CN109280199A - A kind of crystal type anion-exchange membrane and preparation method with micro phase separation structure - Google Patents
A kind of crystal type anion-exchange membrane and preparation method with micro phase separation structure Download PDFInfo
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- CN109280199A CN109280199A CN201811036430.3A CN201811036430A CN109280199A CN 109280199 A CN109280199 A CN 109280199A CN 201811036430 A CN201811036430 A CN 201811036430A CN 109280199 A CN109280199 A CN 109280199A
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- 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
- C08J5/2287—After-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
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- 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
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
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- 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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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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
Abstract
The present invention relates to a kind of crystal type anion-exchange membrane and preparation method with micro phase separation structure, it using SBS elastomer as starting material, is reacted by normal pressure catalytic hydrogenation, crystal type SEBS is made, halogen group is then introduced on phenyl ring, prepares functional polyolefin hydrocarbon copolymer；It is film-made after being configured to homogeneous solution using solution coating technique, and gained membrane material introduces hydroxide ion through quaternization and alkalization, and high performance anion-exchange membrane is made.The anion-exchange membrane has the advantages that and 1) is hydrogenated by SBS elastomer, converts Polyethylene Chain for its polybutadiene chain, meanwhile, retain its polystyrene block, so that the advantage of thermoplastic elastomer and polyolefin is combined together.2) molecular weight of polyolefin block can be greatly improved after star-shaped sbs hydrogenation under the premise of guaranteeing good solubility, the high molecular polyolefine copolymer anion-exchange membrane with excellent filming performance is obtained, the good processing performance of system, mechanical strength and dimensional stability are assigned.
Description
Technical field
The present invention relates to a kind of crystal type anion-exchange membrane and preparation method with micro phase separation structure, belong to yin from
Proton exchange film fuel cell field.
Background technique
In recent years, the energy and environmental crisis that the whole world is on the rise propose higher want to the development of clean energy technology
It asks, wherein anion-exchange membrane fuel cells (AEMFCs) are by electrode reaction is high-efficient, fuel losses rate is low, using non-expensive
Metallic catalyst, fuel range of choice be wide, many advantages such as at low cost and present wide application prospect.As AEMFCs's
Critical component, anion-exchange membrane (AEMs) are both the separator and OH of oxidant and fuel-Conductor, in highly basic
Property under the conditions of chemistry and mechanical stability and ion transmission performance directly determine service life and the performance of AEMFCs.By mesh
Before, various aromatic polymers and aliphatic polymer are used for anion-exchange membrane field in succession, such as polyphenylene oxide, polyfluorene, gather
Aryl ether sulfone, poly(aryl ether ketone), polystyrene, thermoplastic elastomer, polyolefin and other polymers.
In all kinds of polymeric systems, polystyrene-b- (ethylene-co- butylene)-b- polystyrene (SEBS) class thermoplastic
Elastomer is concerned due to abundant raw material, cheap, good micro phase separation structure and chemical stability.They
Polystyrene (PS) block and thermodynamically incompatible intermediate soft segment establish by Covalent bonding together and are responsible for its mechanical property
Physical network (D.Wang, S.Fujinami, H.Liu, K. Nakajima, T.Nishi, Macromolecules, 43,
9049；X.Han,J.Hu,H.L.Liu,Y.Hu, Langmuir,22,3428.).When polymer backbone of the SEBS as AEMs
When, PS block is needed through chemical modification (i.e. chloromethylation and quaternization reaction) (QH Zeng, QL Liu, I
Broadwell,AM Zhu,Y Xiong,XP Tu,J.Membr.Sci.2010,349,237；R Vinodh,A Ilakkiya,S
Elamathi,D Sangeetha,Mater.Sci.Eng.B 2010,167,43；L Sun,J Guo,J Zhou,Q Xu,D
Chu,R Chen,J.Power Sources 2012,202,70；J Zhou,J Guo,D Chu,R Chen, J.Power
Sources 2012,219,272.) transmission channel of hydroxide ion is provided.Theoretically, high performance SEBS is prepared
Base AEMs needs PS functionalization degree as high as possible.But excessively high functionalization degree can seriously increase the water absorption rate of AEMs
(WU) and swellbility (SR), so will lead to the serious destruction of its mechanical property.Moreover business SEBS copolymer initial design
Purpose is used as elastomer, and in-between soft segment does not contribute mechanical stability, it is difficult to meet the requirement of AEMs.
Therefore, the quasi- atmospheric hydrogenation method that passes through of the present invention is to high Isosorbide-5-Nitrae-butadiene unit content polystyrene-b- polybutadiene-b-
Polystyrene (SBS) copolymer carries out hydrogenating reduction, the advantage of thermoplastic elastomer and polyolefin is combined together, invention has
The crystal type anion-exchange membrane of micro phase separation structure.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of crystal type anion friendship with micro phase separation structure
Film and preparation method are changed, is mainly comprised the processes of firstly, by normal pressure catalytic hydrogenation, crystal type is made using SBS as starting material
SEBS；Secondly, introducing halogen-containing functional group on phenyl ring by functional modification, preparation functionalization crystallizes SEBS；Most
Afterwards, hydroxide ion is introduced by quaternization and alkalization, prepares high-performance crystal type anion-exchange membrane.
Technical solution of the present invention:
A kind of crystal type anion-exchange membrane with micro phase separation structure, it is characterised in that main chain is mainly by polystyrene
Block and polyethylene block composition, the two form micro phase separation structure, wherein polystyrene block loading functional group, polyethylene
Block provides good mechanical performance by forming crystalline texture for system.The membrane structure formula are as follows:
A kind of preparation method of the crystal type anion-exchange membrane with micro phase separation structure, it is characterised in that packet
Include following steps:
Step 1: under atmosphere of inert gases, SBS being dissolved in organic solvent, after mixing evenly, is added 1~3 times
The Tri-n-Propylamine of the p-methyl benzenesulfonic acid of double bond mole and 0.5~2 times of p-methyl benzenesulfonic acid mole in SBS, and will be warm
Degree rises to 135~140 DEG C and is heated to reflux 4~8h.After reaction solution is cooling, it is poured into the ethanol solution of hydrochloric acid acidification and stirs
Overnight, products therefrom successively uses ethyl alcohol and deionized water repeated flushing after filtering, and is dried in vacuo 12h at 50 DEG C.
Step 2: in organic solvent by products therefrom dissolution in step 1, after mixing evenly, it is added 0.5~2 times
The functionalized reagent of the catalyst of styrene units mole and 8~12 times of catalyst moles in polymer, 50~60
DEG C reaction 6~12h after, pour into ethyl alcohol and precipitate to obtain crude product, precipitated in ethyl alcohol again after being dissolved with organic solvent
Required product, and 12h is dried in vacuo at 35 DEG C.
Step 3: in organic solvent after completely dissolution by products therefrom in step 2, using solution casting method film,
After standing for 24 hours at 70~90 DEG C off, film is taken to be placed in 80 DEG C of vacuum drying ovens being dried overnight to remove remaining solvent.Then will
The membrane sample immerses in ammonium reagent and alkalizing agent each 48h successively to get the crystal type anion with micro phase separation structure
Exchange membrane.
The present invention is Step 1: organic solvent described in step 3 is toluene, dimethylbenzene, paraxylene, meta-xylene, neighbour
Dimethylbenzene, organic solvent described in step 2 are tetrahydrofuran, chloroform, toluene, dimethylbenzene, chlorobenzene, dichloro-benzenes, N, N- dimethyl
Formamide or carbon tetrachloride.The catalyst is anhydrous stannic chloride, anhydrous zinc chloride, anhydrous titanium tetrachloride；The functionalization
Reagent is chloromethyl methyl ether, chloromethyl ether, Isosorbide-5-Nitrae-dichloro methyl butyl ether；The ammonium reagent is trimethylamine or triethylamine；
The alkalizing agent is NaOH or KOH.
The invention has the advantages that: one, it by SBS elastomer is hydrogenated, is converted its polybutadiene strand to poly-
Ethylene chain, meanwhile, retain its polystyrene block, so that the advantage of thermoplastic elastomer and polyolefin is combined together.Two, star
Type SBS hydrogenated products can greatly improve the molecular weight of polyolefin block under the premise of guaranteeing good solubility, be had
It is strong to assign the good processing performance of system, machinery for the high molecular polyolefine copolymer anion-exchange membrane of excellent filming performance
Degree and dimensional stability.
Detailed description of the invention
Fig. 1 is SBS (A), Hydrogenated SBS (B), Hydrogenated SBS chloromethyl functionalization (C) and prepared anion-exchange membrane (D)
Infrared spectrum.
Fig. 2 is the change curve of anion-exchange membrane ionic conductivity and temperature.
Specific embodiment
It is right with reference to embodiments in order to show the purpose of the present invention, technical solution and advantage more clearly from
The present invention is further described.Following embodiment is merely illustrative, and is not limited the scope of the invention in any way.
Embodiment 1:
Under atmosphere of inert gases, 230mL toluene is added in the 500mL three neck round bottom flask containing 4g type SBS,
After SBS is completely dissolved, 22g p-methyl benzenesulfonic acid (double bond mole in 2 times of SBS) is successively added thereto and 17g tri- is just
Propylamine (1 times of p-methyl benzenesulfonic acid mole), and be warming up to 135 DEG C and be heated to reflux 4h.After reaction solution is cooling, fallen
Enter and be stirred overnight in the ethanol solution containing 10% hydrochloric acid, products therefrom is successively rushed with ethyl alcohol and deionized water repeatedly after filtering
It washes, until filtrate is in neutrality, and places it at 50 DEG C and be dried in vacuo 12h to get crystal type SEBS.
2g crystal type SEBS is added in 60mL chlorobenzene and is stirred evenly at 70 DEG C, is added 1.13mL's at 30 DEG C later
6.2g chloromethyl methyl ether is slowly added dropwise after 30 minutes in anhydrous stannic chloride (1 times of styrene units mole), stirring thereto
(8 times of catalyst moles), and 6h is reacted at 60 DEG C.Reaction solution is poured into ethyl alcohol and precipitates to obtain crude product, then again
Tetrahydrofuran is added to make it dissolve, with ethanol precipitation and repeated flushing is dried in vacuo 12h at 35 DEG C after several times.
The above-mentioned product of 0.3g is weighed, is cast on polyfluortetraethylene plate after being dissolved at 100 DEG C with 10ml dimethylbenzene,
It is stood for 24 hours at 90 DEG C；After film taken off be put into 80 DEG C of vacuum drying ovens dry 12h to remove residual solvent.Later according to
It is secondary that the membrane sample is soaked in 30wt% trimethylamine aqueous solution and 1M NaOH solution 48h to get anion-exchange membrane.
Fig. 1 is the infrared spectrogram of each stage polymer film in the present embodiment.It can be seen from the figure that 1640cm-1
C=C stretching vibration absworption peak and 911cm-1And 967cm-1Corresponding to trans- 1,2 and the absorption peak of Isosorbide-5-Nitrae structure, hydrogenating
It disappears after reaction, illustrates that SBS is successfully hydrogenated.After chloromethylation occurs for Hydrogenated SBS, product is in 1265cm-1Out
The characteristic absorption peak for having showed chloro-methyl group illustrates that chloromethyl has been successfully introduced.And in subsequent quaternary ammoniated and quaternization,
1265cm-1Place's absorption peak fades away, at the same time, 1640cm-1And 3400cm-1Then occur corresponding respectively to the flexible vibration of C-N
Dynamic and OH-1Absorption peak, can prove chloromethyl succeeded it is quaternary ammoniated and alkalization.
The ion exchange capacity of anion-exchange membrane manufactured in the present embodiment is 0.97mmol/g.
As shown in Fig. 2, curve a is the ionic conductivity of film and the relation curve of temperature prepared by the present embodiment, can see
Ionic conductivity is 27.86mS/cm when to 30 DEG C.
Embodiment 2:
Under atmosphere of inert gases, 230mL dimethylbenzene is added to the 500mL three neck round bottom flask containing 4g type SBS
In, after SBS is completely dissolved, 11g p-methyl benzenesulfonic acid (double bond mole in 1 times of SBS) and 8.5g are successively added thereto
Tri-n-Propylamine (1 times of p-methyl benzenesulfonic acid mole), and be warming up to 136 DEG C and be heated to reflux 5h.After reaction solution is cooling, by it
It pours into the ethanol solution containing 10% hydrochloric acid and is stirred overnight, products therefrom is successively rushed with ethyl alcohol and deionized water repeatedly after filtering
It washes, until filtrate is in neutrality, and places it at 50 DEG C and be dried in vacuo 12h to get crystal type SEBS.
2g crystal type SEBS is added in 60mL dichloro-benzenes and is stirred evenly at 70 DEG C, 0.86mL is added at 30 DEG C later
Anhydrous stannic chloride (0.5 times of styrene units mole), stirring 30 minutes after 12.4g Isosorbide-5-Nitrae-is slowly added dropwise thereto
Dichloro methyl butyl ether (9 times of catalyst moles), and 8h is reacted at 55 DEG C.Reaction solution, which is poured into ethyl alcohol, to be precipitated slightly
Chloroform is then added again and makes it dissolve for product, and with ethanol precipitation and repeated flushing is dried in vacuo 12h at 35 DEG C after several times.
The above-mentioned product of 0.3g is weighed, is cast on polyfluortetraethylene plate after being dissolved at 90 DEG C with 10ml toluene,
It is stood for 24 hours at 80 DEG C；After film taken off be put into 80 DEG C of vacuum drying ovens dry 12h to remove residual solvent.Later successively
The membrane sample is soaked in 30wt% trimethylamine aqueous solution and 1M NaOH solution 48h to get anion-exchange membrane.
The ion exchange capacity of anion-exchange membrane manufactured in the present embodiment is 1.39mmol/g.
As shown in Fig. 2, curve b is the ionic conductivity of film and the relation curve of temperature prepared by the present embodiment, can see
Ionic conductivity is 27.46mS/cm when to 30 DEG C.
Embodiment 3:
Under atmosphere of inert gases, 230mL paraxylene is added to tri- mouthfuls of round bottoms of the 500mL containing 4g type SBS and is burnt
Bottle in, after SBS is completely dissolved, successively thereto be added 33g p-methyl benzenesulfonic acid (double bond mole in 3 times of SBS) and
13g Tri-n-Propylamine (0.5 times of p-methyl benzenesulfonic acid mole), and be warming up to 137 DEG C and be heated to reflux 6h.It is cooling to reaction solution
Afterwards, it is poured into the ethanol solution containing 10% hydrochloric acid and is stirred overnight, products therefrom successively uses ethyl alcohol and deionization after filtering
Water repeated flushing until filtrate is in neutrality, and places it at 50 DEG C and is dried in vacuo 12h to get crystal type SEBS.
2g crystal type SEBS is added in 60mL carbon tetrachloride and is stirred evenly at 60 DEG C, is added at 30 DEG C later
13.2g chlorine is slowly added dropwise after 30 minutes in the anhydrous titanium tetrachloride (2 times of styrene units moles) of 1.53mL, stirring thereto
Methyl ether (10 times of catalyst moles), and 12h is reacted at 50 DEG C.Reaction solution is poured into ethyl alcohol and precipitates slightly to produce
Toluene is then added again and makes it dissolve for object, and with ethanol precipitation and repeated flushing is dried in vacuo 12h at 35 DEG C after several times.
The above-mentioned product of 0.3g is weighed, is cast in polyfluortetraethylene plate after being dissolved at 80 DEG C with 10ml meta-xylene
On, it is stood for 24 hours at 70 DEG C；After film taken off be put into 80 DEG C of vacuum drying ovens dry 12h to remove residual solvent.It
The membrane sample is successively soaked in 30wt% triethylamine aqueous solution and 1M KOH solution 48h to get anion-exchange membrane afterwards.
The ion exchange capacity of anion-exchange membrane manufactured in the present embodiment is 1.34mmol/g.
As shown in Fig. 2, curve c is the ionic conductivity of film and the relation curve of temperature prepared by the present embodiment, can see
Ionic conductivity is 30.81mS/cm when to 30 DEG C.
Embodiment 4:
Under atmosphere of inert gases, 230mL ortho-xylene is added to tri- mouthfuls of round bottoms of the 500mL containing 4g star-shaped sbs and is burnt
Bottle in, after SBS is completely dissolved, successively thereto be added 22g p-methyl benzenesulfonic acid (double bond mole in 2 times of SBS) and
34g Tri-n-Propylamine (2 times of p-methyl benzenesulfonic acid moles), and be warming up to 138 DEG C and be heated to reflux 7h.After reaction solution is cooling,
It is poured into the ethanol solution containing 10% hydrochloric acid and is stirred overnight, products therefrom successively uses ethyl alcohol and deionized water anti-after filtering
It is multiple to rinse, until filtrate is in neutrality, and places it at 50 DEG C and be dried in vacuo 12h to get crystal type SEBS.
2g crystal type SEBS is added in 60mL dichloro-benzenes and is stirred evenly at 70 DEG C, 1.36mL is added at 30 DEG C later
Anhydrous titanium tetrachloride (1.5 times of styrene units moles), stirring 30 minutes after 25.5g Isosorbide-5-Nitrae-is slowly added dropwise thereto
Dichloro methyl butyl ether (11 times of catalyst moles), and 7h is reacted at 60 DEG C.Reaction solution is poured into ethyl alcohol and is precipitated
Dimethylbenzene is then added again and makes it dissolve for crude product, and with ethanol precipitation and repeated flushing is dried in vacuo at 35 DEG C after several times
12h。
The above-mentioned product of 0.3g is weighed, is cast in polyfluortetraethylene plate after being dissolved at 90 DEG C with 10ml paraxylene
On, it is stood for 24 hours at 80 DEG C；After film taken off be put into 80 DEG C of vacuum drying ovens dry 12h to remove residual solvent.It
The membrane sample is successively soaked in 30wt% trimethylamine aqueous solution and 1M KOH solution 48h to get anion-exchange membrane afterwards.
The ion exchange capacity of anion-exchange membrane manufactured in the present embodiment is 0.98mmol/g.
As shown in Fig. 2, curve d is the ionic conductivity of film and the relation curve of temperature prepared by the present embodiment, can see
Ionic conductivity is 23.57mS/cm when to 30 DEG C.
Embodiment 5:
Under atmosphere of inert gases, 230mL meta-xylene is added to tri- mouthfuls of round bottoms of the 500mL containing 4g star-shaped sbs and is burnt
Bottle in, after SBS is completely dissolved, successively thereto be added 17g p-methyl benzenesulfonic acid (double bond mole in 2 times of SBS) and
20g Tri-n-Propylamine (1.5 times of p-methyl benzenesulfonic acid moles), and be warming up to 140 DEG C and be heated to reflux 8h.It is cooling to reaction solution
Afterwards, it is poured into the ethanol solution containing 10% hydrochloric acid and is stirred overnight, products therefrom successively uses ethyl alcohol and deionization after filtering
Water repeated flushing until filtrate is in neutrality, and places it at 50 DEG C and is dried in vacuo 12h to get crystal type SEBS.
2g crystal type SEBS is added in 60mL carbon tetrachloride and is stirred evenly at 60 DEG C, is added at 30 DEG C later
33.6g chloromethane is slowly added dropwise after 30 minutes in the anhydrous zinc chloride (2 times of styrene units moles) of 1.63mL, stirring thereto
Base methyl ether (12 times of catalyst moles), and 10h is reacted at 55 DEG C.Reaction solution is poured into ethyl alcohol and precipitates to obtain crude product,
N,N-Dimethylformamide is then added again to make it dissolve, with ethanol precipitation and repeated flushing several times after at 35 DEG C vacuum it is dry
Dry 12h.
The above-mentioned product of 0.3g is weighed, is cast in polyfluortetraethylene plate after being dissolved at 90 DEG C with 10ml ortho-xylene
On, it is stood for 24 hours at 80 DEG C；After film taken off be put into 80 DEG C of vacuum drying ovens dry 12h to remove residual solvent.It
The membrane sample is successively soaked in 30wt% triethylamine aqueous solution and 1M NaOH solution 48h to get anion-exchange membrane afterwards.
The ion exchange capacity of anion-exchange membrane manufactured in the present embodiment is 1.69mmol/g.
As shown in Fig. 2, curve e is the ionic conductivity of film and the relation curve of temperature prepared by the present embodiment, can see
Ionic conductivity is 33.60mS/cm when to 30 DEG C.
Claims (9)
1. a kind of crystal type anion-exchange membrane with micro phase separation structure, which is characterized in that the crystal type anion
The main chain of exchange membrane is mainly made of polystyrene block and polyethylene block, and the two forms micro phase separation structure, wherein polyphenyl
Ethylene block loading functional group, polyethylene block provide good mechanical performance by forming crystalline texture for system；
The structural formula of the film are as follows:
Wherein: R is-CH3Or-CH2CH3。
2. a kind of preparation method of crystal type anion-exchange membrane with micro phase separation structure described in claim 1, special
Sign is following steps:
Step 1: under atmosphere of inert gases, SBS being dissolved in organic solvent, after mixing evenly, 1~3 times of SBS is added
The p-methyl benzenesulfonic acid of middle double bond mole and the Tri-n-Propylamine of 0.5~2 times of p-methyl benzenesulfonic acid mole, and by temperature liter
4~8h is heated to reflux to 135~140 DEG C；After reaction solution is cooling, it is poured into stirred in the ethanol solution of hydrochloric acid acidification
At night, products therefrom successively uses ethyl alcohol and deionized water repeated flushing after filtering, and carries out vacuum drying treatment；
Step 2: in organic solvent by products therefrom dissolution in step 1, after mixing evenly, 0.5~2 times of polymer is added
The catalyst of middle styrene units mole and the functionalized reagent of 8~12 times of catalyst moles react 6 at 50~60 DEG C
It after~12h, pours into ethyl alcohol and precipitates to obtain crude product, precipitate to obtain required production after being dissolved with organic solvent in ethyl alcohol again
Object, and 12h is dried in vacuo at 35 DEG C；
Step 3: in organic solvent after completely dissolution by products therefrom in step 2, using solution casting method film, 70~
After standing for 24 hours at 90 DEG C off, film is taken to and is placed it in vacuum drying oven removing remaining solvent；Then successively by the membrane sample
Each 48h is in immersion ammonium reagent and alkalizing agent to get the crystal type anion-exchange membrane with micro phase separation structure.
3. preparation method according to claim 2, which is characterized in that catalyst described in step 2 is anhydrous four chlorination
Tin, anhydrous zinc chloride, anhydrous titanium tetrachloride, the functionalized reagent are chloromethyl methyl ether, chloromethyl ether, Isosorbide-5-Nitrae-dichloromethane
Oxygroup butane.
4. preparation method according to claim 2 or 3, which is characterized in that ammonium reagent described in step 3 is trimethylamine
Or triethylamine, the alkalizing agent are NaOH or KOH.
5. preparation method according to claim 2 or 3, which is characterized in that Step 1: organic solvent described in step 3
For toluene, dimethylbenzene, paraxylene, meta-xylene, ortho-xylene, organic solvent described in step 2 be tetrahydrofuran, chloroform,
Toluene, dimethylbenzene, chlorobenzene, dichloro-benzenes, N,N-dimethylformamide or carbon tetrachloride.
6. the preparation method according to claim 4, which is characterized in that Step 1: organic solvent described in step 3 is
Toluene, dimethylbenzene, paraxylene, meta-xylene, ortho-xylene, organic solvent described in step 2 are tetrahydrofuran, chloroform, first
Benzene, dimethylbenzene, chlorobenzene, dichloro-benzenes, N,N-dimethylformamide or carbon tetrachloride.
7. according to preparation method described in Claims 2 or 3 or 6, which is characterized in that vacuum drying described in the step one
Treatment temperature is 50 DEG C, time 12h；Vacuum drying oven temperature in the step three is 80 DEG C.
8. the preparation method according to claim 4, which is characterized in that vacuum drying treatment temperature described in the step one
Degree is 50 DEG C, time 12h；Vacuum drying oven temperature in the step three is 80 DEG C.
9. preparation method according to claim 5, which is characterized in that vacuum drying treatment temperature described in the step one
Degree is 50 DEG C, time 12h；Vacuum drying oven temperature in the step three is 80 DEG C.
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| CN110739478B (en) * | 2019-11-07 | 2022-05-17 | 大连理工大学 | Preparation method of long-short side chain blended anion exchange membrane |
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