CN104877136A - Long-branched-chain polysulfone anionic membrane and preparation method thereof - Google Patents
Long-branched-chain polysulfone anionic membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a long-branched-chain polysulfone anionic membrane and a preparation method thereof. The structure of the membrane material is disclosed in the specification. The preparation method comprises the following steps: polysulfone acylation, carbonyl reduction, quaternization, film formation, alkalification and the like. Compared with the traditional anion-exchange membrane sequentially subjected to quaternization and functionalization, the polysulfone anion-exchange membrane contains the long branched chain on the side chain, so that the hydrophilic group is far away from the hydrophobic polymer main chain, thereby enhancing the phase separation driving force in the film formation process, improving the connectivity of the ion channels in the membrane and further enhancing the hydroxide ion conductivity of the membrane. The long alkyl side chain can obviously reduce the degree of swelling of the quaternary ammonium salt membrane and reduce the nucleophilic attack of water or OH-. The long-branched-chain polysulfone anionic membrane can obtain higher ion conductivity on the premise of relatively lower water absorptivity, thereby solving the contradiction in the anionic membrane for a long time.
Description
Technical field
The invention belongs to alkaline anion-exchange membrane technical field, relate to a kind of long-chain branch polysulfones anionic membrane and preparation method thereof.
Background technology
Along with environmental pollution is more and more serious, fuel cell as a kind of novel, green, efficiently chemical energy source enter the eyeball of people, and Proton Exchange Membrane Fuel Cells becomes one of the most ripe fuel cell of research due to many merits such as its energy transformation ratio is high, environmental friendliness, fast startup.Can not the key restriction factors of large-scale commercial but the noble metal catalyst of its costliness also becomes it.Alkaline fuel cell has that oxidized speed is fast, methanol permeability reduces compared with Proton Exchange Membrane Fuel Cells, and topmost advantage is that it can use if the base metals such as Mn, Co are as eelctro-catalyst, reduces its cost of manufacture.
The method that anion-exchange membrane is conventional carries out chloromethylation, functionalization to its main chain, Re-boostering test film forming, the people such as such as Chinese patent 200810047595.0 Zhuan Lin by the chloromethylation to polymkeric substance, quaternary ammoniatedly obtained the comparatively excellent anionic membrane of performance.But still there is the problems such as specific conductivity is lower.The technique means commonly used to improve specific conductivity is at present that the number by increasing functional group improves specific conductivity.But due to the increase of functional group, water-intake rate is inevitable to be increased, and the mechanical property of film can reduce along with the increase of water-content again thereupon.Improve water-intake rate to improve specific conductivity, and the raising of water-intake rate makes mechanical property reduce, this is also the principal contradiction that anionic membrane faces for a long time.
Summary of the invention
The invention provides and a kind of there is high hydroxide radical conductivity, have again the anion-exchange membrane of thermostability and alkaline stability simultaneously concurrently, construct better ionic channel by aqueous favoring, the hydrophobic microphase-separated formed mutually, thus improve the electric conductivity of film.
Another object of the present invention prepares by the difference of acylting agent the anionic membrane possessing branch chain of different length, by anionic membrane polysulfones being carried out to acylations, carbonyl reduction, functionalization prepare long-chain branch.
The technical solution used in the present invention is as follows:
A kind of long-chain branch polysulfones anion-exchange membrane, its long-chain branch polysulfones structure is as follows:
Wherein, n is positive integer, preferably 3,4,5 or 6.
The acylting agent structure used time prepared by the present invention as shown in the formula:
wherein n=1 or 4.
Preparation method of the present invention comprises polysulfones acylations, carbonyl reduction, quaternary ammoniated, film forming, alkalization.Concrete steps are as follows:
(1) acylations: polysulfones is dissolved in a solvent, add acylting agent and anhydrous stannic chloride in anhydrous conditions, normal-temperature reaction 3-10 hour, reaction soln is poured in precipitation agent, filter, washing, drying obtain the polysulfones of acylations, wherein, solvent is methylene dichloride, trichloromethane, precipitation agent is methyl alcohol or ethanol, and acylting agent is 3-bromo propionyl chloro or 6-bromine caproyl chloride;
(2) carbonyl reduction: the polysulfones of acylations step (1) obtained is dissolved in 1,2-ethylene dichloride, adds trifluoroacetic acid and triethyl silicane, 65 DEG C of reaction 12-36 hour, obtain side chain not containing the polysulfones of carbonyl; Wherein trifluoroacetic acid: the volume ratio of triethyl silicane is: 5-8:1;
(3) quaternary ammoniated: side chain step (2) obtained does not dissolve in a solvent containing the polysulfones of carbonyl, adds quaternary ammonium reagent, normal-temperature reaction 5-12 hour; Described solvent is the one in N,N-dimethylacetamide, DMF, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, meta-cresol, dimethyl sulfoxide (DMSO), and quaternary ammonium reagent is Trimethylamine 99;
(4) film forming: the film-casting liquid of step (3) is coated with and casts film, dry;
(5) alkalize: the film that step (4) obtains is washed in deionized water, be dipped to alkalization in 12-48 hour in aqueous sodium hydroxide solution.
Polysulfones anion-exchange membrane of the present invention, mould material structure is compared with the anion-exchange membrane of the quaternary ammoniated functionalization again of tradition, because side chain contains long-chain branch, make hydrophilic radical away from the main polymer chain of hydrophobic, be enhanced to the impellent that is separated in membrane process, improve the connectedness of ionic channel in film, thus improve the hydroxide ion conductivity of film; Significantly can alleviate the swelling capacity of quaternary ammonium salt film with duration alkyl group side chain, reduce water or OH
-nucleophillic attack.Long-chain branch polysulfones anionic membrane can obtain higher ionic conductance under relatively low water-intake rate prerequisite, solves the contradiction that anionic membrane for a long time faces.
Embodiment
Further illustrate technical scheme of the present invention by the following examples.
Embodiment 1:
Because acylation reaction needs anhydrous response; therefore test the appliance requires such as front various flasks to vacuumize under biexhaust pipe; with spirit lamp calcination flask when vacuumizing; after stopping calcination, flask cooling is evacuated down to, then pour the passivity gases such as nitrogen; vacuumize again; 2-3 time and so forth, then under nitrogen protection state, add 1g PSF solid and 40ml methylene dichloride (carry the last week and put into active molecular sieve) dissolved solution.The anhydrous stannic chloride of 2ml is added after having dissolved; reaction to be placed in ice-water bath subsequently, when temperature drops to 3 DEG C after 15 minutes, 1ml acylting agent 3-bromo propionyl chloro and 10ml methylene dichloride be mixed in constant pressure addition funnel; under nitrogen protection, slowly reaction solution is instilled.Because acylation reaction can release hydrogen chloride gas, at another outlet connection bubbler of flask while therefore dripping, then connect a hose and pass in water, carry out the gas that absorption reaction produces, ensure the moderate pressure in flask.Drip 20min to dropwise.Ice-water bath removes subsequently, and reaction is reacted 3h at normal temperatures.After reacted, stir in the dilute hydrochloric acid that reaction solution is poured into several under, then leave standstill, Deng the aqueous solution and reaction solution layering, subsequently lower floor's reaction solution ethanol is separated out, suction filtration, alcohol immersion 12h, again suction filtration, in suction filtration process with deionized water wash several times, white solid is subsequently placed in the dry 12h of vacuum drying oven of 50 DEG C.Obtain the polysulfones of acylations.
The dissolution of solid obtained, in 50ml 1,2-ethylene dichloride, is added dropwise to 10ml trifluoroacetic acid and 2ml triethyl silicane, 65 DEG C of heating reflux reaction 24h.Mixed with the NaOH solution of 0.5M by reaction solution and wash away remaining acid and impurity, ethanol is separated out, suction filtration, alcohol immersion, and deionized water wash several, suction filtration are dry.The solid obtained is dissolved in 10ml DMAc and adds 3ml Trimethylamine 99 and react 12h at normal temperatures.The reaction solution obtained is centrifugal, casting film at 55 DEG C.Again according to the order vacuolar membrane of water, alkali, water, both obtained the polysulfones anionic membrane of side chain containing 3 carbon.
The pH value having absorbed the aqueous solution of the gas that acylation reaction is released is reduced to 6.1 from 6.9.
The acylting agent structure that this example uses is as follows:
The structure of the anionic membrane that this example obtains is as shown in the formula (one):
Side chain contains the polysulfones anionic membrane of 3 carbon side chains when substitution value is only 10%, and water-intake rate reaches 20%.And specific conductivity is 17.6mS cm 20 DEG C time
-1, and when temperature is raised to 80 DEG C, specific conductivity reaches 34.5mScm
-1. visible long-chain branch anionic membrane can obtain higher specific conductivity really in compared with low water absorption situation.
Embodiment 2:
Flask vacuumizes under biexhaust pipe, then under nitrogen protection state, adds 1g PSF solid and 40ml methylene dichloride (carry the last week and put into active molecular sieve) dissolved solution.The anhydrous stannic chloride of 2ml is added after having dissolved; reaction to be placed in ice-water bath subsequently, when temperature drops to 3 DEG C after 15 minutes, 1ml acylting agent 6-bromine caproyl chloride and 10ml methylene dichloride be mixed in constant pressure addition funnel; under nitrogen protection, slowly reaction solution is instilled.Because acylation reaction can release hydrogen chloride gas, at another outlet connection bubbler of flask while therefore dripping, then connect a hose and pass in water, carry out the gas that absorption reaction produces, ensure the moderate pressure in flask.Drip 20min to dropwise.Ice-water bath removes subsequently, and reaction is reacted 3h at normal temperatures.After reacted, stir in the dilute hydrochloric acid that reaction solution is poured into several under, then leave standstill, Deng the aqueous solution and reaction solution layering, subsequently lower floor's reaction solution ethanol is separated out, suction filtration, alcohol immersion 12h, again suction filtration, in suction filtration process with deionized water wash several times, white solid is subsequently placed in the dry 12h of vacuum drying oven of 50 DEG C.Obtain the polysulfones of acylations.
The dissolution of solid obtained, in 50ml 1,2-ethylene dichloride, is added dropwise to 10ml trifluoroacetic acid and 2ml triethyl silicane, 65 DEG C of heating reflux reaction 24h.Mixed with the NaOH solution of 0.5M by reaction solution and wash away remaining acid and impurity, ethanol is separated out, suction filtration, alcohol immersion, and deionized water wash several, suction filtration are dry.The solid obtained is dissolved in 10ml DMAc and adds 3ml Trimethylamine 99 and react 12h at normal temperatures.The reaction solution obtained is centrifugal, casting film at 55 DEG C.Again according to the order vacuolar membrane of water, alkali, water, both obtained the polysulfones anionic membrane of side chain containing 6 carbon.
The acylting agent structure that this example uses is as follows:
The structure of the anionic membrane that this example obtains is as shown in the formula (two):
Side chain contains the polysulfones anionic membrane of 6 carbon side chains when substitution value is only 10%, and water-intake rate reaches 17%.And specific conductivity is 28.9mS cm 20 DEG C time
-1, and when temperature is raised to 60 DEG C, specific conductivity can up to 63mScm
-1. as seen along with the increase specific conductivity of carbon chain lengths increases really thereupon.
Embodiment 3:
Flask vacuumizes under biexhaust pipe, then under nitrogen protection state, adds 0.5g PSF solid and 15ml methylene dichloride (carry the last week and put into active molecular sieve) dissolved solution.The anhydrous stannic chloride of 2ml is added after having dissolved; reaction to be placed in ice-water bath subsequently, when temperature drops to 3 DEG C after 15 minutes, 2ml acylting agent 6-bromine caproyl chloride and 10ml methylene dichloride be mixed in constant pressure addition funnel; under nitrogen protection, slowly reaction solution is instilled.Because acylation reaction can release hydrogen chloride gas, at another outlet connection bubbler of flask while therefore dripping, then connect a hose and pass in water, carry out the gas that absorption reaction produces, ensure the moderate pressure in flask.Drip 20min to dropwise.Ice-water bath removes subsequently, and reaction is reacted 10h at normal temperatures.After reacted, stir in the dilute hydrochloric acid that reaction solution is poured into several under, then leave standstill, Deng the aqueous solution and reaction solution layering, subsequently lower floor's reaction solution ethanol is separated out, suction filtration, alcohol immersion 12h, again suction filtration, in suction filtration process with deionized water wash several times, white solid is subsequently placed in the dry 12h of vacuum drying oven of 50 DEG C.Obtain the polysulfones of acylations.
The dissolution of solid obtained, in 25ml 1,2-ethylene dichloride, is added dropwise to 5ml trifluoroacetic acid and 1ml triethyl silicane, 65 DEG C of heating reflux reaction 24h.Mixed with the NaOH solution of 0.5M by reaction solution and wash away remaining acid and impurity, ethanol is separated out, suction filtration, alcohol immersion, and deionized water wash several, suction filtration are dry.The solid obtained is dissolved in 5ml DMAc and adds 1.5ml Trimethylamine 99 and react 12h at normal temperatures.The reaction solution obtained is centrifugal, casting film at 55 DEG C.Again according to the order vacuolar membrane of water, alkali, water, both obtained the polysulfones anionic membrane of side chain containing 6 carbon.
The acylting agent that this example uses is identical with example 2 with the structure of the anionic membrane obtained.
Side chain contains the polysulfones anionic membrane of 6 carbon side chains when substitution value is 20%, and water-intake rate reaches 23%.And specific conductivity is 34.5mS cm 20 DEG C time
-1, and when temperature is raised to 60 DEG C, specific conductivity can up to 83mS cm
-1.Such long-chain branch polysulfones anionic membrane has mechanical property and chemical property double dominant concurrently.
Claims (10)
1. a long-chain branch polysulfones anion-exchange membrane, is characterized in that, long-chain branch polysulfones structure is as follows:
n is positive integer.
2. a kind of long-chain branch polysulfones anion-exchange membrane according to claim 1, it is characterized in that, described n is 3,4,5 or 6.
3. the preparation method of long-chain branch polysulfones anion-exchange membrane according to claim 1, is characterized in that following steps:
(1) acylations: dissolved in a solvent by polysulfones, add acylting agent and anhydrous stannic chloride in anhydrous conditions, normal-temperature reaction 3-10 hour, poured into by reaction soln in precipitation agent, filters, washing, drying obtains the polysulfones of acylations; Solvent is methylene dichloride or trichloromethane, and precipitation agent is methyl alcohol or ethanol;
Acylting agent structure as shown in the formula:
wherein n=1 or 4.
(2) carbonyl reduction: the polysulfones of acylations step (1) obtained is dissolved in 1,2-ethylene dichloride, adds trifluoroacetic acid and triethyl silicane, 65 DEG C of reaction 12-36 hour, obtain side chain not containing the polysulfones of carbonyl; Wherein trifluoroacetic acid: the volume ratio of triethyl silicane is 5-8:1;
(3) quaternary ammoniated: side chain step (2) obtained does not dissolve in a solvent containing the polysulfones of carbonyl, adds quaternary ammonium reagent, normal-temperature reaction 5-12 hour; Described solvent is the one in N,N-dimethylacetamide, DMF, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, meta-cresol, dimethyl sulfoxide (DMSO), and quaternary ammonium reagent is Trimethylamine 99;
(4) film forming: the film-casting liquid of step (3) is coated with and casts film, dry;
(5) alkalize: the film that step (4) obtains is washed in deionized water, be dipped to alkalization in 12-48 hour in aqueous sodium hydroxide solution.
4. the preparation method of long-chain branch polysulfones anion-exchange membrane according to claim 2, is characterized in that following steps:
(1) acylations: polysulfones is dissolved in a solvent, add acylting agent and anhydrous stannic chloride in anhydrous conditions, normal-temperature reaction 3-10 hour, reaction soln is poured in precipitation agent, filter, washing, drying obtain the polysulfones of acylations, wherein, solvent is methylene dichloride, trichloromethane, precipitation agent is methyl alcohol or ethanol, and acylting agent is 3-bromo propionyl chloro or 6-bromine caproyl chloride;
Acylting agent structure as shown in the formula:
wherein n=1 or 4.
(2) carbonyl reduction: the polysulfones of acylations step (1) obtained is dissolved in 1,2-ethylene dichloride, adds trifluoroacetic acid and triethyl silicane, 65 DEG C of reaction 12-36 hour, obtain side chain not containing the polysulfones of carbonyl; Wherein trifluoroacetic acid: the volume ratio of triethyl silicane is: 5-8:1;
(3) quaternary ammoniated: side chain step (2) obtained does not dissolve in a solvent containing the polysulfones of carbonyl, adds quaternary ammonium reagent, normal-temperature reaction 5-12 hour; Described solvent is the one in N,N-dimethylacetamide, DMF, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, meta-cresol, dimethyl sulfoxide (DMSO), and quaternary ammonium reagent is Trimethylamine 99;
(4) film forming: the film-casting liquid of step (3) is coated with and casts film, dry;
(5) alkalize: the film that step (4) obtains is washed in deionized water, be dipped to alkalization in 12-48 hour in aqueous sodium hydroxide solution.
5. according to the preparation method of the long-chain branch polysulfones anion-exchange membrane described in claim 3 or 4, it is characterized in that: the mass ratio of the polysulfones that step (1) uses and methylene dichloride is 1:20-50.
6. according to the preparation method of the long-chain branch polysulfones anion-exchange membrane described in claim 3 or 4, it is characterized in that: polysulfones: acylting agent: the mass ratio of anhydrous stannic chloride is 1:1-4:2-8.
7. according to the preparation method of long-chain branch polysulfones anion-exchange membrane according to claim 5, it is characterized in that: polysulfones: acylting agent: the mass ratio of anhydrous stannic chloride is 1:1-4:2-8.
8. according to the preparation method of the long-chain branch polysulfones anion-exchange membrane described in claim 3,4 or 7, it is characterized in that: described film-forming method is casting film or casting film-forming.
9. according to the preparation method of long-chain branch polysulfones anion-exchange membrane according to claim 5, it is characterized in that: described film-forming method is casting film or casting film-forming.
10. according to the preparation method of long-chain branch polysulfones anion-exchange membrane according to claim 6, it is characterized in that: described film-forming method is casting film or casting film-forming.
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| CN105968328A (en) * | 2016-06-01 | 2016-09-28 | 中国科学院长春应用化学研究所 | Polyphenyl polymer, preparation method thereof and polyphenyl anion-exchange membrane |
| CN106883327A (en) * | 2015-12-16 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of alkaline anion-exchange membrane and preparation method thereof |
| CN106977719A (en) * | 2017-04-14 | 2017-07-25 | 大连理工大学 | It is a kind of how long branched polyether sulfone/ketone anion-exchange membrane and preparation method thereof |
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| CN107968214B (en) * | 2017-11-09 | 2020-01-24 | 大连理工大学 | Hydrophilic long-side-chain alkaline anion exchange membrane and preparation method thereof |
| CN107968214A (en) * | 2017-11-09 | 2018-04-27 | 大连理工大学 | A kind of hydrophilic long pendant basic anion-exchange membrane and preparation method thereof |
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| CN111313063A (en) * | 2018-12-11 | 2020-06-19 | 中国科学院大连化学物理研究所 | Preparation method of organic-MOF (Metal organic framework) composite alkaline polymer electrolyte membrane and membrane |
| CN112521535A (en) * | 2020-12-17 | 2021-03-19 | 南京理工大学 | Anion exchange membrane with high alkali stability and preparation method thereof |
| CN112980187A (en) * | 2021-04-09 | 2021-06-18 | 陕西国防工业职业技术学院 | Long-side-chain cross-linked polysulfone anion-exchange membrane and preparation method thereof |
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