CN105924587B - A kind of cladodification type side chain polymer anion-exchange membrane and preparation method thereof - Google Patents
A kind of cladodification type side chain polymer anion-exchange membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of cladodification type polymer anion-exchange membranes and preparation method thereof.The preparation of membrane material is based on using chloromethyl polysulphone as macromole evocating agent, and p-chloromethyl styrene is monomer, is reacted using ATRP, and a series of polymer containing cladodification type side-chain structure have been synthesized.It is abundant using its and have higher chemical reactivity end moieties, the low high conductivity alkaline anion-exchange membrane of chloromethylation degree can be prepared by post-processing；In addition, passing through the cladodification degree of modulation side chain, different degrees of microphase-separated can be formed in film, reaches and takes into account anion exchange membrane conductivity-stability target.Anionic membrane adjustability of structure prepared by the present invention is strong, and the conductivity of film is higher, preferable from anti-swelling, is of great significance for the research of the conductivity and stability of balance film.
Description
Technical field
The invention belongs to fuel cell field of membrane material, be related to a kind of cladodification type side chain polymer anion-exchange membrane and its
Preparation method.
Background technique
With the continuous development of global industry, the mankind constantly increase energy demand, depend on conventional fossil fuel for a long time
The problems such as energy resource supply form of burning causes a series of environmental pollution, energy shortage.And fuel cell technology is then benefit
The chemical energy being stored in fuel is changed into electric energy with electrochemical reaction, has been obtained much as a kind of new energy source technology
Concern.Wherein alkaline anion-exchange membrane fuel cell (AAEMFC), since its battery hydrogen reduction overpotential is low, electrode reaction is dynamic
Mechanics is fast, and can be used base metal as catalyst, without carbonate crystallization, fuel permeability be low etc., advantages are ground as numerous scholars
The hot spot studied carefully.
Critical component one of of the anion-exchange membrane (AEM) as fuel cell plays barrier anode and cathode combustion in the battery
The effect of material directly contacted and conduct hydroxide ion, its performance directly affect performance and the service life of battery.Alkali at present
In property anion-exchange membrane fuel cells commercialization process, AEM is primarily present alkaline stability difference and conductivity low two urgently solves greatly
Certainly the problem of.
At present according to reports, the strategy for improving conductivity or raising stability is mainly: (1) increase number of functional groups,
Improve the conductivity of film.Amaranadh Jasti et al. is poly- (sub- by nucleophilic displacement of fluorine-polycondensation reaction synthetic polyamine base block
Aryl ether) (AMPEs) structure anion-exchange membrane, as (DCM=90%) IEC=2.69meq g-1, OH at 30 DEG C-Conductivity
For 107mS cm-1, at 80 DEG C, conductivity is 150mS cm-1[Amaranadh Jasti,et al.,Journal of Power
Sources.2014,267,714-722.]；In the backbone structure that E.Annika Weiber project is combined into, have on single aromatic ring
The polysulfones block polymer of four imidazoles (quaternary amine) cation groups, the film of preparation impregnate 7 days in 40 DEG C, 1M NaOH solution,
There is degradation [E.Annika Weiber, et al., Journal of Membrane Science in about 80% quaternary ammonium functional group
2015,481,164-171.].It is primarily due to the enrichment of cation group, causing main chain, nearby alkali concentration is excessive, hydrogen-oxygen
A possibility that radical ion attack Cationic functional groups, increases, so there is alkaline stability deficiency.(2) introducing crosslinked knot
Structure improves the stability of film.A degree of crosslinking can effectively reduce the swellbility and water absorption rate of alkaline anion-exchange membrane, but
Be polymeric inner covalent cross-linking often using sacrifice ion radical exchange site as cost, cause the reduction of conductivity.Wu Xuemei
Et al. using bifunctional cyclic amine, crosslinking while, increases ionic group number, compensates for crosslinking and conducts to hydroxide ion
The influence [Xuemei Wu, et al .Journal of Membrane Science.2014,459,86-95] of ability.Liu et al.
People is acted on using the dipole of nitrile structure and forms physical force in film, and prepared film shows low water absorption rate and good
From anti-swelling [Qinglin Liu, et al .Journal of Membrane Science.2015,481,9-18.].(3)
Hydrophilic-hydrophobic microphase-separated is constructed in the microstructure of film, takes into account conductivity-stability balance of film.Xu's copper text
Seminar has been experimentally confirmed, and by adjusting polymer architecture, microphase-separated form can be formed in film, for film
The raising of property have very big advantage [Tongwen Xu, et al .Journal of Membrane Science, 2014,470,
229-236].Zhuan Lin seminar, which then devises, increases alkyl side chain type polymer, utilizes the flexible alkane for having hydrophilic functional group
The autohemagglutination effect of base side chain itself forms hydrophobe microphase-separated [L Zhuang, et al .Energy
Environ.Sci.2014,7,354-360.].But the controllability of the alkyl side chain lengths of synthesis is very low, if length is excessive,
It will appear the winding of main chain and side chain, so that solubility property declines polymer in organic solvent；Watanabe et al. is polymerizeing
The fluorene structured synthesizing polyether sulfone ketone block polymer of bis-phenol is introduced in owner's chain, at 30 DEG C, conductivity is 50mS/cm (IEC=
2.54meq.g-1), and under 80 DEG C and 60%RH (relative humidity), maximum stress is 48 megapascal, maintains good mechanicalness
Energy [Masahiro Watanabe, et al .Polym.Chem.2011,2,99-106].
Summary of the invention
For the deficiency of synthetic method in the prior art, the present invention proposes that a kind of fuel cell containing cladodification type side chain is used
Anion-exchange membrane and preparation method thereof.The polymer with cladodification type structure side chain that the present invention synthesizes, applied to preparation
Alkaline anion-exchange membrane shows high conductance, dimensional stability.
The technical scheme is that
A kind of cladodification type side chain polymer anion-exchange membrane is caused using the polymer containing chloro-methyl group as macromolecular
Agent is reacted by ATRP and carries out graft modification, then the anion containing cladodification type side chain is made through quaternary ammonium reaction and alkali process
Exchange membrane.The polymer containing chloro-methyl group is polysulfones, polyether-ether-ketone or biphenyl type polysulfones；The chlorine of the polymer
Methylation range is 0.3-2.0mmolg-1。
The structural representation of the cladodification type side chain polymer anion-exchange membrane are as follows:
Wherein, R=CH2Cl or
A method of above-mentioned cladodification type side chain polymer anion-exchange membrane is prepared, specifically includes the following steps:
The first step, the chloromethylation of main polymer chain
Under inert gas shielding, by 1 parts by weight can chloromethylated polymer be dissolved in organic molten A of 30-60 parts by weight
In, the anhydrous SnCl of 0.04-0.08 parts by weight is added dropwise after being completely dissolved4As catalyst, 40-60 DEG C is increased to temperature
When, the chloromethyl methyl ether (CMME) that 0.1-10 parts by weight are slowly added dropwise is used as chloromethylation reagents, and reaction 8-14 is small at 50-55 DEG C
Shi Hou, quickly stirring precipitating is dried in vacuo at 40-100 DEG C and to obtain for 12-48 hours repeatedly after washing in methanol or ethyl alcohol
Chloromethylated polymer.The polymer containing halomethyl groups, solvent, chloromethyl methyl ether molar ratio be 1:200~
240:9~10；The solvent A is chloroform, 1,2- dichloroethanes or 1,1,2,2- tetrachloroethanes.By controlling differential responses
Time obtains the polymer of different chloromethylation degree (DC).
Second step, the ATRP graft modification of chloromethylated polymer
Under inert gas shielding, chloromethylated polymer is dissolved in organic solvent B；Under the conditions of 60-100 DEG C, successively
CuX and 2 is added, 2 '-bipyridyls add p-chloromethyl styrene (CMS) after mixing evenly, react 4 at 60-130 DEG C~
It 10 hours, is cooled to room temperature, reaction mixture is precipitated in precipitating reagent C, suction filtration obtains faint yellow crude product；It will be faint yellow thick
Product stirs precipitating 10-24h with detergent D, filters, and obtains after being dried in vacuo 12-48 hours at 30-50 DEG C containing cladodification type side
The polymer of chain.
- CH on the chloromethylated polymer2Cl group, p-chloromethyl styrene, CuX, 2,2 '-bipyridyls have
The molar ratio of solvent is 1:(2~20): (0.2~2): (0.6~6): (10~29), the CuX are CuCl or CuBr；Institute
The organic solvent stated is n,N-Dimethylformamide, dimethyl sulfoxide or N-Methyl pyrrolidone；The precipitating reagent C is first
Alcohol/water/HCl mixed liquor or ethanol/water/HCl mixed liquor；The detergent D is the mixed liquor of ethanol/cyclohexane.
Third step, polymer of the quaternary ammoniated modification containing cladodification type side chain
The polymer containing cladodification type side chain that second step is obtained is dissolved completely in organic solvent E, and micro- excess is added
Nitrogen catenation as ionization reagent, obtain mixed liquor after reacting 2-12 hours at 25-50 DEG C；The polymerization
The molar ratio of object, organic solvent and ionization reagent is 1:25:1~6.The organic solvent be n,N-dimethylacetamide,
Bis- methylformamide of N, N-, dimethyl sulfoxide or N-Methyl pyrrolidone；The ionization reagent is 1- methylimidazole
(MIm), N- ethyl imidazol(e) (EIm) or 1- vinyl imidazole (VIm).
4th step, casting film
The mixed liquor that third step is obtained is placed on glass plate along stream film forming, and 40 DEG C -50 DEG C stand 12 hours or more.
5th step, alkali process
By film obtained above from glass pane surface remove, be placed in 1.0M aqueous slkali after impregnating 12-36 hours, spend from
Son washing goes film surface free alkali to obtain cladodification type pendant anionic film after dry.
The present invention causes the difunctionality with halogen atom using more commonly used atom transition free radical polymerization reaction (ATRP)
Single group body, and then the method for synthesis of super branched polymer synthesizes the polymer containing cladodification type side chain.The present invention then synthesizes first
Contain chloro-methyl group (- CH2Cl it is anti-can to complete ATRP graft modification as macromole evocating agent for chloromethyl polysulphone)
It answers, and the monomer p-chloromethyl styrene (CMS) used is a typical bifunctional initiator monomer in itself, according to ATRP
Mechanism produces multibranched polymers side chain.
The invention has the benefit that 1) dissaving polymer contains a large amount of end moieties, there is higher chemical reactivity,
When being applied to alkaline anion-exchange membrane, be conducive to the film that the low high conductivity of chloromethylation degree is obtained by rear modification.2)
The side chain for synthesizing different cladodification degree forms different degrees of microfacies point with reference to the architectural characteristic of dissaving polymer in film
From reaching and take into account anion exchange membrane conductivity-stability target.
Detailed description of the invention
Fig. 1 is the ImOH-BPSf anionic membrane conductivity of the different cladodification degree of chloromethylation degree (DCM=77%)
Change curve (abscissa :-CH on main chain2Cl:VBC represents different cladodification degree).
Fig. 2 is the mode of appearance figure of 1 polysulfones anionic membrane (ImOH-PSf) of case study on implementation.
Fig. 3 is the mode of appearance figure of 6 cladodification type side chain polysulfones anion-exchange membrane (ImOH-BPSf) of case study on implementation.
Specific embodiment
The preparation method of this alkaline anion-exchange membrane is further illustrated below by way of specific implementation case.
Case study on implementation 1:
Synthesis chloromethyl polysulphone (CMPSf): under nitrogen protection, 7g polysulfones is dissolved in chloroform, is added dropwise 420
Microlitre SnCl4, then it is slowly added with syringe 11.9 milliliters of chloromethyl methyl ether；10h is reacted at 55 DEG C, after reaction
Mixture is precipitated in ethanol, is filtered, then impregnate and stir 12h in ethanol, is filtered, is repeatedly rushed with deionized water and ethyl alcohol
It washes, resulting white precipitate is dried in vacuo 24 hours at 60 DEG C.The chloromethylation degree (DCM) of products therefrom is 0.77.
The ionization of chloromethyl polysulphone (CMPSf): taking the CMPSf of 1 molar part to be dissolved in the DMAC of 25 molar parts, is added 1
The 1- methylimidazole (MIm) of molar part, 60 DEG C of reaction 6h.
Casting film: above-mentioned reaction solution being cast on clean glass plate, prolongs stream film forming, dry 18h at 60 DEG C, obtain yin from
Sub- film.
Alkali process: removing film from glass plate, is immersed in 1M sodium hydroxide solution for 24 hours, completes ion exchange, obtain alkalinity
Film.Prepared anionic membrane water absorption rate is 39.26%, swelling ratio 14.84%, and the conductivity at 20 DEG C is 8.73mS
cm-1。
Case study on implementation 2:
Synthesis chloromethyl polysulphone (CMPSf): under nitrogen protection, 7g polysulfones is dissolved in chloroform, is added dropwise 420
Microlitre SnCl4, then it is slowly added with syringe 11.9 milliliters of chloromethyl methyl ether；10h is reacted at 55 DEG C, after reaction
Mixture is precipitated in ethanol, is filtered, then impregnate and stir 12h in ethanol, is filtered, is repeatedly rushed with deionized water and ethyl alcohol
It washes, resulting white precipitate is dried in vacuo 24 hours at 60 DEG C.The chloromethylation degree (DCM) of products therefrom is 0.77.
ATRP reaction synthesis cladodification type side chain polymer (BPSf): the CMPSf about 0.6g, NMP of DCM=77% are weighed
(10ml) makees solvent, is dissolved in four-hole bottle, and to ensure nitrogen protection environment, logical nitrogen-vacuumizes-lead to nitrogen circulation 3~5
0.02g stannous chloride (CuCl) is rapidly joined after secondary and 2,2 '-bipyridyl (Bpy) of 0.09g repeats to lead to again after completely dissolution
Nitrogen-vacuumizes-leads to nitrogen circulation operation, and 0.28ml p-chloromethyl styrene (CMS) is added dropwise with constant pressure funnel,
120 DEG C of reaction 6h；Reaction mixture is poured into ethyl alcohol/deionized water/HCl mixed liquor and is precipitated, and is filtered, and gained crude product soaks again
Bubble stirs 24 hours in ethanol/cyclohexane, filters, and after ethyl alcohol and deionized water repeated flushing 3~5 times, is placed in 40 DEG C very
It is dried for 24 hours in empty drying box.Ethyl alcohol in ethanol/water/HCl mixed liquor, water, HCl volume be 300ml, 100ml, 5ml；Second
Ethyl alcohol in alcohol/hexamethylene mixed liquor, hexamethylene volume be 150ml, 50ml.
The ionization of cladodification type side chain polymer (BPSf): taking the BPSf of 1 molar part to be dissolved in the DMAC of 25 molar parts, is added
The 1- methylimidazole (MIm) of 1.5 molar parts, 45 DEG C of reaction 6h.
Casting film: above-mentioned reaction solution being cast on clean glass plate, prolongs stream film forming, and dry 18h at 45 DEG C is contained
The anionic membrane of cladodification type side chain.
Alkali process: removing from glass plate by film, is immersed in 1M sodium hydroxide solution for 24 hours, completes ion exchange, obtain alkali
Property film.Prepared anionic membrane water absorption rate is 49.09%, swelling ratio 18.45%, and the conductivity at 20 DEG C is
11.28mS·cm-1。
Case study on implementation 3:
Synthesis chloromethyl polysulphone (CMPSf): under nitrogen protection, 7g polysulfones is dissolved in chloroform, is added dropwise 420
Microlitre SnCl4, then it is slowly added with syringe 11.9 milliliters of chloromethyl methyl ether；10h is reacted at 55 DEG C, after reaction
Mixture is precipitated in ethanol, is filtered, then impregnate and stir 12h in ethanol, is filtered, is repeatedly rushed with deionized water and ethyl alcohol
It washes, resulting white precipitate is dried in vacuo 24 hours at 60 DEG C.The chloromethylation degree (DCM) of products therefrom is 0.77.
ATRP reaction synthesis cladodification type side chain polymer (BPSf): the CMPSf about 0.6g, NMP of DCM=77% are weighed
(13ml) makees solvent, is dissolved in four-hole bottle, and to ensure nitrogen protection environment, logical nitrogen-vacuumizes-leads to nitrogen circulation 3~5 time
After rapidly join 0.05g stannous chloride (CuCl) and 2,2 '-bipyridyl (Bpy) of 0.23g repeats to lead to again after completely dissolution
Nitrogen-vacuumizes-leads to nitrogen circulation operation, is added dropwise 0.68ml p-chloromethyl styrene (CMS) with constant pressure funnel, 70
DEG C reaction 10h；Reaction mixture is poured into ethyl alcohol/deionized water/HCl mixed liquor and is precipitated, and is filtered, and gained crude product impregnates again
It is stirred 24 hours in ethanol/cyclohexane, filters, after ethyl alcohol and deionized water repeated flushing 3~5 times, be placed in 40 DEG C of vacuum
It is dried for 24 hours in drying box.
The ionization of cladodification type side chain polymer (BPSf): taking the BPSF of 1 molar part to be dissolved in the DMAC of 25 molar parts, is added
The 1- methylimidazole (MIm) of 2 molar parts, 30 DEG C of reaction 8h.
Casting film: above-mentioned reaction solution being cast on clean glass plate, prolongs stream film forming, and dry 18h at 45 DEG C is contained
The anionic membrane of cladodification type side chain.
Alkali process: removing from glass plate by film, is immersed in 1M sodium hydroxide solution for 24 hours, completes ion exchange, obtain alkali
Property film.Prepared anionic membrane water absorption rate is 50.27%, swelling ratio 21.43%, and the conductivity at 20 DEG C is
14.89mS·cm-1。
Case study on implementation 4:
Synthesis chloromethyl polysulphone (CMPSf): under nitrogen protection, 7g polysulfones is dissolved in chloroform, is added dropwise 420
Microlitre SnCl4, then with 11.9 milliliters of the addition of syringe slowly of chloromethyl methyl ether；14h is reacted at 55 DEG C, after reaction
Mixture is precipitated in ethanol, is filtered, then impregnate and stir 12h in ethanol, is repeatedly rushed with deionized water and ethyl alcohol after suction filtration
It washes, resulting white precipitate is dried in vacuo 24 hours at 60 DEG C；The chloromethylation degree (DCM) of product is 0.77.
ATRP reaction synthesis cladodification type side chain polymer (BPSf): the CMPSf about 0.6g, NMP of DCM=77% are weighed
(23ml) makees solvent, is dissolved in four-hole bottle, and to ensure nitrogen protection environment, logical nitrogen-vacuumizes-leads to nitrogen circulation 3~5 time
After rapidly join 2,2 '-bipyridyl (Bpy) of 0.11g cuprous bromide (CuBr) and 0.36g, after completely dissolution, repeat logical nitrogen again
Gas-vacuumizes-leads to nitrogen circulation operation, is added dropwise 1.10ml p-chloromethyl styrene (CMS) with constant pressure funnel, 100
DEG C reaction 10h；Reaction mixture is poured into ethyl alcohol/deionized water/HCl mixed liquor and is precipitated, and is filtered, and gained crude product soaks again
Bubble stirs 24 hours in ethanol/cyclohexane, filters, and after ethyl alcohol and deionized water repeated flushing 3~5 times, is placed in 40 DEG C very
It is dried for 24 hours in empty drying box.
The ionization of cladodification type side chain polymer (BPSf): taking the BPSF of 1 molar part to be dissolved in the DMAC of 25 molar parts, is added
The 1- methylimidazole (MIm) of 3 molar parts, 50 DEG C of reaction 6h.
Casting film: above-mentioned reaction solution being cast on clean glass plate, prolongs stream film forming, and dry 18h at 45 DEG C is contained
The anionic membrane of cladodification type side chain.
Alkali process: film is removed from glass plate, is immersed in 1M sodium hydroxide solution for 24 hours, is completed ion exchange, obtain alkali
Property film.
Prepared anionic membrane water absorption rate is 48.16%, swelling ratio 22.45%, and the conductivity at 20 DEG C is
16.72mS·cm-1。
Case study on implementation 5:
Synthesis chloromethyl polysulphone (CMPSf): under nitrogen protection, 7g polysulfones is dissolved in chloroform, is added dropwise 420
Microlitre SnCl4, then with 11.9 milliliters of the addition of syringe slowly of chloromethyl methyl ether；10-12h is reacted at 50-55 DEG C, is reacted
After mixture is precipitated in ethanol, filter, then impregnate and stir 12h in ethanol, after suction filtration repeatedly with deionized water and
Ethyl alcohol rinses, and resulting white precipitate is dried in vacuo 24 hours at 60 DEG C；The chloromethylation degree (DCM) of product is 0.77.
ATRP reaction synthesis cladodification type side chain polymer (BPSf): the CMPSf about 0.6g, NMP of DCM=77% are weighed
(28ml) makees solvent, is dissolved in four-hole bottle, and to ensure nitrogen protection environment, logical nitrogen-vacuumizes-leads to nitrogen circulation 3~5 time
After rapidly join 2,2 '-bipyridyl (Bpy) of 0.15g stannous chloride (CuCl) and 0.73g, after completely dissolution, repeat logical nitrogen again
Gas-vacuumizes-leads to nitrogen circulation operation, is added dropwise 2.19ml p-chloromethyl styrene (CMS) with constant pressure funnel, 120
DEG C reaction 6h；Reaction mixture is poured into ethyl alcohol/deionized water/HCl mixed liquor and is precipitated, and is filtered, and gained crude product impregnates again
It is stirred 24 hours in ethanol/cyclohexane, filters, after ethyl alcohol and deionized water repeated flushing 3~5 times, be placed in 40 DEG C of vacuum
It is dried for 24 hours in drying box.
The ionization of cladodification type side chain polymer (BPSf): taking the BPSF of 1 molar part to be dissolved in the DMAC of 25 molar parts, is added
The 1- methylimidazole (MIm) of 4.5 molar parts, 30 DEG C of reaction 12h.
Casting film: above-mentioned reaction solution being cast on clean glass plate, prolongs stream film forming, and dry 18h at 45 DEG C is contained
The anionic membrane of cladodification type side chain.
Alkali process: removing from glass plate by film, is immersed in 1M sodium hydroxide solution for 24 hours, completes ion exchange, obtain alkali
Property film.
Prepared anionic membrane water absorption rate is 79.96%, swelling ratio 24.50%, and the conductivity at 20 DEG C is
17.10mS·cm-1。
Case study on implementation 6:
Synthesis chloromethyl polysulphone (CMPSf): under nitrogen protection, 7g polysulfones is dissolved in chloroform, is added dropwise 420
Microlitre SnCl4, then with 11.9 milliliters of the addition of syringe slowly of chloromethyl methyl ether；10-12h is reacted at 50-55 DEG C, is reacted
After mixture is precipitated in ethanol, impregnated again after suction filtration and stir 12h in ethanol, filtered, repeatedly with deionized water and
Ethyl alcohol rinses, and resulting white precipitate is dried in vacuo 24 hours at 60 DEG C；The chloromethylation degree (DCM) of product is 0.77.
ATRP reaction synthesis cladodification type side chain polymer (BPSf): the CMPSf about 0.6g, NMP of DCM=77% are weighed
(29ml) makees solvent, is dissolved in four-hole bottle, and to ensure nitrogen protection environment, logical nitrogen-vacuumizes-leads to nitrogen circulation 3~5 time
After rapidly join 2,2 '-bipyridyl (Bpy) of 0.19g stannous chloride (CuCl) and 0.91g, after completely dissolution, repeat logical nitrogen again
Gas-vacuumizes-leads to nitrogen circulation operation, and 2.74ml p-chloromethyl styrene (CMS), 115- is added dropwise with constant pressure funnel
120 DEG C of reaction 6h；Reaction mixture is poured into ethyl alcohol/deionized water/HCl mixed liquor and is precipitated, and is filtered, and gained crude product soaks again
Bubble stirs 24 hours in ethanol/cyclohexane, filters, and after ethyl alcohol and deionized water repeated flushing 3~5 times, is placed in 40 DEG C very
It is dried for 24 hours in empty drying box.
The ionization of cladodification type side chain polymer (BPSf): taking the BPSF of 1 molar part to be dissolved in the DMAC of 25 molar parts, is added
The 1- methylimidazole (MIm) of 6 molar parts, 45 DEG C of reaction 6h.
Casting film: above-mentioned reaction solution being cast on clean glass plate, prolongs stream film forming, and dry 18h at 45 DEG C is contained
The anionic membrane of cladodification type side chain.
Alkali process: removing from glass plate by film, is immersed in 1M sodium hydroxide solution for 24 hours, completes ion exchange, obtain alkali
Property film.
Prepared anionic membrane water absorption rate is 99.23%, swelling ratio 32.45%, and the conductivity at 20 DEG C is
23.90mS·cm-1。
Claims (10)
1. a kind of preparation method of cladodification type side chain polymer anion-exchange membrane, which comprises the following steps:
The first step, the chloromethylation of main polymer chain
Under inert gas shielding, the polymer containing chloro-methyl group is dissolved in organic solvent A, the anhydrous SnCl of catalyst is added4,
Chloromethyl methyl ether is added under the conditions of 40~60 DEG C and is used as chloromethylation reagents, react 8-14 hours at 55 DEG C, mixing will be reacted
Object is poured into methanol or ethyl alcohol and is precipitated, and washing, vacuum drying obtain chloromethylated polymer；Described is poly- containing chloro-methyl group
Close object, organic solvent A, anhydrous SnCl4, chloromethyl methyl ether mass ratio be 1:30~60:0.04~0.08:0.1~10；
Second step, the ATRP graft modification of chloromethylated polymer
Under inert gas shielding, chloromethylated polymer is dissolved in organic solvent B, under the conditions of 60~100 DEG C, is sequentially added
CuX and 2,2 '-bipyridyls are added p-chloromethyl styrene CMS, react 4~10 hours at 60-130 DEG C after mixing evenly,
It is cooled to room temperature, reaction mixture is precipitated in precipitating reagent C, suction filtration obtains faint yellow crude product, and faint yellow crude product is used
Detergent D stirring precipitating 10-24h, filters, vacuum drying obtains the polymer containing cladodification type side chain；
- CH on the chloromethylated polymer2Cl group, p-chloromethyl styrene, CuX, 2,2 '-bipyridyls, organic solvent
The molar ratio of B is 1:2~20:0.2~2:0.6~6:10~29；The CuX is CuCl or CuBr；
Third step, polymer of the quaternary ammoniated modification containing cladodification type side chain
The polymer containing cladodification type side chain that second step is obtained is dissolved completely in organic solvent E, is added micro- excessive more
Nitrogen heterocyclic obtains mixed liquor after reacting 2-12 hours at 25-50 DEG C as ionization reagent；The polymer,
The molar ratio of organic solvent E and ionization reagent is 1:25:1~6；The ionization reagent is 1- methylimidazole, N- ethyl
Imidazoles or 1- vinyl imidazole；
4th step, casting film
The mixed liquor that third step is obtained is placed on glass plate and forms a film, and 40 DEG C -50 DEG C stand 12 hours or more；
5th step, alkali process
The film that 4th step is obtained is removed from glass pane surface, is placed in aqueous slkali after impregnating, film surface is washed with deionized water
Free alkali obtains cladodification type side chain polymer anion-exchange membrane after dry.
2. preparation method according to claim 1, which is characterized in that organic solvent A described in the first step be chloroform, 1,
2- dichloroethanes or 1,1,2,2- tetrachloroethanes.
3. preparation method according to claim 1 or 2, which is characterized in that organic solvent B described in second step is N, N-
Dimethylformamide, dimethyl sulfoxide or N-Methyl pyrrolidone.
4. preparation method according to claim 1 or 2, which is characterized in that precipitating reagent C described in second step be methanol/
Water/HCl mixed liquor or ethanol/water/HCl mixed liquor.
5. preparation method according to claim 3, which is characterized in that precipitating reagent C described in second step be methanol/water/
HCl mixed liquor or ethanol/water/HCl mixed liquor.
6. preparation method described according to claim 1 or 2 or 5, which is characterized in that detergent D described in second step is second
Alcohol/hexamethylene mixed liquor.
7. preparation method according to claim 3, which is characterized in that detergent D described in second step is ethyl alcohol/hexamethylene
The mixed liquor of alkane.
8. preparation method described according to claim 1 or 2 or 5 or 7, which is characterized in that organic solvent E described in third step
For n,N-dimethylacetamide, N, bis- methylformamide of N-, dimethyl sulfoxide or N-Methyl pyrrolidone.
9. preparation method according to claim 6, which is characterized in that organic solvent E described in third step is N, N- bis-
Methylacetamide, N, bis- methylformamide of N-, dimethyl sulfoxide or N-Methyl pyrrolidone.
10. a kind of cladodification type side chain polymer anion-exchange membrane, which is characterized in that the cladodification type side chain polymer anion is handed over
Changing film is made by a kind of preparation method of any cladodification type side chain polymer anion-exchange membrane of claim 1-9
's.
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| CN109119662B (en) * | 2018-07-16 | 2022-01-04 | 大连理工大学 | Long-chain branched double-comb-shaped polyaryl indole anion exchange membrane and preparation method thereof |
| CN108899567B (en) * | 2018-07-19 | 2020-09-08 | 安徽大学 | Hyperbranched anion exchange membrane and preparation method thereof |
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| CN109585888B (en) * | 2018-11-07 | 2021-07-06 | 大连理工大学 | Blending type anion exchange membrane and preparation method thereof |
| CN109687004A (en) * | 2018-11-29 | 2019-04-26 | 大连理工大学 | A kind of multipole ion cross-linking type anion-exchange membrane and preparation method thereof |
| CN111410746B (en) * | 2018-12-27 | 2022-04-22 | 万华化学集团股份有限公司 | Hyperbranched polysulfone with controllable branching degree and preparation method thereof |
| CN110534782B (en) * | 2019-08-14 | 2021-01-26 | 北京航空航天大学 | Side chain type high-temperature proton exchange membrane for fuel cell and preparation method thereof |
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