CN103627014B - A kind of preparation method of modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane - Google Patents
A kind of preparation method of modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane Download PDFInfo
- Publication number
- CN103627014B CN103627014B CN201310626202.2A CN201310626202A CN103627014B CN 103627014 B CN103627014 B CN 103627014B CN 201310626202 A CN201310626202 A CN 201310626202A CN 103627014 B CN103627014 B CN 103627014B
- Authority
- CN
- China
- Prior art keywords
- solution
- acrylamido
- methyl isophthalic
- propane sulfonic
- sulfonic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention relates to a kind of preparation method of modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane, belong to polymer dielectric film Material Field.Polyvinylidene difluoride (PVDF), first in nitrogen atmosphere, is dissolved in organic solvent by the present invention, stirs, adds quaternary ammonium alkali alcosol, and reaction for some time, heating, obtains the polyvinylidene difluoride (PVDF) solution of modification; A certain amount of 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS) monomer and initiator are added in modified polyvinilidene fluoride organic solution simultaneously, heating is reacted in nitrogen atmosphere, after cooling by solution-cast on sheet glass, drying and forming-film, namely obtains modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane.Modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane prepared by the present invention, has higher specific conductivity and low methanol permeability, simplifies synthesis step, accelerate commercialization process.
Description
Technical field
The present invention relates to a kind of preparation method of modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane, belong to polymer dielectric film Material Field.
Background technology
Polyvinylidene difluoride (PVDF) (PVDF) film forming properties is good, and thermostability and mechanical property are given prominence to, 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 will carry out modification to polyvinylidene difluoride (PVDF), mainly concentrates on radiation modification and chemical modification aspect at present to the modification of PVDF.Avtive spot is produced after utilizing high energy electron irradiation to make 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 mainly for 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, and the surface of film can not keep smooth.In addition, the sulfonation degree of graft copolymer membrane can't well control and solve at present, and whole preparation process needs a lot of steps just can complete.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, and radiation grafting will have source of radiation, requires higher to appointed condition, 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), but need separately to 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 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, all employ mineral alkali and carry out modified polyvinilidene fluoride and still there is inorganic particles in modification caudacoria, not easily remove, have impact to its specific conductivity and methanol crossover performance.Therefore, need to find a kind of more excellent can make polyvinylidene difluoride (PVDF) film forming before dehydrofluorination produce the modifying agent of double bond isoreactivity point, optimized fabrication process, obtains 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, the method is utilized to obtain proton exchange membrane evenly and not containing 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, 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, obtained solution B, 30-40 DEG C of magnetic agitation 1 ~ 2h in nitrogen atmosphere, obtains solution C simultaneously, (3) by PVDF powder, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS), benzoyl peroxide each composition quality part proportioning 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 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 modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane is obtained.
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.
Film is needed to soak 12 hours in the dilution heat of sulfuric acid of 1mol/L before using.
The present invention utilizes the organic alkali of Tetramethylammonium hydroxide and the dual function of consisting of phase-transferring agent, carries out modification to polyvinylidene difluoride (PVDF), and modified Tetramethylammonium hydroxide easily removes, and obtains comparatively pure proton exchange membrane.
The present invention and current material are compared with technology has following advantage:
1) the modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid 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
Utilize the proton exchange membrane prepared by the present invention, alcohol permeability ratio Nafion117 film little, alcohol-rejecting ability is better.For embodiment 1, methanol permeability reduces 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 utilizing preparation method proposed by the invention to make is low.For embodiment 1, refer to table 1
3) 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
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, 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, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS) monomer, benzoyl peroxide each composition quality part proportioning, taking 0.45g2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS) monomeric substance 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, solution is laid on clean sheet glass, 90 ~ 100 DEG C of vacuum-drying 8h, namely modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane is obtained.
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, 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, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS) monomer, benzoyl peroxide each composition quality part proportioning, taking 1.32g2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS) monomeric substance 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, solution is laid on clean sheet glass, 90 ~ 100 DEG C of vacuum-drying 8h, namely modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane is obtained.
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, 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, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS), benzoyl peroxide each composition quality part proportioning, taking 1.26g2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS) monomeric substance 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, solution is laid on clean sheet glass, 90 ~ 100 DEG C of vacuum-drying 8h, namely modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane is obtained.
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), first dry film is cut into the rectangle diaphragm (area is Sd) that size is about 1cm × 2cm, immerse distilled water solution, take out after abundant swelling 48h, measure the size of wet film, obtain area SW, the swelling capacity size SD of film:
the methanol permeability of film is measured with barrier film method of diffusion.
The table 1 modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-performance of propane sulfonic acid proton exchange membrane under 25oC 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 | 2.01 | 8.5 | 6.8 |
Claims (2)
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, 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) by PVDF powder, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS), benzoyl peroxide each composition quality part proportioning 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 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 modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane is obtained, described quaternary ammonium hydroxide comprises Tetramethylammonium hydroxide or tetraethyl ammonium hydroxide.
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, it is characterized in that, the concentration of quaternary ammonium hydroxide in solution B is 0.016-0.065mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310626202.2A CN103627014B (en) | 2013-11-29 | 2013-11-29 | A kind of preparation method of modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310626202.2A CN103627014B (en) | 2013-11-29 | 2013-11-29 | A kind of preparation method of modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103627014A CN103627014A (en) | 2014-03-12 |
| CN103627014B true CN103627014B (en) | 2016-03-16 |
Family
ID=50208482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310626202.2A Expired - Fee Related CN103627014B (en) | 2013-11-29 | 2013-11-29 | A kind of preparation method of modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103627014B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102279240B1 (en) | 2014-10-29 | 2021-07-19 | 삼성전자주식회사 | Fluid for electrowetting device and electrowetting device comprising the same |
| 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 |
| 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 |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5463506B2 (en) * | 2005-03-16 | 2014-04-09 | 国立大学法人山口大学 | Graft polymer, polymer electrolyte membrane, production method thereof, and fuel cell using the same |
-
2013
- 2013-11-29 CN CN201310626202.2A patent/CN103627014B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103627014A (en) | 2014-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103627014B (en) | A kind of preparation method of modified polyvinilidene fluoride one step grafting 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid proton exchange membrane | |
| CN102496732B (en) | Preparation method of polyvinylidene fluoride grafted p-styrenesulfonic acid proton exchange membrane | |
| CN113667161B (en) | Preparation method of modified poly (vinylidene fluoride-co-hexafluoropropylene) -grafted vinyl imidazole anion exchange membrane | |
| KR100914340B1 (en) | Highly proton conductive crosslinked vinylsulfonic acid polymer electrolyte composite membranes and its preparation method for polymer electrolyte fuel cells | |
| CN102544547A (en) | Alkaline negative ion exchange composite film with alkali stability and preparation and application thereof | |
| CN102850564B (en) | Method for preparing phosphotungstic acid-polyvinylidene fluoride composite proton exchange membrane | |
| KR20070098323A (en) | Reinforced composite electrolyte membrane for fuel cell | |
| CN108997599A (en) | High-intensitive binary is crosslinked alkaline negative ion exchange composite film, preparation method and application | |
| CN103627017B (en) | A kind of preparation method of modified polyvinilidene fluoride dielectric film | |
| CN108794784B (en) | Anion exchange membrane | |
| CN104629081A (en) | Preparation method of pore-filing type proton exchange membrane taking double ether crosslinked porous polybenzimidazole imide as base | |
| CN103626923B (en) | A kind of preparation method of modified polyvinilidene fluoride one step graft phenylethene sulfonic acid proton exchange film | |
| Yuan et al. | H3PO4 imbibed polyacrylamide-graft-chitosan frameworks for high-temperature proton exchange membranes | |
| KR101109143B1 (en) | Preparation method of composite membranes crosslinked with anhydrous electrolyte and polymer electrolyte fuel cell systems using the same | |
| CN114736411A (en) | Conductive polyaniline/graphene oxide modified Nafion composite proton exchange membrane and application thereof | |
| CN102847449B (en) | Preparation method of phosphotungstic acid/polyvinyl alcohol composite proton exchange membrane | |
| CN100499238C (en) | Organic-inorganic compoiste proton exchange film and preparing method | |
| CN103627013B (en) | A kind of preparation method of modified polyvinilidene fluoride one step grafting sulphonic acid betaine (SBMA) proton exchange membrane | |
| CN107978769B (en) | Triazine derivative-based diaphragm for vanadium battery and preparation method thereof | |
| CN104059240B (en) | Preparation method of polyvinylidene fluoride grafted styrene sulfonate electrolyte membrane | |
| CN103360617A (en) | Preparation method of polyvinylidene fluoride-polyvinyl alcohol composite proton exchange membrane | |
| CN103626922A (en) | Method for preparing modified polyvinylidene fluoride one-step grafted 3-sulfonic acid propyl methacrylate (SPMA) proton exchange membrane | |
| CN103980511A (en) | Preparation method for cross-linking type polyvinyl butyral composite proton exchange membrane | |
| CN100592563C (en) | Membrane electrode assembly (MEA), method for its manufacturing and a method for preparing a membrane to be assembled in a MEA | |
| CN106749932B (en) | A kind of sulfonic acid type Kynoar is grafted the preparation method of poly- (α-methylstyrene) copolymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160316 Termination date: 20161129 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |