CN101862608A - Method for preparing self-crosslinking polymer anion exchange membrane - Google Patents
Method for preparing self-crosslinking polymer anion exchange membrane Download PDFInfo
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Abstract
The invention discloses a method for preparing a self-crosslinking polymer anion exchange membrane, which comprises the following steps of chloromethylation, tertiary amination, quaternization and self-crosslinking membrane forming of a polymer, wherein the tertiary amination comprises the steps of dissolving the product of the chloromethylation of the polymer into a solvent to obtain chloromethylated product solution of the polymer (namely, the tertiary ammonium prepared solution); and adding a little low grade secondary amine into the solution, and then stirring and reacting at room temperature to obtain the chloromethylated tertiary ammonium solution of the polymer (namely, the quaternary ammonium prepared solution). The self-crosslinking reaction of the polymer is performed in the process of membrane forming after the quaternization. The method is simple, convenient and highly efficient; and the obtained anion exchange membrane has high ion exchanged capacity, high chemical property, high heat stability, high mechanism property, high conductivity and excellent performance at a high temperature and under the alkali condition.
Description
Technical field
The invention belongs to the amberplex technical field.Be particularly related to a kind of preparation method of polymer anion-exchange membrane.
Background technology
Anion-exchange membrane is the critical material in Separation ﹠ Purification, the electrochemical device, is widely used in water technology, hydrometallurgy, chemical industry and industrial circles such as Chemical Decomposition and alkaline fuel cell.The heat and the chemical stability of traditional polymer anion-exchange membrane are lower, and the quaternary ammonium group under higher temperature or alkali condition in the polymer is easy to degrade, and cause ion exchange capacity to descend.(T.Sata,et?al.,J.Membrane?Sci.,1996,112,161.)
Except the requirement of heat and chemical stability, the mechanical performance of polymer anion-exchange membrane (comprising tensile strength and pliability) also is the key in application index.Often there is the shortcoming that its mechanical performance significantly descends when ion exchange capacity is big in present polymer anion-exchange membrane.At this problem, number of patent application is 200810047595, patent publication No. a kind of preparation method of polymer anion-exchange membrane that has been 101274226 disclosure of the Invention, this method by polymer carry out chloromethylation successively, step quaternized and film forming is constituted, its each step thing is the thing initially to be located of next step, the polymer anion-exchange membrane of gained has stable preferably and high ion exchange capacity its final step is finished after.But the polymer anion-exchange membrane of this method preparation is not suitable for operating under hot conditions.
In order to improve the energy efficiency of aqueous solution electrochemical devices, usually wish and under hot conditions, to operate.Yet common anion-exchange membrane if will obtain high exchange capacity intensity can descend greatly, has limited the application of polymer anion-exchange membrane in aqueous solution electrochemical devices under the high-temperature alkaline condition.
Summary of the invention
Purpose of the present invention is exactly the preparation method that a kind of self-crosslinking polymer anion exchange membrane is provided at the situation of above-mentioned prior art, self-crosslinking polymer anion film heat endurance, mechanical performance and alkali resistance that this method makes are good, the ion exchange capacity height, particularly under the high-temperature alkaline condition, still has excellent mechanical strength, for the raising of alkaline aqueous solution electrochemical device performance provides guarantee.
Technical scheme of the present invention is carried out steps such as chloromethylation, tertiary amineization, quaternized and film forming successively by polymer and is constituted, and its tertiary amineization has step by step following:
1, the product behind the polymer chloromethylation is dissolved in the solvent, to obtain the chloromethylation products solution (tertiary amineization is equipped with liquid) of polymer;
2, in the chloromethylation products solution of polymer, add a little rudimentary secondary amine and stir at normal temperatures and make its sufficient reacting, with the tertiary amine solution (the quaternized liquid that is equipped with) of the chloromethylation that obtains polymer.
As preferably, its rudimentary secondary amine comprises diethylamine, di-n-propylamine, dibutyl amine, and its addition is 0.01~0.2 times of chloromethylation products solution (tertiary amineization is equipped with liquid) weight of polymer; Its mixing time 〉=0.5 at normal temperatures hour, its normal temperature scope is 10 ℃~50 ℃.
The thing that gets of each step is next step thing initially to be located among the present invention.Its chloromethylation, quaternized step with film forming are identical with prior art.
Self-crosslinking polymer anion exchange membrane preparation method of the present invention, its cross-linking reaction be spontaneous carrying out in the process of high temperature film forming, the reaction simple and effective.The exchange capacity of self-crosslinking polymer can be controlled by chloromethyl percent grafting and tertiary amine grafting degree.The present invention is simple, on performance perspective, prepared film mechanical performance, heat endurance and ion exchange capacity are much better than traditional polymer anion-exchange membrane, particularly under hot conditions, film had both had high exchange capacity, still kept excellent mechanical strength; Be convenient to series exploitation to satisfy the needs in different application field.
The specific embodiment
Further describe the preparation method of polymer anion-exchange membrane of the present invention by the following examples.
Embodiment 1:
The polyarylsulfone (PAS) (PASF) of 1 unit of weight is dissolved in 1 of 5 unit of weights, in the 2-dichloroethanes, adds the zinc powder of 0.05 unit of weight, the trifluoroacetic acid of 0.1 unit of weight adds the chloromethyl ether of 1 unit of weight again, stirs 6 hours down at 30 ℃; Said mixture poured into product is precipitated out, with sediment wash with water, dry and smash after be dissolved in the N of 20 unit of weights, dinethylformamide (DMF) obtains the chloromethylation products solution of polyarylsulfone (PAS) (PASF).Get the diethylamine that its above-mentioned molten 1 unit of weight adds 0.01 unit of weight, 30 ℃ of following stirring reactions 2 hours.Heating vaporization trimethylamine aqueous solution fed above-mentioned solution 5 minutes with trimethylamine gas after super-dry; Use casting method in 50 ℃ of drying and forming-films above-mentioned reactant liquor, promptly get anion-exchange membrane.
The solution concentration of above-mentioned chloromethylation step, tertiary amine step and quaternized step does not influence reaction and product property thereof.
Adopt the following similar film of the equal available matter of condition that substitutes in the present embodiment: (1) polyether-ether-ketone (PEEK) or phenolic polyether sulphone (PES-C) replace polyarylsulfone (PAS) (PASF); (2) 1,1-dichloroethanes, chloroform, carrene or toluene replace 1, and the 2-dichloroethanes is as the chloromethyl reaction dissolvent; (3) aluminium powder replaces zinc powder, TFMS, 3,3, and 3-trifluoroacetic acid or 2,3,4,5-tetrafluorobenzoic aid replace trifluoroacetic acid as catalyst; (4) ethanol replaces the precipitating reagent of methyl alcohol as the chloromethylation product; (5) N, N-diethyl acetamide (DMAc), N-methyl pyrrolidone (NMP) or methyl-sulfoxide (DMSO) replace N, and dinethylformamide (DMF) is as tertiary amineization and quaterisation solvent; (6) the tertiary amine reaction uses di-n-propylamine and dibutyl amine to replace diethylamine; (7) the tertiary amine reaction time is between 0.5 to 8 hour; (8) the trimethylamine gas feeding time is no less than 5 minutes; (9) replace casting method with The tape casting; (10) film-forming temperature is between 50-100 ℃.
Embodiment 2:
The polyarylsulfone (PAS) (PASF) of 1 unit of weight is dissolved in 1 of 6 unit of weights, in the 1-dichloroethanes, adds the aluminium powder of 0.1 unit of weight, the TFMS of 0.4 unit of weight adds the chloromethyl ether of 3 unit of weights again, stirs 6 hours down at 30 ℃; Said mixture poured into product is precipitated out, with sediment wash with water, dry and smash after be dissolved in the N of 30 unit of weights, N-diethyl acetamide (DMAc) obtains the chloromethylation products solution of polyarylsulfone (PAS) (PASF).Get the di-n-propylamine that above-mentioned solution 1 unit of weight adds 0.03 unit of weight, 50 ℃ of following stirring reactions 0.5 hour.Heating vaporization trimethylamine aqueous solution fed above-mentioned solution 10 minutes with trimethylamine gas after super-dry; Use The tape casting in 60 ℃ of drying and forming-films above-mentioned reactant liquor, promptly get anion-exchange membrane.
The solution concentration of above-mentioned chloromethylation step, tertiary amine step and quaternized step does not influence reaction and product property.
Adopt the following similar film of the equal available matter of condition that substitutes in the present embodiment: (1) polyether-ether-ketone (PEEK) or phenolic polyether sulphone (PES-C) replace polyarylsulfone (PAS) (PASF); (2) 1,2-dichloroethanes, chloroform, carrene or toluene replace 1, and the 1-dichloroethanes is as the chloromethyl reaction dissolvent; (3) zinc powder replaces aluminium powder, trifluoroacetic acid, 3,3, and 3-trifluoroacetic acid or 2,3,4,5-tetrafluorobenzoic aid replace TFMS as catalyst; (4) methyl alcohol replaces the precipitating reagent of ethanol as the chloromethylation product; (5) N, dinethylformamide (DMF), N-methyl pyrrolidone (NMP) or methyl-sulfoxide (DMSO) replace N, and N-diethyl acetamide (DMAc) is as tertiary amineization and quaterisation solvent; (6) the tertiary amine reaction uses diethylamine and dibutyl amine to replace di-n-propylamine; (7) the tertiary amine reaction time is between 0.5 to 8 hour; (8) the trimethylamine gas feeding time is no less than 5 minutes; (9) replace The tape casting with casting method; (10) film-forming temperature is in the time of 50-100 ℃.
Embodiment 3:
The phenolic polyether sulphone (PES-C) of 1 unit of weight is dissolved in the chloroform of 7 unit of weights, adds the zinc powder of 0.5 unit of weight, 3,3 of 1 unit of weight, the 3-trifluoroacetic acid adds the chloromethyl ether of 5 unit of weights again, stirs 6 hours down at 30 ℃; Said mixture poured into product is precipitated out, with sediment wash with water, dry and smash after be dissolved in the N-methyl pyrrolidone (NMP) of 10 unit of weights, obtain the chloromethylation products solution of phenolic polyether sulphone (PES-C).Get the dibutyl amine that above-mentioned solution 1 unit of weight adds 0.05 unit of weight, 10 ℃ of following stirring reactions 8 hours.Heating vaporization trimethylamine aqueous solution fed above-mentioned solution 15 minutes with trimethylamine gas after super-dry; Use casting method in 80 ℃ of drying and forming-films above-mentioned reactant liquor, promptly get anion-exchange membrane.
The solution concentration of above-mentioned chloromethylation step, tertiary amine step and quaternized step does not influence reaction and product property.
Adopt the following similar film of the equal available matter of condition that substitutes in the present embodiment: (1) polyarylsulfone (PAS) (PASF) or polyether-ether-ketone (PEEK) replace phenolic polyether sulphone (PES-C); (2) 1,2-dichloroethanes, 1,1-dichloroethanes, carrene or toluene replace chloroform as the chloromethyl reaction dissolvent; (3) aluminium powder replaces zinc powder, trifluoroacetic acid, TFMS or 2,3,4, and the 5-tetrafluorobenzoic aid replaces 3,3, and the 3-trifluoroacetic acid is as catalyst; (4) ethanol replaces the precipitating reagent of methyl alcohol as the chloromethylation product; (5) N, dinethylformamide (DMF), N, N-diethyl acetamide (DMAc) or methyl-sulfoxide (DMSO) replace N-methyl pyrrolidone (NMP) as tertiary amineization and quaterisation solvent; (6) the tertiary amine reaction uses diethylamine and di-n-propylamine to replace dibutyl amine; (7) the tertiary amine reaction time is between 0.5 to 8 hour; (8) the trimethylamine gas feeding time is no less than 5 minutes; (9) replace casting method with The tape casting; (10) film-forming temperature is in the time of 50-100 ℃.
Embodiment 4:
Phenolic polyether sulphone (PES-C) by 1 unit of weight is dissolved in 1 of 8 unit of weights, in the 2-dichloroethanes, the zinc powder that adds 0.1 unit of weight, 0.4 the trifluoroacetic acid of unit of weight adds the chloromethyl ether of 3 unit of weights again, stirs 6 hours down at 20 ℃, said mixture poured into product is precipitated out, with sediment wash with water, dry and smash after be dissolved in the N of 20 unit of weights, dinethylformamide (DMF) obtains the chloromethylation products solution of phenolic polyether sulphone (PES-C).Get above-mentioned solution 1 unit of weight, add the diethylamine of 0.08 unit of weight, 40 ℃ of following stirring reactions 2 hours.Heating vaporization trimethylamine aqueous solution fed above-mentioned solution 30 minutes with trimethylamine gas after super-dry; Use casting method in 60 ℃ of drying and forming-films above-mentioned reactant liquor, promptly get anion-exchange membrane.
When other factors constant, only in the chloromethylation of above-mentioned phenolic polyether sulphone (PES-C), temperature when it is stirred is made as 30 ℃, 40 ℃, 50 ℃ respectively, its experimental result then shows: the chloromethylation temperature is high more, its chloromethylation grafting degree is big more, and the ion exchange capacity of polymer anion-exchange membrane is just high more.
The solution concentration of above-mentioned chloromethylation step, tertiary amine step and quaternized step does not influence reaction and product property.
Adopt the following similar film of the equal available matter of condition that substitutes in the present embodiment: (1) polyarylsulfone (PAS) (PASF) or polyether-ether-ketone (PEEK) replace phenolic polyether sulphone (PES-C); (2) 1,1-dichloroethanes, chloroform, carrene or toluene replace 1, and the 2-dichloroethanes is as the chloromethyl reaction dissolvent; (3) aluminium powder replaces zinc powder, TFMS, 3,3, and 3-trifluoroacetic acid or 2,3,4,5-tetrafluorobenzoic aid replace trifluoroacetic acid as catalyst; (4) ethanol replaces the precipitating reagent of methyl alcohol as the chloromethylation product; (5) N, N-diethyl acetamide (DMAc), N-methyl pyrrolidone (NMP) or methyl-sulfoxide (DMSO) replace N, and dinethylformamide (DMF) is as tertiary amineization and quaterisation solvent; (6) the tertiary amine reaction uses di-n-propylamine and dibutyl amine to replace diethylamine; (7) the tertiary amine reaction time is between 0.5 to 8 hour; (8) the trimethylamine gas feeding time is no less than 5 minutes; (9) replace casting method with The tape casting; (10) film-forming temperature is in the time of 50-100 ℃.
Embodiment 5:
The polyether-ether-ketone (PEEK) of 1 unit of weight is dissolved in 1 of 9 unit of weights, in the 2-dichloroethanes, the zinc powder that adds 0.1 unit of weight, 0.4 the trifluoroacetic acid of unit of weight, the chloromethyl ether that adds 3 unit of weights again, stirred 2 hours down at 30 ℃, said mixture poured into product is precipitated out, sediment is washed with water, dry and smash after be dissolved in the N of 20 unit of weights, dinethylformamide (DMF), the chloromethylation products solution of acquisition polyether-ether-ketone (PEEK) is got above-mentioned solution 1 unit of weight, the di-n-propylamine that adds 0.1 unit of weight was 20 ℃ of following stirring reactions 6 hours.Heating vaporization trimethylamine aqueous solution fed above-mentioned solution 5 minutes with trimethylamine gas after super-dry; Use The tape casting in 60 ℃ of drying and forming-films above-mentioned reactant liquor, promptly get anion-exchange membrane.
When other factors constant, only in the chloromethylation of above-mentioned phenolic polyether sulphone (PES-C), its mixing time was made as respectively 4 hours, 6 hours, 8 hours, 12 hours, 16 hours and 20 hours, its experimental result then shows: mixing time is long more, then its chloromethylation grafting degree is big more, polymer anion proton exchange just high more from exchange capacity.
The solution concentration of above-mentioned chloromethylation step, tertiary amine step and quaternized step does not influence reaction and product property.
Adopt the following similar film of the equal available matter of condition that substitutes in the present embodiment: (1) polyarylsulfone (PAS) (PASF) or phenolic polyether sulphone (PES-C) replace polyether-ether-ketone (PEEK); (2) 1,1-dichloroethanes, chloroform, carrene or toluene replace 1, and the 2-dichloroethanes is as the chloromethyl reaction dissolvent; (3) aluminium powder replaces zinc powder, TFMS, 3,3, and 3-trifluoroacetic acid or 2,3,4,5-tetrafluorobenzoic aid replace trifluoroacetic acid as catalyst; (4) ethanol replaces the precipitating reagent of methyl alcohol as the chloromethylation product; (5) N, N-diethyl acetamide (DMAc), N-methyl pyrrolidone (NMP) or methyl-sulfoxide (DMSO) replace N, and dinethylformamide (DMF) is as tertiary amineization and quaterisation solvent; (6) the tertiary amine reaction uses diethylamine and dibutyl amine to replace di-n-propylamine; (7) the tertiary amine reaction time is between 0.5 to 8 hour; (8) the trimethylamine gas feeding time is no less than 5 minutes; (9) replace The tape casting with casting method; (10) film-forming temperature is in the time of 50-100 ℃.
Embodiment 6:
The polyarylsulfone (PAS) (PASF) of 1 unit of weight is dissolved in 1 of 6 unit of weights, in the 1-dichloroethanes, adds the aluminium powder of 0.1 unit of weight, the TFMS of 0.4 unit of weight adds the chloromethyl ether of 3 unit of weights again, stirs 6 hours down at 30 ℃; Said mixture poured into product is precipitated out, with sediment wash with water, dry and smash after be dissolved in the N of 30 unit of weights, N-diethyl acetamide (DMAc) obtains the chloromethylation products solution of polyarylsulfone (PAS) (PASF).Get above-mentioned solution 1 unit of weight, add the diethylamine of 0.01 unit of weight, 30 ℃ of following stirring reactions 3 hours.Heating vaporization trimethylamine aqueous solution fed above-mentioned solution 10 minutes with trimethylamine gas after super-dry; Use The tape casting in 60 ℃ of drying and forming-films above-mentioned reactant liquor, promptly get anion-exchange membrane.
When other factors constant, only the addition with diethylamine changes 0.05,0.10,0.15 and 0.20 respectively into, its experimental result then shows: the amount that adds secondary amine (diethylamine) is many more, and its tertiary amine grafting degree is big more, and the ion exchange capacity of polymer anion proton exchange is just low more.
The solution concentration of above-mentioned chloromethylation step, tertiary amine step and quaternized step does not influence reaction and product property.
Adopt the following similar film of the equal available matter of condition that substitutes in the present embodiment: (1) polyether-ether-ketone (PEEK) or phenolic polyether sulphone (PES-C) replace polyarylsulfone (PAS) (PASF); (2) 1,2-dichloroethanes, chloroform, carrene or toluene replace 1, and the 1-dichloroethanes is as the chloromethyl reaction dissolvent; (3) zinc powder replaces aluminium powder, trifluoroacetic acid, 3,3, and 3-trifluoroacetic acid or 2,3,4,5-tetrafluorobenzoic aid replace TFMS as catalyst; (4) methyl alcohol replaces the precipitating reagent of ethanol as the chloromethylation product; (5) N, dinethylformamide (DMF), N-methyl pyrrolidone (NMP) or methyl-sulfoxide (DMSO) replace N, and N-diethyl acetamide (DMAc) is as tertiary amineization and quaterisation solvent; (6) the tertiary amine reaction uses di-n-propylamine and dibutyl amine to replace diethylamine; (7) the tertiary amine reaction time is between 0.5 to 8 hour; (8) the trimethylamine gas feeding time is no less than 5 minutes; (9) replace The tape casting with casting method; (10) film-forming temperature is in the time of 50-100 ℃.
Embodiment 7:
The polyether-ether-ketone (PEEK) of 1 unit of weight is dissolved in the carrene of 10 unit of weights, adds the aluminium powder of 0.1 unit of weight, 2,3,4 of 0.4 unit of weight, the 5-tetrafluorobenzoic aid adds the chloromethyl ether of 3 unit of weights again, stirs 6 hours down at 30 ℃; Said mixture poured into product is precipitated out, with sediment wash with water, dry and smash after be dissolved in the methyl-sulfoxide (DMSO) of 10 unit of weights, obtain the chloromethylation products solution of polyether-ether-ketone (PEEK).Get above-mentioned solution 1 unit of weight, add the dibutyl amine of 0.12 unit of weight, 20 ℃ of following stirring reactions 6 hours.The triethylamine that adds 0.3 unit of weight again was 30 ℃ of following stirring reactions 2 hours; Use casting method in 100 ℃ of drying and forming-films above-mentioned reactant liquor, promptly get anion-exchange membrane.
The solution concentration of above-mentioned chloromethylation step, tertiary amine step and quaternized step does not influence reaction and product property.
Adopt the following similar film of the equal available matter of condition that substitutes in the present embodiment: (1) polyarylsulfone (PAS) (PASF) or phenolic polyether sulphone (PES-C) replace polyether-ether-ketone (PEEK); (2) 1,2-dichloroethanes, 1,1-dichloroethanes, chloroform or toluene replace carrene as the chloromethyl reaction dissolvent; (3) zinc powder replaces aluminium powder, trifluoroacetic acid, TFMS or 3,3, and the 3-trifluoroacetic acid replaces 2,3,4, and the 5-tetrafluorobenzoic aid is as catalyst; (4) methyl alcohol replaces the precipitating reagent of ethanol as the chloromethylation product; (5) N, dinethylformamide (DMF), N, N-diethyl acetamide (DMAc) or N-methyl pyrrolidone (NMP) replace methyl-sulfoxide (DMSO) as tertiary amineization and quaterisation solvent; (6) the tertiary amine reaction uses diethylamine and di-n-propylamine to replace dibutyl amine; (7) the tertiary amine reaction time is between 0.5 to 8 hour; (8) tripropyl amine (TPA) or tri-n-butylamine replace triethylamine as amination reagent; (9) replace casting method with The tape casting; (10) film-forming temperature is in the time of 50-100 ℃.
Embodiment 8:
The polyarylsulfone (PAS) (PASF) of 1 unit of weight is dissolved in 1 of 11 unit of weights, in the 2-dichloroethanes, adds the zinc powder of 0.05 unit of weight, the TFMS of 0.1 unit of weight adds the chloromethyl ether of 1 unit of weight again, stirs 6 hours down at 30 ℃; Said mixture poured into product is precipitated out, with sediment wash with water, dry and smash after be dissolved in the N of 30 unit of weights, N-diethyl acetamide (DMAc), obtain the chloromethylation products solution of polyarylsulfone (PAS) (PASF), get above-mentioned solution 1 unit of weight, the di-n-propylamine that adds 0.15 unit of weight was 40 ℃ of following stirring reactions 2 hours.The tripropyl amine (TPA) that adds 0.4 unit of weight again was 40 ℃ of following stirring reactions 8 hours; Use The tape casting in 80 ℃ of drying and forming-films above-mentioned reactant liquor, promptly get anion-exchange membrane.
The solution concentration of above-mentioned chloromethylation step, tertiary amine step and quaternized step does not influence reaction and product property.
Adopt the following similar film of the equal available matter of condition that substitutes in the present embodiment: (1) polyether-ether-ketone (PEEK) or phenolic polyether sulphone (PES-C) replace polyarylsulfone (PAS) (PASF); (2) 1,1-dichloroethanes, chloroform, carrene or toluene replace 1, and the 2-dichloroethanes is as the chloromethyl reaction dissolvent; (3) aluminium powder replaces zinc powder, trifluoroacetic acid, 3,3, and 3-trifluoroacetic acid or 2,3,4,5-tetrafluorobenzoic aid replace TFMS as catalyst; (4) methyl alcohol replaces the precipitating reagent of ethanol as the chloromethylation product; (5) N, dinethylformamide (DMF), N-methyl pyrrolidone (NMP) or methyl-sulfoxide (DMSO) replace N, and N-diethyl acetamide (DMAc) is as tertiary amineization and quaterisation solvent; (6) the tertiary amine reaction uses diethylamine and dibutyl amine to replace di-n-propylamine; (7) the tertiary amine reaction time is between 0.5 to 8 hour; (8) triethylamine or tri-n-butylamine replace tripropyl amine (TPA) as amination reagent; (9) replace The tape casting with casting method; (10) film-forming temperature is in the time of 50-100 ℃.
Embodiment 9:
The phenolic polyether sulphone (PES-C) of 1 unit of weight is dissolved in the chloroform of 12 unit of weights, adds the aluminium powder of 0.5 unit of weight, 3,3 of 1 unit of weight, the 3-trifluoroacetic acid adds the chloromethyl ether of 5 unit of weights again, stirs 6 hours down at 30 ℃; Said mixture poured into product is precipitated out, with sediment wash with water, dry and smash after be dissolved in the methyl-sulfoxide (DMSO) of 20 unit of weights, obtain the chloromethylation products solution of phenolic polyether sulphone (PES-C), get above-mentioned solution 1 unit of weight, the dibutyl amine that adds 0.2 unit of weight was 30 ℃ of following stirring reactions 3 hours.The tri-n-butylamine that adds 0.5 unit of weight again was 40 ℃ of following stirring reactions 15 hours; Use casting method in 60 ℃ of drying and forming-films above-mentioned reactant liquor, promptly get anion-exchange membrane.
The solution concentration of above-mentioned chloromethylation step, tertiary amine step and quaternized step does not influence reaction and product property.
Adopt the following similar film of the equal available matter of condition that substitutes in the present embodiment: (1) polyarylsulfone (PAS) (PASF) or polyether-ether-ketone (PEEK) replace phenolic polyether sulphone (PES-C); (2) 1,2-dichloroethanes, 1,1-dichloroethanes, carrene or toluene replace chloroform as the chloromethyl reaction dissolvent; (3) zinc powder replaces aluminium powder, trifluoroacetic acid, TFMS or 2,3,4, and the 5-tetrafluorobenzoic aid replaces 3,3, and the 3-trifluoroacetic acid is as catalyst; (4) methyl alcohol replaces the precipitating reagent of ethanol as the chloromethylation product; (5) N, dinethylformamide (DMF), N, N-diethyl acetamide (DMAc) or N-methyl pyrrolidone (NMP) replace methyl-sulfoxide (DMSO) as tertiary amineization and quaterisation solvent; (6) the tertiary amine reaction uses diethylamine and di-n-propylamine to replace dibutyl amine; (7) the tertiary amine reaction time is between 0.5 to 8 hour; (8) triethylamine or tripropyl amine (TPA) replace tri-n-butylamine as amination reagent; (9) replace casting method with The tape casting; (10) film-forming temperature is in the time of 50-100 ℃.
Claims (3)
1. the preparation method of a self-crosslinking polymer anion exchange membrane carries out steps such as chloromethylation, tertiary amineization, quaternized and film forming successively by polymer and is constituted, and it is step by step following to it is characterized in that described tertiary amineization has:
1) product behind the polymer chloromethylation is dissolved in the solvent, to obtain the chloromethylation products solution (tertiary amineization is equipped with liquid) of polymer;
2) in the chloromethylation products solution of polymer, add a little rudimentary secondary amine and stir at normal temperatures and make its sufficient reacting, with the tertiary amine solution (the quaternized liquid that is equipped with) of the chloromethylation that obtains polymer.
2. the preparation method of a kind of self-crosslinking polymer anion exchange membrane according to claim 1 is characterized in that:
Described rudimentary secondary amine comprises diethylamine, di-n-propylamine, dibutyl amine, and its addition is 0.01~0.2 times of chloromethylation products solution (tertiary amineization is equipped with liquid) weight of polymer.
3. the preparation method of a kind of self-crosslinking polymer anion exchange membrane according to claim 1 and 2 is characterized in that:
Mixing time under the described normal temperature 〉=0.5 hour, its normal temperature scope is 10 ℃~50 ℃.
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CN104086792A (en) * | 2014-06-13 | 2014-10-08 | 北京航空航天大学 | Preparation method of polymer anion exchange membrane |
CN106188543A (en) * | 2016-07-08 | 2016-12-07 | 北京航空航天大学 | A kind of proton-conductive films of flow battery and preparation method thereof |
CN106633136A (en) * | 2016-10-11 | 2017-05-10 | 天津大学 | Preparation method and application of 1-methylimidazole/TMPD (Tetramethyl-para-Phenylene Diamine) collaborative amination membrane based on polyether-ether-ketone |
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CN104086792A (en) * | 2014-06-13 | 2014-10-08 | 北京航空航天大学 | Preparation method of polymer anion exchange membrane |
CN104086792B (en) * | 2014-06-13 | 2017-03-22 | 北京航空航天大学 | Preparation method of polymer anion exchange membrane |
CN106188543A (en) * | 2016-07-08 | 2016-12-07 | 北京航空航天大学 | A kind of proton-conductive films of flow battery and preparation method thereof |
CN106188543B (en) * | 2016-07-08 | 2018-11-30 | 北京航空航天大学 | A kind of proton-conductive films of flow battery and preparation method thereof |
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CN106633136B (en) * | 2016-10-11 | 2019-10-08 | 天津大学 | 1- methylimidazole based on polyether-ether-ketone/TMPD collaboration amination film preparation and application |
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