CN106800647B - Polyphenylene oxide, proton-conductive films containing sulfo group - Google Patents
Polyphenylene oxide, proton-conductive films containing sulfo group Download PDFInfo
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- CN106800647B CN106800647B CN201610154123.XA CN201610154123A CN106800647B CN 106800647 B CN106800647 B CN 106800647B CN 201610154123 A CN201610154123 A CN 201610154123A CN 106800647 B CN106800647 B CN 106800647B
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- 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
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- 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
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- 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
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- 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
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Abstract
The present invention relates to polyphenylene oxide, proton-conductive films containing sulfo group.The purpose of the present invention is to provide a kind of polyphenylene oxide containing sulfo group, by inhibiting the disengaging of the sulfo group caused by heat, thus excellent in te pins of durability.A kind of polyphenylene oxide containing sulfo group, which is characterized in that it includes constituents represented by general formula (1) and general formula (2).
Description
Technical field
The present invention relates to polyphenylene oxide, proton-conductive films containing sulfo group.
Background technique
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 is generated electricity to cathode side for oxygen supply or air using the potential difference generated at electrode both ends.
At this point, needing proton-conducting height, gas saturating as the solid macromolecule electrolyte used in proton-conductive films
The property crossed is low, chemical and mechanical stability is high.
As proton-conductive films, use mainly with Nafion (registered trademark, DuPont Corporation's manufacture) for 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 that insufficient in the proton-conducting in high temperature and low humidity region and manufacturing cost is high.
As the proton-conductive films for overcoming this disadvantage, it is conceived to the matter for importing sulfo group in the macromolecule of hydrocarbon system and being formed
Sub- conductive membranes.For example, can exemplify by substance made of poly arylene ether sulfone sulfonation (for example, see non-patent literature 1), by polyethers
Substance made of ether ketone sulfonation (for example, see patent document 1,2 references) etc..
As other examples, it can also enumerate substance made of polyphenylene oxide sulfonation (for example, see non-patent literature 2).?
In the example, it will be used as substrate as poly- (2, the 6- dimethyl-Isosorbide-5-Nitrae phenylene ether) of the polyphenylene oxide for being used as general engineering plastic, it should
Proton-conductive films are most by one of the material expected since easy modification, economy are excellent.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 6-93114 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2005-255850 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2002-110174 bulletin
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) are p.211-220
Non-patent literature 2:Journal of Applied Polymer Science, Vol.29 (1984) are p.4017-
4027
Summary of the invention
Subject to be solved by the invention
But poly- (2, the 6- dimethyl-Isosorbide-5-Nitrae-phenylene being applied in polymeric membrane is being expected to because economy is excellent
Ether) in the case where, it is difficult to inhibition is directed into the sulfo group on the aromatic rings of main chain backbone by sulfonation and is detached from because of heat.Sulphur
The disengaging of base is the electron rich due to the main chain backbone of polyphenylene oxide and generates.
In order to solve the project, there are document report following methods: using lewis acid and sultone, by alkyl by sulphur
Base imports in female skeleton of polyphenylene oxide (for example, see patent document 3).But in this method, the reactivity of sultone is low, thus
High temperature, prolonged reaction condition are needed, thus is not necessarily practical method.
In addition, the polymer that the sulfo group caused by as inhibiting by heat is detached from, there is a kind of thermal stability of document report
High sulfonation poly arylene ether sulfone based compound is used in and is imported with the monomer of sulfo group on electron-withdrawing aromatic rings and is gathered
(for example, see patent document 4) obtained from conjunction.But this method thus polymerize in order to obtain since the reactivity of monomer is low
Polymerization reaction time required for object is elongated, and there are problems for the economy of polymer.
In addition, in order to improve thermal stability 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 synthetic method complexity.
Therefore, the purpose of the present invention is to provide a kind of good thermal stability, be suitable for material as proton-conductive films
Polyphenylene oxide containing sulfo group.
Solution for solving the problem
In view of the situation, it has made intensive studies to eliminate the associated problem with the above-mentioned prior art, as a result sends out
It is existing, by importing the electron-withdrawing group and aryl of divalent to the main chain backbone of polyphenylene oxide, sulfo group, sulfonated polyphenyl are imported later
For ether to thermostabilization, proton-conducting is excellent, and gas-premeable is small, and also stable proton passes electrochemistry after being capable of forming heat treatment
Guided membrane.
In the present invention, by importing the electron-withdrawing group of divalent to the main chain backbone of polyphenylene oxide, the electricity of female skeleton can be reduced
Son is rich, and three-dimensionally aggregation around female skeleton (mixed body closes う), it is difficult to sulfonation occur.Also, not from female skeleton week
Crowd around and sulfonation preferentially occurs on collection (being spatially easy to happen reaction), side chain aromatic hydrocarbyl.Due to above situation, this hair
In bright, the de- sulfonation caused by heat can be effectively inhibited.
In addition, the present invention can efficiently be manufactured using simple synthetic method, it is able to use cheap general engineering
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, which is characterized in that it includes composition represented by general formula (1) and general formula (2) at
Point.
(in formula (1), R1~R3It is each independently selected from by hydrogen, halogen, alkyl, fluorinated alkyl, allyl, aryl, cyanogen
At least one of the group of base composition；X is the electron-withdrawing group of divalent；Ar1For the virtue for having the group other than sulfo group can be replaced
Base.)
(in formula (2), R4~R6It is each independently selected from by hydrogen, halogen, alkyl, fluorinated alkyl, allyl, aryl, cyanogen
At least one of the group of base composition；X is the electron-withdrawing group of divalent；Ar2To replace the aryl for having at least one sulfo group.)
[2] polyphenylene oxide containing sulfo group as described in [1], wherein relative to the general formula (1) and the general formula (2) institute table
The constituent shown, the ratio of constituent represented by the general formula (1) are 60 moles of %~95 mole %, the general formula
(2) ratio of the constituent represented by is 5 moles of %~40 mole %.
[3] a kind of proton-conductive films, which is characterized 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 good thermal stability, be suitable for the poly- containing sulfo group of material as proton-conductive films
Phenylate.
Specific embodiment
In the present invention, by new sulfonation introduction method, containing for the disengaging, excellent heat stability for inhibiting sulfo group is prepared
The polyphenylene oxide of sulfo group provides ionic conductivity the excellent conduct particularly useful high molecular material of electrolyte membrane for fuel cell.
In the following, embodiments of the present invention (hereinafter also referred to as " present embodiment ") are described in detail.It needs
Bright, the present invention is not limited to the following embodiments and the accompanying drawings, various modifications can be carried out in the range of its main points to implement.
(polyphenylene oxide containing sulfo group)
The polyphenylene oxide containing sulfo group of present embodiment is characterized in that it includes the following general formula (1) and the following general formula (2) institute
The constituent of expression.
(in formula (1), R1~R3It is each independently selected from by hydrogen, halogen, alkyl, fluorinated alkyl, allyl, aryl, cyanogen
At least one of the group of base composition；X is the electron-withdrawing group of divalent；Ar1For the virtue for having the group other than sulfo group can be replaced
Base.)
(in formula (2), R4~R6It is each independently selected from by hydrogen, halogen, alkyl, fluorinated alkyl, allyl, aryl, cyanogen
At least one of the group of base composition；X is the electron-withdrawing group of divalent；Ar2To replace the aryl for having at least one sulfo group.)
In formula (1) and formula (2), preferred following manner.
As R1~R6In alkyl and fluorinated alkyl carbon atom number, preferably 1~12,1~4 more preferable.
As R1~R6Allyl, preferably 2- acrylic, 2- methyl -2- acrylic, 2- hexenyl.
As R1~R6(i.e. main chain side) aryl, preferably phenyl, benzyl.
The electron-withdrawing group of divalent as X can enumerate-C (O)-(carbonyl (ketone group)) ,-S (O)-(sulfoxide) ,-S (O)
2- (sulfone), preferably-C (O)-(carbonyl (ketone group)).
As Ar2(i.e. side chain side) aryl, preferably phenyl, naphthalene, anthryl, benzyl.
In mode of the invention, Ar1For the group for having the group other than sulfo group can be replaced.In addition, Ar2Aromatic rings bone
At least one of substituent group of frame is sulfo group.Herein, binding site of the 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 other than the main chain of polyphenylene oxide, thus
It is able to suppress the disengaging of sulfo group.As a result, it is possible to provide the heat-staple polyphenylene oxide containing sulfo group.
For following reasons, in the polyphenylene oxide containing sulfo group of present embodiment, relative to above-mentioned general formula (1) and general formula
(2) ratio of the constituent represented by, constituent represented by general formula (1) is preferably 60 moles of %~95 mole %, is led to
The ratio of constituent represented by formula (2) is preferably 5 moles of %~40 mole %.It should be noted that by general formula (2) institute table
The constituent shown is also referred to as sulphonation rate relative to the ratio of constituent represented by general formula (1) and general formula (2).
If sulphonation rate can be obtained in above range when the polyphenylene oxide that will contain sulfo group is used as solid polyelectrolyte membrane
High proton conductivity, and high film-strength can be maintained.
In addition, from improve have generating efficiency of the resin as the fuel cell of solid polyelectrolyte membrane in terms of go out
Hair, sulphonation rate are preferably 5 moles of % or more, further preferably 15 moles of % or more, particularly preferably 25 moles of % or more；Separately
Outside, from the swelling aspect for reducing solid polyelectrolyte membrane, preferably 40 moles of % or less, it is more preferably
35% or less.
It should be noted that as long as no special declaration, then the sulphonation rate of resin refers to resin in room temperature (such as 30
DEG C) it is 24 hours dry after value.
The ion exchange capacity of the polyphenylene oxide containing sulfo group as present embodiment, as long as can express desired proton
Conductibility is just not particularly limited, for the reason same as the reasons why 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 found out by conventional method.
It should be noted that the water resistance of resin reduces, in water sometimes in the case where the amount of sulfonation of resin is excessive
Dissolution occurs and decomposes, it is not preferred as proton-conductive films.
Ion exchange capacity can by concentration in the amount and reaction solution of sulfonating agent, using sulfonating agent reaction it is anti-
Between seasonable and reaction temperature adjusts, for example, in the case where improving ion exchange capacity, as long as increase sulfonating agent and prolonging
The long reaction time with sulfonating agent.
The structure of the polyphenylene oxide containing sulfo group about present embodiment, for example, can use infrared absorption spectrum according to
677cm-1、1,140cm-1、3,400cm-1The presence or absence of the absorption peak of sulfo group confirm.
In addition, above structure can also for example pass through1H-NMR confirms.
(manufacturing method of the polyphenylene oxide containing sulfo group)
The manufacturing method of the polyphenylene oxide containing sulfo group of present embodiment is not particularly limited, for example, following sides
Method: importing the electron-withdrawing group and aryl of divalent in the polyphenylene oxide based on, synthesis modification polyphenylene oxide, backward modified gather
Sulfo group is imported in phenylate, synthesizes the polyphenylene oxide containing sulfo group.
The method for synthesizing above-mentioned Noryl is not particularly limited, for example, following methods: utilizing
Friedel-Crafts acylation reaction imports acyl group into the fragrant ring skeleton of polyphenylene oxide, particularly has aromatic hydrocarbyl
Acyl group.
In Friedel-Crafts acylation reaction, more specifically, in the lewis acids such as aluminium chloride, stannic chloride (gold
Belong to halide) in the presence of, react polyphenylene oxide and etheride etc..
As reaction dissolvent, methylene chloride, 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 recorded 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 ether) and poly- (2,3,6- trimethyl -1,4- phenylene ether) or they
The random copolymer of mixture, 2,6- xylenol and 2,3,6- pseudocuminol.
It as above-mentioned etheride, is not particularly limited, compound represented by the following general formula (3) can be enumerated.
(in formula (3), Y is the halogen other than fluorine；R7~R11It is each independently hydrogen, halogen, alkyl, fluorinated alkyl, allyl
Base, aryl, cyano, herein R7~R11At least one of be hydrogen.)
In addition, following compounds can also be enumerated as etheride:, will be in conjunction with carbonyl in above-mentioned general formula (3)
Pendent aromatic alkyl is replaced by phenyl, forms the polycycles aromatic hydrocarbyls such as naphthalene, anthryl.
Further, it is also possible to enumerate following compounds: in above-mentioned general formula (3), the group in conjunction with carbonyl being replaced by benzene
Base, being formed can be in the form of sandwiching alkyl between carbonyl and pendent aromatic alkyl by aryl (such as the benzyl of the two connection
Base etc.).
Acyl group rate based on Friedel-Crafts acylation reaction is particularly preferably 100 moles of %, and more preferably 90
Mole %~100 mole %, 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 of solvent and heat resistance in terms of go out
Hair, preferably 0.25dL/g or more, further preferably 0.30dL/g or more, in addition, viscous from the solution prevented when importing sulfo group
Degree become it is excessively high, improve stirring and liquid conveying etc. operability aspect set out, preferably 1.45dL/g or less, further it is excellent
It is selected as 0.70dL/g or less.
It should be noted that inherent viscosity is found out as follows.That is, 0.5g Noryl is dissolved in chloroform, obtain
The solution of more than two kinds of the various concentration of 100mL or more (concentration 0.5g/dL or less).Then, Ubbelohde viscometer is used at 30 DEG C
Specific viscosity is measured to the solution of various concentration respectively, viscosity when concentration is 0 is exported by the relationship of specific viscosity and concentration, this is glued
Degree is used as inherent viscosity.
As the method for importing sulfo group in whole or in part in above-mentioned Noryl, following methods can be enumerated: in nothing
In the presence of solvent or solvent, react the sulfonating agents such as Noryl and oleum, sulfuric acid, chlorosulfonic acid.
It is imported except through above-mentioned sulfonating agent other than the method for sulfo group, following methods can also be used: importing sulfonated metal
Salt, sulfonation ester group, sulfuryl chlorio etc. carry out ion exchange, esterification, hydrolysis etc., to import sulfo group later.
As solvent, halogenated hydrocarbons such as dichloroethanes, tetrachloroethanes, chloroform, chlorination methylene etc. can be used.
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, preferably 1 hour~10 hours.
In addition, the method recorded in non-patent literature 2 can be used for example as the method for importing sulfo group.That is, will gather
(2,6- dimethyl-Isosorbide-5-Nitrae-phenylene ether) is dissolved in chloroform, and chlorosulfonic acid is added dropwise into the solution, makes its reaction at room temperature,
So as to obtain the polyphenylene oxide containing sulfo group.Polyphenylene oxide containing sulfo group does not dissolve in chloroform with the progress of sulfonating reaction, with nothing
The solid form of setting is precipitated, and can be recycled by filtering.
Fragrant ring skeleton phase in the polyphenylene oxide containing sulfo group of present embodiment, 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-withdrawing group.Therefore, can be
Just (such as 170 DEG C) are also difficult to happen the effect that the sulfo group caused by heat is detached under the high temperature conditions.Also, pass through above-mentioned effect
Fruit, the ion exchange capacity of the polyphenylene oxide containing sulfo group of the present embodiment after being placed under hot conditions and is placed in high temperature
Under the conditions of after the existing polyphenylene oxide containing sulfo group ion exchange capacity compared to bigger.
Other than the constituent represented by the general formula (1) and general formula (2), the polyphenylene oxide containing sulfo group of present embodiment
It may include other constituents, relative to constituent represented by general formula (1) and general formula (2) and other constituents
100 moles of %, the ratio of other constituents are particularly preferably 0 mole of %, more preferably 0 mole of %~10 mole %, preferably
For 0 mole of %~20 mole %.
(proton-conductive films)
The proton-conductive films of present embodiment are characterized in that it includes the polyphenylene oxide containing sulfo group of present embodiment.
The content of the polyphenylene oxide containing sulfo group of 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 of the polyphenylene oxide containing sulfo group of present embodiment), more preferably
95 mass of mass %~100 %, preferably 90 mass of mass %~100 %.
The proton-conductive films of present embodiment can be used as individual solid polyelectrolyte membrane and be suitably used for solid
In high molecular fuel battery, redox flow batteries etc..
The proton-conductive films of present embodiment can for example manufacture as follows: the above-mentioned polyphenylene oxide containing sulfo group is dissolved completely in
Methanol, ethyl alcohol, propyl alcohol, in dimethyl sulfoxide equal solvent (organic solvent) after, formed using the solution to be poured on substrate
It forms a film for membranaceous casting etc., obtained film is dried, to produce proton-conductive films.
As casting, spray-on process, spin-coating method, scraper spray-on process etc. can be specifically enumerated.
As substrate used in casting, glass plate or plastic foil etc. can be enumerated.As plastic foil, preferably poly- pair
Ethylene terephthalate film, polytetrafluoroethylene film, polyimide film.
As the solvent for dissolving the above-mentioned polyphenylene oxide containing sulfo group, for example, methanol, ethyl alcohol, propyl alcohol, isopropanol,
The alcohols such as sec-butyl alcohol, the tert-butyl alcohol；The aklylene glycols monoalkyl such as glycol monoethyl ether, ethylene glycol monoethyl ether, dihydroxypropane single-ether
Ethers；The ethers such as tetrahydrofuran, 1,3- dioxanes；N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide,
Non-proton system's polar solvent such as n-methyl-2-pyrrolidone, acetonitrile；Etc..They can be used alone, can also be by 2 kinds
It is used in mixed way above.
The solid component concentration of the polyphenylene oxide containing sulfo group in the solution used when being poured also depends on the polymer
Molecular weight, the concentration be 5 mass of mass %~40 %, preferably 7 mass of mass %~30 %.
If polymer concentration is lower than the lower limit of above range, it is difficult to thick-film；If being in addition more than the upper limit of above range,
Then solution viscosity is excessively high, it is difficult to form film, be unable to get uniform film sometimes.
About using the drying after the film of above-mentioned casting, kept for 0.1 hour at a temperature of being 50 DEG C~170 DEG C
It is carried out under conditions of~12 hours.
Embodiment
In the following, enumerating embodiment to illustrate embodiments of the present invention, but the present invention is not limited to these embodiments.
As the raw material of embodiment and the polyphenylene oxide containing sulfo group of comparative example, as long as no special declaration, then using poly-
(2,6- dimethyl -1,4- phenylene ether) (S201A, Asahi Chemical Corp's manufacture) (inherent viscosity: 0.47dL/g).
The measuring method and evaluation method of various physical property in embodiment and comparative example are shown as follows.
(1) sulphonation rate
For the polyphenylene oxide containing sulfo group of embodiment and comparative example, utilize1(ECA-500, JEOL plants of formula meetings of H-NMR device
Society's manufacture), in frequency: 500MHz, relaxation time: 5sec, cumulative number: carrying out NMR measurement under conditions of 512 times, room temperature.Institute
The sulphonation rate (%) of the polyphenylene oxide containing sulfo group of synthesis specifically asks method as described in the following Examples.Show the result in table 1.
(2) thermal stability
For the polyphenylene oxide containing sulfo group of embodiment and comparative example, using TGA, under a nitrogen with 10 DEG C/minute of heating rate
The condition of clock is measured.Observe mass loss caused by the evaporation of water in measurement, before most 140 DEG C of first arrival, 140 DEG C~
270 DEG C are observed that sulfo group is detached from caused mass loss, the damage of the quality caused by the decomposition that 270 DEG C or more are observed aromatic rings
It loses.Temperature (sulfo group disengaging start temperature) (DEG C) being detached from by the sulfo group that TGA curve has investigated each polymer.Result is shown
In table 1.
(3) ion exchange capacity
Film 0.02g made by the polyphenylene oxide containing sulfo group for using embodiment and comparative example is impregnated into 25 DEG C of saturation
In NaCl aqueous solution 30mL, placed while stirring 30 minutes.Then, phenolphthalein is used as indicator, while utilizes 0.01N hydrogen
Aqueous solution of sodium oxide carries out acid-base titration to the proton in saturation NaCl aqueous solution.After neutralization, handed over by the way that ion is obtained by filtration
The counter ion counterionsl gegenions for changing base are the polyphenylene oxide containing sulfo group of sodium ion.Obtained polymer is rinsed with pure water, and then at 160 DEG C
It is dried in vacuo, the absolute dry weight after weighing vacuum drying.
The amount of substance of sodium hydroxide required for neutralizing is set as 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 as W (mg), passes through formula: EW=(W/M) -22 finds out equivalent quality EW, and (g/ works as
Amount).In addition, taking the inverse of obtained EW value and 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 replace 5L four-hole boiling flask in be added poly- (2,6- dimethyl -1,4- phenylene ether) (90g),
Methylene chloride (2250mL), is stirred.At room temperature with aluminium chloride is added dropwise in 45 minutes polyphenyl ethereal solutions to above-mentioned production
The dichloromethane solution (750mL) of (109g) and chlorobenzoyl chloride (104g).After completion of dropwise addition, it will react molten using mantle heater
Liquid heating, reacts 6 hours at 40 DEG C, later by reaction solution cooled to room temperature.Reaction solution is carried out after sampling on a small quantity,
It is added into methanol (18L), polymer is precipitated, crude product is recovered by filtration.In addition, the crude product recycled is dissolved in
In chloroform (1.4L), solution is added into methanol (10L), carries out deposition and purification.Sediment is filtered under diminished pressure, recycling is as production
The Noryl (being acylated polyphenylene oxide) of object.
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 ether) is not observed.
It can be seen from this result that the polymer that the constituent represented by generating by the following general formula (4) is constituted.
Oleum (1.3kg) is added into the four-hole boiling flask for having carried out the 3L that argon gas is replaced, it is logical using mechanical agitator
Agitating paddle is crossed to be stirred.Above-mentioned acylation polyphenylene oxide (130g) is slowly added in reaction vessel.It is stirred at room temperature 10
After hour, reaction solution is slowly put into ice water (8L), stops reaction.It is returned by the solid for being filtered under diminished pressure to precipitation
It receives, is cleaned in ion exchange water (5L).It is repeated 9 times same cleaning operation, until the cleaning in the cleaning operation point
Until pH from water reaches 5 or more.Solid after cleaning is dried under reduced pressure 60 hours at 50 DEG C.
The Structural Identification of obtained 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)
It can be seen from this result that the polymerization that the constituent represented by generating by the following general formula (4) and general formula (5) is constituted
Object.
(in formula (5), n is integer.)
?1In the result of H-NMR, the signal (δ 6.24ppm) in the main chain aromatic rings source of polyphenylene oxide will be acylated as base
Standard, using it is unreacted be acylated polyphenyl ether unit aromatic rings source signal area before the sulfonation after reduction amount as pass through
The amount of the position of the aromatic rings of the acylation polyphenyl ether unit of sulfonation is calculated, and sulphonation rate (%) is thus found out.
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, which is detached from start temperature,.
The obtained polyphenylene oxide containing sulfo group is dissolved in methanol, spreads polytetrafluoroethylene (PTFE) on stainless teel pallet
Piece air-dries the sample being coated with 24 hours by casting by solution coating to polytetrafluoroethylene (PTFE) on piece at room temperature.So
Obtain about 4 μm of thickness of membranaceous proton-conductive films.
The ion exchange capacity of the proton-conductive films of embodiment 1 is 1.26meq/g.
<embodiment 2,3>
Change reaction time of oleum Yu above-mentioned acylation polyphenylene oxide like that as shown in table 1, in addition to this with implementation
Example 1 is prepared as the polyphenylene oxide containing sulfo group.
By obtained polymer evaluation result 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
Be heat-treated within 30 minutes in 170 DEG C in furnace in a nitrogen atmosphere.
By the polymer after heat treatment evaluation result is shown in table 1.
<embodiment 5>
Phenyllacetyl chloride is used instead of chlorobenzoyl chloride, prepares the polyphenylene oxide containing sulfo group similarly to Example 1 in addition to this.
The Structural Identification of obtained 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)
It can be seen from this result that the polymerization that the constituent represented by generating by the following general formula (6) and general formula (7) is constituted
Object.
(in formula (7), n is integer.)
?1In the result of H-NMR, the signal (δ 6.24ppm) in the 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 unreacted side chain phenyl source for being acylated polyphenyl ether unit in sulfonation
The reduction amount of front and back is calculated as sulfonated acylation polyphenylene oxide quantity of units, thus finds out sulphonation rate (%).
In addition, being detached from start temperature and ion exchange capacity about sulfo group, also find out similarly to Example 1.
By obtained polymer evaluation result is shown in table 1.
<comparative example 1>
The sulfonation of poly- (2,6- dimethyl -1,4- phenylene ether) is carried out with reference to non-patent literature 2 (especially p.4023).
Chloroform 450g is added into the three-necked flask for having carried out the 500mL that argon gas is replaced, is stirred using mechanical agitator
It mixes.At room temperature with after 30 minutes dropwise addition chlorosulfonic acid 9.0g, poly- (2,6- dimethyl-Isosorbide-5-Nitrae-phenylene ether) 30g is added, in room temperature
Lower stirring 30 minutes.It takes chlorosulfonic acid 14g into dropping funel, after being added dropwise with 20 minutes, is stirred at room temperature 30 minutes.From being precipitated
Solid remove supernatant.Chloroform is added in residue solid, is cleaned, supernatant is removed.As being filtered under diminished pressure to obtained by
To residue recycled, cleaned in ion exchange water (5L).It is repeated 5 times same cleaning operation, until the cleaning
Until the pH of cleaning separation water in operation reaches 5 or more.Solid after cleaning is dried under reduced pressure 24 hours at room temperature.
The Structural Identification of obtained 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)
It can be seen from this result that the polymerization that the constituent represented by generating by the following general formula (8) and general formula (9) is constituted
Object.
?1In the result of H-NMR, the peak near δ 6.2ppm is accredited as to the 3 of sulfonated 2,6- dimethyl benzene ether unit
Position or 5 protons (P), are accredited as 3 and 5 of unsubstituted 2,6- dimethyl benzene ether unit for the peak near δ 6.5ppm
Proton (Q), sulphonation rate=peak area (P)/(area+peak (Q) of peak (P) is found out by the 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 measured in the same manner as with embodiment 1 the case where, result is
l.2meq/g。
2 > of < comparative example
The polyphenylene oxide (sulphonation rate 17.4%) containing sulfo group is obtained using method same as comparative example 1, later by it in nitrogen
Be heat-treated within 30 minutes in 170 DEG C with furnace under gas atmosphere.
By the polymer after heat treatment evaluation result is shown in table 1.
[table 1]
*The evaluation result of polymer after heat treatment
As shown in table 1, in embodiment 1-5, can there will be polyphenyl as the general engineering resin of low price in female skeleton
The sulfo group of the polyphenylene oxide containing sulfo group of ether is detached from start 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 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, which is characterized in that it includes constituent represented by general formula (1) and general formula (2),
In formula (1), R1~R3It is each independently to be selected from and be made of hydrogen, halogen, alkyl, fluorinated alkyl, allyl, aryl, cyano
At least one of group；X is the electron-withdrawing group of divalent；Ar1There is the aryl or unsubstituted of the group other than sulfo group for substitution
Aryl,
In formula (2), R4~R6It is each independently to be selected from and be made of hydrogen, halogen, alkyl, fluorinated alkyl, allyl, aryl, cyano
At least one of group；X is the electron-withdrawing group of divalent；Ar2To replace the aryl for having at least one sulfo group.
2. as described in claim 1 containing the polyphenylene oxide of sulfo group, wherein relative to the general formula (1) and the general formula (2) institute table
The constituent shown, the ratio of constituent represented by the general formula (1) are 60 moles of %~95 mole %, the general formula
(2) ratio of the constituent represented by is 5 moles of %~40 mole %.
3. a kind of proton-conductive films, which is characterized in that it includes the polyphenylene oxide of any of claims 1 or 2 containing sulfo group.
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| Poly(arylene ether)s carrying pendant (3-sulfonated) phenylsulfonyl groups;Kern K, et al.;《Polymer International》;20121231;第61卷;第1249-1255页 |
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