CN106543459B - A kind of preparation method of polybenzimidazoles/modified poly-epoxy chloropropane composite anion exchange membrane - Google Patents

A kind of preparation method of polybenzimidazoles/modified poly-epoxy chloropropane composite anion exchange membrane Download PDF

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CN106543459B
CN106543459B CN201610991062.2A CN201610991062A CN106543459B CN 106543459 B CN106543459 B CN 106543459B CN 201610991062 A CN201610991062 A CN 201610991062A CN 106543459 B CN106543459 B CN 106543459B
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exchange membrane
polybenzimidazoles
epoxy chloropropane
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CN106543459A (en
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储富强
王琳琳
林本才
袁宁一
丁建宁
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Changzhou University
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Abstract

The invention belongs to alkaline fuel cell fields, in particular to the solution for the Hydrin that fluorine-containing polybenzimidazoles solution and imidazole salts are modified a kind of polybenzimidazoles/modified poly-epoxy chloropropane composite anion exchange membrane preparation method: is evaporated into solvent film forming after mixing, washing obtains composite anion exchange membrane to neutrality after the film is impregnated in aqueous slkali again.Preparation method is succinctly efficient, small to environment and human body harm, and composite membrane has preferable ionic conductivity and stable alkali resistance and mechanical performance, can apply in alkaline fuel cell field.

Description

A kind of system of polybenzimidazoles/modified poly-epoxy chloropropane composite anion exchange membrane Preparation Method
Technical field
The invention belongs to alkaline fuel cell field, in particular to a kind of polybenzimidazoles/modified poly-epoxy chloropropane is multiple Close the preparation method of anion-exchange membrane.
Background technique
Alkaline anion-exchange membrane (Anion-exchange membrane, AEM) is alkali anion fuel cell The core component of (Alkaline anion exchange membrane fuel cell, AAEMFC), it is played the role of It is: (1) anode and cathode is separated, fuel and air (oxygen) directly mixing is avoided to react；(2) by anion from Anode passes to cathode forming circuit etc..Alkaline anion-exchange membrane used in usual alkali anion fuel cell needs to meet The following: (1) preferable OH-Conductivity；(2) preferable alkali resistance；(3) preferable mechanical performance；(4) thermal stability is good Etc..
The AEM of most study is quaternary ammonium series anion-exchange membrane at present, in general, the preparation of this kind of alkaline anion-exchange membrane It needs by chloromethylation and quaternization process.However, chloromethylation yield is generally lower, and chloromethylation reagents are special It is not that chloromethyl ether has very big toxicity, in addition, the common trimethylamine (TMA) during quaternization reaction, because it has Very strong volatility, be easy to cause environmental pollution.In addition to this, the anionic membrane of this season alkyl amine type, under alkaline environment Due to OH-Nucleophilic substitution caused by direct attack and hofmann elimination bring it about degradation, lead to the ion-conductance of film Conductance decline.These problems all limit the extensive use of quaternary ammonium salt alkaline anion-exchange membrane, therefore prepare development of new type alkali-resistant fibre Property anion-exchange membrane be the key that develop AAEMFC.
Summary of the invention
It is an object of the invention to: a kind of polybenzimidazoles/modified poly-epoxy chloropropane composite anion exchange membrane is provided Preparation method: by polybenzimidazoles solution and modified poly-epoxy chloropropane solution evaporate after mixing solvent film forming, then will The film washs after impregnating in aqueous slkali to neutrality, obtains composite anion exchange membrane,
Polybenzimidazoles has good thermal stability and excellent mechanical property, especially still may be used under the high temperature conditions To keep excellent mechanical strength, but it is undesirable in terms of compatibility with Hydrin substance, lead to film forming procedure It is middle macroscopical lamination occur and be difficult to realize,
In this regard, being on the one hand modified by fluorine element to polybenzimidazoles in the present invention, imidazole salts are on the other hand utilized Hydrin is modified, perfect compatible, the specific steps of two kinds of film forming matrixes are realized are as follows:
(1) fluorine-containing polybenzimidazoles (PBI) solution is prepared
Polyphosphoric acids PPA is stirred to solid under 140 DEG C, nitrogen protection and is completely dissolved deoxidation in colorless and transparent molten Liquid is simultaneously cooled to room temperature (25 DEG C, similarly hereinafter)；Under nitrogen protection, 3,3 '-benzidine diamines and 2 are added thereto, 2- is bis- Reaction temperature is increased to 100 DEG C, 120 DEG C, 140 DEG C, and reacted respectively at various temperatures by (4- carboxyl phenyl) hexafluoropropane 12h,12h,6h；Reaction system is poured into deionized water after cooling, brown filamentous polymer, immersion or washing copolymer is precipitated To remove extra acid, fluorine-containing polybenzimidazole polymer is obtained after vacuum drying；Finally by resulting fluorine-containing polybenzimidazoles Polymer is dissolved in organic solvent and obtains fluorine-containing polybenzimidazoles solution,
As preferred: polyphosphoric acids PPA, 3 used in this step, bis- (the 4- carboxylics of 3 '-benzidine diamines, 2,2- Base phenyl) hexafluoropropane weight ratio be 27:2.14:3.92,
Heating in dimethyl sulfoxide (DMSO) is added in resulting fluorine-containing polybenzimidazole polymer to make it dissolve, is made into poly- Close the fluorine-containing polybenzimidazoles solution of amber transparent that amount of substance score is 5%；
(2) modified poly-epoxy chloropropane solution is prepared
Hydrin is made into homogeneous phase solution, excessive 1- methylimidazole is added dropwise under the conditions of 60 DEG C, is sufficiently stirred anti- Sticky yellowish-brown liquid should be obtained, is cleaned with ether three times to remove unreacted raw material, rotates to obtain with Rotary Evaporators The Hydrin of imidazole salts modification, is finally dissolved in organic solvent for products therefrom and obtains modified poly-epoxy chloropropane solution,
As preferred: the Hydrin that resulting imidazole salts are modified being dissolved in dimethyl sulfoxide (DMSO) and is made into polymerization The solution that amount of substance score is 5%；
(3) by modified poly-epoxy chlorine third obtained in fluorine-containing polybenzimidazoles solution obtained in step (1) and step (2) Alkane solution is uniformly mixed, and down on clean smooth glass plate, evaporation of solvent is cooled to room temperature and demoulds to obtain composite membrane,
As preferred: the mass ratio that modified poly-epoxy chloropropane and fluorine-containing polybenzimidazoles are controlled when mixing is 1:9~5: 5；
(4) composite membrane obtained in step (3) is immersed in after being impregnated in aqueous slkali and is taken out, be washed with deionized or soak Bubble to neutrality to get polybenzimidazoles/modified poly-epoxy chloropropane composite anion exchange membrane,
Wherein, aqueous slkali is 1~2molL of concentration-1KOH solution, soaking time of the composite membrane in aqueous slkali be 24 ~48h.
The beneficial effects of the present invention are: the present invention is modified by fluorine element to polybenzimidazoles and imidazole salts pair The modification of Hydrin, the perfection for realizing two kinds of film forming matrixes is compatible, makes polybenzimidazoles and modified poly-epoxy chlorine third The common of alkane is possibly realized.The Hydrin of imidazole salts modification, avoids chloromethylation and quaternized, reduces pair The harm of environment and human body, while the introducing of imidazole salts ensure that the ionic conductivity of alkaline anion-exchange membrane；And it uses poly- Benzimidazole provides preferable mechanical performance and chemical stability as base structure, for alkaline anion-exchange membrane, makes this Composite membrane is applied in alkaline fuel cell.
Detailed description of the invention
Fig. 1 is the composite membrane of the modified poly-epoxy chloropropane doping of different proportion and the TGA figure of pure PBI in each embodiment (thermal stability of composite membrane, the rate of heat addition: 10 are tested by the thermogravimetric analyzer (NETZSCH) that German Nai Chi company manufactures ℃·min-1)。
Fig. 2 is to be soaked at 60 DEG C of composite membrane of the modified poly-epoxy chloropropane doping of different proportion in each embodiment 1mol·L-1KOH solution in alkali resistance test chart after 15 days.
Fig. 3 is the Hydrin of the imidazole salts modification of each embodiment preparation1H NMR figure.
Specific embodiment
Embodiment 1
The preparation of the PBI composite anion exchange membrane of 10% modified poly-epoxy chloropropane doping
(1) fluorine-containing polybenzimidazoles (PBI) solution is prepared
27g polyphosphoric acids PPA is stirred to solid under 140 DEG C, nitrogen protection and is completely dissolved deoxidation in colourless Bright solution is simultaneously cooled to room temperature；Under nitrogen protection, 3, the 3 '-benzidine diamines and 3.92g of 2.14g are added thereto 2,2- bis- (4- carboxyl phenyl) hexafluoropropane, are increased to 100 DEG C, 120 DEG C, 140 DEG C for reaction temperature, and divide at various temperatures It Fan Ying not 12h, 12h, 6h；Reaction system is poured into deionized water after cooling, brown filamentous polymer is precipitated, impregnate or is washed Polymer obtains fluorine-containing polybenzimidazole polymer to remove extra acid after vacuum drying；Finally by resulting fluorine-containing polyphenyl And imidazoles polymer is added heating in dimethyl sulfoxide (DMSO) and makes it dissolve, and is made into the brown that polymer quality score is 5% Transparent fluorine-containing polybenzimidazoles solution；
(2) modified poly-epoxy chloropropane solution is prepared
Hydrin is dissolved in dimethyl sulfoxide and is made into homogeneous phase solution, excessive 1- methyl miaow is added dropwise under the conditions of 60 DEG C Azoles is sufficiently stirred reaction and obtains sticky yellowish-brown liquid, is cleaned with ether three times to remove unreacted raw material, is steamed with rotation Hair instrument rotates to obtain the Hydrin of imidazole salts modification, finally by products therefrom be dissolved in dimethyl sulfoxide (DMSO) be made into it is poly- Close the solution that amount of substance score is 5%；
(3) by modified poly-epoxy chlorine third obtained in fluorine-containing polybenzimidazoles solution obtained in step (1) and step (2) It is 1:9 that alkane solution, which is uniformly mixed and controls modified poly-epoxy chloropropane and the mass ratio of fluorine-containing polybenzimidazoles, and mixed liquor is fallen To clean smooth glass plate, evaporation of solvent is cooled to room temperature and demoulds to obtain composite membrane；
(4) composite membrane that step (3) obtains is immersed in 1molL-1KOH solution in take out after 48h, use deionized water Washing obtains polybenzimidazoles/modified poly-epoxy chloropropane composite anion exchange membrane to neutrality.
The ionic conductivity of the anion-exchange membrane that the present embodiment obtains at room temperature are as follows: 28.39mScm-1；At 80 DEG C Under ionic conductivity are as follows: 37.01mScm-1；Tensile strength are as follows: 37.57MPa；Young's modulus are as follows: 931.87MPa；Fracture is stretched Long rate are as follows: 5.582%.
Embodiment 2
The preparation of the PBI composite anion exchange membrane of 20% modified poly-epoxy chloropropane doping
The mass ratio of modified poly-epoxy chloropropane and fluorine-containing polybenzimidazoles is 2:8 in rate-determining steps (3), remaining operation is equal With embodiment 1.
The ionic conductivity of the anion-exchange membrane that the present embodiment obtains at room temperature are as follows: 32.04mScm-1；At 80 DEG C Under ionic conductivity are as follows: 40.21mScm-1；Tensile strength are as follows: 35.44MPa；Young's modulus are as follows: 856.76MPa；Fracture is stretched Long rate are as follows: 6.033%.
Embodiment 3
The preparation of the PBI composite anion exchange membrane of 30% modified poly-epoxy chloropropane doping
The mass ratio of modified poly-epoxy chloropropane and fluorine-containing polybenzimidazoles is 3:7 in rate-determining steps (3), remaining operation is equal With embodiment 1.
The ionic conductivity of the anion-exchange membrane that the present embodiment obtains at room temperature are as follows: 39.01mScm-1；At 80 DEG C Under ionic conductivity are as follows: 45.74mScm-1；Tensile strength are as follows: 30.29MPa；Young's modulus are as follows: 731.67MPa；Fracture is stretched Long rate are as follows: 7.370%.
Embodiment 4
The preparation of the PBI composite anion exchange membrane of 40% modified poly-epoxy chloropropane doping
The mass ratio of modified poly-epoxy chloropropane and fluorine-containing polybenzimidazoles is 4:6 in rate-determining steps (3), remaining operation is equal With embodiment 1.
The ionic conductivity of the anion-exchange membrane that the present embodiment obtains at room temperature are as follows: 42.64mScm-1；At 80 DEG C Under ionic conductivity are as follows: 49.35mScm-1；Tensile strength are as follows: 26.42MPa；Young's modulus are as follows: 586.56MPa；Fracture is stretched Long rate are as follows: 8.669%.
Embodiment 5
The preparation of the PBI composite anion exchange membrane of 50% modified poly-epoxy chloropropane doping
The mass ratio of modified poly-epoxy chloropropane and fluorine-containing polybenzimidazoles is 5:5 in rate-determining steps (3), remaining operation is equal With embodiment 1.
The ionic conductivity of the anion-exchange membrane that the present embodiment obtains at room temperature are as follows: 45.01mScm-1；At 80 DEG C Under ionic conductivity are as follows: 55.74mScm-1；Tensile strength are as follows: 22.07MPa；Young's modulus are as follows: 459.31MPa；Fracture is stretched Long rate are as follows: 9.720%.
Comparative example 1
" bis- (4- carboxyl phenyl) hexafluoropropane of 2,2- " in embodiment 1 are replaced with into equimolar 4,4 '-dicarboxyl two Phenylate, remaining operation are constant:
When operation proceeds to step (3), polybenzimidazoles solution and modified poly-epoxy chloropropane solution be cannot achieve Even mixing, there are apparent layerings, cause subsequent handling that can not carry out.
Comparative example 2
" bis- (4- carboxyl phenyl) hexafluoropropane of 2,2- " in embodiment 1 are replaced with into bis- (the 4- carboxyls of equimolar 2,2- Phenyl) propane, remaining operation is constant:
When operation proceeds to step (3), polybenzimidazoles solution and modified poly-epoxy chloropropane solution be cannot achieve uniformly Mixing, there are apparent layerings, cause process that can not continue.
Comparative example 3
" bis- (4- carboxyl phenyl) hexafluoropropane of 2,2- " in embodiment 1 are replaced with to the change of equimolar following structural formula Object is closed, remaining operation is constant:
Operation is when proceeding to step (3), resulting fluorine-containing polybenzimidazoles solution and modified poly-epoxy chloropropane solution without Method realizes uniformly mixing, and there are apparent layerings, cause process that can not continue.
Comparative example 4
It, will be direct with two phenyl ring in " 2,2- bis- (4- carboxyl phenyl) propane " on the basis of above-mentioned comparative example 2 Connected-H whole use-F substitution, remaining operation are constant:
Operation is when proceeding to step (3), resulting fluorine-containing polybenzimidazoles solution and modified poly-epoxy chloropropane solution without Method realizes uniformly mixing, and there are apparent layerings, cause process that can not continue.

Claims (6)

1. a kind of polybenzimidazoles/modified poly-epoxy chloropropane composite anion exchange membrane preparation method, it is characterised in that: institute Stating preparation method is, polybenzimidazoles solution and modified poly-epoxy chloropropane solution are evaporated solvent film forming after mixing, then Washing obtains composite anion exchange membrane to neutrality after the film is impregnated in aqueous slkali；
The preparation method the specific steps are,
(1) fluorine-containing polybenzimidazoles solution is prepared；
(2) modified poly-epoxy chloropropane solution is prepared
Hydrin is reacted to obtain the Hydrin of imidazole salts modification with 1- methylimidazole, and is dissolved in organic solvent Obtain modified poly-epoxy chloropropane solution；
(3) modified poly-epoxy chloropropane obtained in fluorine-containing polybenzimidazoles solution obtained in step (1) and step (2) is molten Liquid is uniformly mixed and solvent flashing film forming, obtains composite membrane；
(4) composite membrane obtained in step (3) is immersed in after being impregnated in aqueous slkali and is taken out, be washed with deionized or be dipped to Neutrality is to get polybenzimidazoles/modified poly-epoxy chloropropane composite anion exchange membrane.
2. the preparation method of anion-exchange membrane as described in claim 1, it is characterised in that: the concrete operations of step (1) are,
Polyphosphoric acids PPA is stirred under 140 DEG C, nitrogen protection to solid be completely dissolved deoxidation in colourless transparent solution simultaneously It is cooled to room temperature；Under nitrogen protection, 3,3 '-benzidine diamines and 2, bis- (4- carboxyl phenyl) hexafluoros of 2- are added thereto Reaction temperature is increased to 100 DEG C, 120 DEG C, 140 DEG C by propane, and reacts 12h, 12h, 6h respectively at various temperatures；It is cooling Reaction system is poured into deionized water afterwards, brown filamentous polymer is precipitated, impregnates or washing copolymer is to remove extra acid, Fluorine-containing polybenzimidazole polymer is obtained after vacuum drying；Finally resulting fluorine-containing polybenzimidazole polymer is dissolved in organic molten Agent obtains fluorine-containing polybenzimidazoles solution.
3. the preparation method of anion-exchange membrane as claimed in claim 2, it is characterised in that: polyphosphoric acids PPA, 3,3 '-two The weight ratio of bis- (4- carboxyl phenyl) hexafluoropropane of aminobphenyl diamines, 2,2- is 27:2.14:3.92.
4. the preparation method of anion-exchange membrane as described in claim 1, it is characterised in that: the concrete operations of step (2) are,
Hydrin is made into homogeneous phase solution, excessive 1- methylimidazole is added dropwise under the conditions of 60 DEG C, is sufficiently stirred and reacts To sticky yellowish-brown liquid, is cleaned three times with ether to remove unreacted raw material, rotated to obtain imidazoles with Rotary Evaporators The Hydrin of salt modification, is finally dissolved in organic solvent for products therefrom and obtains modified poly-epoxy chloropropane solution.
5. the preparation method of anion-exchange membrane as described in claim 1, it is characterised in that: in step (3), by step (1) Obtained in modified poly-epoxy chloropropane solution obtained in fluorine-containing polybenzimidazoles solution and step (2) be uniformly mixed, down to On clean smooth glass plate, evaporation of solvent is cooled to room temperature and demoulds to obtain composite membrane, and control modified poly-epoxy chloropropane with The mass ratio of fluorine-containing polybenzimidazoles is 1:9~5:5.
6. the preparation method of anion-exchange membrane as described in claim 1, it is characterised in that: alkali soluble described in step (4) Liquid is 1~2molL of concentration-1KOH solution, soaking time of the composite membrane in the aqueous slkali be 24~48h.
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CN108586745B (en) * 2018-04-16 2020-05-05 常州大学 Anion exchange membrane based on fluorinated polybenzimidazole and preparation method thereof
CN109638326B (en) * 2018-12-24 2022-05-27 江汉大学 Preparation method of polybenzimidazole anion exchange membrane
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