CN103113588A - Polysulfone with quaternary ammonium group at side chain and preparation method of polysulfone - Google Patents
Polysulfone with quaternary ammonium group at side chain and preparation method of polysulfone Download PDFInfo
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- CN103113588A CN103113588A CN2013100253157A CN201310025315A CN103113588A CN 103113588 A CN103113588 A CN 103113588A CN 2013100253157 A CN2013100253157 A CN 2013100253157A CN 201310025315 A CN201310025315 A CN 201310025315A CN 103113588 A CN103113588 A CN 103113588A
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Abstract
The invention provides polysulfone with a quaternary ammonium group at a side chain. The content of the quaternary ammonium group in polysulfone is controllable; and polysulfone with the quaternary ammonium group at the side chain can be used for preparing an anionic exchange membrane which is high in electrical conductivity, good in mechanical performances and low in price. The invention further provides a preparation method of polysulfone with the quaternary ammonium group at the side chain. Besides, the invention further provides the anionic exchange membrane.
Description
Technical field
The present invention relates to polymkeric substance and preparation field thereof, relate in particular to a kind of side chain and contain polysulfones of quaternary ammonium group and preparation method thereof.
Background technology
Anion-exchange membrane is that a kind of film body is fixing with the positive charge ion group, can select to see through the film material of negatively charged ion, and it has excellent ion selectivity and mechanical property, obtains broad research and application in recent years in a plurality of fields such as electrolysis, fuel cell.
Anion-exchange membrane is normally by the preparation of the polymkeric substance containing quaternary ammonium group.From a structural point, the contained quaternary ammonium group of traditional anion-exchange membrane is that the benzylic type quaternary ammonium group is as the most frequently used benzyl trimethyl quaternary ammonium group, but the alkali resistance of the benzylic type quaternary ammonium group in this anion-exchange membrane is inadequate, the life-time service that can't meet under the alkaline fuel cell Working environment requires (J.R.Varcoe and R.C.T.Slade, Fuel Cells, 2005,5,187-200.), this is also a bottleneck problem that limits at present the development of alkaline anion-exchange membrane fuel cell.Synthetic method; traditional polymkeric substance containing quaternary ammonium group needs first synthetic polymer main chain usually; then the aryl on described main polymer chain is carried out to chloromethylation; and then react benzyl chloride is converted into to quaternary ammonium group with three grades of ammoniums; not only the introduction volume of step complexity but also quaternary ammonium group is difficult to accurate control, usually also needs to use in addition the chloromethyl ether reagent with carinogenicity in the chloromethylation process.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of side chain polysulfones containing quaternary ammonium group and preparation method thereof, the quaternary ammonium group content of described polysulfones is controlled, and this polymkeric substance can be used in high, the good mechanical property of preparation specific conductivity, cheap anion-exchange membrane.
In order to solve above technical problem, the invention provides the polysulfones of the side chain shown in a kind of formula I containing quaternary ammonium group:
Formula I
X=0.01～1.0 wherein; Y=0～0.99; X+y≤1; N is 1 ~ 400; Wherein Q is quaternary ammonium group; P is 3,4,5 or 6; A
j1, A
j2be respectively one or more in the substituting group that the binary aryl sulfonic acid forms; A
kone or more in the substituting group formed for polyarylate; A
ione or more in the substituting group formed for the monobasic aryl sulfonic acid.
Preferably, described quaternary ammonium group is the substituting group shown in formula II, formula III or formula IV:
Formula II formula III formula IV
Wherein T is the negatively charged ion of band-1 valence charge.
Preferably, the negatively charged ion of described band-1 valence charge is Cl
-, Br
-or I
-.
Preferably, the substituting group that described binary aryl sulfonic acid forms is one or more in the substituting group shown in formula 1 ~ formula 4:
Formula 1 formula 2
Formula 3
Formula 4
Wherein, W is the substituting group shown in formula a ~ formula i:
Formula a formula b formula c formula d
Formula e formula f formula g formula h formula i
The integer that qd is 1～10; The integer that qe is 1～3; The integer that qf is 2～12; The integer that qg is 2～10.
Preferably, the substituting group that described polyarylate forms is one or more in the substituting group shown in formula 1, formula 5 ~ formula 17:
Formula 1 formula 5
Formula 6
Formula 7 formula 8 formulas 9
Formula 10 formulas 11
Formula 12 formula 13 formulas 14
Formula 15 formula 16 formulas 17
Wherein, the integer that ra is 1～4; The integer that rb is 1～9; The integer that rc is 1～2; The integer that rd is 0～2; The integer that re is 0～2.
Preferably, the substituting group that described monobasic aryl sulfonic acid forms is one or more in the substituting group shown in formula 1, formula 5 ~ formula 17.
According to the present invention, the polysulfones shown in described formula I is actually a kind of random copolymers.
The present invention also provides the preparation method of a kind of side chain containing the polysulfones of quaternary ammonium group, comprising:
Side chain shown in formula V is mixed with binary aryl sulfonic acid monomer, polyarylate monomer and/or monobasic aryl sulfonic acid and acid solvent containing the quaternary ammonium group monomer, react 10 ~ 48 hours, obtain the polysulfones of the side chain shown in formula I containing quaternary ammonium group.
Formula V
Wherein Q is quaternary ammonium group; P is 3,4,5 or 6.
Preferably, described quaternary ammonium group is the substituting group shown in formula II, formula III or formula IV:
Formula II formula III formula IV
Wherein T is the negatively charged ion of band-1 valence charge.
Preferably, the negatively charged ion of described band-1 valence charge is Cl
-, Br
-or I
-.
According to the present invention, side chain shown in described formula I is specially containing the preparation method of the polysulfones of quaternary ammonium group: by the compound shown in foregoing formula V and binary aryl sulfonic acid monomer, polyarylate monomer and/or monobasic aryl sulfonic acid and acid solvent add in the reaction flask of logical nitrogen, under certain temperature of reaction, stirring reaction is 10～48 hours, pour reacting liquor while hot into suitable precipitation agent preferably in water, be settled out polymkeric substance, it is neutral filtering and repeatedly being washed till filtrate with deionized water, use the aqueous sodium hydroxide solution soaking at room temperature of 1mol/L after 24 hours resulting polymers, vacuum-drying be able to OH
-the side chain that form exists contains the polymkeric substance of quaternary ammonium group, then will be with OH
-the side chain that form exists is able to other negatively charged ion as Cl with corresponding acid as neutralizations such as HCl, HBr containing the polymkeric substance of quaternary ammonium group
-, Br
-the side chain existed etc. form is containing the polymkeric substance of quaternary ammonium group.
According to the present invention, polyreaction is to react and carry out with sulfuryl between aryl by the aryl sulfonic acid group, schematically as follows:
According to the present invention, described binary aryl sulfonic acid monomer is preferably one or more in the binary aryl sulfonic acid compound shown in formula 18 ~ formula 21, due to described binary aryl sulfonic acid monomer, containing two sulfonic acid functional groups that the sulfuryl reaction can occur, can mean with AA type monomer.
Formula 18
Formula 19
Formula 20
Formula 21
Wherein, M is H
+, tertiary amine anionization salt, monovalent base metal ion or quaternary ammonium salt cationic; The integer that qd is 1～10; The integer that qe is 1～3; W is the substituting group shown in formula a ~ formula i.
According to the present invention, described polyarylate is preferably one or more in the polyarylate shown in formula 22 ~ formula 35, because described polyarylate forms containing two or more phenyl ring, wherein only the sulfuryl reaction can occur in two phenyl ring in the molecule two ends, can mean with BB type monomer.
Polyarylate shown in table 1 formula 22 ~ formula 35
Wherein, the integer that ra is 1～4; The integer that rb is 1～9; The integer that rc is 1～2; The integer that re is 0～2.
According to the present invention, described monobasic aryl sulfonic acid monomer is preferably one or more in the monobasic aryl sulfonic acid compound shown in formula 36 ~ formula 45, due to described monobasic aryl sulfonic acid monomer, simultaneously containing sulfonic group and an aryl functional group that the sulfuryl reaction can occur, can mean with AB type monomer.
Monobasic aryl sulfonic acid compound shown in table 2 formula 36 ~ formula 45
Wherein, M is H
+, tertiary amine anionization salt, monovalent base metal ion or quaternary ammonium salt cationic; The integer that ra is 1～4; The integer that rb is 1～9; The integer that rc is 1～2; The integer that re is 0～2.
According to the present invention, the side chain shown in described formula I is X containing the mol ratio of quaternary ammonium group monomer, AA type monomer, BB type monomer, AB type monomer
qBB: X
aA: X
bB: X
aB, X wherein
qBB, X
aA, X
bBall be greater than zero, X
aBbe greater than zero or equal zero, X
qBB+ X
aA+ X
bB+ X
aB=2, X
qBB+ X
bB=X
aA, 0.01≤X
qBB≤ 1,0≤X
aB≤ 1, add 2 ~ 4L acid solvent by the summation of the amount of every mole of AA type monomer and AB type monomer.According to the present invention, the copolyreaction of described monomer obtains by the sulfuryl reaction.Be preferably 60～100 ℃ according to temperature of reaction of the present invention.
Described acid solvent is preferably the trifluoromethanesulfonic acid that purity is greater than 99%.
The present invention also provides a kind of anion-exchange membrane.According to the present invention, described anion-exchange membrane can be used the side chain shown in formula I to be prepared according to the preparation method about anion-exchange membrane in " the preparation and application technology of ion-exchange membrane " containing the polysulfones of quaternary ammonium group.Anion-exchange membrane prepared by the present invention is due to the polysulfones that has used the side chain shown in formula I containing quaternary ammonium group, and the quaternary ammonium group contained is more, has improved electric conductivity and the switching performance of anion-exchange membrane.In addition, many phenyl ring and ehter bond in the polysulfones molecular chain that the present invention uses, so not only possess intensity but also possess pliability.The present invention has also avoided in traditional anionresin membrane preparation method needing to use the shortcoming of the chloromethyl ether reagent with carinogenicity.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these are described is the restriction for further illustrating the features and advantages of the present invention rather than patent of the present invention being required.
Further describe by the following examples the present invention.
Proton nmr spectra (
1h NMR), by AVANCE AV400, the Bruker record, with heavy water (D
2o) or deuterated dimethyl sulfoxide (DMSO-d6, tetramethylsilane is interior mark) be solvent.Fourier transform infrared spectra (FTIR) is by Vector22, the Bruker record.The molecular weight of polymkeric substance adopts general Ubbelohde viscometer method to characterize, and probe temperature is 30 ° of C, and solvent is 99% methylsulfonic acid, and polymer concentration is 0.3 gram/100 milliliter, and solution properties viscosity unit is dL/g.The anionic electrodeposition conductance of film is measured at known four electrode models of the upper employing of PGSTAT302N type electrochemical workstation (Metrohm China Ltd.), and probe temperature is 25 ℃, and relative humidity is 100%.
Embodiment 1:
Successively by 0.01 mole 2,2 ,-bis-(4-trimethylamine groups) butoxy biphenyl dibromo, 1.00 moles 4,4 ,-phenyl ether disulfonic acid, 0.99 mole 2,2 ,-dimethoxy-biphenyl and 4 liters of trifluoromethanesulfonic acids add in the reaction flask of logical nitrogen, 60 ℃ of lower stirring reactions 48 hours, reacting liquor while hot is poured in a large amount of deionized waters and obtained the polymkeric substance precipitation, it is neutral filtering and repeatedly being washed till filtrate with deionized water, the aqueous sodium hydroxide solution soaking at room temperature that resulting polymers is used to 1mol/L is after 24 hours, and room temperature vacuum-drying be able to OH
-the side chain that form exists is containing the polymkeric substance of quaternary ammonium group.In infrared spectrum at 1310cm
-1with 1150cm
-1the stretching vibration peak of strong sulfuryl appears in left and right, shows the generation of sulfuryl polyreaction; Proton nmr spectra confirms the structure of resulting polymers and the ratio than each structural unit of calculating gained conforms to expection by integration,
1h NMR (400MHz, DMSO-d6) δ (ppm): 7.92-7.00 (Ar-H), 4.16 (OCH
2), 3.85 (OCH
3), 3.24 (CH
2n), 2.97 (CH
3n), 1.50-1.75 (CH
2 cH 2 ?
cH 2 cH
2).; The limiting viscosity of resulting polymers is 0.76dL/g simultaneously, is indicated as high-molecular weight polymer.
Prepared by the following method by wherein said 2,2 ,-bis-(4-trimethylamine groups) butoxy biphenyl dibromo:
Successively by 1.0 moles 2,2 ,-dihydroxybiphenyl, the salt of wormwood of 2.0 moles, the 4-brombutyl trimethylammonium bromide of 2.0 moles and the acetonitrile of 15 liters add in 25 liters of reaction flasks with backflow prolong logical nitrogen, 75 ℃ of lower mechanical stirring are reacted 24 hours, filter, and underpressure distillation is except desolventizing, the gained solid is through the acetonitrile recrystallization, filter, obtain 2,2 ,-bis-(4-trimethylamine groups) butoxy biphenyl dibromo after vacuum-drying, brief note is DNODP
1h NMR (400MHz, D
2o) δ (ppm): 7.41(Ar-H4, t, 2H), 7.27(Ar-H6, d, 2H), 7.09-7.16(Ar-H3& Ar-H5, m, 4H), 4.03(OCH
2, t, 4H), 3.06(CH
2n, t, 4H), 2.88(NCH
3, t, 18H), 1.52-1.70(CH
2 cH 2 ?
cH 2 cH
2, m, 8H), confirmed the structure of compound, reaction formula is as follows:
Embodiment 2:
Successively 0.01 mole of method by embodiment 1 is prepared 2, 2,-bis-(4-trimethylamine groups) butoxy biphenyl dibromo, 1.00 mole 4, 4,-phenyl ether disulfonic acid, 0.99 mole 2, 2,-dimethoxy-biphenyl and 4 liters of trifluoromethanesulfonic acids add in the reaction flask of logical nitrogen, 80 ℃ of lower stirring reactions 24 hours, reacting liquor while hot is poured in a large amount of deionized waters and obtained the polymkeric substance precipitation, it is neutral filtering and repeatedly being washed till filtrate with deionized water, use the aqueous sodium hydroxide solution soaking at room temperature of 1mol/L after 24 hours resulting polymers, room temperature vacuum-drying be able to OH
-the side chain that form exists is containing the polymkeric substance of quaternary ammonium group.In infrared spectrum at 1310cm
-1with 1150cm
-1the stretching vibration peak of strong sulfuryl appears in left and right, shows the generation of sulfuryl polyreaction; Proton nmr spectra confirms the structure of resulting polymers and the ratio than each structural unit of calculating gained conforms to expection by integration,
1h NMR (400MHz, DMSO-d6) δ (ppm): 7.92-7.00 (Ar-H), 4.16 (OCH
2), 3.85 (OCH
3), 3.24 (CH
2n), 2.97 (CH
3n), 1.50-1.75 (CH
2 cH 2 ?
cH 2 cH
2).; The limiting viscosity of resulting polymers is 0.69dL/g simultaneously, is indicated as high-molecular weight polymer.
Embodiment 3:
Successively 0.01 mole of method by embodiment 1 is prepared 2, 2,-bis-(4-trimethylamine groups) butoxy biphenyl dibromo, 1.00 mole 4, 4,-phenyl ether disulfonic acid, 0.99 mole 2, 2,-dimethoxy-biphenyl and 4 liters of trifluoromethanesulfonic acids add in the reaction flask of logical nitrogen, 100 ℃ of lower stirring reactions 10 hours, reacting liquor while hot is poured in a large amount of deionized waters and obtained the polymkeric substance precipitation, it is neutral filtering and repeatedly being washed till filtrate with deionized water, use the aqueous sodium hydroxide solution soaking at room temperature of 1mol/L after 24 hours resulting polymers, room temperature vacuum-drying be able to OH
-the side chain that form exists is containing the polymkeric substance of quaternary ammonium group.In infrared spectrum at 1310cm
-1with 1150cm
-1the stretching vibration peak of strong sulfuryl appears in left and right, shows the generation of sulfuryl polyreaction; Proton nmr spectra confirms the structure of resulting polymers and the ratio than each structural unit of calculating gained conforms to expection by integration,
1h NMR (400MHz, DMSO-d6) δ (ppm): 7.92-7.00 (Ar-H), 4.16 (OCH
2), 3.85 (OCH
3), 3.24 (CH
2n), 2.97 (CH
3n), 1.50-1.75 (CH
2 cH 2 ?
cH 2 cH
2).; The limiting viscosity of resulting polymers is 0.48dL/g simultaneously, is indicated as high-molecular weight polymer.
Embodiment 4:
Successively the method by embodiment 1 of 0.50 mole is prepared 2, 2,-bis-(4-trimethylamine groups) butoxy biphenyl dibromo, 1.00 mole 4, 4,-phenyl ether disulfonic acid, 0.50 mole 2, 2,-dimethoxy-biphenyl and 4 liters of trifluoromethanesulfonic acids add in the reaction flask of logical nitrogen, 100 ℃ of lower stirring reactions 24 hours, reacting liquor while hot is poured in a large amount of deionized waters and obtained the polymkeric substance precipitation, it is neutral filtering and repeatedly being washed till filtrate with deionized water, use the aqueous sodium hydroxide solution soaking at room temperature of 1mol/L after 24 hours resulting polymers, room temperature vacuum-drying be able to OH
-the side chain that form exists is containing the polymkeric substance of quaternary ammonium group.In infrared spectrum at 1310cm
-1with 1150cm
-1the stretching vibration peak of strong sulfuryl appears in left and right, shows the generation of sulfuryl polyreaction; Proton nmr spectra confirms the structure of resulting polymers and the ratio than each structural unit of calculating gained conforms to expection by integration,
1h NMR (400MHz, DMSO-d6) δ (ppm): 7.92-7.00 (Ar-H), 4.16 (OCH
2), 3.85 (OCH
3), 3.24 (CH
2n), 2.97 (CH
3n), 1.50-1.75 (CH
2 cH 2 ?
cH 2 cH
2).; The limiting viscosity of resulting polymers is 0.86dL/g simultaneously, is indicated as high-molecular weight polymer.
Embodiment 5:
Successively the method by embodiment 1 of 0.01 mole is prepared 2, 2,-bis-(4-trimethylamine groups) butoxy biphenyl dibromo, 0.50 mole 4, 4,-phenyl ether disulfonic acid, 0.49 mole 2, 2,-dimethoxy-biphenyl, 1.00 mole 4-phenoxy group Phenylsulfonic acid and 6 liters of trifluoromethanesulfonic acids add in the reaction flask of logical nitrogen, 100 ℃ of lower stirring reactions 24 hours, reacting liquor while hot is poured in a large amount of deionized waters and obtained the polymkeric substance precipitation, it is neutral filtering and repeatedly being washed till filtrate with deionized water, use the aqueous sodium hydroxide solution soaking at room temperature of 1mol/L after 24 hours resulting polymers, room temperature vacuum-drying be able to OH
-the side chain that form exists is containing the polymkeric substance of quaternary ammonium group.In infrared spectrum at 1310cm
-1with 1150cm
-1the stretching vibration peak of strong sulfuryl appears in left and right, shows the generation of sulfuryl polyreaction; Proton nmr spectra confirms the structure of resulting polymers and the ratio than each structural unit of calculating gained conforms to expection by integration,
1h NMR (400MHz, DMSO-d6) δ (ppm): 7.92-7.00 (Ar-H), 4.16 (OCH
2), 3.85 (OCH
3), 3.24 (CH
2n), 2.97 (CH
3n), 1.50-1.75 (CH
2 cH 2 ?
cH 2 cH
2).; The limiting viscosity of resulting polymers is 0.70dL/g simultaneously, is indicated as high-molecular weight polymer.
Embodiment 6:
Getting resulting polymers in 1 gram embodiment 4 is dissolved in 10 gram dimethyl formamides, be mixed with homogeneous solution, be applied on clean horizontal glass plate, 60 ℃ of lower solvent flashings are approximately after 10 hours, film is peeled off, and soaked after 24 hours and obtain the hydroxyl type proton exchange membrane in the sodium hydroxide solution of 1mol/L.Room temperature hydroxide ion specific conductivity is higher than 0.030S/cm, at 60 ° of C, in the NaOH aqueous solution of 1mol/L, soak after 60 days, film still can keep snappiness while specific conductivity without obvious decline, shows that this film has very large application prospect in the alkaline anion-exchange membrane fuel cell.
More than applied specific case principle of the present invention and embodiment are set forth, the explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (7)
1. the side chain shown in a formula I is containing the polysulfones of quaternary ammonium group:
Formula I
X=0.01～1.0 wherein; Y=0～0.99; X+y≤1; N is 1 ~ 400; Wherein Q is quaternary ammonium group; P is 3,4,5 or 6; A
j1, A
j2be respectively one or more in the substituting group that the binary aryl sulfonic acid forms; A
kone or more in the substituting group formed for polyarylate; A
ione or more in the substituting group formed for the monobasic aryl sulfonic acid.
2. side chain according to claim 1, containing the polysulfones of quaternary ammonium group, is characterized in that, the substituting group that described binary aryl sulfonic acid forms is one or more in the substituting group shown in formula 1 ~ formula 4:
Formula 1 formula 2
Formula 3
Formula 4
Wherein, W is the substituting group shown in formula a ~ formula i:
Formula a formula b formula c formula d
Formula e formula f formula g formula h formula i
The integer that qd is 1～10; The integer that qe is 1～3; The integer that qf is 2～12; The integer that qg is 2～10.
3. side chain according to claim 1, containing the polysulfones of quaternary ammonium group, is characterized in that, the substituting group that described polyarylate forms is one or more in the substituting group shown in formula 1, formula 5 ~ formula 17:
Formula 1 formula 5
Formula 6
Formula 7 formula 8 formulas 9
Formula 10 formulas 11
Formula 12 formula 13 formulas 14
Formula 15 formula 16 formulas 17
Wherein, the integer that ra is 1～4; The integer that rb is 1～9; The integer that rc is 1～2; The integer that r is 0～2; The integer that re is 0～2.
4. side chain according to claim 1, containing the polysulfones of quaternary ammonium group, is characterized in that, the substituting group that described monobasic aryl sulfonic acid forms is one or more in the substituting group shown in formula 1, formula 5 ~ formula 17.
5. quaternary ammonium group according to claim 1 is the substituting group shown in formula II, formula III or formula IV:
Formula II formula III formula IV
Wherein T is the negatively charged ion of band-1 valence charge.
6. a side chain claimed in claim 1 is containing the preparation method of the polysulfones of quaternary ammonium group, it is characterized in that, binary aryl sulfonic acid monomer, polyarylate, side chain are contained to quaternary ammonium group monomer and/or monobasic aryl sulfonic acid monomer and acid solvent and add polymerization in the reaction flask that leads to nitrogen to obtain the polysulfones of the side chain shown in formula I containing quaternary ammonium group.
7. an anion-exchange membrane, is characterized in that, right to use requires 1 described side chain to be prepared from containing the polysulfones of quaternary ammonium group.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311857A (en) * | 2014-10-17 | 2015-01-28 | 中国科学技术大学 | Preparation method for double quaternary ammonium side long chain anion-exchange membrane |
| CN113471498A (en) * | 2021-07-07 | 2021-10-01 | 长春工业大学 | Multi-quaternary ammonium side long-chain type polysulfone anion-exchange membrane and preparation method thereof |
| CN115322376A (en) * | 2022-08-15 | 2022-11-11 | 宁夏清研高分子新材料有限公司 | Method for improving conductivity of polysulfone polymer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928393A (en) * | 2009-04-10 | 2010-12-29 | 株式会社东进世美肯 | Polysulfone polymer, preparation method thereof, polymer electrolyte membrane containing polysulfone polymer, membrane electrode assembly and fuel cell |
| US20120273423A1 (en) * | 2011-04-29 | 2012-11-01 | National University Of Singapore | Composite membranes comprising a sulfonated polyarylether and their use in forward osmosis processes |
-
2013
- 2013-01-23 CN CN201310025315.7A patent/CN103113588B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928393A (en) * | 2009-04-10 | 2010-12-29 | 株式会社东进世美肯 | Polysulfone polymer, preparation method thereof, polymer electrolyte membrane containing polysulfone polymer, membrane electrode assembly and fuel cell |
| US20120273423A1 (en) * | 2011-04-29 | 2012-11-01 | National University Of Singapore | Composite membranes comprising a sulfonated polyarylether and their use in forward osmosis processes |
Non-Patent Citations (1)
| Title |
|---|
| ZHENGHUI ZHANG等: "Novel aromatic proton-exchange polyelectrolytes via polyacylation of pre-sulfonated monomers", 《J. MATER. CHEM》, vol. 22, 31 December 2012 (2012-12-31) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311857A (en) * | 2014-10-17 | 2015-01-28 | 中国科学技术大学 | Preparation method for double quaternary ammonium side long chain anion-exchange membrane |
| CN113471498A (en) * | 2021-07-07 | 2021-10-01 | 长春工业大学 | Multi-quaternary ammonium side long-chain type polysulfone anion-exchange membrane and preparation method thereof |
| CN115322376A (en) * | 2022-08-15 | 2022-11-11 | 宁夏清研高分子新材料有限公司 | Method for improving conductivity of polysulfone polymer |
| CN115322376B (en) * | 2022-08-15 | 2024-01-30 | 宁夏清研高分子新材料有限公司 | Method for improving conductivity of polysulfone polymer |
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