CN103113588B - A kind of side chain contains polysulfones of quaternary ammonium group and preparation method thereof - Google Patents
A kind of side chain contains polysulfones of quaternary ammonium group and preparation method thereof Download PDFInfo
- Publication number
- CN103113588B CN103113588B CN201310025315.7A CN201310025315A CN103113588B CN 103113588 B CN103113588 B CN 103113588B CN 201310025315 A CN201310025315 A CN 201310025315A CN 103113588 B CN103113588 B CN 103113588B
- Authority
- CN
- China
- Prior art keywords
- formula
- quaternary ammonium
- ammonium group
- integer
- side chain
- 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.)
- Active
Links
- 0 CCS(CC)/*(/C/C=C1)=C/C/C(/Cc(c*(c*2)S(C)(=O)=O)c2O*(C)C)=C1/OC Chemical compound CCS(CC)/*(/C/C=C1)=C/C/C(/Cc(c*(c*2)S(C)(=O)=O)c2O*(C)C)=C1/OC 0.000 description 1
Landscapes
- Fuel Cell (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention provides a kind of side chain containing the polysulfones of quaternary ammonium group, the quaternary ammonium group content in described polysulfones is controlled, and this side chain can be used in containing the polysulfones of quaternary ammonium group that preparation specific conductivity is high, good mechanical property, cheap anion-exchange membrane.Present invention also offers the preparation method of a kind of side chain containing the polysulfones of quaternary ammonium group; Still further provides a kind of anion-exchange membrane.
Description
Technical field
The present invention relates to polymkeric substance and preparation field thereof, particularly relate 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 fixed with positive charge ion group, and can select the film material through negatively charged ion, it has excellent ion selectivity and mechanical property, obtains extensive investigation and application in recent years in multiple field such as electrolysis, fuel cell.
Anion-exchange membrane is normally prepared by the polymkeric substance containing quaternary ammonium group.From a structural point, quaternary ammonium group contained by traditional anion-exchange membrane is that 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 cannot meet under alkaline fuel cell Working environment requires (J.R.Varcoe and R.C.T.Slade, Fuel Cells, 2005,5,187-200.), this is also the bottleneck problem limiting the development of alkaline anion-exchange membrane fuel cell at present.From synthetic method; traditional polymkeric substance containing quaternary ammonium group needs first synthetic polymer main chain usually; then chloromethylation is carried out to the aryl on described main polymer chain; and then to react with three grades of ammoniums benzyl chloride is converted into quaternary ammonium group; not only step introduction volume that is complicated but also quaternary ammonium group is difficult to accurate control, usually also needs to use the chloromethyl ether reagent with carinogenicity in addition in chloromethylation process.
Summary of the invention
The technical problem to be solved in the present invention is polysulfones providing a kind of side chain 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 preparation specific conductivity high, good mechanical property, 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
Wherein x=0.01 ~ 1.0; 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 binary aryl sulfonic acid formed substituting group in one or more; A
kfor one or more in the substituting group that polyarylate is formed; A
ifor one or more in the substituting group that unitary aryl sulfonic acid is formed.
Preferably, described quaternary ammonium group be formula II, formula III or the substituting group shown in 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 is formed 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
Qd is the integer of 1 ~ 10; Qe is the integer of 1 ~ 3; Qf is the integer of 2 ~ 12; Qg is the integer of 2 ~ 10.
Preferably, the substituting group that described polyarylate is formed is formula 1, one or more in the substituting group shown in formula 5 ~ formula 17:
Formula 1 formula 5
Formula 6
Formula 7 formula 8 formula 9
Formula 10 formula 11
Formula 12 formula 13 formula 14
Formula 15 formula 16 formula 17
Wherein, ra is the integer of 1 ~ 4; Rb is the integer of 1 ~ 9; Rc is the integer of 1 ~ 2; Rd is the integer of 0 ~ 2; Re is the integer of 0 ~ 2.
Preferably, the substituting group that described unitary aryl sulfonic acid is formed is formula 1, one or more in the substituting group shown in formula 5 ~ formula 17.
According to the present invention, the polysulfones shown in described formula I is actually a kind of random copolymers.
Present invention also offers 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 unitary aryl sulfonic acid and acid solvent containing quaternary ammonium group monomer, reacts 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 be formula II, formula III or the substituting group shown in 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 unitary aryl sulfonic acid and acid solvent add in the reaction flask of logical nitrogen, stirring reaction 10 ~ 48 hours under certain temperature of reaction, reacting liquor while hot is poured into suitable precipitation agent preferably in water, be settled out polymkeric substance, it is neutral for filtering and being repeatedly washed till filtrate with deionized water, by the aqueous sodium hydroxide solution soaking at room temperature of resulting polymers 1mol/L after 24 hours, namely vacuum-drying be able to OH
-the side chain that form exists contains the polymkeric substance of quaternary ammonium group, then will with OH
-namely the side chain that form exists is able to other negatively charged ion as Cl containing the polymkeric substance of quaternary ammonium group with corresponding acid such as the neutralizations such as HCl, HBr
-, Br
-the polymkeric substance of quaternary ammonium group is contained etc. the side chain of form existence.
According to the present invention, polyreaction is undertaken by the sulfone glycosylation reaction between aryl sulfonic acid group and aryl, schematically as follows:
According to the present invention, described binary aryl sulfonic acid monomer be preferably in the binary aryl sulfonic acid compound shown in formula 18 ~ formula 21 one or more, because described binary aryl sulfonic acid monomer contains the sulfonic acid functional group that two sulfone glycosylation reaction can occur, can represent with AA type monomer.
Formula 18
Formula 19
Formula 20
Formula 21
Wherein, M is H
+, the anionization salt of tertiary amine, monovalent base metal ion or quaternary ammonium salt cationic; Qd is the integer of 1 ~ 10; Qe is the integer of 1 ~ 3; W is the substituting group shown in formula a ~ formula i.
According to the present invention, described polyarylate be preferably in the polyarylate shown in formula 22 ~ formula 35 one or more, because described polyarylate is containing two or more phenyl ring composition, can be there is sulfone glycosylation reaction in two phenyl ring being wherein only in molecule two ends, can represent with BB type monomer.
Polyarylate shown in table 1 formula 22 ~ formula 35
Wherein, ra is the integer of 1 ~ 4; Rb is the integer of 1 ~ 9; Rc is the integer of 1 ~ 2; Re is the integer of 0 ~ 2.
According to the present invention, described unitary aryl sulfonic acid monomer be preferably in the unitary aryl sulfonic acid compound shown in formula 36 ~ formula 45 one or more, because sulfonic group and an aromatic functional groups of sulfone glycosylation reaction can occur containing one described unitary aryl sulfonic acid monomer simultaneously, can represent with AB type monomer.
Unitary aryl sulfonic acid compound shown in table 2 formula 36 ~ formula 45
Wherein, M is H
+, the anionization salt of tertiary amine, monovalent base metal ion or quaternary ammonium salt cationic; Ra is the integer of 1 ~ 4; Rb is the integer of 1 ~ 9; Rc is the integer of 1 ~ 2; Re is the integer of 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, wherein X
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 is obtained by reacting by sulfuryl.60 ~ 100 DEG C are preferably according to temperature of reaction of the present invention.
Described acid solvent is preferably the trifluoromethanesulfonic acid that purity is greater than 99%.
Present invention also offers a kind of anion-exchange membrane.According to the present invention, described anion-exchange membrane can use 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 owing to employing the polysulfones of the side chain shown in formula I containing quaternary ammonium group, and the quaternary ammonium group contained is more, improves 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.Present invention also avoids the shortcoming needing to use the chloromethyl ether reagent with carinogenicity in conventional anion exchange membrane preparation method.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these describe just as further illustrating the features and advantages of the present invention instead of the restriction to patent requirements of the present invention.
Further describe the present invention by the following examples.
Proton nmr spectra (
1h NMR) by AVANCE AV400, 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, 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 milliliters, and solution properties viscosity unit is dL/g.The anion conductivity of film measures at known four electrode models of the upper employing of PGSTAT302N type electrochemical workstation (Metrohm China Ltd.), and probe temperature is 25 DEG C, and relative humidity is 100%.
Embodiment 1:
Successively by 0.01 mole 2,2 ,-two (4-trimethylamine groups) butoxy-biphenyl dibromo, 1.00 moles 4,4 ,-diphenyl oxide disulfonic acid, 0.99 mole 2,2 ,-dimethoxy-biphenyl and 4 liters of trifluoromethanesulfonic acids add in the reaction flask of logical nitrogen, stirring reaction 48 hours at 60 DEG C, reacting liquor while hot is poured in a large amount of deionized water and obtain polymkeric substance precipitation, it is neutral for filtering and being repeatedly washed till filtrate with deionized water, by the aqueous sodium hydroxide solution soaking at room temperature of resulting polymers 1mol/L after 24 hours, room temperature in vacuo is drying to obtain with OH
-the side chain that form exists is containing the polymkeric substance of quaternary ammonium group.At 1310cm in infrared spectrum
-1with 1150cm
-1there is the stretching vibration peak of strong sulfuryl in left and right, shows the generation of sulfuryl polyreaction; Proton nmr spectra confirms the structure of resulting polymers and is conformed to expection by the ratio of integration structural unit more each than calculating gained,
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.
Wherein said 2,2 ,-two (4-trimethylamine groups) butoxy-biphenyl dibromo is prepared by the following method:
Successively by 1.0 moles 2, the acetonitrile of 2 ,-dihydroxybiphenyl, the salt of wormwood of 2.0 moles, the 4-brombutyl trimethylammonium bromide of 2.0 moles and 15 liters adds band reflux condensing tube and in 25 liters of reaction flasks of logical nitrogen, mechanic whirl-nett reaction 24 hours at 75 DEG C, filters, and underpressure distillation is except desolventizing, gained solid is through recrystallized from acetonitrile, filter, namely obtain 2 after vacuum-drying, 2 ,-two (4-trimethylamine groups) butoxy-biphenyl dibromo, referred to as 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) and, 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), confirm the structure of compound, reaction formula is as follows:
Embodiment 2:
Successively 0.01 mole is prepared by the method for embodiment 12, 2,-two (4-trimethylamine groups) butoxy-biphenyl dibromo, 1.00 moles 4, 4,-diphenyl oxide disulfonic acid, 0.99 mole 2, 2,-dimethoxy-biphenyl and 4 liters of trifluoromethanesulfonic acids add in the reaction flask of logical nitrogen, stirring reaction 24 hours at 80 DEG C, reacting liquor while hot is poured in a large amount of deionized water and obtain polymkeric substance precipitation, it is neutral for filtering and being repeatedly washed till filtrate with deionized water, by the aqueous sodium hydroxide solution soaking at room temperature of resulting polymers 1mol/L after 24 hours, room temperature in vacuo is drying to obtain with OH
-the side chain that form exists is containing the polymkeric substance of quaternary ammonium group.At 1310cm in infrared spectrum
-1with 1150cm
-1there is the stretching vibration peak of strong sulfuryl in left and right, shows the generation of sulfuryl polyreaction; Proton nmr spectra confirms the structure of resulting polymers and is conformed to expection by the ratio of integration structural unit more each than calculating gained,
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 is prepared by the method for embodiment 12, 2,-two (4-trimethylamine groups) butoxy-biphenyl dibromo, 1.00 moles 4, 4,-diphenyl oxide disulfonic acid, 0.99 mole 2, 2,-dimethoxy-biphenyl and 4 liters of trifluoromethanesulfonic acids add in the reaction flask of logical nitrogen, stirring reaction 10 hours at 100 DEG C, reacting liquor while hot is poured in a large amount of deionized water and obtain polymkeric substance precipitation, it is neutral for filtering and being repeatedly washed till filtrate with deionized water, by the aqueous sodium hydroxide solution soaking at room temperature of resulting polymers 1mol/L after 24 hours, room temperature in vacuo is drying to obtain with OH
-the side chain that form exists is containing the polymkeric substance of quaternary ammonium group.At 1310cm in infrared spectrum
-1with 1150cm
-1there is the stretching vibration peak of strong sulfuryl in left and right, shows the generation of sulfuryl polyreaction; Proton nmr spectra confirms the structure of resulting polymers and is conformed to expection by the ratio of integration structural unit more each than calculating gained,
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 by 0.50 mole be prepared by the method for embodiment 12, 2,-two (4-trimethylamine groups) butoxy-biphenyl dibromo, 1.00 moles 4, 4,-diphenyl oxide disulfonic acid, 0.50 mole 2, 2,-dimethoxy-biphenyl and 4 liters of trifluoromethanesulfonic acids add in the reaction flask of logical nitrogen, stirring reaction 24 hours at 100 DEG C, reacting liquor while hot is poured in a large amount of deionized water and obtain polymkeric substance precipitation, it is neutral for filtering and being repeatedly washed till filtrate with deionized water, by the aqueous sodium hydroxide solution soaking at room temperature of resulting polymers 1mol/L after 24 hours, room temperature in vacuo is drying to obtain with OH
-the side chain that form exists is containing the polymkeric substance of quaternary ammonium group.At 1310cm in infrared spectrum
-1with 1150cm
-1there is the stretching vibration peak of strong sulfuryl in left and right, shows the generation of sulfuryl polyreaction; Proton nmr spectra confirms the structure of resulting polymers and is conformed to expection by the ratio of integration structural unit more each than calculating gained,
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 by 0.01 mole be prepared by the method for embodiment 12, 2,-two (4-trimethylamine groups) butoxy-biphenyl dibromo, 0.50 mole 4, 4,-diphenyl oxide disulfonic acid, 0.49 mole 2, 2,-dimethoxy-biphenyl, the 4-phenoxy group Phenylsulfonic acid of 1.00 moles and 6 liters of trifluoromethanesulfonic acids add in the reaction flask of logical nitrogen, stirring reaction 24 hours at 100 DEG C, reacting liquor while hot is poured in a large amount of deionized water and obtain polymkeric substance precipitation, it is neutral for filtering and being repeatedly washed till filtrate with deionized water, by the aqueous sodium hydroxide solution soaking at room temperature of resulting polymers 1mol/L after 24 hours, room temperature in vacuo is drying to obtain with OH
-the side chain that form exists is containing the polymkeric substance of quaternary ammonium group.At 1310cm in infrared spectrum
-1with 1150cm
-1there is the stretching vibration peak of strong sulfuryl in left and right, shows the generation of sulfuryl polyreaction; Proton nmr spectra confirms the structure of resulting polymers and is conformed to expection by the ratio of integration structural unit more each than calculating gained,
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 of embodiment 4 is dissolved in 10 grams of dimethyl formamides, be mixed with homogeneous solution, be applied on clean horizontal glass plate, at 60 DEG C, solvent flashing is after about 10 hours, film is peeled off, and namely immersion obtained hydroxyl type proton exchange membrane after 24 hours in the sodium hydroxide solution of 1mol/L.Room temperature hydroxide ion specific conductivity is higher than 0.030S/cm, at 60 ° of C, soak after 60 days in the NaOH aqueous solution of 1mol/L, film still can keep snappiness simultaneously specific conductivity without obvious decline, show that this film has very large application prospect in alkaline anion-exchange membrane fuel cell.
More than apply specific case to set forth principle of the present invention and embodiment, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping.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 improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (4)
1. the side chain shown in a formula I is containing the polysulfones of quaternary ammonium group:
Wherein x=0.01 ~ 1.0; Y=0 ~ 0.99; X+y < 1; N is 1 ~ 400; Q is quaternary ammonium group; P is 3,4,5 or 6;
A
j1, A
j2be respectively in the substituting group shown in formula 1 ~ formula 4 one or more:
Wherein, W is the substituting group shown in formula a ~ formula i:
Qd is the integer of 1 ~ 10; Qe is the integer of 1 ~ 3; Qf is the integer of 2 ~ 12; Qg is the integer of 2 ~ 10;
A
k, A
ibe respectively in formula 1, the substituting group shown in formula 5 ~ formula 17 one or more:
Wherein, ra is the integer of 1 ~ 4; Rb is the integer of 1 ~ 9; Rc is the integer of 1 ~ 2; Rd is the integer of 0 ~ 2; Re is the integer of 0 ~ 2.
2. quaternary ammonium group according to claim 1 be formula II, formula III or the substituting group shown in formula IV:
Wherein T is the negatively charged ion of band-1 valence charge.
3. a side chain according to 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 quaternary ammonium group monomer and unitary aryl sulfonic acid monomer and acid solvent and add in the reaction flask of logical nitrogen the polysulfones being polymerized and obtaining the side chain shown in formula I and contain quaternary ammonium group.
4. an anion-exchange membrane, is characterized in that, uses the side chain described in claim 1 to be prepared from containing the polysulfones of quaternary ammonium group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310025315.7A CN103113588B (en) | 2013-01-23 | 2013-01-23 | A kind of side chain contains polysulfones of quaternary ammonium group and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310025315.7A CN103113588B (en) | 2013-01-23 | 2013-01-23 | A kind of side chain contains polysulfones of quaternary ammonium group and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103113588A CN103113588A (en) | 2013-05-22 |
| CN103113588B true CN103113588B (en) | 2015-08-12 |
Family
ID=48412012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310025315.7A Active CN103113588B (en) | 2013-01-23 | 2013-01-23 | A kind of side chain contains polysulfones of quaternary ammonium group and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103113588B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311857B (en) * | 2014-10-17 | 2017-07-28 | 中国科学技术大学 | A kind of preparation method of pair of quaternary ammonium side long chain type anion-exchange membrane |
| CN113471498B (en) * | 2021-07-07 | 2022-09-23 | 长春工业大学 | Multi-quaternary ammonium side long-chain type polysulfone anion-exchange membrane and preparation method thereof |
| 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 |
Citations (1)
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9193611B2 (en) * | 2011-04-29 | 2015-11-24 | Basf Se | 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 (1)
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| Novel aromatic proton-exchange polyelectrolytes via polyacylation of pre-sulfonated monomers;Zhenghui Zhang等;《J. Mater. Chem》;20121231;第22卷;13996–14000 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103113588A (en) | 2013-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103059300B (en) | Polypyrron with sulfated side chain and preparation method of polypyrron | |
| CN103214673B (en) | A kind of side chain contains polybenzimidazole of quaternary ammonium group and preparation method thereof | |
| CN105924587B (en) | A kind of cladodification type side chain polymer anion-exchange membrane and preparation method thereof | |
| CN102206386B (en) | Polymer anion-exchange membrane based on imidazole cation and preparation method thereof | |
| CN102049202B (en) | Anion exchange membrane containing fluoro-imidazolium salt polymer and preparation method thereof | |
| CN104829814A (en) | Polymer containing quaternized piperidine group, preparation method thereof, anion exchange membrane, and preparation method thereof | |
| CN110508167A (en) | A kind of preparation method of homogeneous-phase anion exchange film | |
| CN108794784B (en) | Anion exchange membrane | |
| CN108586745A (en) | A kind of anion-exchange membrane and preparation method thereof based on fluorination polybenzimidazoles | |
| CN113150344A (en) | Proton exchange membrane with main polymer chain of aromatic ring structure and preparation method thereof | |
| CN103113588B (en) | A kind of side chain contains polysulfones of quaternary ammonium group and preparation method thereof | |
| CN103012772B (en) | There are alkaline polyarylether ionomer material and the preparation and application thereof of micro phase separation structure | |
| CN102382293B (en) | Polymer anion exchange membrane and preparation method thereof | |
| CN112898539A (en) | Long-side-chain polyaromatic hydrocarbon isatin alkaline membrane for fuel cell and preparation method thereof | |
| CN103788365B (en) | A kind of polyarylether and anion-exchange membrane and preparation method thereof containing quaternary ammonium lateral group | |
| KR102022676B1 (en) | Anion Exchange Membrane with Large Size Ionic Channel for Non-aqueous Vanadium Redox Flow Battery and preparation method thereof | |
| CN103073719B (en) | Polybenzimidazole with sulfonated side chain and preparation method thereof | |
| CN103804631B (en) | Quaternised polyketide of side chain and preparation method thereof, anion-exchange membrane | |
| CN103709379A (en) | Aromatic sulfonated poly ketone and preparation method thereof | |
| CN105199124A (en) | Side-long-chain quaternization polyphenyl ether anion exchange membrane and preparation method thereof | |
| CN103044275B (en) | Qaternized aromatic compound, polyketone with quaternary aromatic groups and methods for preparing quaternized aromatic compound and polyketone with quaternary aromatic groups | |
| CN113307966A (en) | Copolymer containing tetramethyl piperidine oxide quaternary ammonium salt and preparation method and application thereof | |
| CN103087318B (en) | Polysulfones of a kind of pendant sulfonic acid and preparation method thereof | |
| CN104844785B (en) | A kind of cationic polymer, preparation method and anion-exchange membrane, preparation method | |
| CN115477720B (en) | Heterocyclic quaternary ammonium salt functionalized perfluorinated anion exchange resin, preparation method thereof and ion exchange membrane with heterocyclic quaternary ammonium salt functionalized perfluorinated anion exchange resin |
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 |