CN109818025A - The preparation method of sulfonated polyether-ether-ketone and graphene oxide composite membrane - Google Patents
The preparation method of sulfonated polyether-ether-ketone and graphene oxide composite membrane Download PDFInfo
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- CN109818025A CN109818025A CN201910120308.2A CN201910120308A CN109818025A CN 109818025 A CN109818025 A CN 109818025A CN 201910120308 A CN201910120308 A CN 201910120308A CN 109818025 A CN109818025 A CN 109818025A
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- ketone
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The present invention relates to the preparation methods of a kind of sulfonated polyether-ether-ketone and graphene oxide composite membrane, film liquid is made into graphene oxide, nano zine oxide, hydroxyapatite, polypropylene grafted maleic anhydride, sulfonated polyether-ether-ketone, cetyl trimethylammonium bromide and silane coupling agent, composite membrane is made in casting film-forming, with good mechanical performance and proton-conducting, methanol permeability is reduced, can be used as proton exchange membrane applied to direct methanol fuel cell.
Description
Technical field
The invention belongs to composite membrane technology fields, and in particular to a kind of sulfonated polyether-ether-ketone and graphene oxide composite membrane
Preparation method.
Background technique
Proton exchange membrane is one of the core component of Proton Exchange Membrane Fuel Cells and direct alcohol fuel cell, fuel electricity
Pond must meet the following requirement with proton exchange membrane material: (1) inexpensive；(2) high proton conductivity；(3) good mechanics is strong
Spend (anti-swelling) and dimensional stability；(4) excellent chemical stability and electrochemical stability；(5) very low gas or methanol
Permeability；(6) it is matched with catalyst layer；(7) it is used for a long time and stablizes.
A kind of macromolecule of the sulfonated polyether-ether-ketone as glassy state has good thermal stability and mechanical strength, gas
Infiltration coefficient it is lower.In gas separation process, usually with the presence of vapor, and most of membrane material water-resistant stability by
Limitation, and sulfonated polyether-ether-ketone has excellent water resistance, can be used as the high-molecular matrix material in hybridized film.
Graphene shows excellent performance in many fields in recent years, and functionalization product graphene oxide has only
Special two-dimensional layered structure, surface oxygen-containing group rich in, such as :-OH ,-COOH ,-C=O etc., specific surface with higher
With certain mechanical strength, the mechanical stability and ion selectivity of film can be improved by the addition of graphene oxide, and
Certain proton channel is provided.
Summary of the invention
The purpose of the present invention is to provide the preparation methods of a kind of sulfonated polyether-ether-ketone and graphene oxide composite membrane.
The technical solution adopted by the present invention to solve the technical problems is: sulfonated polyether-ether-ketone and graphene oxide composite membrane
Preparation method, comprising the following steps:
1) graphene oxide, nano zine oxide, hydroxyapatite, polypropylene grafted maleic anhydride is taken to be added in ball mill,
The mix powder that ball milling 6-8h must be uniformly mixed；
2) said mixture powder is added in solvent, is ultrasonically treated 30-60min, obtains finely dispersed mixed liquor, mixed
The solid content of liquid is 20-40%；
3) sulfonated polyether-ether-ketone is added in dimethylformamide, is configured to the dispersion liquid that concentration is 10-25wt%；
4) dispersion liquid in step 3) is added in the mixed liquor in step 2), cetyl trimethyl bromination is then added
Ammonium and silane coupling agent, ultrasound simultaneously stir 3-5h and obtain uniform mixed liquor；
5) the uniform mixed liquor of step 4) is coated on clean smooth glass plate, is dried in vacuo 12-24h, is soaked after demoulding
Bubble for 24 hours, then uses deionized water soaking and washing, up to sulfonated polyether-ether-ketone and oxidation after drying in the sulfuric acid solution of 1mol/L
Graphene composite film.
Specifically, graphene oxide, nano zine oxide, hydroxyapatite, polypropylene grafted maleic acid in the step 1)
The mass ratio of acid anhydride is 3-7:1-3:1-2:2-4.
Specifically, solvent is dehydrated alcohol, N-Methyl pyrrolidone, dimethylformamide, dimethyl in the step 2)
One of acetamide.
Specifically, the mass ratio of sulfonated polyether-ether-ketone and graphene oxide is 40-55:2-5 in the step 3).
Specifically, in the step 4) cetyl trimethylammonium bromide, silane coupling agent and graphene oxide quality
Than for 1-2:0.5-1.1:3-7.
Specifically, silane coupling agent is 3-aminopropyltriethoxysilane, 3- (2- aminoethyl)-ammonia in the step 4)
One of propyl trimethoxy silicane and 3- TSL 8330.
The invention has the following advantages: present invention graphene oxide, nano zine oxide, hydroxyapatite, poly- third
Film liquid is made into alkene grafted maleic anhydride, sulfonated polyether-ether-ketone, cetyl trimethylammonium bromide and silane coupling agent, is cast into
Composite membrane is made in film, has good mechanical performance and proton-conducting, reduces methanol permeability, can be used as proton exchange membrane and answer
For direct methanol fuel cell.
Specific embodiment
The following is specific embodiments of the present invention, is described further to technical solution of the present invention, but of the invention
Protection scope is not limited to these examples.It is all to be included in the present invention without departing substantially from the change of present inventive concept or equivalent substitute
Protection scope within.
Embodiment 1
The preparation method of sulfonated polyether-ether-ketone and graphene oxide composite membrane, comprising the following steps:
1) graphene oxide, nano zine oxide, hydroxyapatite, polypropylene grafted maleic anhydride is taken to be added in ball mill,
The mix powder that ball milling 8h must be uniformly mixed, graphene oxide, nano zine oxide, hydroxyapatite, polypropylene grafted Malaysia
The mass ratio of acid anhydrides is 5:2:1:3；
2) said mixture powder is added in dimethylformamide, is ultrasonically treated 40min, obtains finely dispersed mixing
Liquid, the solid content of mixed liquor are 35%；
3) sulfonated polyether-ether-ketone is added in dimethylformamide, is configured to the dispersion liquid that concentration is 15wt%；
4) dispersion liquid in step 3) is added in the mixed liquor in step 2), sulfonated polyether-ether-ketone and graphene oxide
Mass ratio is 40:3, and cetyl trimethylammonium bromide and silane coupling agent 3-aminopropyltriethoxysilane is then added,
The mass ratio of cetyl trimethylammonium bromide, silane coupling agent and graphene oxide is 2:0.5.1:3, and ultrasound simultaneously stirs 4h and obtains
Uniform mixed liquor；
5) the uniform mixed liquor of step 4) is coated on clean smooth glass plate, vacuum drying for 24 hours, is immersed in after demoulding
In the sulfuric acid solution of 1mol/L for 24 hours, deionized water soaking and washing is then used, up to sulfonated polyether-ether-ketone and graphite oxide after drying
Alkene composite membrane.
Embodiment 2
The preparation method of sulfonated polyether-ether-ketone and graphene oxide composite membrane, comprising the following steps:
1) graphene oxide, nano zine oxide, hydroxyapatite, polypropylene grafted maleic anhydride is taken to be added in ball mill,
The mix powder that ball milling 6h must be uniformly mixed, graphene oxide, nano zine oxide, hydroxyapatite, polypropylene grafted Malaysia
The mass ratio of acid anhydrides is 7:3:1.5:4；
2) said mixture powder is added to absolute ethanol, is ultrasonically treated 60min, obtains finely dispersed mixed liquor, mixed
The solid content for closing liquid is 20%；
3) sulfonated polyether-ether-ketone is added in dimethylformamide, is configured to the dispersion liquid that concentration is 20wt%；
4) dispersion liquid in step 3) is added in the mixed liquor in step 2), sulfonated polyether-ether-ketone and graphene oxide
Mass ratio is 55:4, and cetyl trimethylammonium bromide and silane coupling agent 3- (2- aminoethyl)-aminopropyl front three is then added
Oxysilane, the mass ratio of cetyl trimethylammonium bromide, silane coupling agent and graphene oxide are 1:1:5, and ultrasound is simultaneously stirred
It mixes 5h and obtains uniform mixed liquor；
5) the uniform mixed liquor of step 4) is coated on clean smooth glass plate, is dried in vacuo 12h, is immersed in after demoulding
In the sulfuric acid solution of 1mol/L for 24 hours, deionized water soaking and washing is then used, up to sulfonated polyether-ether-ketone and graphite oxide after drying
Alkene composite membrane.
Embodiment 3
The preparation method of sulfonated polyether-ether-ketone and graphene oxide composite membrane, comprising the following steps:
1) graphene oxide, nano zine oxide, hydroxyapatite, polypropylene grafted maleic anhydride is taken to be added in ball mill,
The mix powder that ball milling 7h must be uniformly mixed, graphene oxide, nano zine oxide, hydroxyapatite, polypropylene grafted Malaysia
The mass ratio of acid anhydrides is 3:1:2:3；
2) said mixture powder is added in dimethyl acetamide, is ultrasonically treated 30min, obtains finely dispersed mixing
Liquid, the solid content of mixed liquor are 40%；
3) sulfonated polyether-ether-ketone is added in dimethylformamide, is configured to the dispersion liquid that concentration is 25wt%；
4) dispersion liquid in step 3) is added in the mixed liquor in step 2), sulfonated polyether-ether-ketone and graphene oxide
Mass ratio is 45:2, and cetyl trimethylammonium bromide and silane coupling agent 3- TSL 8330 is then added,
The mass ratio of cetyl trimethylammonium bromide, silane coupling agent and graphene oxide is 1.5:0.8:7, and ultrasound simultaneously stirs 3h and obtains
Uniform mixed liquor；
5) the uniform mixed liquor of step 4) is coated on clean smooth glass plate, is dried in vacuo 18h, is immersed in after demoulding
In the sulfuric acid solution of 1mol/L for 24 hours, deionized water soaking and washing is then used, up to sulfonated polyether-ether-ketone and graphite oxide after drying
Alkene composite membrane.
Embodiment 4
The preparation method of sulfonated polyether-ether-ketone and graphene oxide composite membrane, comprising the following steps:
1) graphene oxide, nano zine oxide, hydroxyapatite, polypropylene grafted maleic anhydride is taken to be added in ball mill,
The mix powder that ball milling 6h must be uniformly mixed, graphene oxide, nano zine oxide, hydroxyapatite, polypropylene grafted Malaysia
The mass ratio of acid anhydrides is 4:2:1:2；
2) said mixture powder is added in N-Methyl pyrrolidone, is ultrasonically treated 50min, obtains finely dispersed mixing
Liquid, the solid content of mixed liquor are 25%；
3) sulfonated polyether-ether-ketone is added in dimethylformamide, is configured to the dispersion liquid that concentration is 1wt%；
4) dispersion liquid in step 3) is added in the mixed liquor in step 2), sulfonated polyether-ether-ketone and graphene oxide
Mass ratio is 50:5, and cetyl trimethylammonium bromide and silane coupling agent 3- (2- aminoethyl)-aminopropyl front three is then added
Oxysilane, the mass ratio of cetyl trimethylammonium bromide, silane coupling agent and graphene oxide are 2:1.1:6, and ultrasound is simultaneously
Stirring 5h obtains uniform mixed liquor；
5) the uniform mixed liquor of step 4) is coated on clean smooth glass plate, is dried in vacuo 20h, is immersed in after demoulding
In the sulfuric acid solution of 1mol/L for 24 hours, deionized water soaking and washing is then used, up to sulfonated polyether-ether-ketone and graphite oxide after drying
Alkene composite membrane.
Claims (6)
1. the preparation method of sulfonated polyether-ether-ketone and graphene oxide composite membrane, which comprises the following steps:
1) graphene oxide, nano zine oxide, hydroxyapatite, polypropylene grafted maleic anhydride is taken to be added in ball mill, ball milling
The mix powder that 6-8h must be uniformly mixed；
2) said mixture powder is added in solvent, is ultrasonically treated 30-60min, obtains finely dispersed mixed liquor, mixed liquor
Solid content is 20-40%；
3) sulfonated polyether-ether-ketone is added in dimethylformamide, is configured to the dispersion liquid that concentration is 10-25wt%；
4) by step 3) dispersion liquid be added step 2) in mixed liquor in, then be added cetyl trimethylammonium bromide and
Silane coupling agent, ultrasound simultaneously stir 3-5h and obtain uniform mixed liquor；
5) the uniform mixed liquor of step 4) is coated on clean smooth glass plate, is dried in vacuo 12-24h, is immersed in after demoulding
In the sulfuric acid solution of 1mol/L for 24 hours, deionized water soaking and washing is then used, up to sulfonated polyether-ether-ketone and graphite oxide after drying
Alkene composite membrane.
2. the preparation method of sulfonated polyether-ether-ketone as described in claim 1 and graphene oxide composite membrane, which is characterized in that institute
State graphene oxide in step 1), nano zine oxide, hydroxyapatite, polypropylene grafted maleic anhydride mass ratio be 3-7:1-
3:1-2:2-4。
3. the preparation method of sulfonated polyether-ether-ketone as described in claim 1 and graphene oxide composite membrane, which is characterized in that institute
Stating solvent in step 2) is one of dehydrated alcohol, N-Methyl pyrrolidone, dimethylformamide, dimethyl acetamide.
4. the preparation method of sulfonated polyether-ether-ketone as described in claim 1 and graphene oxide composite membrane, which is characterized in that institute
Stating the mass ratio of sulfonated polyether-ether-ketone and graphene oxide in step 3) is 40-55:2-5.
5. the preparation method of sulfonated polyether-ether-ketone as described in claim 1 and graphene oxide composite membrane, which is characterized in that institute
The mass ratio for stating cetyl trimethylammonium bromide in step 4), silane coupling agent and graphene oxide is 1-2:0.5-1.1:3-
7。
6. the preparation method of sulfonated polyether-ether-ketone as described in claim 1 and graphene oxide composite membrane, which is characterized in that institute
Stating silane coupling agent in step 4) is 3-aminopropyltriethoxysilane, 3- (2- aminoethyl)-aminopropyl trimethoxysilane
One of with 3- TSL 8330.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113506904A (en) * | 2021-06-02 | 2021-10-15 | 华南理工大学 | Proton exchange membrane and preparation method and application thereof |
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