CN109880287A - The preparation method of sulfonated polyether-ether-ketone and chitosan complex film - Google Patents
The preparation method of sulfonated polyether-ether-ketone and chitosan complex film Download PDFInfo
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- CN109880287A CN109880287A CN201910203588.3A CN201910203588A CN109880287A CN 109880287 A CN109880287 A CN 109880287A CN 201910203588 A CN201910203588 A CN 201910203588A CN 109880287 A CN109880287 A CN 109880287A
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/50—Fuel cells
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The present invention relates to the preparation methods of a kind of sulfonated polyether-ether-ketone and chitosan complex film, the present invention is handled sulfonated polyether-ether-ketone with three (2- methoxyphenyl) phosphines, improve its dissolubility, then film forming liquid casting film-forming is made with chitosan, tartaric acid, the stable chemical performance of film, with good proton conductivity, it can be used for fuel battery proton exchange film.
Description
Technical field
The invention belongs to technical field of polymer composite materials, and in particular to a kind of sulfonated polyether-ether-ketone and chitosan are compound
The preparation method of film.
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.But it is right
In sulfonated polyether-ether-ketone film, highly sulfonated just can guarantee higher proton-conducting, but highly sulfonated will lead to membrane swelling
Increase, alcohol-resistant performance decline.
The blending of soda acid polyelectrolyte is a kind of current conventional means for the proton exchange membrane that processability is excellent.Shell is poly-
For sugar as a kind of natural cationic polyelectrolyte, rich reserves are cheap, and have hydroxyl on its structural unit simultaneously
And amino, there is very flexible reactive adaptation.
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 chitosan complex film.
The technical solution adopted by the present invention to solve the technical problems is: the system of sulfonated polyether-ether-ketone and chitosan complex film
Preparation Method, comprising the following steps:
1) stirring and dissolving in deionized water is added in water soluble chitosan, obtains the chitosan aqueous solution that concentration is 2-5wt%；
2) tartaric acid is added in chitosan aqueous solution according to the ratio of tartaric acid and chitosan mass ratio 1-2:5-7, magnetic
Power is dispersed with stirring uniform mixed liquor A；
3) stirring and dissolving in solvent is added in sulfonated polyether-ether-ketone, three (2- methoxyphenyl) phosphines is then added, are warming up to
60-80 DEG C of reaction 12-15h, is cooled to room temperature to obtain mixed liquid B after reaction；
4) mixed liquor A is added under agitation in mixed liquid B, then heats to 55-75 DEG C of dropwise addition crosslinking agent, be added dropwise
Finish insulation reaction 1-2h；
5) it is cooled to room temperature after reaction, reaction solution is cast to casting film-forming on cleaned glass plate, in going after drying
Soaking and water washing obtains product film for 24 hours in ionized water.
Specifically, water soluble chitosan is carboxymethyl chitosan or Quaternary Ammonium Salt of Chitosan in the step 1).
Specifically, solvent is N-Methyl pyrrolidone, dimethyl sulfoxide, dimethylformamide, diformazan in the step 3)
One of yl acetamide.
Specifically, the mass ratio of sulfonated polyether-ether-ketone and chitosan is 5-10:3-7, three (2- methoxyl groups in the step 3)
Phenyl) phosphine additional amount be sulfonated polyether-ether-ketone quality 1-3%.
Specifically, sulfonated polyether-ether-ketone preparation step is as follows in the step 3): according to the matter of polyether-ether-ketone and the concentrated sulfuric acid
Amount is reacted than dry polyether-ether-ketone particle is added in the concentrated sulfuric acid for 0.11-0.15:1 in 45~50 DEG C, through precipitating, mistake
Filter, washing, obtain sulfonated polyether-ether-ketone.
Specifically, crosslinking agent is epoxychloropropane in the step 4), and the additional amount of epoxychloropropane is chitosan mass
0.5-4%.
The invention has the following advantages: the present invention with three (2- methoxyphenyl) phosphines to sulfonated polyether-ether-ketone at
Reason, improves its dissolubility, and film forming liquid casting film-forming is then made with chitosan, tartaric acid, and the stable chemical performance of film has good
Good proton conductivity, can be used for fuel battery proton exchange film.
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 chitosan complex film, comprising the following steps:
1) stirring and dissolving in deionized water is added in carboxymethyl chitosan, obtains the chitosan aqueous solution that concentration is 3wt%；
2) tartaric acid is added in chitosan aqueous solution according to the ratio of tartaric acid and chitosan mass ratio 1-6, magnetic force stirs
Mix the mixed liquor A that is uniformly dispersed to obtain；
3) dry polyether-ether-ketone particle is added to dense sulphur for 0.14:1 according to the mass ratio of polyether-ether-ketone and the concentrated sulfuric acid
It is reacted in acid in 50 DEG C, is precipitated, is filtered, washed, be prepared into sulfonated polyether-ether-ketone.
Stirring and dissolving in dimethyl acetamide, the mass ratio of sulfonated polyether-ether-ketone and chitosan is added in sulfonated polyether-ether-ketone
For 7:5, three (2- methoxyphenyl) phosphines for accounting for sulfonated polyether-ether-ketone quality 2% are then added, are warming up to 75 DEG C of reaction 15h, instead
Mixed liquid B is cooled to room temperature to obtain after answering；
4) mixed liquor A is added under agitation in mixed liquid B, then heats to 60 DEG C of dropwise addition crosslinking agent epoxy chloropropionates
Alkane, the additional amount of epoxychloropropane are the 2% of chitosan mass, and insulation reaction 1h is added dropwise；
5) it is cooled to room temperature after reaction, reaction solution is cast to casting film-forming on cleaned glass plate, in going after drying
Soaking and water washing obtains product film for 24 hours in ionized water.
Embodiment 2
The preparation method of sulfonated polyether-ether-ketone and chitosan complex film, comprising the following steps:
1) stirring and dissolving in deionized water is added in Quaternary Ammonium Salt of Chitosan, obtains the chitosan aqueous solution that concentration is 4wt%；
2) tartaric acid is added in chitosan aqueous solution according to the ratio of tartaric acid and chitosan mass ratio 1.5:7, magnetic force
It is dispersed with stirring uniform mixed liquor A；
3) dry polyether-ether-ketone particle is added to dense sulphur for 0.15:1 according to the mass ratio of polyether-ether-ketone and the concentrated sulfuric acid
It is reacted in acid in 45 DEG C, is precipitated, is filtered, washed, be prepared into sulfonated polyether-ether-ketone.
Stirring and dissolving in N-Methyl pyrrolidone, the quality of sulfonated polyether-ether-ketone and chitosan is added in sulfonated polyether-ether-ketone
Than three (2- methoxyphenyl) phosphines for accounting for sulfonated polyether-ether-ketone quality 1% being then added, are warming up to 60 DEG C of reaction 12h for 5:3,
It is cooled to room temperature to obtain mixed liquid B after reaction；
4) mixed liquor A is added under agitation in mixed liquid B, then heats to 75 DEG C of dropwise addition crosslinking agent epoxy chloropropionates
Alkane, the additional amount of epoxychloropropane are the 3% of chitosan mass, and insulation reaction 1.5h is added dropwise；
5) it is cooled to room temperature after reaction, reaction solution is cast to casting film-forming on cleaned glass plate, in going after drying
Soaking and water washing obtains product film for 24 hours in ionized water.
Embodiment 3
The preparation method of sulfonated polyether-ether-ketone and chitosan complex film, comprising the following steps:
1) stirring and dissolving in deionized water is added in Quaternary Ammonium Salt of Chitosan, obtains the chitosan aqueous solution that concentration is 2wt%；
2) tartaric acid is added in chitosan aqueous solution according to the ratio of tartaric acid and chitosan mass ratio 2:6.5, magnetic force
It is dispersed with stirring uniform mixed liquor A；
3) dry polyether-ether-ketone particle is added to dense sulphur for 0.13:1 according to the mass ratio of polyether-ether-ketone and the concentrated sulfuric acid
It is reacted in acid in 48 DEG C, is precipitated, is filtered, washed, be prepared into sulfonated polyether-ether-ketone.
Stirring and dissolving in dimethylformamide, the mass ratio of sulfonated polyether-ether-ketone and chitosan is added in sulfonated polyether-ether-ketone
For 10:7, three (2- methoxyphenyl) phosphines for accounting for sulfonated polyether-ether-ketone quality 3% are then added, are warming up to 80 DEG C of reaction 14h, instead
Mixed liquid B is cooled to room temperature to obtain after answering；
4) mixed liquor A is added under agitation in mixed liquid B, then heats to 70 DEG C of dropwise addition crosslinking agent epoxy chloropropionates
Alkane, the additional amount of epoxychloropropane are the 4% of chitosan mass, and insulation reaction 2h is added dropwise；
5) it is cooled to room temperature after reaction, reaction solution is cast to casting film-forming on cleaned glass plate, in going after drying
Soaking and water washing obtains product film for 24 hours in ionized water.
Embodiment 4
The preparation method of sulfonated polyether-ether-ketone and chitosan complex film, comprising the following steps:
1) stirring and dissolving in deionized water is added in carboxymethyl chitosan, obtains the chitosan aqueous solution that concentration is 5wt%；
2) tartaric acid is added in chitosan aqueous solution according to the ratio of tartaric acid and chitosan mass ratio 1.4:5, magnetic force
It is dispersed with stirring uniform mixed liquor A；
3) dry polyether-ether-ketone particle is added to dense sulphur for 0.11:1 according to the mass ratio of polyether-ether-ketone and the concentrated sulfuric acid
It is reacted in acid in 45 DEG C, is precipitated, is filtered, washed, be prepared into sulfonated polyether-ether-ketone.
By stirring and dissolving in sulfonated polyether-ether-ketone addition dimethyl sulfoxide, the mass ratio of sulfonated polyether-ether-ketone and chitosan is
Then 9:4 is added three (2- methoxyphenyl) phosphines for accounting for sulfonated polyether-ether-ketone quality 1.5%, is warming up to 70 DEG C of reaction 13h, instead
Mixed liquid B is cooled to room temperature to obtain after answering；
4) mixed liquor A is added under agitation in mixed liquid B, then heats to 55 DEG C of dropwise addition crosslinking agent epoxy chloropropionates
Alkane, the additional amount of epoxychloropropane are the 0.5% of chitosan mass, and insulation reaction 2h is added dropwise；
5) it is cooled to room temperature after reaction, reaction solution is cast to casting film-forming on cleaned glass plate, in going after drying
Soaking and water washing obtains product film for 24 hours in ionized water.
Claims (6)
1. the preparation method of sulfonated polyether-ether-ketone and chitosan complex film, which comprises the following steps:
1) stirring and dissolving in deionized water is added in water soluble chitosan, obtains the chitosan aqueous solution that concentration is 2-5wt%；
2) tartaric acid is added in chitosan aqueous solution according to the ratio of tartaric acid and chitosan mass ratio 1-2:5-7, magnetic force stirs
Mix the mixed liquor A that is uniformly dispersed to obtain；
3) stirring and dissolving in solvent is added in sulfonated polyether-ether-ketone, three (2- methoxyphenyl) phosphines is then added, are warming up to 60-80
DEG C reaction 12-15h, be cooled to room temperature to obtain mixed liquid B after reaction；
4) mixed liquor A is added under agitation in mixed liquid B, then heats to 55-75 DEG C of dropwise addition crosslinking agent, is added dropwise
Insulation reaction 1-2h；
5) it is cooled to room temperature after reaction, reaction solution is cast to casting film-forming on cleaned glass plate, in deionization after drying
Soaking and water washing obtains product film for 24 hours in water.
2. the preparation method of sulfonated polyether-ether-ketone as described in claim 1 and chitosan complex film, which is characterized in that the step
It is rapid 1) in water soluble chitosan be carboxymethyl chitosan or Quaternary Ammonium Salt of Chitosan.
3. the preparation method of sulfonated polyether-ether-ketone as described in claim 1 and chitosan complex film, which is characterized in that the step
It is rapid 3) in solvent be one of N-Methyl pyrrolidone, dimethyl sulfoxide, dimethylformamide, dimethyl acetamide.
4. the preparation method of sulfonated polyether-ether-ketone as described in claim 1 and chitosan complex film, which is characterized in that the step
It is rapid 3) in the mass ratio of sulfonated polyether-ether-ketone and chitosan be 5-10:3-7, the additional amount of three (2- methoxyphenyl) phosphines is sulfonation
The 1-3% of polyether-ether-ketone quality.
5. the preparation method of sulfonated polyether-ether-ketone as described in claim 1 and chitosan complex film, which is characterized in that the step
It is rapid 3) in sulfonated polyether-ether-ketone preparation step it is as follows: according to the mass ratio of polyether-ether-ketone and the concentrated sulfuric acid be 0.11-0.15:1 will do
Dry polyether-ether-ketone particle is added in the concentrated sulfuric acid to react in 45~50 DEG C, is precipitated, is filtered, washed, obtains sulfonated polyether-ether-ketone.
6. the preparation method of sulfonated polyether-ether-ketone as described in claim 1 and chitosan complex film, which is characterized in that the step
It is rapid 4) in crosslinking agent be epoxychloropropane, the additional amount of epoxychloropropane is the 0.5-4% of chitosan mass.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1569024A (en) * | 2004-04-30 | 2005-01-26 | 天津大学 | Novel post-operation antiadhesive materials and its preparation method |
| CN104874300A (en) * | 2015-04-30 | 2015-09-02 | 天津大学 | Chitosan-sulfonated carbon molecular sieve hybrid composite membrane and preparation and application |
| US20180272274A1 (en) * | 2017-03-23 | 2018-09-27 | Korea Research Institute Of Chemical Technology | Separation membrane for olefin separation and olefin separation method using the same |
-
2019
- 2019-03-18 CN CN201910203588.3A patent/CN109880287A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1569024A (en) * | 2004-04-30 | 2005-01-26 | 天津大学 | Novel post-operation antiadhesive materials and its preparation method |
| CN104874300A (en) * | 2015-04-30 | 2015-09-02 | 天津大学 | Chitosan-sulfonated carbon molecular sieve hybrid composite membrane and preparation and application |
| US20180272274A1 (en) * | 2017-03-23 | 2018-09-27 | Korea Research Institute Of Chemical Technology | Separation membrane for olefin separation and olefin separation method using the same |
Non-Patent Citations (1)
| Title |
|---|
| 薛艳红 等: ""磺化聚醚醚酮与壳聚糖共混制备直接甲醇燃料电池用质子交换膜"", 《高分子学报》 * |
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