CN102139190A - Method for preparing epoxy morpholine quaternary ammonium salt-modified polybenzimidazole anion exchange membrane - Google Patents
Method for preparing epoxy morpholine quaternary ammonium salt-modified polybenzimidazole anion exchange membrane Download PDFInfo
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Abstract
The invention relates to a method for preparing an epoxy morpholine quaternary ammonium salt-modified polybenzimidazole anion exchange membrane, which comprises the steps of: at first, adding chloroepoxy propane and N-methylmorpholine to an acetonitrile solvent, controlling reaction time and temperature to obtain epoxy morpholine quaternary ammonium salt, then dissolving an amino-containing polybenzimidazole homopolymer or copolymer in an organic solvent, reacting the organic solvent with the epoxy morpholine quaternary ammonium salt to obtain epoxy morpholine quaternary ammonium salt-modified polybenzimidazole, then dissolving the epoxy morpholine quaternary ammonium salt-modified polybenzimidazole in the organic solvent, adding a diepoxy crosslinking agent to the organic solvent, and performing casting membrane forming to obtain the epoxy morpholine quaternary ammonium salt-modified polybenzimidazole anion exchange membrane with excellent properties, wherein the anion electric conductivity of the membrane can reach 0.06S/cm. The epoxy quaternary ammonium salt compound-modified polybenzimidazole crosslinking membrane has quite extensive industrial application prospect in the fields such as alkali fuel cell, water treatment, heavy metal ion recovery and the like.
Description
Technical field
The present invention relates to a kind of preparation method of anion-exchange membrane, especially relate to the preparation method of the quaternary ammonium salt-modified polybenzimidazoles anion-exchange membrane of a kind of epoxy morpholine.This anion-exchange membrane can be applied to liquid flow energy storage battery, alkaline fuel cell, and water treatment, heavy metal ion recovery wait each big technical field.
Background technology
Anion-exchange membrane is generally done main chain with macromolecule, transportable anion on the active group of positively charged and the active group on the side chain band.Present most of anion-exchange membrane, its active group all are the quaternary ammonium salts that adopts the trimethylamine type, and structural formula is :-N
+(CH
3)
3Its synthetic route adopts the method for chloromethylation more, promptly earlier polymer is carried out chloromethylation with chloromethyl ether, uses trimethylamine quaternized again, obtains quaternised anion-exchange membrane.But there is poor heat resistance mostly in present business-like anion-exchange membrane, and alkali resistance is poor, the low deficiency that waits of electrical conductivity, and also the chloromethyl ether that uses has strong carcinogenicity.
Chinese patent 200710072040.7 discloses a kind of modified anion exchange membrane and preparation method thereof, and the preparation method of its modified anion exchange membrane realizes by following steps: (one) batching; (2) basement membrane preparation; (3) impregnation film preparation; (4) chloromethylation of impregnation film; (5) amination.This method has improved the hydrophily of film greatly by adding titanium dioxide.But the method for chloromethylation is used extremely toxic substance usually, is unfavorable for health and suitability for industrialized production.
From point of practical application, be necessary to invent a kind of environmental friendliness, hear resistance, alkali resistance, the anion exchange membrane material of excellent combination properties such as good mechanical property and electrical conductivity height.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, the preparation method of the quaternary ammonium salt-modified polybenzimidazoles anion-exchange membrane of a kind of epoxy morpholine is provided, its course of reaction does not have obvious harm to human body and environment, prepared anion-exchange membrane, mechanical performance is strong, alkali resistance is good, and has quite high electrical conductivity.
For achieving the above object, the present invention at first adds epoxychloropropane and N-methylmorpholine in second cyanogen solvent, control reaction time and temperature, obtain epoxy morpholine quaternary ammonium salt, after will containing amino polybenzimidazoles homopolymers or copolymer then and being dissolved in organic solvent, react with epoxy morpholine quaternary ammonium salt, obtain the quaternary ammonium salt-modified polybenzimidazoles of epoxy morpholine, again that the epoxy morpholine is quaternary ammonium salt-modified polybenzimidazoles is dissolved in the organic solvent, add the bis-epoxy crosslinking agent, the cast film forming obtains having the fuel cell quaternary ammonium salt-modified polybenzimidazoles anion-exchange membrane of epoxy morpholine of premium properties.
The structural formula of the quaternary ammonium salt-modified polybenzimidazoles anion-exchange membrane of epoxy morpholine of the present invention is:
x
1，x
2＝1000-100000，y
1，y
2＝1000-100000，x
1∶y
1＝1∶1-100，x
2∶y
2＝1∶1-100
The concrete preparation method of the quaternary ammonium salt-modified polybenzimidazoles anion-exchange membrane of epoxy morpholine of the present invention is as follows:
The first step: in the three-necked bottle of drying, add second cyanogen earlier, add N-methylmorpholine and epoxychloropropane then successively, wherein the volume ratio of N-methylmorpholine and second cyanogen is 0.5-4: 1, and mol ratios such as N-methylmorpholine and epoxychloropropane maintenance; After fully stirring, logical inert gas also is warming up to 20-80 ℃, react to stop heating after 4-48 hour, and suction filtration also fully washs the epoxy morpholine quaternary ammonium salt that obtains with ether, again with the acetone washing, and abundant dried for standby in vacuum drying oven;
Second step: in the three-necked bottle of drying, add and contain amino polybenzimidazoles and dimethyl sulfoxide (DMSO), logical inert gas shielding, the mass ratio that contains amino polybenzimidazoles and dimethyl sulfoxide (DMSO) is 0.01-0.2: 1; After waiting to contain amino polybenzimidazoles and fully dissolving, add epoxy morpholine quaternary ammonium salt, wherein epoxy morpholine quaternary ammonium salt remains on 1 with the mol ratio that contains amino polybenzimidazoles: 1-10: 1; Be warming up to 50-120 ℃, reacted 2-20 hour; After reaction finishes, the product precipitating in poor solvent, with the unreacted epoxy morpholine of thorough removal quaternary ammonium salt, is obtained the quaternary ammonium salt-modified polybenzimidazoles of epoxy morpholine abundant dried for standby in vacuum drying oven;
The 3rd step: in the conical flask of drying, add quaternary ammonium salt-modified polybenzimidazoles and the dimethyl sulfoxide (DMSO) of epoxy morpholine, the polybenzimidazoles that the epoxy morpholine is quaternary ammonium salt-modified and the mass ratio of dimethyl sulfoxide (DMSO) are 0.01-0.2: 1; Fully after the dissolving, add the bis-epoxy crosslinking agent, the mass ratio of the polybenzimidazoles that bis-epoxy crosslinking agent and epoxy morpholine are quaternary ammonium salt-modified is 0.05-0.2: 1; After stirring, polymer solution is filtered, be poured over then on the smooth clean glass plate, 50-140 ℃ was descended dry 5-48 hour, again in vacuum drying oven, under the uniform temp dry 1-24 hour, obtain the quaternary ammonium salt-modified crosslinked polybenzimidazole membrane of epoxy morpholine;
The 4th step: the crosslinked polybenzimidazole membrane that the epoxy morpholine of above-mentioned preparation is quaternary ammonium salt-modified is immersed in the aqueous slkali of 0.2-10mol/L, spend deionised water after 4-48 hour to neutral, promptly obtain the quaternary ammonium salt-modified polybenzimidazoles anion-exchange membrane of epoxy morpholine of hydroxide ion type.
Among the present invention, described poor solvent is acetone, water, methyl alcohol, ethanol, n-hexane or cyclohexane.
Described bis-epoxy crosslinking agent is bisphenol A epoxide resin or DGEEG.
Described aqueous slkali is sodium hydroxide solution or potassium hydroxide solution
The inventive method is easy, the reaction condition gentleness, and course of reaction does not have obvious harm to human body and environment, the quaternary ammonium salt-modified polybenzimidazoles anion-exchange membrane of prepared epoxy morpholine, mechanical performance is strong, and alkali resistance is good, and have quite high electrical conductivity, can reach 0.06S/cm.At liquid flow energy storage battery, alkaline fuel cell, water treatment, heavy metal ion recovery wait each big field, have very wide prospect in industrial application.
Description of drawings
Fig. 1 contains the nuclear magnetic spectrogram of amino polybenzimidazoles
1H NMR (DMSO-D
6)
The nuclear magnetic spectrogram of Fig. 2 epoxy morpholine quaternary ammonium salt
1H NMR (H
2O-D
6)
The nuclear magnetic spectrogram of the quaternary ammonium salt-modified polybenzimidazoles of epoxy morpholine that Fig. 3 embodiment 1 obtains
1H NMR (DMSO-D
6)
The nuclear magnetic spectrogram of the quaternary ammonium salt-modified polybenzimidazoles of epoxy morpholine that Fig. 4 embodiment 2 obtains
1H NMR (DMSO-D
6)
The nuclear magnetic spectrogram of the quaternary ammonium salt-modified polybenzimidazoles of epoxy morpholine that Fig. 5 embodiment 3 obtains
1H NMR (DMSO-D
6)
The specific embodiment
Below by specific embodiment technical scheme of the present invention is further described.Following embodiment further specifies of the present invention, rather than limits the scope of the invention.
(1) in the three-necked bottle of 100ml drying, add 5ml second cyanogen earlier, add 20ml (0.18mol) N-methylmorpholine then, 14.7ml (0.18mol) epoxychloropropane, after fully stirring, logical nitrogen also heats up 40 ℃, react and stop heating after 48 hours, have a large amount of white solids to produce.Suction filtration also fully washs the epoxy morpholine quaternary ammonium salt that obtains three times with ether, and acetone washs once, in vacuum drying oven 50 ℃ abundant dry 10h are stand-by down.
(2) in the three-necked bottle of 100ml drying, add the amino polybenzimidazoles that contains of 0.646g (2mmol), the 17.6ml dimethyl sulfoxide (DMSO), logical nitrogen protection is warming up to 80 ℃.After waiting to contain amino polybenzimidazoles and fully dissolving, reduce to room temperature and add 0.387g (2mmol) epoxy morpholine quaternary ammonium salt, and be warming up to 85 ℃, reacted 10 hours.After reaction finished, in acetone, and with acetone washing three times, reusable heat ethanol fully washed subsequently, with the unreacted quaternary ammonium salt of thorough removal with the product chromatography.The faint yellow quaternized polybenzimidazoles that obtains in vacuum drying oven 60 ℃ fully dry 10 hours stand-by.
(3) in the conical flask of drying, add the quaternized polybenzimidazoles of 0.5g, the 6ml dimethyl sulfoxide (DMSO), fully after the dissolving, add the bisphenol A type epoxy resin of 0.03g, magnetic agitation is after 30 minutes, polymer solution is filtered with glass, be poured over then on the smooth clean glass plate.Under 80 ℃, forced air drying in vacuum drying oven, under the uniform temp, obtained the quaternary ammonium salt-modified crosslinked polybenzimidazole membrane of epoxy morpholine with the dimethyl sulfoxide (DMSO) in the abundant removal film in dry 5 hours after 10 hours again.
(4) under the normal temperature, the crosslinked polybenzimidazole membrane that the epoxy morpholine of above-mentioned preparation is quaternary ammonium salt-modified was immersed in the sodium hydrate aqueous solution of 2mol/L after 48 hours, spent deionised water 24 hours, to neutral, promptly obtain the quaternary ammonium salt-modified polybenzimidazoles anion-exchange membrane of epoxy morpholine of hydroxide ion type.
(1) in the three-necked bottle of 100ml drying, add 5ml second cyanogen earlier, add 20ml (0.18mol) N-methylmorpholine then, 14.7ml (0.18mol) epoxychloropropane, after fully stirring, logical nitrogen also heats up 40 ℃, react and stop heating after 48 hours, have a large amount of white solids to produce.Suction filtration also fully washs the epoxy morpholine quaternary ammonium salt that obtains three times with ether, and acetone washs once, in vacuum drying oven 50 ℃ abundant dry 10h are stand-by down.
(2) in the three-necked bottle of 100ml drying, add the amino polybenzimidazoles that contains of 0.646g (2mmol), the 17.6ml dimethyl sulfoxide (DMSO), logical nitrogen protection is warming up to 80 ℃.After waiting to contain amino polybenzimidazoles and fully dissolving, reduce to room temperature and add 0.580g (3mmol) epoxy morpholine quaternary ammonium salt, and be warming up to 85 ℃, reacted 10 hours.After reaction finished, in acetone, and with acetone washing three times, reusable heat ethanol fully washed subsequently, with the unreacted quaternary ammonium salt of thorough removal with the product chromatography.The faint yellow quaternized polybenzimidazoles that obtains in vacuum drying oven 60 ℃ fully dry 10 hours stand-by.
(3) in the conical flask of drying, add the quaternized polybenzimidazoles of 0.5g, the 6ml dimethyl sulfoxide (DMSO), fully after the dissolving, add the bisphenol A type epoxy resin of 0.03g, magnetic agitation is after 30 minutes, polymer solution is filtered with glass, be poured over then on the smooth clean glass plate.Under 80 ℃, forced air drying in vacuum drying oven, under the uniform temp, obtained the quaternary ammonium salt-modified crosslinked polybenzimidazole membrane of epoxy morpholine with the dimethyl sulfoxide (DMSO) in the abundant removal film in dry 5 hours after 10 hours again.
(4) under the normal temperature, the crosslinked polybenzimidazole membrane that the epoxy morpholine of above-mentioned preparation is quaternary ammonium salt-modified was immersed in the sodium hydrate aqueous solution of 2mol/L after 48 hours, spent deionised water 24 hours, to neutral, promptly obtain the quaternary ammonium salt-modified polybenzimidazoles anion-exchange membrane of epoxy morpholine of hydroxide ion type.
(1) in the three-necked bottle of 100ml drying, add 5ml second cyanogen earlier, add 20ml (0.18mol) N-methylmorpholine then, 14.7ml (0.18mol) epoxychloropropane, after fully stirring, logical nitrogen also heats up 40 ℃, react and stop heating after 48 hours, have a large amount of white solids to produce.Suction filtration also fully washs the epoxy morpholine quaternary ammonium salt that obtains three times with ether, and acetone washs once, in vacuum drying oven 50 ℃ abundant dry 10h are stand-by down.
(2) in the three-necked bottle of 100ml drying, add the amino polybenzimidazoles that contains of 0.646g (2mmol), the 17.6ml dimethyl sulfoxide (DMSO), logical nitrogen protection is warming up to 80 ℃.After waiting to contain amino polybenzimidazoles and fully dissolving, reduce to room temperature and add 0.774g (4mmol) epoxy morpholine quaternary ammonium salt, and be warming up to 85 ℃, reacted 10 hours.After reaction finished, in acetone, and with acetone washing three times, reusable heat ethanol fully washed subsequently, with the unreacted quaternary ammonium salt of thorough removal with the product chromatography.The faint yellow quaternized polybenzimidazoles that obtains in vacuum drying oven 60 ℃ fully dry 10 hours stand-by.
(3) in the conical flask of drying, add the quaternized polybenzimidazoles of 0.5g, the 6ml dimethyl sulfoxide (DMSO), fully after the dissolving, add the bisphenol A type epoxy resin of 0.03g, magnetic agitation is after 30 minutes, polymer solution is filtered with glass, be poured over then on the smooth clean glass plate.Under 80 ℃, forced air drying in vacuum drying oven, under the uniform temp, obtained the quaternary ammonium salt-modified crosslinked polybenzimidazole membrane of epoxy morpholine with the dimethyl sulfoxide (DMSO) in the abundant removal film in dry 5 hours after 10 hours again.
(4) under the normal temperature, the crosslinked polybenzimidazole membrane that the epoxy morpholine of above-mentioned preparation is quaternary ammonium salt-modified was immersed in the sodium hydrate aqueous solution of 2mol/L after 48 hours, spent deionised water 24 hours, to neutral, promptly obtain the quaternary ammonium salt-modified polybenzimidazoles anion-exchange membrane of epoxy morpholine of hydroxide ion type.
Quaternary ammonium salt-modified polybenzimidazoles of epoxy morpholine and the crosslinked anion-exchange membrane of making are carried out nuclear-magnetism and IR Characterization respectively, and the result proves that the product of gained is a target product.
Characterization result is as follows:
Fig. 1 contains amino polybenzimidazoles
1H NMR is with DMSO-d
6Be solvent, the ownership at each peak is indicated in collection of illustrative plates that respectively 7.41-8.25ppm is the chemical shift of 1 to 5 hydrogen on the phenyl ring, 12.90-13.10ppm is on the imidazole ring-and the chemical shift of NH hydrogen, 5.35-5.80ppm is the chemical shift of amino hydrogen on the phenyl ring.
Fig. 2 is an epoxy morpholine quaternary ammonium salt
1H NMR is with H
2O-d
6Be solvent, the ownership at each peak is indicated in collection of illustrative plates respectively, 3.95-4.00ppm be the chemical shift of 1 hydrogen linking to each other with morpholine O atom, 3.40-3.60 be link to each other with the N atom 2, the chemical shift of 3 hydrogen, 3.18-3.27 be the chemical shift of 6,4 hydrogen on methyl and the epoxychloropropane in the morpholine, 2.68-2.72 and 2.94-2.97 be on the epoxychloropropane two isomery hydrogen 5 chemical shift.
Fig. 3,4, the 5th, epoxy morpholine quaternary ammonium salt and contain amino polybenzimidazoles mol ratio and be respectively reaction in 1: 1,1.5: 1,2: 1, the nuclear magnetic spectrogram of the quaternary ammonium salt-modified polybenzimidazoles of epoxy morpholine that obtains among three embodiment of the present invention
1H NMR is with DMSO-d
6Be solvent, the ownership at each peak is indicated in collection of illustrative plates respectively, and its each peak position and Fig. 1 are basic identical among Fig. 2, but new-NH peak occurred at the 5.80-6.20 place, and the proved response product is a target product.
Claims (4)
1. the preparation method of the quaternary ammonium salt-modified polybenzimidazoles anion-exchange membrane of epoxy morpholine is characterized in that may further comprise the steps:
1) in the three-necked bottle of drying, add second cyanogen earlier, add N-methylmorpholine and epoxychloropropane then successively, wherein the volume ratio of N-methylmorpholine and second cyanogen is 0.5-4: 1, mol ratios such as N-methylmorpholine and epoxychloropropane maintenance; After fully stirring, logical inert gas also is warming up to 20-80 ℃, react to stop heating after 4-48 hour, and suction filtration also fully washs the epoxy morpholine quaternary ammonium salt that obtains with ether, again with the acetone washing, and abundant dried for standby in vacuum drying oven;
2) in the three-necked bottle of drying, add and contain amino polybenzimidazoles and dimethyl sulfoxide (DMSO), logical inert gas shielding, the mass ratio that contains amino polybenzimidazoles and dimethyl sulfoxide (DMSO) is 0.01-0.2: 1; After waiting to contain amino polybenzimidazoles and fully dissolving, add epoxy morpholine quaternary ammonium salt, wherein epoxy morpholine quaternary ammonium salt remains on 1 with the mol ratio that contains amino polybenzimidazoles: 1-10: 1; Be warming up to 50-120 ℃, reacted 2-20 hour; After reaction finishes, the product precipitating in poor solvent, with the unreacted epoxy morpholine of thorough removal quaternary ammonium salt, is obtained the quaternary ammonium salt-modified polybenzimidazoles of epoxy morpholine abundant dried for standby in vacuum drying oven;
3) in the conical flask of drying, add quaternary ammonium salt-modified polybenzimidazoles and the dimethyl sulfoxide (DMSO) of epoxy morpholine, the polybenzimidazoles that the epoxy morpholine is quaternary ammonium salt-modified and the mass ratio of dimethyl sulfoxide (DMSO) are 0.01-0.2: 1; Fully after the dissolving, add the bis-epoxy crosslinking agent, the mass ratio of the polybenzimidazoles that bis-epoxy crosslinking agent and epoxy morpholine are quaternary ammonium salt-modified is 0.05-0.2: 1; After stirring, polymer solution is filtered, be poured over then on the smooth clean glass plate, 50-140 ℃ was descended dry 5-48 hour, again in vacuum drying oven, under the uniform temp dry 1-24 hour, obtain the quaternary ammonium salt-modified crosslinked polybenzimidazole membrane of epoxy morpholine;
4) the epoxy morpholine of above-mentioned preparation is quaternary ammonium salt-modified crosslinked polybenzimidazole membrane is immersed in the aqueous slkali of 0.2-10mol/L, spend deionised water after 4-48 hour to neutral, promptly obtain the quaternary ammonium salt-modified polybenzimidazoles anion-exchange membrane of epoxy morpholine of hydroxide ion type.
2. according to the preparation method of the quaternary ammonium salt-modified polybenzimidazoles anion-exchange membrane of epoxy morpholine of claim 1, it is characterized in that described poor solvent is acetone, water, methyl alcohol, ethanol, n-hexane or cyclohexane.
3. according to the preparation method of the quaternary ammonium salt-modified polybenzimidazoles anion-exchange membrane of epoxy morpholine of claim 1, it is characterized in that described bis-epoxy crosslinking agent is bisphenol A epoxide resin or DGEEG.
4. according to the preparation method of the quaternary ammonium salt-modified polybenzimidazoles anion-exchange membrane of epoxy morpholine of claim 1, it is characterized in that described aqueous slkali is sodium hydroxide solution or potassium hydroxide solution.
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| CN105647453A (en) * | 2016-01-15 | 2016-06-08 | 李娜 | Anticorrosion antibacterial epoxy sealant and preparation method thereof |
| CN106543459A (en) * | 2016-11-10 | 2017-03-29 | 常州大学 | A kind of preparation method of polybenzimidazoles/modified poly-epoxy chloropropane composite anion exchange membrane |
| CN107887626A (en) * | 2017-11-09 | 2018-04-06 | 中国科学院上海有机化学研究所 | One kind is crosslinked compound high temperature proton exchange film and preparation method thereof |
| CN109411795A (en) * | 2018-10-25 | 2019-03-01 | 东北大学 | Preparation method for the polybenzimidazole polymer dielectric film in flow battery |
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| CN110564150A (en) * | 2019-08-09 | 2019-12-13 | 上海交通大学 | long side chain type quaternized polybenzimidazole crosslinked membrane and preparation method thereof |
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| CN107887626A (en) * | 2017-11-09 | 2018-04-06 | 中国科学院上海有机化学研究所 | One kind is crosslinked compound high temperature proton exchange film and preparation method thereof |
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| CN110564150A (en) * | 2019-08-09 | 2019-12-13 | 上海交通大学 | long side chain type quaternized polybenzimidazole crosslinked membrane and preparation method thereof |
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