CN104530723B - A kind of block copolymer anion exchange membrane for fuel cell and preparation method thereof - Google Patents
A kind of block copolymer anion exchange membrane for fuel cell and preparation method thereof Download PDFInfo
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- CN104530723B CN104530723B CN201510031338.8A CN201510031338A CN104530723B CN 104530723 B CN104530723 B CN 104530723B CN 201510031338 A CN201510031338 A CN 201510031338A CN 104530723 B CN104530723 B CN 104530723B
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- block copolymer
- exchange membrane
- anion exchange
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 47
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000000446 fuel Substances 0.000 title claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 32
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 30
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 28
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- JFDZBHWFFUWGJE-KWCOIAHCSA-N benzonitrile Chemical group N#[11C]C1=CC=CC=C1 JFDZBHWFFUWGJE-KWCOIAHCSA-N 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 43
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- -1 1,1,2,2-tetra-chloroethene Alkane Chemical class 0.000 claims description 15
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229940106691 bisphenol a Drugs 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 6
- 238000007306 functionalization reaction Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000003808 methanol extraction Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- ISNICOKBNZOJQG-UHFFFAOYSA-N 1,1,2,3,3-pentamethylguanidine Chemical compound CN=C(N(C)C)N(C)C ISNICOKBNZOJQG-UHFFFAOYSA-N 0.000 claims description 2
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 125000005506 phthalide group Chemical group 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 230000008961 swelling Effects 0.000 abstract description 16
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 abstract description 14
- 230000005540 biological transmission Effects 0.000 abstract description 12
- 150000002500 ions Chemical class 0.000 abstract description 7
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 238000012360 testing method Methods 0.000 description 14
- 238000005893 bromination reaction Methods 0.000 description 11
- 238000005342 ion exchange Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 230000031709 bromination Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000005191 phase separation Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 125000005997 bromomethyl group Chemical group 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229920000090 poly(aryl ether) Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000000711 cancerogenic effect Effects 0.000 description 3
- 231100000315 carcinogenic Toxicity 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 229920001585 atactic polymer Polymers 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 238000007265 chloromethylation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- 231100000004 severe toxicity Toxicity 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000002579 anti-swelling effect Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
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
Abstract
A kind of block copolymer anion exchange membrane for fuel cell and preparation method thereof, relates to alkaline fuel cell.Described block copolymer anion exchange membrane, its molecular structure includes the hydrophilic section containing phenolphthalein side base and the hydrophobic section containing benzonitrile structure.Preparation method: 1) synthesis of hydrophilic section；2) synthesis of hydrophobic section；3) synthesis of block copolymer；4) synthesis of bromomethylation block copolymer；5) preparation of block copolymer anion exchange membrane.Preparation process does not use chloromethyl ether reagent, phenolphthalein side based structures is introduced in its hydrophilic section by MOLECULE DESIGN, highly polar itrile group structure is introduced in its hydrophobic section, make film have ion transmission channel, high-moisture percentage and the low swelling characteristic of prosperity, show higher ionic conductivity and preferably fuel battery performance.
Description
Technical field
The present invention relates to alkaline fuel cell, be specifically related to a kind of block copolymer anion for fuel cell and hand over
Change film and preparation method thereof.
Background technology
Fuel cell (Fuel Cell) is a kind of chemistry utilizing chemical reaction technology to be stored in fuel and oxidant
Can Efficient Conversion be directly the TRT of electric energy, there is high efficiency, high-energy-density, environmental friendliness, the advantage such as easy to carry,
It is considered forth generation generation technology.At present, the alkaline anion-exchange membrane fuel cell with anion exchange membrane as polyelectrolyte
(AEMFCs) because having that battery electrode reactivity is high, can use the features such as base metal electrode catalyst, low-corrosiveness and
Receive much concern, have become as the study hotspot of current fuel cell field.Wherein, anion exchange membrane is crucial group of AEMFCs
Part, plays conduction OH-Ion and the effect of obstruct fuel infiltration, the performance that decide fuel cell is good and bad.
At present, major part anion exchange membrane is based on common random polymer, is re-introduced into by chloromethylation
Ion-exchange group, this process to use the chloromethyl ether reagent that severe toxicity is carcinogenic.Chloromethylation degree and activation due to polymer
The more difficult control in position, the ion-exchange group distribution of the film of preparation is random, be hardly formed continuous effective OH-Ion transmission is logical
Road, the ionic conductivity causing film is relatively low.Hickner research group (Macromolecules (2010,43,2349-2356))
By using bromating agent that benzyl carries out bromination reaction, and then amino-functionalization introduces ion-exchange group, can avoid using chlorine
Methyl ether reagent.The film of preparation can possess relatively high ion exchange volume, but owing to this membrane material is based on common atactic polymer, anti-
Swelling behavior is poor, and while the moisture content and electrical conductivity rising of film, the swelling of film increases the most accordingly, and the machinery of telolemma is strong
Degree reduces, and causes fuel battery performance to decline.Li research group (Journal of Membrane Science (2013,436,
202-212)) being prepared for anion exchange membrane by synthetic segmented copolymer, they are more higher than atactic polymer film shows
Electrical conductivity and mechanical performance, but when high ion exchange volume, swelling resistance is the most poor, and preparation process uses chloromethyl ether examination
Agent.
Summary of the invention
It is an object of the invention to the disadvantages mentioned above in order to overcome prior art with not enough, it is provided that a kind of for fuel cell
Block copolymer anion exchange membrane and preparation method thereof.
Described block copolymer anion exchange membrane, its molecular structure includes the hydrophilic section containing phenolphthalein side base and containing benzene
The hydrophobic section of formonitrile HCN structure, its molecular structural formula is as follows:
Wherein, the integer of m=5～50, the integer of n=5～50, R is It is selected from (a)～(d) any one.
The preparation method of described block copolymer anion exchange membrane, comprises the following steps:
1) synthesis of hydrophilic section: by double for 3,3-(4-hydroxyl-3,5-3,5-dimethylphenyl) Phthalides with there is Ar1The difluoro of structure
Monomer feeds with the mol ratio of m/ (m+1), in the presence of nitrogen protection and the Anhydrous potassium carbonate of 2.5～4 moles and toluene, molten
Solution is in polar non-solute, prior to 140～150 DEG C of reactions 4～6h, then is warmed up to 160～180 DEG C of reactions 10～12h, then
Add 5% (m+1) mole containing Ar1Two fluorine monomers of structure, continue reaction 1～2h at 160～180 DEG C, use alcohol water after cooling
Solution precipitates, filters, washs, is dried, and i.e. obtains hydrophilic section；
2) synthesis of hydrophobic section: by 2,6-difluorobenzonilyile with there is Ar2Double hydroxyl aromatic ring monomers of structure are with m/'s (m+1)
Mol ratio feeds, and in the presence of nitrogen protection and the Anhydrous potassium carbonate of 2.5～4 moles and toluene, is dissolved in aprotic, polar
Solvent, prior to 140～150 DEG C of reactions 4～6h, then is warmed up to 160～180 DEG C of reactions 10～12h, is subsequently adding 5% (m+1) and rubs
You containing Ar2Double hydroxyl aromatic ring monomers of structure, 160～180 DEG C continue reaction 1～2h, after cooling with alcohol-water solution precipitation,
Filter, wash, be dried, i.e. obtain hydrophobic section；
3) synthesis of block copolymer: by step 1) hydrophilic section prepared and step 2) hydrophobic section prepared is with equimolar ratio
Charging, in the presence of nitrogen protection and the Anhydrous potassium carbonate of 2.5～4 moles and toluene, is dissolved in polar non-solute, first
React 3～4h in 140～150 DEG C, then be warmed up to 160～180 DEG C of reactions 18～20h, by alcohol-water solution precipitation, mistake after cooling
Filter, wash, be dried, obtain block copolymer；
4) synthesis of bromomethylation block copolymer: by step 3) block copolymer that obtains is dissolved in 1,1,2,2-tetrachloro
Ethane, is subsequently adding N-bromosuccinimide and initiator, after reaction, and cooling, with methanol extraction, filter, wash, be dried,
Obtain bromomethylation block copolymer；
5) preparation of block copolymer anion exchange membrane: by step 4) the bromomethylation block copolymer that obtains and function
Change reagent and join dissolving in polar non-solute, obtain casting solution after reaction, then casting solution is coated on a glass, heating
Solvent flashing obtains solid film, washs after then solid film is dipped in alkali liquor reaction, i.e. obtains block copolymer anion and hands over
Change film.
In step 1) in, described in there is Ar1Two fluorine monomers of structure are selected from 4,4'-difluorodiphenyl sulfone, 4,4'-difluoro two
One in benzophenone, 4,4'-DfBP, 3,3'-DfBP etc..
In step 2) in, described in there is Ar2Double hydroxyl aromatic ring monomers of structure be selected from 4,4'-sulfonyldiphenol, 4,
One in 4'-dihydroxy benaophenonel, bisphenol-A, 4,4'-xenol etc..
In step 4) in, the mol ratio of described block copolymer, N-bromosuccinimide and initiator can be 1: (0.1
～1.5): (0.01～0.075)；Described initiator is selected from benzoyl peroxide or azodiisobutyronitrile etc.；Described reaction
Condition can react 4～6h at 85 DEG C.
In step 5) in, described bromomethylation block copolymer can be 1: 5 with the mol ratio of functionalized reagent；Described function
Change reagent and be selected from the one in trimethylamine aqueous solution, pentamethyl guanidine, 1-Methylimidazole., DMIZ 1,2 dimethylimidazole etc.；Described instead
The condition answered can react 12～24h at 40～50 DEG C；Described alkali liquor is selected from potassium hydroxide solution or sodium hydroxide solution etc.；Institute
State solid film is dipped in alkali liquor reaction time can be 24～48h；Described washing can use deionized water wash.
In step 1), 2), 3), 5) in, described polar non-solute is selected from N-Methyl pyrrolidone, N, N-dimethyl
One in Methanamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide etc..
Preparation process of the present invention does not use chloromethyl ether reagent, introduces phenolphthalein side base junction by MOLECULE DESIGN in its hydrophilic section
Structure, introduces highly polar itrile group structure in its hydrophobic section, makes film have the ion transmission channel of prosperity, high-moisture percentage and low swelling
Characteristic, shows higher ionic conductivity and preferably fuel battery performance.
It is an advantage of the current invention that:
1) hydrophilic segment and the block poly (arylene ether nitrile) anion of hydrophobic segment of long sequence different length is comprised by preparation
Exchange membrane, makes film have significant micro phase separation structure, it is achieved that the microstructure of film is controlled, contributes to film and forms continuous effective
OH-Ion transmission channel.
2) this preparation method uses bromomethylation method, it is to avoid height to be used in common anion exchange membrane preparation process
Poison high carcinogenic chloromethyl ether reagent.
3) introduce rigidity and the phenolphthalein side based structures of big steric hindrance by MOLECULE DESIGN in the hydrophilic section of block copolymer, strengthen
The water holding capacity of film and promote the formation of ion transmission channel；Introduce highly polar itrile group structure in its hydrophobic section, enhance
The swelling resistance of film.Thus overcome the defect that the high-moisture percentage of existing anion exchange membrane can not get both with low swelling ratio.
4) hydrophilic section at film introduces tetramethyl phenolphthalein cellular construction, containing four bromination avtive spots, and can be by bromination
Reaction controlling is in the position of design.And bromination reaction activity is high, efficiency is high, degree of bromination is controlled, is thus accurately controlled film
The position of ion-exchange group and number.Introduce four functional groups it addition, the highest in a repetitive, significantly carry
The density of high functional group and the formation of concentration class, beneficially ion channel and the raising of electrical conductivity.
5) anion exchange membrane prepared contains high-moisture percentage, electrical conductivity and low swelling ratio simultaneously, possesses good change
Learn stability and heat stability, show the fuel battery performance of excellence.
Accompanying drawing explanation
Fig. 1 is the bromomethylation block copolymer nuclear magnetic resonance map of preparation in embodiment 1.
Fig. 2 is the anion exchange membrane nuclear magnetic resonance map of preparation in embodiment 1.
Fig. 3 is the afm scan figure of the anion exchange membrane of preparation in embodiment 1.
Detailed description of the invention
In order to be illustrated more clearly that the present invention, following example will the present invention is described further in conjunction with accompanying drawing.
Embodiment 1
The present embodiment has the block polyaryl ether-nitrile-sulfone anion exchange membrane of 20 sections of hydrophilic section and 20 sections of hydrophobic section with synthesis
As a example by, structural formula is as follows, and concrete preparation method comprises the following steps:
Wherein, m=20, n=20, R be H or
1) synthesis of hydrophilic segment: by double for the 3,3-of 7.489g (20mmol) (i.e. m=20) (4-hydroxyl-3,5-dimethyl
Phenyl) Phthalide, the 4,4'-difluorodiphenyl sulfone of 5.334g (21mmol) (i.e. m+1=21), the Anhydrous potassium carbonate of 4.789g and some
Toluene is dissolved in N,N-dimethylacetamide, and nitrogen is protected, and prior to 145 DEG C of reaction 4.5h, then is warmed up to 170 DEG C of reaction 12h, then
Adding the 4 of 0.267g (1.05mmol) (i.e. 5% (m+1)) mole, 4'-difluorodiphenyl sulfone, in 170 DEG C of continuation reaction 1h, cooling
Precipitate with methanol aqueous solution (methanol is 1/1 with the volume ratio of water), filter, wash, be dried afterwards, i.e. obtain hydrophilic segment.
2) synthesis of hydrophobic segment: by 2,6-difluorobenzonilyile, the 4.794g of 2.782g (20mmol) (i.e. n=20)
(21mmol) bisphenol-A of (i.e. n+1=21), the Anhydrous potassium carbonate of 4.789g and some toluene are dissolved in N,N-dimethylacetamide,
Nitrogen is protected, and prior to 145 DEG C of reaction 4.5h, then is warmed up to 165 DEG C of reaction 12h, is subsequently adding 0.240g (1.05mmol) (i.e.
5% (n+1)) mole bisphenol-A, 165 DEG C continue reaction 1h, after cooling, with methanol aqueous solution, (methanol with the volume ratio of water is
1/1) precipitate, filter, wash, be dried, i.e. obtain hydrophobic segment.
3) synthesis of block polyaryl ether-nitrile-sulfone: by the hydrophilic section of 5.592g and the hydrophobic section of 3.601g, 4.789g anhydrous
Potassium carbonate and some toluene are dissolved in N,N-dimethylacetamide, and nitrogen is protected, and prior to 145 DEG C of reaction 4h, then are warmed up to 170 DEG C instead
Answer 20h, precipitate with methanol aqueous solution (methanol is 1/1 with the volume ratio of water), filter, wash, be dried after cooling, obtain block and gather
Aryl oxide nitrile sulfone.
4) synthesis of bromomethylation block polyaryl ether-nitrile-sulfone: 1g block copolymer of polyarylether nitrile is dissolved in 1,1,2,2-tetra-
Ethyl chloride, is subsequently adding N-bromosuccinimide and 58.2mg (0.24mmol) peroxidating of 0.856g (4.809mmol)
Benzoyl, reacts 4.5h at 85 DEG C, after cooling with methanol extraction, filter, wash, be dried, obtain the poly-virtue of bromomethylation block
Ether nitrile sulfone.
5) preparation of anion exchange membrane: by 0.25g bromomethylation block poly (arylene ether nitrile) sulfone copolymer and the 1-of 0.158ml
Methylimidazole. joins in a certain amount of dimethyl sulfoxide, reacts 18h in 45 DEG C, is finally coated on a glass by this casting solution,
Heating solvent flashing obtains solid film, this film is soaked in potassium hydroxide alkali liquor, fully washs with deionized water after reaction 24h
Block polyaryl ether-nitrile-sulfone anion exchange membrane to imidazoles functionalization.
6) test: determined the structure (Fig. 2) of bromination degree (Fig. 1) and anion exchange membrane by nuclear magnetic resonance technique.Logical
Cross phase separation structure and the ion transmission channel (Fig. 3) of atomic force microscope observation film.Back titration method tests the ion of film and hands over
Change capacity.Test dry film at 30 DEG C and the moisture content of 60 DEG C and swelling ratio.The anion of preparation is determined by alternating current impedance instrument
The ionic conductivity of film.
7) test result be the bromination degree of block polymer be 74%, the most each hydrophilic unit contains bromomethyl number and is
2.96 it is individual.The chemical constitution of film is confirmed through nuclear magnetic resonance technique.The anion exchange membrane of preparation forms significant hydrophobe
Micro phase separation structure and the OH of prosperity-Ion transmission channel (Fig. 3).Ion exchange capacity theoretical value 2.25mmol g-1, test
Value is 2.17mmol g-1.Film is respectively 71.74% and 90.58% at the moisture content of 30 DEG C and 60 DEG C, and film is at 30 DEG C and 60 DEG C
Swelling respectively 25.47% and 33.38%.Film is respectively 47.8 × 10 in the ionic conductivity of 30 DEG C and 80 DEG C-3mS·cm-1
With 101.6 × 10-3mS·cm-1。
Embodiment 2
The present embodiment has the block polyaryl ether-nitrile-sulfone anion exchange membrane of 10 sections of hydrophilic section and 20 sections of hydrophobic section with synthesis
As a example by, structural formula is as follows, and concrete preparation method comprises the following steps:
Wherein, m=10, n=20, R be H or
1) synthesis of hydrophilic segment: by double for the 3,3-of 3.745g (10mmol) (i.e. m=10) (4-hydroxyl-3,5-dimethyl
Phenyl) Phthalide, the 4,4'-difluorodiphenyl sulfone of 2.794g (11mmol) (i.e. m+1=11), the Anhydrous potassium carbonate of 2.395g and some
Toluene is dissolved in N,N-dimethylacetamide, and nitrogen is protected, and prior to 145 DEG C of reaction 4.5h, then is warmed up to 165 DEG C of reaction 12h, then
Adding the 4 of 0.134g (0.55mmol) (i.e. 5% (m+1)) mole, 4'-difluorodiphenyl sulfone, in 165 DEG C of continuation reaction 1h, cooling
Precipitate with methanol aqueous solution (methanol is 1/1 with the volume ratio of water), filter, wash, be dried afterwards, i.e. obtain hydrophilic segment.
2) synthesis of hydrophobic segment: by 2,6-difluorobenzonilyile, the 4.794g of 2.782g (20mmol) (i.e. n=20)
(21mmol) bisphenol-A of (i.e. n+1=21), the Anhydrous potassium carbonate of 4.789g and some toluene are dissolved in N,N-dimethylacetamide,
Nitrogen is protected, and prior to 145 DEG C of reaction 4.5h, then is warmed up to 165 DEG C of reaction 12h, is subsequently adding 0.240g (1.05mmol) (i.e.
5% (n+1)) mole bisphenol-A, 165 DEG C continue reaction 1h, after cooling, with methanol aqueous solution, (methanol with the volume ratio of water is
1/1) precipitate, filter, wash, be dried, i.e. obtain hydrophobic segment.
3) synthesis of block polyaryl ether-nitrile-sulfone: by the hydrophilic section of 2.796g and the hydrophobic section of 3.601g, 4.789g anhydrous
Potassium carbonate and some toluene are dissolved in N,N-dimethylacetamide, and nitrogen is protected, and prior to 145 DEG C of reaction 4h, then are warmed up to 168 DEG C instead
Answer 20h, precipitate with methanol aqueous solution (methanol is 1/1 with the volume ratio of water), filter, wash, be dried after cooling, obtain block and gather
Aryl oxide nitrile sulfone.
4) synthesis of bromomethylation block polyaryl ether-nitrile-sulfone: 1g block copolymer of polyarylether nitrile is dissolved in 1,1,2,2-tetra-
Ethyl chloride, is subsequently adding N-bromosuccinimide and 29.1mg (0.12mmol) peroxidating of 0.428g (2.405mmol)
Benzoyl, reacts 5h at 85 DEG C, after cooling with methanol extraction, filter, wash, be dried, obtain bromomethylation block polyarylether
Nitrile sulfone.
5) preparation of anion exchange membrane: by 0.25g bromomethylation block poly (arylene ether nitrile) sulfone copolymer and the 1-of 0.079ml
Methylimidazole. joins in a certain amount of dimethyl sulfoxide, reacts 20h in 45 DEG C, is finally coated on a glass by this casting solution,
Heating solvent flashing obtains solid film, this film is soaked in potassium hydroxide alkali liquor, fully washs with deionized water after reaction 24h
Block polyaryl ether-nitrile-sulfone anion exchange membrane to imidazoles functionalization.
6) test: determined the structure (Fig. 2) of bromination degree (Fig. 1) and anion exchange membrane by nuclear magnetic resonance technique.Logical
Cross phase separation structure and the ion transmission channel of atomic force microscope observation film.Back titration method tests the ion exchange of film to be held
Amount.Test dry film at 30 DEG C and the moisture content of 60 DEG C and swelling ratio.The anionic membrane of preparation is determined by alternating current impedance instrument
Ionic conductivity.
7) test result be the bromination degree of block polymer be 73%, the most each hydrophilic unit contains bromomethyl number and is
2.92 it is individual.The chemical constitution of film is confirmed through nuclear magnetic resonance technique.The anion exchange membrane of preparation forms significant hydrophobe
Micro phase separation structure and the OH of prosperity-Ion transmission channel.Ion exchange capacity theoretical value 1.64mmol g-1, test value is
1.58mmolg-1.Film is respectively 43.14% and 53.92% at the moisture content of 30 DEG C and 60 DEG C, swelling at 30 DEG C and 60 DEG C of film
It is respectively 18.34% and 23.19%.Film is respectively 32.7 × 10 in the ionic conductivity of 30 DEG C and 80 DEG C-3mS·cm-1With
75.7×10-3mS·cm-1。
Embodiment 3
The present embodiment is as a example by synthesis guanidine functionalization block polyaryl ether-nitrile-sulfone anion exchange membrane, and structural formula is as follows:
Wherein, m=20, n=20, R be H or
In addition to following characteristics, other details steps of the preparation method of the present embodiment and method of testing are with embodiment 1.
1) synthesis of hydrophilic segment: reactant is the double (4-hydroxyl-3,5-of 3,3-of 7.489g (20mmol) (i.e. m=20)
3,5-dimethylphenyl) Phthalide, the 3 of 3.994g (21mmol) (i.e. m+1=21), 3'-DfBP, the Anhydrous potassium carbonate of 3.456g,
Polar non-solute is N-Methyl pyrrolidone.
2) synthesis of hydrophobic segment: reactant is the 2,6-difluorobenzonilyile of 2.782g (20mmol) (i.e. n=20), 5.256g
(21mmol) the 4 of (i.e. n+1=21), 4'-sulfonyldiphenol, the Anhydrous potassium carbonate of 4.146g, polar non-solute is N-
Methyl pyrrolidone.
3) synthesis of block polyaryl ether-nitrile-sulfone: reactant is hydrophilic section and the hydrophobic section of 5.706g, the 5.528g of 5.526g
Anhydrous potassium carbonate, polar non-solute is N-Methyl pyrrolidone.
4) test result be the bromination degree of block polymer be 82%, the most each hydrophilic unit contains bromomethyl number and is
3.28 it is individual.The chemical constitution of film is confirmed through nuclear magnetic resonance technique.The anion exchange membrane of preparation forms significant hydrophobe
Micro phase separation structure and the OH of prosperity-Ion transmission channel.Ion exchange capacity theoretical value 2.43mmol g-1, test value is
2.25mmolg-1.Film is respectively 76.82% and 89.67% at the moisture content of 30 DEG C and 60 DEG C, swelling at 30 DEG C and 60 DEG C of film
It is respectively 28.53% and 39.21%.Film is respectively 52.8 × 10 in the ionic conductivity of 30 DEG C and 80 DEG C-3mS·cm-1With
91.7×10-3mS·cm-1。
Embodiment 4
The present embodiment is as a example by synthesis imidazoles functionalization block poly (arylene ether nitrile) ketone anion exchange membrane, and structural formula is as follows:
Wherein, m=10, n=20, R be H or
In addition to following characteristics, other details steps of the preparation method of the present embodiment and method of testing are with embodiment 2:
1) synthesis of hydrophilic segment: reactant is the double (4-hydroxyl-3,5-of 3,3-of 3.745g (10mmol) (i.e. m=10)
3,5-dimethylphenyl) Phthalide, the 4,4'-difluoro benzophenone of 2.398g (11mmol) (i.e. m+1=11), the Carbon Dioxide of 2.395g
Potassium, polar non-solute is DMF.
2) synthesis of hydrophobic segment: reactant is the 2,6-difluorobenzonilyile of 2.782g (20mmol) (i.e. n=20), 3.910g
(21mmol) the 4 of (i.e. n+1=21), 4'-xenol, the Anhydrous potassium carbonate of 4.789g, polar non-solute is N, N-diformazan
Base Methanamide.
3) synthesis of block poly (arylene ether nitrile) ketone: reactant is hydrophilic section and the hydrophobic section of 5.706g, the 5.528g of 5.526g
Anhydrous potassium carbonate, polar non-solute is DMF.
4) test result be the bromination degree of block polymer be 78%, the most each hydrophilic unit contains bromomethyl number and is
3.12 it is individual.The chemical constitution of film is confirmed through nuclear magnetic resonance technique.The anion exchange membrane of preparation forms significant hydrophobe
Micro phase separation structure and the OH of prosperity-Ion transmission channel.Ion exchange capacity theoretical value 1.72mmol g-1, test value is
1.66mmolg-1.Film is respectively 38.57% and 49.57% at the moisture content of 30 DEG C and 60 DEG C, swelling at 30 DEG C and 60 DEG C of film
It is respectively 16.81% and 20.92%.Film is respectively 28.9 × 10 in the ionic conductivity of 30 DEG C and 80 DEG C-3mS·cm-1With
61.6×10-3mS·cm-1。
The material of anion exchange membrane of the present invention is the block copolymer of polyarylether nitrile containing phenolphthalein side base, comprises in its structure
The hydrophilic segment of long sequence and hydrophobic segment.Wherein, hydrophilic section contains rigidity and the phenolphthalein structure of big steric hindrance, and hydrophobic section contains by force
The itrile group structure of polarity.The anion exchange membrane thus prepared have prosperity ion transmission channel, possess high-moisture percentage and
Low swelling ratio characteristic, its moisture content reaches as high as 90.58%, and ionic conductivity reaches as high as 101.6 × 10-3mS·cm-1, and
Swelling ratio is only 33.38%, overcomes what existing anion exchange membrane high-moisture percentage, high conductivity and low swelling ratio can not get both
Shortcoming, and preparation process do not uses the carcinogenic chloromethyl ether reagent of severe toxicity, before alkaline fuel cell field has wide application
Scape.
Claims (9)
1. the block copolymer anion exchange membrane for fuel cell, it is characterised in that its molecular structure includes containing phenol
The hydrophilic section of phthalein side base and the hydrophobic section containing benzonitrile structure, its molecular structural formula is as follows:
Wherein, the integer of m=5～50, the integer of n=5～50, R be H, It is selected from (a)～(d) any one；
The preparation method of a kind of block copolymer anion exchange membrane the most as claimed in claim 1, it is characterised in that include following
Step:
1) synthesis of hydrophilic section: by double for 3,3-(4-hydroxyl-3,5-3,5-dimethylphenyl) Phthalides with there is Ar1Two fluorine monomers of structure
Feed with the mol ratio of m/ (m+1), in the presence of nitrogen protection and the Anhydrous potassium carbonate of 2.5～4 moles and toluene, be dissolved in
Polar non-solute, prior to 140～150 DEG C of reactions 4～6h, then is warmed up to 160～180 DEG C of reactions 10～12h, is subsequently adding
5% (m+1) mole containing Ar1Two fluorine monomers of structure, continue reaction 1～2h at 160～180 DEG C, use alcohol-water solution after cooling
Precipitate, filter, wash, be dried, i.e. obtain hydrophilic section；
2) synthesis of hydrophobic section: by 2,6-difluorobenzonilyile with there is Ar2Double hydroxyl aromatic ring monomers of structure with m/ (m+1) mole
Than charging, in the presence of nitrogen protection and the Anhydrous potassium carbonate of 2.5～4 moles and toluene, it is dissolved in polar non-solute,
Prior to 140～150 DEG C of reactions 4～6h, then it is warmed up to 160～180 DEG C of reactions 10～12h, is subsequently adding 5% (m+1) mole
Containing Ar2Double hydroxyl aromatic ring monomers of structure, continue reaction 1～2h at 160～180 DEG C, by alcohol-water solution precipitation, mistake after cooling
Filter, wash, be dried, i.e. obtain hydrophobic section；
3) synthesis of block copolymer: by step 1) hydrophilic section and the step 2 prepared) hydrophobic section prepared enters with equimolar ratio
Material, in the presence of nitrogen protection and the Anhydrous potassium carbonate of 2.5～4 moles and toluene, is dissolved in polar non-solute, prior to
140～150 DEG C reaction 3～4h, then be warmed up to 160～180 DEG C reaction 18～20h, after cooling with alcohol-water solution precipitation, filter,
Wash, be dried, obtain block copolymer；
4) synthesis of bromomethylation block copolymer: by step 3) block copolymer that obtains is dissolved in 1,1,2,2-tetra-chloroethene
Alkane, is subsequently adding N-bromosuccinimide and initiator, after reaction, and cooling, with methanol extraction, filter, wash, be dried,
Bromomethylation block copolymer；
5) preparation of block copolymer anion exchange membrane: by step 4) the bromomethylation block copolymer that obtains tries with functionalization
Agent joins in polar non-solute dissolves, and obtains casting solution, then coated on a glass by casting solution after reaction, heating volatilization
Solvent obtains solid film, washs, i.e. obtain block copolymer anion exchange membrane after then solid film is dipped in alkali liquor reaction；
Described bromomethylation block copolymer is 1: 5 with the mol ratio of functionalized reagent；Described functionalized reagent is water-soluble selected from trimethylamine
One in liquid, pentamethyl guanidine, 1-Methylimidazole., DMIZ 1,2 dimethylimidazole.
The preparation method of a kind of block copolymer anion exchange membrane the most as claimed in claim 2, it is characterised in that in step 1)
In, described in there is Ar1Two fluorine monomers of structure are selected from 4,4'-difluorodiphenyl sulfone, 4,4'-difluoro benzophenone, 4,4'-difluoro connection
One in benzene, 3,3'-DfBP.
The preparation method of a kind of block copolymer anion exchange membrane the most as claimed in claim 2, it is characterised in that in step 2)
In, described in there is Ar2Double hydroxyl aromatic ring monomers of structure selected from 4,4'-sulfonyldiphenol, 4,4'-dihydroxy benaophenonel,
One in bisphenol-A, 4,4'-xenol.
The preparation method of a kind of block copolymer anion exchange membrane the most as claimed in claim 2, it is characterised in that in step 4)
In, the mol ratio of described block copolymer, N-bromosuccinimide and initiator is 1: (0.1～1.5): (0.01～
0.075)。
The preparation method of a kind of block copolymer anion exchange membrane the most as claimed in claim 2, it is characterised in that in step 4)
In, described initiator is selected from benzoyl peroxide or azodiisobutyronitrile.
The preparation method of a kind of block copolymer anion exchange membrane the most as claimed in claim 2, it is characterised in that in step 4)
In, the condition of described reaction is to react 4～6h at 85 DEG C.
The preparation method of a kind of block copolymer anion exchange membrane the most as claimed in claim 2, it is characterised in that in step 5)
In, the condition of described reaction is to react 12～24h at 40～50 DEG C；Described alkali liquor is molten selected from potassium hydroxide solution or sodium hydroxide
Liquid；The described time that solid film is dipped in alkali liquor reaction is 24～48h；Described washing uses deionized water wash.
The preparation method of a kind of block copolymer anion exchange membrane the most as claimed in claim 2, it is characterised in that in step 1),
2), 3), 5) in, described polar non-solute be selected from N-Methyl pyrrolidone, DMF, N, N-dimethyl second
One in amide, dimethyl sulfoxide.
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| CN101501917A (en) * | 2005-06-01 | 2009-08-05 | 复合燃料公司 | Ion-conducting polymers containing pendant ion conducting groups |
| CN102015830A (en) * | 2008-05-08 | 2011-04-13 | 东洋纺织株式会社 | Novel sulfonic acid group-containing segmentalized block copolymer, use thereof, and method for producing novel block copolymer |
| CN102869448A (en) * | 2009-09-24 | 2013-01-09 | 乔治亚州技术研究公司 | Anion exchange polyelectrolytes |
| CN103717677A (en) * | 2011-07-12 | 2014-04-09 | 科腾聚合物美国有限责任公司 | Modified sulfonated block copolymers and the preparation thereof |
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| CN101501917A (en) * | 2005-06-01 | 2009-08-05 | 复合燃料公司 | Ion-conducting polymers containing pendant ion conducting groups |
| CN102015830A (en) * | 2008-05-08 | 2011-04-13 | 东洋纺织株式会社 | Novel sulfonic acid group-containing segmentalized block copolymer, use thereof, and method for producing novel block copolymer |
| CN102869448A (en) * | 2009-09-24 | 2013-01-09 | 乔治亚州技术研究公司 | Anion exchange polyelectrolytes |
| CN103717677A (en) * | 2011-07-12 | 2014-04-09 | 科腾聚合物美国有限责任公司 | Modified sulfonated block copolymers and the preparation thereof |
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