CN101862608B - 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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- CN101862608B CN101862608B CN2010101743605A CN201010174360A CN101862608B CN 101862608 B CN101862608 B CN 101862608B CN 2010101743605 A CN2010101743605 A CN 2010101743605A CN 201010174360 A CN201010174360 A CN 201010174360A CN 101862608 B CN101862608 B CN 101862608B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 41
- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 30
- 238000004132 cross linking Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title abstract description 22
- 238000007265 chloromethylation reaction Methods 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 150000003512 tertiary amines Chemical class 0.000 claims description 31
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 28
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 9
- 150000003335 secondary amines Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 42
- 238000005576 amination reaction Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 2
- 238000005956 quaternization reaction Methods 0.000 abstract 2
- 150000002500 ions Chemical group 0.000 abstract 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 36
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 36
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000004696 Poly ether ether ketone Substances 0.000 description 26
- 229920002530 polyetherether ketone Polymers 0.000 description 26
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 22
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 22
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 238000001035 drying Methods 0.000 description 18
- 239000004721 Polyphenylene oxide Substances 0.000 description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 17
- 229920000570 polyether Polymers 0.000 description 17
- 125000001174 sulfone group Chemical group 0.000 description 17
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 14
- 238000005266 casting Methods 0.000 description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 13
- 239000004411 aluminium Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 238000010345 tape casting Methods 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 12
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000001376 precipitating effect Effects 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 239000013049 sediment Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 8
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000009834 vaporization Methods 0.000 description 6
- 230000008016 vaporization Effects 0.000 description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 5
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
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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, in water technology, hydrometallurgy, chemical industry and industrial circles such as Chemical Decomposition and alkaline fuel cell, is widely used.The heat and the chemical stability of conventional 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.To 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 constitutes, its each step thing is the thing initially to be located of next step, the polymer anion-exchange membrane that its final step is accomplished the back gained has stable preferably and high ion exchange capacity.But the polymer anion-exchange membrane of this method preparation does not suit under hot conditions, to operate.
In order to improve the energy efficiency of aqueous solution electrochemical devices, usually hope 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
The object of the invention is exactly the preparation method that a kind of self-crosslinking polymer anion exchange membrane is provided to 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; Ion exchange capacity is high; 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 according to the 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 through chloromethyl percent grafting and tertiary amine grafting degree.The present invention is simple; See that from performance perspective prepared film mechanical performance, heat endurance and ion exchange capacity are much better than the conventional 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
Below pass through the preparation method of embodiment further explain polymer anion-exchange membrane of the present invention.
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, sediment is dissolved in the N of 20 unit of weights with water washing, drying and after smashing, dinethylformamide (DMF) obtains the chloromethylation products solution of polyarylsulfone (PAS) (PASF).Get it and above-mentionedly dissolve the diethylamine that 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; With above-mentioned reactant liquor with casting method in 50 ℃ of drying and forming-films, 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.
Substitute condition below adopting in the present embodiment and all can obtain kin film: (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, sediment is dissolved in the N of 30 unit of weights with water washing, drying and after smashing, 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; With above-mentioned reactant liquor with The tape casting in 60 ℃ of drying and forming-films, 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.
Substitute condition below adopting in the present embodiment and all can obtain kin film: (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, sediment is dissolved in the N-methyl pyrrolidone (NMP) of 10 unit of weights with water washing, drying and after smashing, 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; With above-mentioned reactant liquor with casting method in 80 ℃ of drying and forming-films, 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.
Substitute condition below adopting in the present embodiment and all can obtain kin film: (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, adds the zinc powder of 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; Sediment is dissolved in the N of 20 unit of weights with water washing, drying and after smashing, 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; With above-mentioned reactant liquor with casting method in 60 ℃ of drying and forming-films, 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, and 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.
Substitute condition below adopting in the present embodiment and all can obtain kin film: (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, adds the zinc powder of 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 2 hours down at 30 ℃; Said mixture poured into product is precipitated out, sediment is dissolved in the N of 20 unit of weights, dinethylformamide (DMF) with water washing, drying and after smashing; Obtain the chloromethylation products solution of polyether-ether-ketone (PEEK); Get above-mentioned solution 1 unit of weight, add the di-n-propylamine of 0.1 unit of weight, 20 ℃ of following stirring reactions 6 hours.Heating vaporization trimethylamine aqueous solution fed above-mentioned solution 5 minutes with trimethylamine gas after super-dry; With above-mentioned reactant liquor with The tape casting in 60 ℃ of drying and forming-films, 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, and 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.
Substitute condition below adopting in the present embodiment and all can obtain kin film: (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, sediment is dissolved in the N of 30 unit of weights with water washing, drying and after smashing, 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; With above-mentioned reactant liquor with The tape casting in 60 ℃ of drying and forming-films, 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.
Substitute condition below adopting in the present embodiment and all can obtain kin film: (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, sediment is dissolved in the methyl-sulfoxide (DMSO) of 10 unit of weights with water washing, drying and after smashing, 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; With above-mentioned reactant liquor with casting method in 100 ℃ of drying and forming-films, 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.
Substitute condition below adopting in the present embodiment and all can obtain kin film: (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; Sediment is dissolved in the N of 30 unit of weights with water washing, drying and after smashing; N-diethyl acetamide (DMAc), the chloromethylation products solution of acquisition polyarylsulfone (PAS) (PASF) is got 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; With above-mentioned reactant liquor with The tape casting in 80 ℃ of drying and forming-films, 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.
Substitute condition below adopting in the present embodiment and all can obtain kin film: (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; Sediment is dissolved in the methyl-sulfoxide (DMSO) of 20 unit of weights with water washing, drying and after smashing; Obtain the chloromethylation products solution of phenolic polyether sulphone (PES-C); Get above-mentioned solution 1 unit of weight, add the dibutyl amine of 0.2 unit of weight, 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; With above-mentioned reactant liquor with casting method in 60 ℃ of drying and forming-films, 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.
Substitute condition below adopting in the present embodiment and all can obtain kin film: (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 (2)
1. the preparation method of a self-crosslinking polymer anion exchange membrane comprises chloromethylation, tertiary amineization, the quaternized and film forming step of being carried out successively by polymer, it is characterized in that:
Described tertiary amineization has step by step following:
1) product behind the polymer chloromethylation is dissolved in the solvent, to obtain the chloromethylation products solution 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 of the chloromethylation that obtains polymer; Described rudimentary secondary amine is selected from diethylamine, di-n-propylamine, dibutyl amine, and its addition is 0.01 ~ 0.2 times of chloromethylation products solution weight of polymer.
2. the preparation method of a kind of self-crosslinking polymer anion exchange membrane according to claim 1 is characterized in that:
Mixing time under the described normal temperature >=0.5 hour.
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| CN101091881A (en) * | 2007-04-17 | 2007-12-26 | 哈尔滨工业大学 | Modified anion exchange membrane and preparation method |
| CN101274226A (en) * | 2008-05-06 | 2008-10-01 | 武汉大学 | Method for preparing polymer anion-exchange membrane |
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Patent Citations (4)
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| US4029582A (en) * | 1974-07-11 | 1977-06-14 | Daicel, Ltd. | Poly(arylether-sulfone) semipermeable membrane comprising substituted halomethyl and/or quaternary nitrogen groups |
| CN1039738A (en) * | 1988-07-29 | 1990-02-21 | 旭硝子株式会社 | Anionite |
| CN101091881A (en) * | 2007-04-17 | 2007-12-26 | 哈尔滨工业大学 | Modified anion exchange membrane and preparation method |
| CN101274226A (en) * | 2008-05-06 | 2008-10-01 | 武汉大学 | Method for preparing polymer anion-exchange membrane |
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