CN104804182A - Sulfonated poly ether sulfone, and preparation method and application thereof in electrical actuator preparation - Google Patents
Sulfonated poly ether sulfone, and preparation method and application thereof in electrical actuator preparation Download PDFInfo
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- CN104804182A CN104804182A CN201510164264.5A CN201510164264A CN104804182A CN 104804182 A CN104804182 A CN 104804182A CN 201510164264 A CN201510164264 A CN 201510164264A CN 104804182 A CN104804182 A CN 104804182A
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- polyether sulphone
- derivative
- sulfonated polyether
- reaction
- sulfonated
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- 239000004695 Polyether sulfone Substances 0.000 title claims abstract description 21
- 229920006393 polyether sulfone Polymers 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 71
- 229920000570 polyether Polymers 0.000 claims abstract description 69
- 125000001174 sulfone group Chemical group 0.000 claims abstract description 69
- 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 abstract description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 239000002905 metal composite material Substances 0.000 claims abstract description 9
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 24
- 238000000967 suction filtration Methods 0.000 claims description 19
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 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
- 238000001326 spin-polarised Auger electron spectroscopy Methods 0.000 claims description 15
- 238000006277 sulfonation reaction Methods 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 10
- HSASKNPEYJOZHA-UHFFFAOYSA-N 2-[3-(carboxymethoxy)-5-(1-hydroxy-2-oxo-2-phenylethyl)phenoxy]acetic acid Chemical compound C(=O)(O)COC=1C=C(C(C(C2=CC=CC=C2)=O)O)C=C(C=1)OCC(=O)O HSASKNPEYJOZHA-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000007265 chloromethylation reaction Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 229930185605 Bisphenol Natural products 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 5
- 150000003384 small molecules Chemical class 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- -1 polyoxyethylene Polymers 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 238000005342 ion exchange Methods 0.000 abstract description 14
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 abstract 3
- 229910006069 SO3H Inorganic materials 0.000 abstract 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 abstract 2
- ISRUGXGCCGIOQO-UHFFFAOYSA-N Rhoden Chemical compound CNC(=O)OC1=CC=CC=C1OC(C)C ISRUGXGCCGIOQO-UHFFFAOYSA-N 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229920000557 Nafion® Polymers 0.000 description 12
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 10
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000002329 infrared spectrum Methods 0.000 description 8
- 239000003014 ion exchange membrane Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229920002492 poly(sulfone) Polymers 0.000 description 7
- 150000003460 sulfonic acids Chemical class 0.000 description 6
- ZHXISMXDCUJVCY-UHFFFAOYSA-N 2-phenylsulfanylethanamine;hydrochloride Chemical compound [Cl-].[NH3+]CCSC1=CC=CC=C1 ZHXISMXDCUJVCY-UHFFFAOYSA-N 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229920001746 electroactive polymer Polymers 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007772 electroless plating Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QSKKXNSTGHZSQB-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.[Pt+2] QSKKXNSTGHZSQB-UHFFFAOYSA-N 0.000 description 2
- 210000000721 basilar membrane Anatomy 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 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 description 1
- CWGSOQVETBJTME-UHFFFAOYSA-N 3-(2-phenylethenyl)pyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=CC=2C=CC=CC=2)=C1 CWGSOQVETBJTME-UHFFFAOYSA-N 0.000 description 1
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 1
- GIXNHONPKYUROG-UHFFFAOYSA-N 4-(9h-fluoren-1-yl)phenol Chemical class C1=CC(O)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C12 GIXNHONPKYUROG-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 0 CC(C)(C)c(cc1)ccc1S(*(cc1)ccc1Oc1ccc(C(C)(*)c(cc2)cc*2OC(C)(C)C)cc1)(=O)=[U] Chemical compound CC(C)(C)c(cc1)ccc1S(*(cc1)ccc1Oc1ccc(C(C)(*)c(cc2)cc*2OC(C)(C)C)cc1)(=O)=[U] 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920003935 Flemion® Polymers 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical group [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000002977 biomimetic material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000005586 carbonic acid group Chemical group 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002220 fluorenes Chemical group 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 210000004379 membrane Anatomy 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920013655 poly(bisphenol-A sulfone) Polymers 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
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- 230000035945 sensitivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- 210000001835 viscera Anatomy 0.000 description 1
Landscapes
- Polyethers (AREA)
Abstract
Sulfonated poly ether sulphone or a sulfonated poly ether sulphone derivative is a phenyl sulfone and 2,2-bis(4-hydroxyphenyl)propane or fluorene-9-bisphenol (BHPF) or polyethylene glycol modified fluorene-9-bisphenol sulfonated block polymer; sulfonated poly ether sulphone, the sulfonated poly ether sulphone derivative or the polyethylene glycol modified sulfonated poly ether sulphone derivative has the structural formula shown in the specification, wherein R1 refers to H or SO3H, and R2 refers to H or SO3H. Sulfonated poly ether sulfone can be used for preparing an ionic polymer-metal composite electrical actuator. Sulfonated poly ether sulfone has a higher ion-exchange equivalent, and a wider mechanical performance adjusting range, and is relatively low in cost.
Description
Technical field
The present invention relates to sulfonated polyether sulphone (SPAES) and derivative thereof and ion-exchange polymer/metal composite electric actuator and the application in machinery is bionical.
Technical background
Ion-exchange polymer-metal composite (Ionic Polymer-Metal Composite, IPMC), as the emerging intelligent material of a class, enjoys the good reputation of " artificial-muscle ".The electric actuator prepared by IPMC has that driving voltage is low, activation manners is simple, relative deformation amount is large, lightweight and the advantage such as operational safety, is with a wide range of applications in fields such as strain gauge, artificial-muscle, biomimetic material, flexible mechanical actuator and bio-medical materials.
IPMC is made up of ion-exchange polymer (perfluorinated sulfonic acid (as Nafion), perfluor carbonic acid (as Flemion) etc.) and the inert metal nano-electrode that is adsorbed on polymkeric substance both sides.The constitutional features of Nafion is: main chain is carbon fluorine skeleton, has the function of hydrophobic; Side chain is acid group, has hydrophilic function.Owing to containing hydrophilic and hydrophobic group simultaneously, after crystalline film, define the microchannel of countless fluid molecules as moisture movement in ion-exchange membrane, diameter is between 0.5 ~ 5nm.1993, the Asaka seminar of Japan and the Shanhinpoor seminar of the U.S. found simultaneously: under electric field, deformation occurs IPMC, produces certain stress to external world, is therefore expected to IPMC to be used for electroluminescent driving mechanism.The actuation mechanism generally accepted for people is: under electric field action, hydrated cation carries certain solvent molecule (as water molecules) by small interior conduit to movable cathode, thus cause the contraction of anode and the expansion of negative electrode, macroscopically atarting material occurs bending and deformation, and shows certain power and displacement output to external world.Otherwise, mechanical deformation is applied to IPMC, causes the imbalance of its surface charge to distribute, cause surface field change, displacement/force transducer can be prepared with this.
At present, also there is output rating relatively little, non-water working hour shorter, the shortcoming such as cost is high in IPMC, these shortcomings seriously hinder its application development.Principal element from base film material low moisture storage capacity, ion-exchange equivalent.But the molecular structure of existing Nafion film (main chain is C-F structure) is very stable, modification is carried out to it and is difficult to realize, and adopt merely doping vario-property, again by the face of the high cost of Nafion film, IPMC cannot be promoted on a large scale.Therefore, preparation has macroion exchanging equivalent, high conductivity, high water absorbing capacity and Novel ion exchange polymer with low cost, in order to replace existing perfluorinated sulfonic acid polymer, becomes the bottleneck of IPMC development research.In this respect, Chinese scholars have accumulated and has explored some early stages.Sulfonated polystyrene (SPS), sulfonated phenylethylene-ethylene copolymer (SPSE), sulfonated polyether-ether-ketone (SPEEK), styrene-maleimide segmented copolymer are prepared IPMC by trial for studying, because they have superior ion-exchange capacity, specific conductivity, the IPMC prepared thus shows desirable actuating performance.Compared with conventional Nafion base IPMC, the IPMC prepared by these polymkeric substance exports quite at voltage of alternating current bottom offset, but power exports obviously enhancing; The displacement that there is not conventional IPMC under direct voltage drive relaxes, reply phenomenon.But the defects such as water content is lower, poor chemical stability that these ion-exchange membranees also exist, the problem such as cause working hour short, mechanics output performance unstable.
Polysulfones is the special engineering plastics that a class has superior mechanical property, processing characteristics, thermostability, chemical stability.The structural formula of conventional bisphenol-a polysulfone (PSF) is as follows.Polysulfones after hydrophilic modifying can possess certain ion-exchange capacity, replaces conventional Nafion, launches application in water treatment, fuel cell plasma exchange resin field.According to our investigation, still there is no polysulfones and derivative thereof for the report of IPMC.Before ion exchange resin, hydrophilic modifying to be carried out to polysulfones, make its main chain brings hydrophilic functional groups sulfonic group, hydroxyl or carboxylic acid group etc.In addition, relative to phenyl ring, the electron donation of fluorenes ring is stronger, therefore can the more hydrophilic radical of grafting.The sulfonation degree of polysulfones and the ion-exchange equivalent of film and water-intake rate closely related, according to our test result: sulfonation degree be 70% the ion-exchange equivalent that has of SPSF be 1.65meq/g, this numerical value is about the twice of perfluorinated sulfonic acid polymer (Nafion) under the same terms.Meanwhile, water regain also greatly increases, and is conducive to for the work of IPMC long-time stable provides water to support.Therefore, be that template carries out suitable structure design with polysulfones, be expected to obtain cheap, ion-exchange performance is superior, can be used for the Novel ion exchange resin of IPMC.
United States Patent (USP) (6,475,639) and (6,109,852) describe a kind of preparation process of artificial thews material, and artificial thews material is as some applied researcies of actuator and sensor, comprise the invention of underwater fish, the invention etc. of mechanical tong.Other patent is also mainly some explorative research to electroactive polymer, wherein at medical field, describe the design of artificial thews material for heart gas booster compressor, the design of the micropump that human implantable is used for the treatment of, as the drive unit of " microcapsule " robot checked for human internal organs, and for the reparation etc. of human muscle.In other application aspect, mainly contain: the actuating invention Braille display utilizing electroactive polymer; A kind of valve and rotation motor is developed based on electroactive polymer material deformation principle; The sensor designed by electroactive polymer.But involved artificial thews material not power export not little, have breakthrough in the problems such as the dependence of wet environment.
The perfluorinated ion-exchange membrane of the porous of the perfluorinated ion-exchange membrane of a kind of porous of Chinese patent and method for making and the performance optimization of purposes (200710191892.8) proposition processing machinery, and it is used for artificial-muscle driving mechanism, power can be improved export, lengthen working hours; Graphene-ionic polymer electric actuator and preparation method thereof and application (201110165842.9) propose to develop the Graphene electrodes being used for IPMC.
Different from above-mentioned patent, the present invention proposes to use polyether sulphone (SPAES) and derivative thereof as ion-exchange membrane, preparation novel I PMC electric actuator.
Summary of the invention
Ion-exchange polymer/metal composite the electric actuator that the present invention relates to sulfonated polyether sulphone (SPAES) and derivative thereof and prepare with it, and the application in machinery is bionical.
Technical scheme of the present invention is as follows:
A kind of sulfonated polyether sulphone or sulfonated polyether sulphone derivative, it is sulfobenzide and 2,2-bis-(4-hydroxy phenyl) propane or bisphenol fluorene [BHPF, 9, two (4-hydroxyphenyl) fluorenes of 9-] or the sulfonated block polymer of polyethyleneglycol modified bisphenol fluorene: sulfonated polyether sulphone, sulfonated polyether sulphone derivative or polyethyleneglycol modified sulfonation polyarylsulphone derivative, its structural formula is as follows:
Wherein: R
1with R
2for SO
3h;
Or structural formula is:
Wherein: R
1with R
2for SO
3h, R
3for H or CH
2-O-(-CH
2-CH
2-O-)
m-CH
3polyether chain, R
4with R
5for H or SO
3h.
Prepare a method for above-mentioned sulfonated polyether sulphone, it comprises the following steps:
Step 1, by 1.0 moles 4,2,2-bis-(4-hydroxy phenyl) propane (dihydroxyphenyl propane, BPA) of 4 '-dichloro diphenyl sulfone (DCDPS), 1.0-1.8 mole and the K of excessive 15%
2cO
3add in reaction flask, solubilizing agent N,N-dimethylacetamide (DMAc) and water entrainer toluene, then load onto the prolong of band water trap, stir, N
2135 DEG C of reaction 3h are slowly warming up under protection, and remove the water of dereaction generation, be warming up to 155 DEG C afterwards and continue reaction 14h, after reaction terminates, N is added in reaction flask, N-N,N-DIMETHYLACETAMIDE, by product dilution, is poured into afterwards in methyl alcohol and is settled out product polyether sulphone (PAES), and suction filtration is dry, product uses 1 again, 2-ethylene dichloride stirring and dissolving 2h, is precipitated out afterwards thoroughly to remove the impurity such as inorganic salt, small molecules again, obtains polyether sulphone in methyl alcohol;
Step 2, above-mentioned polyether sulphone is dissolved in 1, in 2-ethylene dichloride, added and be equipped with in the reaction flask of constant pressure funnel, stir, measure chlorsulfonic acid and be dissolved in 1, pour in 2-ethylene dichloride in constant pressure funnel, the mass ratio of polyether sulphone and chlorsulfonic acid is between 1:2-2.5, coutroi velocity, chlorsulfonic acid is dropwise instilled in polyether sulphone solution in 2h, and then continue reaction 2h, the solvent in reaction system is boiled off after having reacted, obtain amber solid product sulfonated polyether sulphone (SPAES), product is heated with stirring to 60 DEG C of 1h in the KOH solution of 3%, in the HCl solution of 5%, 60 DEG C are heated with stirring to again after suction filtration washing, last suction filtration, after washing, dry, sulfonated polyether sulphone.
Prepare a method for above-mentioned sulfonated polyether sulphone derivative, it comprises the following steps:
Step 1, by mol ratio be the DCDPS of 1:1 and bisphenol fluorene (BHPF), excessive 15% K
2cO
3, dry methyl-sulphoxide (DMSO) and water entrainer toluene adds in reaction flask, then loads onto the prolong of band water trap, stirring, N
2135 DEG C of reaction 3h are slowly warming up under protection, and remove the water of dereaction generation, be warming up to afterwards between 170-190 DEG C and continue reaction 20h, after reaction terminates, in flask, add DMSO product polyether sulphone derivative (BHPF-PAES) is diluted, pour in methyl alcohol afterwards and be precipitated out, suction filtration is dry, dry complete product uses DMAc stirring and dissolving 2h again, be precipitated out again afterwards thoroughly to remove the impurity such as inorganic salt, small molecules in methyl alcohol, then wash suction filtration dry, obtain polyether sulphone derivative;
Step 2, above-mentioned polyether sulphone derivative (BHPF-PAES) is dissolved in 1, in 2-ethylene dichloride, chlorsulfonic acid (consumption of chlorsulfonic acid determines the sulfonation degree of polyether sulphone derivative) is dissolved in 1, in 2-ethylene dichloride, between polyether sulphone derivative and the mass ratio 1:2-1:6.5 of chlorsulfonic acid, by 1 of chlorsulfonic acid, 2-dichloroethane solution is in dropwise at room temperature instillation polyether sulphone derivative solution, whole process need 2h, continue reaction 1h more afterwards, after reaction terminates, boil off 1, 2-ethylene dichloride, product sulfonated polyether sulfone derivatives (SBHPF-SPAES) distilled water wash several, suction filtration, dry, obtain sulfonated polyether sulfone derivatives.
Prepare a method for above-mentioned polyethyleneglycol modified sulfonation polyarylsulphone derivative, it comprises the following steps:
Step 1, by above-mentioned obtained sulfonated polyether sulfone derivatives (SBHPF-SPAES) with 1,2-ethylene dichloride dissolves, dissolve completely, add the catalyst S nCl of chloromethylation reagents Isosorbide-5-Nitrae-two (chlorine methoxyl group) butane (BCMB) and catalytic amount
4the ratio of the consumption of SBHPF-SPAES and BCMB is that BCMB 1-2.5 mole saved by every chain of SBHPF-SPAES, under room temperature (25 DEG C), react 3h, it is precipitation agent that reaction terminates rear ethanol, and resulting polymer is separated out, use N successively, N-N,N-DIMETHYLACETAMIDE (DMAc), dilute hydrochloric acid washed product polymkeric substance, more repeatedly wash with distilled water, to washings not chloride ion-containing, vacuum-drying, obtains the sulfonated polyether sulfone derivatives of chloromethylation;
Step 2, the sulfonated polyether sulfone derivatives of chloromethylation is placed in stirring, the four-hole bottle of thermometer and reflux condensing tube, add DMAc and make it dissolve completely, then add polyoxyethylene glycol (PEGME-750) and Na respectively
2cO
3pEGME-750 consumption is the BCMB consumption of equimolar step 1, stirring reaction at 70 DEG C, it is precipitation agent that reaction terminates rear ethanol, sulfonation polyarylsulphone derivative (PEG-SBHPF-SPAES) polymkeric substance making product polyethyleneglycol modified is separated out, repeatedly wash with distilled water again, vacuum-drying, obtain polyethyleneglycol modified sulfonated polyether sulfone derivatives (PEG-SBHPF-SPAES).
Above-mentioned sulfonated polyether sulphone, sulfonated polyether sulphone derivative and polyethyleneglycol modified sulfonated polyether sulfone derivatives may be used for preparing ion-exchange polymer/metal composite electric actuator.
Electric actuator of the present invention is made up of ion-exchange membrane (a), electrode (b) and extraneous power supply (signal generator), as shown in Figure 1.
Ion-exchange membrane described in above-mentioned electric actuator is Sulfonated polyether sulphone (SPAES) or Sulfonated polyether sulphone derivative, and thickness is 50 μm-300 μm; Electrode is the nano metal electrodes such as Pt, Au or Ag, and thickness is 1 μm-10 μm; Electrical signal can be the sine wave of voltage 0.5-5V, frequency 0.1-20Hz, square wave or choppy sea.
The present invention also provides a kind of beam type electric actuator.After input electrical signal, producing displacement and power output, is mechanical energy by electric energy conversion.Its power output performance is higher than the perfluorinated sulfonic acid base beam type electric actuator of same specification; Displacement deflection is between 5-70 °.
Present invention employs Sulfonated polyether sulphone and the polyether sulphone derivative substrate polymer material as electric actuator, embed conductive metal electrode in its both sides, input electrical signal obtains new polymers electric actuator.Relative to perfluorinated sulfonic acid (Nafion), perfluor carbonic acid (Flexmion), the sulfonated polyether ether ketone (SPEEK) of routine, the SPAES in the present invention possesses advantage:
1. Sulfonated polyether sulphone and polyether sulphone derivative can have higher ion-exchange equivalent.Containing a large amount of phenyl ring in the polymer backbone that the present invention relates to, can to replace, the multiple sulfonic acid of grafting, carbonic acid group, promote the ion-exchange capacity of basilar membrane, and then improve the electromechanical performance of electric actuator.
2. Sulfonated polyether sulphone and polyether sulphone derivative can have wider mechanical property regulation range.Be grafted with hydrophilic polyglycol group above SPAES of the present invention, both can regulate the mechanical property of basilar membrane, by the hydrophilic ability increasing film, thus maintain the response of long electric actuation.
3. relatively perfluorinated sulfonic acid (Nafion), perfluor carbonic acid (Flexmion), Sulfonated polyether sulphone and polyether sulphone derivative cheap.
Accompanying drawing explanation
Infrared spectra comparison diagram before and after the sulfonation of Fig. 1 polyether sulphone;
The scanning electron microscope (SEM) photograph of Fig. 2 sulfonated polyether sulfone derivatives base IPMC.A, front; B, section;
The structural representation of Fig. 3 Inventive polymers electric actuator, wherein a is ion-exchange membrane; B is electrode;
Fig. 4 IPMC power exports test set schematic diagram, and wherein 1 is the driver module of IPMC; 2 be IPMC power export measurement module; 3 is computer; 4 is IPMC;
Fig. 5 IPMC power exports test set pictorial diagram;
The electric actuation video recording sectional drawing of Fig. 6 sulfonated polyether sulfone derivatives base IPMC.
Embodiment
Embodiment 1: synthesis polyether sulphone
Add in 100mL round-bottomed flask, 4,4 '-dichloro diphenyl sulfone (DCDPS) 2.5g, 2,2-bis-(4-hydroxy phenyl) propane (dihydroxyphenyl propane, BPA) 1.9861g, the K of excessive 15%
2cO
31.381g, solvent N,N-dimethylacetamide (DMAc) 13mL, water entrainer toluene 6.5mL, then load onto the prolong of band water trap, magnetic agitation, N
2slowly be warming up to 135 DEG C of reaction 3h under protection, with the water generated except dereaction, be warming up to 155 DEG C afterwards and continue reaction 14h.After reaction terminates, in flask, add a certain amount of DMAc by product dilution, pour into afterwards in 100mL methyl alcohol and be settled out product (polyether sulphone, PAES), suction filtration is dry, product uses 1,2-ethylene dichloride stirring and dissolving 2h again, is precipitated out afterwards thoroughly to remove the impurity such as inorganic salt, small molecules in methyl alcohol again, then suction filtration is washed dry, weigh, obtain product 3.9831g, productive rate 88.%.
Embodiment 2: synthesis sulfonated polyether sulphone
Take 1g PAES to be dissolved in 15mL 1 is housed, 2-ethylene dichloride be connected in the round-bottomed flask of constant pressure funnel, magnetic agitation, measure 100 μ L chlorsulfonic acids again and be dissolved in 10ml 1, pour in 2-ethylene dichloride in constant pressure funnel, coutroi velocity, makes chlorsulfonic acid dropwise instill in PAES solution in 2h, and then continues reaction 2h.React rear use Rotary Evaporators and boil off solvent in reaction system, obtain amber solid product (sulfonated polyether sulphone, SPAES), product is heated with stirring to 60 DEG C of 1h in the KOH solution of 3%, in the HCl solution of 5%, 60 DEG C are heated with stirring to again after suction filtration washing, after last suction filtration washed several times with water, dry.Repeat above step and the consumption of chlorsulfonic acid is changed respectively into 200 μ L, 230 μ L, 250 μ L, 285 μ L, 300 μ L, simultaneously in order to keep the concentration of chlorosulfonic acid solution constant, the consumption of corresponding change 1,2-ethylene dichloride, obtains the SPAES of different sulfonation degree.
Embodiment 3: synthesis polyether sulphone derivative (4, the polyether sulphone derivative that 4 '-dichloro diphenyl sulfone and bisphenol fluorene condensation obtain)
DCDPS and bisphenol fluorene (BHPF) that mol ratio is 1:1 is added, the K of excessive 15% in 100mL round-bottomed flask
2cO
3(before use in an oven 180 DEG C at dry 24h), dry methyl-sulphoxide (DMSO) and water entrainer toluene, then load onto the prolong being with water trap, magnetic agitation, N
2slowly be warming up to 135 DEG C of reaction 3h under protection, with the water generated except dereaction, be warming up to afterwards between 170-190 DEG C and continue reaction 20h.After reaction terminates, in flask, add a certain amount of DMSO product polyether sulphone derivative (BHPF-PAES) is diluted, pour into afterwards in 100mL methyl alcohol and be precipitated out, suction filtration is dry, dry complete product uses DMAc stirring and dissolving 2h again, be precipitated out again afterwards thoroughly to remove the impurity such as inorganic salt, small molecules in methyl alcohol, then wash suction filtration dry.
Embodiment 4: synthesis sulfonated polyether sulfone derivatives
Take above-mentioned BHPF-PAES 1.2g and be dissolved in a certain amount of 10mL1, in 2-ethylene dichloride, measure 0.22g-1.44g chlorsulfonic acid and be dissolved in a certain amount of 5mL1, in 2-ethylene dichloride, by 1 of chlorsulfonic acid, 2-dichloroethane solution is in dropwise at room temperature instillation polyether sulphone derivative solution, whole process need 2h, continues reaction 1h, after reaction terminates afterwards again, revolve and boil off 1,2-ethylene dichloride, product (sulfonated polyether sulfone derivatives, SBHPF-SPAES) distilled water wash several, suction filtration, dry.
Embodiment 5: the sulfonation polyarylsulphone derivative that synthesizing polyethylene glycol is modified
By the 1.8gSBHPF-SPAES of embodiment 4, dissolve with 20mL1,2-ethylene dichloride, dissolve completely, 0.24g chloromethylation reagents Isosorbide-5-Nitrae-two (chlorine methoxyl group) butane (BCMB) added and a little catalyst S nCl
4, under room temperature (25 DEG C), react 3h.To terminate rear ethanol be precipitation agent in reaction, resulting polymer separated out, uses N,N-dimethylacetamide (DMAc) successively, dilute hydrochloric acid washes resulting polymer, more repeatedly wash with distilled water, to washings not chloride ion-containing, and vacuum-drying.Chloromethylation SBHPF-SPAES is placed in stirring, the four-hole bottle of thermometer and reflux condensing tube, add DMAc and make it dissolve completely, then add 1.5g PEGME-750 and 0.6gNa respectively
2cO
3, stirring reaction at 70 DEG C, it is precipitation agent that reaction terminates rear ethanol, product (polyethyleneglycol modified sulfonation polyarylsulphone derivative, PEG-SBHPF-SPAES) polymkeric substance is separated out, more repeatedly washs with distilled water, vacuum-drying.
Embodiment 6: preparation ion exchange polymer membrane
Use DMAc as solvent product dried in above-described embodiment 2,4,5, be made into the solution of 15%, pour in homemade film forming grinding tool, add a little DMSO, in an oven at 70 DEG C, dry film forming, be more slowly warming up to 140 DEG C of anneal 2h, prepare thickness respectively and be in film between 50 μm-300 μm.
Infrared spectroscopy
The sample of embodiment 1-5 is done infrared spectra respectively, and the infrared spectra of embodiment 1-2 lists in Fig. 1.In the infrared spectra of PAES, 1580,1500,1487cm
-1there is the framework characteristic peak of phenyl ring in place, 3020cm
-1place is C-H stretching vibration peak on phenyl ring, 1241,1147cm
-1for asymmetric, the symmetrical absorption peak of O=S=O, 1009cm
-1there is the absorption peak of Ar-O-Ar in place.After sulfonation, in the infrared spectra of SPAES, 3555cm
-1there is the O-H vibration peak of sulfonic acid in place, 1400cm
-1place is C-H flexural vibration peak on phenyl ring, 1327,1280cm
-1place is asymmetric, the symmetrical absorption peak of O=S=O in sulfonic acid, 1050cm
-1place is the vibration peak of S-OH.In the infrared spectra of BHPF-PAES, in double bond, the stretching vibration peak of C-H and C=C appears at 3085cm respectively
-1and 1647cm
-1, 860cm
-1and 991cm
-1for double bond is hydrocarbon.After sulfonation, in the infrared spectra of SBHPF-SPAES, 3550cm
-1there is the O-H vibration peak of sulfonic acid in place, 1310,1260cm
-1place is asymmetric, the symmetrical absorption peak of O=S=O in sulfonic acid, 1050cm
-1place is the vibration peak of S-OH.After grafting PEG, in the infrared spectra of PEG-SBHPF-SPAES, 2962,2884cm
-1newly there is C-H in place
2stretching vibration peak.
Mechanics Performance Testing
Electronic universal tester is adopted to carry out tensile property test to the sample of embodiment 1-5 and business Nafion blank film.The results are shown in table 1.
Water-intake rate is tested
Under room temperature, embodiment 1-5 sample and business Nafion blank film are soaked 24h in deionized water, after taking-up, carefully dries surface-moisture, test its quality with analytical balance, as quality (M1) under saturated water suction state.Then, sample is put into vacuum drying oven, dry 24h at 70 DEG C, the quality (M2) of test desciccator diaphragm.The water-intake rate of sample is calculated by formula (M1-M2)/M2.
Ion-exchange equivalent is tested
The ion-exchange equivalent (IEC) of embodiment 1-5 sample and business Nafion film is tested (table 1).Prepared desciccator diaphragm sample is immersed in 8h in the NaCl solution of 2mol/L, the hydrogen ion in sulfonic acid group is exchanged by sodium ion, use the standard NaOH solution of 0.1mol/L to carry out titration afterwards, the calculation formula of IEC is as follows:
V in formula
naOHthe volume of the NaOH solution be consumed, M
naOHbe the concentration of NaOH, W is the weight of dry film.
Table 1 water-intake rate, IEC, mechanical property result
Preparation ion exchange polymer membrane-metal composite (IPMC)
By the film prepared in embodiment 2-5, use the two sides of 1200 order sand papering films, carry out surface coarsening process, then with the film after distilled water ultrasonic cleaning for several times polishing; The hydrochloric acid soln afterwards film being placed in 2mol/L boils 30min to remove additive and the ion of film, afterwards rinsed clean in deionized water; Then film is placed in deionized water and boils 30min to remove the acid used, and make film water-swelling.Film through pre-treatment is placed in the platinum ammonium compound water solution ([Pt (NH prepared in advance
3)
4] Cl
2, 2mg/mL, pH are about 10) at room temperature soak 12h.
42 DEG C of water-baths are placed in, magnetic agitation by being equipped with in the beaker of deionized water by the film sample after ion-exchange.Main electroless plating reaction: add 500 μ L 5% sodium borohydride solutions every 30min, totally 7 times, and progressively temperature is increased to 60 DEG C.Secondary electroless plating reaction: the film through main electroless plating reaction is soaked 12h as in platinum ammonium compound water solution before again, adds a certain amount of 5% hydroxylamine hydrochloride solution and 20% hydrazine hydrate solution every 30min afterwards, and be progressively warming up to 60 DEG C.The sample prepared is soaked as in 0.2mol/L LiCl solution, for subsequent use.
Sem test
Its surface deposition Pt nano particle particle of ion exchange polymer membrane-metal composite 4 IPMC films of above-mentioned preparation, observes the particle diameter of metallic particles and the thickness of metal level by scanning electronic microscope (SEM).Wherein, Fig. 2 listed in by the SEM picture of PEG-SBHPF-SPAES base IPMC.
Electromechanics performance test
Electromechanical Testing Platform comprises signal generator, force transducer and multifunctional data acquisition card composition.Signal generator (SP864, Nanjing) can at 0 ~ 10V voltage, 0.1 ~ 100Hz frequency downconverted sine, square wave and triangular signal, and device is shown in Fig. 4; Force transducer (FEMTO-10000, Switzerland) range is 10mN, and sensitivity is 1 μ N; Multifunctional data acquisition card (NI, 6024E) adopts Lapview (v14.0) support programs, and device is shown in Fig. 5.Embodiment 2-5 sample IPMC sample is of a size of 20 × 2 × 0.33mm
3, test under air atmosphere, electric actuation video recording sectional drawing lists in Fig. 6.The results are shown in Table 2.
The electric actuation performance of IPMC and correlation parameter in table 2 example 11
Claims (5)
1. a sulfonated polyether sulphone or sulfonated polyether sulphone derivative, it is characterized in that: it is sulfobenzide and 2, the sulfonated block polymer of 2-bis-(4-hydroxy phenyl) propane or bisphenol fluorene or polyethyleneglycol modified bisphenol fluorene: sulfonated polyether sulphone, sulfonated polyether sulphone derivative or polyethyleneglycol modified sulfonation polyarylsulphone derivative, its structural formula is as follows:
Wherein: R
1and R
2for SO
3h.Or
Wherein: R
1, R
2for SO
3h, R
3for H or CH
2-O-(-CH
2-CH
2-O-)
m-CH
3polyether chain, R
4with R
5for H or SO
3h.
2. prepare a method for sulfonated polyether sulphone according to claim 1, it is characterized in that it comprises the following steps:
Step 1, by 1 mole 4,2,2-bis-(4-hydroxy phenyl) propane of 4 '-dichloro diphenyl sulfone, 1.0-1.8 mole and the K of excessive 15%
2cO
3add in reaction flask, solubilizing agent N,N-dimethylacetamide and water entrainer toluene, then load onto the prolong of band water trap, stir, N
2135 DEG C of reaction 3h are slowly warming up under protection, and remove the water of dereaction generation, be warming up to 155 DEG C afterwards and continue reaction 14h, after reaction terminates, N is added in reaction flask, N-N,N-DIMETHYLACETAMIDE, by product dilution, is poured into afterwards in methyl alcohol and is settled out product polyether sulphone, and suction filtration is dry, product uses 1 again, 2-ethylene dichloride stirring and dissolving 2h, is precipitated out afterwards thoroughly to remove the impurity such as inorganic salt, small molecules again, obtains polyether sulphone in methyl alcohol;
Step 2, polyether sulphone is dissolved in 1, in 2-ethylene dichloride, added and be equipped with in the reaction flask of constant pressure funnel, stir, measure chlorsulfonic acid and be dissolved in 1, pour in 2-ethylene dichloride in constant pressure funnel, the mass ratio of polyether sulphone and chlorsulfonic acid is between 1:2-1:2.5, coutroi velocity, chlorsulfonic acid is dropwise instilled in polyether sulphone solution in 2h, and then continue reaction 2h, the solvent in reaction system is boiled off after having reacted, obtain amber solid product sulfonated polyether sulphone, product is heated with stirring to 60 DEG C of 1h in the KOH solution of 3%, in the HCl solution of 5%, 60 DEG C are heated with stirring to again after suction filtration washing, last suction filtration, after washing, dry, sulfonated polyether sulphone.
3. prepare a method for sulfonated polyether sulphone derivative according to claim 1, it is characterized in that it comprises the following steps:
Step 1, be 4 of 1:1 by mol ratio, 4 '-dichloro diphenyl sulfone and bisphenol fluorene, excessive 15% K
2cO
3, dry methyl-sulphoxide and water entrainer toluene adds in reaction flask, then load onto the prolong of band water trap, stir, N
2135 DEG C of reaction 3h are slowly warming up under protection, and remove the water of dereaction generation, be warming up to afterwards between 170-190 DEG C and continue reaction 20h, after reaction terminates, in flask, add methyl-sulphoxide product polyether sulphone derivative is diluted, pour in methyl alcohol afterwards and be precipitated out, suction filtration is dry, and dry complete product uses N again, N-N,N-DIMETHYLACETAMIDE stirring and dissolving 2h, be precipitated out in methyl alcohol more afterwards, then washing, suction filtration, drying, obtain polyether sulphone derivative;
Step 2, the polyether sulphone derivative described in step 1 is dissolved in 1, in 2-ethylene dichloride, chlorsulfonic acid is dissolved in 1, in 2-ethylene dichloride, between polyether sulphone derivative and the mass ratio 1:2-1:6.5 of chlorsulfonic acid, by 1,2-dichloroethane solution of chlorsulfonic acid in dropwise at room temperature instillation polyether sulphone derivative solution, whole process need 2h, continue reaction 1h more afterwards, after reaction terminates, boil off 1,2-ethylene dichloride, product sulfonated polyether sulfone derivatives distilled water wash several, suction filtration, dry, obtain sulfonated polyether sulfone derivatives.
4. prepare a method for above-mentioned polyethyleneglycol modified sulfonation polyarylsulphone derivative, it is characterized in that it comprises the following steps:
Step 1, sulfonated polyether sulfone derivatives 1,2-ethylene dichloride to be dissolved, dissolve completely, add chloromethylation reagents Isosorbide-5-Nitrae-two (chlorine methoxyl group) butane (BCMB) and a little catalyst S nCl
4the ratio of the consumption of SBHPF-SPAES and BCMB is that BCMB 1-2.5 mole saved by every chain of SBHPF-SPAES, under room temperature, react 3h, it is precipitation agent that reaction terminates rear ethanol, and resulting polymer is separated out, use N successively, N-N,N-DIMETHYLACETAMIDE, dilute hydrochloric acid washed product polymkeric substance, more repeatedly wash with distilled water, to washings not chloride ion-containing, vacuum-drying, obtains the sulfonated polyether sulfone derivatives of chloromethylation;
Step 2, the sulfonated polyether sulfone derivatives of chloromethylation is placed in stirring, the four-hole bottle of thermometer and reflux condensing tube, add N, N N,N-DIMETHYLACETAMIDE makes it dissolve completely, then adds polyoxyethylene glycol and Na respectively
2cO
3pEGME-750 consumption is the BCMB consumption of equimolar step 1, stirring reaction at 70 DEG C, it is precipitation agent that reaction terminates rear ethanol, and the sulfonation polyarylsulphone derivative making product polyethyleneglycol modified is separated out, more repeatedly washs with distilled water, vacuum-drying, obtains polyethyleneglycol modified sulfonated polyether sulfone derivatives.
5. sulfonated polyether sulphone according to claim 1, sulfonated polyether sulphone derivative and polyethyleneglycol modified sulfonated polyether sulfone derivatives are preparing the application in ion-exchange polymer/metal composite electric actuator.
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| CN116023649A (en) * | 2023-01-16 | 2023-04-28 | 华侨大学 | One-pot method for synthesizing fluorene block-containing polyarylether polymer and anion exchange membrane thereof |
| CN116023649B (en) * | 2023-01-16 | 2024-06-07 | 华侨大学 | One-pot method for synthesizing fluorene block-containing polyarylether polymer and anion exchange membrane thereof |
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