CN103304945A - Perfluorosulfonic acid ion exchange membrane and preparation method thereof - Google Patents
Perfluorosulfonic acid ion exchange membrane and preparation method thereof Download PDFInfo
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- CN103304945A CN103304945A CN2012100602346A CN201210060234A CN103304945A CN 103304945 A CN103304945 A CN 103304945A CN 2012100602346 A CN2012100602346 A CN 2012100602346A CN 201210060234 A CN201210060234 A CN 201210060234A CN 103304945 A CN103304945 A CN 103304945A
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Abstract
The invention relates to a perfluorosulfonic acid ion exchange membrane which is composed of a carbon-fluorine cross-linked network skeleton structure and a perfluoro side chain connected with a network chain and containing a sulfonic group and a preparation method thereof. The perfluorosulfonic acid ion exchange membrane is prepared by successive tape casting and copolymerization of a solution composed of a perfluorodialkene monomer containing a proton exchange functional group and a perfluoromonoolefine monomer containing a proton exchange functional group on a horizontal and smooth glass plate or hastelloy plate. The cross-linking type perfluorosulfonic acid ion exchange membrane prepared in the invention has excellent proton conductivity, good dimensional stability and mechanical strength and superior medium penetration resistance and chemical stability.
Description
Technical field
The invention belongs to functional polymer mould material field, relate to a kind of all-vanadium flow battery, Proton Exchange Membrane Fuel Cells and ionic membrane chlorine industry ion-exchange membrane, particularly a kind of cross-linking perfluorinated sulfonic acid ion exchange membrane and preparation method thereof.
Background technology
In all-vanadium flow battery, Proton Exchange Membrane Fuel Cells and ionic membrane chloralkali process device, one of parts of most critical are exactly perfluorinated sulfonic acid ion exchange membrane.
Though existing perfluorinated sulfonic acid ion exchange membrane uses for many years, but still have many defectives,, poor dimensional stability too high as swelling ratio, not high, the anti-medium osmosis performance of physical strength are undesirable etc.Such as in direct methanol fuel cell, methanol permeability is very big, has become fatal problem.Therefore how to improve physical strength, dimensional stability, the proton conductivity of perfluorinated sulfonic acid ion exchange membrane, the seepage of reduction working medium is the key subjects that perfluorinated sulfonic acid ion exchange membrane faces.
For can the good perfluorinated sulfonic acid ionic membrane of processability, the various countries investigator have done multiple mode has been carried out in a large amount of work to the perfluorinated sulfonic acid ionic membrane improvement.
Bo Yang (Electrochemistry Comunication 2004, (6): 231-236) etc. usefulness sulfonated polyether-ether-ketone (SPEEK) film is affixed on the perfluorinated sulfonic acid ionic membrane, and the method for employing hot pressing, they are sticked together, be prepared into the Nafion-Speek-Nafion composite ionic membrane, purpose is in order to reduce the seepage of working medium.But owing to do not have chemical bond crosslinked between the two membranes, layer is relatively poor with the associativity of layer, and demixing phenomenon takes place in application process easily, thereby causes the resistance of composite ionic membrane to increase, and because the chemical stability of sulfonated polyether-ether-ketone is undesirable, so be undesirable the work-ing life of these films.
Japanese Patent JP-B-5-75835 adopts perfluorinated sulfonic resin to flood the physical strength that the polytetrafluoroethylstephanoporate stephanoporate medium comes reinforcing membrane.Yet the porous medium of tetrafluoroethylene is because polytetrafluoroethylmaterial material is softer relatively, and enhancement is also insufficient.
Japanese Patent JP-B-7-68377 proposed a kind of method, with the porous medium that perfluorinated ion exchange resin filling polyolefine is made, purpose is the physical strength for reinforcing membrane, reduces the seepage of working medium, but its chemical durability is undesirable, thereby has problems aspect permanent stability.And owing to do not possess the intervention of the porous medium of ionic conduction ability, reduced the ionic conduction path, made the ionic conductance of film descend.
Chinese patent CN101383404 has proposed a kind of method that crosslinking reaction takes place between perfluorinated sulfonic acid ion exchange membrane and the non-perfluoroalkanes sulfonic acid ion exchange membrane that makes, and prepares the perfluoroparaffin/non-perfluoroparaffin composite ionic membrane with good combination.Yet this compound and crosslinkedly also only carry out in two bed interfaces, be difficult to guarantee the stable homogeneous of the mechanical property of whole composite membrane, and its chemical durability is undesirable, thereby aspect permanent stability existing problems.
Chinese patent CN101764234 has proposed to add diamines or polyamines linking agent in the perfluorinated sulfonic acid film-casting liquid, as quadrol, propylene diamine, butanediamine etc.Sulfonic acid group and amine in the film are reacted, form crosslinking structure, improve the performance of film.But the stability of this crosslinking structure in the chemical environment of electrolyzer is undesirable, thereby has problems aspect permanent stability.
US Patent No. 20070031715 has proposed the cross-linking method of the crosslinked generation sulphonyl of SULPHURYL CHLORIDE acid anhydride, formed sulphonyl acid anhydride crosslinking structure can improve the physical strength of film effectively in the method, but this crosslinking structure also exists shortcoming: sulphonyl acid anhydride unit wherein is unsettled in some chemical environments, such as easily decomposing in alkaline environment.
Though above document has proposed many methods such ion-exchange membrane has been carried out certain improvement in performance, but these methods have just been improved the performance of some aspects of film, do not take other side into account, the performance of other side is decreased on the contrary, therefore undesirable situation can take place.
The current demand for development ion-exchange membrane of using the industry of ionic membrane must satisfy following technical requirements: high chemical stability, high proton conductivity, high antiseep ability, high physical strength and dimensional stability.
Yet with regard to existing technology, can't satisfy these requirements.Such as, for existing perfluorinated sulfonic acid ion exchange membrane, when proton conductivity raise, the equivalent value of (per) fluoropolymer will descend, and the physical strength of film also can decrease, and the leakage performance of film also can decrease.If adopt the mode of non-perfluor to improve these performances, then resulting film can be undesirable because of chemical durability, and have problems aspect permanent stability.
Therefore development possesses high proton conductivity, has high chemical stability, high antiseep ability, high physical strength and the ion-exchange membrane of dimensional stability simultaneously again and has important practical significance.
Summary of the invention
At the deficiencies in the prior art, the object of the present invention is to provide perfluorinated sulfonic acid ionic membrane of a kind of superior performance and preparation method thereof.This film can have high proton conductivity, also has simultaneously high physical strength and dimensional stability, high leakage performance and has excellent chemical stability.Therefore can be used in better in all-vanadium flow battery, Proton Exchange Membrane Fuel Cells and the ionic membrane chlorine industry.In research process, the inventor finds can obtain the polymkeric substance of different densities when the perfluor monoolefine monomer copolymerization of perfluor diolefinic monomer and various combination, and those can generate in the prescription of the bigger perfluorinated sulfonic acid polymer of density, and the chain length of two kinds of perfluor monoolefine monomers that match all has a certain distance.Being that the perfluor monoolefine of short chain and the perfluor monoolefine of long-chain cooperate and the copolymerization of perfluor diolefine, is to generate the bigger cross-linking perfluorinated polymkeric substance of density.And physical strength and the dimensional stability of the bigger perfluorinated sulfonic acid ionic membrane of these density are all very good, and particularly leakage performance is very excellent, and this internal structure that shows the perfluorinated sulfonic acid polymer that these density are bigger is dense.
Technical scheme of the present invention is as follows:
Perfluorinated ion-exchange membrane of the present invention is made up of with the perfluor side chain that contains sulfonic acid group that links to each other with network chain carbon fluorine cross-linked network skeleton structure, except sulfonic acid group, carboxyl and ehter bond can also be arranged on the side chain.Carbon fluorine cross-linked network skeleton structure provides good mechanical property, and the perfluor side chain that contains sulfonic acid group provides good ion exchanging function, and the perfluor structure provides excellent chemical stability.
The preparation process of perfluorinated ionic membrane of the present invention comprises the following steps:
(1) the perfluor diolefinic monomer that will contain the proton exchange functional group is dissolved in the solvent, adds the combination of perfluor monoolefine monomer and the initiator that contain the proton exchange functional group again, and stirring and dissolving evenly back is stand-by.
(2) use the hydrostomia method that the solution that step (1) obtains is become film in level and level and smooth sheet glass or Hastelloy surface of steel plate hydrostomia, adjust the film that liquid volume added can obtain different thickness.
(3) film that step (2) is obtained is heated to certain temperature, and peels off from planar surface after experience for some time, obtains perfluorinated sulfonic acid ion exchange membrane of the present invention.
Solvent described in the step (1) is N, the mixture of a kind of or several solvents in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), the N-N-methyl-2-2-pyrrolidone N-.
The perfluor diolefinic monomer that contains the proton exchange functional group described in the step (1) is to contain a sulfonic acid group and molecules two carbon-to-carbon double bonds at least, such as but not limited to: perfluor-1,6-sodium disulfonate base-2,4-hexadiene, perfluor-1,10-sodium disulfonate base-4,6-certain herbaceous plants with big flowers diene.Be 2～40% when the concentration in solution is represented with mass percent.
At least contain a sulfonic acid group in each molecule during the perfluor monoolefine monomer combination that contains the proton exchange functional group described in the step (1) refers to make up with a carbon-to-carbon double bond, this combination is made up of two or more this class monomer, and the difference between the various molecules comprises the difference of molecular chain length at least.These monomers are selected from, such as but not limited to: perfluor-3-sodium sulfonate group-1-propylene, perfluor-4-sodium sulfonate group-1-butylene, perfluor-6-sodium sulfonate group-1-hexene, perfluor-4-(sodium sulfonate group) vinyl butyl ether base ether, perfluor-5-(sodium sulfonate group) pentyloxy vinyl ether, perfluor-7-(sodium sulfonate group) ethoxy ethylene in heptan base ether.Be 2～50% when the concentration in solution is represented with mass percent.
Initiator described in the step (1) is selected from benzoyl peroxide, Diisopropyl azodicarboxylate, and the consumption of described initiator is for adding the 0.1wt～3wt% of amount of monomer.
Heating temperature described in the step (3) is 50～180 ℃, and be 15～3000 minutes heat-up time, and temperature-rise period wherein can comprise gradient increased temperature.
Compared with prior art, excellent results of the present invention is as follows:
1. the present invention adopts the perfluor diolefinic monomer that contains the ion exchanging function group to participate in polymerization, forms to have the structure of carbon fluorine cross-linked network skeleton, has strengthened bonding force between the interior molecular chain of film, thereby has improved physical strength and the dimensional stability of film significantly.Perfluor monoolefine monomer by preferred different chain length makes up and the copolymerization of perfluor diolefine again, can obtain the very fine and close perfluorinated ion-exchange membrane of network structure, thereby make ion-exchange membrane of the present invention have good mechanical property and anti-medium seepage property.
2. the structure owing to carbon fluorine cross-linked network skeleton has good mechanical property and dimensional stability, thereby can suitably increase the massfraction of intramolecularly sulfonic acid group, thereby can improve the proton conductivity of film under the situation that keeps the favorable mechanical performance.
3. in the structure of carbon fluorine cross-linked network skeleton, because the formation of grid, the position relation between the building block has been subjected to very strong constraint, thereby the swelling ratio of ionic membrane is restricted, and therefore helps to improve the anti-medium seepage property of ionic membrane.
4. the ion-exchange membrane of the inventive method preparation is the perfluor film, and it can have excellent chemical stability and work-ing life.
Embodiment
The invention will be further described by the following examples, rather than to the restriction of content of the present invention.
Embodiment 1
With perfluor 1,10-sodium disulfonate base-4,6-certain herbaceous plants with big flowers diene 60g, perfluor-3-sodium sulfonate group-1-propylene 50g, perfluor-5-(sodium sulfonate group) pentyloxy vinyl ether 50g, Diisopropyl azodicarboxylate 0.5g dissolve in 800g N, in the dinethylformamide, after stirring, in level and level and smooth glass pane surface hydrostomia film forming, in 50 ℃ of insulations 10 hours, and then in 10 hours film forming of 75 ℃ of insulations.After peeling off, sheet glass obtains cross-linking perfluorinated ion-exchange membrane.
Embodiment 2
With perfluor 1,10-sodium disulfonate base-4,6-certain herbaceous plants with big flowers diene 60g, perfluor-4-(sodium sulfonate group)-1-butylene 50g, perfluor-7-(sodium sulfonate group) ethoxy ethylene in heptan base ether 50g, Diisopropyl azodicarboxylate 0.5g dissolves in 800g N, in the dinethylformamide, after stirring, in level and level and smooth glass pane surface hydrostomia film forming, in 50 ℃ of insulations 10 hours, and then in 10 hours film forming of 75 ℃ of insulations.After peeling off, sheet glass obtains cross-linking perfluorinated ion-exchange membrane.
Embodiment 3
With perfluor-1,6-sodium disulfonate base-2,4-hexadiene 60g, perfluor-4-(sodium sulfonate group) butylene 50g, perfluor-5-(sodium sulfonate group) pentyloxy vinyl ether 50g, Diisopropyl azodicarboxylate 0.5g dissolve in 800g N, in the dinethylformamide, after stirring, in level and level and smooth glass pane surface hydrostomia film forming, in 50 ℃ of insulations 10 hours, and then in 10 hours film forming of 75 ℃ of insulations.After peeling off, sheet glass obtains cross-linking perfluorinated ion-exchange membrane.
Embodiment 4
With perfluor-1,6-sodium disulfonate base-2,4-hexadiene 60g, perfluor-6-sodium sulfonate group-1-hexene 50g, perfluor-7-(sodium sulfonate group) ethoxy ethylene in heptan base ether 50g, Diisopropyl azodicarboxylate 0.5g dissolve in 800g N, in the dinethylformamide, after stirring, in level and level and smooth glass pane surface hydrostomia film forming, in 50 ℃ of insulations 10 hours, and then in 10 hours film forming of 75 ℃ of insulations.After peeling off, sheet glass obtains cross-linking perfluorinated ion-exchange membrane.
Perfluorinated ion-exchange membrane performance to each embodiment gained is tested, and compares with du pont company commodity perfluorinated sulfonic acid ionic membrane Nafion117, and the result is as shown in table 1.
Wherein:
The testing method of thickness adopts standard GB/T6672-2001
The testing method of proton conductivity adopts standard GB/T20042.3-2009
The testing method of exchange capacity adopts standard GB/T8144
The testing method of tensile strength adopts standard GB/T20042.3-2009
The testing method of air penetrability adopts standard GB/T20042.3-2009
The measuring method of swelling ratio adopts standard GB/T20042.3-2009
Table 1 embodiment of the invention film and Nafion 117 film properties test results
Claims (7)
1. a cross-linking perfluorinated ion-exchange membrane is characterized in that: be made up of with the perfluor side chain that contains sulfonic acid group that links to each other with network chain carbon fluorine cross-linked network skeleton structure.
2. the preparation method of a kind of cross-linking perfluorinated ion-exchange membrane as claimed in claim 1 is characterized in that comprising the steps:
(1) combination that will contain the perfluor diolefinic monomer of proton exchange functional group and contain the perfluor monoolefine monomer of proton exchange functional group is dissolved in the solvent, initiator is dissolved in wherein again, and it is stand-by to stir.
(2) use the hydrostomia method that the solution that step (1) obtains is become film in level and level and smooth sheet glass or Hastelloy surface of steel plate hydrostomia.
(3) film that step (2) is obtained is heated to certain temperature, peels off from planar surface after experience for some time, obtains cross-linking perfluorinated sulfonic acid ion exchange membrane of the present invention.
3. preparation method as claimed in claim 2, it is characterized in that: the solvent described in the step (1) is N, the mixture of a kind of or several solvents in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), the N-N-methyl-2-2-pyrrolidone N-.
4. preparation method as claimed in claim 2, it is characterized in that: the perfluor diolefinic monomer that contains the proton exchange functional group described in the step (1) is the molecule that contains a sulfonic acid group and two carbon-to-carbon double bonds at least, be selected from perfluor-1,6-sodium disulfonate base-2,4-hexadiene, perfluor-1,10-sodium disulfonate base-4, a kind of or its mixture in the 6-certain herbaceous plants with big flowers diene.Be 2～40% when the concentration in solution is represented with mass percent.
5. preparation method as claimed in claim 2 is characterized in that: the perfluor monoolefine monomer combination that contains the proton exchange functional group described in the step (1) refer to contain at least in each molecule in this combination a sulfonic acid group with a carbon-to-carbon double bond; This combination is made up of two or more this class monomer, and wherein the difference between the various molecules comprises the difference of molecular chain length at least.Molecule in the combination is selected from perfluor-3-sodium sulfonate group-1-propylene, perfluor-4-sodium sulfonate group-1-butylene, perfluor-6-sodium sulfonate group-1-hexene, perfluor-4-(sodium sulfonate group) vinyl butyl ether base ether, perfluor-5-(sodium sulfonate group) pentyloxy vinyl ether, perfluor-7-(sodium sulfonate group) ethoxy ethylene in heptan base ether.Be 2～50% when the concentration in solution is represented with mass percent.
6. preparation method as claimed in claim 2, it is characterized in that: the initiator described in the step (1) is selected from benzoyl peroxide, Diisopropyl azodicarboxylate, and the consumption of described initiator is for adding the 0.1wt～3wt%. of monomer mass
7. preparation method as claimed in claim 2, it is characterized in that: the Heating temperature described in the step (3) is 50～180 ℃, be 15～3000 minutes heat-up time.
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| CN108329494A (en) * | 2017-12-22 | 2018-07-27 | 江苏国立化工科技有限公司 | The preparation method of perfluorosulfonic acid ion film |
| CN110372889A (en) * | 2019-08-02 | 2019-10-25 | 辽宁格瑞帕洛孚新能源有限公司 | A kind of preparation method of solion |
| WO2023148027A1 (en) * | 2022-02-04 | 2023-08-10 | Solvay Specialty Polymers Italy S.P.A. | Method for preparing functionalized polymers |
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| CN101745320A (en) * | 2009-12-10 | 2010-06-23 | 山东东岳神舟新材料有限公司 | Doped crosslinking chemical stable ion exchange membrane and preparation method thereof |
| CN101764235A (en) * | 2009-11-13 | 2010-06-30 | 山东东岳高分子材料有限公司 | Ion exchange membrane with interpenetrating network structure and preparation method thereof |
| CN101757860A (en) * | 2009-11-13 | 2010-06-30 | 山东东岳高分子材料有限公司 | Ion exchange membrane with interpenetrating network structure and preparation method thereof |
| CN101791526A (en) * | 2009-12-09 | 2010-08-04 | 山东东岳高分子材料有限公司 | Fluorine-containing network structure ion exchange membrane based on fluoroethyl vinyl ether polyalcohol and preparation method thereof |
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2012
- 2012-03-09 CN CN2012100602346A patent/CN103304945A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101764235A (en) * | 2009-11-13 | 2010-06-30 | 山东东岳高分子材料有限公司 | Ion exchange membrane with interpenetrating network structure and preparation method thereof |
| CN101757860A (en) * | 2009-11-13 | 2010-06-30 | 山东东岳高分子材料有限公司 | Ion exchange membrane with interpenetrating network structure and preparation method thereof |
| CN101791526A (en) * | 2009-12-09 | 2010-08-04 | 山东东岳高分子材料有限公司 | Fluorine-containing network structure ion exchange membrane based on fluoroethyl vinyl ether polyalcohol and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108329494A (en) * | 2017-12-22 | 2018-07-27 | 江苏国立化工科技有限公司 | The preparation method of perfluorosulfonic acid ion film |
| CN110372889A (en) * | 2019-08-02 | 2019-10-25 | 辽宁格瑞帕洛孚新能源有限公司 | A kind of preparation method of solion |
| WO2023148027A1 (en) * | 2022-02-04 | 2023-08-10 | Solvay Specialty Polymers Italy S.P.A. | Method for preparing functionalized polymers |
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Application publication date: 20130918 |