CN107189291A - A kind of preparation method of the heat-resistant polymer dielectric film based on polyvinyl chloride - Google Patents
A kind of preparation method of the heat-resistant polymer dielectric film based on polyvinyl chloride Download PDFInfo
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- CN107189291A CN107189291A CN201710298873.9A CN201710298873A CN107189291A CN 107189291 A CN107189291 A CN 107189291A CN 201710298873 A CN201710298873 A CN 201710298873A CN 107189291 A CN107189291 A CN 107189291A
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- polyvinyl chloride
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- polymer dielectric
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- 229920000642 polymer Polymers 0.000 title claims abstract description 75
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 47
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 51
- 239000002131 composite material Substances 0.000 claims abstract description 39
- 239000012528 membrane Substances 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000005266 casting Methods 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 11
- 239000010452 phosphate Substances 0.000 claims abstract description 11
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- 230000002708 enhancing effect Effects 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- 229920013655 poly(bisphenol-A sulfone) Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 229920000131 polyvinylidene Polymers 0.000 claims description 3
- KDHWOCLBMVSZPG-UHFFFAOYSA-N 3-imidazol-1-ylpropan-1-amine Chemical class NCCCN1C=CN=C1 KDHWOCLBMVSZPG-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract 2
- 239000012456 homogeneous solution Substances 0.000 abstract 1
- 238000005956 quaternization reaction Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000008961 swelling Effects 0.000 description 9
- 229920002492 poly(sulfone) Polymers 0.000 description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920002480 polybenzimidazole Polymers 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- -1 imidazoyl side chain Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C08L27/22—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment
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- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- C08K3/32—Phosphorus-containing compounds
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
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- H01M8/0239—Organic resins; Organic polymers
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- H01M8/00—Fuel cells; Manufacture thereof
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/22—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers modified by chemical after-treatment
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- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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Abstract
The invention belongs to new material and technical field of membrane, there is provided a kind of preparation method of the heat-resistant polymer dielectric film based on polyvinyl chloride.The preparation method is comprised the steps of：(1) PVC is dissolved in polar organic solvent, heating and stirred to being completely dissolved；(2) APIm and enhanced polymer are dissolved in above-mentioned mixed liquor, heating stirring obtains transparent and homogeneous solution；(3) composite film material is obtained using solution casting method；(4) above-mentioned composite membrane is fully immersed in phosphate aqueous solution and carries out acid doping, obtain high temperature resistant type polymer dielectric film.Regulate and control contents of the APIm in film in the present invention, realize the control of the different quaternization degrees of PVC, and the addition of enhanced polymer, enhance the stability and mechanical performance of film, the composite membrane of preparation has good conductive capability under the conditions of not humidified at 100~180 DEG C.
Description
Technical field
The invention belongs to new material and technical field of membrane, it is related to a kind of heat-resistant polymer electrolyte based on polyvinyl chloride
The preparation method of film.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFCs) is a kind of the chemical energy in fuel and oxidant directly to be changed into electricity
The energy conversion apparatus of energy, it conducts electric current between the electrode of battery two is realized by electrolyte of polymer film.It is now widely used for
PEMFC polymer dielectric film perfluor type sulfonate film (such as Nafion series membranes of E.I.Du Pont Company's production).This kind of membrane material by
Heavy dependence water when sulfonic acid group in film transmits proton so that using this kind of membrane material as the PEMFC of electrolyte work temperature
Degree is usually 80 DEG C or so.The PEMFC worked in this case will be faced with catalyst CO poisonings, hydro-thermal difficult management, electrode
The problems such as kinetic reaction is slow.While the complex manufacturing of perfluorinated sulfonic acid class membrane material, its cost is very high, this will restriction
PEMFC large-scale application and development.
Phosphoric acid is a kind of inorganic proton acid with higher boiling, low volatility, because itself uniqueness is from dissociation capability,
Still there is higher proton conductivity by the hydrogen bond network structure of phosphoric acid molecules formation under non-aqueous conditions.By it and contain
It is the common method for preparing heat-resistant polymer dielectric film to have the polymer of basic group compound.Such as at present by numerous studies
Phosphate-doped polybenzimidazoles (PBI) system membrane material.
However, extensive phosphate-doped PBI films of research at present, exist PBI polymer dissolve in organic solvent it is difficult,
Raw material has the problems such as carcinogenicity, production process are complicated, cost is high.Therefore develop and design cost is cheap, production process is easy, property
Energy high temperature resistant type polymer membrane electrolyte material that is excellent, being applied under the conditions of 100 DEG C of high temperature above will be promoted greatly
PEMFC application and development.
The content of the invention
For the technical problem present on, it is an object of the invention to provide a kind of new cheap, high-performance
High temperature resistant type polymer dielectric film preparation method, the present invention be based on polyvinyl chloride (PVC) polymer in chloro and 1-
The nucleophilic substitution between amino in (3- aminopropyls) imidazoles (APIm) compound, imidazoyl side chain group is incorporated into
In PVC skeletons, while to have the bisphenol-a polysulfone (PSU) of favorable compatibility, poly- (vinylidene fluoride-co- hexafluoros third with PVC
Alkene) (PVDF-6F), the polymer such as polypyrrole alkanone (PVP) be enhancing component, prepare and mixed with good stability and phosphoric acid
The membrane material of miscellaneous ability, then by phosphate-doped, finally obtain under the conditions of high temperature (100~180 DEG C) is not humidified still with good
The heat-resistant polymer membrane materials for electrolyte of good conductive capability.Prepared heat-resistant polymer dielectric film is brownish red,
One fine and close membrane material, ability is passed to good phosphate-doped ability and excellent proton.
Technical solution of the present invention is：
A kind of preparation method of the heat-resistant polymer dielectric film based on polyvinyl chloride, comprises the following steps：
(1) under the conditions of 25~70 DEG C, polyvinyl chloride (PVC) is added in polar organic solvent, stirring and dissolving is obtained
Bright quality solubility is 1~3% polyvinyl chloride solution；
(2) add quaternizing agent into above-mentioned polyvinyl chloride solution to be mixed, the quaternizing agent is 1- (3- ammonia
Base propyl group) imidazoles (APIm), the mol ratio of wherein polyvinyl chloride and 1- (3- aminopropyls) imidazoles is 1:0.3~1；And then to mixed
Close and enhancing polymer is added in solution, continue to stir 4~8 hours, transparent homogeneous Casting solution is obtained, wherein strengthening polymer
The mass ratio for accounting for enhancing polymer and polyvinyl chloride sum is 0.05~0.15:1；The enhancing polymer is bisphenol-a polysulfone
(PSU) one kind in, poly- (vinylidene fluoride-co- hexafluoropropenes) (PVDF-6F) or polypyrrole alkanone (PVP)；
(3) composite film material is prepared using solution casting method, wherein film forming procedure is solvent flashing at a temperature of 60-100 DEG C,
Film formation time is 12~48 hours；
(4) above-mentioned composite film material is fully immersed in the phosphate aqueous solution that mass fraction is 60%~85% at room temperature
Middle carry out acid doping, soak time is 24~72 hours, obtains heat-resistant polymer dielectric film；The phosphoric acid wherein adulterated is with answering
The mass ratio for closing membrane material is 0.7~3.7:1.
Further, the polar organic solvent in the step (1) is DMA or N, N- dimethyl methyl
Acid amides.
Beneficial effects of the present invention are：
(a) the heat-resistant polymer electrolyte prepared by is based on PVC polymer, and raw material is easy to get, cheap, and technique letter
It is single easy, it is adapted to large-scale industrial production；
(b) introducing of alkyl imidazole side chain so that the composite membrane based on PVC has larger free volume, beneficial to phosphoric acid
Doping, and then obtain higher electrical conductivity, 0.29S/cm can reach under 180 DEG C of non-aqueous conditions, and show good
Good stability；
(c) it is poly- by introducing PSU, PVDF-6F, PVP with excellent compatibility etc. in the PVC composite membranes that APIm is grafted
Compound, can further enhance the machinery and dimensional stability of composite membrane, and composite membrane shows good stability；
(d) the grafting degree of pendant alkyl group imidazole group can be realized by simply regulating and controlling APIm and PVC ratio, come
The regulation and control of phosphate-doped content are realized, the composite membrane with different phosphate-doped contents and different electrical conductivity is prepared, is easy to exploitation
Series of products meet the demand in different application field.
Brief description of the drawings
Fig. 1 is the heat-resistant polymer dielectric film (PVC-APIm (1 that obtains in embodiment 1:1)/PA) do not humidifying bar
Under part, electrical conductivity variation with temperature situation.
Embodiment
Below by embodiment, the invention will be further described.
Embodiment 1, prepares PVC-APIm (1:1) method of/PA composite membranes, is comprised the steps of：
(1) 0.15gPVC is weighed, in being dissolved under 25 DEG C of stirring conditions in 15gN, N- dimethylacetamide solutions, is obtained
Polymer solubility is 1% clear polymer solution；
(2) using mol ratio as PVC:APIm=1:1 proportionate relationship, APIm is added into above-mentioned PVC solution, continues to stir
4 hours, obtain transparent homogeneous Casting solution；
(3) composite film material is prepared using solution casting method, wherein film forming procedure is the solvent flashing at a temperature of 60 DEG C,
Film formation time is 48 hours；
(4) above-mentioned composite membrane is fully immersed in into progress acid in the phosphate aqueous solution that mass fraction is 85% at room temperature to mix
Miscellaneous, soak time is 24 hours, obtains high temperature resistant type polymer dielectric film.
Resulting heat-resistant polymer dielectric film has good phosphate-doped ability, and phosphoric acid quality weightening is
370%, while also having good pliability and dimensional stability, phosphate-doped caudacoria material volume swelling ratio is 180%.
Resulting heat-resistant polymer dielectric film has excellent proton conductive, under the conditions of 180 DEG C do not humidify
Electrical conductivity is 0.29S/cm.Fig. 1 is the heat-resistant polymer dielectric film (PVC-APIm (1 obtained by the present embodiment:1)/PA)
Under the conditions of not humidifying, electrical conductivity variation with temperature situation.The electrical conductivity of composite membrane is above 0.01S/ in test scope
Cm, illustrates that the composite membrane prepared by the present embodiment fully meets PEMFC use requirement.
Embodiment 2, prepares PVC-APIm (1:0.5) method of/PA composite membranes, is comprised the steps of：
(1) 0.15gPVC is weighed, in being dissolved under 50 DEG C of stirring conditions in 7.5gN, dinethylformamide solution, is obtained
Polymer solubility is 2% clear polymer solution；
(2) using mol ratio as PVC:APIm=1:0.5 proportionate relationship, adds APIm into above-mentioned PVC solution, continues to stir
Mix 6 hours, obtain transparent homogeneous Casting solution；
(3) composite film material is prepared using solution casting method, wherein film forming procedure is the solvent flashing at a temperature of 80 DEG C,
Film formation time is 24 hours；
(4) above-mentioned composite membrane is fully immersed in into progress acid in the phosphate aqueous solution that mass fraction is 75% at room temperature to mix
Miscellaneous, soak time is 48 hours, obtains high temperature resistant type polymer dielectric film.
Resulting heat-resistant polymer dielectric film has good phosphate-doped ability, and phosphoric acid quality weightening is
100%, while also having good pliability and dimensional stability, phosphate-doped caudacoria material volume swelling ratio is 80%.
Resulting heat-resistant polymer dielectric film has excellent proton conductive, under the conditions of 180 DEG C do not humidify
Electrical conductivity is 0.04S/cm.
Embodiment 3, prepares PVC-APIm (1:0.3) method of/PA composite membranes, is comprised the steps of：
(1) 0.15gPVC is weighed, in being dissolved under 50 DEG C of stirring conditions in 7gN, dinethylformamide solution, is gathered
Compound solubility is 3% clear polymer solution；
(2) using mol ratio as PVC:APIm=1:0.3 proportionate relationship, adds APIm into above-mentioned PVC solution, continues to stir
Mix 8 hours, obtain transparent homogeneous Casting solution；
(3) composite film material is prepared using solution casting method, wherein film forming procedure be volatilized at a temperature of 100 DEG C it is molten
Agent, film formation time is 12 hours；
(4) above-mentioned composite membrane is fully immersed in into progress acid in the phosphate aqueous solution that mass fraction is 85% at room temperature to mix
Miscellaneous, soak time is 24 hours, obtains high temperature resistant type polymer dielectric film.
Resulting heat-resistant polymer dielectric film has good phosphate-doped ability, and phosphoric acid quality weightening is
70%, while also having good pliability and dimensional stability, phosphate-doped caudacoria material volume swelling ratio is 40%.
Resulting heat-resistant polymer dielectric film has excellent proton conductive, under the conditions of 180 DEG C do not humidify
Electrical conductivity is 0.02S/cm.
Embodiment 4, prepares PVC-APIm (1:1) method of/15%PSU/PA composite membranes, is comprised the steps of：
(1) 0.15gPVC is weighed, in being dissolved under 70 DEG C of stirring conditions in 15gN, dinethylformamide solution, is obtained
Polymer solubility is 1% clear polymer solution；
(2) using mol ratio as PVC:APIm=1:1 proportionate relationship, adds APIm, with mass ratio into above-mentioned PVC solution
PSU:(PSU+PVC)=0.15:1 proportionate relationship adds enhancing polymer P SU into above-mentioned mixed solution, continues to stir 8
Hour, obtain transparent homogeneous Casting solution；
(3) composite film material is prepared using solution casting method, wherein film forming procedure be volatilized at a temperature of 100 DEG C it is molten
Agent, film formation time is 12 hours；
(4) above-mentioned composite membrane is fully immersed in into progress acid in the phosphate aqueous solution that mass fraction is 60% at room temperature to mix
Miscellaneous, soak time is 72 hours, obtains high temperature resistant type polymer dielectric film.
Resulting heat-resistant polymer dielectric film has good phosphate-doped ability, and phosphoric acid quality weightening is
160%, while also having good pliability and dimensional stability, phosphate-doped caudacoria material volume swelling ratio is 110%.
Resulting heat-resistant polymer dielectric film has excellent proton conductive, under the conditions of 180 DEG C do not humidify
Electrical conductivity is 0.07S/cm.
Embodiment 5, prepares PVC-APIm (1:0.5) method of/15%PSU/PA composite membranes, is comprised the steps of：
(1) 0.15gPVC is weighed, in being dissolved under 70 DEG C of stirring conditions in 15gN, dinethylformamide solution, is obtained
Polymer solubility is 1% clear polymer solution；
(2) using mol ratio as PVC:APIm=1:0.5 proportionate relationship, adds APIm, with quality into above-mentioned PVC solution
Compare PSU:(PSU+PVC)=0.15:1 proportionate relationship adds enhancing polymer P SU into above-mentioned mixed solution, continues to stir
6 hours, obtain transparent homogeneous Casting solution；
(3) composite film material is prepared using solution casting method, wherein film forming procedure is the solvent flashing at a temperature of 80 DEG C,
Film formation time is 24 hours；
(4) above-mentioned composite membrane is fully immersed in into progress acid in the phosphate aqueous solution that mass fraction is 85% at room temperature to mix
Miscellaneous, soak time is 24 hours, obtains high temperature resistant type polymer dielectric film.
Resulting heat-resistant polymer dielectric film has good phosphate-doped ability, and phosphoric acid quality weightening is
140%, while also having good pliability and dimensional stability, phosphate-doped caudacoria material volume swelling ratio is 80%.
Resulting heat-resistant polymer dielectric film has excellent proton conductive, under the conditions of 180 DEG C do not humidify
Electrical conductivity is 0.06S/cm.
Embodiment 6, prepares PVC-APIm (1:1) method of/5%PVDF-6F/PA composite membranes, is comprised the steps of：
(1) 0.15gPVC is weighed, in being dissolved under 60 DEG C of stirring conditions in 15gN, dinethylformamide solution, is obtained
Polymer solubility is 1% clear polymer solution；
(2) using mol ratio as PVC:APIm=1:1 proportionate relationship, adds APIm, with mass ratio into above-mentioned PVC solution
PVDF-6F:(PVDF-6F+PVC)=0.05:1 proportionate relationship adds enhancing polymer P VDF- into above-mentioned mixed solution
6F, continues to stir 8 hours, obtains transparent homogeneous Casting solution；
(3) composite film material is prepared using solution casting method, wherein film forming procedure is the solvent flashing at a temperature of 80 DEG C,
Film formation time is 24 hours；
(4) above-mentioned composite membrane is fully immersed in into progress acid in the phosphate aqueous solution that mass fraction is 75% at room temperature to mix
Miscellaneous, soak time is 72 hours, obtains high temperature resistant type polymer dielectric film.
Resulting heat-resistant polymer dielectric film has good phosphate-doped ability, and phosphoric acid quality weightening is
260%, while also having good pliability and dimensional stability, phosphate-doped caudacoria material volume swelling ratio is 130%.
Resulting heat-resistant polymer dielectric film has excellent proton conductive, under the conditions of 180 DEG C do not humidify
Electrical conductivity is 0.13S/cm.
Embodiment 7, prepares PVC-APIm (1:0.5) method of/5%PVDF-6F/PA composite membranes, is comprised the steps of：
(1) 0.15gPVC is weighed, in being dissolved under 60 DEG C of stirring conditions in 15gN, N- dimethylacetamide solutions, is obtained
Polymer solubility is 1% clear polymer solution；
(2) using mol ratio as PVC:APIm=1:0.5 proportionate relationship, adds APIm, with quality into above-mentioned PVC solution
Compare PVDF-6F:(PVDF-6F+PVC)=0.05:1 proportionate relationship adds enhancing polymer into above-mentioned mixed solution
PVDF-6F, continues to stir 4 hours, obtains transparent homogeneous Casting solution；
(3) composite film material is prepared using solution casting method, wherein film forming procedure is the solvent flashing at a temperature of 80 DEG C,
Film formation time is 24 hours；
(4) above-mentioned composite membrane is fully immersed in into progress acid in the phosphate aqueous solution that mass fraction is 85% at room temperature to mix
Miscellaneous, soak time is 24 hours, obtains high temperature resistant type polymer dielectric film.
Resulting heat-resistant polymer dielectric film has good phosphate-doped ability, and phosphoric acid quality weightening is
130%, while also having good pliability and dimensional stability, phosphate-doped caudacoria material volume swelling ratio is 75%.
Resulting heat-resistant polymer dielectric film has excellent proton conductive, under the conditions of 180 DEG C do not humidify
Electrical conductivity is 0.08S/cm.
Embodiment 8, prepares PVC-APIm (1:1) method of/13%PVP/PA composite membranes, is comprised the steps of：
(1) 0.15gPVC is weighed, in being dissolved under 60 DEG C of stirring conditions in 15gN, N- dimethylacetamide solutions, is obtained
Polymer solubility is 1% clear polymer solution；
(2) using mol ratio as PVC:APIm=1:1 proportionate relationship, adds APIm, with mass ratio into above-mentioned PVC solution
PVP:(PVP+PVC)=0.13:1 proportionate relationship adds enhancing polymer P VP into above-mentioned mixed solution, continues to stir 6
Hour, obtain transparent homogeneous Casting solution；
(3) composite film material is prepared using solution casting method, wherein film forming procedure is the solvent flashing at a temperature of 60 DEG C,
Film formation time is 48 hours；
(4) above-mentioned composite membrane is fully immersed in into progress acid in the phosphate aqueous solution that mass fraction is 75% at room temperature to mix
Miscellaneous, soak time is 24 hours, obtains high temperature resistant type polymer dielectric film.
Resulting heat-resistant polymer dielectric film has good phosphate-doped ability, and phosphoric acid quality weightening is
320%, while also having good pliability and dimensional stability, phosphate-doped caudacoria material volume swelling ratio is 65%.
Resulting heat-resistant polymer dielectric film has excellent proton conductive, under the conditions of 180 DEG C do not humidify
Electrical conductivity is 0.17S/cm.
In summary embodiment test result understands that the phosphate-doped content of the heat-resistant polymer dielectric film of preparation is
70%~370%, with higher electrical conductivity 0.02S/cm~0.29S/cm, while having good dimensional stability, volume
Swelling ratio 40%~180%.Illustrate that the present embodiment has been made the high temperature resistant with high conductance and good dimensional stability and gathered
Polymer electrolyte membrane, the membrane materials for electrolyte available for devices such as fuel cell, flow batteries.
Claims (2)
1. a kind of preparation method of the heat-resistant polymer dielectric film based on polyvinyl chloride, it is characterised in that including following step
Suddenly：
(1) under the conditions of 25~70 DEG C, polyvinyl chloride is added in polar organic solvent, stirring and dissolving obtains transparent quality
Solubility is 1~3% polyvinyl chloride solution；
(2) add 1- (3- aminopropyls) imidazoles into above-mentioned polyvinyl chloride solution to be mixed, wherein polyvinyl chloride and 1- (3-
Aminopropyl) imidazoles mol ratio be 1:0.3~1；And then enhancing polymer is added into mixed solution, continue stirring 4~8 small
When, transparent homogeneous Casting solution is obtained, wherein enhancing polymer accounts for enhancing polymer and the mass ratio of polyvinyl chloride sum is
0.05~0.15:1；The enhancing polymer is bisphenol-a polysulfone, poly- (vinylidene fluoride-co- hexafluoropropenes) or polypyrrole
One kind in alkanone；
(3) composite film material is prepared using solution casting method, wherein film forming procedure is solvent flashing, film forming at a temperature of 60-100 DEG C
Time is 12~48 hours；
(4) above-mentioned composite film material is fully immersed in the phosphate aqueous solution that mass fraction is 60%~85% at room temperature
Row acid doping, soak time is 24~72 hours, obtains heat-resistant polymer dielectric film；The phosphoric acid and composite membrane wherein adulterated
The mass ratio of material is 0.7~3.7:1.
2. a kind of preparation method of heat-resistant polymer dielectric film based on polyvinyl chloride according to claim 1, its
It is characterised by, the polar organic solvent in step (1) is DMA or DMF.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108258290A (en) * | 2018-01-31 | 2018-07-06 | 东北大学 | Phosphate-doped prepares the high temperature proton exchange film method with layer assembly structure based on spin coating technique |
| CN108570157A (en) * | 2018-04-24 | 2018-09-25 | 东北大学 | A kind of preparation method of the polymer anion film based on crassitude cation |
| CN108878973A (en) * | 2018-07-10 | 2018-11-23 | 哈尔滨理工大学 | A kind of preparation method of polyvinyl chloride-based polymer dielectric film |
| CN112834540A (en) * | 2019-11-22 | 2021-05-25 | 中国科学院大连化学物理研究所 | Determining PBI/H3PO4Method for measuring content of phosphoric acid in doped film |
| CN113754971A (en) * | 2021-10-25 | 2021-12-07 | 西北工业技术研究院(台州)有限公司 | PVC pipe fitting material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006055157A2 (en) * | 2004-11-16 | 2006-05-26 | Hoku Scientific, Inc. | Novel membrane and membrane electrode assemblies |
| CN104437119A (en) * | 2014-11-05 | 2015-03-25 | 福州大学 | Polymer microporous membrane based on polyvinyl chloride ion liquid and preparation method of polymer microporous membrane |
| CN104558646A (en) * | 2014-12-24 | 2015-04-29 | 福州大学 | Preparation and application of ionic liquid-polyvinyl chloride membrane with anion response |
| CN104607059A (en) * | 2015-02-09 | 2015-05-13 | 福州大学 | Preparation method of vinyl chloride polymer ionic liquid porous membrane |
-
2017
- 2017-05-03 CN CN201710298873.9A patent/CN107189291B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006055157A2 (en) * | 2004-11-16 | 2006-05-26 | Hoku Scientific, Inc. | Novel membrane and membrane electrode assemblies |
| CN104437119A (en) * | 2014-11-05 | 2015-03-25 | 福州大学 | Polymer microporous membrane based on polyvinyl chloride ion liquid and preparation method of polymer microporous membrane |
| CN104558646A (en) * | 2014-12-24 | 2015-04-29 | 福州大学 | Preparation and application of ionic liquid-polyvinyl chloride membrane with anion response |
| CN104607059A (en) * | 2015-02-09 | 2015-05-13 | 福州大学 | Preparation method of vinyl chloride polymer ionic liquid porous membrane |
Non-Patent Citations (3)
| Title |
|---|
| JATINDRANATH MAITI，等: "Imidazolium functionalized poly(vinyl chloride-co-vinyl acetate)-based anion exchange membrane", 《INRERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
| JINGSHUAI YANG，等: "Phosphoric acid doped imidazolium polysulfone membranes for high temperature proton exchange membrane fuel cells", 《JOURNAL OF POWER SOURCES》 * |
| JINGSHUAI YANG，等: "Preparation and investigation of various imidazolium-functionalized poly(2,6-dimethyl-1,4-phenylene oxide) anion exchange membranes", 《ELECTROCHIMICA ACTA》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108258290A (en) * | 2018-01-31 | 2018-07-06 | 东北大学 | Phosphate-doped prepares the high temperature proton exchange film method with layer assembly structure based on spin coating technique |
| CN108258290B (en) * | 2018-01-31 | 2020-04-03 | 东北大学 | Method for preparing high-temperature proton exchange membrane with layer-by-layer assembly structure based on spin coating technology by doping phosphoric acid |
| CN108570157A (en) * | 2018-04-24 | 2018-09-25 | 东北大学 | A kind of preparation method of the polymer anion film based on crassitude cation |
| CN108570157B (en) * | 2018-04-24 | 2020-06-05 | 东北大学 | Preparation method of polymer anionic membrane based on methylpyrrolidine cations |
| CN108878973A (en) * | 2018-07-10 | 2018-11-23 | 哈尔滨理工大学 | A kind of preparation method of polyvinyl chloride-based polymer dielectric film |
| CN108878973B (en) * | 2018-07-10 | 2022-01-25 | 哈尔滨理工大学 | Preparation method of polyvinyl chloride-based polymer electrolyte membrane |
| CN112834540A (en) * | 2019-11-22 | 2021-05-25 | 中国科学院大连化学物理研究所 | Determining PBI/H3PO4Method for measuring content of phosphoric acid in doped film |
| CN113754971A (en) * | 2021-10-25 | 2021-12-07 | 西北工业技术研究院(台州)有限公司 | PVC pipe fitting material and preparation method thereof |
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