CN103627014A - Method for preparing modified polyvinylidene fluoride one-step grafted 2-acrylyl amino-2-methyl-1-proplate sulfonic acid proton exchange membrane - Google Patents
Method for preparing modified polyvinylidene fluoride one-step grafted 2-acrylyl amino-2-methyl-1-proplate sulfonic acid proton exchange membrane Download PDFInfo
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Abstract
The invention relates to a method for preparing a modified polyvinylidene fluoride one-step grafted 2-acrylyl amino-2-methyl-1-proplate sulfonic acid proton exchange membrane, which belongs to the field of polymer electrolyte membrane materials. The method provided by the invention comprises the following steps: firstly dissolving polyvinylidene fluoride in an organic solvent in a nitrogen atmosphere, stirring, adding a quaternary ammonium base alcohol solution, reacting for a period of time, and heating to obtain a modified polyvinylidene fluoride solution; meanwhile, adding a certain amount of 2-acrylyl amino-2-methyl-1-proplate sulfonic acid (AMPS) monomers and an initiator in the organic modified polyvinylidene fluoride solution, heating to react in the nitrogen atmosphere, cooling and casting the solution onto a glass plate, drying the solution to a membrane to obtain the modified polyvinylidene fluoride one-step grafted 2-acrylyl amino-2-methyl-1-proplate sulfonic acid proton exchange membrane. The modified polyvinylidene fluoride one-step grafted 2-acrylyl amino-2-methyl-1-proplate sulfonic acid proton exchange membrane prepared by the method provided by the invention has high conductivity and low methanol permeability, the synthesis steps are simplified, and the commercialization process is accelerated.
Description
Technical field
The preparation method who the present invention relates to a kind of modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane, belongs to polymer dielectric film Material Field.
Background technology
Polyvinylidene difluoride (PVDF) (PVDF) film forming properties is good, and thermostability and mechanical property are outstanding, the preferred material of Chang Zuowei mould material.People have utilized polyvinylidene difluoride (PVDF) as base material, have developed the dielectric film of novel alternative Nafion film, as polyvinylidene difluoride (PVDF) graft phenylethene sulfonate film (PVDF-g-PSSA).But the preparation of this dielectric film, key is to carry out modification to polyvinylidene difluoride (PVDF), at present the modification of PVDF is mainly concentrated on to radiation modification and chemical modification aspect.Utilize high energy electron irradiation to make to produce avtive spot after pvdf membrane surface activation process, carry out the monomer that grafting or copolymerization contain hydrophilic radical, but source of radiation is higher to equipment requirements, is unfavorable for suitability for industrialized production, and avtive spot is easily oxidized in modification PVDF, preserve more difficult.And chemical modification is carried out strong acid after mainly for polyvinylidene difluoride (PVDF) film forming or highly basic is processed, modification time is long, easily causes film to become fragile, and follow-up grafting inequality can make film deform, and it is smooth that the surface of film can not keep.In addition, the sulfonation degree of graft copolymer membrane can't well be controlled and solve at present, and whole preparation process needs a lot of steps just can complete.The shortcoming of these methods is only on the surface of film, to slough HF to produce carbon-carbon double bond, and graft reaction only carries out on the surface of film, and radiation grafting will have source of radiation, and appointed condition is had relatively high expectations, and structure and the character of modification caudacoria are unstable.
The patent No. is that 201110430199.8 Chinese invention patent discloses and utilizes the alcoholic solution of NaOH, KOH to carry out modification to polyvinylidene difluoride (PVDF), but need to separately add consisting of phase-transferring agent.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 be 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).These two patents, have all used mineral alkali to come still to have inorganic particles in modified polyvinilidene fluoride and modification caudacoria, are difficult for removing, all influential to its specific conductivity and methanol crossover performance.Therefore, need to find a kind of better front dehydrofluorination of polyvinylidene difluoride (PVDF) film forming that can make and produce the modifying agent of two key isoreactivity points, optimize preparation process, obtain the good proton exchange membrane of performance.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of simple modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane, utilize the method to make proton exchange membrane evenly and do not contain impurity, specific conductivity is large, and methanol permeability is low.
Technical solution:
Preparation method of the present invention is as follows:
(1) take certain mass polyvinylidene difluoride (PVDF) in dimethyl sulfoxide (DMSO), wherein every gram of polyvinylidene difluoride (PVDF) needs dimethyl sulfoxide (DMSO) 15～20mL, heats at 60～80 ℃ and stir 0.5～1h in oil bath pan, obtains clear solution A, (2) by the volume ratio of solution A and 2.77mol/L quaternary ammonium hydroxide alcoholic solution, be that the quaternary ammonium hydroxide alcoholic solution that 50:0.3～1.2 measure certain volume slowly adds in solution A, make solution B, 30-40 ℃ of magnetic agitation 1～2h in nitrogen atmosphere, obtains solution C simultaneously, (3) press PVDF powder, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS), each composition quality part proportioning of benzoyl peroxide is respectively 88～68 parts, 10～30 parts, 2 parts, taking 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS) is dissolved in solution C, heated and stirred makes its dissolving, add again initiator benzoyl peroxide, in nitrogen atmosphere, oil bath heating is 80～90 ℃, after reaction 24h, solution is laid on clean sheet glass, 90～100 ℃ of vacuum-drying 8h, obtain modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane.
Described quaternary ammonium hydroxide comprises Tetramethylammonium hydroxide or tetraethyl ammonium hydroxide.
Further: the concentration of quaternary ammonium hydroxide in solution B is 0.016-0.065mol/L.
Before use, need film in the dilution heat of sulfuric acid of 1mol/L, to soak 12 hours.
The present invention utilizes the dual function of organic alkali and the consisting of phase-transferring agent of Tetramethylammonium hydroxide, and polyvinylidene difluoride (PVDF) is carried out to modification, and after modification, Tetramethylammonium hydroxide is easily removed, and obtains comparatively pure proton exchange membrane.
The present invention compare with technology with current material have advantages of as follows:
1) the modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane conductivity excellent performance that utilizes preparation method proposed by the invention to make, its specific conductivity is greater than the specific conductivity of Nafion117 film.Take embodiment 1 as example, refer to table 1
Utilize the prepared proton exchange membrane of the present invention, alcohol permeability ratio Nafion117 film little, alcohol-rejecting ability is better.Take embodiment 1 as example, and methanol permeability has reduced an order of magnitude, refers to table 1.
2) the modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane swelling capacity Nafion117 film that utilizes preparation method proposed by the invention to make is low.Take embodiment 1 as example, refer to table 1
3) preparation technology of the proton exchange membrane that prepared by 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
Preparation method of the present invention is as follows:
(1) take 4g polyvinylidene difluoride (PVDF) in dimethyl sulfoxide (DMSO), wherein every gram of polyvinylidene difluoride (PVDF) needs dimethyl sulfoxide (DMSO) 15mL, heats at 60 ℃ and stir 1h in oil bath pan, obtains clear solution A, (2) by the volume ratio of solution A and 2.77mol/L Tetramethylammonium hydroxide methanol solution, be 50:0.3, measuring 0.36mL Tetramethylammonium hydroxide methanol solution slowly adds in solution A, make solution B, 30-40 ℃ of magnetic agitation 1h in nitrogen atmosphere, obtains solution C simultaneously, (3) press PVDF powder, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS) monomer, each composition quality part proportioning of benzoyl peroxide, taking 0.45g2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS) monomeric substance is dissolved in solution C, heated and stirred makes its dissolving, add again 0.05g initiator benzoyl peroxide, in nitrogen atmosphere, oil bath heating is 80～90 ℃, after reaction 24h, solution is laid on clean sheet glass, 90～100 ℃ of vacuum-drying 8h, obtain modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane.
Embodiment 2
Preparation method is as follows:
(1) take 3g polyvinylidene difluoride (PVDF) in dimethyl sulfoxide (DMSO), wherein every gram of polyvinylidene difluoride (PVDF) needs dimethyl sulfoxide (DMSO) 20mL, heats at 80 ℃ and stir 0.5h in oil bath pan, obtains clear solution A, (2) by the volume ratio of solution A and 2.77mol/L Tetramethylammonium hydroxide methanol solution, be that the Tetramethylammonium hydroxide methanol solution that 50:0.6 measures 0.68mL slowly adds in solution A, make solution B, 30-40 ℃ of magnetic agitation 1～2h in nitrogen atmosphere, obtains solution C simultaneously, (3) press PVDF powder, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS) monomer, each composition quality part proportioning of benzoyl peroxide, taking 1.32g2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS) monomeric substance is dissolved in solution C, heated and stirred makes its dissolving, add again 0.09g initiator benzoyl peroxide, in nitrogen atmosphere, oil bath heating is 80～90 ℃, after reaction 24h, solution is laid on clean sheet glass, 90～100 ℃ of vacuum-drying 8h, obtain modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane.
Embodiment 3
Preparation method is as follows:
(1) take 4g polyvinylidene difluoride (PVDF) in dimethyl sulfoxide (DMSO), wherein every gram of polyvinylidene difluoride (PVDF) needs dimethyl sulfoxide (DMSO) 15mL, heats at 70 ℃ and stir 1h in oil bath pan, obtains clear solution A, (2) by the volume ratio of solution A and 2.77mol/L Tetramethylammonium hydroxide first solution, be 50:0.9, measuring 1.2mL Tetramethylammonium hydroxide methanol solution slowly adds in solution A, make solution B, 30-40 ℃ of magnetic agitation 1～2h in nitrogen atmosphere, obtains solution C simultaneously, (3) press PVDF powder, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS), each composition quality part proportioning of benzoyl peroxide, taking 1.26g2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS) monomeric substance is dissolved in solution C, heated and stirred makes its dissolving, add again 0.106g initiator benzoyl peroxide, in nitrogen atmosphere, oil bath heating is 80～90 ℃, after reaction 24h, solution is laid on clean sheet glass, 90～100 ℃ of vacuum-drying 8h, obtain modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane.
Comparative example as a comparison, we utilize Nafion117 film, its methanol permeability, swelling capacity and specific conductivity and the prepared proton exchange membrane of the present invention are compared, Nafion117 film is soaked a few hours in deionized water, by two electrode AC impedance methods, survey its specific conductivity; By swelling capacity (SD), carry out the swelling behavior of characterization of membrane, first dry film being cut into size is the rectangle diaphragm of about 1cm * 2cm (area is Sd), immerses distilled water solution, fully after swelling 48h, take out, the size of measuring wet film, obtains area SW, the swelling capacity size SD of film:
with barrier film method of diffusion, measure the methanol permeability of film.
The one step grafting 2-acrylamido-2-performance of methyl isophthalic acid-propane sulfonic acid proton exchange membrane under 25oC and the comparison of Nafion117 film of table 1 modified polyvinilidene fluoride
| 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 | 2.01 | 8.5 | 6.8 |
Claims (3)
1. the preparation method of modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane, it is characterized in that, 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, in oil bath pan, heat at 60～80 ℃ and stir 0.5～1h, obtain clear solution A, (2) by the volume ratio of solution A and 2.77mol/L quaternary ammonium hydroxide alcoholic solution, be that the quaternary ammonium hydroxide alcoholic solution that 50:0.3～1.2 measure certain volume slowly adds in solution A, make solution B, 30-40 ℃ of magnetic agitation 1～2h in nitrogen atmosphere, obtains solution C simultaneously, (3) press PVDF powder, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS), each composition quality part proportioning of benzoyl peroxide is respectively 88～68 parts, 10～30 parts, 2 parts, taking 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS) is dissolved in solution C, heated and stirred makes its dissolving, add again initiator benzoyl peroxide, in nitrogen atmosphere, oil bath heating is 80～90 ℃, after reaction 24h, solution is laid on clean sheet glass, 90～100 ℃ of vacuum-drying 8h, obtain modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane.
2. the preparation method of a kind of modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane according to claim 1, is characterized in that in step (1), quaternary ammonium hydroxide comprises Tetramethylammonium hydroxide or tetraethyl ammonium hydroxide.
3. the preparation method of a kind of modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane according to claim 1, is characterized in that, the concentration of quaternary ammonium hydroxide B in solution is 0.016-0.065mol/L.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9823461B2 (en) | 2014-10-29 | 2017-11-21 | Samsung Electronics Co., Ltd. | Fluid for electrowetting device and electrowetting device including same |
| CN111004468A (en) * | 2019-11-27 | 2020-04-14 | 安徽欣鼎高分子材料有限公司 | Preparation method and application of damping shock-absorbing rubber |
| CN112072108A (en) * | 2020-09-14 | 2020-12-11 | 福建巨电新能源股份有限公司 | Conductive adhesive for lithium battery and preparation method thereof |
| CN113667161A (en) * | 2021-07-02 | 2021-11-19 | 浙江工业大学 | Preparation method of modified poly (vinylidene fluoride-co-hexafluoropropylene) -grafted vinyl imidazole anion exchange membrane |
| CN115322279A (en) * | 2022-08-11 | 2022-11-11 | 乳源东阳光氟树脂有限公司 | 1, 1-difluoroethylene copolymer and preparation method and application thereof |
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| WO2006098484A2 (en) * | 2005-03-16 | 2006-09-21 | Toyota Jidosha Kabushiki Kaisha | Graft polymer |
| CN101787141A (en) * | 2009-12-25 | 2010-07-28 | 内蒙古科技大学 | Method for preparing proton exchange membrane with polyvinylidene fluoride grafted and grafting copolymerized with 2-acrylamido-2-methylpropanesulfonic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2006098484A2 (en) * | 2005-03-16 | 2006-09-21 | Toyota Jidosha Kabushiki Kaisha | Graft polymer |
| CN101787141A (en) * | 2009-12-25 | 2010-07-28 | 内蒙古科技大学 | Method for preparing proton exchange membrane with polyvinylidene fluoride grafted and grafting copolymerized with 2-acrylamido-2-methylpropanesulfonic acid |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9823461B2 (en) | 2014-10-29 | 2017-11-21 | Samsung Electronics Co., Ltd. | Fluid for electrowetting device and electrowetting device including same |
| CN111004468A (en) * | 2019-11-27 | 2020-04-14 | 安徽欣鼎高分子材料有限公司 | Preparation method and application of damping shock-absorbing rubber |
| CN111004468B (en) * | 2019-11-27 | 2023-03-28 | 安徽欣鼎高分子材料有限公司 | Preparation method and application of damping shock-absorbing rubber |
| CN112072108A (en) * | 2020-09-14 | 2020-12-11 | 福建巨电新能源股份有限公司 | Conductive adhesive for lithium battery and preparation method thereof |
| CN113667161A (en) * | 2021-07-02 | 2021-11-19 | 浙江工业大学 | Preparation method of modified poly (vinylidene fluoride-co-hexafluoropropylene) -grafted vinyl imidazole anion exchange membrane |
| CN113667161B (en) * | 2021-07-02 | 2022-06-21 | 浙江工业大学 | Preparation method of modified poly (vinylidene fluoride-co-hexafluoropropylene) -grafted vinyl imidazole anion exchange membrane |
| CN115322279A (en) * | 2022-08-11 | 2022-11-11 | 乳源东阳光氟树脂有限公司 | 1, 1-difluoroethylene copolymer and preparation method and application thereof |
| CN115322279B (en) * | 2022-08-11 | 2024-01-26 | 乳源东阳光氟树脂有限公司 | 1, 1-difluoroethylene copolymer and preparation method and application thereof |
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