CN103627013B - A kind of preparation method of modified polyvinilidene fluoride one step grafting sulphonic acid betaine (SBMA) proton exchange membrane - Google Patents
A kind of preparation method of modified polyvinilidene fluoride one step grafting sulphonic acid betaine (SBMA) proton exchange membrane Download PDFInfo
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- CN103627013B CN103627013B CN201310626107.2A CN201310626107A CN103627013B CN 103627013 B CN103627013 B CN 103627013B CN 201310626107 A CN201310626107 A CN 201310626107A CN 103627013 B CN103627013 B CN 103627013B
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Abstract
The present invention relates to a kind of preparation method of modified polyvinilidene fluoride one step grafting sulphonic acid betaine proton exchange membrane, belong to electrolyte film in fuel cell Material Field.The present invention is first in nitrogen atmosphere, polyvinylidene difluoride (PVDF) is dissolved in dimethyl sulfoxide (DMSO), heated and stirred makes polyvinylidene difluoride (PVDF) fully dissolve, add quaternary ammonium alkali alcosol, after for some time, the quaternary ammonium hydroxide that heating volatilization unreacted is complete and relevant fluoride product thereof, obtain the polyvinylidene difluoride (PVDF) solution of modification.A certain amount of sulphonic acid betaine (SSA) and initiator are added in above-mentioned solution simultaneously, heating is also reacted in nitrogen atmosphere, after cooling, solution is laid on sheet glass, vacuum-drying film forming, namely obtains modified polyvinilidene fluoride grafting sulphonic acid betaine proton exchange membrane.Modified polyvinilidene fluoride grafting sulphonic acid betaine proton exchange membrane prepared by the present invention, dimensional stability is good, methanol permeability is little, simplifies synthesis step, is convenient to industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of modified polyvinilidene fluoride one step grafting sulphonic acid betaine proton exchange membrane, belong to electrolyte film in fuel cell Material Field.
Background technology
Since perfluoro sulfonic acid membrane comes out, obtain the extensive concern of researchist, the Nafion film of E.I.Du Pont Company commercially shows well, but Nafion film methanol permeability is low, the shortcoming that poor dimensional stability, cost are high constrains its commercialization process, and therefore scholars place hope on and develop alternative membrane of good performance.
Polyvinylidene difluoride (PVDF) (PVDF) as a kind of partially fluorinated thing, chemical stability and good heat stability, suitable with perfluoro-compound, be the first-selection of mould material always.Nowadays scholars have utilized polyvinylidene difluoride (PVDF) as base material, have developed the dielectric film of novel replaced Nafion film, as polyvinylidene difluoride (PVDF) graft phenylethene sulfonate film (PVDF-g-PSSA).But the preparation of this dielectric film, key is polyvinylidene fluoride modified.At present the modification of PVDF is mainly concentrated on to the surface modification aspect of the film be prepared into by PVDF powder.Powder produces avtive spot after utilizing high energy electron irradiation to make pvdf membrane surface activation process after preparing film forming, and carry out grafting or copolymerization containing can the monomer of proton conducting, source of radiation is higher to equipment requirements.Or to carrying out strong acid or highly basic process after polyvinylidene difluoride (PVDF) film forming, modification time is long, easily causes film to become fragile, and follow-up grafting inequality can make film deform, the surface of film can not keep smooth.The shortcoming of these methods only sloughs HF to produce carbon-carbon double bond on the surface of film, and graft reaction only carries out on the surface of film, the structure of modification caudacoria and character instability.
The patent No. be 201110430199.8 Chinese invention patent disclose the alcoholic solution utilizing NaOH, KOH and can carry out modification to polyvinylidene difluoride (PVDF).The patent No. is the preparation method that the Chinese invention patent of 200910216867.X discloses a kind of modified polyvinilidene fluoride graft-blending 2-acrylamide-2-methylpro panesulfonic acid (AMPS) proton exchange membrane, the method take polyvinylidene difluoride (PVDF) as matrix, adopts sodium orthosilicate to prepare proton exchange membrane to its modification and then graft-blending 2-acrylamide-2-methylpro panesulfonic acid (AMPS).But these two patents, all employ mineral alkali and carry out modified polyvinilidene fluoride and still there is inorganic particles in modification caudacoria, have impact to its specific conductivity and methanol crossover performance.Therefore, need to find a kind of can make polyvinylidene difluoride (PVDF) film forming before dehydrofluorination produce the modifying agent of double bond isoreactivity point, this residue reagent and reacted associated products thereof volatilize completely being heated in membrane process, then a step grafting sulphonic acid betaine monomer in organic solution, the polyvinylidene difluoride (PVDF) grafting sulphonic acid betaine proton exchange membrane not containing impurity in obtained film.
Technology contents
The object of the present invention is to provide a kind of preparation method of simple modified polyvinilidene fluoride one step grafting sulphonic acid betaine (SBMA) proton exchange membrane, after utilizing Tetramethylammonium hydroxide modified polyvinilidene fluoride, grafting sulphonic acid betaine, synthesis is containing impurity, specific conductivity is large and methanol permeability is low modified polyvinilidene fluoride one step grafting sulphonic acid betaine proton exchange membrane.
Technical solution:
The concrete preparation method of the present invention:
(1) take certain mass polyvinylidene difluoride (PVDF) in dimethyl sulfoxide (DMSO), wherein every gram of polyvinylidene difluoride (PVDF) needs dimethyl sulfoxide (DMSO) 15 ~ 20mL, stirs 0.5 ~ 1h, obtain clear solution A in oil bath pan at heating 60 ~ 80 DEG C; (2) be that the quaternary ammonium hydroxide alcoholic solution that 50:0.3 ~ 1.2 measure certain volume slowly adds in solution A by the volume ratio of solution A and 2.77mol/L quaternary ammonium hydroxide alcoholic solution, the concentration of obtained solution B(wherein quaternary ammonium hydroxide B is in the solution 0.016-0.065mol/L), 30-40 DEG C of magnetic agitation 1 ~ 2h in nitrogen atmosphere, obtains solution C simultaneously; (3) 88 ~ 68 parts are respectively by PVDF powder, sulphonic acid betaine (SBMA), benzoyl peroxide each composition quality part proportioning, 10 ~ 30 parts, 2 parts, taking sulphonic acid betaine (SBMA) is dissolved in solution C, heated and stirred makes it dissolve, add initiator benzoyl peroxide again, oil bath heating 80 ~ 90 DEG C in nitrogen atmosphere, after reaction 24h, solution is laid on clean sheet glass, 90 ~ 100 DEG C of vacuum-drying 8h, namely obtain modified polyvinilidene fluorine second one step grafting sulphonic acid betaine proton exchange membrane.
Described quaternary ammonium hydroxide comprises Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide.
Further: the concentration of quaternary ammonium hydroxide B is in the solution 0.016-0.065mol/L.
Film is needed to soak 12 hours in the dilution heat of sulfuric acid of 1mol/L before using.
First polyvinylidene difluoride (PVDF) is dissolved in organic solvent and makes macromolecular solution by the present invention, and quaternary ammonium hydroxide alcoholic solution can make PVDF macromolecular solution remove HF by elimination reaction, produces the carbon-carbon double bond with avtive spot; In sulphonic acid betaine, sulfonate radical can carry proton, be conducive to the conduction of proton in film, under the condition having initiator, with avtive spot generation graft reaction in the PVDF after quaternary ammonium ammonium alkali modification, namely obtain modified polyvinilidene fluoride one step grafting sulphonic acid betaine proton exchange membrane.
The present invention and current material are compared with technology has following advantage:
1) the modified polyvinilidene fluoride one step grafting sulphonic acid betaine proton exchange membrane conductivity excellent performance utilizing preparation method proposed by the invention to make, its specific conductivity is greater than the specific conductivity of Nafion117 film.For embodiment 1, refer to table 1
2) utilize the proton exchange membrane prepared by the present invention, little than Nafion117 film of methanol permeability, alcohol-rejecting ability is better.For embodiment 1, methanol permeability reduces an order of magnitude, refers to table 1.
3) the modified polyvinilidene fluoride one step grafting sulphonic acid betaine proton exchange membrane swelling capacity Nafion117 film utilizing preparation method proposed by the invention to make is low.For embodiment 1, refer to table 1
4) preparation technology of proton exchange membrane for preparing of the present invention is simple, and film cost is lower than Nafion117 film, and synthesis step is few, is easy to industrialization.
Embodiment
Embodiment 1
Concrete preparation method:
(1) take 4g polyvinylidene difluoride (PVDF) in dimethyl sulfoxide (DMSO), wherein every gram of polyvinylidene difluoride (PVDF) needs dimethyl sulfoxide (DMSO) 15mL, stirs 1h, obtain clear solution A in oil bath pan at heating 60 DEG C; (2) be 50:0.3 by the volume ratio of solution A and 2.77mol/L Tetramethylammonium hydroxide methanol solution, measure 0.36mL Tetramethylammonium hydroxide methanol solution slowly to add in solution A, obtained solution B, 30-40 DEG C of magnetic agitation 1h in nitrogen atmosphere, obtains solution C simultaneously; (3) by PVDF powder, sulphonic acid betaine (SBMA), benzoyl peroxide each composition quality part proportioning, taking 0.45g sulphonic acid betaine (SBMA) is dissolved in solution C, heated and stirred makes it dissolve, add 0.05g initiator benzoyl peroxide again, oil bath heating 80 ~ 90 DEG C in nitrogen atmosphere, after reaction 24h, is laid on solution on clean sheet glass, 90 ~ 100 DEG C of vacuum-drying 8h, namely obtain modified polyvinilidene fluoride one step grafting sulphonic acid betaine proton exchange membrane.
Embodiment 2
Concrete preparation method:
(1) take 3g polyvinylidene difluoride (PVDF) in dimethyl sulfoxide (DMSO), wherein every gram of polyvinylidene difluoride (PVDF) needs dimethyl sulfoxide (DMSO) 20mL, stirs 0.5h, obtain clear solution A in oil bath pan at heating 80 DEG C; (2) be that the Tetramethylammonium hydroxide methanol solution that 50:0.6 measures 0.68mL slowly adds in solution A by the volume ratio of solution A and 2.77mol/L Tetramethylammonium hydroxide methanol solution, obtained solution B, 30-40 DEG C of magnetic agitation 1 ~ 2h in nitrogen atmosphere, obtains solution C simultaneously; (3) by PVDF powder, sulphonic acid betaine (SBMA), benzoyl peroxide each composition quality part proportioning, taking 1.32g sulphonic acid betaine (SBMA) is dissolved in solution C, heated and stirred makes it dissolve, add 0.09g initiator benzoyl peroxide again, oil bath heating 80 ~ 90 DEG C in nitrogen atmosphere, after reaction 24h, is laid on solution on clean sheet glass, 90 ~ 100 DEG C of vacuum-drying 8h, namely obtain modified polyvinilidene fluoride one step grafting sulphonic acid betaine proton exchange membrane.
Embodiment 3
Concrete preparation method:
(1) take 4g polyvinylidene difluoride (PVDF) in dimethyl sulfoxide (DMSO), wherein every gram of polyvinylidene difluoride (PVDF) needs dimethyl sulfoxide (DMSO) 15mL, stirs 1h, obtain clear solution A in oil bath pan at heating 70 DEG C; (2) be 50:0.9 by the volume ratio of solution A and 2.77mol/L Tetramethylammonium hydroxide first solution, measure 1.2mL Tetramethylammonium hydroxide methanol solution slowly to add in solution A, obtained solution B, 30-40 DEG C of magnetic agitation 1 ~ 2h in nitrogen atmosphere, obtains solution C simultaneously; (3) by PVDF powder, sulphonic acid betaine (SBMA), benzoyl peroxide each composition quality part proportioning, taking 1.26g sulphonic acid betaine (SBMA) is dissolved in solution C, heated and stirred makes it dissolve, add 0.106g initiator benzoyl peroxide again, oil bath heating 80 ~ 90 DEG C in nitrogen atmosphere, after reaction 24h, is laid on solution on clean sheet glass, 90 ~ 100 DEG C of vacuum-drying 8h, namely obtain modified polyvinilidene fluoride one step grafting sulphonic acid betaine proton exchange membrane.
Comparative example is as comparing, we utilize Nafion117 film, proton exchange membrane prepared by its methanol permeability, swelling capacity and specific conductivity and the present invention is compared, Nafion117 film is soaked a few hours in deionized water, survey its specific conductivity by two electrode AC impedance methods; Carry out the swelling behavior of characterization of membrane by swelling capacity (SD), (area is S first dry film to be cut into the rectangle diaphragm that size is about 1cm × 2cm
d), immerse distilled water solution, take out after abundant swelling 48h, measure the size of wet film, obtain area S
w, the swelling capacity size of film
the methanol permeability of film is measured with barrier film method of diffusion.
The performance of table 1 modified polyvinilidene fluoride one step grafting sulphonic acid betaine proton exchange membrane at 25 DEG C compares with Nafion117 film
| Sample number | Specific conductivity (10 -3S/cm） | Swelling capacity (%) in water | Methanol permeability (10 -7cm 2/s） |
| Nafion117 | 1.76 | 33.4 | 20.6 |
| Sample | 1.89 | 10.2 | 5.23 |
Claims (2)
1. the preparation method of a modified polyvinilidene fluoride one step grafting sulphonic acid betaine proton exchange membrane, it is characterized in that, concrete preparation method is as follows: (1) takes certain mass polyvinylidene difluoride (PVDF) in dimethyl sulfoxide (DMSO), wherein every gram of polyvinylidene difluoride (PVDF) needs dimethyl sulfoxide (DMSO) 15 ~ 20mL, stir 0.5 ~ 1h heat 60 ~ 80 DEG C in oil bath pan at, obtain clear solution A; (2) be that the quaternary ammonium hydroxide alcoholic solution that 50:0.3 ~ 1.2 measure certain volume slowly adds in solution A by the volume ratio of solution A and 2.77mol/L quaternary ammonium hydroxide alcoholic solution, obtained solution B, 30-40 DEG C of magnetic agitation 1 ~ 2h in nitrogen atmosphere, obtains solution C simultaneously; (3) 88 ~ 68 parts are respectively by PVDF powder, sulphonic acid betaine (SBMA), benzoyl peroxide each composition quality part proportioning, 10 ~ 30 parts, 2 parts, taking sulphonic acid betaine (SBMA) is dissolved in solution C, heated and stirred makes it dissolve, add initiator benzoyl peroxide again, oil bath heating 80 ~ 90 DEG C in nitrogen atmosphere, after reaction 24h, solution is laid on clean sheet glass, 90 ~ 100 DEG C of vacuum-drying 8h, namely obtain modified polyvinilidene fluoride one step grafting sulphonic acid betaine proton exchange membrane; Described quaternary ammonium hydroxide Tetramethylammonium hydroxide.
2. the preparation method of a kind of modified polyvinilidene fluoride one step grafting sulphonic acid betaine proton exchange membrane according to claim 1, is characterized in that the concentration of the B in the solution of quaternary ammonium hydroxide in step (2) is 0.016-0.065mol/L.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102496732A (en) * | 2011-12-20 | 2012-06-13 | 湖北大学 | Preparation method of polyvinylidene fluoride grafted p-styrenesulfonic acid proton exchange membrane |
| CN102558595A (en) * | 2011-12-15 | 2012-07-11 | 宁波大学 | Surface modification method for polyvinylidene fluoride (PVDF) film or polyvinyl chloride (PVC) film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102558595A (en) * | 2011-12-15 | 2012-07-11 | 宁波大学 | Surface modification method for polyvinylidene fluoride (PVDF) film or polyvinyl chloride (PVC) film |
| CN102496732A (en) * | 2011-12-20 | 2012-06-13 | 湖北大学 | Preparation method of polyvinylidene fluoride grafted p-styrenesulfonic acid proton exchange membrane |
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