CN103936991A - Polymer polyelectrolyte at least containing one hydrophilic block component and synthesis method thereof - Google Patents
Polymer polyelectrolyte at least containing one hydrophilic block component and synthesis method thereof Download PDFInfo
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- CN103936991A CN103936991A CN201310021736.2A CN201310021736A CN103936991A CN 103936991 A CN103936991 A CN 103936991A CN 201310021736 A CN201310021736 A CN 201310021736A CN 103936991 A CN103936991 A CN 103936991A
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- polyelectrolyte
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- multipolymer
- component
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- OHBQPCCCRFSCAX-UHFFFAOYSA-N COc(cc1)ccc1OC Chemical compound COc(cc1)ccc1OC OHBQPCCCRFSCAX-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- 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
Abstract
The invention discloses a polymer polyelectrolyte at least containing one hydrophilic block component and a synthesis method thereof, the polymer polyelectrolyte is shown as the following structure:-{-[-(-Ar2-Y-Ar3-Y-) n-Ar2-Y-]a-(Ar1-X-Ar1)b-Y-(Ar2)c-} k-, and the synthetic steps are as follows: step 1), first preparing a hydrophilic polymer M part with a set molecular weight; step 2), copolymerizing the hydrophilic polymer M part which is prepared in the step 1) and used as a multi-functional component with other multi-functional components, wherein the other multi-functional components participating in the copolymerization do not contain any component with hydrophilic ionic functional groups. A membrane material synthesized by the polymer polyelectrolyte not only can be used as a proton conducting diaphragm of a fuel cell, and can also be used as a high performance separating membrane material.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of multipolymer polyelectrolyte and synthetic method that at least contains a hydrophilic block component.
Background technology
Polyelectrolyte (polyelectrolyte) claim again polymer electrolyte, refers to the polymer of the ionic groups that ionize with many energy in main chain or side chain.
Polyelectrolyte has the dual structure feature of polymer long-chain and the ionization of small molecules ionogen concurrently, have the not available functional performance of common polymer (as glutinous in increased, flocculation, electrostatic interaction etc.), these characteristics make it have very extensive and important application.In recent years, along with the development of membrane science and technology research, polyelectrolyte has obtained tremendous development as a kind of emerging mould material.People develop into synthetic polymer to the research of polyelectrolyte from natural polymer; From low density electric charge polyelectrolyte, develop into High Density Charge polyelectrolyte; From compound polyelectrolyte, develop into amphipathic block polyelectrolyte.
Summary of the invention
For addressing the above problem, the object of this invention is to provide a kind of multipolymer polyelectrolyte and synthetic method that at least contains a hydrophilic block component, the synthetic prepared mould material of multipolymer polyelectrolyte has very strong mechanical property.
For realizing above-mentioned technical purpose, reach above-mentioned technique effect, the present invention is achieved through the following technical solutions:
At least, containing the multipolymer polyelectrolyte of a hydrophilic block component, composition structure is:
-{-[-(Ar2-Y-Ar3-Y-)
n-Ar2-Y-]
a-(Ar1-X-Ar1)
b-Y-(Ar2)
c-}
k-
.... or
-{-[-Ar3-Y-(-Ar2-Y-Ar3-Y-)
n-]
a-(Ar2)
b-Y-(Ar1-X-Ar1)
c-}
k-
... ...., wherein--[(Ar2-Y-Ar3-Y-)
n-Ar2-Y-]
a--be hydrophilic polymer M part,
Ar1 is phenyl, Nai Ji, triphenyl, benzene cyano group or-Ar4--R1-Ar5--, wherein R1 is-C (O)--,--S (O)
2--,--P (O) (C
6h
5)--,--C (O)-Ar-C (O)--or--C (O)-Ar6-S (O)
2--, Ar4, Ar5, Ar6 is aromatic group or substituted aroma group;
Ar2 is-O-Ar7-R2-Ar8-O--;
R2 is single covalent linkage, naphthenic hydrocarbon C
2h
2n-2;
Ar7, Ar8 is aromatic group or substituted aroma group;
Wherein X is-C (O)--,--S (O)
2--,--P (O) (C
6h
5)--,
--C (O)-Ar-C (O)--or--C (O)-Ar6-S (O)
2--, Ar4, Ar5, Ar6 is aromatic group or substituted aroma group;
Y is-S-,-O-;
N is 0 to 20 integer;
K is 20 to 200 integer;
A, b, c, for mole number or be per-cent, wherein a+c=b;
Ar3 is the aromatic portion with hydrophilic and ionic groups, and its structure is:
Z is hydrogen atom or strong electron-withdrawing group group, is CN, NO
2or CF
3;
A is-C (O)--,--S (O)
2--;
B is--O--,--S--,--CH
2--or--OCH
2cH
2o--;
Ar is aromatic group or substituted aroma group;
Ra, Rb is-SO
3h,--COOH,--PO
3h or--SO
2nHSO
2r, Ra, Rb is identical or different,--SO
2nHSO
2in R, R is CF
2n+1;
X, y, g, is 1 to 100 integer.
Further, described hydrophilic polymer M is partly aromatics, is polyaryletherketone, polyether sulphone, polyarylether or polyhenylene, and the number-average molecular weight of this class segment is between 500-8000, and the polymerization degree is between 1-20; At described hydrophilic polymer M, partly comprise a class with the component of hydrophilic ionic group, it can be sulfonation group-SO with ionic group
3h, hydroxy-acid group-COOH, phosphate group-PO
3h or sulfimide group-SO
2nHSO
2r, wherein R is CnF2n+1.
Further, described ionogen is as high-performance separation membrane material.
Further, the proton conductive barrier film that described ionogen is used as fuel cell.
Further, described ionogen is as the conductive component in coating ink used.
Synthetic described at least containing the method for the multipolymer polyelectrolyte of a hydrophilic block component, comprise the following steps:
Step 1) the hydrophilic polymer M part of molecular weight is set in first preparation;
Step 2) using step 1) the hydrophilic polymer M for preparing part carries out copolymerization again as a kind of multi-functional component and other polyfunctional group component, wherein participates in no longer comprising any composition with hydrophilic ionic functional group in other components of copolymerization.
The invention has the beneficial effects as follows:
1, the multipolymer polyelectrolyte that at least contains a hydrophilic block component that the present invention synthesizes adopts some high-modulus monomers, segment, therefore prepared mould material has very strong mechanical property, when practical application, after segmented copolymer of the present invention can being dissolved in to organic solvent, on dull and stereotyped coating machine, be coated with continuously masking, and then with the prepared film of protonic acid acidification, result obtains having hydrophilic/hydrophilic amphipathic membrane material;
2, the present invention synthesize at least containing causing in ionogen chain hydrophilic block due to the difference of the consistency with other parts and the aspects such as swelling in water medium because hydrophilic block exists in the multipolymer polyelectrolyte of a hydrophilic block component, therefore after film forming, can other parts there is microphase-separated in hydrophilic block; And bring the difference of intermiscibility by controlling, design different hydrophilic block, thus microphase separation degree effectively controlled, and this being separated can form a kind of " hydrophilic channel " structure; Such mould material not only can be used as fuel cell proton conductive barrier film, also can be used as high-performance separation membrane material, as water treatment aspect have high-throughput, high rejection the membrane materials such as nanofiltration, reverse osmosis, micro-filtration and ultrafiltration.
Above-mentioned explanation is only the general introduction of technical solution of the present invention, in order to better understand technique means of the present invention, and can be implemented according to the content of specification sheets, below with preferred embodiment of the present invention, is described in detail as follows.The specific embodiment of the present invention is provided in detail by following examples.
Embodiment
Below in conjunction with embodiment, describe the present invention in detail.
At least, containing the multipolymer polyelectrolyte of a hydrophilic block component, composition structure is:
-{-[-(Ar2-Y-Ar3-Y-)
n-Ar2-Y-]
a-(Ar1-X-Ar1)
b-Y-(Ar2)
c-}
k-
.... or
-{-[-Ar3-Y-(-Ar2-Y-Ar3-Y-)
n-]
a-(Ar2)
b-Y-(Ar1-X-Ar1)
c-}
k-
... ...., wherein--[(Ar2-Y-Ar3-Y-)
n-Ar2-Y-]
a--be hydrophilic polymer M part,
Ar1 is phenyl, Nai Ji, triphenyl, benzene cyano group or-Ar4--R1-Ar5--, wherein R1 is-C (O)--,--S (O)
2--,--P (O) (C
6h
5)--,--C (O)-Ar-C (O) one or--C (O)-Ar6-S (O)
2--Ar4, Ar5, Ar6 is aromatic group or substituted aroma group;
Ar2 is-O-Ar7-R2-Ar8-O--;
R2 is single covalent linkage, naphthenic hydrocarbon C
2h
2n-2;
Ar7, Ar8 is aromatic group or substituted aroma group;
Wherein X is-C (O)--,--S (O)
2--,--P (O) (C
6h
5)--,
--C (O)-Ar-C (O)--or--C (O)-Ar6-S (O)
2--, Ar4, Ar5, Ar6 is aromatic group or substituted aroma group;
Y is-S-,-O-;
N is 0 to 20 integer;
K is 20 to 200 integer;
A, b, c, for mole number or be per-cent, wherein a+c=b;
Ar3 is the aromatic portion with hydrophilic and ionic groups, and its structure is:
Z is hydrogen atom or strong electron-withdrawing group group, is CN, NO
2or CF
3;
A is-C (O)--,--S (O)
2--;
B is--O--,--S--,--CH
2--or--OCH
2cH
2o--;
Ar is aromatic group or substituted aroma group;
Ra, Rb is-SO
3h,--COOH,--PO
3h or--SO
2nHSO
2r, Ra, Rb is identical or different,--SO
2nHSO
2in R, R is CF
2n+1;
X, y, g, is 1 to 100 integer.
Further, described hydrophilic polymer M is partly aromatics, is polyaryletherketone, polyether sulphone, polyarylether or polyhenylene, and the number-average molecular weight of this class segment is between 500-8000, and the polymerization degree is between 1-20; At described hydrophilic polymer M, partly comprise a class with the component of hydrophilic ionic group, it can be sulfonation group-SO with ionic group
3h, hydroxy-acid group-COOH, phosphate group-PO
3h or sulfimide group-SO
2nHSO
2r, wherein R is CnF2n+1.
Further, described ionogen is as high-performance separation membrane material.
Further, the proton conductive barrier film that described ionogen is used as fuel cell.
Further, described ionogen is as the conductive component in coating ink used.
Synthetic described at least containing the method for the multipolymer polyelectrolyte of a hydrophilic block component, comprise the following steps:
Step 1) the hydrophilic polymer M part of molecular weight is set in first preparation;
Step 2) using step 1) the hydrophilic polymer M for preparing part carries out copolymerization again as a kind of multi-functional component and other polyfunctional group component, wherein participates in no longer comprising any composition with hydrophilic ionic functional group in other components of copolymerization.
Embodiment 1
The sulfonated monomers (1) at least adopting containing the multipolymer polyelectrolyte of a hydrophilic block component
Hydrophilic polymer M part: add 7.45 grams to bigeminy phenol in the there-necked flask of one 250 milliliters, 17.4 grams of sulfonated monomerss (1), 7.2 grams of salt of wormwood, 120 milliliters of methyl-sulphoxides, after 50 milliliters of toluene, install thermometer, water trap, pass into drying nitrogen, after reaction is warmed up to 135 degree, stop 3 hours, then be warmed up to 180 degree 3 hours, then system cools to room temperature reaction and completes and obtain hydrophilic polymer M part.
Synthetic containing the multipolymer polyelectrolyte of a hydrophilic block component at least: add 7.4 grams to 4 to filling in 250 milliliters of there-necked flasks of the hydrophilic polymer M part having prepared, 4 '-cyclohexylene biphenol, 7.3 grams of difluorobenzene sulfones, 5.6 grams of salt of wormwood, 80 milliliters of methyl-sulphoxides, after 60 milliliters of toluene, install thermometer, water trap, pass into drying nitrogen, after reaction is warmed up to 135 degree, stop 3 hours, be then warmed up to 180 degree 3 hours.Reaction completes, and system cools to room temperature, pours 400 ml methanol/water (1: 1) precipitation into and obtains white polymer, after then washing with water several times, is dried and obtains 33.7 grams of multipolymer polyelectrolyte.The number-average molecular weight of gained multipolymer polyelectrolyte is 41000, and weight-average molecular weight is 61000.
Embodiment 2
The sulfonated monomers (2) at least adopting containing the multipolymer polyelectrolyte of a hydrophilic block component
Hydrophilic polymer M part: add 7.45 grams to bigeminy phenol in the there-necked flask of one 250 milliliters, 23.2 grams of sulfonated monomerss (2), 7.5 grams of salt of wormwood, 140 milliliters of methyl-sulphoxides, after 50 milliliters of toluene, install thermometer, water trap, pass into drying nitrogen, after reaction is warmed up to 135 degree, stop 3 hours, then be warmed up to 180 degree 3 hours, then system cools to room temperature reaction and completes and obtain hydrophilic polymer M part.
Synthetic containing the multipolymer polyelectrolyte of a hydrophilic block component at least: add 10.1 gram 4 to filling in 250 milliliters of there-necked flasks of the hydrophilic polymer M part having prepared, 4 '-(hexafluoro isopropylidene) diphenol, 7.1 grams of difluorobenzene sulfones, 5.5 grams of salt of wormwood, 60 milliliters of methyl-sulphoxides, after 60 milliliters of toluene, install thermometer, water trap, pass into drying nitrogen, after reaction is warmed up to 135 degree, stop 3 hours, be then warmed up to 180 degree 3 hours.Reaction completes, and system cools to room temperature, pours 400 ml methanol/water (1: 1) precipitation into and obtains white polymer, after then washing with water several times, is dried and obtains 33.7 grams of multipolymer polyelectrolyte.The number-average molecular weight of gained multipolymer polyelectrolyte is 46000, and weight-average molecular weight is 66000.
Embodiment 3
The sulfonated monomers (3) at least adopting containing the multipolymer polyelectrolyte of a hydrophilic block component
Hydrophilic polymer M part: add 13.5 gram 4 in the there-necked flask of one 250 milliliters, 4 '-(hexafluoro isopropylidene) diphenol, 23.3 grams of sulfonated monomerss (3), 7.5 grams of salt of wormwood, 180 milliliters of methyl-sulphoxides, after 70 milliliters of toluene, install thermometer, water trap, pass into drying nitrogen, reaction stops 3 hours after being warmed up to 135 degree, is then warmed up to 180 degree 3 hours, and then system cools to room temperature reaction and completes and obtain hydrophilic polymer M part.
Synthetic containing the multipolymer polyelectrolyte of a hydrophilic block component at least: add 10.5 gram 9 to filling in 250 milliliters of there-necked flasks of the hydrophilic polymer M part having prepared, 9-bis-(4-hydroxyphenyl) fluorenes, 7.25 grams of difluorobenzene sulfones, 5.6 grams of salt of wormwood, 120 milliliters of methyl-sulphoxides, after 60 milliliters of toluene, install thermometer, water trap, pass into drying nitrogen, after reaction is warmed up to 135 degree, stop 3 hours, be then warmed up to 180 degree 3 hours.Reaction completes, and system cools to room temperature, pours 400 ml methanol/water (1: 1) precipitation into and obtains white polymer, after then washing with water several times, is dried and obtains 48.7 grams of multipolymer polyelectrolyte.The number-average molecular weight of gained multipolymer polyelectrolyte is 45000, and weight-average molecular weight is 63000.
Embodiment 4
The sulfonated monomers (4) at least adopting containing the multipolymer polyelectrolyte of a hydrophilic block component
Hydrophilic polymer M part: add 7.64 grams to bigeminy phenol in the there-necked flask of one 250 milliliters, 17.8 grams of sulfonated monomerss (4), 7.66 gram salt of wormwood, 120 milliliters of methyl-sulphoxides, after 60 milliliters of toluene, install thermometer, water trap, pass into drying nitrogen, after reaction is warmed up to 135 degree, stop 3 hours, then be warmed up to 180 degree 3 hours, then system cools to room temperature reaction and completes and obtain hydrophilic polymer M part.
Synthetic containing the multipolymer polyelectrolyte of a hydrophilic block component at least: add 11.1 gram 4 to filling in 250 milliliters of there-necked flasks of the hydrophilic polymer M part having prepared, 4 '-(hexafluoro isopropylidene) diphenol, 7.2 grams of difluorobenzene sulfones, 5.5 grams of salt of wormwood, 70 milliliters of methyl-sulphoxides, after 60 milliliters of toluene, install thermometer, water trap, pass into drying nitrogen, after reaction is warmed up to 135 degree, stop 3 hours, be then warmed up to 180 degree 3 hours.Reaction completes, and system cools to room temperature, pours 400 ml methanol/water (1: 1) precipitation into and obtains white polymer, after then washing with water several times, is dried and obtains 35.7 grams of multipolymer polyelectrolyte.The number-average molecular weight of gained multipolymer polyelectrolyte is 43000, and weight-average molecular weight is 56000.
Polyelectrolyte Application Example:
According to the multipolymer polyelectrolyte of embodiment 1 synthesized, can be used as the proton conductive barrier film of fuel cell: the multipolymer polyelectrolyte of embodiment 1 synthesized is dissolved in after DMAc (10%), coating preparation flat sheet membrane, through 2M vitriolization after 2 hours, with distilled water immersion 4 hours, through measuring the electric conductivity of the barrier film of resulting 50 micron thickness, be 0.035S/cm.
Multipolymer polyelectrolyte according to embodiment 1 synthesized can be used for preparing Nano filtering composite membrane in addition: the multipolymer polyelectrolyte of embodiment 1 synthesized is dissolved in after IPA (0.5%), be applied on the porous support layer of PS, dry, washing obtains nanofiltration membrane.Adopt this nanofiltration membrane of cross-flow mode to have 88%NaCl rejection to the feeding liquid that in pending water, NaCl content is 2500mg/L.
The preferred embodiment that the foregoing is only invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (6)
1. at least containing the multipolymer polyelectrolyte of a hydrophilic block component, it is characterized in that, composition structure is:
-{-[-(Ar2-Y-Ar3-Y-)
n-Ar2-Y-]
a-(Ar1-X-Ar1)
b-Y-(Ar2)
c-}
k-
.... or
-{-[-Ar3-Y-(-Ar2-Y-Ar3-Y-)
n-]
a-(Ar2)
b-Y-(Ar1-X-Ar1)
c-}
k-
... ...., wherein--[(Ar2-Y-Ar3-Y-)
n-Ar2-Y-]
a--be hydrophilic polymer M part,
Ar1 is phenyl, Nai Ji, triphenyl, benzene cyano group or-Ar4--R1-Ar5--, wherein R1 is-C (O)--,--S (O)
2--,--P (O) (C
6h
5)--,--C (O)-Ar-C (O)--or--C (O)-Ar6-S (O)
2--Ar4, Ar5, Ar6 is aromatic group or substituted aroma group;
Ar2 is-O-Ar7-R2-Ar8-O--;
R2 is single covalent linkage, naphthenic hydrocarbon C
2h
2n-2;
Ar7, Ar8 is aromatic group or substituted aroma group;
Wherein X is-C (O)--,--S (O)
2--,--P (O) (C
6h
5)--,
--C (O)-Ar-C (O)--or--C (O)-Ar6-S (O)
2--, Ar4, Ar5, Ar6 is aromatic group or substituted aroma group;
Y is-S-,-O-;
N is 0 to 20 integer;
K is 20 to 200 integer;
A, b, c, for mole number or be per-cent, wherein a+c=b;
Ar3 is the aromatic portion with hydrophilic and ionic groups, and its structure is:
Z is hydrogen atom or strong electron-withdrawing group group, is CN, NO
2or CF
3;
A is-C (O)--,--S (O)
2--;
B is--O--,--S--,--CH
2--or--OCH
2cH
2o--;
Ar is aromatic group or substituted aroma group;
Ra, Rb is-SO
3h,--COOH,--PO
3h or--SO
2nHSO
2r, Ra, Rb is identical or different,--SO
2nHSO
2in R, R is CF
2n+1;
X, y, g, is 1 to 100 integer.
2. according to claim 1 at least containing the multipolymer polyelectrolyte of a hydrophilic block component, it is characterized in that: described hydrophilic polymer M is partly aromatics, for polyaryletherketone, polyether sulphone, polyarylether or polyhenylene, the number-average molecular weight of this class segment is between 500-8000, and the polymerization degree is between 1-20; At described hydrophilic polymer M, partly comprise a class with the component of hydrophilic ionic group, it can be sulfonation group-SO with ionic group
3h, hydroxy-acid group-COOH, phosphate group-PO
3h or sulfimide group-SO
2nHSO
2r, wherein R is CnF2n+1.
3. according to claim 1 at least containing the multipolymer polyelectrolyte of a hydrophilic block component, it is characterized in that: described ionogen is as high-performance separation membrane material.
4. according to claim 1 at least containing the multipolymer polyelectrolyte of a hydrophilic block component, it is characterized in that: the proton conductive barrier film that described ionogen is used as fuel cell.
5. according to claim 1 at least containing the multipolymer polyelectrolyte of a hydrophilic block component, it is characterized in that: described ionogen is as the conductive component in coating ink used.
6. the method that at least contains the multipolymer polyelectrolyte of a hydrophilic block component synthetic claimed in claim 1, is characterized in that, comprises the following steps:
Step 1) the hydrophilic polymer M part of molecular weight is set in first preparation;
Step 2) using step 1) the hydrophilic polymer M for preparing part carries out copolymerization again as a kind of multi-functional component and other polyfunctional group component, wherein participates in no longer comprising any composition with hydrophilic ionic functional group in other components of copolymerization.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214678A (en) * | 2013-05-06 | 2013-07-24 | 曹曙光 | Multi-segmented copolymer polyelectrolyte with amphipathy and synthetic method thereof |
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| US20040101730A1 (en) * | 2001-05-08 | 2004-05-27 | Tetsuji Hirano | Polymer electrolyte for solid polymer type fuel cell and fuel cell |
| CN1669169A (en) * | 2002-05-13 | 2005-09-14 | 复合燃料公司 | Ion conductive block copolymers |
| CN1902260A (en) * | 2003-11-13 | 2007-01-24 | 复合燃料公司 | Ion conductive copolymers containing one or more hydrophobic oligomers |
| CN101375457A (en) * | 2005-05-24 | 2009-02-25 | 复合燃料公司 | Ion conductive copolymers containing ion-conducting oligomers |
| CN101633734A (en) * | 2003-09-30 | 2010-01-27 | 住友化学株式会社 | Block copolymers and use thereof |
| CN102803341A (en) * | 2009-06-16 | 2012-11-28 | 巴斯夫欧洲公司 | Aromatic polyethersulfone block copolymers |
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| US20040101730A1 (en) * | 2001-05-08 | 2004-05-27 | Tetsuji Hirano | Polymer electrolyte for solid polymer type fuel cell and fuel cell |
| CN1669169A (en) * | 2002-05-13 | 2005-09-14 | 复合燃料公司 | Ion conductive block copolymers |
| CN101633734A (en) * | 2003-09-30 | 2010-01-27 | 住友化学株式会社 | Block copolymers and use thereof |
| CN1902260A (en) * | 2003-11-13 | 2007-01-24 | 复合燃料公司 | Ion conductive copolymers containing one or more hydrophobic oligomers |
| CN101375457A (en) * | 2005-05-24 | 2009-02-25 | 复合燃料公司 | Ion conductive copolymers containing ion-conducting oligomers |
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