CN102382293B - Polymer anion exchange membrane and preparation method thereof - Google Patents
Polymer anion exchange membrane and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to ionomer fields, are related to a kind of anion-exchange membrane that can be used for alkaline fuel cell, and the invention discloses a kind of anionic polymer, repetitive unit is as follows:
A kind of new polymers anion-exchange membrane of good performance based on imidazole salts is prepared using above-mentioned anionic polymer, overcome the poor problem of quaternary polymer anion-exchange membrane chemical stability, the use of chloromethyl ether in traditional polymer anion-exchange membrane preparation process is avoided simultaneously, reduces the harm to human body and environment.
Description
Technical field
The present invention relates to a kind of polymer anion-exchange membrane and preparation method thereof, relate in particular to a kind of anion-exchange membrane that can be used for alkaline fuel cell and preparation method thereof.
Background technology
Anion-exchange membrane has been widely used in the industrial circles such as water treatment, hydrometallurgy, chemical separation and alkaline fuel cell.The preparation method of traditional quaternary polymer anion-exchange membrane will be through the process of chloromethylation when introducing ion-exchange group; and to use hypertoxic carcinogenic substance chloromethyl ether in the chloromethylation process, this has great harm to environment protection and human health.Alkaline polymer electrolyte membrane is one of core component of alkaline anion-exchange membrane fuel cell, and the quality of its performance directly determines performance and the life-span of battery.The research of alkaline polymer electrolyte starts from 1994.(Fauvarque.Electrochim Acta 1998 is that matrix mixing potassium hydroxide and water form polymkeric substance with PEO 43:1163-1170) to Guinot etc. first, and its room-temperature conductivity scope is 10
-3～10
-4S/cm.Thereafter, many researchists have carried out the research work of alkaline solid polymer electrolyte.The Watanabe seminar of Japan, domestic Wuhan University, China Science ﹠ Technology University, Chinese Academy of Sciences Changchun should be changed the seminar such as institute and carry out a few thing based on quaternary ammonium salt alkaline polymer electrolyte membrane field.The people such as Lin (Chem.Mater., 2010,22,6718-6725) method of employing in-situ polymerization has prepared the anion-exchange membrane based on alkali ionic liquid, the method is simple and safe, and the anion-exchange membrane of preparation has higher specific conductivity, but this film is owing to be the fats main polymer chain, the water absorption and swelling rate is higher, and dimensional stability is relatively relatively poor.Therefore, the alkaline fuel cell polymer dielectric film still exists a lot of problems to demand researchist's solution urgently:
1) traditional quaternary ammonium salt polymer is in preparation process, and highly toxic substance chloromethyl ether one of the raw material that is absolutely necessary is so that the preparation of alkaline anion-exchange membrane has very large harm to human body and environment.
2) QAS polymer is in the halomethylation process, be difficult to accomplish accurately to control position and the level of response of halomethylation, can produce a lot of side reactions, affect the overall performance of polymkeric substance, and the polymers obtained anion-exchange membrane thermostability of traditional preparation technology, poor chemical stability, particularly under comparatively high temps or alkaline environment, degrade easily.Therefore developing synthesizing new becomes the focus of people's research for the polymer anion-exchange membrane material of alkaline fuel cell.
Good alkaline polymer anion-exchange membrane outside the good thermostability and chemical stability, also will have good mechanical property and alkali resistance except possessing higher ionic conductivity.
But the anion-exchange membrane of reporting in the prior art is difficult to satisfy simultaneously above-mentioned requirements, such as: (the J.Membr.Sci.2009 such as Wu, 338,51.) silicon-dioxide of preparation/poly-2,6-dimethyl-1,4-phenylate inorganic hybridisation anion exchange membrane has good mechanical property, but specific conductivity is but not high by (1～8 * 10-3Scm-1).(the Macromolecules such as Wang, 2010,43,3895) the polyether sulfone alkaline anion-exchange membrane that contains the guanidinesalt group of preparation can reach 7.4 * 10-2S cm-1 in the 60oC ionic conductivity, but this anion-exchange membrane water-intake rate is up to 107%, the mechanical property of the too high destruction anion-exchange membrane of water-intake rate.
Summary of the invention
The object of the invention provides a kind of well behaved new polymers anion-exchange membrane based on imidazole salts and preparation method thereof, overcome the relatively poor problem of quaternary polymer anion-exchange membrane chemical stability, avoid simultaneously the use of chloromethyl ether in the traditional polymer anion-exchange membrane preparation process, reduced the harm to human body and environment.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of anionic polymer, and the repeating unit of described anionic polymer is as follows:
In the formula, wherein n is 0～7 integer; R
1Alkyl for C1～C4; R
2Be methyl or H; X is selected from I, Br, Cl, SCN, BF
4, NO
3, PF
6, CF
3SO
3, N (CN)
2, [N (SO
2CF
3)
2], a kind of among the OH, Ar is selected from a kind of in the group that following structural formula represents:
In the technique scheme, the polymerization degree of described anionic polymer and molecular weight can be controlled according to the length of polymerization time.
The preparation method of above-mentioned anionic polymer may further comprise the steps:
In the presence of alkali, under the protection of inert gas atmosphere, make the monomer that contains the imidazoles functional group, the monomer that contains the Ar structure carry out nucleophilic substitution reaction, obtain anionic polymer;
The described structural formula that contains the monomer of imidazoles functional group is:
The monomer of the described Ar of containing structure is selected from:
In the technique scheme, described alkali is a kind of in yellow soda ash, salt of wormwood or the cesium carbonate.
In the technique scheme, the preparation method of described anionic polymer is characterized in that, specifically may further comprise the steps:
(1) will contain the monomer of imidazoles functional group, the monomer that contains the Ar structure, toluene, alkali and be dissolved in solvent, in 110～130 ℃ of back flow reaction 4～8 hours, the water azeotropic removal of water that generates in toluene and the reaction system; Described high boiling solvent is selected from: a kind of in DMF (149～156 ℃ of boiling points), methyl-sulphoxide (189 ℃ of boiling points), the N-Methyl pyrrolidone (203 ℃ of boiling points);
(2) promote temperature of reaction to 140～170 ℃, and temperature of reaction is not higher than solvent boiling point, reacted 4～30 hours, prepare anionic polymer.
Further in the technical scheme, above-mentioned anionic polymer is dissolved in the solvent, the method by solution-cast prepares anion-exchange membrane, and anion-exchange membrane is soaked in basic solution (potassium hydroxide or sodium hydroxide solution), and can get negatively charged ion is OH
-Alkaline anion-exchange membrane.
The polymer anion-exchange membrane based on imidazole salts that the present invention's claimed aforesaid method of while prepares, described alkaline anion-exchange membrane can be applied to the alkaline fuel cell field.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. the present invention is prepared into anion-exchange membrane with imidazole salts, compares with traditional quaternary ammonium salt anion-exchange membrane, and the anion-exchange membrane based on imidazole salts of the present invention's preparation has better thermostability and alkali resistance;
2. the present invention prepares alkaline anion-exchange membrane take aromatic ring as main polymer chain, so that the polymer anion film has better mechanical property and dimensional stability;
3. the present invention adopts the method for simple anionresin to prepare alkaline anion-exchange membrane, has avoided the use of carcinogenic substance chloromethyl ether in traditional quaternary anionic membrane preparation process, and preparation process is relatively simple and safe;
4. the present invention carries out polymerization with the polymerization single polymerization monomer functionalization first again and obtains functional polymer, has overcome the position of difficult accurately control halomethylation in traditional anion-exchange membrane preparation process and the defective of level of response;
5. the polymer anion-exchange membrane of the present invention's design can change different negatively charged ion according to actual needs, and the anion-exchange membrane that obtains having different anions is immersed in and obtains alkaline anion-exchange membrane in the alkali lye.This polymer film has remarkable alkali resistance, can be used for alkaline fuel cell.
Description of drawings
Fig. 1 is the Infrared Characterization figure as a result of embodiment two gained anion-exchange membranes;
Fig. 2 is the alkali resistance test result figure among the embodiment eight.
Embodiment
The invention will be further described below in conjunction with drawings and Examples:
Embodiment one:
Preparation contains the monomer of imidazoles functional group
(reference: Macromolecules 2010,43,10196-10200).
1) in three-necked bottle, adds 2,7-, two bromo-9,9-two (6 '-bromohexane base) fluorenes (5.0g, 7.7mmol), para hydroxybenzene boric acid (1.2g, 8.5mmol), 40ml tetrahydrofuran (THF) and 30ml 2M K
2CO
3Solution, nitrogen protection adds catalyst P dCl
2(dppf) 160mg, the temperature to 70 that slowly raises ℃ was reacted 24 hours.Crude product is through extraction, the column chromatography light yellow crystal 2 of purifying to get, 7-two (4 '-hydroxy phenyl)-9,9-two (6 '-bromohexane) fluorenes 3.46g, productive rate 66.2%.
2) in three-necked bottle, add 2,7-two (4 '-hydroxy phenyl)-9,9-two (6 '-bromohexane) fluorenes (2.0g, 2.96mmol); 1,2 dimethylimidazole (1ml, 12.5mmol); the 20ml acetonitrile, nitrogen protection was 70 ℃ of lower reactions 12 hours.Crude product obtains faint yellow solid 2.45g, productive rate 95.3% after anhydrous diethyl ether, washed with dichloromethane.
Other preparations that contain the monomer of imidazoles functional group also can be referring to above-mentioned preparation method.
Embodiment two:
In three-necked flask, add 0.005mol
0.005mol
0.011mol Cs
2CO
3, 30ml methyl-sulphoxide and 15ml toluene.Under the nitrogen protection, be warming up to 120 ℃ of reactions 4 hours, remove the water that generates in the reaction process, slowly be warming up to 140 ℃, back flow reaction 8 hours.Then the polymkeric substance that obtains deionized water Precipitation uses deionized water, washing with alcohol repeatedly, drying for standby.After fully being dissolved into the 0.1g resulting polymers in the DMF, polymers soln is dripped on the polyfluortetraethylene plate, drying is 2 hours under 70 ℃, prepares Br-type anion-exchange membrane.
The bromine type anion-exchange membrane of gained is placed 1M KOH solution, 60 ℃ of lower immersions 24 hours, treat Br
-Complete exchange becomes OH
-After, obtain OH
-The type anion-exchange membrane.
Employing FT-IR Varian CP-3800spectrometer carries out the infrared structure sign to two types anion-exchange membrane.Measurement range is 4000-400cm
-1Its result as shown in Figure 1, wherein A is the infrared spectrogram of Br-type anion-exchange membrane, B is OH
-The infrared spectrogram of type anion-exchange membrane.C is OH
-The type anion-exchange membrane soaks the infrared spectrogram after 108 hours in 60 ℃ 1M KOH solution.Wherein, 1586cm
-1And 744cm
-1Be the infrared signature absorption of imidazole ring, 2935,2856cm
-1The place is-CH
2-charateristic avsorption band, 465-1637cm
-1. about be the charateristic avsorption band of phenyl ring.3421cm
-1. the broad peak of locating is O-H, the characteristic absorption band of N-H, and this proves that also this material has good wetting ability 1317 and 1151cm
-1The absorption peak of sulfoxide, 1245cm
-1The absorption peak proof aryl oxide (O-) existence of structure at place.Comprehensive above the analysis knows that this anion-exchange membrane is target product, contains the polymkeric substance of imidazoles functional group.C compares with B, does not have significantly to absorb the variation of position, illustrates that this polymkeric substance can keep Stability Analysis of Structures in basic solution, have good alkali resistance.
The OH that present embodiment obtains
-Type anion-exchange membrane loading capacity is 1.01mmol/g, and ionic conductance is 2.54 * 10 under the room temperature
-2S cm
-1, 90 ℃ of lower ionic conductances are 5.63 * 10
-2S cm
-1Tensile strength is 50.41MPa, and Young's modulus is 1.52GPa, and elongation at break is 12.65%.
Embodiment three:
In three-necked flask, add 0.005mol
0.005mol
0.011mol K
2CO
3, 30ml methyl-sulphoxide and 15ml toluene.Under the nitrogen protection, be warming up to 120 ℃ of reactions 4 hours, remove the water that generates in the reaction process, slowly be warming up to 140 ℃, back flow reaction 16 hours.Then the polymkeric substance that obtains deionized water Precipitation uses deionized water, washing with alcohol repeatedly, drying for standby.After fully being dissolved into the 0.1g resulting polymers in the methyl-sulphoxide, polymers soln is dripped on the polyfluortetraethylene plate, drying is 6 hours under 70 ℃, prepares Br-type anion-exchange membrane.
The bromine type anion-exchange membrane of gained is positioned in the 1M KOH solution, 60 ℃ of lower immersions 24 hours, treats Br
-Complete exchange becomes OH
-After, remove remaining KOH with deionized water, obtain OH
-The type anion-exchange membrane.
The OH that present embodiment obtains
-Type anion-exchange membrane loading capacity is 1.12mmol/g, and ionic conductance is 1.37 * 10 under the room temperature
-2S cm
-1, 90 ℃ of lower ionic conductances are 6.02 * 10
-2S cm
-1Tensile strength is 44.67MPa, and Young's modulus is 1.45GPa, and elongation at break is 9.65%.
Embodiment four:
In three-necked flask, add 0.005mol
0.005mol
0.011mol K
2CO
3, 30ml methyl-sulphoxide and 15ml toluene.Under the nitrogen protection, be warming up to 120 ℃ of reactions 4 hours, remove the water that generates in the reaction process, slowly be warming up to 160 ℃, back flow reaction 8 hours.Then the polymkeric substance that obtains deionized water Precipitation uses deionized water, washing with alcohol repeatedly, drying for standby.After fully being dissolved into the 0.1g resulting polymers in the methyl-sulphoxide, polymers soln is dripped on the polyfluortetraethylene plate, drying is 6 hours under 70 ℃, prepares Br-type anion-exchange membrane.
The bromine type anion-exchange membrane of gained is positioned in the 1M KOH solution, 60 ℃ of lower immersions 24 hours, treats Br
-Complete exchange becomes OH
-After, remove remaining KOH with deionized water, obtain OH
-The type anion-exchange membrane.
The OH that present embodiment obtains
-Type anion-exchange membrane loading capacity is 0.87mmol/g, and ionic conductance is 0.91 * 10 under the room temperature
-2S cm
-1, 90 ℃ of lower ionic conductances are 3.23 * 10
-2S cm
-1Tensile strength is 47.50MPa, and Young's modulus is 1.29GPa, and elongation at break is 11.61%.
Embodiment five:
In three-necked flask, add 0.005mol
0.005mol
0.011mol K
2CO
3, 30ml methyl-sulphoxide and 15ml toluene.Under the nitrogen protection, be warming up to 120 ℃ of reactions 4 hours, remove the water that generates in the reaction process, slowly be warming up to 140 ℃, back flow reaction 20 hours.Then the polymkeric substance that obtains deionized water Precipitation uses deionized water, washing with alcohol repeatedly, drying for standby.After fully being dissolved into the 0.1g resulting polymers in the DMF, polymers soln is dripped on the polyfluortetraethylene plate, drying is 2 hours under 70 ℃, prepares Br-type anion-exchange membrane.
The bromine type anion-exchange membrane of gained is positioned in the 1M KOH solution, 60 ℃ of lower immersions 24 hours, treats Br
-Complete exchange becomes OH
-After, remove remaining KOH with deionized water, obtain OH
-The type anion-exchange membrane.
The OH that present embodiment obtains
-Type anion-exchange membrane loading capacity is 0.73mmol/g, and ionic conductance is 0.65 * 10 under the room temperature
-2S cm
-1, 90 ℃ of lower ionic conductances are 2.51 * 10
-2S cm
-1Tensile strength is 38.52MPa, and Young's modulus is 1.76GPa, and elongation at break is 15.52%.
Embodiment six:
In three-necked flask, add 0.005mol
0.005mol
0.011mol K
2CO
3, 30ml methyl-sulphoxide and 15ml toluene.Under the nitrogen protection, be warming up to 120 ℃ of reactions 4 hours, remove the water that generates in the reaction process, slowly be warming up to 140 ℃, back flow reaction 20 hours.Then the polymkeric substance that obtains deionized water Precipitation uses deionized water, washing with alcohol repeatedly, drying for standby.After fully being dissolved into the 0.1g resulting polymers in the DMF, polymers soln is dripped on the polyfluortetraethylene plate, drying is 2 hours under 70 ℃, prepares Br-type anion-exchange membrane.
The bromine type anion-exchange membrane of gained is positioned in the 1M KOH solution, 60 ℃ of lower immersions 24 hours, treats Br
-Complete exchange becomes OH
-After, remove remaining KOH with deionized water, obtain OH
-The type anion-exchange membrane.
The OH that present embodiment obtains
-Type anion-exchange membrane loading capacity is 0.73mmol/g, and ionic conductance is 0.65 * 10 under the room temperature
-2S cm
-1, 90 ℃ of lower ionic conductances are 2.51 * 10
-2S cm
-1Tensile strength is 53.87MPa, and Young's modulus is 1.88GPa, and elongation at break is 10.43%.
Embodiment seven:
In three-necked flask, add 0.005mol
0.005mol
0.011mol K
2CO
3, 30ml methyl-sulphoxide and 15ml toluene.Under the nitrogen protection, be warming up to 120 ℃ of reactions 4 hours, remove the water that generates in the reaction process, slowly be warming up to 140 ℃, back flow reaction 8 hours.Then the polymkeric substance that obtains deionized water Precipitation uses deionized water, washing with alcohol repeatedly, drying for standby.After fully being dissolved into the 0.1g resulting polymers in the methyl-sulphoxide, polymers soln is dripped on the polyfluortetraethylene plate, drying is 6 hours under 70 ℃, prepares Br-type anion-exchange membrane.
The bromine type anion-exchange membrane of gained is positioned in the 1M KOH solution, 60 ℃ of lower immersions 24 hours, treats Br
-Complete exchange becomes OH
-After, remove remaining KOH with deionized water, obtain OH
-The type anion-exchange membrane.
The OH that present embodiment obtains
-Type anion-exchange membrane loading capacity is 0.89mmol/g, and ionic conductance is 1.08 * 10 under the room temperature
-2S cm
-1, 90 ℃ of lower ionic conductances are 4.32 * 10
-2S cm
-1Tensile strength is 38.66MPa, and Young's modulus is 1.21GPa, and elongation at break is 16.44%.
Embodiment eight:
OH with the preparation of ratio described in the example two
-The type anion-exchange membrane is sample, carry out the alkali resistance test based on the polymer anion-exchange membrane of imidazole salts, (Macromolecules 2010 with reference to literary composition in the alkaline resistance properties test of anion-exchange membrane, 43,3890-3896) described method, anion-exchange membrane is dipped in 60 ℃ the 1M KOH solution, take out at regular intervals film, be immersed in the deionized water KOH residual in the Ex-all film, adopt AC impedence method to survey the specific conductivity of anion-exchange membrane, Range of measuring temp is 30 ℃～90 ℃.Test result as shown in Figure 2, the result shows the increase along with soak time in alkali lye, the specific conductivity of anion-exchange membrane downward trend do not occur as traditional quaternary ammonium salt anion-exchange membrane.Experimental results show that the polymer anion-exchange membrane based on ionic liquid that the present invention prepares has good alkali resistance.
Claims (5)
1. an anionic polymer is characterized in that, the repeating unit of described anionic polymer is as follows:
In the formula, wherein n is 0～7 integer; R
1Alkyl for C 1～C4; R
2Be methyl or H; X is selected from I, Br, Cl, SCN, BF
4, NO
3, PF
6, CF
3SO
3, N (CN)
2, [N (SO
2CF
3)
2], a kind of among the OH, Ar is selected from a kind of in the group that following structural formula represents:
2. the preparation method of the described anionic polymer of claim 1 is characterized in that, may further comprise the steps:
In the presence of alkali, under the protection of inert gas atmosphere, make the monomer that contains the imidazoles functional group, the monomer that contains the Ar structure carry out nucleophilic substitution reaction, obtain anionic polymer;
The described structural formula that contains the monomer of imidazoles functional group is:
The monomer of the described Ar of containing structure is selected from:
,
,
Or
3. the preparation method of described anionic polymer according to claim 2 is characterized in that, described alkali is a kind of in yellow soda ash, salt of wormwood or the cesium carbonate.
4. the preparation method of described anionic polymer according to claim 3 is characterized in that, specifically may further comprise the steps:
(1) will contain the monomer of imidazoles functional group, the monomer that contains the Ar structure, toluene, alkali and be dissolved in solvent, in 110～130 ℃ of reactions 4～8 hours, the water azeotropic removal of water that generates in toluene and the reaction system; Described solvent is selected from: a kind of in DMF, methyl-sulphoxide, the N-Methyl pyrrolidone;
(2) promote temperature of reaction to 140～170 ℃, and temperature of reaction is not higher than solvent boiling point, back flow reaction 4～30 hours prepares anionic polymer.
5. polymer anion-exchange membrane that adopts the preparation of the described anionic polymer of claim 1.
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| CN108794784B (en) * | 2016-01-29 | 2021-06-22 | 广东融塑新材料有限公司 | Anion exchange membrane |
| EP3473659A1 (en) * | 2017-10-17 | 2019-04-24 | Evonik Degussa GmbH | Polymeric anions conducting membranes |
| CN113166335B (en) | 2018-12-11 | 2023-09-29 | 3M创新有限公司 | Copolymers having cationic nitrogen-containing groups and anion exchange membranes made therefrom |
| CN110862533B (en) * | 2019-11-25 | 2022-06-17 | 九江天赐高新材料有限公司 | Preparation method of polyion liquid for lithium battery polymer solid electrolyte |
| CN112619441A (en) * | 2021-01-15 | 2021-04-09 | 福州大学 | Anion exchange membrane and solvent-free preparation method thereof |
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| CN102050911A (en) * | 2010-11-23 | 2011-05-11 | 苏州大学 | Polymer anion exchange membrane and preparation method thereof |
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