CN106279693B - 一种侧链含苯并咪唑聚芳醚酮/砜及其制备方法与应用 - Google Patents
一种侧链含苯并咪唑聚芳醚酮/砜及其制备方法与应用 Download PDFInfo
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- CN106279693B CN106279693B CN201610782617.2A CN201610782617A CN106279693B CN 106279693 B CN106279693 B CN 106279693B CN 201610782617 A CN201610782617 A CN 201610782617A CN 106279693 B CN106279693 B CN 106279693B
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- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229920006260 polyaryletherketone Polymers 0.000 title claims abstract description 30
- 150000003457 sulfones Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 239000000178 monomer Substances 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 21
- 229910052731 fluorine Inorganic materials 0.000 claims description 21
- 239000011737 fluorine Substances 0.000 claims description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 238000001556 precipitation Methods 0.000 claims description 18
- -1 4,4 '-methylene Chemical group 0.000 claims description 17
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 17
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 229930185605 Bisphenol Natural products 0.000 claims description 10
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003495 polar organic solvent Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical group C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 5
- 229940106691 bisphenol a Drugs 0.000 claims description 5
- 125000005594 diketone group Chemical group 0.000 claims description 4
- 229920006254 polymer film Polymers 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229940113088 dimethylacetamide Drugs 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- KDFGCKXYSYXQTO-UHFFFAOYSA-N phenol 1,2,3,4-tetramethyl-5-phenylbenzene Chemical compound C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.CC=1C(=C(C(=C(C1)C1=CC=CC=C1)C)C)C KDFGCKXYSYXQTO-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 1
- GZSRSEKMHAYHNS-UHFFFAOYSA-N C1(=CC=CC=C1)S(=O)(=O)C1=CC=CC=C1.[F] Chemical compound C1(=CC=CC=C1)S(=O)(=O)C1=CC=CC=C1.[F] GZSRSEKMHAYHNS-UHFFFAOYSA-N 0.000 claims 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical class C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 238000000643 oven drying Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 229920002480 polybenzimidazole Polymers 0.000 abstract description 3
- 239000004693 Polybenzimidazole Substances 0.000 abstract 1
- 230000009878 intermolecular interaction Effects 0.000 abstract 1
- 230000008863 intramolecular interaction Effects 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 235000019441 ethanol Nutrition 0.000 description 12
- 239000012528 membrane Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical class CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 0 C*1Oc(ccc(Clc(cc2)cc(C3Nc4ccccc4N3)c2Oc2ccc(*c(cc3)ccc3OCCC*C(C)(C)C)cc2)c2)c2-c2nc(C=CCC3)c3[n]2C1 Chemical compound C*1Oc(ccc(Clc(cc2)cc(C3Nc4ccccc4N3)c2Oc2ccc(*c(cc3)ccc3OCCC*C(C)(C)C)cc2)c2)c2-c2nc(C=CCC3)c3[n]2C1 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical class CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000090 poly(aryl ether) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4056—(I) or (II) containing sulfur
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
- C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
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- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Engineering & Computer Science (AREA)
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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyethers (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
本发明提供了一种侧链含苯并咪唑聚芳醚酮/砜及其制备方法与应用，所述的侧链含苯并咪唑聚芳醚酮/砜为主链由式(I)所示的重复结构单元构成的分子量在7000～12000的磺化聚合物，或者为主链由式(II)所示的重复结构单元构成的分子量在7000～12000的非磺化聚合物；本发明利用一步合成法制备得到侧链含苯并咪唑聚芳醚酮/砜聚合物，不仅简化了合成步骤，而且苯并咪唑与磺酸基团分子内和分子间的相互作用解决了高磺化度聚合物溶于水、聚苯并咪唑溶解性差等问题，可以进一步改善聚合物的综合性能；
Description
(一)技术领域
本发明涉及一类高分子材料及其制备方法与应用，尤其是主链含醚酮或者醚砜结构，侧链含苯并咪唑及磺酸根基团的聚合物及其合成方法与应用。
(二)背景技术
聚芳醚、聚酰亚胺、聚苯并咪唑等芳香型聚合物以其优异的热化学稳定性和机械性能以及具有良好的抗水解和耐腐蚀等性能广泛应用在航空航天等领域，而且它们的磺化产物作为质子交换膜材料亦得到广泛研究。
为了获得高的质子传导率，需要提高聚合物的磺化度。磺化聚芳醚类聚合物主要通过后磺化和直接共聚的方法得到。后磺化法是用适当的磺化试剂对已合成的聚合物进行磺化，从而将磺酸基团引入到聚合物中；直接共聚法是指先合成含有磺酸基团的磺化单体再进行聚合。与聚合物的后磺化改性相比，采用磺化单体直接聚合成磺化聚合物的方法，便于从分子设计上控制聚合反应。Ueda等人(J.Polym.Sci.,1993,31(4):853～858.)首先制备了带磺酸钠侧基的磺化4,4’-二氯二苯砜单体，并通过直接聚合的方法与双酚A缩聚合成了含有磺酸钠基团的磺化聚芳醚砜共聚物，通过调整非磺化单体与磺化单体的比例，进而控制聚合物中磺酸基团的含量，从而控制磺化度，而且避免了后磺化引起的降解、交联等其他副反应。
但是高磺化度的磺化聚芳醚类材料遇水严重溶胀，使得材料的机械性能降低，抗氧化稳定性降低，大大降低了膜材料的寿命。为了克服这一问题，我们希望引入苯并咪唑基团，利用其与磺酸基之间的协同作用，可以提高膜材料的热稳定性和化学稳定性。Y.Fu等(Electrochemistry Communication.，2006,8(8)：1386～1390)报导了含苯并咪唑基团的聚合物与磺化聚醚醚酮共混膜，由于苯并咪唑与磺酸基之间的相互作用，可以不依赖水的情况下传导质子，在高温或者低湿度时仍具有较好的质子传导能力。另外那辉等人(CN101357984A)也公开了利用含有羧基的磺化聚芳醚酮与邻苯二胺的反应，合成了侧链中同时含有磺酸基和苯并咪唑基团的聚芳醚酮类聚合物。上述两种方法都是以含羧基的磺化聚芳醚酮作中间聚合物接上咪唑进行改性。本发明旨在以4,4’-亚甲基-2,2’-苯并咪唑双酚等单体为原料，利用一步合成法直接缩聚得到磺化度不同的侧链含苯并咪唑聚芳醚酮/砜。
(三)发明内容
本发明的目的是从分子结构设计出发，提供一种侧链含苯并咪唑聚芳醚酮/砜及其制备方法与应用，该聚合物的侧链中可同时含有磺酸基和苯并咪唑基团，利用两者间的离子交联结构，可以有效提高材料的热稳定性、机械性能、抗氧化稳定性。
本发明可以通过改变单体结构及其比例，制备出不同磺化度、不同苯并咪唑含量的聚芳醚酮/砜聚合物。
为实现上述目的，本发明采用如下技术方案：
一种侧链含苯并咪唑聚芳醚酮/砜，其为主链由式(I)所示的重复结构单元构成的分子量在7000～12000的磺化聚合物，或者为主链由式(II)所示的重复结构单元构成的分子量在7000～12000的非磺化聚合物：
式(I)中：
m＝0或1，n＝0或1，且m≤n；
式(I)或(II)中：
A1、A3各自独立为：
A2为下列之一：
本发明还提供了所述侧链含苯并咪唑聚芳醚酮/砜的制备方法，所述的制备方法为：
所述磺化聚合物的制备：
惰性气体(如氮气)保护下，以双酚单体、二氟单体为聚合原料，碱性物质为催化剂，甲苯为带水剂，在非质子极性有机溶剂中，于120～260℃下反应1～24h，之后反应液经后处理，得到式(I)所示聚合物；
所述的双酚单体为4,4’-亚甲基-2,2’-苯并咪唑双酚与其他双酚单体物质的量之比1：0～10(优选1：5～10)的混合物，其中0的含义是只有单一的4,4’-亚甲基-2,2’-苯并咪唑双酚，不含其他双酚单体；所述的其他双酚单体选自下列之一：双酚A、双酚S、六氟双酚A、四甲基联苯二酚或叔丁基对苯二酚；
所述的二氟单体为非磺化二氟单体与磺化二氟单体物质的量之比1：0.1～10(优选1：0.1～5)的混合物；所述的非磺化二氟单体选自4,4’-二氟二苯酮、4,4’-二氟三苯二酮或4,4’-二氟二苯砜；所述的磺化二氟单体选自3,3’-二磺酸钠-4,4’-二氟二苯酮或3,3’-二磺酸钠-4,4’-二氟二苯砜；
所述的碱性物质为无水碳酸钠或无水碳酸钾；
所述的非质子极性有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲基亚砜、环丁砜或二苯砜；
所述二氟单体与双酚单体的物质的量之比为1：0.98～1.02；
所述二氟单体与催化剂的物质的量之比为1：1.01～3；
所述甲苯的体积用量为所述非质子极性有机溶剂体积的30％～90％；
所述非质子极性有机溶剂的用量为：使反应液的固含量(除了非质子极性有机溶剂与甲苯之外所有物料的质量总含量)控制在10wt％～30wt％；
所述反应液后处理的方法为：停止反应后，待反应液冷却至50～80℃，将反应液倒入无水乙醇中，析出沉淀，过滤收集沉淀得到粗产物，所得粗产物重新用聚合反应中所采用的非质子极性有机溶剂溶解，离心去无机盐，再加入无水乙醇中析出沉淀，过滤，滤饼置于真空烘箱中干燥(100～150℃，10～24h)，即得目标产物。
所述非磺化聚合物的制备：
将所述的二氟单体替换为非磺化二氟单体，即4,4’-二氟二苯酮、4,4’-二氟三苯二酮或4,4’-二氟二苯砜，其余操作条件均与式(I)所示聚合物的制备相同，即得到式(II)所示聚合物。
本发明所述的侧链含苯并咪唑聚芳醚酮/砜可应用于燃料电池隔膜的制备。
具体的，所述应用的方法为：将本发明所述的侧链含苯并咪唑聚芳醚酮/砜溶于N,N’-二甲基乙酰胺(DMAc)中配制成5％(w/v，g/mL)的溶液，以0.01～0.05g/cm2的量浇铸于玻璃板上，然后将玻璃板放置于60℃烘箱中保温12h，再升温至90℃保温6h，最后于110℃真空烘箱中干燥12h，得到均质聚合物薄膜(厚度50～200μm)，待自然冷却至室温(20～30℃)后，于去离子水中揭膜，再将从玻璃板上揭下来的聚合物薄膜置于1mol/L硫酸溶液中浸泡24h(以充分质子化)，最后用去离子水洗涤(以去除多余酸)，自然晾干，待用。
将制得的聚合物薄膜样品固定于测试池，利用交流阻抗仪(Hewlett Packard4294A)和两电极交流阻抗法，测定聚合物薄膜的电导率。测试频率范围为0.1～106Hz，电压为10mV。测定时，将样品夹紧在2个不锈钢圆片电极之间，然后将电极放入测试池内，在不同温度的100％相对湿度环境中，平衡一定时间，多次测量直至阻抗趋于稳定，计算公式如下：
其中，σ为膜的质子电导率(S cm-1)；L为膜的厚度(cm)；R为测得的质子膜的电阻(Ω)，通过交流阻抗谱中复平面半圆高频端最低点与实轴Re(Z’)的交点得出；S为膜的面积(cm2)。
本发明的有益效果在于：利用一步合成法制备得到侧链含苯并咪唑聚芳醚酮/砜聚合物，而现有技术中大多是先合成带活性官能团的中间聚合物，再与二胺反应得到目标聚合物。本发明不仅简化了合成步骤，而且苯并咪唑与磺酸基团分子内和分子间的相互作用解决了高磺化度聚合物溶于水、聚苯并咪唑溶解性差等问题，可以进一步改善聚合物的综合性能。
(四)附图说明
图1：实施例1制备的侧链含苯并咪唑的磺化聚芳醚酮的核磁谱图；
图2：实施例1制备的侧链含苯并咪唑的磺化聚芳醚酮的DSC曲线。
(五)具体实施方式
下面结合具体实施例对本发明作进一步说明，但本发明所要求保护的范围并不局限于实例所涉及的范围。
实施例1
在装有磁力搅拌器、通氮管、分水器和冷凝管的100mL三颈烧瓶中加入式(i)所示的4,4’-二氟二苯酮(0.4364g，2mmol)，式(ii)所示的3,3’-二磺酸钠-4,4’-二氟二苯酮(1.2669g，3mmol)，式(iii)所示的六氟双酚A(1.5130g，4.5mmol)，式(iv)所示的4,4’-亚甲基-2,2’-苯并咪唑双酚(0.2162g，0.5mmol)和碳酸钾(0.8293g，6mmol)，用17mL N,N-二甲基乙酰胺溶解，加入15mL甲苯作带水剂，先通氮除氧10min，升温至145～150℃回流4h，蒸出甲苯，再升温至160～165℃继续反应20h(溶液粘度明显增大)，停止反应。待反应液冷却，用5mL N,N-二甲基乙酰胺将反应液稀释，倒入200mL乙醇中，析出沉淀，过滤得到粗产品。粗产品重新用17mL N,N-二甲基乙酰胺溶解，离心去无机盐，再加入200mL乙醇中析出沉淀，过滤，滤饼置于100℃真空烘箱中干燥12h，得到目标聚合物2.97g，结构式如下：
将所得聚合物以DMSO-d6为溶剂，在AVANCE III 500MHz上测定聚合物的核磁共振谱，结果见图1。将所得聚合物置于氮气氛围中，利用TA DSCQ200扫描差热分析仪，以10℃/min的升温速率进行热性能测试，结果见图2。
将所得聚合物配制成浓度为0.5g/dL的DMF溶液，在25℃下用乌氏粘度计测得其特性粘度为0.76dL/g。
计算公式如下所示：
其中，ηinh代表特性粘度，t代表聚合物溶液流经毛细管的时间，t0代表纯溶剂流经毛细管的时间，C代表聚合物溶液浓度。
实施例2
在装有磁力搅拌器、通氮管、分水器和冷凝管的100mL三颈烧瓶中加入式(v)所示的4,4’-二氟二苯砜(0.7628g，3mmol)，式(ii)所示的3,3’-二磺酸钠-4,4’-二氟二苯酮(0.8446g，2mmol)，式(iii)所示的六氟双酚A(1.3449g，4mmol)，式(iv)所示的4,4’-亚甲基-2,2’-苯并咪唑双酚(0.4325g，1mmol)和碳酸钾(0.8293g，6mmol)，用17mL N,N-二甲基乙酰胺溶解，加入15mL甲苯作带水剂，先通氮除氧10min，升温至145～150℃回流4h，蒸出甲苯，再升温至160～165℃继续反应22h(溶液粘度明显增大)，停止反应。待反应液冷却，用5mL N,N-二甲基乙酰胺将反应液稀释，倒入200mL乙醇中，析出沉淀，过滤得到粗产品。粗产品重新用17mL N,N-二甲基乙酰胺溶解，离心去无机盐，再加入200mL乙醇中析出沉淀，过滤，滤饼置于100℃真空烘箱中干燥12h，得到目标聚合物2.87g，结构式如下：
将所得聚合物配制成浓度为0.5g/dL的DMF溶液，在25℃下用乌氏粘度计测得其特性粘度为0.74dL/g。
实施例3
在装有磁力搅拌器、通氮管、分水器和冷凝管的100mL三颈烧瓶中加入式(v)所示的4,4’-二氟二苯砜(0.2542g，1mmol)，式(ii)所示的3,3’-二磺酸钠-4,4’-二氟二苯酮(1.6892g，4mmol)，式(vi)所示的双酚A(0.6849g，3mmol)，式(iv)所示的4,4’-亚甲基-2,2’-苯并咪唑双酚(0.8649g，2mmol)和碳酸钾(0.8293g，6mmol)，用17mL N,N-二甲基乙酰胺溶解，加入15mL甲苯作带水剂，先通氮除氧10min，升温至145～150℃回流4h，蒸出甲苯，再升温至160～165℃继续反应22h(溶液粘度明显增大)，停止反应。待反应液冷却，用5mL N,N-二甲基乙酰胺将反应液稀释，倒入200mL乙醇中，析出沉淀，过滤得到粗产品。粗产品重新用17mL N,N-二甲基乙酰胺溶解，离心去无机盐，再加入200mL乙醇中析出沉淀，过滤，滤饼置于100℃真空烘箱中干燥12h，得到目标聚合物3.03g，结构式如下：
将所得聚合物配制成浓度为0.5g/dL的DMF溶液，在25℃下用乌氏粘度计测得其特性粘度为0.69dL/g。
实施例4
在装有磁力搅拌器、通氮管、分水器和冷凝管的100mL三颈烧瓶中加入式(v)所示的4,4’-二氟二苯砜(1.0170g，4mmol)，式(vii)所示的3,3’-二磺酸钠-4,4’-二氟二苯砜(0.4583g，1mmol)，式(iii)所示的六氟双酚A(0.6725g，2mmol)，式(iv)所示的4,4’-亚甲基-2,2’-苯并咪唑双酚(1.2974g，3mmol)和碳酸钾(0.8293g，6mmol)，用17mL二甲基亚砜溶解，加入15mL甲苯作带水剂，先通氮除氧10min，升温至150℃回流4h，蒸出甲苯，再升温至180℃继续反应24h(溶液粘度明显增大)，停止反应。待反应液冷却，用5mL二甲基亚砜将反应液稀释，倒入200mL乙醇中，析出沉淀，过滤得到粗产品。粗产品重新用17mL二甲基亚砜溶解，离心去无机盐，再加入200mL乙醇中析出沉淀，过滤，滤饼置于100℃真空烘箱中干燥12h，得到目标聚合物2.92g，结构式如下：
将所得聚合物配制成浓度为0.5g/dL的DMF溶液，在25℃下用乌氏粘度计测得其特性粘度为0.65dL/g。
实施例5
在装有磁力搅拌器、通氮管、分水器和冷凝管的100mL三颈烧瓶中加入式(i)所示的4,4’-二氟二苯酮(1.0910g，5mmol)，式(vi)所示的双酚A(0.9132g，4mmol)，式(iv)所示的4,4’-亚甲基-2,2’-苯并咪唑双酚(0.4325g，1mmol)和碳酸钾(0.8293g，6mmol)，用17mLN,N-二甲基乙酰胺溶解，加入15mL甲苯作带水剂，先通氮除氧10min，升温至145～150℃回流4h，蒸出甲苯，再升温至160～165℃继续反应18h(溶液粘度明显增大)，停止反应。待反应液冷却，用5mL N,N-二甲基乙酰胺将反应液稀释，倒入200mL乙醇中，析出沉淀，过滤得到粗产品。粗产品重新用17mL N,N-二甲基乙酰胺溶解，离心去无机盐，再加入200mL乙醇中析出沉淀，过滤，滤饼置于100℃真空烘箱中干燥12h，得到目标聚合物2.06g，结构式如下：
将聚合物配制成浓度为0.5g/dL的DMF溶液，在25℃下用乌氏粘度计测得其特性粘度为0.57dL/g。
实施例6
在装有磁力搅拌器、通氮管、分水器和冷凝管的100mL三颈烧瓶中加入式(i)所示的4,4’-二氟二苯酮(1.0910g，5mmol)，式(iv)所示的4,4’-亚甲基-2,2’-苯并咪唑双酚(2.1623g，5mmol)和碳酸钾(0.8293g，6mmol)，用17mL N,N-二甲基乙酰胺溶解，加入15mL甲苯作带水剂，先通氮除氧10min，升温至145～150℃回流4h，蒸出甲苯，再升温至160～165℃继续反应20h(溶液粘度明显增大)，停止反应。待反应液冷却，用5mL N,N-二甲基乙酰胺将反应液稀释，倒入200mL乙醇中，析出沉淀，过滤得到粗产品。粗产品重新用17mL N,N-二甲基乙酰胺溶解，离心去无机盐，再加入200mL乙醇中析出沉淀，过滤，滤饼置于100℃真空烘箱中干燥12h，得到目标聚合物2.75g，结构式如下：
将所得聚合物配制成浓度为0.5g/dL的DMF溶液，在25℃下用乌氏粘度计测得其特性粘度为0.59dL/g。
应用实施例
取1g实施例1制备的聚合物溶于20mLDMAc中配制成5％(w/v)的溶液，取10mL溶液浇铸于玻璃板(5×5cm)上，将玻璃板放置于60℃烘箱中保温12h，再升温至90℃保温6h，最后于110℃真空烘箱中干燥12h，得到棕色均质透明聚合物薄膜。待自然冷却至室温后，于去离子水中揭膜。再将薄膜置于1mol/L硫酸溶液中浸泡24h以充分质子化，用去离子水洗涤以去除多余酸，最后晾干，待用。
将制得的薄膜样品固定于测试池，在测试频率范围为0.1～106Hz，电压为10mV，100％相对湿度环境条件下测定不同温度下离子膜的电导率，平衡一定时间，多次测量直至阻抗趋于稳定。得到离子膜在25℃时的电导率为0.012(S cm-1)，当温度升高到80℃，电导率也增大到0.087(S cm-1)，说明离子膜具有良好的电导率，且离子膜的玻璃化转变温度(DSC曲线)可达到221℃，因此，制得的离子膜可用做燃料电池隔膜。
根据上述实施例，一步合成法制备侧链含苯并咪唑聚芳醚酮/砜的方法有效可行。上述实施例用来解释说明本发明，而不是对本发明进行限制，在本发明的精神和权利要求的保护范围内，对本发明作出的任何修改和改变，都落入本发明的保护范围。
Claims (9)
1.一种侧链含苯并咪唑聚芳醚酮/砜，其特征在于，所述的侧链含苯并咪唑聚芳醚酮/砜为主链由式(I)所示的重复结构单元构成的分子量在7000～12000的磺化聚合物，或者为主链由式(II)所示的重复结构单元构成的分子量在7000～12000的非磺化聚合物：
式(I)中：
m＝1，n＝1；
式(I)或(II)中：
A1、A3各自独立为：
A2为下列之一：
2.如权利要求1所述的侧链含苯并咪唑聚芳醚酮/砜的制备方法，其特征在于：
所述的侧链含苯并咪唑聚芳醚酮/砜为主链由式(I)所示的重复结构单元构成的分子量在7000～12000的磺化聚合物，其制备方法为：
惰性气体保护下，以双酚单体、二氟单体为聚合原料，碱性物质为催化剂，甲苯为带水剂，在非质子极性有机溶剂中，于120～260℃下反应1～24h，之后反应液经后处理，得到式(I)所示聚合物；
所述的双酚单体为4,4’-亚甲基-2,2’-苯并咪唑双酚与其他双酚单体物质的量之比1：5～10的混合物；所述的其他双酚单体选自下列之一：双酚A、六氟双酚A或四甲基联苯二酚；
所述的二氟单体为非磺化二氟单体与磺化二氟单体物质的量之比1：0.1～10的混合物；所述的非磺化二氟单体选自4,4’-二氟二苯酮、4,4’-二氟三苯二酮或4,4’-二氟二苯砜；所述的磺化二氟单体选自3,3’-二磺酸钠-4,4’-二氟二苯酮或3,3’-二磺酸钠-4,4’-二氟二苯砜；
所述的碱性物质为无水碳酸钠或无水碳酸钾；
所述的非质子极性有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲基亚砜、环丁砜或二苯砜；
所述二氟单体与双酚单体的物质的量之比为1：0.98～1.02；
所述二氟单体与催化剂的物质的量之比为1：1.01～3。
3.如权利要求2所述的侧链含苯并咪唑聚芳醚酮/砜的制备方法，其特征在于：
将所述的二氟单体替换为非磺化二氟单体，即所述的二氟单体为4,4’-二氟二苯酮、4,4’-二氟三苯二酮或4,4’-二氟二苯砜，则得到的侧链含苯并咪唑聚芳醚酮/砜为主链由式(II)所示的重复结构单元构成的分子量在7000～12000的非磺化聚合物。
4.如权利要求2或3所述的侧链含苯并咪唑聚芳醚酮/砜的制备方法，其特征在于，所述甲苯的体积用量为所述非质子极性有机溶剂体积的30％～90％。
5.如权利要求2或3所述的侧链含苯并咪唑聚芳醚酮/砜的制备方法，其特征在于，所述非质子极性有机溶剂的用量为：使反应液的固含量控制在10wt％～30wt％。
6.如权利要求2所述的侧链含苯并咪唑聚芳醚酮/砜的制备方法，其特征在于，所述的二氟单体为非磺化二氟单体与磺化二氟单体物质的量之比1：0.1～5的混合物。
7.如权利要求2或3所述的侧链含苯并咪唑聚芳醚酮/砜的制备方法，其特征在于，所述反应液后处理的方法为：停止反应后，待反应液冷却至50～80℃，将反应液倒入无水乙醇中，析出沉淀，过滤收集沉淀得到粗产物，所得粗产物重新用聚合反应中所采用的非质子极性有机溶剂溶解，离心去无机盐，再加入无水乙醇中析出沉淀，过滤，滤饼置于真空烘箱中干燥，即得目标产物。
8.如权利要求1所述的侧链含苯并咪唑聚芳醚酮/砜在燃料电池隔膜制备中的应用。
9.如权利要求8所述的应用，其特征在于，所述应用的方法为：将所述的侧链含苯并咪唑聚芳醚酮/砜溶于DMAc中配制成5％的溶液，以0.01～0.05g/cm2的量浇铸于玻璃板上，然后将玻璃板放置于60℃烘箱中保温12h，再升温至90℃保温6h，最后于110℃真空烘箱中干燥12h，得到均质聚合物薄膜，待自然冷却至室温后，于去离子水中揭膜，再将从玻璃板上揭下来的聚合物薄膜置于1mol/L硫酸溶液中浸泡24h，最后用去离子水洗涤，自然晾干，待用。
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