CN105085847B - A kind of sulfuryl amine aromatic polymer, its preparation method and application - Google Patents
A kind of sulfuryl amine aromatic polymer, its preparation method and application Download PDFInfo
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- CN105085847B CN105085847B CN201410224933.9A CN201410224933A CN105085847B CN 105085847 B CN105085847 B CN 105085847B CN 201410224933 A CN201410224933 A CN 201410224933A CN 105085847 B CN105085847 B CN 105085847B
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- sulfuryl amine
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- 229920000642 polymer Polymers 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims description 16
- 125000003118 aryl group Chemical group 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000000446 fuel Substances 0.000 claims abstract description 15
- 125000003277 amino group Chemical group 0.000 claims abstract description 14
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract description 14
- 238000000909 electrodialysis Methods 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000011973 solid acid Substances 0.000 claims abstract description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 39
- 239000011347 resin Substances 0.000 claims description 38
- 229920005989 resin Polymers 0.000 claims description 38
- -1 sulfuryl amine Chemical class 0.000 claims description 34
- 239000003153 chemical reaction reagent Substances 0.000 claims description 30
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 21
- 229920002530 polyetherether ketone Polymers 0.000 claims description 21
- 229910021529 ammonia Inorganic materials 0.000 claims description 19
- 229920002492 poly(sulfone) Polymers 0.000 claims description 17
- 238000005660 chlorination reaction Methods 0.000 claims description 16
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 8
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 5
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 5
- 150000003457 sulfones Chemical class 0.000 claims description 5
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000004155 Chlorine dioxide Substances 0.000 claims description 2
- GQUXCEBYXMIFRE-UHFFFAOYSA-N ClS(=O)(=O)O.C[SiH](C)C Chemical compound ClS(=O)(=O)O.C[SiH](C)C GQUXCEBYXMIFRE-UHFFFAOYSA-N 0.000 claims description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 2
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 2
- 229920002480 polybenzimidazole Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 2
- 230000003252 repetitive effect Effects 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims 1
- 229920002223 polystyrene Polymers 0.000 claims 1
- 229940124530 sulfonamide Drugs 0.000 claims 1
- 150000003456 sulfonamides Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 239000010409 thin film Substances 0.000 abstract description 4
- 150000001263 acyl chlorides Chemical group 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 2
- BZCGWAXQDLXLQM-UHFFFAOYSA-N phosphoryl trichloride Chemical class ClP(Cl)(Cl)=O.ClP(Cl)(Cl)=O BZCGWAXQDLXLQM-UHFFFAOYSA-N 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000012528 membrane Substances 0.000 description 20
- 239000010408 film Substances 0.000 description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000006277 sulfonation reaction Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229920005547 polycyclic aromatic hydrocarbon Polymers 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 230000009435 amidation Effects 0.000 description 4
- 238000007112 amidation reaction Methods 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- BWQOPMJTQPWHOZ-UHFFFAOYSA-N (2,3-difluorophenyl)-phenylmethanone Chemical compound FC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1F BWQOPMJTQPWHOZ-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010345 tape casting Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 230000006103 sulfonylation Effects 0.000 description 2
- 238000005694 sulfonylation reaction Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical group [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910006074 SO2NH2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000011938 amidation process Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 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
The present invention provides a kind of sulfuryl amine aromatic polymer.The polymer contains sulfuryl amine group using aromatic polymer as main chain in side chain.Due to sulfuryl amine group have hydrophobicity, offer proton can be provided at high temperature, and cross-linking reaction can be carried out with groups such as acyl chlorides, sulfonic acid chloride, phosphoryl chloride phosphorus oxychlorides, therefore with good barrier, electric conductivity and mechanical strength etc. when the sulfuryl amine aromatic polymer is as thin-film material, have a good application prospect in multiple fields such as fuel cell, flow battery, electrodialysis and solid acid catalysts.
Description
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of sulfuryl amine aromatic polymer and its preparation
Membrane can be made in method, the resin, applied to flow battery, methanol fuel cell, hydrogen fuel cell, electrodialysis, lithium from
In the multiple fields such as sub- secondary cell.
Background technology
Ion exchange membrane material is as a kind of widely applied high performance material, in fields such as chlor-alkali, new energy, water process
Key player is play, application range is more and more wider, and demand is increasing.Homogeneous proton exchange membrane material is uniform because of its film forming
Fine and close, the advantages that conductivity is high, isolation performance is good, in occupation of more and more important position in amberplex.
The widely used homogeneous ion-exchange membrane of people has two kinds at present, and a kind of is the nafion films using E.I.Du Pont Company as generation
The perfluoro sulfonic acid membrane of table, another is the non-fluorine ion exchange membrane using sulfonated poly aromatic race amberplex as representative.
Perfluoro sulfonic acid membrane has high conductivity and chemical stability, and application range is most wide in actual production.But its is soft
The backbone structure of property makes its permeability higher, since the leakage of electrolyte or fuel causes battery efficiency in new energy battery
Reduce；And perfluorosulfonic acid proton exchange film cost is very high, its application in a fuel cell is caused to be restricted.
The sulfonate resin of fragrant backbone structure makes methanol permeability more much lower than perfluorinated sulfonic acid because of its stiff backbone structure.
But traditional aromatic series amberplex is come by aromatic resin sulfonation mostly, this resin is because its conductive group
For acid weaker benzene sulfonic acid root, causing it, ionic conductivity is weaker under low sulfonation degree, and membrane surface resistance is big.And pass through raising
Sulfonation degree improves electric conductivity, but the enhancing of ionic membrane water imbibition, chemical stability can be caused to be deteriorated, swelling ratio become larger it is even molten
Solution is in water.
The content of the invention
The present invention provides a kind of sulfuryl amine aromatic polymer, which has mechanical strength height, barrier property
The advantages that strong, be expected to be applied to flow battery, methanol fuel cell, hydrogen fuel cell, electrodialysis, lithium rechargeable battery etc.
Field.
The technical scheme is that：A kind of sulfuryl amine aromatic polymer, is the side using aromatic polymer as main chain
Chain contains the polymer of sulfuryl amine group, its general structure is as follows：
Wherein, it is 1 to 1000 integer that Ar, which refers to aromatic group and its derivatives group, repetitive unit m,；M refers to H+Or
Person's metal ion.
The polyaromatic polymer include but not limited to poly- biphenyl, polysulfones, polyether sulfone, polybenzimidazoles, polyether-ketone,
Polyether-ether-ketone, polyphenylene oxide, polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide sulfone, poly aromatic acid amides, poly aromatic acid imide, polyphenyl second
Any one in alkene, styrol copolymer etc., and the derivative of any one in aforementioned polymer.
The metal ion includes but not limited to H+、Li+、Na+、K+、Ca+、Mg2+、Fe3+、Cu2+Deng.
Preferably, in the sulfuryl amine aromatic polymer, the molar content of sulfuryl amine group account for polymer always from
The 0.001%-100% of subbase group molar content.
Present invention also offers a kind of synthetic method of the sulfuryl amine polyaromatic polymer, include the following steps：
Step 1：Aromatic polymer and sulfonated reagent, chlorination reagent are subjected to sulfonating reaction and chlorination reaction, obtain sulphur
Chloride aromatic polymer；Alternatively, the fragrant monomer containing sulfonic acid group is carried out polymerisation, sulfonated aromatic polymerization is obtained
Thing, then carries out chlorination reaction by aromatic sulfonated polymer and chlorination reagent, obtains sulfonating chlorinating aromatic polymer；
Step 2：Sulfonating chlorinating aromatic polymer is subjected to amidatioon processing, obtains sulfuryl amine polyaromatic resins.
In the step 1, sulfonating reaction is divided into situations below with chlorination reaction according to the difference of reaction reagent：
(1) when sulfonated reagent is different from chlorination reagent, aromatic polymer and sulfonated reagent is first subjected to sulfonating reaction, obtained
To aromatic sulfonated polymer, chlorination reaction then is carried out with chlorination reagent, obtains sulfonating chlorinating aromatic polymer；
(2) when sulfonated reagent and chlorination reagent are same reagent, by aromatic polymer and the sulfonated reagent or/and chlorination
Reagent carries out sulfonating reaction, chlorination reaction, obtains sulfonating chlorinating aromatic polymer.
In the step 1, sulfonated reagent includes but not limited to the concentrated sulfuric acid, oleum, sulfur trioxide, chlorosulfonic acid, sulphur
Mixture more than one or both of acyl chlorides, trimethyl silane chlorosulfonic acid, sulfamic acid etc..Preferably, described is dense
The mass fraction of sulfuric acid is 50%-100%.
In the step 1, chlorination reagent include but not limited to chlorine, phosgene, chlorine dioxide, thionyl chloride, dichloride sulfone,
One or more kinds of mixtures in chlorosulfonic acid, phosphorus oxychloride, phosphorus pentachloride, phosphorus trichloride etc..
In the step 1, in aromatic sulfonated polymer, the molar ratio of benzene ring structure and sulfonic acid group is preferably 1:4
To 1:0.001；In sulfonating chlorinating aromatic polymer, the molar ratio of benzene ring structure and sulfonic acid chloride group is preferably 1:4 to 1:
0.001。
In the step 2, amination treatment refers at a suitable temperature using liquefied ammonia, ammonia, the mixing comprising ammonia
Gas or solution comprising ammonia etc. handle the sulfonating chlorinating aromatic polymer, make sulfonic acid chloride group therein
It is converted into sulfuryl amine group.
In the step 2, amination treatment temperature is preferably -180 DEG C -300 DEG C.
In the step 2, the solution of ammonia can be that ammonia dissolving obtains in a solvent or other are changed in a solvent
Compound is obtained by chemically reacting generation ammonia.
In the step 2, sulfonating chlorinating aromatic polymer carry out after amidatioon processing obtained sulfuryl amine group for-
SO2NH2When, H can be carried out as needed+Exchange, it is-SO to obtain sulfuryl amine group2The aromatic polymer of NHM, M refer to metal
Ion.
In conclusion sulfuryl amine polyaromatic resins of the present invention, when in use, can be used alone, also may be used
To be used in mixed way with other resins or additive.
In conclusion the present invention provides a kind of sulfuryl amine aromatic polymer, the polymer is due in fragrant adoption
Contain sulphonyl amine side chain in compound backbone structure, has the following advantages：
(1) because sulfuryl amine group has hydrophobicity, therefore the swelling of the thin-film material of polymer preparation in water is utilized
Degree declines to a great extent, while hydrophilic water and metal ion group, free radical etc. are difficult to permeate, therefore the side chain is in protection main chain
While, the barrier of thin-film material is also greatly enhanced, it is possible to applied to fuel cell, flow battery and electric osmose
In the devices such as analysis, to solve the problems, such as material in membrane both sides Cross slot interference；
(2) because sulfonamide structure can dissociate offer proton, therefore the film prepared using the polymer at high temperature
Material still has the electrical conductivity relative to sulfonic acid higher under high temperature low-moisture conditions, so especially suitable for high temperature proton exchange
Membrane cell field；
(3) sulfuryl amine group and then can produce cross-linked structure, therefore with the radical reaction such as acyl chlorides, sulfonic acid chloride, phosphoryl chloride phosphorus oxychloride
The thin-film material prepared using the polymer is easy to improve film strength, resistance to swelling and inoxidizability；
(4) preparation method is simple, can be expanded on the basis of existing sulfate resin production line, the three wastes of generation compared with
Few, composition is simple, and processing is convenient；
(5) the aromatic polymer structural controllability described in is good, can put into ratio by adjusting technological process and material,
Ion exchange capacity, ionic group species and the ratio of polymer are controlled, so as to control the final performance of polymeric material；
(6) the aromatic polymer dissolubility described in is good, can be well dissolved in general intensive polar solvent such as DMSO,
In DMF, DMAc etc., and processability and film forming are good.
In addition, experiments verify that, the ion exchange capacity of sulfuryl amine aromatic polymer of the invention can be controlled in 0-
5meq/g, stable chemical performance, favorable solubility, film forming is good, cross-linking, therefore in fuel cell, flow battery, electric osmose
The multiple fields such as analysis and solid acid catalyst have a good application prospect.
Brief description of the drawings
Fig. 1 is the nuclear magnetic resonance spectroscopy of obtained sulfuryl amine polyether-ether-ketone in the embodiment of the present invention 1；
Fig. 2 is that the Nafion212 films of obtained proton exchange membrane and E.I.Du Pont Company exist in the embodiment of the present invention 1,2 and 3
Proton conductivity under 100% damp condition compares figure.
Embodiment
The present invention is described in further detail below in conjunction with attached drawing embodiment, it should be pointed out that implementation as described below
Example is intended to be easy to the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1：
In the present embodiment, sulfuryl amine polyaromatic polymer is using polyether-ether-ketone as main chain, and side chain is benzene sulfonamido
The polymer of group.For the polymer using polyether-ether-ketone as raw material, sulfuric acid is sulfonated reagent, and thionyl chloride is chloride reagent, liquefied ammonia
For amidation reagent, it is made by reactions such as chloride, amidatioons.
Specific preparation method includes the following steps：
Step 1：In the three-necked flask of 50ml, it is 98% concentrated sulfuric acid to add 20ml mass percent concentrations, is then stirred
1g polyether-ether-ketone resin powder is added, is warming up to 40 DEG C, sulfonating reaction 12h；After reaction, reaction product is poured into frozen water
In, resin is separated out, is fully washed with deionized water, obtains the polyether-ether-ketone resin of sulfonation.
Step 2：The polyether-ether-ketone resin for the sulfonation that step 1 is obtained is added in the three-necked flask of 50ml, adds 20ml's
Thionyl chloride, reflux react 24h after resin dissolving；After reaction, reaction product is poured into 200ml mixture of ice and water,
The resin that filtering, washing separate out, after freeze-drying, obtains the polyether-ether-ketone resin of sulfonating chlorinating.
Step 3：The polyether-ether-ketone resin for the sulfonating chlorinating that step 2 is obtained puts into tri- mouthfuls of the 50ml equipped with 20ml liquefied ammonia
In bottle, 5h is reacted at -80 DEG C, is then slowly heated up, treat that liquefied ammonia volatilizees, washing removes ammonium chloride, and sulfuryl amine is obtained after drying
Polyetheretherketonepolymer polymer.
The nuclear magnetic resonance spectroscopy of the polyetheretherketonepolymer polymer of above-mentioned sulfuryl amine is as shown in Figure 1, there it can be seen that the tree
Sulfuryl amine group is substantially contained in the structure of fat.
Sulfuryl amine polyetheretherketonepolymer polymer obtained above is formed a film using the tape casting, obtains sulfuryl amine polyether-ether-ketone
Proton exchange membrane, it is specific as follows：
Sulfuryl amine polyetheretherketonepolymer polymer is dissolved in DMSO, 10% solution is configured to, is cast on a glass,
120 DEG C of dry 24h, 24h is exchanged in the hydrochloric acid of 2.5N, then with deionized water washes clean, obtains sulfuryl amine after taking off
Polyetheretherketoneproton proton exchange film A1, it is preserved in deionized water.
After measured, proton exchange membrane A1 made from the above method, IEC 1.4mmol/g, moisture content 11.2% are linear molten
Swollen rate 0.04%, tensile strength 80.5MPa, elongation at break 95.6%, proton conductivity is shown in Fig. 2, shows the proton exchange membrane
With good conductivity, the conductivity of the nafion211 films of its conductivity and E.I.Du Pont Company has same order.
Embodiment 2：
In the present embodiment, sulfuryl amine polyaromatic polymer is using polysulfones as main chain, and side chain is benzsulfamide group
Polymer.The polymer is using polysulfones as raw material, and chlorosulfonic acid is sulfonated reagent and chloride reagent, and ammonia is amidation reagent, leads to
The reactions such as chloride, amidatioon are crossed to be made.
Specific preparation method includes the following steps：
Step 1：In the three-necked flask of 50ml, 20ml dichloromethane is added, then stirring adds 1g polysulfone resin particles,
After to be dissolved, the 3ml chlorosulfonic acids being dissolved in 10ml dichloromethane are slowly instilled, react 3h under ice-water bath；After reaction,
Reaction product is poured into frozen water, resin is separated out, is fully washed with deionized water, is freeze-dried, obtains sulfonating chlorinating polysulfones tree
Fat.
Step 2：Step 1 is obtained sulfonating chlorinating polysulfone resin to put into equipped with 50ml there-necked flasks, is passed through ammonia at room temperature
Gas, after reacting 5h, treats that ammonia fully volatilizees, and takes out resin, and washing removes ammonium chloride, sulfuryl amine polysulfones tree is obtained after drying
Fat.
The nuclear magnetic resonance spectroscopy of above-mentioned sulfuryl amine polysulfone polymer is similar to Figure 1, there it can be seen that the resin
Sulfuryl amine group is substantially contained in structure.
Sulfuryl amine polysulfone polymer obtained above is formed a film using the tape casting, obtains sulfuryl amine polyether-ether-ketone proton
Exchange membrane, it is specific as follows：
Sulfuryl amine polysulfone polymer is dissolved in DMSO, 10% solution is configured to, is cast on a glass, 120
DEG C dry 24h, 24h is exchanged in the hydrochloric acid of 2.5N, then with deionized water washes clean, obtains sulfuryl amine polysulfones after taking off
Proton exchange membrane A2, it is preserved in deionized water.
After measured, proton exchange membrane A2 made from the above method, IEC 1.45mmol/g, moisture content 20.3% are linear molten
Swollen rate 0.15%, tensile strength 30.5MPa, elongation at break 25.6%, proton conductivity is shown in Fig. 2, shows the proton exchange membrane
With good conductivity, its conductivity is with the conductivity of the nafion211 films of E.I.Du Pont Company under the identical order of magnitude.
Embodiment 3：
In the present embodiment, sulfuryl amine polyaromatic polymer is using polyether-ether-ketone as main chain, and side chain is benzene sulfonamido
The polymer of group.For the polymer using polyether-ether-ketone as raw material, oleum is sulfonated reagent, and phosphorus oxychloride is chloride reagent,
Ammonium hydroxide is amidation reagent, is made by reactions such as sulfonation, chloride, amidatioons.
Specific preparation method includes the following steps：
Step 1：In the three-necked flask of 50ml, it is 98% concentrated sulfuric acid to add 20ml mass percent concentrations, is then stirred
1g polyether-ether-ketone resin powder is added, 5ml oleums are slowly added dropwise, reacts 2h；Reaction product is poured into frozen water, separates out tree
Fat, is fully washed with deionized water, obtains the polyether-ether-ketone resin of sulfonation.
Step 2：The polyether-ether-ketone resin for the sulfonation that step 1 is obtained is added in the three-necked flask of 50ml, adds 20ml's
Phosphorus oxychloride, reflux react 24h after resin dissolving；After reaction, reaction product is poured into 200ml mixture of ice and water,
The resin that filtering, washing separate out, after freeze-drying, obtains the polyether-ether-ketone resin of sulfonating chlorinating.
Step 3：The polyether-ether-ketone resin for the sulfonating chlorinating that step 2 is obtained is put into equipped with 20ml mass fractions 15%
In the 50ml there-necked flasks of ammonium hydroxide, 24h is reacted at room temperature, and after filtering, residue washing removes ammonium chloride, and sulfuryl amine is obtained after drying
Polyetheretherketonepolymer polymer.
The nuclear magnetic resonance spectroscopy of the polyetheretherketonepolymer polymer of above-mentioned sulfuryl amine is similar to Figure 1, there it can be seen that should
Sulfuryl amine group is substantially contained in the structure of resin.
Sulfuryl amine polyetheretherketonepolymer polymer obtained above is formed a film using the tape casting, obtains sulfuryl amine polyether-ether-ketone
Proton exchange membrane, it is specific as follows：
Sulfuryl amine polyetheretherketonepolymer polymer is dissolved in DMSO, 10% solution is configured to, is cast on a glass,
120 DEG C of dry 24h, 24h is exchanged in the hydrochloric acid of 2.5N, then with deionized water washes clean, obtains sulfuryl amine after taking off
Polyetheretherketoneproton proton exchange film A3, it is preserved in deionized water.
After measured, proton exchange membrane A3 made from the above method, IEC 1.6mmol/g, moisture content 30.5% are linear molten
Swollen rate 0.15%, tensile strength 62.5MPa, elongation at break 65.3%, proton conductivity is shown in Fig. 2, show the proton exchange membrane
With good conductivity, the conductivity of the nafion211 films of its conductivity and E.I.Du Pont Company has same order.
Embodiment 4：
In the present embodiment, sulfuryl amine polyaromatic polymer is using polyether-ether-ketone as main chain, and side chain is benzene sulfonamido
The polymer of group.The polymer is using difluoro benzophenone, sulfonation difluoro benzophenone and hydroquinone as raw material, using thionyl chloride as acyl
Chlorination reagent, liquefied ammonia are amidation reagent, are made by polymerisation, chloride, amidation process.
Specific preparation method includes the following steps：
Step 1：In the three-necked flask of 50ml, 20mlDMF is added, then stirring adds 0.625g sulfonation difluorodiphenyls
Ketone, 0.107g difluoro benzophenones, 0.269g hydroquinones and 1.35g potassium carbonate, after 140 DEG C are reacted 4h, are warming up to 200 DEG C of reactions
24h；Reaction product is poured into frozen water after reaction, resin is separated out, is fully washed with deionized water, is freeze-dried, obtains
Sulfonylation polysulfone resin.
Step 2：The polysulfone resin for the sulfonylation that step 1 is obtained is added in the three-necked flask of 50ml, adds the chlorine of 20ml
Change sulfoxide, reflux reacts 24h after resin dissolving；After reaction, reaction product is poured into 200ml mixture of ice and water, mistake
The resin that filter, washing separate out, after freeze-drying, obtains the polysulfone resin of sulfonating chlorinating.
Step 3：The polysulfone resin for the sulfonating chlorinating that step 2 is obtained puts into the 50ml there-necked flasks equipped with 20ml liquefied ammonia
In, 5h is reacted at -80 DEG C, is slowly heated up, treats that liquefied ammonia volatilizees, washing removes ammonium chloride, and the polysulfones of sulfuryl amine is obtained after drying
Polymer.
The nuclear magnetic resonance spectroscopy of the polyetheretherketonepolymer polymer of above-mentioned sulfuryl amine is similar to Figure 1, there it can be seen that should
Sulfuryl amine group is substantially contained in the structure of resin.
Identical with above-described embodiment 1-3, after measured, proton exchange membrane A4 obtained above has good tensile strength,
Good fracture strength, relatively low linear swelling ratio, and good conductivity.
Technical scheme and beneficial effect is described in detail in embodiment described above, it should be understood that
The foregoing is merely the specific embodiment of the present invention, it is not intended to limit the invention, it is all to be done in the spirit of the present invention
Any modification, supplementary, and equivalent replacement etc., should all be included in the protection scope of the present invention.
Claims (6)
- A kind of 1. sulfonamide being applied in fuel cell, flow battery, electrodialysis, lithium battery and solid acid catalyst field To change the preparation method of aromatic polymer, be using aromatic polymer as main chain, side chain contains the polymer of sulfuryl amine group, its General structure is as follows：Wherein, it is 1 to 1000 integer that Ar, which refers to aromatic group and its derivatives group, repetitive unit m,；M refers to H+；The preparation method of the sulfuryl amine aromatic polymer includes the following steps：Step 1：Aromatic polymer is mixed with sulfonated reagent, chlorination reagent, sulfonating reaction and chlorination reaction is carried out, obtains sulphur Chloride aromatic polymer；Step 2：Sulfonating chlorinating aromatic polymer is subjected to amidatioon processing, obtains sulfuryl amine polyaromatic resins.
- 2. it is applied to fuel cell, flow battery, electrodialysis, lithium battery and solid acid catalyst as claimed in claim 1 The preparation method of sulfuryl amine aromatic polymer in field, it is characterized in that：The aromatic polymer include poly- biphenyl, Polysulfones, polyether sulfone, polybenzimidazoles, polyether-ketone, polyether-ether-ketone, polyphenylene oxide, polyphenylene sulfide, polyphenylene sulfide sulfone, poly aromatic acid amides, Poly aromatic acid imide, any one in polystyrene, styrol copolymer, and the derivative of any one in aforementioned polymer Thing.
- 3. it is applied to fuel cell, flow battery, electrodialysis, lithium battery and solid acid catalyst as claimed in claim 1 The preparation method of sulfuryl amine aromatic polymer in field, it is characterized in that：In the step 1, sulfonated reagent includes dense One or both of sulfuric acid, oleum, sulfur trioxide, chlorosulfonic acid, chlorosulfuric acid, trimethyl silane chlorosulfonic acid, sulfamic acid Mixture above.
- 4. it is applied to fuel cell, flow battery, electrodialysis, lithium battery and solid acid catalyst as claimed in claim 1 The preparation method of sulfuryl amine aromatic polymer in field, it is characterized in that：In the step 1, chlorination reagent include chlorine, Phosgene, chlorine dioxide, thionyl chloride, dichloride sulfone, chlorosulfonic acid, phosphorus oxychloride, phosphorus pentachloride, one kind in phosphorus trichloride or Two or more mixtures.
- 5. it is applied to fuel cell, flow battery, electrodialysis, lithium battery and solid acid catalyst as claimed in claim 1 The preparation method of sulfuryl amine aromatic polymer in field, it is characterized in that：Using liquefied ammonia, ammonia in the amidatioon processing Gas, the mixed gas comprising ammonia, or the solution comprising ammonia handle the sulfonating chlorinating aromatic polymer, make Sulfonic acid chloride group therein is converted into sulfuryl amine group.
- 6. it is applied to fuel cell, flow battery, electrodialysis, lithium battery and solid acid catalyst as claimed in claim 1 The preparation method of sulfuryl amine aromatic polymer in field, it is characterized in that：In the step 2, amidatioon treatment temperature For -180 DEG C -300 DEG C.
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| FR3024146B1 (en) * | 2014-07-23 | 2018-02-16 | Cdp Innovation | NOVEL POLYMERS CONTAINING BIS (SULFONYL) GRAFTED LITHIUM OR SODIUM SALTS, PROCESSES FOR THEIR PREPARATION AND THEIR USE AS ELECTROLYTES FOR BATTERIES |
| FR3024145B1 (en) * | 2014-07-23 | 2018-03-16 | Cdp Innovation | NOVEL POLYMERS CONTAINING SULFONAMIDE LITHIUM OR SODIUM SALTS, PROCESSES FOR THEIR PREPARATION AND USES THEREOF AS ELECTROLYTES FOR BATTERIES |
| CN104710639B (en) * | 2015-03-03 | 2017-12-01 | 上海交通大学 | A kind of preparation method based on perfluor sulfonyl amine anion-exchange membrane |
| CN105633444B (en) * | 2016-03-28 | 2018-01-05 | 西华大学 | A kind of polyethers ketone amberplex and preparation method and application |
| CN108155414B (en) * | 2016-12-06 | 2019-07-16 | 中国科学院宁波材料技术与工程研究所 | Fluoropolymer lithium ion conductor, preparation method and the application of self-plasticization |
| CN108017927A (en) * | 2017-12-04 | 2018-05-11 | 南通龙翔新材料科技股份有限公司 | A kind of organic pigment sulfonyl chloride derivatives preparation method |
| CN108258170B (en) * | 2017-12-05 | 2021-07-16 | 宜宾天原集团股份有限公司 | Preparation method of polyether-ether-ketone-based lithium battery diaphragm |
| CN109589809B (en) * | 2018-12-27 | 2021-06-29 | 山东天维膜技术有限公司 | Preparation method of cation exchange membrane with multiple cross-linked structure |
| CN110003412B (en) * | 2019-04-15 | 2020-07-28 | 西南交通大学 | Method for carrying out surface modification on polyether-ether-ketone, polyether-ether-ketone material and application thereof |
| CN112029103A (en) * | 2020-08-05 | 2020-12-04 | 杭州晟聚环保科技有限公司 | Preparation of acid-base ion modified polymer and porous membrane thereof |
| CN114614058B (en) * | 2020-12-04 | 2024-05-07 | 中国石油化工股份有限公司 | Thin-layer composite proton exchange membrane and preparation method and application thereof |
| CN113363011B (en) * | 2021-04-30 | 2022-08-19 | 北京纳米能源与系统研究所 | Solvent-free polymer ion conductor and preparation method and application thereof |
| CN115010973B (en) * | 2022-07-01 | 2023-06-02 | 盐城师范学院 | Polymer electrolyte membrane and preparation and application thereof |
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