably.
In mathematical expression 8, (n1+n2)/(n1+n2+n3+n4) be preferably 0.05～0.5 scope.When (n1+n2)/(n1+n2+n3+n4) less than 0.05 the time, have to be difficult to obtain sufficient proton-conducting, and the tendency that descends easily of the output of fuel cell.When (n1+n2)/(n1+n2+n3+n4) greater than 0.5 the time, the tendency that has the output of the quantitative change fuel cell too much of methyl alcohol penetrate film to descend easily.(n1+n2)/(n1+n2+n3+n4) more preferably scope is 0.07～0.4.In addition, when the concentration of the methanol aqueous solution that is used as fuel was hanged down, under (n1+n2)/(n1+n2+n3+n4) the big situation, it is big that proton-conducting becomes, and therefore, the output of fuel cell raises.On the other hand, when using the methanol aqueous solution of high density, under (n1+n2)/(n1+n2+n3+n4) the little situation, can suppress its output and reduce, can increase the output of fuel cell along with methyl alcohol penetrate.
In mathematical expression 9, (n2+n4)/(n1+n2+n3+n4) be preferably 0.05～0.95 scope.When (n2+n4)/(n1+n2+n3+n4) less than 0.05 the time, when bonding electrodes and catalyzer and ion-exchange membrane, have easy generation to engage bad tendency, when its greater than 0.95 the time, have swelling property to become big tendency easily.(n2+n4)/(n1+n2+n3+n4) preferred scope is 0.2～0.8 scope.When (n1+n2)/(n1+n2+n3+n4) less than 0.2 the time, (n2+n4)/(n1+n2+n3+n4) be preferably 0.4～0.8 scope.In addition, when the value of (n1+n2)/(n1+n2+n3+n4) greater than 0.2 the time, (n2+n4)/(n1+n2+n3+n4) be preferably 0.1～0.5 scope.
Polyelectrolyte membrane of the present invention during as the proton exchange membrane of the fuel cell that uses hydrogen to act as a fuel, is preferably being satisfied following mathematical expression 1,10 and 11.
0.9≤(n1+n2+n3+n4)/(n1+n2+n3+n4+n5)≤1.0 (mathematical expression 1)
0.3≤(n1+n2)/(n1+n2+n3+n4)≤0.7 (mathematical expression 10)
0.01≤(n2+n4)/(n1+n2+n3+n4)≤0.25 (mathematical expression 11)
(in the mathematical expression, n1～n4 represents to contain the repeating unit mole % separately of chemical formula 4～7 expressions in the sulfonic group polymer molecule, and n5 represents to contain the mole % of other repeating units in the sulfonic group polymer molecule.)
In mathematical expression 1, (n1+n2+n3+n4)/(n1+n2+n3+n4+n5) be preferably 0.9～1.0 scope, more preferably 0.95～1.0 scope, more preferably 0.96～1.0 scope.Contain the situation of structure other repeating units in addition of chemical formula 4～7 expressions, other repeating units are with respect to always repeating unitary ratio 0.001～0.04 scope more preferably.
In mathematical expression 10, (n1+n2)/(n1+n2+n3+n4) be preferably 0.3～0.7 scope.When (n1+n2)/(n1+n2+n3+n4) less than 0.3 the time, have to be difficult to obtain sufficient proton-conducting, and the tendency of the easy step-down of output of fuel cell.When (n1+n2)/(n1+n2+n3+n4) greater than 0.7 the time, have the swelling property of film to become excessive, and tendencies such as apt to cause breakage and output reduction.(n1+n2)/(n1+n2+n3+n4) preferred scope is 0.35～0.7, more preferably 0.4～0.5 scope.
In mathematical expression 11, (n2+n4)/(n1+n2+n3+n4) be preferably 0.01～0.25 scope.When (n2+n4)/(n1+n2+n3+n4) less than 0.01 the time, have bad tendency take place to engage when bonding electrodes and catalyzer and ion-exchange membrane easily, when its greater than 0.25 the time, have swelling property too to become big tendency.(n2+n4)/(n1+n2+n3+n4) preferred scope is 0.1～0.2 scope.
Contain the polyelectrolyte membrane that contains the sulfonic group polymkeric substance of the present invention, can bonding electrodes and catalyzer and make polyelectrolyte membrane/assembly of electrode.In addition, with respect to the film beyond polyelectrolyte membrane of the present invention or its, can use of the present invention contain the sulfonic group polymkeric substance as with the caking agent of electrode and catalyzer.With the sulfonic group polymkeric substance that contains of the present invention when the caking agent, the Y in the preferred chemical formula 4 and 5 is that hydrogen, sulfonic group are acid type.When under the state of sulfonic group and salt forming cation, using, also can behind joint, sulfonic group be made acid type by acid treatment.
Containing in the sulfonic group polymkeric substance in the present invention, below will being shown in as the Chemical formula 2 5A～25BJ of the concrete example of preferred construction, but scope of the present invention is not limited to these.
Figure S2006800207570D00351
Figure S2006800207570D00361
Figure S2006800207570D00371
Figure S2006800207570D00381
Figure S2006800207570D00391
Figure S2006800207570D00401
Figure S2006800207570D00421
Figure S2006800207570D00431
Figure S2006800207570D00441
In Chemical formula 2 5A～25BJ, the proton-conducting of Chemical formula 2 5A, 25C, 25E, 25J, 25M, 25N, 25BE, 25BF and swell-resistant excellence, therefore preferred, further preferred Chemical formula 2 5A, 25C, 25E, most preferably Chemical formula 2 5A.In addition, when its structure of representing for Chemical formula 2 5BC, the scale resistance of polymkeric substance improves, and is therefore preferred.In addition, when its structure of representing for Chemical formula 2 5BD, polymkeric substance has bridging property, therefore can improve physical property and weather resistance.
In above-mentioned Chemical formula 2 5A～25BJ, preferred n, m, o, p, q satisfy following mathematical expression 16～18.
0.9≤(n+m+o+p)/(n+m+o+p+q)≤1.0 (mathematical expression 16)
0.05≤(n+m)/(n+m+o+p)≤0.7 (mathematical expression 17)
0.01≤(m+p)/(n+m+o+p)≤0.95 (mathematical expression 18)
In mathematical expression 16, (n+m+o+p)/(n+m+o+p+q) be preferably 0.9～1.0 scope.(n+m+o+p)/(n+m+o+p+q) more preferably 0.95～1.0 scope, more preferably 0.96～1.0 scope.At q is not 0 o'clock, (q)/(n+m+o+p+q) 0.001～0.04 scope more preferably.
In mathematical expression 17, (n+m)/(n+m+o+p) be preferably 0.05～0.7 scope.As (n+m)/when (n+m+o+p) being lower than 0.05, the tendency that is difficult to obtain sufficient proton-conducting is arranged.As (n+m)/when (n+m+o+p) being higher than 0.7, there is swelling property to enlarge markedly or becomes water-soluble and be difficult to tendency as polyelectrolyte membrane.
In mathematical expression 18, (m+p)/(n+m+o+p) be preferably 0.01～0.95 scope.When (m+p)/(n+m+o+p) less than 0.01 the time, the tendency that is difficult to be improved fully effect is arranged, when its greater than 0.95 the time, have the swelling property of film to become big tendency easily.
Contain in the sulfonic group polymkeric substance of the present invention, the flexibility of the repeating structures of chemical formula 5 and 7 expressions by improving polymkeric substance reduces with destruction and the second-order transition temperature that is difficult to carry out relative deformation, in the processibility when improve making polyelectrolyte membrane/assembly of electrode, also have and in polyelectrolyte membrane/assembly of electrode, improve with the connectivity of electrode, improve the effect of physical durability etc.In addition, the repeating structures of chemical formula 4 and 6 expressions have and dwindle the overall swelling property of polymkeric substance, or the effect of dwindling methanol permeability.
Polyelectrolyte membrane of the present invention during as the proton exchange membrane of the direct methanol fuel cell of directly using methanol aqueous solution to act as a fuel, is preferably being satisfied following mathematical expression 16,19 and 20.
0.9≤(n+m+o+p)/(n+m+o+p+q)≤1.0 (mathematical expression 16)
0.05≤(n+m)/(n+m+o+p)≤0.5 (mathematical expression 19)
0.05≤(m+p)/(n+m+o+p)≤0.95 (mathematical expression 20)
In mathematical expression 16, (n+m+o+p)/(n+m+o+p+q) be preferably 0.9～1.0 scope.(n+m+o+p)/(n+m+o+p+q) more preferably 0.95～1.0 scope, more preferably 0.96～1.0 scope.At q is not 0 o'clock, (q)/(n+m+o+p+q) 0.001～0.04 scope more preferably.
In mathematical expression 19, (n+m)/(n+m+o+p) be preferably 0.05～0.5 scope.When (n+m)/(n+m+o+p) less than 0.05 the time, the tendency of the easy step-down of output that can not obtain sufficient ionic conductivity, fuel cell is arranged.When (n+m)/(n+m+o+p) greater than 0.5 the time, the tendency that have the quantitative change of methyl alcohol penetrate film too much, the output of fuel cell reduces easily.(n+m)/(n+m+o+p) preferred scope is 0.07～0.4.In addition, when the concentration of the methanol aqueous solution that is used as fuel was hanged down, proton-conducting became big under (n+m)/(n+m+o+p) the big situation, and therefore, the output of fuel cell raises.On the other hand, when using the methanol aqueous solution of high density, under (n+m)/(n+m+o+p) the little situation, can suppress its output and reduce, can increase the output of fuel cell along with methyl alcohol penetrate.
In mathematical expression 20, value (m+p)/(n+m+o+p) is preferably 0.05～0.95 scope.When (m+p)/(n+m+o+p) less than 0.05 the time, when bonding electrodes and catalyzer and ion-exchange membrane, have easy generation to engage bad tendency, when its greater than 0.95 the time, the tendency that has swelling property to become excessive.(m+p)/(n+m+o+p) preferred scope is 0.2～0.8.Less than 0.25 o'clock, (m+p)/(n+m+o+p) be preferably 0.4～0.8 scope in the value of (n+m)/(n+m+o+p).In addition, greater than 0.25 o'clock, (m+p)/(n+m+o+p) be preferably 0.1～0.5 scope in the value of (n+m)/(n+m+o+p).
Polyelectrolyte membrane of the present invention during as the proton exchange membrane of the polymer electrolyte fuel cell that uses hydrogen to act as a fuel, is preferably being satisfied following mathematical expression 16,21 and 22.
0.9≤(n+m+o+p)/(n+m+o+p+q)≤1.0 (mathematical expression 16)
0.3≤(n+m)/(n+m+o+p)≤0.7 (mathematical expression 21)
0.01≤(m+p)/(n+m+o+p)≤0.25 (mathematical expression 22)
In mathematical expression 16, (n+m+o+p)/(n+m+o+p+q) be preferably 0.9～1.0 scope.(n+m+o+p)/(n+m+o+p+q) more preferably 0.95～1.0 scope, more preferably 0.96～1.0 scope.At q is not 0 o'clock, (q)/(n+m+o+p+q) 0.001～0.04 scope more preferably.
In mathematical expression 21, (n+m)/(n+m+o+p) be preferably 0.3～0.7 scope.When (n+m)/(n+m+o+p) less than 0.3 the time, the tendency of the easy step-down of output that can not obtain sufficient proton-conducting, fuel cell is arranged.When (n+m)/(n+m+o+p) greater than 0.7 the time, the swelling property of the film tendencies such as the damaged and output reduction of excessive, easy generation that become are arranged.(n+m)/(n+m+o+p) preferred scope is 0.35～0.7, more preferably 0.4～0.5.
In mathematical expression 22, value (m+p)/(n+m+o+p) is preferably 0.01～0.25 scope.When (m+p)/(n+m+o+p) less than 0.01 the time, when bonding electrodes and catalyzer and ion-exchange membrane, have easy generation to engage bad tendency, when its greater than 0.25 the time, the tendency that has swelling property to become excessive.(m+p)/(n+m+o+p) preferred scope is 0.1～0.2 scope.
Of the present invention contain the sulfonic group polymkeric substance can by the compound that contains 6～29 expressions of following Chemical formula 2 as monomeric mixture that must composition, utilize aromatic nucleophilie nuclear substituting reaction to carry out polymerization.
Figure S2006800207570D00481
In Chemical formula 2 6～29, X represents-S (=O) 2-group or C (=O)-and group, Y represents the positively charged ion of H or 1 valency, Z 7And Z 10In independent respectively expression Cl atom, F atom, I atom, Br atom, the nitro any, Z 8And Z 11Respectively independent expression OH group, SH group ,-O-NH-C (=O)-the R group ,-S-NH-C (=O)-[R represents aromatic series or aliphatic alkyl in the R group any.], Z 9Expression O atom, S atom ,-C (CH 3) 2-group ,-C (CF 3) 2-group ,-CH 2In-group, the cyclohexyl any, Ar 3Be illustrated in the aromatic group of electron-withdrawing groups such as perfluoroalkyls such as having sulfo group, carbonyl, alkylsulfonyl, phosphino-, cyano group, trifluoromethyl in the molecule, nitro, halogen.
The concrete example of the compound of Chemical formula 26 expressions can be enumerated: 3,3 '-disulfo-4,4 '-dichloro diphenyl sulfone, 3,3 '-disulfo-4,4 '-difluorodiphenyl sulfone, 3,3 '-disulfo-4,4 '-dichloro diphenylketone, 3,3 '-disulfo-4,4 '-difluorodiphenyl sulfone, 3,3 '-disulfo butyl-4,4 '-dichloro diphenyl sulfone, 3,3 '-disulfo butyl-4,4 '-difluorodiphenyl sulfone, 3,3 '-disulfo butyl-4,4 '-difluorodiphenyl base ketone, 3,3 '-disulfo butyl-4, the salt of 4 '-difluorodiphenyl sulfone and these sulfonic groups and 1 valency positively charged ion kind etc.1 valency positively charged ion kind can be enumerated: sodium, potassium and other metal object kinds and various amines etc., but can not be limited to these.In the compound of Chemical formula 26 expressions, sulfonic group becomes the examples for compounds of salt can be enumerated: 3, and 3 '-sodium disulfonate-4,4 '-dichloro diphenyl sulfone, 3,3 '-sodium disulfonate-4,4 '-difluorodiphenyl sulfone, 3,3 '-sodium disulfonate-4,4 '-dichloro diphenylketone, 3,3 '-sodium disulfonate-4,4 '-difluorodiphenyl sulfone, 3,3 '-sodium disulfonate-4,4 '-difluorodiphenyl base ketone, 3,3 '-disulfonic acid potassium 4,4 '-dichloro diphenyl sulfone, 3,3 '-disulfonic acid potassium 4,4 '-difluorodiphenyl sulfone, 3,3 '-disulfonic acid potassium 4,4 '-dichloro diphenylketone, 3,3 '-disulfonic acid potassium 4,4 '-difluorodiphenyl sulfone, 3,3 '-disulfonic acid potassium 4,4 '-difluorodiphenyl base ketone etc.
The concrete example of the compound of Chemical formula 27 expressions can exemplify: 2,2-two (4-hydroxyphenyl) propane, two (4-hydroxyphenyl) methane, 2,2-two (4-hydroxyphenyl) HFC-236fa, 4,4 '-phenyl disulfide mercaptan, 4,4 '-oxygen hexichol mercaptan, two (4-hydroxyphenyl) thioether, 4,4 '-dihydroxydiphenyl ether, 1,1-two (4-hydroxyphenyl) hexanaphthene etc., preferred 4,4 '-phenyl disulfide mercaptan, two (4-hydroxyphenyl) thioether, 1,1-two (4-hydroxyphenyl) hexanaphthene.
The flexibility of the monomer of the structure of Chemical formula 27 expression by improving polymkeric substance reduces with destruction and the second-order transition temperature that is difficult to carry out relative deformation, in the processibility when improve making polyelectrolyte membrane/assembly of electrode, also have and in polyelectrolyte membrane/assembly of electrode, improve with the connectivity of electrode, improve the effect of physical durability etc.
The compound of Chemical formula 28 expression can be set forth in the disengaging base that has on the same aromatic nucleus in the nucleophilic substitution reactions such as halogen, nitro and with the compound of the electron-withdrawing group of its sensitization.As concrete example, can enumerate: 2,6-dichlorobenzonitrile, 2,4 dichloro benzene formonitrile HCN, 2,6-difluorobenzonitrile, 2,4-difluorobenzonitrile, 4,4 '-dichloro diphenyl sulfone, 4,4 '-difluorodiphenyl sulfone, 4,4 '-difluoro benzophenone, 4,4 '-dichloro benzophenone, decafluorobiphenyl etc., but be not limited to these, also can use in aromatic nucleophilie nuclear substituting reaction, to have active other aromatic series dihalo compounds, aromatic dinitro compound, aromatic series dicyano compound etc.
The concrete example of the compound of Chemical formula 29 expressions can be enumerated: 4, and 4 '-'-biphenyl diphenol, 4,4 '-dimercapto '-biphenyl diphenol etc., preferred 4,4 '-'-biphenyl diphenol.
In above-mentioned aromatic nucleophilie nuclear substituting reaction, also can with the compound of Chemical formula 2 6～29 expression and with other various sensitization di halo aromatic compounds and dinitrobenzene aromatics, biphenol compound, two thiol compounds as monomer.
The example of other bisphenol cpds or two thiol compounds can be enumerated: 9,9-two (4-hydroxyphenyl) fluorenes, 9,9-two (3-methyl-4-hydroxyphenyl) fluorenes, 4,4 '-'-biphenyl diphenol, two (4-hydroxyphenyl) sulfone, 1,1-two (4-hydroxyphenyl) ethane, 2,2-two (4-hydroxyphenyl) butane, 3,3-two (4-hydroxyphenyl) pentane, 2,2-two (4-hydroxyl-3, 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-hydroxyphenyl) phenylmethane, two (4-hydroxyphenyl) ditan, Resorcinol, Resorcinol, two (4-hydroxyphenyl) ketone, 1, the 4-phenylene dimercaptan, 1, the 3-phenylene dimercaptan, phenolphthalein etc., also can use in addition to can be used in various aromatic diols of poly (arylene ether) based compound polymeric or various aromatic series two mercaptan that utilize aromatic nucleophilie nuclear substituting reaction, be not limited to above-claimed cpd.
Utilize the situation that contains the sulfonic group polymkeric substance among aromatic nucleophilie nuclear substituting reaction polymerization the present invention, add Chemical formula 2 6～29 expressions structure compound and add other sensitization di halo aromatic compounds, dinitrobenzene aromatics and aromatic diol class or aromatic series dithiols as required, and in the presence of basic cpd, make its reaction, can obtain polymkeric substance thus.Mol ratio by making reactive halogen in the monomer or nitro and reactive hydroxyl and thiol group is mol ratio arbitrarily, can adjust the polymerization degree of the polymkeric substance that obtains, be preferably 0.8～1.2,0.9～1.1 scope more preferably, 0.95～1.05 scope more preferably, when it is 1, can obtain the polymkeric substance of high-polymerization degree, therefore most preferably.
Polymerization can be carried out under 0～350 ℃ temperature range, but is preferably 50～250 ℃ scope.When it is lower than 0 ℃, the tendency that existence can not fully be reacted, when it is higher than 3 50 ℃, the tendency that has polymkeric substance to begin to decompose.Reaction also can be carried out under solvent-free, but preferably carries out in solvent.The solvent that can use can be enumerated: 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, get final product so long as in aromatic nucleophilie nuclear substituting reaction, can be used as the solvent of stable solvent use.These organic solvents can use separately, and the mixture that also can be used as more than 2 kinds uses.
Basic cpd can be enumerated: sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus etc., so long as can make the basic cpd of the active phenoxide structures of aromatic diol class and aromatic series dimercapto compound formation, can be not limited to these and use.When using the basic cpd of 100 moles of amounts more than the % with respect to the summation of bisphenol cpd and two thiol compounds, can carry out polymerization well, preferred basic cpd is the scope of 105～125 moles of % with respect to the summation of bisphenol cpd or two thiol compounds.When the amount of bisphenol cpd or two thiol compounds is too much, can cause the generation of side reactions such as decomposing, therefore not preferred.
In addition; in above-mentioned polyreaction; also basic cpd be can not use, and bisphenol cpd or two thiol compounds and isocyanate compound reaction carrying out material and sensitization di halo aromatic compound and the dinitrobenzene aromatics direct reaction that carbamylization forms made.
In aromatic nucleophilie nuclear substituting reaction, side reaction takes place sometimes generate water.At this moment, can make with the irrelevant toluene of polymer solvent etc. to coexist as in the reaction system, as azeotrope with water except that going to system.As with the method for water except that going to system, also can use water-absorbing materials such as molecular sieve.Carry out the situation of aromatic nucleophilie nuclear substituting reaction in solvent, the preferred so that polymer concentration that obtains is the amount of the scope of 5～50 weight % monomer of packing into.When its during less than 5 weight %, the tendency that has the polymerization degree to be difficult to rise.On the other hand, when its during greater than 50 weight %, the viscosity of the system that responds is too high, the tendency of the aftertreatment difficulty of reactant.After polyreaction finishes, desolvate by utilizing evaporation from reaction soln, to remove, and wash residual thing as required, desirable polymkeric substance can be obtained.In addition, in also can the be low solvent, polymkeric substance is precipitated as solid, utilize sedimentary leaching to obtain polymkeric substance by the solubleness that reaction soln is added polymkeric substance.In addition, also can obtain polymers soln by crossing the salt that filters out the side reaction generation.
The invention still further relates to a kind of sulfonic group polymkeric substance that contains, it has the structure of following Chemical formula 12 expressions.
Figure S2006800207570D00511
(in Chemical formula 12, X represents-S (=O) 2-group or C (=O)-and group, Y represents the positively charged ion of H or 1 valency, Z 1, Z 2And Z 3Any of independent respectively expression O or S atom.Ar 1Represent 2 yuan of organic groups, Ar 2, Ar 3And Ar 4Expression does not contain 2 yuan of organic groups of ionic group, Ar respectively 5Represent 3 yuan of organic groups.N, m, o represent the positive number more than 1 respectively.The part of surrounding in [] is represented minimum repeating unit, and each repeating unit is bonding randomly, and same repeating unit is bonding continuously also.)
In Chemical formula 12, when X be-S (=O) 2During-group, polymkeric substance and monomeric solvability raise, and therefore, carry out polymerization and processing easily, and be preferred.In addition, when X be C (=O)-during group, can give the polymkeric substance photocrosslinking reaction, thereby improve its mechanical characteristics and weather resistance, therefore preferred.Work as Z 1, Z 2And Z 3All be the O atomic time, monomeric cost and toxicity do not raise, and are not easy to take place painted etc., therefore preferred in the polymerization.Compare for the situation of O atom with it, it is that S atomic time scale resistance raises.
In Chemical formula 12, when Y is H (proton), be suitable as proton exchange resins and proton exchange membrane.Y represents the positively charged ion of H or 1 valency, and the positively charged ion of 1 valency for example can be enumerated: alkalimetal ion such as Na, K, Li and ammonium ion, quaternary ammonium salt etc.When the positively charged ion of 1 valency was the alkalimetal ion of Na, K, Li etc., sulfonic thermostability raise, and in complete processings such as system film, dissolving, shaping, can at high temperature handle, and can improve the processibility of polymkeric substance.Become the sulfonic group of an alkali metal salt,, can convert sulfonic group to by in strong acid such as sulfuric acid, hydrochloric acid, perchloric acid or its aqueous solution, polymkeric substance being handled.Have sulfonic polymkeric substance and demonstrate high proton-conducting, can be used as proton exchange resins and proton exchange membrane.Wherein, proton exchange membrane can when using polymkeric substance of the present invention, can obtain having the fuel cell of excellent performance as the ionogen of polymer electrolyte fuel cell.
Ar in the Chemical formula 12 2Preferably do not contain aromatic group ionic group, that have electron-withdrawing group.The example of electron-withdrawing group can be enumerated: perfluoroalkyls such as sulfo group, carbonyl, alkylsulfonyl, phosphino-, cyano group, trifluoromethyl, nitro, halogen etc., preferred cyano group, sulfo group, carbonyl.And, Ar 1And Ar 2Be preferably the group more than a kind in the structure that is selected from following chemical formula 8～11 expressions.
Figure S2006800207570D00531
When it was the structure of chemical formula 8, the solvability in solvent raise, and is therefore preferred.In addition, when it is the structure of chemical formula 9, can give the polymkeric substance photocrosslinking reaction, therefore preferred.In addition, when it was the structure of Chemical formula 10 or 11, the swelling property of polymkeric substance diminished, and is therefore preferred.In chemical formula 8～10, preferred Chemical formula 10 or 11 structure, the most preferably structure of Chemical formula 11.
Ar in the Chemical formula 12 4Be preferably any in the structure of the structure of following chemical formula 8～11 expressions and 30 expressions of following chemical formula, in these scopes, also can contain a plurality of structures.
Figure S2006800207570D00532
(in chemical formula 30, X represents-S (=O) 2-group or C (=O)-and group, Y represents the positively charged ion of H or 1 valency.)
Ar in the Chemical formula 12 1And Ar 3, so long as do not contain ionic group, known 2 yuan of groups arbitrarily of mainly being made of the group of aromatic series get final product, and can enumerate 2 yuan of aromatic groups that are selected from the family that following chemical formula 31A～31N represents as preferred examples.
Figure S2006800207570D00541
(in chemical formula 31A～31N, R represents methyl, and r represents 0～2 integer, and s represents the integer more than 1.)
R is that 1 or 2 polymkeric substance is difficult to obtain high molecular weight polymers sometimes, so r is preferably 0.Ar 1And Ar 3Preferred structure be following Chemical formula 1 4～16 and 32 the expression structures, wherein, can be single structure, also can constitute by a plurality of structures.
Figure S2006800207570D00542
(in chemical formula 32, Z 4Expression O atom or S atom, p represents the integer more than 1.)
In chemical formula 32, p is preferably 1～50 integer, more preferably 1～20 integer.In addition, the Z in the chemical formula 32 4Be preferably the S atom.N is preferably 1, when it is 2～20 integer, the softening temperature of polymkeric substance is reduced, and makes its connectivity with electrode good, therefore preferably.At Ar 1And Ar 3When constituting, be preferably any and the structure of chemical formula 32 expressions in the structure of Chemical formula 1 4～16 expression by a plurality of structures.By importing the structure of chemical formula 32 expressions, following advantage is arranged: the softening temperature of polymkeric substance reduces, and makes its connectivity with electrode good, or the raising of the physical durability of fuel cell.At this moment, the ratio of the structure of chemical formula 32 expressions is preferably 1～99 mole of %, more preferably the scope of 5～80 moles of %, the more preferably scope of 10～75 moles of %.
Ar in the Chemical formula 12 5, do not get final product so long as do not have the aromatic group of ionic group, be preferably the structure of following chemical formula 33 expressions.
In the present invention, n, the m in the Chemical formula 12, o preferably satisfy following mathematical expression 23 and 24.
0.05≤n/ (n+m)≤0.8 (mathematical expression 23)
0.001≤o/ (n+m+o)≤0.1 (mathematical expression 24)
When n/ (n+m) less than 0.05 the time, have ionic conductivity significantly to reduce, be difficult to tendency as ion-exchange membrane and proton exchange membrane.When n/ (n+m) greater than 0.8 the time, have that swelling property enlarges markedly, ion-exchange membrane and proton exchange membrane mechanical characteristics when moisture absorption reduce and the tendency that film is dissolved in the problem of water etc. takes place easily.N/ (n+m) is 0.3～0.7 scope more preferably, more preferably 0.35～0.5 scope.
When o/ (n+m+o) less than 0.001 the time, the tendency that is difficult to obtain fully stabilization effect is arranged, when its greater than 0.1 the time, have the ionic conductivity of ion-exchange membrane and proton exchange membrane to reduce, the tendency of problems such as the right reduction of polymer poly take place easily.O/ (n+m+o) is 0.005～0.05 scope more preferably, more preferably 0.01～0.04 scope.
The invention still further relates to a kind of sulfonic group polymkeric substance that contains, it has the structure of following Chemical formula 13 expressions.
Figure S2006800207570D00561
(in Chemical formula 13, X represents-S (=O) 2-group or C (=O)-and group, Y represents the positively charged ion of H or 1 valency, Z 5, Z 6And Z 7In independent respectively expression O or the S atom any.Ar 6Represent any in the structure of following Chemical formula 1 4～16 expressions, Ar 7Represent any in the structure of following Chemical formula 1 7～24 expressions, Ar 8Represent any in the structure of following chemical formula 8～11 expressions, Ar 9Represent 3 yuan of organic groups.N ', n ", m ', m " represent the integer more than 1, o ', o respectively " represent o ' and o respectively " any be not 0 the integer more than 0.The part of surrounding in [] is represented minimum repeating unit, and each repeating unit is bonding randomly, and same repeating unit is bonding continuously also.)
Figure S2006800207570D00571
(in Chemical formula 17 and Chemical formula 18, the integer of p ' expression 2～50.)
Figure S2006800207570D00572
In Chemical formula 13, when X be-S (=O) 2During-group, polymkeric substance and monomeric solvability raise, and therefore, carry out polymerization and processing easily, and be preferred.In addition, when X be-C (=O) during group, can give the polymkeric substance photocrosslinking reaction, thereby its mechanical characteristics and weather resistance are improved, therefore preferred.Work as Z 1, Z 2And Z 3All be the O atomic time, monomeric cost and toxicity do not raise, and are not easy to take place painted etc., therefore preferred in the polymerization.Compare for the situation of O atom with it, it is that S atomic time scale resistance raises.
In Chemical formula 13, when Y is H (proton), be suitable as proton exchange resins and proton exchange membrane.Y represents the positively charged ion of H or 1 valency, and the positively charged ion of 1 valency for example can be enumerated: alkalimetal ion such as Na, K, Li and ammonium ion, quaternary ammonium salt etc.When the positively charged ion of 1 valency was alkalimetal ion such as Na, K, Li, sulfonic thermostability raise, and in complete processings such as system film, dissolving, shaping, can at high temperature handle, and can improve the processibility of polymkeric substance.Become the sulfonic group of an alkali metal salt,, can convert sulfonic group to by in strong acid such as sulfuric acid, hydrochloric acid, perchloric acid or its aqueous solution, polymkeric substance being handled.Have sulfonic polymkeric substance and demonstrate high ionic conductivity, can be used as proton exchange resins and proton exchange membrane.Wherein, proton exchange membrane can when using polymkeric substance of the present invention, can obtain having the fuel cell of excellent performance as the ionogen of polymer electrolyte fuel cell.
Ar in the Chemical formula 13 8Preferably do not contain aromatic group ionic group, that have electron-withdrawing group.The example of electron-withdrawing group can be enumerated: perfluoroalkyls such as sulfo group, carbonyl, alkylsulfonyl, phosphino-, cyano group, trifluoromethyl, nitro, halogen etc., preferred cyano group, sulfo group, carbonyl.And, Ar 8Be preferably the group more than a kind in the structure that is selected from following chemical formula 8～11 expressions.
Figure S2006800207570D00581
When it was the structure of chemical formula 8, the solvability in solvent raise, and is therefore preferred.In addition, when it is the structure of chemical formula 9, can give the polymkeric substance photocrosslinking reaction, therefore preferred.In addition, when it was the structure of Chemical formula 10 or 11, the swelling property of polymkeric substance diminished, and is therefore preferred.In chemical formula 8～10, preferred Chemical formula 10 or 11 structure, the most preferably structure of Chemical formula 11.
Ar in the Chemical formula 13 6, so long as do not contain ionic group, known 2 yuan of groups arbitrarily of mainly being made of the group of aromatic series get final product, and can enumerate 2 yuan of aromatic groups that are selected from the family that following chemical formula 34A～34G represents as preferred examples.
Figure S2006800207570D00591
(in chemical formula 34A～34G, R represents methyl, and r represents 0～2 integer.)
R is that 1 or 2 polymkeric substance is difficult to obtain high molecular weight polymers sometimes, so r is preferably 0.Ar 6Preferred structure be the structure of following Chemical formula 1 4～16 expressions, wherein, can be single structure, also can constitute by a plurality of structures.Wherein, more preferably Chemical formula 14 or 15 structure, the structure of further preferred Chemical formula 14.
Figure S2006800207570D00601
Ar in the Chemical formula 13 7, so long as do not contain ionic group, known 2 yuan of groups arbitrarily of mainly being made of the group of aromatic series get final product, and can enumerate 2 yuan of aromatic groups that are selected from the family that following chemical formula 35A～35H represents as preferred examples.
Figure S2006800207570D00602
(in chemical formula 35A～35H, R represents methyl, and r represents 0～2 integer, and s represents the integer more than 1.)
R is that 1 or 2 polymkeric substance is difficult to obtain high molecular weight polymers sometimes, so r is preferably 0.Ar 7Preferred structure be the structure of following Chemical formula 1 7～24 expressions, wherein, can be single structure, also can constitute by a plurality of structures.Wherein, the more preferably structure of Chemical formula 1 7～20, further preferred Chemical formula 19 or 20 structure.
Figure S2006800207570D00611
(in Chemical formula 17 and Chemical formula 18, the integer of p ' expression 2～50.)
P ' in the Chemical formula 17 or 18 is 2～20 scope more preferably, more preferably 2～10 scope.The structure that also can contain the different a plurality of kinds of p '.
Because of Ar 7Be to be selected from the structure more than a kind in the family that the structure by Chemical formula 1 7～18 expression constitutes and to have following advantage: by reducing the second-order transition temperature of polymkeric substance, in the processibility when improve making polyelectrolyte membrane/assembly of electrode, also have and in polyelectrolyte membrane/assembly of electrode, improve with the connectivity of electrode, improve physical durability etc.At this moment, the ratio of the structure of Chemical formula 1 7～20 expressions is with respect to Ar 6, Ar 7And Ar 9The total of the structure of expression is preferably 1～99 mole of %, more preferably 5～80 moles of %, the more preferably scope of 10～75 moles of %.
Ar in the Chemical formula 13 9Represent 3 yuan of organic groups, be preferably the group of aromatic series, the structure of preferred following chemical formula 33 expressions.I.e. this Ar 9Be preferably phenyl.
Figure S2006800207570D00612
Z in the Chemical formula 13 7Be preferably the O atom.
N ' in the Chemical formula 13, n ", m ', m ", o ', o " preferably satisfy following mathematical expression 4～7.
0.05≤(n '+n ")/(n '+n "+m '+m ")≤0.8 (mathematical expression 4)
0.001≤(o '+o ")/(n '+n "+m '+m "+o '+o ")≤0.1 (mathematical expression 5)
0.01≤(n '/n ")≤100 (mathematical expressions 6)
0.01≤(m '/m ")≤100 (mathematical expressions 7)
When (n '+n ")/(n '+n "+m '+m ") less than 0.05 the time, have ionic conductivity significantly to reduce and be difficult to tendency as ion-exchange membrane and proton exchange membrane.When (n '+n ")/(n '+n "+m '+m ") greater than 0.8 the time, have that swelling property enlarges markedly, ion-exchange membrane and proton exchange membrane mechanical characteristics when moisture absorption reduce and the tendency that film is dissolved in the problem of water etc. take place easily.(n '+n ")/(n '+n "+m '+m ") more preferably 0.3～0.7 scope, more preferably 0.35～0.5 scope.
When (o '+o ")/(n '+n "+m '+m "+o '+o ") less than 0.001 the time, the tendency that is difficult to obtain fully stabilization effect is arranged, when its greater than 0.1 the time, have the ionic conductivity of ion-exchange membrane and proton exchange membrane to reduce, the tendency of problems such as the right reduction of polymer poly take place easily.(o '+o ")/(n '+n "+m '+m "+o '+o ") more preferably 0.005～0.05 scope, more preferably 0.01～0.04 scope.
N '/n " and m '/m " be preferably 0.01～100 scope, more preferably 0.11～10 scope respectively.
Chemical formula 12 or 13 expressions contain the sulfonic group polymkeric substance, in molecule, have the structure of following chemical formula 36 expressions.By having the structure of chemical formula 36 expressions, the free radical weather resistance improves, and for example can give excellent weather resistance when the polyelectrolyte membrane of using as fuel cell.
Figure S2006800207570D00631
By the sulfonic group polymkeric substance that contains of the present invention that use has the structure of Chemical formula 12 or Chemical formula 13 expressions, the oozing out of the reduction of ionic conductivity and added ingredients, stripping etc. can not taken place and the polyelectrolyte membrane of ionic conductivity, weather resistance and excellent in workability.
Contain the polyelectrolyte membrane that contains the sulfonic group polymkeric substance of the present invention, can bonding electrodes and catalyzer and make polyelectrolyte membrane/assembly of electrode.In addition, with respect to the film beyond the polyelectrolyte membrane of the present invention, can use of the present invention contain the sulfonic group polymkeric substance as with the caking agent of electrode and catalyzer.With the sulfonic group polymkeric substance that contains of the present invention when the caking agent, the Y in preferred Chemical formula 12 and the Chemical formula 13 is that H, sulfonic group are acid type.When under the state of sulfonic group and salt forming cation, using, also can behind joint, sulfonic group be made acid type by acid treatment.
The sulfonic group polymkeric substance that contains of the present invention, in the structures of above-mentioned Chemical formula 12 or 13 expressions, each repeating unit put in order can be alternately, block, in random any.If segmented copolymer then shows the tendency that ionic conductivity and water-absorbent raise.
Contain in the sulfonic group polymkeric substance of the present invention, below will being shown in as the chemical formula 37A～37BX of the concrete example of preferred construction, but scope of the present invention is not limited to these.
Figure S2006800207570D00651
Figure S2006800207570D00661
Figure S2006800207570D00671
Figure S2006800207570D00681
Figure S2006800207570D00691
Figure S2006800207570D00701
Figure S2006800207570D00711
Figure S2006800207570D00731
Figure S2006800207570D00741
Figure S2006800207570D00751
Figure S2006800207570D00761
In chemical formula 37A～37BX, most preferred structure is chemical formula 37A, 37E, 37Q, 37R, 37W, 37X, 37BM, 37BN, secondly preferred construction is chemical formula 37I, 37K, 37M, 37O, 37AU, 37AV, 37BA, 37BB, 37BG, 37BH, and preferred construction is chemical formula 37C, 37G, 37S, 37T, 37AC, 37AD, 37AI, 37AJ, 37BS, 37BT once more.
When containing the sulfonic group polymkeric substance, preferably satisfying following mathematical expression 5,25 and 26 with of the present invention as the proton exchange membrane of the direct methanol fuel cell of directly using methanol aqueous solution to act as a fuel.
0.001≤(o '+o ")/(n '+n "+m '+m "+o '+o ")≤0.1 (mathematical expression 5)
0.05≤(n '+n "+o ')/(n '+n "+m '+m "+o '+o ")≤0.5 (mathematical expression 25)
0.05≤(n "+m ")/(n '+n "+m '+m ")≤0.95 (mathematical expression 26)
When (o '+o ")/(n '+n "+m '+m "+o '+o ") less than 0.001 the time, the tendency that is difficult to obtain fully stabilization effect is arranged, when its greater than 0.1 the time, have the proton-conducting of proton exchange membrane to reduce, the tendency of problems such as the right reduction of polymer poly take place easily.(o '+o ")/(n '+n "+m '+m "+o '+o ") more preferably 0.005～0.05 scope, more preferably 0.01～0.04 scope.
When (n '+n "+o ')/(n '+n "+m '+m "+o '+o ") less than 0.05 the time, have to be difficult to obtain sufficient proton-conducting and the tendency of the easy step-down of output of fuel cell.When its greater than 0.5 the time, the tendency of the easy step-down of output of the too much and fuel cell of the quantitative change that the methyl alcohol penetrate film arranged.(n '+n "+o ')/(n '+n "+m '+m "+o '+o ") preferred scope is 0.05～0.4.In addition, as the concentration of the methanol aqueous solution of fuel when low, (n '+n "+o ')/(n '+n "+m '+m "+o '+o ") under the big situation, it is big that proton-conducting becomes, therefore, the output of fuel cell raises.On the other hand, when using the methanol aqueous solution of high density, (n '+n "+o ')/(n '+n "+m '+m "+o '+o ") under the little situation, can suppress its output and reduce along with methyl alcohol penetrate, the output of fuel cell can be increased.
(n "+m ")/(n '+n "+m '+m ") be preferably 0.05～0.95 scope.When (n "+m ")/(n '+n "+m '+m ") less than 0.05 the time, when bonding electrodes and catalyzer and proton exchange membrane, have easy generation to engage bad tendency, when its greater than 0.95 the time, have swelling property too to become big tendency.(n "+m ")/(n '+n "+m '+m ") preferred scope be 0.2～0.8 scope.(n '+n "+o ')/(n '+n "+m '+m "+o '+o ") less than 0.25 o'clock, (n "+m ")/(n '+n "+m '+m ") 0.4～0.8 scope more preferably.In addition, (n '+n "+o ')/(n '+n "+m '+m "+o '+o ") greater than 0.25 o'clock, (n "+m ")/(n '+n "+m '+m ") 0.1～0.5 scope more preferably.
Polyelectrolyte membrane of the present invention during as the proton exchange membrane of the fuel cell that uses hydrogen to act as a fuel, is preferably being satisfied following mathematical expression 5,27 and 28.
0.001≤(o '+o ")/(n '+n "+m '+m "+o '+o ")≤0.1 (mathematical expression 5)
0.3≤(n '+n "+o ')/(n '+n "+m '+m "+o '+o ")≤0.7 (mathematical expression 27)
0.01≤(n "+m ")/(n '+n "+m '+m ")≤0.25 (mathematical expression 28)
When (o '+o ")/(n '+n "+m '+m "+o '+o ") less than 0.001 the time, the tendency that is difficult to obtain fully stabilization effect is arranged, when its greater than 0.1 the time, have the proton-conducting of proton exchange membrane to reduce, the tendency of problems such as the right reduction of polymer poly take place easily.(o '+o ")/(n '+n "+m '+m "+o '+o ") more preferably 0.005～0.05 scope, more preferably 0.01～0.04 scope.
When (n '+n "+o ')/(n '+n "+m '+m "+o '+o ") less than 0.3 the time, have to be difficult to obtain sufficient proton-conducting, and the tendency of the easy step-down of output of fuel cell.When its greater than 0.7 the time, have the swelling property of film to become tendency that excessive and apt to cause breakage and output reduces etc., (n '+n "+o ')/(n '+n "+m '+m "+o '+o ") more preferably 0.35～0.7 scope, more preferably 0.4～0.5 scope.
(n "+m ")/(n '+n "+m '+m ") be preferably 0.01～0.25 scope.When its less than 0.01 the time, when bonding electrodes and catalyzer and proton exchange membrane, have easy generation to engage bad tendency, when its greater than 0.25 the time, the tendency that has swelling property to become excessive.(n "+m ")/(n '+n "+m '+m ") 0.1～0.2 scope more preferably.
For the sulfonic group polymkeric substance that contains of the present invention, also can be by be necessary composition for example with the monomer of structure and monomer with sulfonic group or derivatives thereof with above-mentioned chemical formula 36, add other monomers as required again and carry out polymerization and obtain.In addition, also can obtain by importing sulfonic group after carrying out polymerization in the polymer of monomers that will use structure with above-mentioned chemical formula 36.Perhaps can and not contain sulfonic polymkeric substance yet and carry out polymerization in advance, in its polymkeric substance, import the structure of sulfonic group and chemical formula 36 again and obtain the structure of above-mentioned chemical formula 36.
One of preferred form that contains the sulfonic group polymkeric substance of the present invention, can by the compound that contains 39 expressions of chemical formula 38 and chemical formula as monomeric mixture that must composition, utilize aromatic nucleophilie nuclear substituting reaction to carry out polymerization.
Figure S2006800207570D00801
(in above-mentioned chemical formula, the positively charged ion of Y ' expression H or 1 valency, Z 8The expression halogen atom, X ' expression-S (=O) 2-group or C (=O)-and group, Ar 10The expression aromatic group, Z 9The derivative of expression OH group or SH group and these groups, p " expression 1 or 2.)
The concrete example of the compound of chemical formula 38 expressions can be enumerated: 3,3 '-disulfo-4,4 '-dichloro diphenyl sulfone, 3,3 '-disulfo-4,4 '-difluorodiphenyl sulfone, 3,3 '-disulfo-4,4 '-dichloro diphenylketone, 3,3 '-disulfo-4,4 '-difluorodiphenyl sulfone, 3,3 '-disulfo butyl-4,4 '-dichloro diphenyl sulfone, 3,3 '-disulfo butyl-4,4 '-difluorodiphenyl sulfone, 3,3 '-disulfo butyl-4,4 '-difluorodiphenyl base ketone, 3,3 '-disulfo butyl-4, the salt of 4 '-difluorodiphenyl sulfone and these sulfonic groups and 1 valency positively charged ion kind etc.1 valency positively charged ion kind can be enumerated: sodium, potassium and other metal object kinds and various amines etc., but can not be limited to these.In the compound of chemical formula 38 expressions, sulfonic group becomes the examples for compounds of salt can be enumerated: 3, and 3 '-sodium disulfonate-4,4 '-dichloro diphenyl sulfone, 3,3 '-sodium disulfonate-4,4 '-difluorodiphenyl sulfone, 3,3 '-sodium disulfonate-4,4 '-dichloro diphenylketone, 3,3 '-sodium disulfonate-4,4 '-difluorodiphenyl sulfone, 3,3 '-sodium disulfonate-4,4 '-difluorodiphenyl base ketone, 3,3 '-disulfonic acid potassium 4,4 '-dichloro diphenyl sulfone, 3,3 '-disulfonic acid potassium 4,4 '-difluorodiphenyl sulfone, 3,3 '-disulfonic acid potassium 4,4 '-dichloro diphenylketone, 3,3 '-disulfonic acid potassium 4,4 '-difluorodiphenyl sulfone, 3,3 '-disulfonic acid potassium 4,4 '-difluorodiphenyl base ketone etc., preferred 3,3 '-sodium disulfonate-4,4 '-dichloro diphenyl sulfone, 3,3 '-sodium disulfonate-4,4 '-difluorodiphenyl sulfone.
As the compound of chemical formula 39 expressions, can enumerate the such compound of following chemical formula 39A～39L as an example, but be not limited to these.
Wherein, the compound of preferred chemical formula 39A～39D, the compound of further preferred chemical formula 39A.
In above-mentioned aromatic nucleophilie nuclear substituting reaction, carry out copolymerization with other various sensitization di halo aromatic compounds, dinitrobenzene aromatics, bisphenol cpd, two thiol compounds as monomer by compound, can obtain the sulfonic group polymkeric substance that contains of the present invention chemical formula 38,39 expressions.
The example of sensitization di halo aromatic compound can be enumerated: 2,6-dichlorobenzonitrile, 2,4-dichlorobenzonitrile, 2,6-difluorobenzonitrile, 2,4-difluorobenzonitrile, 4,4 '-dichloro diphenyl sulfone, 4,4 '-difluorodiphenyl sulfone, 4,4 '-difluoro benzophenone, 4,4 '-dichloro benzophenone, decafluorobiphenyl etc., but be not limited to these, also can use in aromatic nucleophilie nuclear substituting reaction, to have active other aromatic series dihalo compounds, aromatic dinitro compound, aromatic series dicyano compound etc.Wherein preferably, 2,6-dichlorobenzonitrile, 2,4 dichloro benzene formonitrile HCN, 2,6-difluorobenzonitrile, 2,4 difluorobenzene formonitrile HCN, more preferably 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile.
The example of bisphenol cpd or two thiol compounds can be enumerated: 9,9-two (4-hydroxyphenyl) fluorenes, 9,9-two (3-methyl-4-hydroxyphenyl) fluorenes, 4,4 '-'-biphenyl diphenol, 4,4 '-dimercapto biphenyl, two (4-hydroxyphenyl) sulfone, 1,1-two (4-hydroxyphenyl) ethane, 2,2-two (4-hydroxyphenyl) propane, 1,1-two (4-hydroxyphenyl) hexanaphthene, two (4-hydroxyphenyl) methane, 2,2-two (4-hydroxyphenyl) butane, 3,3-two (4-hydroxyphenyl) pentane, 2,2-two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) propane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl) methane, two (4-hydroxyl-2,5-3,5-dimethylphenyl) methane, two (4-hydroxyphenyl) phenylmethane, two (4-hydroxyphenyl) ditan, 2,2-two (4-hydroxyphenyl) HFC-236fa, Resorcinol, ask dihydroxy-benzene, two (4-hydroxyphenyl) ketone, 4,4 '-phenyl disulfide phenol, 4,4 '- , 1,3-two (4-hydroxyphenyl) diamantane, 2,2-two (4-hydroxyphenyl) diamantane, 4,4 '-sulfo-hexichol mercaptan, 1,3-phenylene dimercaptan, 1,4-phenylene dimercaptan, phenolphthalein, poly-(
Figure S2006800207570D00832
Phenyl) bis-phenol etc. also can use the various aromatic diols of polymeric or aromatic series two mercaptan that can be used in the polyarylene ether compound that utilizes aromatic nucleophilie nuclear substituting reaction in addition, and be not limited to above-claimed cpd.And the preferred examples in the compound of usefulness can be enumerated: 4, and 4 '-'-biphenyl diphenol, 9,9-two (4-hydroxyphenyl) fluorenes, 1,3-two (4-hydroxyphenyl) diamantane, 4,4 '-sulfo-biphenol, 4,4 '-
Figure S2006800207570D00833
, 4,4 '-sulfo-hexichol mercaptan, poly-(
Figure S2006800207570D00834
Phenyl) bis-phenol.Use the situation of multiple bisphenol cpd or two thiol compounds, make to be selected from 4 '-'-biphenyl diphenol, 9 by 4,9-two (4-hydroxyphenyl) fluorenes, 1, the compound more than a kind in the family that 3-two (4-hydroxyphenyl) diamantane constitutes and being selected from by 4,4 '-sulfo-biphenol, 4,4 '-
Figure S2006800207570D00835
, 4-4 '-sulfo-hexichol mercaptan, 2,2-two (4-hydroxyphenyl) HFC-236fa, 2,2-two (4-hydroxyphenyl) propane, 4,4 '-dihydroxyl ditan, 1,1-two (4-hydroxyphenyl) hexanaphthene, poly-( Phenyl) compound more than a kind in the family of bis-phenol formation makes up, and can improve connectivity, processibility and the weather resistance of polyelectrolyte membrane, and is preferred.
Utilize the situation that contains the sulfonic group polymkeric substance among aromatic nucleophilie nuclear substituting reaction polymerization the present invention, the compound of structure that can be by making 39 expressions of chemical formula 38 and chemical formula and add other sensitization di halo aromatic compounds, dinitrobenzene aromatics and bisphenol cpd as required or two thiol compounds is reacted and obtained polymkeric substance in the presence of basic cpd.Mol ratio by making reactive halogen in the monomer or nitro and reactive hydroxyl or sulfydryl is mol ratio arbitrarily, can adjust the polymerization degree of the polymkeric substance that obtains, be preferably 0.8～1.2 scope, 0.9～1.1 scope more preferably, further preferred 0.95～1.05 scope, when it is 1, can obtain the polymkeric substance of high-polymerization degree, therefore most preferably.
The sulfonic group content that contains the sulfonic group polymkeric substance of the present invention, be preferably the scope of 0.1～5.0meq/g, more preferably the scope of 0.3～5.0meq/g, the more preferably scope of 0.3～3.5meq/g, the more preferably scope of 0.5～3.5meq/g, the more preferably scope of 1.0～2.5meq/g.When sulfonic group content during less than 0.1meq/g, as polyelectrolyte membrane the time, there is demonstration not go out the tendency of sufficient ionic conductivity, when its during greater than 5.0meq/g, as polyelectrolyte membrane the time, have the swelling of film to become excessive, easily problem that film is dissolved in water, the tendency that reaches capacity of ionic conductivity simultaneously take place.Need to prove that sulfonic group content utilizes volumetry described later to obtain as loading capacity after can sulfonic group being set at the acid type structure by acidic aqueous solution processing etc.
In addition, the second-order transition temperature that contains the sulfonic group polymkeric substance of the present invention is preferably in the scope that is preferably 130 ℃～220 ℃ in 130 ℃～270 ℃ the scope, especially.When second-order transition temperature is lower than 130 ℃, the inadequate tendency of thermotolerance is arranged when the polyelectrolyte membrane, when second-order transition temperature is higher than 270 ℃, and then when being higher than 220 ℃, the tendency that has processibility to reduce when making polyelectrolyte membrane/assembly of electrode.By its second-order transition temperature be in 130 ℃～270 ℃ the scope, in particularly 130 ℃～220 ℃ the scope, the excellent in workability when making polyelectrolyte membrane/assembly of electrode, the thermotolerance the when battery that acts as a fuel simultaneously uses is also good especially.Need to prove, determine by Measurement of Dynamic Viscoelasticity described later in this said second-order transition temperature.
In the present invention, utilize aromatic nucleophilie nuclear substituting reaction that the sulfonic group poly (arylene ether) based compound that contains that formation contains the sulfonic group polymkeric substance is carried out the polymeric situation, can obtain polymkeric substance by sensitization difluoro aromatics and/or dichloro aromatics and aromatic diol class are reacted.Polymerization can be carried out 0～350 ℃ temperature range, is preferably 50～250 ℃ temperature.When temperature is lower than 0 ℃, the tendency that existence can not fully be reacted, when temperature is higher than 350 ℃, the tendency that has polymkeric substance to begin to decompose.Reaction also can be carried out under solvent-free, but preferably carries out in solvent.The solvent that can use can be enumerated: 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, get final product so long as in aromatic nucleophilie nuclear substituting reaction, can be used as the solvent of stable solvent use.These organic solvents can use separately, and the mixture that also can be used as more than 2 kinds uses.Basic cpd can be enumerated: sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus etc. so long as can make the aromatic diol class form the basic cpd of active phenoxide structures, can be not limited to these and use.
When reach two thiol compounds with respect to bisphenol cpd
Figure S2006800207570D00851
When using the basic cpd of the above amount of 100 moles of %, can carry out polymerization well, preferred basic cpd is the scope of 105～125 moles of % with respect to bisphenol cpd and two thiol compounds.When the amount of basic cpd is too much, can cause the generation of side reactions such as decomposing, therefore not preferred.
In addition; in above-mentioned polyreaction; also can not use basic cpd, and make isocyanate compound reaction carrying out material and sensitization di halo aromatic compound and the dinitrobenzene aromatics direct reaction that carbamylization forms such as bisphenol cpd or two thiol compounds and phenylcarbimide.
In aromatic nucleophilie nuclear substituting reaction, side reaction takes place sometimes generate water.At this moment, can make with the irrelevant toluene of polymer solvent etc. to coexist as in the reaction system, as azeotrope with water except that going to system.As with the method for water except that going to system, also can use water-retaining agents such as molecular sieve.Carry out the situation of aromatic nucleophilie nuclear substituting reaction in solvent, the preferred so that polymer concentration that obtains is the amount of the scope of 5～50 weight % monomer of packing into.When its during less than 5 weight %, the tendency that has the polymerization degree to be difficult to rise.On the other hand, when its during greater than 50 weight %, the viscosity of the system that responds is too high, the tendency of the aftertreatment difficulty of reactant.
Polymerization is made the polymkeric substance with the high chain distribution of randomness preferably at the disposable input monomer of initial reaction stage.After polyreaction finishes, desolvate by utilizing evaporation from reaction soln, to remove, and wash residual thing as required, desirable polymkeric substance can be obtained.In addition, in also can the be low solvent, polymkeric substance is precipitated as solid, utilize sedimentary leaching to obtain polymkeric substance by the solubleness that reaction soln is added polymkeric substance.Also can be as required before precipitation generates, carry out filtration treatment, remove the salt that side reaction generates and obtain polymers soln.
In addition, the sulfonic group polymkeric substance that contains of the present invention utilizes the polymkeric substance logarithm viscosity of the method mensuration of narrating later to be preferably more than the 0.1dL/g.When logarithm viscosity during less than 0.1dL/g, the tendency that when being shaped, has film to become fragile easily as polyelectrolyte membrane.Its logarithm viscosity is more preferably more than the 0.3dL/g.On the other hand, when logarithm viscosity surpasses 5dL/g, the problem that polymkeric substance is difficult to processibility aspects such as dissolving that is easy to generate is arranged.Need to prove that the solvent of measuring logarithm viscosity generally can use N-N-methyl-2-2-pyrrolidone N-, N,N-dimethylacetamide isopolarity organic solvent, but when the solvability of polymkeric substance in these solvents is low, also can use the vitriol oil to measure.
With the situation that contains the sulfonic group polymkeric substance as polyelectrolyte membrane of the present invention, also this can be contained the sulfonic group polymkeric substance uses with monomeric form, but also can be by using as resin combination with other combination of polymers, other polymkeric substance for example have: polyester such as polyethylene terephthalate, polybutylene terephthalate, PEN; Nylon 6, nylon 6,6, nylon 6,10, nylon 12 etc. are polyamide-based; Polymethylmethacrylate, polymethacrylate; Acrylic ester such as polymethyl acrylate, polyacrylate(s) resin, polyacrylic resin, polymethyl acrylic acid be resin, comprise cellulose-based resins such as the various polyolefine of polyethylene, polypropylene, polystyrene and diene polymer, polyurethane series resin, rhodia, ethyl cellulose; Aromatic series based polymers such as polyene propyl ester, aromatic poly, polycarbonate, polyphenylene sulfide, polyphenylene oxide, polysulfones, polyethersulfone, polyether-ether-ketone, polyetherimide, polyimide, polyamidoimide, polybenzimidazole, polybenzoxazole, polybenzothiozole; Heat-curing resins such as Resins, epoxy, phenol resins, novolac resin, benzoxazine colophony etc. are not particularly limited.The resin combination of itself and alkaline polymers such as polybenzimidazole and polyvinyl pyridine can be described as the preferred combination in order to improve polymer sizes stability.In these alkaline polymers, use the situation that contains the acidic-group alkaline polymer that acidic-groups such as sulfonic group, phosphonate group are arranged that further imports, consider more preferably from the processibility aspect of resin combination.
These are when using as resin combination, and the content that contains the sulfonic group polymkeric substance of the present invention is preferably below the above 100 quality % of 50 overall quality % of resin combination.More preferably below the above 100 quality % of 70 quality %.When the content that contains the sulfonic group polymkeric substance of the present invention is lower than the overall 50 quality % of resin combination, there is the sulfonic group concentration step-down of the polyelectrolyte membrane contain this resin combination and is difficult to obtain the tendency of good ionic conductivity, in addition, have that to contain sulfonic unit be the tendency that ionic degree of mobilization that discontinuous phase conducts reduces.
Need to prove, the resin combination that contains the sulfonic group polymkeric substance and contain it of the present invention also can contain for example various additives such as antioxidant, thermo-stabilizer, surface slip agent, bonding imparting agent, softening agent, linking agent, viscosity modifier, static inhibitor, antiseptic-germicide, defoamer, dispersion agent, polymerization retarder as required.
As the above-mentioned acidic-group alkaline polymer that contains, that can preferably use the structural unit that contains 40 expressions of following chemical formula contains the acidic-group polybenzimidazole.
Figure S2006800207570D00871
(in chemical formula 40, m 1The integer of expression 1～4, R 1Expression can form 4 yuan of aromatic series bonding unit of imidazole ring, R 2Represent 2 yuan of aromatic series bonding unit, R 1And R 2Can be aromatic monocycle, also can be the bonding body or the fused rings of a plurality of aromatic nucleus, also can have stable substituting group.Z 3Expression sulfonic group and/or phosphonate group, its part also can become the salt structure)
The synthetic path that contains acidic-group polybenzimidazole based compound of containing the structural unit of above-mentioned chemical formula 40 expressions is not particularly limited, but usually can by be selected from the family that constitutes by aromatic series tetraamine that can form the imidazole ring in the compound and their derivative more than one compound and more than one the reaction of compound that is selected from the family that constitutes by aromatic dicarboxylic acid and derivative thereof synthesize.At this moment, contain the dicarboxylic acid of sulfonic group and phosphonate group or their salt at least a portion by use, can in the polybenzimidazole that obtains, import sulfonic group and phosphonate group as the dicarboxylic acid that uses.The dicarboxylic acid that contains sulfonic group and phosphonate group can make up more than one respectively and use, and contains the sulfonic group dicarboxylic acid and contains the phosphonate group dicarboxylic acid but also can use simultaneously.
At this, benzoglyoxaline as the integrant of polybenzimidazole based compound is the bonding unit, has the aromatic dicarboxylic acid bonding unit of sulfonic group and/or phosphonate group, neither has aromatic dicarboxylic acid bonding unit and other bonding unit that sulfonic group does not have phosphonate group yet, preferably carries out bonding by random polymerization and/or alternating polymerization.In addition, these polymerized forms are not limited to a kind of, also can be that two or more polymerized form is in same compound and deposit.
The resin combination that contains the sulfonic group polymkeric substance and contain it of the present invention can be made moldinies such as fiber and film with arbitrary method such as extruding, spinning, rolling or casting.Wherein, preferably form by the solution that is dissolved in appropriate solvent.In addition, also can be dissolved in appropriate solvent and make liquid composite.This solvent can use and be selected from N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N, mixed solvent in the combination of ethers such as ketones such as alcohols, acetone, diethyl ether, water etc. such as non-proton property polar solvent such as N-diethyl acetamide, dimethyl sulfoxide (DMSO), N-N-methyl-2-2-pyrrolidone N-, hexamethyl phosphonic amide, N-morpholine oxide and methyl alcohol, ethanol etc., but be not limited to these.These solvents also can use multiple mixing within the bounds of possibility.
Compound concentration in the solution is preferably the scope of 0.1～50 quality %.When the compound concentration in the solution is lower than 0.1 quality %, there is the tendency that is difficult to obtain good shaping thing, when it surpasses 50 quality %, the tendency that exists processibility to worsen.
By solution formed film, fiber etc. the time, more preferably its concentration is the scope of 5～50 weight %, further the scope of preferred 10～40 weight %.When solution was used as caking agent, more preferably its concentration was the scope of 0.1～20 weight %.With solution when the caking agent, also can contain other compositions such as the carbon particles of catalyzer such as supporting Pt, Pt-Ru and fluoro-resin.
The method that obtains molding by solution can be used present known method and carry out.For example, by heating, drying under reduced pressure, impregnated in that can to carry out blended compound non-solvent with the solvent of dissolved compound medium, removing desolvates can obtain molding.When solvent is organic solvent, preferably distills to remove and desolvate by heating or drying under reduced pressure.At this moment, can be as required be configured as different shapes such as fibrous, film like, particulate state, tabular, funnel-form, tubulose, spherical, bulk with the form that is combined into other compounds.When making up with the solubility behavior similar compounds, can carry out aspect the good shaping preferred.Sulfonic group in the molding that obtains like this can be containing with the salifiable form of positively charged ion kind shape, but also can convert the free sulfonic group to by carrying out acid treatment as required.
In the present invention, can make polyelectrolyte membrane by the resin combination that contains the sulfonic group polymkeric substance and contain it.As the method for shaping polyelectrolyte membrane, most preferably the teeming practice that is undertaken by solution removes as described above from the solution of casting and desolvates, and can obtain polyelectrolyte membrane.As this solution, also can enumerate: using has N-N-methyl-2-2-pyrrolidone N-, N, the solution of organic solvents such as dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO); According to circumstances be selected from mixed solvent in the combination of alcohols, ketone, water etc. etc.Consider from the homogeneity of ion-conductive membranes, preferably desolvate by dry removing.In addition, for fear of the decomposition of compound and solvent and rotten, also preferably under reduced pressure, under alap temperature, carry out drying.In addition, when the viscosity of solution was high, when at high temperature casting when heated substrates and solution, the viscosity of solution reduced, and can easily cast.
The thickness of the solution when casting is not particularly limited, and is preferably 10～1500 μ m, more preferably 50～500 μ m.When the thickness of solution during less than 10 μ m, existence can not keep the tendency as the form of polyelectrolyte membrane, when its during greater than 1500 μ m, have the tendency that forms uneven polyelectrolyte membrane easily.
The method of the casting thickness of control solution can be used known method.For example, can use material feeder, wing etc. to make constant thickness or use prevents that effusive frame of solution and glass dish etc. from making the casting constant area, with the amount and the concentration control thickness of solution.The solution that casting is good can be made uniform film by the speed of removing of adjusting solvent.For example, when adding the heat extraction solvent, can be set at low temperature and reduce velocity of evaporation in the initial stage.In addition, when impregnated in non-solvent such as water, solution can be placed reasonable time in air and in the rare gas element and be adjusted the setting rate and the solvent of compound comparably and remove speed.
Polyelectrolyte membrane of the present invention can be made thickness arbitrarily according to purpose, but considers from the ionic conductivity aspect, and is preferably thin as far as possible.Thickness is preferably the scope of 5～300 μ m, the scope of 5～100 μ m more preferably, and the scope of 5～50 μ m more preferably, the scope of 10～50 μ m more preferably most preferably is the scope of 20～50 μ m.When thickness during, the use difficulty of polyelectrolyte membrane there is, when making fuel cell, is short-circuited easily etc. or is difficult to satisfy the tendency of the characteristic of regulation less than 5 μ m.When thickness during, there is the resistance value of polyelectrolyte membrane to raise, the power generation performance of fuel cell reduces or make the tendency of difficulty greater than 300 μ m.
When polyelectrolyte membrane of the present invention was used as ion-conductive membranes, the sulfonic group in the film also can contain the sulfonic group that becomes metal-salt, but also can convert free sulfonic acid by suitable acid treatment to.At this moment, by in the heated in water solution of sulfuric acid, hydrochloric acid etc. or not carry out heatedly film being carried out dip treating be effective.
In addition, the ionic conductance of polyelectrolyte membrane of the present invention is preferably 1.0 * 10 -3More than the S/cm.When ionic conductance is 1.0 * 10 -3When S/cm is above, exists in and use the tendency that can obtain good output in the fuel cell that polyelectrolyte membrane is arranged, when it is lower than 1.0 * 10 -3During S/cm, there is the tendency of the output reduction of fuel cell.
Polyelectrolyte membrane of the present invention is to being that the direct methanol fuel cell of fuel also is useful with methyl alcohol.Special preferred fabrication mean thickness is the film of 50 μ m, and uses the 5M methanol aqueous solution, is shown as 7mmol/ (m 25 ℃ of methyl alcohol penetrate speed of measuring down 2Sec) polyelectrolyte membrane of Yi Xia value.Can give the power generation characteristics of fuel cell excellence this moment.In addition, further the particular methanol penetration speed is 4mmol/ (m 2Sec) below, 1mmol/m more preferably 2Below the sec.The methyl alcohol penetrate characteristic depends on thickness sometimes, is that the situation of the sample of 50 μ m is narrated to being made into mean thickness in above-mentioned methyl alcohol penetrate speed, but in fact when using ion-conductive membranes as fuel cell, can not limit thickness especially.Need to prove that above-mentioned mean thickness is the film of 50 μ m, represent the film of the scope of mean thickness 48 μ m～mean thicknesss 52 μ m in fact.
Containing the sulfonic group polymkeric substance and containing in the polyelectrolyte membrane that its resin combination obtains by of the present invention, contain the situation of carrying out crosslinked composition by heat and/or light, by utilizing thermal treatment and/or photo-irradiation treatment in molecular chain, to import crosslinking structure, can make the dimensional stability of film excellent more.Heating temperature when carrying out heat cross-linking is different because of the structure of bridging property polymkeric substance, the kind of crosslinkable groups, the import volume of crosslinkable groups etc., is generally 150～450 ℃, is preferably 200～400 ℃.Heat-up time is different because of structure of Heating temperature and bridging property polymkeric substance etc., is generally 0.01～50 hour, is preferably 0.02～24 hour.Pressure can be in normal pressure, decompression, the pressurization any.In addition, atmosphere can be any of air atmosphere, nitrogen atmosphere, argon atmosphere.When Heating temperature was high, preferred sulfonic group was done salifiable state and is heat-treated.In addition, the light source when being used to carry out photo-crosslinking is not particularly limited, and can use Cooper-Hewitt lamp, high pressure mercury vapour lamp, xenon lamp, metal halide lamp etc.The illuminated line amount is different because of polymer architecture and thickness thereof, is generally 100～50000mJ/cm 2, be preferably 300～30000mJ/cm 2
In addition, by above-mentioned polyelectrolyte membrane of the present invention or film etc. are engaged in electrode, can obtain conjugant as the polyelectrolyte membrane of polyelectrolyte membrane/assembly of electrode of the present invention or film etc. and electrode.The making method of this conjugant can be used present known method and carry out, and for example has: at the electrode surface adhesive-applying polyelectrolyte membrane and electrode are carried out bonding method or polyelectrolyte membrane and electrode are carried out method of heating and pressurizing etc.Wherein, preferably will carry out bonding method in electrode surface with the adhesive applicating that the resin combination that contains the sulfonic group polymkeric substance and contain it of the present invention is a main component.It has been generally acknowledged that this is because the cementability of polyelectrolyte membrane and electrode improves, and the cause that the damage of the ionic conductivity of polyelectrolyte membrane is tailed off.
Need to prove, also can be by the sulfonic group polymkeric substance that contains of the present invention is used for electrode catalyst layer and forms polyelectrolyte membrane/assembly of electrode.
Also can use the conjugant of above-mentioned polyelectrolyte membrane or film etc. and electrode to make fuel cell.For example, the battery that by the polyelectrolyte membrane that will have the oxygen utmost point, fuel electrodes and dispose in the mode that is held on this oxygen utmost point and this fuel electrodes and in the oxygen utmost point side oxygenant port plate that formed the oxygenant stream is set, the fuel port plate that has formed fuel flow path is set in the fuel electrodes side can be made this fuel cell as elementary cell.Polyelectrolyte membrane of the present invention or film etc. are particularly suitable for the fuel cell of solid polymer type.The ionic conductivity of polyelectrolyte membrane of the present invention and excellent in te pins of durability can be born the running under the high temperature, and the excellent in workability when making polyelectrolyte membrane/assembly of electrode can provide the fuel cell of making easily, having good output.The sulfonic group polymkeric substance that contains of the present invention by adjusting the sulfonic acid base unit weight in the polymkeric substance, can be preferred for methyl alcohol being the direct methanol fuel cell of fuel and being the polymer electrolyte fuel cell of fuel with hydrogen.In addition, also go for other materials such as dme, hydrogen, formic acid, in addition, also can be used as dielectric film, separatory membrane plasma exchange membrane is used for known any purposes as the fuel cell of fuel.
[embodiment]
Use embodiment to specifically describe the present invention below, but the present invention is not limited to these embodiment.
＜embodiment 1A～12A 〉
Various mensuration are following carries out.
Soltion viscosity: the concentration with 0.5g/dl is dissolved in N-Methyl pyrrolidone with polymer powder, in 30 ℃ thermostatic bath, use Ni Buluode type viscometer to carry out viscosimetric analysis, with logarithm viscosity (ln[ta/tb]/estimate c) that (ta is drippage number second of sample solution, tb is drippage number second of only solvent, and c is a polymer concentration).
TGA: use Shimadzu Seisakusho Ltd. to heat weight analysis instrument (TGA-50), in argon atmosphere, measure (in the way, keeping fully removing in 30 minutes moisture down) at 150 ℃ with 10 ℃/min of heat-up rate.
Ionic conductivity is measured: measure with on the probe (tetrafluoroethylene resin (Teflon (registered trademark)) system), with platinum line (diameter: 0.2mm) be placed on the surface of rectangle film sample in self-control, in the fixed temperature and humidity baking oven (the Na ガ ノ of Co., Ltd. science machinery production institute, LH-20-01) of 80 ℃ of 95%RH, keep sample, utilize the alternating-current impedance between the 1250FREQUENCYRESPONSE ANALYSER of SOLARTRON company mensuration platinum line.Change pole distance and measure, had from the gradient of the estimated resistance measurement value of pole distance and C-C curve by plotting, the electric conductivity behind the contact resistance that the formula below utilizing has been calculated cancellation between film and the platinum line is as the index of ionic conductivity.In addition, impregnated in the ultrapure water that remains on 25 ℃ and carry out same mensuration, also calculated the electric conductivity in the water by measuring probe.
Wide [the cm] * thickness of electric conductivity [S/cm]=1/ film [cm] * resistance interpolar gradient [Ω/cm]
Sulfonic group content: the quality of the sample that is determined under the nitrogen atmosphere a whole night dry, and after carrying out stir process with aqueous sodium hydroxide solution, (meq/g) obtain as loading capacity (IEC) by the back titration that utilizes aqueous hydrochloric acid to carry out.
Methyl alcohol penetrate speed: calculate by the following method: the film that will flood 24 hours in being adjusted into 25 ℃ the methanol aqueous solution of 5M (mol) sandwiches H type groove, inject the 5M methanol aqueous solution of 100ml in a side of groove, in another groove, inject the ultrapure water (18M Ω cm) of 100ml, on one side at 25 ℃ of grooves that stir both sides down, (area of ion-exchange membrane is 2.0cm Yi Bian use gas chromatograph for determination to be diffused into quantity of methyl alcohol in the ultrapure water by ion-exchange membrane 2).
Second-order transition temperature: use オ リ エ Application テ Star Network to make Rheogel-E4000, film sample to the wide 5mm of sample, effective long 15mm of sample stretches sinusoidal wave, carry out Measurement of Dynamic Viscoelasticity for 2 ℃/minute with heat-up rate, will be defined as second-order transition temperature by the temperature temperature that spring rate begins to reduce that rises.
HNMR measures: sample dissolution in deuterated dimethyl sulfoxide, is used the バ リ ア Application GEMINI200NMR of company optical splitter, measure under 80 ℃.
Generating is estimated: carry a spot of ultrapure water of adding and Virahol in Pt/Ru catalyzer (TEC61E54 of Tianzhonggui Metal Industrial Co., Ltd) and after getting wet at carbon, add 20%Nafion (registered trademark) solution (article number: SE-20192), be 2.5: 1 that E.I.Du Pont Company makes so that carbon carries the mass ratio of Pt/Ru catalyzer and Nafion (registered trademark).Stir then, prepared anode catalyzer cream.Utilizing silk screen printing to apply drying this catalyzer cream, is 2mg/cm so that become the adhesion amount of the last platinum of Toray corporate system carbon paper TGPH-060 of gas diffusion layers 2, be made into anode belt electrode catalyst layer carbon paper.In addition, carry in the Pt catalyzer (TEC10V40E of Tianzhonggui Metal Industrial Co., Ltd) at carbon and to add a spot of ultrapure water and Virahol and after getting wet, add 20%Nafion (registered trademark) solution (article number: SE-20192) that E.I.Du Pont Company makes, so that carbon carries the mass ratio of Pt catalyzer and Nafion (registered trademark) is 2.5: 1, stir, prepared catalyst for cathode cream.With this catalyzer cream apply, drying so that be 1mg/cm at the adhesion amount of having implemented platinum on the Toray corporate system carbon paper TGPH-060 of waterproof processing 2, be made into negative electrode belt electrode catalyst layer carbon paper.Clamping film sample between above-mentioned two kinds of belt electrode catalyst layer carbon papers so that electrode catalyst layer and film sample join, utilizes pressure sintering to pressurize, heat 3 minutes under 130 ℃, 8MPa, makes polyelectrolyte membrane/assembly of electrode thus.
This conjugant pack the evaluation of into Electrochem corporate system with fuel cell groove FC25-02SP, use fuel cell power generation trier (the Dongyang テ Network ニ カ of Co., Ltd. manufacturing) to carry out power generation test.Under 40 ℃ of groove temperature, on one side antianode and negative electrode methanol aqueous solution (1.5ml/min) and the high purity oxygen (80ml/min) of supplying with the 2mol/l that is adjusted into 40 ℃ respectively generate electricity on one side.
(embodiment 1A)
Take by weighing 3,3 '-disulfo-4,4 '-dichloro diphenyl sulfone, 2 sodium salts (are called for short: S-DCDPS) 9.6228g (0.019588mole), 2, the 6-dichlorobenzonitrile (be called for short: DCBN) 3.1102g (0.018082mole), (be called for short: DPE) (big Japanese ink is made SPECIANOLDPE-PL, lot number C106) (in chemical formula, contains the mixture of ingredients of n=1～7 to contain the terminal hydroxyl phenylene ether oligomer.The average group of utilizing NMR to measure becomes n=4.0.) 20.71319g (0.037670mole), salt of wormwood 5.9873g (0.043321mole) add in the 200ml four neck flasks, feeds nitrogen.Add the N-N-methyl-2-2-pyrrolidone N-of 100ml and carry out heated and stirred, make temperature of reaction rise to 195～200 ℃, make its reaction 13 hours.After the naturally cooling, polymer fluid is injected water, make polymer precipitation become fibrous, obtain by containing the polymkeric substance that sulfonic group poly (arylene ether) based compound constitutes.What obtain polymer impregnatedly after 1 day, carries out drying in fresh water.The logarithm viscosity of polymkeric substance is shown as 0.36.
Polymkeric substance 20g is dissolved in NMP 80ml, and into about 500 μ m thickness, distillation is removed NMP after become film like in the top casting of hot plate upper glass plates, and dipping is more than a whole night in water.The film that obtains dip treating 1 day in dilute sulphuric acid (vitriol oil 6ml, water 300ml), the acidic-group in the polymkeric substance become the acid type structure from salt type Structure Conversion after, per 1 hour dipping is 2 times in pure water, thus sour composition is removed and is carried out drying.Measure the ionic conductivity of this film, under 80 ℃ of 95%RH, be shown as 0.15S/cm, in 25 ℃ of water, be shown as the value of 0.032S/cm.It is 286 ℃ that this film is measured the beginning loss of weight temperature (is that benchmark is measured with the sample weight under 200 ℃) that obtains by thermogravimetric, and the temperature of loss of weight 3% is 352 ℃.The IEC that obtains by titration is shown as 1.23meq/g.Methyl alcohol penetrate speed is shown as 2.6mmol/ (m 2Sec).Fig. 1 is expression by the film that containing of obtaining among the embodiment 1A, sulfonic group poly (arylene ether) based compound constituted 1The HNMR wave spectrum reaches the figure by the structural formula of this wave spectrum ownership.Integrated value by the wave spectrum of Fig. 1 learns, the mean value of the n among the figure in the structural formula shows and is about 4.4.
(embodiment 2A)
Take by weighing S-DCDPS 10.2452g (0.020855mole), DCBN 9.2246g (0.053628mole), DPE (big Japanese ink is made SPECIANOL DPE-PL, lot number C106) 20.4777g (0.03724mole), 4,4 '-dihydroxy diphenyl ether 7.5307g (0.03724mole), salt of wormwood 11.8385g (0.08566mole) add in the 200ml four neck flasks, feed nitrogen.Add the N-N-methyl-2-2-pyrrolidone N-of 140ml and carry out heated and stirred, make temperature of reaction rise to 195～200 ℃, make its reaction 16 hours.After the naturally cooling, polymer fluid is injected water, make polymer precipitation become fibrous, obtain by containing the polymkeric substance that sulfonic group poly (arylene ether) based compound constitutes.What obtain polymer impregnatedly after 1 day, carries out drying in fresh water.The logarithm viscosity of polymkeric substance is shown as 0.90.
20g is dissolved in NMP80ml with polymkeric substance, and into about 500 μ m thickness, distillation is removed NMP after become film like in the top casting of hot plate upper glass plates, and dipping is more than a whole night in water.The film that obtains dip treating 1 day in dilute sulphuric acid (vitriol oil 6ml, water 300ml), the acidic-group in the polymkeric substance become the acid type structure from salt type Structure Conversion after, per 1 hour dipping is 2 times in pure water, thus sour composition is removed and is carried out drying.Measure the ionic conductivity of this film, under 80 ℃ of 95%RH, be shown as 0.05S/cm, in 25 ℃ of water, be shown as the value of 0.019S/cm.The temperature (is benchmark mensuration with 200 ℃ of sample weights down) of measuring the beginning loss of weight obtain by thermogravimetric of this film is 297 ℃, and the temperature during loss of weight 3% is 362 ℃.The IEC that obtains by titration is shown as 0.90meq/g.Methyl alcohol penetrate speed is shown as 1.2mmol/ (m 2Sec).The second-order transition temperature that is obtained by Measurement of Dynamic Viscoelasticity is 153 ℃.
Fig. 2 is expression by the film that containing of obtaining among the embodiment 2A, sulfonic group poly (arylene ether) based compound constituted 1The HNMR wave spectrum reaches the figure by the structural formula of this wave spectrum ownership.Integrated value by the wave spectrum of Fig. 2 learns, the mean value of the n among the figure in the structural formula shows and is about 2.0.
(embodiment 3A)
Take by weighing S-DCDPS11.0125g (0.022417mole), DCBN4.0134g (0.02333mole), DPE (big Japanese ink is made SPECIANOL DPE-PL, lot number C106) 12.5779g (0.022875mole), 4,4 '-dihydroxy diphenyl ether 4.6255g (0.022875mole), salt of wormwood 7.2715g (0.05261mole) add in the 200ml four neck flasks, feed nitrogen.Add the N-N-methyl-2-2-pyrrolidone N-of 100ml and carry out heated and stirred, make temperature of reaction rise to 195～200 ℃, make its reaction 15 hours.After the naturally cooling, polymer fluid is injected water, make polymer precipitation become fibrous, obtain by containing the polymkeric substance that sulfonic group poly (arylene ether) based compound constitutes.What obtain polymer impregnatedly carries out drying in fresh water after 1 day.The logarithm viscosity of polymkeric substance is shown as 0.56.
20g is dissolved in NMP80ml with polymkeric substance, and into about 500 μ m thickness, distillation is removed NMP after become film like in the top casting of hot plate upper glass plates, and dipping is more than a whole night in water.The film that obtains dip treating 1 day in dilute sulphuric acid (vitriol oil 6ml, water 300ml), the acidic-group in the polymkeric substance become the acid type structure from salt type Structure Conversion after, per 1 hour dipping is 2 times in pure water, thus sour composition is removed and is carried out drying.Measure the ionic conductivity of this film, under 80 ℃ of 95%RH, be shown as 0.19S/cm, in 25 ℃ of water, be shown as the value of 0.090S/cm.The temperature (is benchmark mensuration with 200 ℃ of sample weights down) of measuring the beginning loss of weight obtain by thermogravimetric of this film is 284 ℃, and the temperature during loss of weight 3% is 346 ℃.The IEC that obtains by titration is shown as 1.52meq/g.Methyl alcohol penetrate speed is shown as 4.4mmol/ (m 2Sec).The second-order transition temperature that is obtained by Measurement of Dynamic Viscoelasticity is 162 ℃.
(embodiment 4A)
Take by weighing S-DCDPS10.0608g (0.02048mole), DCBN5.7477g (0.03341mole), DPE (big Japanese ink is made SPECIANOL DPE-PL, lot number C106) 14.8173g (0.026947mole), 4,4 '-dihydroxy diphenyl ether 5.4490g (0.026947mole), salt of wormwood 8.5661g (0.061979mole) add in the 200ml four neck flasks, feed nitrogen.Add the N-N-methyl-2-2-pyrrolidone N-of 110ml and carry out heated and stirred, make temperature of reaction rise to 195～200 ℃, make its reaction 15 hours.After the naturally cooling, polymer fluid is injected water, make polymer precipitation become fibrous, obtain by containing the polymkeric substance that sulfonic group poly (arylene ether) based compound constitutes.What obtain polymer impregnatedly carries out drying in fresh water after 1 day.The logarithm viscosity of polymkeric substance is shown as 0.51.
20g is dissolved in NMP80ml with polymkeric substance, and into about 500 μ m thickness, distillation is removed NMP after become film like in the top casting of hot plate upper glass plates, and dipping is more than a whole night in water.The film that obtains dip treating 1 day in dilute sulphuric acid (vitriol oil 6ml, water 300ml), the acidic-group in the polymkeric substance become the acid type structure from salt type Structure Conversion after, per 1 hour dipping is 2 times in pure water, thus sour composition is removed and is carried out drying.Measure the ionic conductivity of this film, under 80 ℃ of 95%RH, be shown as 0.11S/cm, in 25 ℃ of water, be shown as the value of 0.042S/cm.The temperature (is benchmark mensuration with 200 ℃ of sample weights down) of measuring the beginning loss of weight obtain by thermogravimetric of this film is 303 ℃, and the temperature during loss of weight 3% is 361 ℃.The IEC that obtains by titration is shown as 1.21meq/g.Methyl alcohol penetrate speed is shown as 2.6mmol/ (m 2Sec).
(embodiment 5A)
Take by weighing S-DCDPS8.1896g (0.016671mole), DCBN9.6001g (0.055811mole), DPE (big Japanese ink is made SPECIANOL DPE-PL, lot number C106) 10.3532g (0.018121mole), 4,4 '-dihydroxy diphenyl ether 10.9925g (0.054362mole), salt of wormwood 11.5205g (0.08336mole) add in the 200ml four neck flasks, feed nitrogen.Add the N-N-methyl-2-2-pyrrolidone N-of 110ml and carry out heated and stirred, make temperature of reaction rise to 195～200 ℃, make its reaction 14 hours.After the naturally cooling, polymer fluid is injected water, make polymer precipitation become fibrous, obtain by containing the polymkeric substance that sulfonic group poly (arylene ether) based compound constitutes.What obtain polymer impregnatedly carries out drying in fresh water after 1 day.The logarithm viscosity of polymkeric substance is shown as 0.93.
20g is dissolved in NMP80ml with polymkeric substance, and into about 500 μ m thickness, distillation is removed NMP after become film like in the top casting of hot plate upper glass plates, and dipping is more than a whole night in water.The film that obtains dip treating 1 day in dilute sulphuric acid (vitriol oil 6ml, water 300ml), the acidic-group in the polymkeric substance become the acid type structure from salt type Structure Conversion after, per 1 hour dipping is 2 times in pure water, thus sour composition is removed and is carried out drying.Measure the ionic conductivity of this film, under 80 ℃ of 95%RH, be shown as 0.05S/cm, in 25 ℃ of water, be shown as the value of 0.018S/cm.The temperature (is benchmark mensuration with 200 ℃ of sample weights down) of measuring the beginning loss of weight obtain by thermogravimetric of this film is 304 ℃, and the temperature during loss of weight 3% is 365 ℃.The IEC that obtains by titration is shown as 0.93meq/g.Methyl alcohol penetrate speed is shown as 1.1mmol/ (m 2Sec).The second-order transition temperature that is obtained by Measurement of Dynamic Viscoelasticity is 173 ℃.
(embodiment 6A)
Take by weighing 3,3 '-disulfo-4,4 '-difluoro benzophenone, 2 sodium salt 6.1115g (0.01447mole), DCBN 5.8085g (0.03377mole), DPE (big Japanese ink is made SPECIANOLDPE-PL, lot number C106) 13.7812g (0.02412mole), 4,4 '-dihydroxy diphenyl ether 4.8774g (0.02412mole), salt of wormwood 6.6675g (0.05548mole) add in the 200ml four neck flasks, feed nitrogen.Add the N-N-methyl-2-2-pyrrolidone N-of 90ml and carry out heated and stirred, make temperature of reaction rise to 195～200 ℃, make its reaction 18 hours.After the naturally cooling, polymer fluid is injected water, make polymer precipitation become fibrous, obtain by containing the polymkeric substance that sulfonic group poly (arylene ether) based compound constitutes.What obtain polymer impregnatedly carries out drying in fresh water after 1 day.The logarithm viscosity of polymkeric substance is shown as 0.58.
20g is dissolved in NMP80ml with polymkeric substance, and into about 500 μ m thickness, distillation is removed NMP after become film like in the top casting of hot plate upper glass plates, and dipping is more than a whole night in water.The film that obtains dip treating 1 day in dilute sulphuric acid (vitriol oil 6ml, water 300ml), the acidic-group in the polymkeric substance become the acid type structure from salt type Structure Conversion after, per 1 hour dipping is 2 times in pure water, thus sour composition is removed and is carried out drying.Measure the ionic conductivity of this film, under 80 ℃ of 95%RH, be shown as 0.06S/cm, in 25 ℃ of water, be shown as the value of 0.21S/cm.The temperature (is benchmark mensuration with 200 ℃ of sample weights down) of measuring the beginning loss of weight obtain by thermogravimetric of this film is 297 ℃, and the temperature during loss of weight 3% is 362 ℃.The IEC that obtains by titration is shown as 1.03meq/g.Methyl alcohol penetrate speed is shown as 1.3mmol/ (m 2Sec).
(embodiment 7A)
Take by weighing S-DCDPS7.1016g (0.01446mole), DCBN6.3941g (0.03717mole), DPE (big Japanese ink is made SPECIANOL DPE-PL, lot number C106) 14.7491g (0.025815mole), 4,4 '-'-biphenyl diphenol 4.8069g (0.025815mole), salt of wormwood 8.2060g (0.059373mole) add in the 200ml four neck flasks, feed nitrogen.Add the N-N-methyl-2-2-pyrrolidone N-of 100ml and carry out heated and stirred, make temperature of reaction rise to 195～200 ℃, make its reaction 15 hours.After the naturally cooling, polymer fluid is injected water, make polymer precipitation become fibrous.What obtain polymer impregnatedly carries out drying in fresh water after 1 day.The logarithm viscosity of polymkeric substance is shown as 0.79.
20g is dissolved in NMP80ml with polymkeric substance, and into about 500 μ m thickness, distillation is removed NMP after become film like in the top casting of hot plate upper glass plates, and dipping is more than a whole night in water.The film that obtains dip treating 1 day in dilute sulphuric acid (vitriol oil 6ml, water 300ml), the acidic-group in the polymkeric substance become the acid type structure from salt type Structure Conversion after, per 1 hour dipping is 2 times in pure water, thus sour composition is removed and is carried out drying.Measure the ionic conductivity of this film, under 80 ℃ of 95%RH, be shown as 0.08S/cm, in 25 ℃ of water, be shown as the value of 0.040S/cm.The IEC that obtains by titration is shown as 0.95meq/g.Methyl alcohol penetrate speed is shown as 1.0mmol/ (m 2Sec).
(embodiment 8A)
Take by weighing S-DCDPS 8.3450g (0.016987mole), 4,4 '-dichloro diphenyl sulfone 9.9040g (0.03449mole), DPE (big Japanese ink is made SPECIANOL DPE-PL, lot number C106) 14.7056g (0.025738mole), 4,4 '-dihydroxy diphenyl ether 5.2045g (0.025738mole), salt of wormwood 8.1817g (0.05920mole) add in the 200ml four neck flasks, feed nitrogen.Add the N-N-methyl-2-2-pyrrolidone N-of 115ml and carry out heated and stirred, make temperature of reaction rise to 195～200 ℃, make its reaction 19 hours.After the naturally cooling, polymer fluid is injected water, make polymer precipitation become fibrous, obtain by containing the polymkeric substance that sulfonic group poly (arylene ether) based compound constitutes.What obtain polymer impregnatedly carries out drying in fresh water after 1 day.The logarithm viscosity of polymkeric substance is shown as 0.67.
20g is dissolved in NMP80ml with polymkeric substance, and into about 500 μ m thickness, distillation is removed NMP after become film like in the top casting of hot plate upper glass plates, and dipping is more than a whole night in water.The film that obtains dip treating 1 day in dilute sulphuric acid (vitriol oil 6ml, water 300ml), the acidic-group in the polymkeric substance become the acid type structure from salt type Structure Conversion after, per 1 hour dipping is 2 times in pure water, thus sour composition is removed and is carried out drying.Measure the ionic conductivity of this film, under 80 ℃ of 95%RH, be shown as 0.08S/cm, in 25 ℃ of water, be shown as the value of 0.037S/cm.The IEC that obtains by titration is shown as 0.94meq/g.Methyl alcohol penetrate speed is shown as 2.9mmol/ (m 2Sec).
(embodiment 9A)
Take by weighing 3,3 ' 4,4 '-tetramino sulfobenzide 1.500g (5.389 * 10 -3Mole), 2,5-dicarboxyl Phenylsulfonic acid 1.445g (5.389 * 10 -3Mole), polyphosphoric acid (five phosphorus oxide content, 75 quality %) 20.5g, five phosphorus oxide 16.5g add in the aggregation container.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 is carried out naturally cooling after finishing, and adds entry and takes out polymkeric substance, uses home-use stirrer to wash repeatedly, is neutral to the pH test paper, obtains by containing the polymkeric substance that sulfonic group poly (arylene ether) based compound constitutes.The polymkeric substance that obtains is 80 ℃ of following drying under reduced pressure a whole nights.The logarithm viscosity of polymkeric substance shows 2.19.With this polymkeric substance 1g heating for dissolving in the N-of 10ml N-methyl-2-2-pyrrolidone N-, after the system film that is made into by embodiment 3A mixes with solution 40ml, adjust casting thickness, in addition, operate equally with embodiment 1A, be made into by the mixed film that contains the thickness 50 μ m that the resin combination that contains sulfonic group poly (arylene ether) based compound of the present invention constitutes.The content that contains sulfonic group poly (arylene ether) based compound in this resin combination is 91 quality %.
Measure the ionic conductivity of this film, in 25 ℃ of water, be shown as the value of 0.06S/cm.Methyl alcohol penetrate speed is shown as 3.5mmol/ (m 2Sec).
(embodiment 10A)
Take by weighing 3,3 ' 4,4 '-tetramino sulfobenzide 1.830g (6.575 * 10 -3Mole), 3,5-dicarboxyl Phenylsulfonic acid 1.084g (4.405 * 10 -3Mole), terephthalic acid 0.360g (2.170 * 10 -3Mole), polyphosphoric acid (five phosphorus oxide content, 75 quality %) 20.5g, five phosphorus oxide 16.5g add in the aggregation container.Feed nitrogen, on oil bath slowly stir on one side, be warming up to 100 ℃ on one side.100 ℃ down keep 1 hour after, be warming up to 150 ℃ of polymerizations 1 hour, be warming up to 200 ℃ of polymerase 17s hour.Polymerization is carried out naturally cooling after finishing, and adds entry and takes out polymkeric substance, uses home-use stirrer to wash repeatedly, is neutral to the pH test paper, obtains by containing the polymkeric substance that sulfonic group poly (arylene ether) based compound constitutes.The polymkeric substance that obtains is 80 ℃ of following drying under reduced pressure a whole nights.Use the logarithm viscosity of the polymkeric substance of sulfuric acid mensuration to be shown as 1.07.
Use this polymkeric substance 1g, use with the same method of embodiment 9A and mix with solution 40ml, made by containing the mixed film that the resin combination that contains sulfonic group poly (arylene ether) based compound of the present invention constitutes with the system film that is made into by embodiment 3A.The content that contains sulfonic group poly (arylene ether) based compound in this resin combination is 91 quality %.
Measure the ionic conductivity of this film, in 25 ℃ of water, be shown as the value of 0.04S/cm.Methyl alcohol penetrate speed is shown as 2.9mmol/ (m 2Sec).
(embodiment 11A)
The film that use is made by embodiment 2A has been implemented generating evaluation as the film sample with aforesaid method, is 0.34V in the current density of 100mA, can obtain good power generation characteristics.
(embodiment 12A)
Replace Nafion (registered trademark) solution, 10 quality %N-N-methyl-2-2-pyrrolidone N-s have been used by embodiment 1A synthetic polymkeric substance, in addition, the same method of making method with the polyelectrolyte membrane/assembly of electrode in estimating with above-mentioned generating, the film that use is made by embodiment 2A has been made polyelectrolyte membrane/assembly of electrode as the film sample.Polyelectrolyte membrane/assembly of electrode that visual observations obtains is the good conjugant that does not have electrode to come off.
＜embodiment 1B～13B, comparative example 1B～6B 〉
Various mensuration are following carries out.Need to prove, owing to the evaluation of soltion viscosity, ionic conductivity is carried out with above-mentioned method, so not repeat specification.
Methanol permeability: obtain methanol permeability by the methyl alcohol penetrate speed of obtaining with above-mentioned method and the thickness of sample.
With hydrogen is the generating evaluation of the fuel cell (PEFC) of fuel: in 20%Nafion (registered trademark) solution that E.I.Du Pont Company makes, add after 40% commercially available carbon carries Pt catalyzer (the catalyst for fuel cell TEC10V40E of Tianzhonggui Metal Industrial Co., Ltd) and a spot of ultrapure water and Virahol, be stirred to evenly, be prepared into catalyzer cream.With this catalyzer cream apply equably, drying so that the adhesion amount of platinum is 0.5mg/cm on Toray corporate system carbon paper TGPH-060 2, made belt electrode catalyst layer gas diffusion layers.Clamping ion-exchange membrane between above-mentioned belt electrode catalyst layer gas diffusion layers so that electrode catalyst layer is connected with film, utilizes pressure sintering to pressurize, heat 3 minutes under 130 ℃, 2MPa, makes polyelectrolyte membrane/assembly of electrode thus.This conjugant pack the evaluation of into Electrochem corporate system with fuel cell groove FC25-02SP, under 80 ℃ of groove temperature, antianode and negative electrode supply with hydrogen and the air of crossing at 75 ℃ of following humidifications respectively, estimated power generation characteristics.Current density is 0.5A/cm in the time of will just beginning 2The time output voltage be made as the initial stage characteristic.In addition, as durability evaluation,, under above-mentioned condition, carried out continuous operation simultaneously with 1 hour 1 time ratio measuring open circuit voltage.It is the durable time that value when the open circuit voltage ratio has just been begun reduces by 10% time set when above.With 1000 hours was that the upper limit is carried out durability evaluation.
The directly generating evaluation of methanol fuel cell (DMFC): carry a spot of ultrapure water of adding and Virahol in Pt/Ru catalyzer (TEC61E54 of Tianzhonggui Metal Industrial Co., Ltd) and after getting wet at carbon, add 20%Nafion (registered trademark) solution (article number: SE-20192), be 2.5: 1 that E.I.Du Pont Company makes so that carbon carries the weight ratio of Pt/Ru catalyzer and Nafion.Stir then, prepared anode catalyzer cream.Utilize silk screen printing to apply drying this catalyzer cream, so that the adhesion amount of making platinum on the carbon paper TGPH-060 in the Toray company that becomes gas diffusion layers is 2mg/cm 2, made anode belt electrode catalyst layer carbon paper.In addition, carry in the Pt catalyzer (TEC10V40E of Tianzhonggui Metal Industrial Co., Ltd) at carbon and to add a spot of ultrapure water and Virahol and after getting wet, add 20%Nafion (registered trademark) solution that E.I.Du Pont Company makes (article number: SE-20192) and stir, so that carbon carries the weight ratio of Pt catalyzer and Nafion is 2.5: 1, stir, prepared catalyst for cathode cream.With this catalyzer cream apply, drying so that the adhesion amount of making platinum on the carbon paper TGPH-060 in the Toray company that has implemented waterproof processing is 1mg/cm 2, made negative electrode belt electrode catalyst layer carbon paper.Clamping film sample between above-mentioned two kinds of belt electrode catalyst layer carbon papers so that electrode catalyst layer is connected with the film sample, utilizes pressure sintering to pressurize, heat 3 minutes under 180 ℃, 8MPa, makes film-electrode bond thus.This conjugant pack the manufacturing evaluation of into Electrochem company with fuel cell groove FC25-02SP, use fuel cell power generation trier (make in Network ニ カ in Co., Ltd. Dongyang) to carry out power generation test.Antianodes and negative electrode are supplied with the high purity air (80ml/min) that is adjusted into 40 ℃ respectively and generate electricity in methanol aqueous solution (1.5ml/min) one side of 5mol/L on one side down 40 ℃ of groove temperature.The mensuration current density is 0.02A/cm 2The time output voltage and the resistance value of measuring with electric current blocking method.
Loading capacity: take by weighing 100 ℃ dry 1 hour down, and the weight that room temperature has been placed the sample of a whole night under nitrogen atmosphere, carry out stir process with aqueous sodium hydroxide solution after, obtain loading capacity by the back titration that utilizes aqueous hydrochloric acid.
Second-order transition temperature: with the wide 10mm of chuck, be heated to 250 ℃ from 50 ℃, give the dynamic strain of 10Hz simultaneously, use Rheogel E-4000 (eastern machine Industrial Co., Ltd company make) to measure dynamic viscoelastic with 2 ℃/minute 5mm is wide acid type films.The temperature of the flex point that will reduce greatly along with the rising E ' of temperature is set at second-order transition temperature.
(embodiment 1B)
Take by weighing 3,3 '-sodium disulfonate-4,4 '-dichloro diphenyl sulfone (is called for short: S-DCDPS) 6.9499g (14.15mmol), 2, the 6-dichlorobenzonitrile (is called for short: DCBN) 9.7340g (56.59mol), 4, (be called for short: BP) (be called for short: BPS) 7.7199g (35.37mmol), salt of wormwood 10.7542g (77.82mmol), dry good molecular sieve 3-A 7g add in the 200ml four neck flasks 6.5860g (35.37mmol), two (4-hydroxyphenyl) thioether 4 '-'-biphenyl diphenol, feed nitrogen.Add 80ml the N-N-methyl-2-2-pyrrolidone N-(be called for short: NMP), 150 ℃ stir 30 minutes down after, make temperature of reaction rise to 195-200 ℃, fully rise to roughly standard with the viscosity of system and proceed reaction (about 10 hours).Behind the naturally cooling, remove settled molecular sieve, and it is fibrous that it is precipitated in water.The polymkeric substance that obtains washs in boiling water after 1 hour and carries out drying.The logarithm viscosity of polymkeric substance is shown as 1.08dL/g.Fig. 3 be expression use VARIAN corporate system GEMINI-200, in deuterated dimethyl sulfoxide, measure under the room temperature by the embodiment 1B synthetic polymkeric substance among the present invention 1The figure of H-NMR wave spectrum.Among the figure, NMP represents from the polymer solvent that contains as impurity in the polymkeric substance to be the signal of N-N-methyl-2-2-pyrrolidone N-, and DMSO represents the signal from the dimethyl sulfoxide (DMSO) in the deuterated dimethyl sulfoxide, H 2O represents the signal from the water that is adsorbed in polymkeric substance.
Polymkeric substance 7g is dissolved in NMP 28gl, in the top casting of hot plate upper glass plates into about 400 μ m thickness, in heating 0.5 hour under 80 ℃, 120 ℃ of heating 0.5 hour down, after heating 0.5 hour under 150 ℃, in 150 ℃ baking oven of nitrogen atmosphere dry 1 hour, stripping film from the sheet glass.The film that obtains flooded in the pure water of room temperature after 1 day, and dipping is 2 hours in the aqueous sulfuric acid of 2mol/L.Then, be neutral with pure water washing film to washing water, be positioned over and carry out drying in the air, obtain polyelectrolyte membrane.The polyelectrolyte membrane that obtains is estimated.Fig. 7 is the figure of the dynamic visco-elastic property of the polyelectrolyte membrane that obtains of the embodiment 1B by among the present invention that expression uses Rheogel E-4000 (eastern machine Industrial Co., Ltd make) to measure.
(embodiment 2B)
Replace BPS, use 4, and 4 '-sulfo-hexichol mercaptan (be called for short: TBT) 4.6054g (18.39mmol), with the quantitative change of BP 9.7472g (52.35mmol) more, in addition, similarly make polyelectrolyte membrane with embodiment 1B and estimate.Fig. 4 is the expression GEMINI-200 that uses VARIAN company and make, in deuterated dimethyl sulfoxide, measure under the room temperature by the embodiment 2B synthetic polymkeric substance among the present invention 1The figure of H-NMR wave spectrum.Among the figure, it is the signal of N-N-methyl-2-2-pyrrolidone N-that NMP represents to come the polymer solvent that contains as impurity in the comfortable polymkeric substance, and DMSO represents the signal from the dimethyl sulfoxide (DMSO) in the deuterated dimethyl sulfoxide, H 2O represents the signal from the water that is adsorbed in polymkeric substance.
(embodiment 3B～6B)
Except that the amount of change S-DCDPS, DCBN, BPS, BP, similarly make polyelectrolyte membrane with embodiment 1B and estimate.Fig. 5 is the expression GEMINI-200 that uses VARIAN company and make, in deuterated dimethyl sulfoxide, measure under the room temperature by the embodiment 3B synthetic polymkeric substance among the present invention 1The figure of H-NMR wave spectrum, Fig. 6 be the expression GEMINI-200 that uses VARIAN company and make, in deuterated dimethyl sulfoxide, measure under the room temperature by the embodiment 4B synthetic polymkeric substance among the present invention 1The figure of H-NMR wave spectrum.Among the figure, it is the signal of N-N-methyl-2-2-pyrrolidone N-that NMP represents to come the polymer solvent that contains as impurity in the comfortable polymkeric substance, and DMSO represents the signal from the dimethyl sulfoxide (DMSO) in the deuterated dimethyl sulfoxide, H 2O represents the signal from the water that is adsorbed in polymkeric substance.
(embodiment 7B)
Replace BPS, use 2, and 2-two (4-hydroxyphenyl) propane (be called for short: BPA) 8.0743g (35.37mmol), in addition, similarly make polyelectrolyte membrane with embodiment 1B and estimate.
(embodiment 8B)
Replace BPS, use 2, and 2-two (4-hydroxyphenyl) HFC-236fa (be called for short: BPF) 11.8919g (35.37mmol), in addition, similarly make polyelectrolyte membrane with embodiment 1B and estimate.
(embodiment 9B～12B)
Except that each monomeric mol ratio of change, similarly make polyelectrolyte membrane with embodiment 1B and estimate.
(embodiment 13B)
Replace BPS, use 1,1-two (4-hydroxyphenyl) hexanaphthene (be called for short: BPH) 9.4915g (35.37mmol), in addition, similarly make polyelectrolyte membrane with embodiment 1B and estimate by the mol ratio of change S-DCDPS and DCBN.
(comparative example 1B)
Utilization structure is known, by with S-DCDPS, BP and DCBN polymerization so that the mol ratio of S-DCDPS and DCBN is the total mole number of 16: 84, S-DCDPS and DCBN equal following chemical formula 41 that the mole number of BP obtains contain the sulfonic group polymkeric substance, in addition, similarly make polyelectrolyte membrane with embodiment 1B and estimate.
Figure S2006800207570D01061
(comparative example 2B)
Utilization structure is known, by with S-DCDPS, BP and DCBN polymerization so that the mol ratio of S-DCDPS and DCBN is the total mole number of 20: 80, S-DCDPS and DCBN equal following chemical formula 42 that the mole number of BP obtains contain the sulfonic group polymkeric substance, in addition, similarly make polyelectrolyte membrane with embodiment 1B and estimate.
Figure S2006800207570D01071
(comparative example 3B)
Utilization structure is known, by with S-DCDPS, BP and DCBN polymerization so that the mol ratio of S-DCDPS and DCBN is the total mole number of 44: 56, S-DCDPS and DCBN equal following chemical formula 43 that the mole number of BP obtains contain the sulfonic group polymkeric substance, in addition, similarly make polyelectrolyte membrane with embodiment 1B and estimate.
Figure S2006800207570D01072
(comparative example 4B)
Utilization structure is known, by with S-DCDPS, BP and 4, the polymerization of 4 '-dichloro diphenyl sulfone is so that S-DCDPS and 4, the mol ratio of 4 '-dichloro diphenyl sulfone is 50: 50, S-DCDPS and 4, the total mole number of 4 '-dichloro diphenyl sulfone equal the mole number of BP and the following chemical formula 44 that obtains contain the sulfonic group polymkeric substance, in addition, similarly make polyelectrolyte membrane with embodiment 1B and estimate.
Figure S2006800207570D01073
(comparative example 5B)
The commercially available Nafion as ion-exchange membrane (registered trademark) 112 various evaluations have been carried out.
(comparative example 6B)
The commercially available Nafion as ion-exchange membrane (registered trademark) 117 various evaluations have been carried out.
The evaluation result of the ion-exchange membrane of the polyelectrolyte membrane of embodiment 1B～13B and comparative example 1B～6B is shown in table 1.
[table 1]
Polymkeric substance is formed (monomeric mol ratio) Logarithm viscosity (dL/g) Thickness [μ m] Loading capacity [meq/g] Methanol permeability [μ mol m -1· sec -1] Softening temperature (℃) Ionic conductivity [S/cm] PEFC estimates DMFC estimates
Chemical formula S-DC DPS DC BN BP BPS TBT BPA BPF BPH
n+m o+p n+o m+p 80℃ 95％RH In 25 ℃ of water Initial stage voltage The durable time Output voltage (V) Resistance value
Embodiment 1B 25A 10 40 25 25 1.08 35 1.06 0.053 230 - 0.017 - - 0.37 430
Embodiment 2B 25E 10 40 37 13 0.98 33 1.00 0.045 220 - 0.023 - - 0.38 420
Embodiment 3B 25A 8 42 25 25 1.12 25 0.93 0.038 230 - 0.013 - - 0.39 510
Embodiment 4B 25A 22 28 45 5 1.13 51 2.01 - - 0.26 - 0.72 721 - -
Embodiment 5B 25A 7 43 25 25 0.99 20 0.89 0.032 240 - 0.010 - - 0.40 530
Embodiment 6B 25A 18 32 42 8 1.15 30 1.83 - - 0.18 - 0.68 More than 1000 - -
Embodiment 7B 25B 10 40 25 25 0.87 34 1.03 0.056 230 - 0.018 - - 0.37 460
Embodiment 8B 25C 10 40 25 25 0.91 33 1.05 0.059 230 - 0.019 - - 0.38 470
Embodiment 9B 25A 8 42 12 38 0.86 31 0.91 0.031 190 - 0.014 - - 0.41 530
Embodiment 10B 25A 10 40 12 38 0.93 32 1.02 0.063 200 - 0.025 - - 0.40 440
Embodiment 11B 25A 14 36 25 25 0.92 33 1.34 0.164 205 - 0.061 - - 0.42 270
Embodiment 12B 25A 6 44 12 38 1.32 33 0.71 0.014 180 - 0.008 - - 0.36 590
Embodiment 13B 25BE 12 38 25 25 1.22 32 1.13 0.067 210 - 0.020 - - 0.39 380
Comparative example 1B - 1.12 25 0.90 0.035 More than 250 - 0.012 - - 0.33 1410
Comparative example 2B - 1.23 30 1.10 0.059 More than 250 - 0.023 - - 0.31 780
Comparative example 3B - 1.22 60 2.04 0.43 More than 250 0.25 - 0.71 534 - -
Comparative example 4B - 1.34 52 2.07 0.52 More than 250 0.22 - 0.68 152 - -
Comparative example 5B Nafion (registered trademark) 112 - 50 0.90 0.41 90 0.18 0.11 0.70 More than 1000 0.23 270
Comparative example 6B Nafion (registered trademark) 117 - 200 0.90 0.67 - 0.18 0.10 - - 0.33 350
As shown in Table 1, compare with the ion-exchange membrane (comparative example 1B, 2B, 6B) of comparative example, the polyelectrolyte membrane of direct methanol fuel cell (DMFC) usefulness among the present invention (the softening temperature step-down of embodiment 1B～3B, 5B, 7B～13B), thereby connectivity improves, resistance value reduces, thereby can obtain high output voltage.And as can be known, compare with existing Nafion as ion-exchange membrane (registered trademark) 117 (comparative example 6B), its methanol permeability reduces significantly, is the ion-exchange membrane of anti-methanol permeability excellence.
In addition we know, comparing with the ion-exchange membrane of comparative example (comparative example 3B, 4B), is the polyelectrolyte membrane (embodiment 4B, 6B) of fuel cell (PEFC) usefulness of fuel with hydrogen, though initial stage voltage is identical, but the durable time increases substantially, and is the ion-exchange membrane of excellent in te pins of durability.And as can be known, demonstrate equal weather resistance with existing Nafion (registered trademark) 112 (comparative example 5B) as ion-exchange membrane, and demonstrate equal above initial stage voltage, therefore, as the generation of hydrofluoric acid less and the little hydrocarbon system ion-exchange membrane of carrying capacity of environment when discarded, the characteristic that has abundant excellence.From these situations, the sulfonic group polymkeric substance that contains of the present invention by being used for the fuel cell polyelectrolyte membrane, can improve its characteristic greatly, and is big to the contribution of industry.
＜embodiment 1C～8C, comparative example 1C～3C 〉
Various mensuration are following carries out.Need to prove, owing to the evaluation of soltion viscosity is carried out with above-mentioned method, so do not repeat explanation.
Ionic conductivity is measured: with above-mentioned method, measure alternating-current impedance in the atmosphere of 80 ℃ of 95%RH, calculate electric conductivity as the ionic conductivity index.
The Fenton test: 0.0199g is dissolved in the water of 500ml with ferrous sulfate (7 hydrate), adds 20% aquae hydrogenii dioxidi 150g, adds entry and stirring fully again, is that 1L has prepared Fenton reagent with the total amount.The about 80mg of ion-exchange membrane that has measured weight in advance after under 100 ℃ dry 1 hour be impregnated in the about 50cc of the Fenton reagent of putting into beaker, after handling 3 hours under 66 ℃, use the glass filter filtration residue, be determined at 100 ℃ of down dry weight after 1 hour.Obtain weight after the processing with respect to the remaining % of the weight before handling.
Generating is estimated: after 40% commercially available carbon of adding carries Pt catalyzer (the catalyst for fuel cell TEC10V40E of Tianzhonggui Metal Industrial Co., Ltd) and a spot of ultrapure water and Virahol in 20%Nafion (registered trademark) solution that E.I.Du Pont Company makes, be stirred to evenly, prepared catalyzer cream.With this catalyzer cream apply equably, drying so that the adhesion amount of platinum is 0.5mg/cm on the carbon paper TGPH-060 that Toray company makes 2, made belt electrode catalyst layer gas diffusion layers.Clamping ion-exchange membrane between above-mentioned belt electrode catalyst layer gas diffusion layers so that electrode catalyst layer is connected with film, utilizes pressure sintering to pressurize, heat 3 minutes under 130 ℃, 2Mpa, makes polyelectrolyte membrane/assembly of electrode thus.This conjugant Electrochem company of packing into make is estimated with fuel cell groove FC25-02SP, under 80 ℃ of groove temperature, antianode and negative electrode supply with hydrogen and the air of crossing at 75 ℃ of following humidifications respectively, estimated power generation characteristics.Current density is 0.5A/cm in the time of will just beginning 2The time output voltage be set at the initial stage characteristic.In addition, as durability evaluation,, under above-mentioned condition, carried out continuous operation simultaneously with 1 hour 1 time ratio measuring open circuit voltage.It is the durable time that value when the open circuit voltage ratio has just been begun reduces by 10% time set when above.With 1000 hours was that the upper limit has been carried out durability evaluation.
Loading capacity: take by weighing the weight of descending dry 1 hour and under room temperature under the nitrogen atmosphere, having placed the sample of a whole night at 100 ℃, carried out obtaining loading capacity by the back titration that utilizes aqueous hydrochloric acid after the stir process with aqueous sodium hydroxide solution.
(embodiment 1C)
Take by weighing 3,3 '-sodium disulfonate-4,4 '-dichloro diphenyl sulfone (is called for short: S-DCDPS) 12.1091g (24.65mmol), 2, the 6-dichlorobenzonitrile (is called for short: DCBN) 5.3963g (31.37mol), 4,4 '-'-biphenyl diphenol (is called for short: BP) 10.3275g (55.46mmol), 10-(2, the 5-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phosphine phenanthrene-10-oxide compound (abbreviation: DHPPP) in 0.1817g (0.56mol), salt of wormwood 8.5170g (61.62mmol), the dry good molecular sieve 3-A 5g adding 200ml four neck flasks, feed nitrogen.Add 80ml the N-N-methyl-2-2-pyrrolidone N-(be called for short: NMP) and 150 ℃ stir 30 minutes down after, make temperature of reaction rise to 195-200 ℃, fully rise to roughly standard with the viscosity of system and proceed reaction (about 20 hours).Behind the naturally cooling, remove settled molecular sieve, and it is fibrous that it is precipitated in water.The polymkeric substance that obtains washs in boiling water after 1 hour and carries out drying.Polymkeric substance 7g is dissolved in NMP 28g, in the top casting of hot plate upper glass plates into about 400 μ m thickness, in heating 0.5 hour under 80 ℃, 120 ℃ of heating 0.5 hour down, after heating 0.5 hour under 150 ℃, in 150 ℃ baking oven of nitrogen atmosphere dry 1 hour, and from the sheet glass stripping film.The film that obtains flooded in the pure water of room temperature after 1 day, and dipping is 2 hours in the aqueous sulfuric acid of 2mol/L.Then, be neutral with pure water washing film to washing water, be positioned over and carry out drying in the air, obtain polyelectrolyte membrane.The polyelectrolyte membrane that obtains is estimated.
(embodiment 2C)
With the quantitative change of BP 10.1189g (54.34mmol) more,, in addition, similarly make polyelectrolyte membrane with embodiment 1C and estimate the quantitative change of DHPPP 0.5450g (1.68mmol) more.Fig. 8 is the expression GEMINI-200 that uses VARIAN company and make, in deuterated dimethyl sulfoxide, measure under the room temperature by the embodiment 2C synthetic polymkeric substance among the present invention 1The figure of H-NMR wave spectrum.Among the figure, it is the signal of N-N-methyl-2-2-pyrrolidone N-that NMP represents to come the polymer solvent that contains as impurity in the comfortable polymkeric substance, and DMSO represents the signal from the dimethyl sulfoxide (DMSO) in the deuterated dimethyl sulfoxide, H 2O represents the signal from the water that is adsorbed in polymkeric substance.
(embodiment 3C)
With the quantitative change of BP 9.1800g (49.30mmol) more, with the quantitative change of DHPPP 0.3633g (1.12mmol) more, further adding two (4-hydroxyphenyl) thioether (is called for short: BPS) 1.2228g (5.60mmol), in addition, similarly make polyelectrolyte membrane with embodiment 1C and estimate.Fig. 9 is the expression GEMINI-200 that uses VARIAN company and make, in deuterated dimethyl sulfoxide, measure under the room temperature by the embodiment 3C synthetic polymkeric substance among the present invention 1The figure of H-NMR wave spectrum.Among the figure, it is the signal of N-N-methyl-2-2-pyrrolidone N-that NMP represents to come the polymer solvent that contains as impurity in the comfortable polymkeric substance, and DMSO represents the signal from the dimethyl sulfoxide (DMSO) in the deuterated dimethyl sulfoxide, H 2O represents the signal from the water that is adsorbed in polymkeric substance.
(embodiment 4C～8C)
Except that the various monomeric ratio of componentss of change, similarly make polyelectrolyte membrane with embodiment 1C～3C and estimate.
(comparative example 1C)
Utilization structure is known, by with S-DCDPS, BP and DCBN polymerization so that the mol ratio of S-DCDPS and DCBN is the total mole number of 44: 56, S-DCDPS and DCBN equal the following chemical formula 43 that the mole number of BP obtains structure contain the sulfonic group polymkeric substance, in addition, similarly make polyelectrolyte membrane with embodiment 1C and estimate.
Figure S2006800207570D01131
(comparative example 2C)
Utilization structure is known, by with S-DCDPS, BP and 4, the polymerization of 4 '-dichloro diphenyl sulfone is so that S-DCDPS and 4, the mol ratio of 4 '-dichloro diphenyl sulfone is 50: 50, S-DCDPS and 4, the total mole number of 4 '-dichloro diphenyl sulfone equal the mole number of BP and following chemical formula 44 structures that obtain contain the sulfonic group polymkeric substance, in addition, similarly make polyelectrolyte membrane with embodiment 1C and estimate.
(comparative example 3C)
The commercially available Nafion as ion-exchange membrane (registered trademark) 112 various evaluations have been carried out.
The evaluation result of the ion-exchange membrane of the polyelectrolyte membrane of embodiment 1C～8C and comparative example 1C～3C is shown in table 2.
[table 2]
Polymkeric substance is formed (monomeric mol ratio) Logarithm viscosity (dL/g) Thickness [μ m] Loading capacity [meq/g] Ionic conductivity [S/cm] Fenton test (remaining %) PEFG estimates
Chemical formula S-DCDPS DCBN DCDPS BP BPS DHPPP 80℃95％RH Initial stage voltage (V) The durable time (hr)
Embodiment 1C 37A 22 28 - 49.5 - 0.5 1.11 34 2.01 0.26 73 0.70 670
Embodiment 2C 37A 22 28 - 48.5 - 1.5 1.06 32 1.99 0.25 80 0.69 712
Embodiment 3C 37Q 22 28 - 44 5 1 0.96 31 2.02 0.28 70 0.69 772
Embodiment 4C 37A 20 30 - 49.5 - 0.5 1.32 34 1.92 0.23 83 0.70 More than 1000
Embodiment 5C 37I 25 25 49.5 - 0.5 1.25 32 2.03 0.21 37 0.68 352
Embodiment 6C 37A 25 25 - 49 - 1 1.08 33 2.23 0.32 40 0.73 389
Embodiment 7C 37Q 23 27 - 43 5 2 1.03 31 2.10 0.27 71 0.72 613
Embodiment 8C 37Q 22 28 - 40 8 2 0.98 32 2.08 0.26 75 0.71 703
Comparative example 1C - 22 28 - - - - 1.05 35 2.05 0.25 38 0.69 514
Comparative example 2C - 25 - 25 - - - 1.33 40 2.06 0.22 12 0.67 163
Comparative example 3C Nafion (registered trademark) 112 49 0.90 0.18 100 0.69 More than 1000
As shown in Table 2, the polyelectrolyte membrane of embodiment 1C～8C is compared with the existing hydrocarbon system ion-exchange membrane of comparative example 1C, 2C, and the remaining % in the Fenton test is big, anti-free radical excellence.Thereby the generating weather resistance improves greatly, is shown as the ion-exchange membrane of excellent in te pins of durability.In addition, it is the such problem of ion-exchange membrane that there is not commercially available fluorine in polyelectrolyte membrane of the present invention, promptly, make because of operating condition is different deleterious hydrofluoric acid sneak in the expellant gas, big etc. when discarded to the load of environment, it is the ion-exchange membrane that initial stage voltage and weather resistance all demonstrate almost equal performance, therefore, be effectively as the use in solid polymer fuel cell proton exchange membrane, big to the contribution of industry.
Can think that this disclosed embodiment and embodiment are illustration with all aspects just, and without limits.Scope of the present invention is not above-mentioned explanation and by shown in claims, is intended to comprise and the equal meaning of claims and the whole changes in the scope.
The possibility of industrial application
According to the sulfonic group poly (arylene ether) based compound that contains of the present invention, can provide the polyelectrolyte membrane of ionic conductivity not only excellent but also heat resistance, processability and excellent in dimensional stability. It can be used for using hydrogen or methyl alcohol as fuel cell and the water electrolyser of raw material as amberplex, also is hopeful as various electrolyte for batteries, humidification film, humidity regulation film, display element, sensor, adhesive class, additive etc.

Claims (39)

1. one kind contains the sulfonic group polymkeric substance, and it contains the constituent that following Chemical formula 1 is represented at molecular chain.
Figure S2006800207570C00011
In Chemical formula 1, X represents the positively charged ion kind of hydrogen or 1 valency, and Y represents sulfo group or ketone group, and n represents the arbitrary integer more than 2.
2. the sulfonic group polymkeric substance that contains as claimed in claim 1, it also contains the constituent that following Chemical formula 2 is represented.
Figure S2006800207570C00012
In Chemical formula 2, n represents the arbitrary integer more than 2.
3. the sulfonic group polymkeric substance that contains as claimed in claim 1, wherein, sulfonic group content is in the scope of 0.3～5.0meq/g.
4. the sulfonic group polymkeric substance that contains as claimed in claim 1, it is the terminal dihydroxy compound of following chemical formula 3 expressions, obtains as the part of monomer component by using the composition by the different a plurality of compositions of n constitute and average group becomes the scope of 1＜n≤10.
Figure S2006800207570C00013
In chemical formula 3, n represents the integer arbitrarily more than 0.
5. one kind contains the sulfonic group polymkeric substance, and its structure with following chemical formula 4～7 expressions is as necessary repeating unit.
In chemical formula 4～7, X represents-S (=O) 2-group or C (=O)-and group, Y represents the positively charged ion of H or 1 valency, Z 1, Z 2, Z 4, Z 5In independent respectively expression O or the S atom any, Z 3, Z 6Respectively independent expression O atom, S atom ,-C (CH 3) 2-group ,-C (CF 3) 2-group ,-CH 2In-group, the cyclohexyl any.
6. the sulfonic group polymkeric substance that contains as claimed in claim 5, wherein, above-mentioned Ar 1And above-mentioned Ar 2It is the group more than a kind that is selected from the structure of following chemical formula 8～11 expressions.
Figure S2006800207570C00022
7. the sulfonic group polymkeric substance that contains as claimed in claim 5, wherein, above-mentioned Z 1, above-mentioned Z 2, above-mentioned Z 4, above-mentioned Z 5It all is the O atom.
8. the sulfonic group polymkeric substance that contains as claimed in claim 5, wherein, above-mentioned Z 3And above-mentioned Z 6It all is the S atom.
9. the sulfonic group polymkeric substance that contains as claimed in claim 5, wherein, above-mentioned X is-S (=O) 2-group.
10. the sulfonic group polymkeric substance that contains as claimed in claim 5, wherein, above-mentioned Ar 1And above-mentioned Ar 2It is the group more than a kind that is selected from the structure of following Chemical formula 10 and Chemical formula 11 expression.
Figure S2006800207570C00031
11. the sulfonic group polymkeric substance that contains as claimed in claim 5, it satisfies following mathematical expression 1～3.
0.9≤(n1+n2+n3+n4)/(n1+n2+n3+n4+n5)≤1.0 (mathematical expression 1)
0.05≤(n1+n2)/(n1+n2+n3+n4)≤0.7 (mathematical expression 2)
0.01≤(n2+n4)/(n1+n2+n3+n4)≤0.95 (mathematical expression 3)
In the mathematical expression, n1～n4 represents the above-mentioned repeating unit mole % separately that contains above-mentioned chemical formula 4～7 expressions in the sulfonic group polymer molecule, and n5 represents the above-mentioned mole % that contains other repeating units in the sulfonic group polymer molecule.
12. one kind contains the sulfonic group polymkeric substance, it has the structure of following Chemical formula 12 expressions.
Figure S2006800207570C00041
In Chemical formula 12, X represents-S (=O) 2-group or C (=O)-and group, Y represents the positively charged ion of H or 1 valency, Z 1, Z 2And Z 3Any of independent respectively expression O or S atom.Ar 1Represent 2 yuan of organic groups, Ar 2, Ar 3And Ar 4Expression does not contain 2 yuan of organic groups of ionic group, Ar respectively 5Represent 3 yuan of organic groups.N, m, o represent the positive number more than 1 respectively.The part of surrounding in [] is represented minimum repeating unit, and each repeating unit is bonding randomly, and same repeating unit is bonding continuously.
13. one kind contains the sulfonic group polymkeric substance, it has the structure of following Chemical formula 13 expressions.
Figure S2006800207570C00051
In Chemical formula 13, X represents-S (=O) 2-group or C (=O)-and group, Y represents the positively charged ion of H or 1 valency, Z 5, Z 6And Z 7In independent respectively expression O or the S atom any.Ar 6Represent any in the structure of following Chemical formula 1 4～16 expressions, Ar 7Represent any in the structure of following Chemical formula 1 7～24 expressions, Ar 8Represent any in the structure of following chemical formula 8～11 expressions, Ar 9Represent 3 yuan of organic groups.N ', n ", m ', m " represent the integer more than 1, o ', o respectively " represent o ' and o respectively " any be not 0 the integer more than 0.The part of surrounding in [] is represented minimum repeating unit, and each repeating unit is bonding randomly, and same repeating unit is bonding continuously,
Figure S2006800207570C00061
In Chemical formula 17 and Chemical formula 18, the integer of p ' expression 2～50.
14. the sulfonic group polymkeric substance that contains as claimed in claim 13, wherein, Ar 7It is the structure of any expression in the following Chemical formula 1 7～20.
15. the sulfonic group polymkeric substance that contains as claimed in claim 13, wherein, Ar 7It is the structure of following Chemical formula 19 or 20 expressions.
Figure S2006800207570C00073
16. the sulfonic group polymkeric substance that contains as claimed in claim 13, wherein, Ar 9It is phenyl.
17. the sulfonic group polymkeric substance that contains as claimed in claim 13, wherein, Z 7It is the O atom.
18., wherein, n ', n in the above-mentioned Chemical formula 13 as the claim 13 described sulfonic group polymkeric substance that contain ", m ', m ", o ', o " satisfy following mathematical expression 4～7.
0.05≤(n '+n ")/(n '+n "+m '+m ")≤0.8 (mathematical expression 4)
0.001≤(o '+o ")/(n '+n "+m '+m "+o '+o ")≤0.1 (mathematical expression 5)
0.01≤(n '/n ")≤100 (mathematical expressions 6)
0.01≤(m '/m ")≤100 (mathematical expressions 7)
19. as each described sulfonic group polymkeric substance that contains in the claim 1～18, its second-order transition temperature is in 130 ℃～270 ℃ the scope.
20. as each described sulfonic group polymkeric substance that contains in the claim 1～18, its second-order transition temperature is in 130 ℃～220 ℃ the scope.
21. manufacture method that contains the sulfonic group polymkeric substance, it is to be used for obtaining each described method that contains the sulfonic group polymkeric substance of claim 1～4, wherein, above-mentioned at least a kind of containing compound that the sulfonic group polymkeric substance uses 3 expressions of following chemical formula as monomer component, and obtain by the polymerization that utilizes aromatic nucleophilie nuclear substituting reaction.
Figure S2006800207570C00081
In chemical formula 3, n represents the arbitrary integer more than 2.
22. a resin combination, it contains each described sulfonic group polymkeric substance that contains in the claim 1～18.
23. resin combination as claimed in claim 22, wherein, the above-mentioned content that contains the sulfonic group polymkeric substance is 50～100 quality %.
24. a polyelectrolyte membrane, it contains the described resin combination of claim 22.
25. a polyelectrolyte membrane, it contains each described sulfonic group polymkeric substance that contains in the claim 1～18.
26. the manufacture method of a polyelectrolyte membrane, it is a method of making the described polyelectrolyte membrane of claim 25, and it comprises: will contain the above-mentioned solution that contains sulfonic group polymkeric substance and solvent and cast so that casting thickness is the operation of the scope of 10～1500 μ m; Good solution carries out the exsiccant operation to make casting.
The requirement 25 described polyelectrolyte membranes 27. a polyelectrolyte membrane/assembly of electrode, its use are had the right.
Requirement 27 described polyelectrolyte membrane/assembly of electrode 28. a fuel cell, its use are had the right.
29. fuel cell as claimed in claim 28, it is used as fuel with methyl alcohol.
30. a polyelectrolyte membrane/assembly of electrode, it is used for electrode catalyst layer with each described sulfonic group polymkeric substance that contains in the claim 1～18.
31. a fuel cell, it has used the described polyelectrolyte membrane/assembly of electrode of claim 30.
32. polyelectrolyte membrane, it contains structure with 4～7 expressions of following chemical formula and contains the sulfonic group polymkeric substance as necessary repeating unit, the described sulfonic group polymkeric substance that contains satisfies following mathematical expression 1,8 and 9, and described polyelectrolyte membrane is used for direct methanol fuel cell.
Figure S2006800207570C00101
In chemical formula 4～7, X represents-S (=O) 2-group or C (=O)-and group, Y represents the positively charged ion of H or 1 valency, Z 1, Z 2, Z 4, Z 5In independent respectively expression O or the S atom any, Z 3, Z 6Respectively independent expression O atom, S atom ,-C (CH 3) 2-group ,-C (CF 3) 2-group ,-CH 2In-group, the cyclohexyl any.
0.9≤(n1+n2+n3+n4)/(n1+n2+n3+n4+n5)≤1.0 (mathematical expression 1)
0.05≤(n1+n2)/(n1+n2+n3+n4)≤0.5 (mathematical expression 8)
0.05≤(n2+n4)/(n1+n2+n3+n4)≤0.95 (mathematical expression 9)
In the mathematical expression, n1～n4 represents the above-mentioned repeating unit mole % separately that contains above-mentioned chemical formula 4～7 expressions in the sulfonic group polymer molecule, and n5 represents the above-mentioned mole % that contains other repeating units in the sulfonic group polymer molecule.
33. polyelectrolyte membrane, it contains structure with 4～7 expressions of following chemical formula and contains the sulfonic group polymkeric substance as necessary repeating unit, the described sulfonic group polymkeric substance that contains satisfies following mathematical expression 1,10 and 11, and it is the polymer electrolyte fuel cell of fuel that described polyelectrolyte membrane is used for hydrogen.
Figure S2006800207570C00111
In chemical formula 4～7, X represents-S (=O) 2-group or C (=O)-and group, Y represents the positively charged ion of H or 1 valency, Z 1, Z 2, Z 3, Z 4In independent respectively expression O or the S atom any, Z 3, Z 6Respectively independent expression O atom, S atom ,-C (CH 3) 2-group ,-C (CF 3) 2-group ,-CH 2In-group, the cyclohexyl any.
0.9≤(n1+n2+n3+n4)/(n1+n2+n3+n4+n5)≤1.0 (mathematical expression 1)
0.3≤(n1+n2)/(n1+n2+n3+n4)≤0.7 (mathematical expression 10)
0.01≤(n2+n4)/(n1+n2+n3+n4)≤0.25 (mathematical expression 11)
In the mathematical expression, n1～n4 represents the above-mentioned repeating unit mole % separately that contains above-mentioned chemical formula 4～7 expressions in the sulfonic group polymer molecule, and n5 represents the above-mentioned mole % that contains other repeating units in the sulfonic group polymer molecule.
34. polyelectrolyte membrane, what it contained structure with 3 expressions of following Chemical formula 1 contains the sulfonic group polymkeric substance, wherein, the n '+n in the above-mentioned Chemical formula 13 "+m '+m "+o '+o " satisfy following mathematical expression 5,12 and 13, described polyelectrolyte membrane is used for direct methanol fuel cell.
In Chemical formula 13, X represents-S (=O) 2-group or C (=O)-and group, Y represents the positively charged ion of H or 1 valency, Z 5, Z 6And Z 7In independent respectively expression O or the S atom any.Ar 6Represent any in the structure of following Chemical formula 1 4～16 expressions, Ar 7Represent any in the structure of following Chemical formula 1 7～24 expressions, Ar 8Represent any in the structure of following chemical formula 8～11 expressions, Ar 9Represent 3 yuan of organic groups.N ', n ", m ', m " represent the integer more than 1, o ', o respectively " represent o ' and o respectively " any be not 0 the integer more than 0.The part of surrounding in [] is represented minimum repeating unit, and each repeating unit is bonding randomly, and same repeating unit is bonding continuously.
Figure S2006800207570C00131
In Chemical formula 17 and Chemical formula 18, the integer of p ' expression 2～50.
0.001≤(o '+o ")/(n '+n "+m '+m "+o '+o ")≤0.1 (mathematical expression 5)
0.05≤(n '+n "+o ')/(n '+n "+m '+m "+o '+o ")≤0.5 (mathematical expression 12)
0.05≤(n "+m ")/(n '+n "+m '+m ")≤0.95 (mathematical expression 13)
35. polyelectrolyte membrane, what it contained structure with 3 expressions of following Chemical formula 1 contains the sulfonic group polymkeric substance, wherein, n '+n in the above-mentioned Chemical formula 13 "+m '+m "+o '+o " satisfy following mathematical expression 5,14 and 15, it is the polymer electrolyte fuel cell of fuel that described polyelectrolyte membrane is used for hydrogen.
In Chemical formula 13, X represents-S (=O) 2-group or C (=O)-and group, Y represents the positively charged ion of H or 1 valency, Z 5, Z 6And Z 7In independent respectively expression O or the S atom any.Ar 6Represent any in the structure of following Chemical formula 1 4～16 expressions, Ar 7Represent any in the structure of following Chemical formula 1 7～24 expressions, Ar 8Represent any in the structure of following chemical formula 8～11 expressions, Ar 9Represent 3 yuan of organic groups.N ', n ", m ', m " represent the integer more than 1, o ', o respectively " represent o ' and o respectively " any be not 0 the integer more than 0.The part of surrounding in [] is represented minimum repeating unit, and each repeating unit is bonding randomly, and same repeating unit is bonding continuously.
Figure S2006800207570C00161
In Chemical formula 17 and Chemical formula 18, the integer of p ' expression 2～50.
[several 5]
0.001≤(o '+o ")/(n '+n "+m '+m "+o '+o ")≤0.1 (mathematical expression 5)
0.3≤(n '+n "+o ')/(n '+n "+m '+m "+o '+o ")≤0.7 (mathematical expression 14)
0.01≤(n "+m ")/(n '+n "+m '+m ")≤0.25 (mathematical expression 15)
36. the manufacture method of a polyelectrolyte membrane, it is a method of making each described polyelectrolyte membrane in the claim 32～35, and it comprises: will contain that the above-mentioned solution that contains sulfonic group polymkeric substance and solvent is cast so that casting thickness is the operation of the scope of 10～1500 μ m; Good solution carries out the exsiccant operation to make casting.
Each described polyelectrolyte membrane in the requirement 32～35 37. a polyelectrolyte membrane/assembly of electrode, its use are had the right.
Requirement 37 described polyelectrolyte membrane/assembly of electrode 38. a fuel cell, its use are had the right.
39. fuel cell as claimed in claim 38, it is used as fuel with methyl alcohol.
CN2006800207570A 2005-06-09 2006-06-06 Sulfonic acid group-containing polymer, method for producing same, resin composition containing such sulfonic acid group-containing polymer, polymer electrolyte membrane, polymer electrolyte membrane/electrode adapter, fuel cell Expired - Fee Related CN101218281B (en)

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WO2013040985A1 (en) * 2011-09-20 2013-03-28 Toray Advanced Materials Research Laboratories (China) Co., Ltd. Sulfonic acid group-containing polymer, sulfonic acid group-containing aromatic compound and method of making the same, as well as polymer electrolyte material, polymer electrolyte molded product and solid polymer fuel cell using the same
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