CN106800647A - Polyphenylene oxide, proton-conductive films containing sulfo group - Google Patents

Polyphenylene oxide, proton-conductive films containing sulfo group Download PDF

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CN106800647A
CN106800647A CN201610154123.XA CN201610154123A CN106800647A CN 106800647 A CN106800647 A CN 106800647A CN 201610154123 A CN201610154123 A CN 201610154123A CN 106800647 A CN106800647 A CN 106800647A
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sulfo group
polyphenylene oxide
formula
group
proton
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CN106800647B (en
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福圆真
福圆真一
西野宏
三井昭
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Asahi Kasei Corp
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Asahi Kasei Kogyo KK
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/326—Polymers modified by chemical after-treatment with inorganic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • Y02E60/50—Fuel cells

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Polymers & Plastics (AREA)
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  • Electrochemistry (AREA)
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  • Polyethers (AREA)
  • Fuel Cell (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

Polyphenylene oxide, proton-conductive films the present invention relates to contain sulfo group.It is an object of the invention to provide a kind of polyphenylene oxide containing sulfo group, it passes through to suppress the disengaging of the sulfo group caused by heat, so that excellent in te pins of durability.A kind of polyphenylene oxide containing sulfo group, it is characterised in that it includes formula (1) and the constituent represented by formula (2).

Description

Polyphenylene oxide, proton-conductive films containing sulfo group
Technical field
Polyphenylene oxide, proton-conductive films the present invention relates to contain sulfo group.
Background technology
In solid polymer fuel cell, in the two sides bonding electrodes of proton-conductive films, to proton-conductive films-electrode knot The anode-side supply hydrogen of structure, oxygen or air are supplied to cathode side, are generated electricity using the potential difference produced at electrode two ends.
Now, as the solid macromolecule electrolyte used in proton-conductive films, it is necessary to proton-conducting is high, gas is saturating The property crossed is low, chemical and mechanical stability is high.
As proton-conductive films, employ mainly with Nafion (registration mark, du pont company manufacture) as typical example The very expensive perfluoro alkyl sulfonic acid polymer of price.Although the film of perfluorinated sulfonic acid system shows that high proton conductivity and height are steady It is qualitative, but there is a problem of the proton-conducting deficiency in high temperature and low humidity region and be more expensive to manufacture.
As the proton-conductive films for overcoming this shortcoming, it is conceived to the matter for importing sulfo group and being formed in the macromolecule of hydrocarbon system Sub- conductive membranes.For example, can exemplify by the material (for example, see non-patent literature 1) of poly arylene ether sulfone sulfonation, by polyethers Material (for example, see patent document 1,2 references) of ether ketone sulfonation etc..
As other examples, can also enumerate the material (for example, see non-patent literature 2) of polyphenylene oxide sulfonation. In the example, as base material, it is somebody's turn to do as poly- (2, the 6- dimethyl-Isosorbide-5-Nitrae phenylene ether) of the polyphenylene oxide as general engineering plastic Proton-conductive films are excellent due to easy modified, economy, thus are most to be subject to one of material for expecting.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 6-93114 publications
Patent document 2：Japanese Unexamined Patent Publication 2005-255850 publications
Patent document 3：Japanese Unexamined Patent Publication 2002-110174 publications
Patent document 4：No. 2002/0091225 specification of U.S. Patent Application Publication No. (page 1~2)
Non-patent literature
Non-patent literature l：Journal of Membrane Science, Vol.83 (1993) is p.211-220
Non-patent literature 2：Journal of Applied Polymer Science, Vol.29 (1984) is p.4017- 4027
The content of the invention
The invention problem to be solved
But, because economy is excellent be expected to be applied to polymeric membrane in poly- (2,6- dimethyl-Isosorbide-5-Nitrae-phenylene Ether) in the case of, it is difficult to the sulfo group for suppressing to be directed into by sulfonation on the aromatic rings of main chain backbone is departed from because of heat.Sulphur The disengaging of base is produced due to the electron rich of the main chain backbone of polyphenylene oxide.
In order to solve the problem, there are the following methods of document report：Using lewis acid and sultone, by alkyl by sulphur In female skeleton of base importing polyphenylene oxide (for example, see patent document 3).But, in the method, sultone it is reactive low, thus High temperature, prolonged reaction condition are needed, thus is not necessarily practical method.
In addition, the polymer departed from as the sulfo group inhibited caused by heat, there is a kind of heat endurance of document report Sulfonation poly arylene ether sulfone based compound high, its monomer for being used on electron-withdrawing aromatic rings being imported with sulfo group is gathered (for example, see patent document 4) obtained from conjunction.But, the method is reactive low due to monomer, thus in order to be polymerized Polymerization reaction time required for thing is elongated, and the economy of polymer has problem.
Additionally, in order to improve heat endurance and proton conductive, it is also reported that the non-fluorine-type aromatic series high score of height design Sub- film, but there is a problem of that synthetic method is complicated.
Therefore, it is an object of the invention to provide a kind of good thermal stability, the suitable material as proton-conductive films Polyphenylene oxide containing sulfo group.
Scheme for solving problem
In view of the situation, had made intensive studies to eliminate the problem associated with above-mentioned prior art, as a result sent out It is existing, by importing the electron withdraw group and aryl of divalence to the main chain backbone of polyphenylene oxide, sulfo group, sulfonated polyphenyl are imported afterwards To thermally-stabilised, proton-conducting is excellent, and gas-premeable is small for ether, can form the proton that electrochemistry after heat treatment also stablizes and pass Guided membrane.
In the present invention, by the electron withdraw group that divalence is imported to the main chain backbone of polyphenylene oxide, it is possible to decrease the electricity of female skeleton Son is rich, and three-dimensionally aggregation around female skeleton (mixed body closes う), it is difficult to which sulfonation occurs.Also, not from female skeleton week Crowd around and preferential on collection (be spatially susceptible to reaction), side chain aromatic hydrocarbyl sulfonation occurs.Due to above-mentioned situation, this hair In bright, can effectively suppress the de- sulfonation caused by heat.
In addition, the present invention can efficiently be manufactured using simple synthetic method, cheap general engineering can be used Plastics, it can be said that economically also excellent.
That is, the present invention is as described below.
[1] a kind of polyphenylene oxide containing sulfo group, it is characterised in that its include formula (1) and the composition represented by formula (2) into Point.
(in formula (1), R1~R3It is each independently selected from by hydrogen, halogen, alkyl, fluorinated alkyl, pi-allyl, aryl, cyanogen At least one in the group of base composition；X is the electron withdraw group of divalence；Ar1There is the virtue of the group beyond sulfo group for that can replace Base.)
(in formula (2), R4~R6It is each independently selected from by hydrogen, halogen, alkyl, fluorinated alkyl, pi-allyl, aryl, cyanogen At least one in the group of base composition；X is the electron withdraw group of divalence；Ar2There is the aryl of at least one sulfo group for substitution.)
[2] polyphenylene oxide containing sulfo group as described in [1], wherein, relative to the formula (1) and the formula (2) institute table The constituent for showing, the ratio of the constituent represented by the formula (1) is 60 moles of %~95 mole %, the formula (2) ratio of the constituent represented by is 5 moles of %~40 mole %.
[3] a kind of proton-conductive films, it is characterised in that it includes the polyphenylene oxide containing sulfo group described in [1] or [2].
The effect of invention
In accordance with the invention it is possible to provide the gathering containing sulfo group of good thermal stability, the suitable material as proton-conductive films Phenylate.
Specific embodiment
In the present invention, by new sulfonation introduction method, prepare and inhibit the disengaging of sulfo group, excellent heat stability to contain The polyphenylene oxide of sulfo group, there is provided ionic conductivity it is excellent as the particularly useful macromolecular material of electrolyte membrane for fuel cell.
Below, embodiments of the present invention (hereinafter also referred to as " present embodiment ") are described in detail.Need Bright, the present invention is not limited to following implementation method, can carry out various modifications in the range of its main points to implement.
(polyphenylene oxide containing sulfo group)
The polyphenylene oxide containing sulfo group of present embodiment is characterised by that it includes following formulas (1) and following formulas (2) institute The constituent of expression.
(in formula (1), R1~R3It is each independently selected from by hydrogen, halogen, alkyl, fluorinated alkyl, pi-allyl, aryl, cyanogen At least one in the group of base composition；X is the electron withdraw group of divalence；Ar1There is the virtue of the group beyond sulfo group for that can replace Base.)
(in formula (2), R4~R6It is each independently selected from by hydrogen, halogen, alkyl, fluorinated alkyl, pi-allyl, aryl, cyanogen At least one in the group of base composition；X is the electron withdraw group of divalence；Ar2There is the aryl of at least one sulfo group for substitution.)
In formula (1) and formula (2), preferred following manner.
As R1~R6In alkyl and fluorinated alkyl carbon number, preferably 1~12, more preferably 1~4.
As R1~R6Pi-allyl, preferably 2- acrylic, 2- methyl -2- acrylic, 2- hexenyls.
As R1~R6(i.e. main chain side) aryl, preferably phenyl, benzyl.
As the electron withdraw group of the divalence of X ,-C (O)-(carbonyl (ketone group)) ,-S (O)-(sulfoxide) ,-S (O) can be enumerated 2- (sulfone), preferably-C (O)-(carbonyl (ketone group)).
As Ar2(i.e. side chain side) aryl, preferably phenyl, naphthyl, anthryl, benzyl.
In mode of the invention, Ar1There is the group of the group beyond sulfo group for that can replace.In addition, Ar2Aromatic rings bone At least one of substitution base of frame is sulfo group.Herein, the binding site to sulfo group in fragrant ring skeleton is not particularly limited. In addition, the number of the binding site of sulfo group can be one, or two or three.
In mode of the invention, by being selectively introduced sulfo group on the aromatic rings beyond the main chain of polyphenylene oxide, so that The disengaging of sulfo group can be suppressed.As a result, the heat-staple polyphenylene oxide containing sulfo group can be provided.
For following reasons, in the polyphenylene oxide containing sulfo group of present embodiment, relative to above-mentioned formula (1) and formula (2) constituent represented by, the ratio of the constituent represented by formula (1) is preferably 60 moles of %~95 mole %, leads to The ratio of the constituent represented by formula (2) is preferably 5 moles of %~40 mole %.It should be noted that by formula (2) institute table The constituent for showing is also referred to as sulphonation rate relative to the ratio of the constituent represented by formula (1) and formula (2).
If sulphonation rate is in above range, when the polyphenylene oxide containing sulfo group is used as into solid polyelectrolyte membrane, can obtain High proton conductivity, and film-strength high can be maintained.
In addition, going out in terms of raising possesses generating efficiency of the resin as the fuel cell of solid polyelectrolyte membrane Hair, sulphonation rate is preferably 5 moles of more than %, more preferably 15 moles more than %, particularly preferably 25 moles of more than %；Separately Outward, from the swelling aspect for reducing solid polyelectrolyte membrane, preferably 40 moles below %, more preferably Less than 35%.
It should be noted that as long as no special declaration, then the sulphonation rate of resin refers in room temperature (such as 30 by resin DEG C) dry 24 hours after value.
As the ion exchange capacity of the polyphenylene oxide containing sulfo group of present embodiment, as long as desired proton can be shown Conductibility is just not particularly limited, the reasons why same the reasons why for sulphonation rate, preferably 0.5~3.5meq/g (milliequivalent/ G), it is more preferably 1.2~2.5meq/g.
It should be noted that ion exchange capacity can be obtained by conventional method.
It should be noted that in the case where the amount of sulfonation of resin is excessive, the water resistance reduction of resin, in water sometimes Generation is dissolved and is decomposed, not preferred as proton-conductive films.
Ion exchange capacity can by the concentration in the amount of sulfonating agent and reaction solution, using sulfonating agent reaction it is anti- Between seasonable and reaction temperature is adjusted, for example, in the case where ion exchange capacity is improved, as long as increase sulfonating agent and prolong Reaction time with sulfonating agent long.
The structure of the polyphenylene oxide containing sulfo group on present embodiment, for example can using infrared absorption spectrum according to 677cm-1、1,140cm-1、3,400cm-1The presence or absence of the absworption peak of sulfo group confirm.
In addition, said structure can also for example pass through1H-NMR confirms.
(manufacture method of the polyphenylene oxide containing sulfo group)
Manufacture method to the polyphenylene oxide containing sulfo group of present embodiment is not particularly limited, for example, can enumerate following sides Method：Import the electron withdraw group and aryl of divalence in polyphenylene oxide based on, synthesis modification polyphenylene oxide, it is backward modified poly- Sulfo group, polyphenylene oxide of the synthesis containing sulfo group are imported in phenylate.
Method to synthesizing above-mentioned Noryl is not particularly limited, for example, can enumerate following methods：Utilize Friedel-Crafts acylation reactions, have aromatic hydrocarbyl to importing acyl group in the fragrant ring skeleton of polyphenylene oxide, being particularly Acyl group.
In Friedel-Crafts acylation reactions, more specifically, in the lewis acids such as aluminium chloride, stannic chloride (gold Category halide) in the presence of, reacted polyphenylene oxide and etheride etc..
As reaction dissolvent, dichloromethane, chloroform, chlorination methylene etc. are used.
As reaction condition, Li, Q. can be used；Liu,L.；Liang,S.；Li,Q.；Jin,B.；Bai,R.； Polym.Chem.2014,5,2425-2432. the condition described in.
Polyphenylene oxide as above-mentioned basis is not particularly limited, it is preferably poly- (2,6- dimethyl-Isosorbide-5-Nitrae-phenylene ether), poly- The block copolymer of (2,6- dimethyl -1,4- phenylene ethers) and poly- (2,3,6- trimethyl -1,4- phenylene ethers) or they The random copolymer of mixture, 2,6- xylenols and 2,3,6- pseudocuminols.
As above-mentioned etheride, it is not particularly limited, the compound represented by following formulas (3) can be enumerated.
(in formula (3), Y is the halogen beyond fluorine；R7~R11It is each independently hydrogen, halogen, alkyl, fluorinated alkyl, allyl Base, aryl, cyano group, herein R7~R11At least one of be hydrogen.)
In addition, as etheride, following compounds can also be enumerated：In above-mentioned formula (3), by what is combined with carbonyl Pendent aromatic alkyl is replaced by phenyl, forms the polycycle aromatic hydrocarbyls such as naphthyl, anthryl.
Further, it is also possible to enumerate following compounds：In above-mentioned formula (3), the group combined with carbonyl is replaced by benzene Base, forms aryl (such as benzyl that can link both in the form of sandwiching alkyl between carbonyl and pendent aromatic alkyl Base etc.).
Acyl group rate based on Friedel-Crafts acylation reactions is particularly preferably 100 moles of %, more preferably 90 Mole %~100 mole %, it is preferably 85 moles of %~100 mole %.
It should be noted that acyl group rate can pass through1H-NMR confirms.
As the inherent viscosity of polyphenylene oxide, from improve import sulfo group after with the separation property and heat resistance of solvent in terms of go out Hair, preferably more than 0.25dL/g, more preferably more than 0.30dL/g, in addition, solution when preventing from importing sulfo group glues Degree become it is too high, improve stirring and liquid conveying etc. operational aspect set out, preferably below 1.45dL/g, further it is excellent Elect below 0.70dL/g as.
It should be noted that inherent viscosity is obtained as follows.That is, 0.5g Noryls are dissolved in chloroform, are obtained The solution of more than two kinds of the various concentrations of more than 100mL (below concentration 0.5g/dL).Then, Ubbelohde viscometer is used at 30 DEG C Solution to various concentrations determines specific viscosity respectively, and viscosity when concentration is 0 is derived by the relation of specific viscosity and concentration, and this is glued Degree is used as inherent viscosity.
Method as sulfo group is imported in above-mentioned Noryl in whole or in part, can enumerate following methods：In nothing In the presence of solvent or solvent, reacted the sulfonating agents such as Noryl and oleum, sulfuric acid, chlorosulfonic acid.
In addition to the method for sulfo group is imported by above-mentioned sulfonating agent, it would however also be possible to employ following methods：Import sulfonated metal Salt, sulfonation ester group, sulfuryl chlorio etc., carry out ion exchange, de- esterification, hydrolysis etc., so as to import sulfo group afterwards.
As solvent, it is possible to use halogenated hydrocarbon such as dichloroethanes, tetrachloroethanes, chloroform, chlorination methylene etc..
Reaction temperature is not particularly limited, usually -20 DEG C~180 DEG C, preferably 0 DEG C~100 DEG C.
Reaction time is usually 0.5 hour~48 hours, is preferably 1 hour~10 hours.
In addition, the method as sulfo group is imported, such as can use the method described in non-patent literature 2.That is, will be poly- (2,6- dimethyl-Isosorbide-5-Nitrae-phenylene ether) are dissolved in chloroform, to chlorosulfonic acid is added dropwise in the solution, at room temperature react it, Such that it is able to obtain the polyphenylene oxide containing sulfo group.Polyphenylene oxide containing sulfo group does not dissolve in chloroform with the carrying out of sulfonating reaction, with nothing The solid form of setting is separated out, and can be reclaimed by filtering.
In the polyphenylene oxide containing sulfo group of present embodiment, the fragrant ring skeleton phase with the main chain of the polyphenylene oxide of electron rich Than importing sulfo group for being bound to the fragrant ring skeleton of side chain of fragrant ring skeleton by electron withdraw group.Therefore, can be Just (such as 170 DEG C) are also difficult to the effect that the sulfo group caused by heat departs under the high temperature conditions.Also, by above-mentioned effect Really, the ion exchange capacity of the polyphenylene oxide containing sulfo group of the present embodiment after being positioned under hot conditions be positioned over high temperature Under the conditions of after the existing polyphenylene oxide containing sulfo group ion exchange capacity compared to bigger.
In addition to the constituent represented by formula (1) and formula (2), the polyphenylene oxide containing sulfo group of present embodiment Other constituents can be included, relative to the constituent represented by formula (1) and formula (2) and other constituents 100 moles of %, the ratio of other constituents is particularly preferably 0 mole of %, more preferably 0 mole %~10 mole %, preferably It is 0 mole of %~20 mole %.
(proton-conductive films)
The proton-conductive films of present embodiment are characterised by, its polyphenylene oxide containing sulfo group for including present embodiment.
The content of the polyphenylene oxide containing sulfo group of the present embodiment in the proton-conductive films of present embodiment is particularly preferably 100 mass % (that is, the proton-conductive films of present embodiment are made up of the polyphenylene oxide containing sulfo group of present embodiment), more preferably 95 mass %~100 mass %, it is preferably 90 mass %~100 mass %.
The proton-conductive films of present embodiment can be suitably used for solid as single solid polyelectrolyte membrane In high molecular fuel battery, redox flow batteries etc..
The proton-conductive films of present embodiment can for example be manufactured as follows：The above-mentioned polyphenylene oxide containing sulfo group is dissolved completely in After in methyl alcohol, ethanol, propyl alcohol, dimethyl sulfoxide (DMSO) equal solvent (organic solvent), it is molded using the solution is poured on base material For membranaceous casting etc. carries out film forming, resulting film is dried, so as to produce proton-conductive films.
As casting, spray-on process, spin-coating method, scraper spray-on process etc. can be specifically enumerated.
As the base material used in casting, glass plate or plastic foil etc. can be enumerated.Used as plastic foil, it is right preferably to gather PET film, poly tetrafluoroethylene, polyimide film.
As the solvent for dissolving the above-mentioned polyphenylene oxide containing sulfo group, can for example enumerate methyl alcohol, ethanol, propyl alcohol, isopropanol, The alcohols such as sec-butyl alcohol, the tert-butyl alcohol；The aklylene glycol monoalkyl such as glycol monoethyl ether, ethylene glycol monoethyl ether, dihydroxypropane single-ether Ethers；The ethers such as tetrahydrofuran, 1,3- dioxs；N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), Non-proton system's polar solvent such as METHYLPYRROLIDONE, acetonitrile；Etc..They can be used alone, it is also possible to by 2 kinds It is mixed above to use.
The solid component concentration of the polyphenylene oxide containing sulfo group in the solution used when being poured into a mould also depends on the polymer Molecular weight, the concentration is 5 mass %~40 mass %, be preferably 7 mass %~30 mass %.
If polymer concentration is difficult to thick-film less than the lower limit of above range；If in addition more than the upper limit of above range, Then solution viscosity is too high, it is difficult to form film, and uniform film cannot be obtained sometimes.
Can be to be kept for 0.1 hour at a temperature of 50 DEG C~170 DEG C on the drying after the masking using above-mentioned cast Carried out under conditions of~12 hours.
Embodiment
Below, embodiment is enumerated to illustrate embodiments of the present invention, but the present invention is not limited to these embodiments.
As embodiment and the raw material of the polyphenylene oxide containing sulfo group of comparative example, as long as no special declaration, then using poly- (2,6- dimethyl -1,4- phenylene ethers) (S201A, Asahi Chemical Corp's manufacture) (inherent viscosity：0.47dL/g).
The assay method and evaluation method of the various physical property in embodiment and comparative example is illustrated below.
(1) sulphonation rate
For embodiment and the polyphenylene oxide containing sulfo group of comparative example, utilize1(ECA-500, JEOL plant of formula meeting of H-NMR devices Society manufactures), in frequency：500MHz, relaxation time：5sec, cumulative number：512 times, carry out NMR measure under conditions of room temperature.Institute The sulphonation rate (%) of the polyphenylene oxide containing sulfo group of synthesis specifically seeks method as described in the following Examples.Show the result in table 1.
(2) heat endurance
For embodiment and the polyphenylene oxide containing sulfo group of comparative example, using TGA, under a nitrogen with 10 DEG C/minute of programming rate The condition of clock is measured.In measure, most 140 DEG C of first arrival before observe water evaporation caused by mass loss, 140 DEG C~ 270 DEG C are observed that sulfo group departs from caused mass loss, observe that the quality caused by the decomposition of aromatic rings is damaged more than 270 DEG C Lose.The temperature (sulfo group disengaging started temperature) (DEG C) the sulfo group disengaging of each polymer has been investigated by TGA curves.Result is shown In table 1.
(3) ion exchange capacity
25 DEG C of saturation will be impregnated into using the film 0.02g made by the polyphenylene oxide containing sulfo group of embodiment and comparative example In NaCl aqueous solution 30mL, stir while placing 30 minutes.Then, phenolphthalein is used as indicator, while using 0.01N hydrogen Aqueous solution of sodium oxide carries out acid-base titration to the proton in the saturation NaCl aqueous solution.After neutralization, handed over by being filtrated to get ion The counter ion counterionsl gegenions for changing base are the polyphenylene oxide containing sulfo group of sodium ion.Resulting polymer is rinsed with pure water, and then at 160 DEG C It is vacuum dried, is weighed the absolute dry weight after vacuum drying.
The amount of substance of the NaOH required for neutralization is set to M (mmol), is sodium by the counter ion counterionsl gegenions of ion-exchange group The quality of the polyphenylene oxide containing sulfo group of ion is set to W (mg), by formula：EW=(W/M) -22 obtains equivalent quality EW, and (g/ works as Amount).Additionally, EW values obtained by taking reciprocal and being multiplied by 1000 times, ion exchange capacity meq/g (milliequivalent/g) is calculated.
Hereinafter, each embodiment and each comparative example are described in detail.
<Embodiment 1>
To carried out argon gas displacement 5L four-hole boiling flask in add poly- (2,6- dimethyl -1,4- phenylene ethers) (90g), Dichloromethane (2250mL), is stirred.At room temperature with aluminium chloride is added dropwise in 45 minutes polyphenyl ethereal solutions to above-mentioned making The dichloromethane solution (750mL) of (109g) and chlorobenzoyl chloride (104g).After completion of dropwise addition, will react molten using mantle heater Liquid is heated up, and is reacted 6 hours at 40 DEG C, and reaction solution is naturally cooled into room temperature afterwards.After being sampled on a small quantity to reaction solution, Add into methyl alcohol (18L), separate out polymer, crude product is recovered by filtration.Additionally, the crude product that will be reclaimed is dissolved in In chloroform (1.4L), solution is added into methyl alcohol (10L), carry out deposition and purification.Sediment filtration under diminished pressure is reclaimed as product The Noryl (acylation polyphenylene oxide) of thing.
The Structural Identification of Noryl passes through1H-NMR is carried out.
1H-NMR(THF-d8) δ 7.84 (s, 2.0H), 7.48 (m, 3.0H), 6.24 (s, 1.0H), 1.86 (m, 6.4H)
The signal of raw material (2,6- dimethyl -1,4- phenylene ethers) is not observed.
From the result, the polymer that the constituent represented by following formulas (4) is constituted is generated.
Oleum (1.3kg) is added in four-hole boiling flask to the 3L for having carried out argon gas displacement, it is logical using mechanical agitator Agitating paddle is crossed to be stirred.Above-mentioned acylation polyphenylene oxide (130g) is lentamente added in reaction vessel.It is stirred at room temperature 10 After hour, reaction solution is lentamente put into frozen water (8L), stop reaction.The solid for separating out is returned by filtration under diminished pressure Receive, cleaned in ion exchange water (5L).Same cleaning operation is repeated 9 times, until the cleaning point in the cleaning operation Untill more than 5 being reached from the pH of water.By the solid after cleaning in 50 DEG C of drying under reduced pressure 60 hours.
The Structural Identification of resulting polymer passes through1H-NMR is carried out.
1H-NMR(THF-d8) δ 8.17-7.45 (m, 3.5H), 6.24 (s, 1.0H), 1.86 (s, 5.7H)
From the result, the polymerization that the constituent represented by following formulas (4) and formula (5) is constituted is generated Thing.
(in formula (5), n is integer.)
1In the result of H-NMR, the signal (δ 6.24ppm) in main chain aromatic rings source of polyphenylene oxide will be acylated as base Standard, using the area of the signal in the aromatic rings source of unreacted acylation polyphenyl ether unit before the sulfonation after decrement as warp The amount of the position of the aromatic rings of the acylation polyphenyl ether unit of sulfonation is calculated, and thus obtains sulphonation rate (%).
The sulphonation rate of the polyphenylene oxide containing sulfo group of embodiment 1 is 31.5%.
In addition, it is 185 DEG C that the sulfo group of the polyphenylene oxide containing sulfo group of embodiment 1 departs from started temperature.
The resulting polyphenylene oxide containing sulfo group is dissolved in methyl alcohol, polytetrafluoroethylene (PTFE) is spread on stainless teel pallet Piece, by casting by solution coating to teflon plate, the sample that will be coated with is air-dried 24 hours at room temperature.So Obtain the membranaceous proton-conductive films of about 4 μm of thickness.
The ion exchange capacity of the proton-conductive films of embodiment 1 is 1.26meq/g.
<Embodiment 2,3>
The reaction time of oleum and above-mentioned acylation polyphenylene oxide is changed like that as shown in table 1, in addition with implementation Example 1 is prepared as the polyphenylene oxide containing sulfo group.
The evaluation result of resulting polymer is shown in table 1.
<Embodiment 4>
After obtaining the acylation polyphenylene oxide (sulphonation rate 31.5%) containing sulfo group using method similarly to Example 1, by it In 170 DEG C be heat-treated within 30 minutes in stove in a nitrogen atmosphere.
The evaluation result of the polymer after heat treatment is shown in table 1.
<Embodiment 5>
Phenyllacetyl chloride is used instead of chlorobenzoyl chloride, the polyphenylene oxide containing sulfo group is prepared similarly to Example 1 in addition.
The Structural Identification of resulting polymer passes through1H-NMR is carried out.
1H-NMR(THF-d8) δ 7.15-7.45 (m, 3.4H), 6.24 (s, 1.0H), 3.93 (s, 2.0H), 1.86 (s, 5.9H)
From the result, the polymerization that the constituent represented by following formulas (6) and formula (7) is constituted is generated Thing.
(in formula (7), n is integer.)
1In the result of H-NMR, the signal (δ 6.24ppm) in main chain aromatic rings source of polyphenylene oxide will be acylated as base Standard, by the area of the signal (δ 7.15-7.45ppm) in the side chain phenyl source of unreacted acylation polyphenyl ether unit in sulfonation Front and rear decrement is calculated as sulfonated acylation polyphenylene oxide quantity of units, thus obtains sulphonation rate (%).
In addition, departing from started temperature and ion exchange capacity on sulfo group, also obtain similarly to Example 1.
The evaluation result of resulting polymer is shown in table 1.
<Comparative example 1>
The sulfonation of poly- (2,6- dimethyl -1,4- phenylene ethers) is carried out with reference to non-patent literature 2 (particularly p.4023).
Chloroform 450g is added in there-necked flask to the 500mL for having carried out argon gas displacement, is stirred using mechanical agitator Mix.After chlorosulfonic acid 9.0g was added dropwise with 30 minutes at room temperature, poly- (2,6- dimethyl-Isosorbide-5-Nitrae-phenylene ether) 30g is added, in room temperature Lower stirring 30 minutes.Chlorosulfonic acid 14g is taken in dropping funel, after being added dropwise with 20 minutes, is stirred at room temperature 30 minutes.From being separated out Solid remove supernatant.Chloroform is added in residue solid, is cleaned, remove supernatant.As filtration under diminished pressure to obtained by To residue reclaimed, cleaned in ion exchange water (5L).Same cleaning operation is repeated 5 times, until the cleaning Untill the pH of the cleaning separation water in operation reaches more than 5.By drying under reduced pressure 24 hours at room temperature of the solid after cleaning.
The Structural Identification of resulting polymer passes through1H-NMR is carried out.
1H-NMR(DMSO-d6∶CDCl3=1: 2 (v/v)) δ 6.45 (s, 2.0H), 6.16 (0.21H), 2.51 (s, 0.88H), 2.06 (s, 6.0H), 1.99 (s, 0.88H)
From the result, the polymerization that the constituent represented by following formulas (8) and formula (9) is constituted is generated Thing.
1In the result of H-NMR, the peak near δ 6.2ppm is accredited as the 3 of sulfonated 2,6- dimethyl benzene ether units Position or the proton (P) of 5,3 and 5 of unsubstituted 2,6- dimethyl benzenes ether unit are accredited as by the peak near δ 6.5ppm Proton (Q), sulphonation rate=peak area (P)/(area+peak (Q) of peak (P) is obtained by area ratio (the ratio between integrated value) at its peak Area/2) × 100 (%).
The sulphonation rate of the polyphenylene oxide containing sulfo group of comparative example 1 is 17.4%.
The ion exchange capacity of the polyphenylene oxide containing sulfo group of comparative example 1 is determined in the same manner as the situation of embodiment 1, as a result for l.2meq/g。
The ＞ of ＜ comparative examples 2
The polyphenylene oxide (sulphonation rate 17.4%) containing sulfo group is obtained using the method same with comparative example 1, afterwards by it in nitrogen Carry out being heat-treated for 30 minutes in 170 DEG C with stove under gas atmosphere.
The evaluation result of the polymer after heat treatment is shown in table 1.
【Table 1】
*The evaluation result of the polymer after heat treatment
As shown in table 1, in embodiment 1-5, can there will be the polyphenyl as general engineering resin at a low price in female skeleton The sulfo group of the polyphenylene oxide containing sulfo group of ether departs from started temperature and improves to can be substantially resistant to the degree by membrance casting condition.
Industrial applicibility
Polyphenylene oxide containing sulfo group of the invention is industrially applicable as proton-conductive films, and the proton-conductive films are used as solid Body polyelectrolyte membrane can be suitable in polymer electrolyte fuel cell, redox flow batteries etc..

Claims (3)

1. a kind of polyphenylene oxide containing sulfo group, it is characterised in that it includes formula (1) and the constituent represented by formula (2),
In formula (1), R1~R3It is each independently to be selected from and is made up of hydrogen, halogen, alkyl, fluorinated alkyl, pi-allyl, aryl, cyano group Group at least one；X is the electron withdraw group of divalence；Ar1There is the aryl of the group beyond sulfo group for that can replace,
In formula (2), R4~R6It is each independently to be selected from and is made up of hydrogen, halogen, alkyl, fluorinated alkyl, pi-allyl, aryl, cyano group Group at least one；X is the electron withdraw group of divalence；Ar2There is the aryl of at least one sulfo group for substitution.
2. the polyphenylene oxide of sulfo group is contained as claimed in claim 1, wherein, relative to the formula (1) and the formula (2) institute table The constituent for showing, the ratio of the constituent represented by the formula (1) is 60 moles of %~95 mole %, the formula (2) ratio of the constituent represented by is 5 moles of %~40 mole %.
3. a kind of proton-conductive films, it is characterised in that it includes the polyphenylene oxide containing sulfo group described in claim 1 or 2.
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