CN1978038B - Method for preparing homogeneous-phase anion exchange film - Google Patents
Method for preparing homogeneous-phase anion exchange film Download PDFInfo
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- CN1978038B CN1978038B CN200510123023A CN200510123023A CN1978038B CN 1978038 B CN1978038 B CN 1978038B CN 200510123023 A CN200510123023 A CN 200510123023A CN 200510123023 A CN200510123023 A CN 200510123023A CN 1978038 B CN1978038 B CN 1978038B
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- 238000000034 method Methods 0.000 title abstract description 18
- 238000005349 anion exchange Methods 0.000 title description 14
- 238000005576 amination reaction Methods 0.000 claims abstract description 34
- 238000002360 preparation method Methods 0.000 claims abstract description 30
- 238000005266 casting Methods 0.000 claims abstract description 22
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 20
- 239000012528 membrane Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims abstract 7
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 36
- 239000000047 product Substances 0.000 claims description 27
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- -1 poly(2,6-dimethyl 1,4 phenylene oxide) Polymers 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 5
- 229920002530 polyetherether ketone Polymers 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011968 lewis acid catalyst Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 3
- 229920013655 poly(bisphenol-A sulfone) Polymers 0.000 claims description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 2
- 239000006121 base glass Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- YSCVYRUCAPMZFG-UHFFFAOYSA-K trichlorotin Chemical compound Cl[Sn](Cl)Cl YSCVYRUCAPMZFG-UHFFFAOYSA-K 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 3
- 239000002244 precipitate Substances 0.000 claims 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 1
- 239000004695 Polyether sulfone Substances 0.000 claims 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims 1
- 239000012346 acetyl chloride Substances 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 239000004745 nonwoven fabric Substances 0.000 claims 1
- 229920002852 poly(2,6-dimethyl-1,4-phenylene oxide) polymer Polymers 0.000 claims 1
- 229920001643 poly(ether ketone) Polymers 0.000 claims 1
- 229920006393 polyether sulfone Polymers 0.000 claims 1
- 229920012287 polyphenylene sulfone Polymers 0.000 claims 1
- 238000007790 scraping Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 4
- 238000000909 electrodialysis Methods 0.000 abstract description 3
- 238000010612 desalination reaction Methods 0.000 abstract description 2
- 125000000129 anionic group Chemical group 0.000 abstract 1
- 239000012267 brine Substances 0.000 abstract 1
- 238000000502 dialysis Methods 0.000 abstract 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 24
- 239000003153 chemical reaction reagent Substances 0.000 description 11
- 238000005342 ion exchange Methods 0.000 description 9
- 125000002252 acyl group Chemical group 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000002329 infrared spectrum Methods 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 230000021736 acetylation Effects 0.000 description 5
- 238000006640 acetylation reaction Methods 0.000 description 5
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 5
- 230000031709 bromination Effects 0.000 description 5
- 238000005893 bromination reaction Methods 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000007265 chloromethylation reaction Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 206010016825 Flushing Diseases 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 230000003381 solubilizing effect Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical group C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 206010023126 Jaundice Diseases 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 2
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 description 2
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 2
- 229920000491 Polyphenylsulfone Polymers 0.000 description 2
- 229920003295 Radel® Polymers 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000357 carcinogen Toxicity 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- YUMNZEWYPUBSQA-UHFFFAOYSA-N 1-(chloromethoxy)octane Chemical compound CCCCCCCCOCCl YUMNZEWYPUBSQA-UHFFFAOYSA-N 0.000 description 1
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical compound CCCCOC CXBDYQVECUFKRK-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 101000880855 Mus musculus Uridylate-specific endoribonuclease Proteins 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- FXXACINHVKSMDR-UHFFFAOYSA-N acetyl bromide Chemical compound CC(Br)=O FXXACINHVKSMDR-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 125000005252 haloacyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Abstract
The present invention relates to a preparation method of homogeneous anion-exchange membrane. Said method includes three processes of membrane-casting liquor preparation, membrane-forming and amination. Said invention also provides the concrete steps of above-mentioned every process. Said homogeneous anion-exchange membrane has extensive application field, it can be used for making concentration or desalination of dilute brine solution in electrodialysis method, can be used as electrolytic diaphragm in metallurgical industry, can be used as diffusive dialysis membrane for recovering acid and can be used as anionic selective electrode, etc.
Description
Technical field:
The invention belongs to the membrane technology field, particularly adopt Fu-Ke prepared in reaction to have the polymer of the acid halide group of easy amination, and be the method that matrix prepares homogeneous-phase anion exchange film with prepared polymer.
Background technology:
At present anion-exchange membrane has been widely used in various industrial circles, as: rare salting liquid is concentrated electroosmose process or desalination, as the electrolyte membrane in the hydrometallurgy industry, from spent acid recovered acid, as anion-selective electrode, as the alkaline fuel cell barrier film etc.But the prior art for preparing anion-exchange membrane is difficult, and main cause is to need to adopt the chloromethylation step among the traditional preparation method, will use the carcinogen chloromethyl ether like this, so people is seeking the method for not using chloromethyl ether and preparing anion-exchange membrane always.
U.S.'s " synthesizing " magazine (Synthesis, 1974,560) has been reported use 1-chloro-4-chlorine methyl butyl ether and 1, follows the method that amination makes anion-exchange membrane thereby long-chain chloromethyl ethers such as 4-dimethoxy-butane carry out chloromethylation.U.S.'s " polymer science-polymer chemistry " magazine (J Poym Sci:Pomy Chem Ed, 1985,23,1839) has proposed to make the method that chloromethylation reagent prepares anion-exchange membrane with chloromethyl octyl ether and chloromethylated polymer methyl ether.Because the preparation of employed long-chain chloromethylether is complicated, its practical prospect is little in the said method; Because of steric effect, its chloromethylation step compares difficulty in addition, causes productive rate too low.
Holland " membrane science and technical journal " (Journel of Membrane Science, 2001,183 (2): 193-200) reported to be that raw material prepares a series of homogeneous-phase anion exchange film by methyl bromination and phenyl ring bromination, but the bromine that uses in the bromination process also is a noxious material with polyphenylene oxide; And carry out owing to be reflected under the higher temperature, need to use higher boiling toxic solvent chlorobenzene, in film forming procedure, must remove these solvents again, be not good at, environment is had pollution, and cost is also higher if handle.And the methyl brominated product is very active, is easy to generate the crosslinked film-forming process subsequently that makes and becomes difficult.
Chinese patent application numbers 200410041520.3 has proposed a kind of quaternary amine type anionite and preparation method thereof; on polystyrene, introduce the controlled alpha-halogen acetyl group of loading, prepare the quaternary amine type anionite of different exchange capacities again with amine or ammonia cross-linking reaction by Fu-Ke reaction.But the raw material that it adopts is a granules of polystyrene, and product is ion exchange resin rather than film, and its restricted application can not be used for electrodialysis, diaphragm electrolysis or fuel cell barrier film etc.; And because of active ion is constantly fallen inactivation by exchange, need frequent regeneration in the use, operating process can not be continuous, and need in the regeneration to consume a large amount of alkali lye, and the discharging of regenerated liquid also can cause secondary pollution to environment.
Holland " reactive functionality polymer " magazine (Ractive ﹠amp; Functiona lPolymer, 1999,42:235-242) reported to be reflected at and introduce acetyl group on the crosslinked polystyrene, and then bromination, amination prepare anion exchange resin by Fu-Ke.But the raw material that said method adopts also is a granules of polystyrene, and the acetyl bromide product facile hydrolysis after the bromination makes the exchange capacity after its amination not high, influences its application; Equally, can inactivation needs frequent regeneration because active ion is constantly fallen by exchange in the use; And product is ion exchange resin rather than film, all can't use in fields such as electrodialysis, diaphragm electrolysis or fuel cell barrier films, thereby restricted application.
Summary of the invention:
The present invention proposes a kind of preparation method of homogeneous-phase anion exchange film, overcoming the above-mentioned defective of prior art, for the preparation of homogeneous-phase anion exchange film provides a more simple and direct approach.
The preparation method of homogeneous-phase anion exchange film of the present invention comprises the preparation of casting solution, film forming and amination step;
Being prepared as of described casting solution: in solvent, be connected to the polymer that electron donating group comprises methyl, hydroxyl or methoxyl group on phenyl ring and the phenyl ring with containing on the high polymer main chain, with lewis acid catalyst and chloracetyl chloride be 1 in molar ratio: 0.5-2: 0.5-2, at 20-60 ℃ of stirring reaction 1-8 hour, obtain the thick precipitation of black and from reactant liquor, separate out;
It is characterized in that: should thick precipitation dissolve settling step more earlier, and obtain the chloroacetylation product of polymer through alcohols;
Described film forming step is: dried above-mentioned product is dissolved in the 3-4.5 gram good solvent by every gram product fully dissolves standing and defoaming again, with gained casting solution knifing and at room temperature natural film forming on base glass plate, nonwoven or fabric;
Described amination step is: is 1 in 30-70 ℃ of temperature at amine and water volume ratio with the above-mentioned film that makes: amination in the solution of 1-5.5 concentration, and take out and be drying to obtain homogeneous-phase anion exchange film.
The described polymer that has electron donating group comprises poly-(2,6-dimethyl 1,4 penylene oxygen) (PPO), PPSU (Radel), bisphenol a polysulfone (Udel), polyether sulfone (PES), polyether-ether-ketone (PEEK) or polyether-ketone (PEK).
The used alcohols of described precipitation dissolving comprises methyl alcohol or ethanol.
Described lewis acid catalyst comprises aluminum trichloride (anhydrous), Antimony pentachloride, tin trichloride or ferric trichloride.
Solvent used in the preparation of described casting solution comprises chloroform, 1,1-dichloroethanes, 1,2-dichloroethanes, chlorobenzene or carrene.
Described amine comprises trimethylamine, dimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine or diethylamine.
The solvent of described chloroacetylation product comprises N, dinethylformamide (DMF), N, N-diethyl acetamide (DMAc), methyl-sulfoxide (DMSO) or chlorobenzene.
Compared with prior art, because adopting, the present invention carries out chloroacetylation by Fu-Ke reaction pair polymer earlier, by alcohols product dissolving earlier is precipitated out again, carry out aminating reaction again, make membrane material functionalization lotus positive electricity, not only avoided prior art to use the strong carcinogen chloromethyl ether, made operating process safer, and need not loaded down with trivial details, time-consuming functionalization post processing; Because the present invention obtains the reactant of different chloroacetylation degree by Fu-control of Ke reaction condition; and then again by the kind of aminating agent, the concentration of amination liquid; the adjusting of amination time and these factors of amination temperature comes its lotus positive electricity degree is controlled, and can obtain homogeneous-phase anion exchange film different exchange capacities, stable performance.The inventive method has easy, rapid and safe advantage from work angle; From performance perspective, the film that makes has homogeneous phase stable performance, ion exchange capacity height, the strong characteristics of resistance tocrocking; And but the seriation exploitation is to satisfy the needs in different application field.
The specific embodiment:
Further describe the preparation method of anion-exchange membrane of the present invention by the following examples.
Embodiment 1: be solvent with the chloroform, reactant molar ratio is for gathering (2,6-dimethyl 1,4 penylene oxygen) (PPO): aluminum trichloride (anhydrous) (AlCl
3): chloracetyl chloride (CAC)=1: 1.25: 1.25 o'clock 40 ℃ of reactions, is that amination reagent prepares homogeneous phase quaternary amine type anion-exchange membrane with the trimethylamine solution
(1) preparation of casting solution: successively 1molppo and 1.25mol aluminum trichloride (anhydrous) are dissolved in and electric mixer is housed and fills in the 250ml there-necked flask of 100ml chloroform, treat that under agitation it fully dissolves after, slowly drip the 20ml chloracetyl chloride with constant pressure funnel; , with ethanol product chloroacetylation ppo is precipitated out again after four hours 40 ℃ of reactions with ethanol elder generation solubilizing reaction product.60 ℃ of vacuum drying.
Dried product is carried out infrared spectrum analysis, at 1700cm
-1Strong acyl group peak appears in the place, illustrates to have connected the chloracetyl group on the ppo phenyl ring.
By the N of the corresponding 3.5ml of a gram chloroacetylation ppo, the ratio of dinethylformamide (DMF) is dissolved among the 35mlDMF standing over night with halo acyl group ppo10 gram.
(2) film forming: the casting solution after the deaeration is applied directly on the clean glass plate film forming in the air with glass bar.
(3) amination: the film that makes is immersed in the trimethylamine solution of 1mol/l, after 48 hours, film is taken out, till do not have a trimethylamine, make the transition in the NaCl solution with its immersion 1mol/l again with a large amount of water flushings 40 ℃ of following aminations.
After measured, the moisture content of gained film is 167.1%, and ion exchange capacity (IEC) is the 1.15meq/g dry film, and film resistance is 0.2 Ω cm
2
In the present embodiment if adopt PPSU (Radel), bisphenol a polysulfone (Udel), polyether sulfone (PES), polyether-ether-ketone (PEEK) or polyether-ketone (PEK) replace poly-(2,6-dimethyl 1,4 penylene oxygen) (PPO), with 1, the 1-dichloroethanes, 1, the 2-dichloroethanes, chlorobenzene or carrene surrogate response solvent chloroform, dissolution precipitation etoh solvent with methyl alcohol surrogate response thing, the solvent chlorobenzene that casting solution is used, N, N-diethyl acetamide (DMAc) replaces N, dinethylformamide (DMF) is used triethylamine, tripropyl amine (TPA), tri-n-butylamine replaces trimethylamine as amination reagent, and available is film similarly.
Embodiment 2: be solvent with the chloroform, reactant molar ratio is PPO: AlCl
3: CAC=1: 40 ℃ reactions, with diethylamine solution be amination reagent prepare homogeneous phase tertiary amine-type anion-exchange membrane at 1.25: 1.25
(1) preparation of casting solution: successively 1molPPO and 1.25mol aluminum trichloride (anhydrous) are dissolved in the 250ml there-necked flask that fills the 100ml chloroform, treat that under agitation it fully dissolves after, slowly drip the 20ml chloracetyl chloride with constant pressure funnel., with ethanol product chloroacetylation PPO is precipitated out again after four hours 40 ℃ of reactions with ethanol elder generation solubilizing reaction product.60 ℃ of vacuum drying.
Dried product is carried out infrared spectrum analysis, at 1700cm
-1Strong acyl group peak appears in the place, illustrates to have connected the chloracetyl group on the PPO phenyl ring.
By the N of the corresponding 3.5ml of a gram chloroacetylation PPO, the ratio of dinethylformamide (DMF) is dissolved among the 35mlDMF standing over night with chloroacetylation PPO (APPO) 10 grams.
(2) film forming: the casting solution after the deaeration is applied directly on the clean glass plate film forming in the air with glass bar.
(3) amination: the film that makes is immersed in the solution of 1mol/l, after 48 hours, film is taken out, till do not have a diethylamine, make the transition in the NaCl solution with its immersion 1mol/l again with a large amount of water flushings 40 ℃ of aminations.
After measured, the moisture content of gained film is 180.3%, and ion exchange capacity (IEC) is the 1.02meq/g dry film, and film resistance is 1.3 Ω cm
2
If adopt dimethylamine solution to replace diethylamine solution as amination reagent, also available can similar homogeneous phase tertiary amine-type anion-exchange membrane.
Embodiment 3: be solvent with the chloroform, reactant molar ratio is for gathering (2,6-dimethyl 1,4 penylene oxygen) (PPO): AlCl
3: CAC=1: 1.25: 1.25, under different temperatures, react, be that amination reagent prepares homogeneous phase quaternary amine type anion-exchange membrane with the trimethylamine solution
(1) preparation of casting solution: successively 1mol PPO and 1.25mol aluminum trichloride (anhydrous) are dissolved in the 250ml there-necked flask that fills the 100ml chloroform; after treating that under agitation it fully dissolves; slowly drip the 20ml chloracetyl chloride with constant pressure funnel; adopt 20 ℃ of reaction temperatures, 30 ℃, 40 ℃, 50 ℃, 60 ℃ to react respectively; after question response is complete; with ethanol solubilizing reaction product, with ethanol product chloroacetylation PPO is precipitated out again, earlier 60 ℃ of vacuum drying.
Dried product is carried out infrared spectrum analysis, at 1700cm
-1Strong acyl group peak appears in the place, illustrates to have connected the chloracetyl group on the PPO phenyl ring.
By the N of the corresponding 3.5ml of a gram chloroacetylation PPO, the ratio of dinethylformamide (DMF) is dissolved among the 35mlDMF standing over night with chloroacetylation PPO 10 grams.
(2) film forming: the casting solution after the deaeration is applied directly on the clean glass plate film forming in the air with glass bar.
(3) amination: the film that makes is immersed in the trimethylamine solution of 1mol/l, after 48 hours, film is taken out, till do not have a trimethylamine, make the transition in the NaCl solution with its immersion 1mol/l again with a large amount of water flushings 40 ℃ of aminations
The performance characterization of the various films of gained is as shown in the table after measured:
| Reaction temperature (℃) | Film forming | Moisture content (w%) | IEC (meq/ restrains dry film) |
| 20 | Be insoluble to DMF | ||
| 30 | But film forming | 210.3 | 0.83 |
| 40 | Well | 167.1 | 1.17 |
| 50 | More crisp, jaundice | 154.3 | 0.86 |
| 60 | Very crisp | 58.6 | 0.94 |
In the last table, IEC represents ion exchange capacity; Moisture content (w%)=100%* (W wet film-W dry film)/W dry film.
Embodiment 4: the fixation reaction temperature is 40 ℃, reactant molar ratio PPO: CAC=1: 1, and the amount that changes aluminum trichloride (anhydrous) is carried out chloroacetylation, is that amination reagent prepares quaternary amine type homogeneous-phase anion exchange film with the trimethylamine solution
(1) preparation of casting solution: keep the amount of chloracetyl chloride (CAC), PPO to be respectively 1.25mol, 1mol, the amount that changes aluminum trichloride (anhydrous) successively is respectively 0.5mol, 0.7mol, 1.25mol, 1.5mol; Press the step operation of embodiment 1, obtain chloroacetylation product (APPO) respectively.
Dried each product is carried out infrared spectrum analysis, all at 1700cm
-1Strong acyl group peak appears in the place, illustrates on the PPO segment phenyl ring to have connected the chloracetyl group.
By the N of the corresponding 3.5ml of a gram chloroacetylation PPO, the ratio of dinethylformamide (DMF) is dissolved among every 35mlDMF standing over night with per 10 grams of various chloroacetylation PPO (APPO).
(2) film forming; Each casting solution after the deaeration is applied directly on the clean glass plate film forming in the air with glass bar.
(3) amination: the various films of gained are all operated by the step of embodiment 1.
The performance characterization of the various films of gained is as shown in the table after measured:
| CAC(mol) | PPO(mol) | AlCl 3(mol) | Film forming | Moisture content (w%) | IEC (meq/ restrains dry film) |
| 1 | 1 | 0.5 | Insoluble | ||
| 1 | 1 | 0.75 | Insoluble |
| CAC(mol) | PPO(mol) | AlCl 3(mol) | Film forming | Moisture content (w%) | IEC (meq/ restrains dry film) |
| 1 | 1 | 1.25 | Film forming | 180.2 | 0.48 |
| 1 | 1 | 2 | Very crisp | 50.6 | 0.91 |
In the last table, IEC represents ion exchange capacity; Moisture content (w%)=100%* (W wet film-W dry film)/W dry film.
Embodiment 5: fixedly the amount of PPO is 1mol, changes the amount of chloracetyl chloride (CAC) and anhydrous AlCl3 but its molar ratio remains unchanged and carries out chlorine acetylation at 1: 1, is that amination reagent prepares homogeneous-phase anion exchange film with the trimethylamine solution
(1) preparation of casting solution: keep the amount of PPO to be 1mol, the amount of chloracetyl chloride (CAC) and aluminum trichloride (anhydrous) is got 0.5mol, 0.75mol, 1mol, 1.5mol successively simultaneously.Step by embodiment 1 is operated, and obtains chloroacetylation product (APPO) respectively.
Dried each product is carried out infrared spectrum analysis, all at 1700cm
-1Strong acyl group peak appears in the place, illustrates on the PPO segment phenyl ring to have connected the chloracetyl group.
By the N of the corresponding 3.5ml of a gram chloroacetylation PPO, the ratio of dinethylformamide (DMF) is dissolved among every 35mlDMF standing over night with per 10 grams of various chloroacetylation PPO (APPO).
(2) film forming: the step with embodiment 2 is operated.
(3) quaternary ammoniated: the step with embodiment 1 is operated.
After measured, the performance characterization of the various films of gained is as shown in the table:
| CAC(mol) | PPO(mol) | AlCl 3(mol) | Film forming | Moisture content (w%) | IEC (meq/ restrains dry film) |
| 1 | 0.5 | 0.5 | Insoluble | ||
| 1 | 0.75 | 0.75 | Part is insoluble | ||
| 1 | 2 | 2 | More crisp, jaundice | 138.1 | 0.58 |
In the last table, IEC represents ion exchange capacity; Moisture content (w%)=100%* (W wet film-W dry film)/W dry film.
Embodiment 6: the fixation reaction temperature is 40 ℃, gets PPO, aluminum trichloride (anhydrous), each 1mol of chloracetyl chloride (CAC), 1.25mol, 1.25mol respectively, and the change reaction time is carried out chlorine acetylation.With the trimethylamine solution is that amination reagent prepares quaternary amine type homogeneous-phase anion exchange film
(1) preparation of casting solution: get PPO, aluminum trichloride (anhydrous), each 1mol of chloracetyl chloride (CAC), 1.25mol, 1.25mol respectively, reacted respectively 1 hour, two hours, three hours, four hours, eight hours; Step by embodiment 1 is carried out chlorine acetylation, obtains chloroacetylation product (APPO) respectively.
Dried each product is carried out infrared spectrum analysis, all at 1700cm
-1Strong acyl group peak appears in the place, illustrates on the PPO segment phenyl ring to have connected the chloracetyl group.
By the N of the corresponding 3.5ml of a gram chloroacetylation PPO, the ratio of dinethylformamide (DMF) is dissolved among every 35mlDMF standing over night with per 10 grams of various chloroacetylation PPO (APPO).
(2) film forming: with embodiment 2
(3) quaternary ammoniated: with embodiment 1.
It is as shown in the table for the performance characterization of the various films of gained after measured:
| Reaction time (h) | w％ | IEC (meq/ restrains dry film) | Rm(Ω.cm2) |
| 1 | 166.1 | 0.41 | 1805 |
| 2 | 191.8 | 0.61 | 183.3 |
| 3 | 194.4 | 0.75 | 173 |
| 4 | 167.1 | 0.78 | 170 |
| 8 | 201.3 | 0.92 | 23 |
In the last table, IEC represents ion exchange capacity; Moisture content (w%)=100%* (W wet film-W dry film)/W dry film; Rm represents film resistance.
Embodiment 7: getting PPO, CAC, each 1mol of aluminum trichloride (anhydrous), 1.25mol, 1.25mol respectively, react at 40 ℃, is that amination reagent prepares quaternary amine type homogeneous-phase anion exchange film with the trimethylamine solution of variable concentrations
(1) preparation of casting solution: the step by embodiment 1 is carried out chlorine acetylation.
Dried product is carried out infrared spectrum analysis, at 1700cm
-1Strong acyl group peak appears in the place, illustrates to have connected the chloracetyl group on the PPO phenyl ring.
By the N of the corresponding 3.5ml of a gram chloroacetylation PPO, the ratio of dinethylformamide (DMF) is dissolved among the 35mlDMF standing over night with chloroacetylation PPO (APPO) 10 grams.
(2) film forming: with embodiment 2
(3) quaternary ammoniated: get six films that make and immerse molar concentration respectively respectively for 2.5mol/l, 1.67mol/l, 1.43mol/l, 1.12mol/l, 0.91mol/l is in the trimethylamine solution of 0.77mol/l, 20 ℃ of aminations 48 hours.The performance characterization of the various films of gained is as shown in table 5 after measured:
| Trimethylamine concentration (mol/L) | Moisture content (w%) | IEC (meq/g dry film) | Rm(Ω·cm 2) | tcl | Em(eV) |
| 1+1(2.5) | 2.108 | 1.14 | 18.7 | 0.834 | 10.5 |
| 1+2(1.67) | 2.021 | 1.17 | 18.6 | 0.839 | 10.65 |
| +2.5(1.43) | 1.908 | 1.03 | 34.4 | 0.86 | 11.3 |
| 1+3.5(1.12) | 1.907 | 0.803 | 89.2 | 0.836 | 10.55 |
| 1+4.5(0.91) | 1.753 | 0.78 | 170 | 0.821 | 10.07 |
| Trimethylamine concentration (mol/L) | Moisture content (w%) | IEC (meq/g dry film) | Rm(Ω·cm 2) | tcl | Em(eV) |
| 1+5.5(0.77) | 1.822 | 0.76 | 158 | 0.824 | 10.17 |
In the last table, IEC represents ion exchange capacity; Moisture content (w%)=100%* (W wet film-W dry film)/W dry film; Rm represents film resistance, and Em represents film potential, and tcl represents transference number of ions.
Embodiment 8: get PPO, CAC, each 1mol of aluminum trichloride (anhydrous) respectively, 1.25mol, 1.25mol react under 40 ℃, the trimethylamine solution that with concentration is 0.91mol/L is that amination reagent prepares quaternary amine type homogeneous-phase anion exchange film under different amination temperature
(1) preparation of casting solution: carry out chlorine acetylation by embodiment 1 step.Dried product is carried out infrared spectrum analysis, at 1700cm
-1Strong acyl group peak appears in the place, illustrates to have connected the chloracetyl group on the ppo phenyl ring.By the N of the corresponding 3.5ml of a gram chloroacetylation ppo, the ratio of dinethylformamide (DMF) is dissolved among the 35mlDMF standing over night with chloroacetylation ppo (APPO) 10 grams.
(2) film forming: with embodiment 2.
(3) quaternary ammoniated: get six films that make and immerse respectively in the trimethylamine solution that molar concentration is 0.91mol/l respectively at 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ of following aminations 48 hours.
The performance characterization of the various films of gained is as shown in table 6 after measured
| The amination temperature (℃) | Moisture content | IEC (meq/g dry film) | Rm(Ω·cm 2) | Em(eV) | tcl- |
| 30 | 1.683 | 0.78 | 170 | 9.83 | 0.82 |
| 40 | 2.428 | 1.15 | 0.2 | 11.3 | 0.86 |
| 50 | 2.45 | 1.02 | 46.4 | 11.15 | 0.856 |
| 60 | 2.32 | 0.733 | 133 | 9.45 | 0.807 |
| 70 | 2.21 | 0.678 | 491 | 5.3 | 0.35 |
In the last table, IEC represents ion exchange capacity; Moisture content (w%)=100%* (W wet film-W dry film)/W dry film; Rm represents film resistance, and Em represents film potential, and tcl represents transference number of ions.
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| CN104877136A (en) * | 2015-04-30 | 2015-09-02 | 大连理工大学 | Long-branched-chain polysulfone anionic membrane and preparation method thereof |
| CN109585888A (en) * | 2018-11-07 | 2019-04-05 | 大连理工大学 | A kind of blending type anion-exchange membrane and preparation method thereof |
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