CN105733004A - Preparation method of full-interpenetrating-type quaternized chitosan anion exchange membrane - Google Patents
Preparation method of full-interpenetrating-type quaternized chitosan anion exchange membrane Download PDFInfo
- Publication number
- CN105733004A CN105733004A CN201610256583.3A CN201610256583A CN105733004A CN 105733004 A CN105733004 A CN 105733004A CN 201610256583 A CN201610256583 A CN 201610256583A CN 105733004 A CN105733004 A CN 105733004A
- Authority
- CN
- China
- Prior art keywords
- membrane
- anion exchange
- trimethyl chitosan
- preparation
- chitosan chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2212—Natural macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- H—ELECTRICITY
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
-
- H—ELECTRICITY
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a preparation method of a full-interpenetrating-type quaternized chitosan anion exchange membrane. The preparation method comprises the steps that quaternized chitosan (QCS) with a macromolecular skeleton structure is completely dissolved to serve as membrane-based liquid by taking an acetic acid solution as a solvent; natural macromoleclar polymer cellulose with a polyhydroxy structure is uniformly doped into acetic acid membrane casting liquid of quaternized chitosan, and the two macromoleclar polymers are subjected to chemical crosslinking by taking glutaraldehyde as a cross-linking agent to obtain anion exchange membrane casting liquid with a full-interpenetrating network structure; the membrane casting liquid is cast into a membrane on a glass plate through a tape casting method, and the membrane which is dried to have the constant weight is immersed into a potassium hydroxide solution to prepare the hydroxyl ion-type anion exchange membrane. The anion membrane prepared through the method has the excellent alkali-resisting stability and the good mechanical property, and the conductivity of the membrane is effectively improved.
Description
Technical field
The invention belongs to field of fuel cell technology, relate to the film electrolyte technology of preparing of anion-exchange membrane fuel cells, the preparation method being specifically related to a kind of n-trimethyl chitosan chloride film with full inierpeneirating network structure.
Background technology
DMFC (DMFCs) not only has the feature of energy conversion efficiency height, environmental friendliness, zero-emission nitrogen, oxysulfide, and volume is little, simple in construction, and its fuel is prone to storage and transport, therefore suffers from the extensive concern of all circles.Wherein anion-exchange membrane fuel cells (AEMFCs), with non-precious metal for catalyst, cost is low, the benefit of higher fuel cell, therefore the relevant report of its research is also got more and more.As the core of AEMFCs, desirable anion exchange membrane must possess excellent alkali stability, and stronger mechanical performance is to guarantee that fuel cell can the operation of lasting stability.Natural polymers chitosan (CS) is carried out quaternised modified obtained by n-trimethyl chitosan chloride (QCS).It has semi-rigid macromolecular scaffold and excellent film forming ability, and the anion exchange membrane that quaternary ammonium group is formed as anionic electroconductive group is widely used.Regrettably, because that anion exchange membrane transmits in a fuel cell is OH-Ion, therefore it must use in alkaline environment, quaternary ammonium group also exists Hofmann degradation and nucleophilic substitution in alkaline environment, it is impossible to enough long-time stable exist in polymer backbone, so many researcheres get down to improves the problem that quaternary ammonium group is unstable.Being effectively improved the method that quaternary ammonium group is degraded at present is find other alkali resistant cationic electroconductive groups to replace quaternary ammonium group, but these non-quaternary ammonium cations conduction group is difficult to be grafted on chitosan skeleton.There is research to point out, by conduction group " locking " in the internal structure of film, quaternary ammonium group degraded can be slowed down by chemical crosslink technique.Existing research is pointed out, utilizing glutaraldehyde to make n-trimethyl chitosan chloride be internally formed half interpenetrating network structure as cross-linking agent, though slowing down the degradation rate of quaternary ammonium group, but its swellbility still has 87%, being immersed in 24h in 2MNaOH solution under room temperature, loss electrical conductivity reaches 7.5%.Its skeleton in high concentration alkali solution another starts to degrade, it is impossible to enough stable existences are in aqueous slkali.
Summary of the invention
The present invention provides a kind of method preparing full interpenetrating type n-trimethyl chitosan chloride anion exchange membrane, and prepared anion exchange membrane material has the alkali stability of excellence and excellent mechanical performance, can be used as the anion exchange membrane electrolyte of alkaline fuel cell.
The preparation method of full interpenetrating type n-trimethyl chitosan chloride anion exchange membrane, comprises the following steps that
(1) weighing 2g substitution value is 10%-30% n-trimethyl chitosan chloride powder, join in the flask of 2% (v/v) acetic acid solvent of 30mL, mechanical agitation is carried out under heating, after being completely dissolved to n-trimethyl chitosan chloride, add cellulose powder so that in anionic membrane, cellulosic weight/mass percentage composition is 25-50%, continue heated and stirred, until being completely dissolved, obtain casting solution；
(2) being added to casting solution by the glutaraldehyde solution that mass fraction is 2-5%, casting solution mass fraction shared by glutaraldehyde solution is 1%-5%, continues heated and stirred 5min, supersonic oscillations 10min, evacuation and centrifugal degassing；Then adopt the tape casting in the glass plate top casting film forming of level, taken off standby after film natural air drying.
(3) composite membrane prepared is immersed 24h in 0.1MKOH aqueous solution and carry out ion exchange, then composite membrane is fixed between two pieces of polyfluortetraethylene plates, be placed in 40 DEG C of drying in oven to film constant weight.
Anionic membrane prepared by the present invention has the alkaline resistance properties of excellence, by film immersion in 10MNaOH solution after 240h, conductivity variations is less, tend towards stability, show excellent alkali stability, meanwhile, after having the n-trimethyl chitosan chloride anion exchange film immersion deionized water 24h of full inierpeneirating network structure, up to 21% (see table 1), swellbility is minimum illustrates that the method can effectively improve the alkali stability of quaternary ammonium type anion exchange membrane.In sum, full IPN n-trimethyl chitosan chloride anionic membrane prepared by the present invention, compared with the composite membrane that existing fuel cell uses, have the advantage that
(1), in n-trimethyl chitosan chloride film after cross-linked cellulose, improve film stability in high concentration alkali solution.
(2) the full inierpeneirating network structure formed is by OH-" locking ", among micropore cave, promotes ion exchange capacity and the electrical conductivity of film.
(3) there are some researches show, full inierpeneirating network structure can make more to tamp closely inside anion exchange membrane, and process is simple, it is easy to control.
Accompanying drawing explanation
Fig. 1 is the preparation process figure of anionic membrane.
Fig. 2 is pure chistosan film, embodiment 1, embodiment 2, the infrared spectrogram of embodiment 3.
Fig. 3 is pure QCS film, embodiment 1, embodiment 2, embodiment 3 anionic membrane thermal stability determination result in N2 atmosphere.
Fig. 4 is pure QCS film, embodiment 1, embodiment 2, embodiment 3 anionic membrane conductivity variations situation at different temperatures.
Fig. 5 be embodiment 2 preparation anion exchange membrane room temperature under in 10MNaOH solution, impregnate ion exchange capacity situation of change after different time.
Fig. 6 is after impregnating different time in 10MNaOH solution under anion exchange membrane prepared by embodiment 2, conductivity values situation of change under 70 DEG C of conditions.
Table 1 is pure QCS film, embodiment 1, embodiment 2, embodiment 3, the anionic membrane of preparation swellbility at room temperature, moisture content, hot strength, elongation at break, the measurement result of ion exchange capacity.
Detailed description of the invention
The method further illustrating the present invention by the following examples.
Embodiment 1
(1) 2g substitution value 20 ± 1.8% n-trimethyl chitosan chloride powder is weighed, join in the flask of the acetic acid solution 30ml containing 2% (v/v), mechanical agitation is carried out heating in water bath 40 DEG C, after being completely dissolved to n-trimethyl chitosan chloride, adding cellulose powder 0.67g, making cellulose mass percent in the anionic membrane prepared is 25%, continues mechanical agitation, until being completely dissolved, obtain casting solution.
(2) joining in the middle of casting solution by the glutaraldehyde solution of mass fraction 2%, casting solution mass fraction shared by glutaraldehyde solution is 2%, fully reacts 5min, supersonic oscillations 10min, evacuation and centrifugal degassing.Then adopt the tape casting in the glass plate top casting film forming of level, taken off after film natural air drying.
(3) composite membrane is immersed 24h in 0.1MKOH aqueous solution and carries out ion exchange, then composite membrane is fixed between two pieces of polyfluortetraethylene plates, be placed in 40 DEG C of drying in oven to film constant weight.
Embodiment 2
(1) weighing 2.0g substitution value is 20 ± 1.8% n-trimethyl chitosan chloride powder, join in the flask of the acetic acid solution 30ml containing 2% (v/v), mechanical agitation is carried out heating in water bath 40 DEG C, after being completely dissolved to n-trimethyl chitosan chloride, adding cellulose powder 1.0g, making cellulose mass percent in the anionic membrane prepared is 33%, continues mechanical agitation, until being completely dissolved, obtain casting solution.
(2) joining in the middle of casting solution by the glutaraldehyde solution () of mass fraction 2%, casting solution quality shared by glutaraldehyde solution is 2%, fully reacts 5min, supersonic oscillations 10min, evacuation and centrifugal degassing.Then adopt the tape casting in the glass plate top casting film forming of level, taken off after film natural air drying.
(3) composite membrane is immersed 24h in 0.1MKOH aqueous solution and carries out ion exchange, then composite membrane is fixed between two pieces of polyfluortetraethylene plates, be placed in 40 DEG C of drying in oven to film constant weight.
Embodiment 3
(1) weighing 2.0g substitution value is 20 ± 1.8% n-trimethyl chitosan chloride powder, join in the flask of the acetic acid solution 30ml containing 2% (v/v), mechanical agitation is carried out heating in water bath 40 DEG C, after being completely dissolved to n-trimethyl chitosan chloride, adding cellulose powder 2.0g, making cellulose mass percent in the anionic membrane prepared is 50%, continues mechanical agitation, until being completely dissolved, obtain casting solution.
(2) joining in the middle of casting solution by the glutaraldehyde solution () of mass fraction 2%, casting solution quality shared by glutaraldehyde solution is 2%, fully reacts 5min, supersonic oscillations 10min, evacuation and centrifugal degassing.Then adopt the tape casting in the glass plate top casting film forming of level, taken off after film natural air drying.
(3) composite membrane is immersed 24h in 0.1MKOH aqueous solution and carries out ion exchange, then composite membrane is fixed between two pieces of polyfluortetraethylene plates, be placed in 40 DEG C of drying in oven to film constant weight.
Embodiment 4
(1) weighing 2.0g substitution value is 10 ± 2.5% n-trimethyl chitosan chloride powder, join in the flask of the acetic acid solution 30ml containing 2% (v/v), heating in water bath 40 DEG C carries out mechanical agitation, after being completely dissolved to n-trimethyl chitosan chloride, add cellulose powder 1.0g, continuing mechanical agitation, until being completely dissolved, obtaining casting solution.
(2) joining in the middle of casting solution by the glutaraldehyde solution of mass fraction 2%, casting solution mass fraction shared by glutaraldehyde solution is 2%, fully reacts 5min, ultrasonic wave concussion 10min, evacuation and centrifugal degassing.Then adopt the tape casting in the glass plate top casting film forming of level, taken off after natural air drying.
(3) composite membrane is immersed 24h in 0.1MKOH aqueous solution and carries out ion exchange, then composite membrane is fixed between two pieces of polyfluortetraethylene plates, be placed in 40 DEG C of drying in oven to film constant weight.
Embodiment 5
(1) weighing 2.0g substitution value is 30 ± 3.1% n-trimethyl chitosan chloride powder, join in the flask of the acetic acid solution 30ml containing 2% (v/v), heating in water bath 40 DEG C carries out mechanical agitation, after being completely dissolved to n-trimethyl chitosan chloride, add cellulose powder 1.0g, continuing mechanical agitation, until being completely dissolved, obtaining casting solution.
(2) joining in the middle of casting solution by the glutaraldehyde solution of mass fraction 2%, casting solution mass fraction shared by glutaraldehyde solution is 2%, fully reacts 5min, ultrasonic wave concussion 10min, evacuation and centrifugal degassing.Then adopt the tape casting in the glass plate top casting film forming of level, taken off after natural air drying.
(3) composite membrane is immersed 24h in 0.1MKOH aqueous solution and carries out ion exchange, then composite membrane is fixed between two pieces of polyfluortetraethylene plates, be placed in 40 DEG C of drying in oven to film constant weight.
Embodiment 6
(1) weighing 2.0g substitution value is 20 ± 1.8% n-trimethyl chitosan chloride powder, join in the flask of the acetic acid solution 30ml containing 2% (v/v), heating in water bath 40 DEG C carries out mechanical agitation, after being completely dissolved to n-trimethyl chitosan chloride, add cellulose powder 1.0g, continuing mechanical agitation, until being completely dissolved, obtaining casting solution.
(2) joining in the middle of casting solution by the glutaraldehyde solution of mass fraction 2%, casting solution mass fraction shared by glutaraldehyde solution is 1%, fully reacts 5min, ultrasonic wave concussion 10min, evacuation and centrifugal degassing.Then adopt the tape casting in the glass plate top casting film forming of level, taken off after natural air drying.
(3) composite membrane is immersed 24h in 0.1MKOH aqueous solution and carries out ion exchange, then composite membrane is fixed between two pieces of polyfluortetraethylene plates, be placed in 40 DEG C of drying in oven to film constant weight.
Embodiment 7
(1) weighing 2.0g substitution value is 20 ± 1.8% n-trimethyl chitosan chloride powder, join in the flask of the acetic acid solution 30ml containing 2% (v/v), heating in water bath 40 DEG C carries out mechanical agitation, after being completely dissolved to n-trimethyl chitosan chloride, add cellulose powder 1.0g, continuing mechanical agitation, until being completely dissolved, obtaining casting solution.
(2) joining in the middle of casting solution by the glutaraldehyde solution of mass fraction 3%, casting solution mass fraction shared by glutaraldehyde solution is 3%, fully reacts 5min, ultrasonic wave concussion 10min, evacuation and centrifugal degassing.Then adopt the tape casting in the glass plate top casting film forming of level, taken off after natural air drying.
(3) composite membrane is immersed 24h in 0.1MKOH aqueous solution and carries out ion exchange, then composite membrane is fixed between two pieces of polyfluortetraethylene plates, be placed in 40 DEG C of drying in oven to film constant weight.
Embodiment 8
(1) weighing 2.0g substitution value is 20 ± 1.8% n-trimethyl chitosan chloride powder, join in the flask of the acetic acid solution 30ml containing 2% (v/v), heating in water bath 40 DEG C carries out mechanical agitation, after being completely dissolved to n-trimethyl chitosan chloride, add cellulose powder 1.0g, continuing mechanical agitation, until being completely dissolved, obtaining casting solution.
(2) joining in the middle of casting solution by the glutaraldehyde solution of mass fraction 4%, casting solution mass fraction shared by glutaraldehyde solution is 4%, fully reacts 5min, ultrasonic wave concussion 10min, evacuation and centrifugal degassing.Then adopt the tape casting in the glass plate top casting film forming of level, taken off after natural air drying.
(3) composite membrane is immersed 24h in 0.1MKOH aqueous solution and carries out ion exchange, then composite membrane is fixed between two pieces of polyfluortetraethylene plates, be placed in 40 DEG C of drying in oven to film constant weight.
Embodiment 9
(1) weighing 2.0g substitution value is 20 ± 1.8% n-trimethyl chitosan chloride powder, join in the flask of the acetic acid solution 30ml containing 2% (v/v), heating in water bath 40 DEG C carries out mechanical agitation, after being completely dissolved to n-trimethyl chitosan chloride, add cellulose powder 1.0g, continuing mechanical agitation, until being completely dissolved, obtaining casting solution.
(2) joining in the middle of casting solution by the glutaraldehyde solution of mass fraction 5%, casting solution mass fraction shared by glutaraldehyde solution is 5%, fully reacts 5min, ultrasonic wave concussion 10min, evacuation and centrifugal degassing.Then adopt the tape casting in the glass plate top casting film forming of level, taken off after natural air drying.
(3) composite membrane is immersed 24h in 0.1MKOH aqueous solution and carries out ion exchange, then composite membrane is fixed between two pieces of polyfluortetraethylene plates, be placed in 40 DEG C of drying in oven to film constant weight.
Table 1
Claims (6)
1. the preparation method of a full interpenetrating type n-trimethyl chitosan chloride anion exchange membrane, it is characterised in that comprise the following steps that
Step (1), weigh 2g n-trimethyl chitosan chloride powder, join in the flask of acetic acid solvent of 30mL, mechanical agitation is carried out under heating, after being completely dissolved to n-trimethyl chitosan chloride, add cellulose powder so that in anionic membrane, cellulosic weight/mass percentage composition is 25-50%, continue heated and stirred, until being completely dissolved, obtain casting solution；
Step (2), adding glutaraldehyde solution in casting solution, casting solution mass fraction shared by glutaraldehyde solution is 1%-5%, continues heated and stirred, supersonic oscillations, evacuation and centrifugal degassing；Then adopt the tape casting in the glass plate top casting film forming of level, taken off standby after film natural air drying；
Step (3), the composite membrane prepared is immersed in KOH aqueous solution and carry out ion exchange, then composite membrane is fixed between two pieces of polyfluortetraethylene plates, dry to film constant weight.
2. the preparation method of a kind of full interpenetrating type n-trimethyl chitosan chloride anion exchange membrane according to claim 1, it is characterised in that in described step (1), n-trimethyl chitosan chloride powder substitution value is 10%-30%.
3. the preparation method of a kind of full interpenetrating type n-trimethyl chitosan chloride anion exchange membrane according to claim 1, it is characterised in that in described step (1), acetic acid solvent is 2% (v/v) acetic acid solvent.
4. the preparation method of a kind of full interpenetrating type n-trimethyl chitosan chloride anion exchange membrane according to claim 1, it is characterised in that in described step (2), the mass fraction of glutaraldehyde solution is 2-5%.
5. the preparation method of a kind of full interpenetrating type n-trimethyl chitosan chloride anion exchange membrane according to claim 1, it is characterised in that in described step (2), stirs 5min, supersonic oscillations 10min.
6. the preparation method of a kind of full interpenetrating type n-trimethyl chitosan chloride anion exchange membrane according to claim 1, it is characterised in that in described step (3), immerses the composite membrane prepared 24h in 0.1MKOH aqueous solution and carries out ion exchange, be placed in 40oC drying in oven is to film constant weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610256583.3A CN105733004B (en) | 2016-04-21 | 2016-04-21 | A kind of preparation method of full interpenetrating type n-trimethyl chitosan chloride anion-exchange membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610256583.3A CN105733004B (en) | 2016-04-21 | 2016-04-21 | A kind of preparation method of full interpenetrating type n-trimethyl chitosan chloride anion-exchange membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105733004A true CN105733004A (en) | 2016-07-06 |
| CN105733004B CN105733004B (en) | 2018-12-25 |
Family
ID=56255985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610256583.3A Expired - Fee Related CN105733004B (en) | 2016-04-21 | 2016-04-21 | A kind of preparation method of full interpenetrating type n-trimethyl chitosan chloride anion-exchange membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105733004B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106374125A (en) * | 2016-09-07 | 2017-02-01 | 辽宁石油化工大学 | Preparation method for full interpenetration type anion exchange membrane containing crosslinked guanidine molecules |
| CN106784949A (en) * | 2016-12-08 | 2017-05-31 | 辽宁石油化工大学 | A kind of preparation method of the full interpenetrating type anion-exchange membranes of crosslinking QCS CM Guanidine |
| CN110433673A (en) * | 2019-07-08 | 2019-11-12 | 淮阴师范学院 | A kind of quaternary ammonium salt functionalization polysulfones-nano-attapulgite stone hybrid anion exchange membrane and preparation method thereof |
| CN113801353A (en) * | 2021-09-26 | 2021-12-17 | 辽宁石油化工大学 | Preparation method of quaternized chitosan-ethyl silicate organic/inorganic hybrid membrane |
| JP2023515491A (en) * | 2020-02-20 | 2023-04-13 | 漢陽大学校エリカ産学協力団 | Composite fiber, solid electrolyte containing the same, and metal-air battery containing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079818B (en) * | 2010-12-07 | 2012-11-21 | 天津工业大学 | Electroactive polymer material and preparation method thereof |
| CN103554526B (en) * | 2013-10-18 | 2015-03-04 | 辽宁石油化工大学 | Double-quaternary ammonium positive ion molecule introduced anion-exchange membrane and preparation method thereof |
| CN105085959B (en) * | 2015-09-17 | 2018-03-09 | 辽宁石油化工大学 | A kind of preparation method of the anionic membrane of introducing N alkyl double-core morpholine cations |
-
2016
- 2016-04-21 CN CN201610256583.3A patent/CN105733004B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106374125A (en) * | 2016-09-07 | 2017-02-01 | 辽宁石油化工大学 | Preparation method for full interpenetration type anion exchange membrane containing crosslinked guanidine molecules |
| CN106784949A (en) * | 2016-12-08 | 2017-05-31 | 辽宁石油化工大学 | A kind of preparation method of the full interpenetrating type anion-exchange membranes of crosslinking QCS CM Guanidine |
| CN110433673A (en) * | 2019-07-08 | 2019-11-12 | 淮阴师范学院 | A kind of quaternary ammonium salt functionalization polysulfones-nano-attapulgite stone hybrid anion exchange membrane and preparation method thereof |
| JP2023515491A (en) * | 2020-02-20 | 2023-04-13 | 漢陽大学校エリカ産学協力団 | Composite fiber, solid electrolyte containing the same, and metal-air battery containing the same |
| JP7448998B2 (en) | 2020-02-20 | 2024-03-13 | 漢陽大学校エリカ産学協力団 | Composite fiber, solid electrolyte containing the same, and metal-air battery containing the same |
| CN113801353A (en) * | 2021-09-26 | 2021-12-17 | 辽宁石油化工大学 | Preparation method of quaternized chitosan-ethyl silicate organic/inorganic hybrid membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105733004B (en) | 2018-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105733004A (en) | Preparation method of full-interpenetrating-type quaternized chitosan anion exchange membrane | |
| Yang et al. | Preparation and characterization of poly (vinyl alcohol)/sodium alginate blended membrane for alkaline solid polymer electrolytes membrane | |
| CN101003637B (en) | Polymer electrolyte membrane, method of preparing the same and fuel cell employing the same | |
| CN109390617B (en) | Cross-linked polybenzimidazole basic anion exchange membrane and preparation and application thereof | |
| Zarrin et al. | High durable PEK-based anion exchange membrane for elevated temperature alkaline fuel cells | |
| Qiu et al. | Alkaline imidazolium-and quaternary ammonium-functionalized anion exchange membranes for alkaline fuel cell applications | |
| Meenakshi et al. | Chitosan‐polyvinyl alcohol‐sulfonated polyethersulfone mixed‐matrix membranes as methanol‐barrier electrolytes for DMFCs | |
| CN103521276B (en) | A kind of carbon nano tube-doped type alkaline negative ion exchange composite film and its preparation method and application | |
| Liu et al. | Novel crosslinked alkaline exchange membranes based on poly (phthalazinone ether ketone) for anion exchange membrane fuel cell applications | |
| Yang et al. | Formation and investigation of dual cross-linked high temperature proton exchange membranes based on vinylimidazolium-functionalized poly (2, 6-dimethyl-1, 4-phenylene oxide) and polystyrene | |
| CN102544547A (en) | Alkaline negative ion exchange composite film with alkali stability and preparation and application thereof | |
| CN106750441A (en) | A kind of poly- triazole ionic liquid of cross-linking type/polybenzimidazoles high temperature proton exchange film and preparation method thereof | |
| Xu et al. | Cross-linked anion exchange membranes with flexible, long-chain, bis-imidazolium cation cross-linker | |
| Jensen et al. | A stability study of alkali doped PBI membranes for alkaline electrolyzer cells | |
| Si et al. | Phosphoric acid‐doped imidazolium ionomers with enhanced stability for anhydrous proton‐exchange membrane applications | |
| CN115594807A (en) | Preparation method and application of hole ether crosslinking type anion exchange membrane based on polyarylene piperidine copolymer | |
| CN108164724B (en) | Aromatic dihydric phenol cross-linked polyaryl ether type anion exchange membrane and preparation method thereof | |
| Liu et al. | Preparation and investigation of 1-(3-aminopropyl) imidazole functionalized polyvinyl chloride/poly (ether ketone cardo) membranes for HT-PEMFCs | |
| Zhang et al. | Multi‐cation side‐chain‐type containing piperidinium group poly (2, 6‐dimethyl‐1, 4‐phenylene oxide) alkaline anion exchange membranes | |
| CN101853947B (en) | Compound crosslinking alkaline polymer film for fuel cell, preparation method and application | |
| CN102093585A (en) | Crosslinked heterocyclic polyarylether alkaline electrolyte membrane and preparation method thereof | |
| CN106784949A (en) | A kind of preparation method of the full interpenetrating type anion-exchange membranes of crosslinking QCS CM Guanidine | |
| CN107834089A (en) | A kind of high temperature proton exchange film available for membrane cell and its preparation method and application | |
| Cao et al. | Biomass-based anion exchange membranes using poly (ionic liquid) filled bacterial cellulose with superior ionic conductivity and significantly improved strength | |
| CN108075161A (en) | A kind of preparation method of N1- long chain alkanes substitution -4,5- methylimidazole type alkaline anion-exchange membranes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181225 |