CN1765958A - Method for preparing cross-linked polyimide membrane - Google Patents

Method for preparing cross-linked polyimide membrane Download PDF

Info

Publication number
CN1765958A
CN1765958A CNA2005101105124A CN200510110512A CN1765958A CN 1765958 A CN1765958 A CN 1765958A CN A2005101105124 A CNA2005101105124 A CN A2005101105124A CN 200510110512 A CN200510110512 A CN 200510110512A CN 1765958 A CN1765958 A CN 1765958A
Authority
CN
China
Prior art keywords
sulfonated
polyimide
cross
diamine monomer
linked
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA2005101105124A
Other languages
Chinese (zh)
Other versions
CN100404588C (en
Inventor
房建华
郭晓霞
陈斌武
蔡华明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Jiaotong University
Shanghai Chlor Alkali Chemical Co Ltd
Original Assignee
Shanghai Jiaotong University
Shanghai Chlor Alkali Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Jiaotong University, Shanghai Chlor Alkali Chemical Co Ltd filed Critical Shanghai Jiaotong University
Priority to CNB2005101105124A priority Critical patent/CN100404588C/en
Publication of CN1765958A publication Critical patent/CN1765958A/en
Application granted granted Critical
Publication of CN100404588C publication Critical patent/CN100404588C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention relates to a new method to prepare crosslinking polysulfonimides membrane, which comprises: dissolving the material in organic solvent with phosphoric anhydride, film forming with liquid moulding, drying for 2~20h at 60~200Deg; then, drying in vacuum for 1~30h at 100~200Deg; dipping the membrane in deionized water, clearing to neutrality, and drying in vacuum. This method is simple and economical. This product has well water resistance and high proton conductivity and wide application in fuel cell, ion exchange resin and sensor.

Description

A kind of method for preparing cross-linked polyimide membrane
Technical field
The present invention relates to the preparation method of functional high molecule material, particularly the preparation method of cross-linked polyimide membrane.
Background technology
Polyimide is a class high-performance polymer, has the excellent heat resistance energy, very high mechanical strength and modulus, excellent electric property and favorable chemical resistance energy.Obtained using widely in aerospace industry with for field such as electronic industry.Hexa-atomic ring-like sulfonated polyimide is new a member in the polyimide family that develops in recent years.These materials have the potential application prospect at aspects such as fuel cell, ion exchange resin, membrane sepn and transmitters.Especially aspect fuel cell, sulfonated polyimide is considered to one of novel proton exchange membranes material that is hopeful most practicability.French Patent 9605707 (1996) has been reported the preparation method of sulfonated polyimide first, its used sulfonated diamine monomer is 2,2 '-benzidine-disulfonic acid (BDSA), the test-results that the sulfonated polyimide that makes with this sulfonated diamine monomer is applied to fuel cell (hydrogen/oxygen system) shows that its power generation performance can reach perfluor class sulfonated polymer, as the level of the Nafion117 of Du Pont, but the water tolerance of this sulfonated polyimide film is very poor.Japanese Patent JP2003064048, JP2003064181, JP2003068326, JP2004155998 discloses sulfonated diamine monomer and the preparation method of corresponding sulfonated polyimide and the proton conduction performance and the water tolerance of these materials of a series of novel structures, and the water tolerance of sulfonated polyimide can be improved greatly by the sulfonated diamine monomer is carried out rational molecular designing.But use the especially requirement of high temperature (＞100 ℃) occasion from reality, the water tolerance of these polymkeric substance also needs further raising.Therefore, this area needs sulfonated polyimide film of hydrolysis under the high temperature and preparation method thereof.
Summary of the invention
One of purpose of the present invention provides a kind of method for preparing cross-linked polyimide membrane;
Another object of the present invention provides a kind of cross-linked polyimide membrane of hydrolysis at high temperature, to overcome the deficiency of prior art.
The preparation method of cross-linked polyimide membrane of the present invention comprises the steps:
Sulfonated polyimide is dissolved in the organic solvent that contains Vanadium Pentoxide in FLAKES, with this solution casting on flat board, in 60～200 ℃ dry 2～20 hours down, then in vacuum, 100～200 ℃ dry 1～30 hour down; Film is peeled off and is washed till neutrality with deionized water from flat board, under vacuum, dry, obtain cross-linked polyimide membrane;
Wherein organic solvent is selected from methyl-sulphoxide, N-N-methyl-2-2-pyrrolidone N-, N, a kind of in dinethylformamide, the N,N-dimethylacetamide;
The content of Vanadium Pentoxide in FLAKES in organic solvent is 0.1～20wt%; The content of sulfonated polyimide is 1～40wt%;
Said flat board is selected from sheet glass, polyfluortetraethylene plate or stainless steel plate.
The thickness range of the cross-linked polyimide membrane of the present invention's preparation is 1～1000 μ m.
The preparation method of sulfonated polyimide used in the present invention comprises the steps:
Sulfonated diamine monomer, non-sulfonated diamine monomer are dissolved under room temperature, nitrogen atmosphere in meta-cresol, the triethylamine mixed solvent, in reaction flask, add 1,4,5,8-naphthalene dicarboxylic anhydride and phenylformic acid, reaction system is heated to 70～100 ℃, and under this temperature, reacted 2～10 hours, and then rise to 170～190 ℃, and reacted 5～50 hours, the reaction solution volume ratio is methyl alcohol/hydrochloric acid soln precipitating of 3: 1, obtains sulfonated polyimide;
Wherein sulfonated diamine monomer and the monomeric mol ratio of non-sulfonated diamine are 20: 1～1: 20,1,4,5, the mol ratio of 8-naphthalene dicarboxylic anhydride and diamine monomer is 1: 1, and the triethylamine mole number is the thousandth of polymerization single polymerization monomer total mole number, and the phenylformic acid mole number is 1,4,5, the 1-2 of 8-naphthalene dicarboxylic anhydride doubly;
Wherein the sulfonated diamine monomer is selected from
Figure A20051011051200061
Figure A20051011051200062
Or
Figure A20051011051200063
X is-,-CH 2-,-O-or-S-;
Y is Or
Figure A20051011051200065
Z is-(CH 2) m-SO 3H, m=1～6 or
Figure A20051011051200066
Non-sulfonated diamine monomer is selected from
9,9-two (4-aminophenyl)-fluorenes or
Figure A20051011051200068
A is-CH 2-,-C (CH 3) 2-,-O-or-S-;
The chemical structural formula of sulfonated polyimide used in the present invention is as follows:
Figure A20051011051200071
In the formula, 0＜b＜1, n=10～500:
R 1For
Figure A20051011051200072
R 2Be selected from:
X is-,-CH 2,-O--S-;
Or
Figure A20051011051200074
Y is
Figure A20051011051200075
Figure A20051011051200076
Or
Figure A20051011051200077
, Z is
Figure A20051011051200078
M=1-6 or
Figure A20051011051200079
R 3Be selected from:
Figure A200510110512000710
A is-CH 2-,-C (CH 3) 2-,-O-or-S-;
Or 9,9-two (4-aminophenyl)-fluorenes;
Or
Method with Vanadium Pentoxide in FLAKES Processing of Preparation cross-linked polyimide membrane disclosed by the invention is compared with the method for existing preparation cross-linked polyimide membrane, has advantage simple to operate, that cost is low.
With the cross-linked polyimide membrane of the inventive method preparation, its use properties such as water tolerance etc. are greatly improved.Cross-linked polyimide NTDA-ODADS/BAPF (5/1) film soaks one month (720 hours) in 100 ℃ deionized water, still has mechanical strength preferably, and uncrosslinked sulfonated polyimide NTDA-ODADS/BAPF (5/1) film soaked 1 hour in 100 ℃ deionized water, swelling promptly takes place dissolve then.On the other hand, cross-linked polyimide NTDA-ODADS/BAPF (5/1) film proton conductivity under 60 ℃, 100% relative humidity is 0.13S/cm, proton conductivity is 0.20S/cm under 130 ℃, 100% relative humidity, illustrate that cross-linked polyimide membrane of the present invention is increasing the water-proof while, still keeps very high proton conductivity.
Cross-linked polyimide membrane of the present invention has a wide range of applications at aspects such as fuel cell, ion exchange resin, membrane sepn and transmitters.Especially aspect fuel cell,, the work-ing life of fuel cell will be improved significantly by improving the water tolerance of the proton exchange membrane in the fuel cell.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
The preparation of embodiment 1 sulfonated polyimide NTDA-ODADS/BAPF (5/1):
NTDA refers to 1,4,5,8-naphthalene dicarboxylic anhydride, and ODADS refers to 4,4 '-diaminodiphenyl oxide-2,2 '-disulfonic acid, BAPF refers to 9,9-two (4-aminophenyl) fluorenes;
Be equipped with to exsiccant and add 0.7200 gram (2.0mmol) ODADS in the 100mL three-necked bottle of prolong and import and export of nitrogen, 0.1392 gram (0.4mmol) BAPF, 10mL meta-cresol and 0.68mL triethylamine.After treating that diamine monomer dissolves fully, add 0.6432 gram (2.4mmol) NTDA and 0.42 gram phenylformic acid again.This reaction mixture at room temperature stirred 0.5 hour, was warming up to 80 ℃ of reactions 4 hours then, continued to be warming up to 180 ℃ of reactions 20 hours.After reaction finishes, resulting highly viscous polymers soln, dilute with the 10mL meta-cresol, pour into the 200mL volume ratio then lentamente and be in methyl alcohol/hydrochloric acid soln of 3: 1, obtain fibery precipitate, filter, and with methanol wash repeatedly, under vacuum condition, dry, obtain 1.8 gram sulfonated polyimide NTDA-ODADS/BAPF (5/1).
The preparation of embodiment 2 cross-linked polyimide NTDA-ODADS/BAPF (5/1) films:
The resulting 1.8 gram exsiccant sulfonated polyimides of embodiment 1 are dissolved in the methyl-sulphoxide that 20mL contains the 10wt% Vanadium Pentoxide in FLAKES, with resulting solution casting to sheet glass, 80 ℃ and 150 ℃ respectively dry 2 hours and 10 hours down, and then under 150 ℃, vacuum drying 20 hours.Sulfonated polyimide is peeled off from the cast glass plate, be washed till neutrality with deionized water, dry under vacuum then, obtain sulfonated polyimide NTDA-ODADS/BAPF (5/1) film, its thickness is 40 μ m.
The performance of embodiment 3 cross-linked polyimide NTDA-ODADS/BAPF (5/1) films:
Embodiment 2 resulting cross-linked polyimide NTDA-ODADS/BAPF (5/1) films are put into carry out dissolubility test in the methyl-sulphoxide, find that this film can not dissolve fully in methyl-sulphoxide, show taken place crosslinked.Film is immersed in 100 ℃ the deionized water one month (720 hours), finds that film still has mechanical strength preferably.The proton conductivity of film is 0.13S/cm under 60 ℃, 100% relative humidity, and the proton conductivity of film is 0.20S/cm under 130 ℃, 100% relative humidity.
The film that has soaked in 100 ℃ deionized water one month is carried out stretching strength determination immediately, and measured tensile strength is 10～12MPa.
Comparative example 1: the preparation of uncrosslinked sulfonated polyimide NTDA-ODADS/BAPF (5/1) film:
1.8 gram embodiment, 1 resulting sulfonated polyimide NTDA-ODADS/BAPF (5/1) is dissolved in the 20mL methyl-sulphoxide, and to sheet glass, difference is dry 10 hours under 80 ℃ with resulting solution casting.Sulfonated polyimide is peeled off from the cast glass plate, be placed in the methyl alcohol of 60 ℃ of 200mL and soaked 3 hours, dry under vacuum then, obtain uncrosslinked sulfonated polyimide NTDA-ODADS/BAPF (5/1) film, its thickness is 40 μ m.
Comparative example 2: comparative example 1 resulting uncrosslinked sulfonated polyimide NTDA-ODADS/BAPF (5/1) film is immersed in 100 ℃ the deionized water 1 hour, find that swelling dissolving fully in deionized water then at first takes place this film, shows that this uncrosslinked film does not have water tolerance under 100 ℃.
The preparation of embodiment 4 sulfonated polyimide NTDA-BSPOB/BAPF (4/1):
NTDA refers to 1,4,5,8-naphthalene dicarboxylic anhydride, and BSPOB refers to 3,3-two (4-sulfonic group phenoxy group) p-diaminodiphenyl, BAPF refers to 9,9-two (4-aminophenyl) fluorenes;
Be equipped with to exsiccant and add 2.112 gram (4.0mmol) BSPOB in the 100mL three-necked bottle of prolong and import and export of nitrogen, 0.348 gram (1.0mmol) BAPF, 35mL meta-cresol and 1.36mL triethylamine.After treating that diamine monomer dissolves fully, add 1.34 gram (5.0mmol) NTDA and 0.866 gram phenylformic acid again.This reaction mixture at room temperature stirred 0.5 hour, was warming up to 80 ℃ of reactions 4 hours then, continued to be warming up to 180 ℃ of reactions 20 hours.After reaction finishes, resulting highly viscous polymers soln, dilute with the 20mL meta-cresol, pour into the 400mL volume ratio then lentamente and be in methyl alcohol/hydrochloric acid soln of 3: 1, obtain fibery precipitate, filter, and with methanol wash repeatedly, under vacuum condition, dry, obtain 4.42 gram sulfonated polyimide NTDA-BSPOB/BAPF (4/1).
The preparation of embodiment 5 cross-linked polyimide NTDA-BSPOB/BAPF (4/1) films:
2.0 gram embodiment 4 resulting exsiccant sulfonated polyimides are dissolved in the methyl-sulphoxide that 30mL contains the 5wt% Vanadium Pentoxide in FLAKES, with resulting solution casting to sheet glass, 80 ℃ and 150 ℃ respectively dry 2 hours and 10 hours down, and then under 150 ℃, vacuum drying 20 hours.Sulfonated polyimide is peeled off from the cast glass plate, be washed till neutrality with deionized water, dry under vacuum then, obtain sulfonated polyimide NTDA-ODADS/BAPF (5/1) film, its thickness is 30 μ m.
The performance of embodiment 6 cross-linked polyimide NTDA-BSPOB/BAPF (4/1) films:
Embodiment 5 resulting cross-linked polyimide NTDA-BSPOB/BAPF (4/1) films are put into carry out dissolubility test in the methyl-sulphoxide, find that this film can not dissolve fully in methyl-sulphoxide, show taken place crosslinked.Film is immersed in 100 ℃ the deionized water one month (720 hours), finds that film still has mechanical strength preferably.The proton conductivity of film is 0.11S/cm under 60 ℃, 100% relative humidity, and the proton conductivity of film is 0.17S/cm under 130 ℃, 100% relative humidity.
The film that has soaked in 100 ℃ deionized water one month is carried out stretching strength determination immediately, and measured tensile strength is 13～15MPa.
Comparative example 3: the preparation of uncrosslinked sulfonated polyimide NTDA-BSPOB/BAPF (4/1) film:
2.0 gram embodiment, 4 resulting sulfonated polyimide NTDA-BSPOB/BAPF (4/1) are dissolved in the 30mL methyl-sulphoxide, and to sheet glass, difference is dry 10 hours under 80 ℃ with resulting solution casting.Sulfonated polyimide is peeled off from the cast glass plate, be placed in the methyl alcohol of 60 ℃ of 200mL and soaked 3 hours, dry under vacuum then, obtain uncrosslinked sulfonated polyimide NTDA-BSPOB/BAPF (4/1) film, its thickness is 30 μ m.
Comparative example 4: comparative example 3 resulting uncrosslinked sulfonated polyimide NTDA-BSPOB/BAPF (4/1) films are immersed in 100 ℃ the deionized water 150 hours, find that this film has become fragment, show that the water tolerance of this uncrosslinked film under 100 ℃ is very poor.

Claims (5)

1. the method with sulfonated polyimide feedstock production cross-linked polyimide membrane is characterized in that, comprises the steps:
Sulfonated polyimide is dissolved in the organic solvent that contains Vanadium Pentoxide in FLAKES, with this solution casting on flat board, in 60～200 ℃ dry 2～20 hours down, then in vacuum, 100～200 ℃ dry 1～30 hour down; Film is peeled off and is washed till neutrality with deionized water from flat board, under vacuum, dry, obtain cross-linked polyimide membrane;
Used organic solvent is selected from methyl-sulphoxide, N-N-methyl-2-2-pyrrolidone N-, N, a kind of in dinethylformamide or the N,N-dimethylacetamide; The content of Vanadium Pentoxide in FLAKES in organic solvent is 0.1～20wt%; Content in the sulfonated polyimide raw material organic solvent is 1～40wt%.
2. the preparation method of cross-linked polyimide membrane according to claim 1 is characterized in that, wherein said sulfonated polyimide is prepared as follows:
Sulfonated diamine monomer, non-sulfonated diamine monomer are dissolved under room temperature, nitrogen atmosphere in meta-cresol, the triethylamine mixed solvent, in reaction flask, add 1,4,5,8-naphthalene dicarboxylic anhydride and phenylformic acid, reaction system is heated to 70～100 ℃, and under this temperature, reacted 2～10 hours, and then rise to 170～190 ℃, and reacted 5～50 hours, reaction solution obtains sulfonated polyimide with methyl alcohol/hydrochloric acid soln precipitating;
Wherein sulfonated diamine monomer and the monomeric mol ratio of non-sulfonated diamine are 20: 1～1: 20,1,4,5, the mol ratio of 8-naphthalene dicarboxylic anhydride and diamine monomer is 1: 1, and the triethylamine mole number is the thousandth of polymerization single polymerization monomer total mole number, and the phenylformic acid mole number is 1,4,5, the 1-2 of 8-naphthalene dicarboxylic anhydride doubly;
Wherein the sulfonated diamine monomer is selected from
Figure A2005101105120002C1
X is-,-CH 2-,-O-or-S-;
Or
Figure A2005101105120002C2
Y is
Figure A2005101105120002C3
Or
Or
Figure A2005101105120003C1
Z is-(CH 2) m-SO 3H, m=1～6 or
Non-sulfonated diamine monomer is selected from
Figure A2005101105120003C3
A is-CH 2-,-C (CH 3) 2-,-O-or-S-;
Or 9,9-two (4-aminophenyl)-fluorenes;
Or
Figure A2005101105120003C4
3. the preparation method of cross-linked polyimide membrane according to claim 2 is characterized in that, wherein the chemical structural formula of sulfonated polyimide raw material is:
In the formula, 0
Figure A2005101105120003C5
R 1For
R 2Be selected from:
Figure A2005101105120003C7
X is-,-CH 2-,-O--S-;
Or
Figure A2005101105120003C8
Or
Figure A2005101105120003C9
Or
Figure A2005101105120003C10
For Or
Figure A2005101105120003C12
R 3Be selected from:
Figure A2005101105120004C1
A is-CH 2-,-C (CH 3) 2-,-O-or-S-;
Or 9,9-two (4-aminophenyl)-fluorenes;
Or
4. a cross-linked polyimide membrane is characterized in that, by each described preparation method's preparation of claim 1-3.
5. cross-linked polyimide membrane according to claim 4 is characterized in that thickness range is 1～1000 μ m.
CNB2005101105124A 2005-11-18 2005-11-18 Method for preparing cross-linked polyimide membrane Expired - Fee Related CN100404588C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2005101105124A CN100404588C (en) 2005-11-18 2005-11-18 Method for preparing cross-linked polyimide membrane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2005101105124A CN100404588C (en) 2005-11-18 2005-11-18 Method for preparing cross-linked polyimide membrane

Publications (2)

Publication Number Publication Date
CN1765958A true CN1765958A (en) 2006-05-03
CN100404588C CN100404588C (en) 2008-07-23

Family

ID=36742090

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2005101105124A Expired - Fee Related CN100404588C (en) 2005-11-18 2005-11-18 Method for preparing cross-linked polyimide membrane

Country Status (1)

Country Link
CN (1) CN100404588C (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101775149A (en) * 2010-03-03 2010-07-14 中国科学院长春应用化学研究所 Crosslinked sulfonated polyimide membrane and preparation method thereof
CN101407592B (en) * 2008-11-20 2011-06-08 上海交通大学 Preparation of glyoxalinyl-containing sulphonation polyimides covalence-ionomer membrane
CN102842726A (en) * 2011-06-21 2012-12-26 东丽纤维研究所（中国）有限公司 Silsesquioxane hybridized sulfonated polyimide proton exchange membrane and its preparation method
CN105771676A (en) * 2016-01-26 2016-07-20 南京理工大学 High-flux anti-pollution sulfonated polyamide composite nanofiltration membrane and preparation method thereof
CN108043232A (en) * 2017-12-06 2018-05-18 上海交通大学 A kind of hexatomic ring polyimide copolymer seperation film and its preparation method and application
CN111607088A (en) * 2020-06-01 2020-09-01 素水能源科技（上海）有限公司 Self-crosslinking sulfonated polyimide copolymer, proton exchange membrane and preparation method thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7157548B2 (en) * 2001-08-22 2007-01-02 Hanyang Hak Won Co., Ltd. Crosslinked sulfonated polyimide films
DE10205852A1 (en) * 2002-02-13 2003-08-21 Creavis Tech & Innovation Gmbh Electrolyte membrane with diffusion barrier, these comprehensive membrane electrode units, manufacturing processes and special uses
KR100464317B1 (en) * 2002-07-06 2005-01-03 삼성에스디아이 주식회사 Proton-conducting polymer containing acid group in side chain, polymer membrane prepared with them and fuel cell using the same
CN1264597C (en) * 2004-10-20 2006-07-19 中山大学 Inhibiting alcohol proton exchanging film and its preparation process
CN1253491C (en) * 2004-11-05 2006-04-26 中国科学院长春应用化学研究所 Process for synthesis of sulfonated polyimide proton transmission film

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101407592B (en) * 2008-11-20 2011-06-08 上海交通大学 Preparation of glyoxalinyl-containing sulphonation polyimides covalence-ionomer membrane
CN101775149A (en) * 2010-03-03 2010-07-14 中国科学院长春应用化学研究所 Crosslinked sulfonated polyimide membrane and preparation method thereof
CN102842726A (en) * 2011-06-21 2012-12-26 东丽纤维研究所（中国）有限公司 Silsesquioxane hybridized sulfonated polyimide proton exchange membrane and its preparation method
CN102842726B (en) * 2011-06-21 2016-05-04 东丽纤维研究所（中国）有限公司 Silsesquioxane hydridization sulfonated polyimide proton exchange membrane and preparation method thereof
CN105771676A (en) * 2016-01-26 2016-07-20 南京理工大学 High-flux anti-pollution sulfonated polyamide composite nanofiltration membrane and preparation method thereof
CN108043232A (en) * 2017-12-06 2018-05-18 上海交通大学 A kind of hexatomic ring polyimide copolymer seperation film and its preparation method and application
CN111607088A (en) * 2020-06-01 2020-09-01 素水能源科技（上海）有限公司 Self-crosslinking sulfonated polyimide copolymer, proton exchange membrane and preparation method thereof

Also Published As

Publication number Publication date
CN100404588C (en) 2008-07-23

Similar Documents

Publication Publication Date Title
CN110224166B (en) Phosphoric acid-doped cross-linked polybenzimidazole high-temperature proton exchange membrane and preparation method thereof
Ni et al. Novel proton exchange membranes based on structure-optimized poly (ether ether ketone ketone) s and nanocrystalline cellulose
CN1765958A (en) Method for preparing cross-linked polyimide membrane
KR100902411B1 (en) Partially sulfonated PBI, method for preparing the same, MEA for fuel cell using the PBI and method for preparing the same
CN110041552B (en) Composite high-temperature proton exchange membrane based on sulfonated aryl ether type polybenzimidazole and sulfonated polysilsesquioxane and preparation method thereof
CN1871736A (en) Composite electrolyte with crosslinking agents
CN1637044A (en) Method for preparing poly(2,5-benzimidazole)
KR100800313B1 (en) Organic-inorganic hybrid membranes containing sulfonated polyhedral oligosilsesquioxane nanoparticles for direct methanol fuel cell applications
CN102842726A (en) Silsesquioxane hybridized sulfonated polyimide proton exchange membrane and its preparation method
CN1309766C (en) Cross-linked sulfonated polyimide membrane preparation method
CN107082996B (en) Graphene oxide cross-linked polyimide semi-interpenetrating network type composite membrane and preparation thereof
CN111403785A (en) Sulfonated polyaryletherketone sulfone composite membrane and preparation method thereof
CN1305935C (en) Serial electrically active polyaryl ether ketone polymers and their prepn process
CN1969416A (en) Solid polymer electrolyte membrane, method for producing same, and solid polymer fuel cell
CN106751839A (en) Fuel cell polymer microsphere/sulfonated poly aryl ether ketone sulfone proton exchange membrane material, preparation method and applications containing amino
Yu et al. Facile fabrication of sulfonated poly (aryl ether sulfone)/polybenzoxazine crosslinked membrane for vanadium flow battery application
CN1834135A (en) Method of preparing sulfonated polymer/polyazole compound proton exchange membrane
CN1148338C (en) Fluorine-containing trifluorostyrene monomer and its synthesis and use
JP4039275B2 (en) Cross-linked polyarylene ether sulfone
CN115207423A (en) Preparation method of sodium lignosulfonate modified attapulgite chitosan proton exchange membrane
CN1189504C (en) Process for preparing novel crosslinkable polyarylether ketone sulfonated film
CN100336843C (en) Sulfonated high polymer containing bisphenol fluorine, synthesis and application thereof
KR20190026133A (en) Anion-exchange membrane based on aminated poly(tyrene-ethylene-butylene-styrene) copolymer and manufacturing method thereof
CN114188583A (en) Composite proton exchange membrane and preparation method and application thereof
CN101024701A (en) Sulfonated polysulfide-ether-sulfone crosslinking film and preparing method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20080723

Termination date: 20121118