CN108039441B - A kind of fluorine-containing diblock polymer anion fuel cell membranes and preparation method - Google Patents

A kind of fluorine-containing diblock polymer anion fuel cell membranes and preparation method Download PDF

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CN108039441B
CN108039441B CN201711200069.9A CN201711200069A CN108039441B CN 108039441 B CN108039441 B CN 108039441B CN 201711200069 A CN201711200069 A CN 201711200069A CN 108039441 B CN108039441 B CN 108039441B
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pvbc
fluorine
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fuel cell
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CN108039441A (en
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王一光
祝萌
许海龙
张民
张小娟
苏延霞
李南文
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Northwestern Polytechnical University
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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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0221—Organic resins; Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • 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
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The present invention relates to a kind of fluorine-containing diblock polymer anion fuel cell membranes and preparation methods, are prepared for two kinds of fluorine-containing polystyrene type diblock polymers using RAFT polymerization, then under homogeneous state by quaternization, obtain quaternization anionic membrane.The addition of block structure and fluorine in the anionic membrane contributes to form small ion channel, and conductivity is made to reach as high as 86.1mS cm‑1；The alkaline-resisting high temperature resistant of fluoropolymer makes anion-exchange membrane have good mechanical strength and dimensional stability, reaches 86% or more in 20 days stability inferiors of high temperature alkaline environment (1M NaOH, 80 DEG C).Furthermore the fluo anion film of high conductivity of the invention, long-life and high mechanical strength is with a wide range of applications in fuel cell membranes field.

Description

A kind of fluorine-containing diblock polymer anion fuel cell membranes and preparation method
Technical field
The present invention relates to a kind of fluorine-containing diblock polymer anion fuel cell membranes and preparation methods, are related to a kind of fluorine-containing Synthesis, characterization and the application performance as fuel cell barrier film material of block polymer long-life fuel cell film.
Background technique
Free radical polymerization is industrially to prepare the important method of polymer, and have lot of advantages: applicable monomer range is wide, Polymerizing condition is mild, and system is influenced small by impurity, can polymerize to obtain the polymer etc. of high molecular weight.Compared to traditional freedom Base polymerization, Invertible ideal (Reversible Addition Fragmentation Chain Transfer, RAFT) a kind of efficient chain-transferring agent is introduced in conventional free radical polymerization system, living chain in polymerization process Regulate and control in the presence of the polymer that can synthesize special topological structure and to molecular weight and its distribution etc..In addition, RAFT polymerize Also important approach is provided to prepare block copolymer.Block polymer has excellent phase separation performance, is preparing ion There is potential application prospect in terms of exchange membrane.Currently, being used for the segmented copolymer of amberplex only with RAFT polymerization synthesis There is a small amount of document report.
Currently, traditional energy is petered out with the development of society, energy issue of world becomes increasingly conspicuous, and cause many Environmental problem, so that demand of the people to clean energy resource is more urgent.Fuel cell (Fuel Cell) technology is a kind of energy turn It changes rate height and environmental-friendly free of contamination energy technology efficiently can convert electric energy for chemical energy by electrochemical reaction, And (Varcoe, J.R.etc.Energy Environ.Sci.2014,7,3135-3191) is not limited by Carnot cycle.More In kind of fuel cell, alkaline anion-exchange membrane fuel cell is because its electrode reaction rate is high, and without using noble metal conduct Many advantages, such as catalyst, receives extensive attention (Li, the N. of people；Guiver,M.D.Macromolecules 2014, 47,2175-2198).Anion-exchange membrane (AEMs) is the key component of the types of fuel cells, it play conduction hydroxyl from Son and the double action for separating cathode and anode, its performance by the performance for being directly related to fuel cell, energy efficiency and use the longevity Life, thus it is most important to the research of AEMs.Currently, be commonly used in prepare AEMs polymer relate generally to it is following several: Polysulfones (Mohanty, A.D.etc.Macromolecules 2014,47,1973-1980), polyarylene ethers (Wang, J.etc.Macromolecules 2010,43,3890-3896), polyphenylene (Hibbs, M.R.etc.Macromolecules 2009,42,8316-8321), polystyrene (Luo, Y.etc.J.Power Sources.2010,195,3765-3771) gathers Etherimide (Wang, G.etc.J.Membr.Sci.2009,326,4-8), 12 polyphenylene oxide (Li, ), N.etc.J.Am.Chem.Soc.2013,135,10124-10133 polyolefin (Noonan, K.J.etc.J.Am.Chem.Soc.2012,134,18161-18164).Solution two is mainly puted forth effort in the preparation of existing AEMs material A critical issue: one is improving the hydroxide ion conductivity of AEMs；The second is improving the alkaline stability of AEMs.
Summary of the invention
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes a kind of fluorine-containing diblock polymer anion fuel electricity Pond film and preparation method prepare fluorine-containing block type anion-exchange membrane using RAFT polymerization and this novel anionic film exist Application performance in fuel cell.
Technical solution
A kind of fluorine-containing diblock polymer anion fuel cell membranes, it is characterised in that: the fluorine-containing diblock polymer The structural formula of anion fuel cell membranes are as follows:
A kind of fluorine-containing diblock polymer anion fuel cell membranes, it is characterised in that: the fluorine-containing diblock polymer The structural formula of anion fuel cell membranes are as follows:
A method of preparing the fluorine-containing diblock polymer anion fuel cell membranes, it is characterised in that step is such as Under:
The preparation of step 1, the first block: by 4- 1-chloro-4-methyl-benzene VBC, chain-transferring agent trithiocarbonate, initiator Azodiisobutyronitrile and N-Methyl pyrrolidone mix and are put into magnetic rotor, and Chain transfer agent and initiator additional amount are rubbed Your ratio range is that the molar ratio of 10~5,4- 1-chloro-4-methyl-benzene and chain-transferring agent is 400~600, N-Methyl pyrrolidone Additional amount be 5~10mL, air in bottle is removed using freeze-thaw pump circulation method three times, is subsequently placed at 70~85 DEG C of oil baths It heats, reacts 24~48 hours in pot；
It is quenched after reaction with liquid nitrogen, again with methanol is precipitated after being dissolved product with tetrahydrofuran THF, by what is settled out Polymer passes through filtered on buchner funnel, cleans the polymer polymerizeing three times repeatedly；
After polymer is placed the long period at room temperature, it is then transferred in vacuum drying oven, vacuum drying at 50~80 DEG C, directly Until quality no longer changes, the first block PVBC is obtainedx；
The preparation of step 2, the second block: by 4- fluorobenzene ethene 4FS, the first block PVBCx, initiator azodiisobutyronitrile AIBN mixes and is put into magnetic rotor, and the molar ratio range of Chain transfer agent and initiator additional amount is 10~5,4- fluorobenzene Ethylene 4FS and the first block PVBCxMolar ratio be 500~900, and suitable N-Methyl pyrrolidone is added by PVBCxIt is complete Air in bottle is removed using freeze-thaw pump circulation method three times, is subsequently placed in 70~85 DEG C of oil bath pans and heats, instead by fully dissolved It answers 24~48 hours；
It is quenched after reaction with liquid nitrogen, again with methanol is precipitated after being dissolved product with tetrahydrofuran THF, by what is settled out Polymer passes through filtered on buchner funnel, cleans the polymer polymerizeing three times repeatedly；
After polymer is placed the long period at room temperature, it is then transferred in vacuum drying oven, vacuum drying at 50~80 DEG C, directly Until quality no longer changes, the second block polymer PVBC is obtainedx-b-P4FSy, structural formula are as follows:
Step 3: by the second block polymer PVBCx-b-P4FSyIt is dissolved in and obtains the solution that mass ratio is 20% in NMP, and It is added the tetrahydrofuran solution of trimethylamine thereto, the additional amount of trimethylamine is five times of equivalents of benzyl chloride group and to drip in polymer Entering polymer of a certain amount of methanol after amination can just dissolve, and reaction be sufficiently stirred at room temperature 24~48 hours；Add The concentration for entering the tetrahydrofuran solution of trimethylamine is 30wt%
It is described after reaction to drip this solution solidifying 24 on plate glass and under the conditions of being put into baking oven at 70~80 DEG C ~48 hours, then 12~24 hours are handled under 50~80 DEG C of vacuum conditions to remove extra solvent；
Gained film is immersed in 24~48h in the NaOH solution of 1M, finally obtains and contains after being rinsed well with deionized water Fluorine diblock polymer anion fuel cell membranes PVBCx-b-P4FSy- OH, structural formula are as follows:
In the preparation of second block of step 2, replaces 4- fluorobenzene ethene 4FS with 2,3,4,5,6- pentafluorostyrene PFS, obtain To the second block section polymer P VBCx-b-PPFSy, structural formula are as follows:
Then to the second block section polymer P VBCx-b-PPFSyImplementation steps 3, obtain fluorine-containing diblock polymer yin from Sub- fuel cell membranes PVBCx-b-PPFSy- OH, structural formula are as follows:
Beneficial effect
A kind of fluorine-containing diblock polymer anion fuel cell membranes proposed by the present invention and preparation method, have selected two kinds Different fluorochemical monomers: 4- fluorobenzene ethene (4FS) and 2,3,4,5,6- pentafluorostyrenes (PFS), and utilize RAFT polymerization It is respectively synthesized fluorine-containing diblock copolymer with 4- 1-chloro-4-methyl-benzene.Then with the tetrahydrofuran solution of trimethylamine to polymerization Object carries out homogeneous amination treatment, and under the conditions of 80 DEG C, and solidification obtains anionic membrane.The fuel battery performance of the film has Following advantage: 1) conductivity is high, reaches 86.1mS cm at room temperature-1Left and right is higher than most of anion-exchange membranes；2) mechanicalness Can be good, tensile strength can reach 26.7 ± 0.4MPa, and Young's modulus range is 355~254MPa or so, elongation at break Range is 8.7~14.2%；(3) service life is long, and at 80 DEG C in 10M sodium hydrate aqueous solution, conductivity is maintained at after 20 days 86% or so.The present invention determines the corresponding relationship between the chemical structure of the polymer and fuel cell film properties respectively, takes off Shown in it rule and mechanism.
The present invention is prepared for fluorine-containing diblock polymer using RAFT polymerization, and by amination prepare anion fuel Battery membranes.In structure design, block polymer has excellent phase separation performance, and the addition of fluorine can further promote its phase point From generation, contribute to form small ion channel, conductivity reaches as high as 86.1mS cm at room temperature-1；And fluoropolymer Alkaline-resisting high temperature resistant makes anion-exchange membrane have good mechanical strength and dimensional stability, in high temperature alkaline environment (1M NaOH, 80 DEG C) stability inferior reached 86% or more 20 days.Since the present invention can provide high conductivity, long-life and high machinery are strong The polymer film of degree, therefore have a good application prospect in terms of fuel cell membranes.
Detailed description of the invention
The hydrogen of Fig. 1 polymer 2,3 composes nuclear magnetic resonance figures
The hydrogen of a polymer 2,4 composes nuclear magnetic resonance figures；The hydrogen of b polymer 3,5 composes nuclear magnetic resonance figures
The fourier infrared of Fig. 2 polymer 2,3,4 composes comparison diagram FTIR spectra of:(a) PVBC263-b-P4FS194, (b)PVBC263-b-PPFS110,(c)PVBC263-b-P4FS194-OH and(d)PVBC263-b-PPFS110-OH membranes.
The temperature of Fig. 3 polymer 4 and 5-conductivity relational graph Bicarbonate conductivity of (a) PVBC263- b-P4FS140-OH,(b)PVBC263-b-P4FS194-OH,(c)PVBC263-b-PPFS38-OH and(d)PVBC263-b-PPFS110- OH AEMs as a function of temperature.
The water absorption rate of Fig. 4 polymer 4,5-temperature relation figure and swelling ratio-temperature relation figure (The dependence of water uptake and swelling ratio on temperature:(a)PVBC263-b-P4FS140-OH,(b) PVBC263-b-P4FS194-OH,(c)PVBC263-b-PPFS38-OH and(d)PVBC263-b-PPFS110-OH AEMs.)
Conductivity variation-time diagram (Hydroxide under the conditions of the dipping by lye of 4,5 film of Fig. 5 polymer conductivity as a function of time for:(a)PVBC263-b-P4FS140-OH(3.88meq./g),(b) PVBC263-b-P4FS194-OH(3.19meq./g),(c)PVBC263-b-PPFS38-OH(4.27meq./g)and(d)PVBC263- b-PPFS110-OH(3.19meq./g)AEMs after immersion in 1M NaOH at 80℃.)
Gel permeation chromatogram (GPC profiles of (a) PVBC of Fig. 6 polymer 1263,(b)PVBC263-b- P4FS140,(c)PVBC263-b-P4FS194,(d)PVBC263-b-P4FS38and(e)PVBC263-b-PPFS110in DMF phase.)
Fig. 7 preparation process
Specific embodiment
Now in conjunction with embodiment, attached drawing, the invention will be further described:
Specific preparation process is as follows:
One, polymer 1
1) the addition 4- 1-chloro-4-methyl-benzene in the round-bottomed flask of 100ml, chain-transferring agent trithiocarbonate (DDMAT), And initiator azodiisobutyronitrile (AIBN), three's molar ratio are 1667:5:1, and are put into magnetic rotor, using freezing three times Defrosting pump circulation method removes air in bottle, is subsequently placed in 70 DEG C of oil bath pans and heats, and reacts 24 hours.Liquid is used after reaction Nitrogen is quenched, and again with methanol is precipitated after being dissolved product with THF, and the polymer settled out is passed through filtered on buchner funnel, so anti- It is multiple to clean the polymer polymerizeing three times.After polymer is placed the long period at room temperature, it is then transferred in vacuum drying oven, 50 DEG C Lower vacuum drying obtains the first block PVBC until quality no longer changesx；
Two, polymer 2,3
1) preparation of the second block is with the first block, by fluorochemical monomer 4- fluorobenzene ethene (4FS) or 2,3,4,5,6- five fluorine Styrene (PFS), PVBCx, initiator azodiisobutyronitrile (AIBN) is added sequentially in the round-bottomed flask of 100ml, and three rubs You are than being 3416:5:1, reaction process and product processing and the first block PVBCxUnanimously, it finally obtains such as institute in structural formula 1,2 The fluorine-containing diblock polymer PVBC shownx-b-P4FSyOr PVBCx-b-PPFSy；
Three, polymer 4,5
1) polymer obtained in step 3 is dissolved in and obtains mass ratio in NMP as 20% solution, and three are added thereto The tetrahydrofuran solution (30wt%) of methylamine, additional amount are five times of equivalents of benzyl chloride group in polymer, and instill proper amount of methanol, Reaction 24 hours is sufficiently stirred at room temperature.By this solution drop solidifying 24 on plate glass and under the conditions of being put into baking oven at 80 DEG C Hour, then 12 hours are handled under 50 DEG C of vacuum conditions to remove extra solvent and trimethylamine, it finally obtains such as structural formula 3,4 Shown in product PVBCx-b-P4FSy- OH or PVBCx-b-PPFSy-OH。
The present invention is described with specific embodiment below.
Embodiment 1, the first block polymer PVBC263Preparation
The addition 4- 1-chloro-4-methyl-benzene in the round-bottomed flask of 100ml, chain-transferring agent trithiocarbonate (TTC), and Initiator azodiisobutyronitrile (AIBN), three's molar ratio is 1667:5:1, and is put into magnetic rotor, uses freeze-thaw three times Pump circulation method removes air in bottle, is subsequently placed in 70 DEG C of oil bath pans and heats, and reacts 24 hours.It is quenched after reaction with liquid nitrogen It goes out, again with methanol is precipitated after being dissolved product with THF, the polymer settled out is passed through into filtered on buchner funnel, repeatedly three It is secondary to clean the polymer polymerizeing.After polymer is placed the long period at room temperature, it is then transferred in vacuum drying oven, it is true at 50 DEG C Sky drying, until quality no longer changes, obtains the first block PVBC263；
Embodiment 2, fluorine-containing diblock polymer PVBC263-b-P4FS140Preparation
The preparation of fluorine-containing second block is with the first block, by 4- fluorobenzene ethene (4FS) (5.0g, 41mmol), PVBC263 (2.0g, 36.7kg/mol, 0.05mmol), initiator azodiisobutyronitrile (2.0mg, 0.012mmol) are added sequentially to 100ml Round-bottomed flask in, reaction process and product processing it is consistent with the first block, the reaction time be 12 hours, finally obtain fluorine-containing two Block polymer PVBC263-b-P4FS140.Acquired results are as shown in the table:
a Polymerization conditions:Macro-PVBC263(0.7g,49.3kg/mol,0.1mmol),4FS monomer(40mmol),polymerization time:12h,polymerization temperature:70℃,mR: PVBC precursor(PVBC263),I:AIBN.
bThe monomer conversion was calculated by UV–vis analysis；
c Calculated by 1H NMR analysis.
d The PDI or Mw/Mn values were determined by GPC analysis.
Embodiment 3, step are the same as implementation example 2.Prepare the second block P4FS194When initiator azodiisobutyronitrile addition Amount is 4mg (0.024mmol), and the reaction time is 24 hours.Acquired results are as shown in the table:
a Polymerization conditions:Macro-PVBC263(0.7g,49.3kg/mol,0.1mmol),4FS monomer(40mmol),polymerization time:24h,polymerization temperature:70℃,mR: PVBC precursor(PVBC263),I:AIBN.
bThe monomer conversion was calculated by UV–vis analysis；
c Calculated by 1H NMR analysis.
d The PDI or Mw/Mn values were determined by GPC analysis.
Embodiment 4, fluorine-containing diblock polymer PVBC263-b-PPFS38Preparation
By 2,3,4,5,6- pentafluorostyrenes (PFS) (5.0g, 26mmol), PVBC263(2.0g,36.7kg/mol, 0.05mmol), initiator azodiisobutyronitrile (2.0mg, 0.012mmol) is added sequentially in the round-bottomed flask of 100ml, reaction Process and product processing are consistent with the first block, and the reaction time is 12 hours, finally obtain fluorine-containing diblock polymer PVBC263- b-PPFS38.Acquired results are as shown in the table:
a Polymerization conditions:Macro-PVBC263(0.7g,49.3kg/mol,0.1mmol),PFS monomer(26mmol),polymerization time:12h,polymerization temperature:70℃,mR: PVBC precursor(PVBC263),I:AIBN.
bThe monomer conversion was calculated by UV–vis analysis；
c Calculated by 1H NMR analysis.
d The PDI or Mw/Mn values were determined by GPC analysis.
Embodiment 5, step are the same as implementation example 4.The second block PPFS will be prepared110When initiator azodiisobutyronitrile plus Entering amount is 4mg (0.024mmol), and the reaction time is 24 hours.Acquired results are as shown in the table:
a Polymerization conditions:Macro-PVBC263(0.7g,49.3kg/mol,0.1mmol),PFS monomer(26mmol),polymerization time:24h,polymerization temperature:70℃,mR: PVBC precursor(PVBC263),I:AIBN.
bThe monomer conversion was calculated by UV–vis analysis；
c Calculated by 1H NMR analysis.
d The PDI or Mw/Mn values were determined by GPC analysis.
The amination treatment of embodiment 6, fluorine-containing diblock polymer 2 and 3
Polymer 2 and 3 is dissolved in respectively and obtains the solution that mass ratio is 20% in NMP, and trimethylamine is added thereto Tetrahydrofuran solution (30wt%), additional amount are five times of equivalents of benzyl chloride group in polymer, and instill proper amount of methanol, in room temperature Under be sufficiently stirred reaction 24 hours.Use is added deionized water and product is precipitated after reaction, after being dried with filtered on buchner funnel again It is dissolved with NMP, and is precipitated with deionized water, cleaned repeatedly three times, finally obtain product.
Embodiment 7, fluorine-containing diblock polymer anion exchange membrane
Polymer 2 and 3 is dissolved in respectively and obtains the solution that mass ratio is 20% in NMP, and trimethylamine is added thereto Tetrahydrofuran solution (30wt%), additional amount are five times of equivalents of benzyl chloride group in polymer, and instill proper amount of methanol, in room temperature Under be sufficiently stirred reaction 24 hours.This solution is dripped and is solidified 24 hours on plate glass and under the conditions of being put into baking oven at 80 DEG C, 12 hours are handled under 50 DEG C of vacuum conditions again to remove extra solvent and trimethylamine.Gained film is immersed in the NaOH of 1M 48h in solution finally obtains the product as shown in structural formula 3 and 4 after being rinsed well with deionized water.
Embodiment 8, to fluorine-containing diblock polymer anion exchange membrane synthesized in example 7 is implemented, test its fuel Battery film properties.The measurement of conductivity uses Solartron SI 1260A Impedance/Gain-Phase type point at room temperature Analyzer；The relationship of (20,40,60,80 DEG C) testing conductive rate and temperature at different temperatures；In 80 DEG C of different sodium hydroxide solutions The variation tendency of testing conductive rate under (1M) soaking time (0-20 day).

Claims (4)

1. a kind of fluorine-containing diblock polymer anion fuel cell membranes, it is characterised in that: the fluorine-containing diblock polymer yin The structural formula of ion fuel battery membranes are as follows:
Wherein, x=263, y=194 or 140.
2. a kind of fluorine-containing diblock polymer anion fuel cell membranes, it is characterised in that: the fluorine-containing diblock polymer yin The structural formula of ion fuel battery membranes are as follows:
Wherein, x=263, y=110 or 38.
3. a kind of method for preparing fluorine-containing diblock polymer anion fuel cell membranes described in claim 1, it is characterised in that Steps are as follows:
The preparation of step 1, the first block: by 4- 1-chloro-4-methyl-benzene VBC, chain-transferring agent trithiocarbonate, initiator azo Bis-isobutyronitrile and N-Methyl pyrrolidone mix and are put into magnetic rotor, the molar ratio of Chain transfer agent and initiator additional amount Value range be that the molar ratio of 10~5,4- 1-chloro-4-methyl-benzene and chain-transferring agent is 400~600, and N-Methyl pyrrolidone adds Entering amount is 5~10mL, removes air in bottle using freeze-thaw pump circulation method three times, is subsequently placed in 70~85 DEG C of oil bath pans Heating is reacted 24~48 hours；
It is quenched after reaction with liquid nitrogen, again with methanol is precipitated after being dissolved product with tetrahydrofuran THF, the polymerization that will be settled out Object passes through filtered on buchner funnel, cleans the polymer polymerizeing three times repeatedly；
It after polymer is placed the long period at room temperature, is then transferred in vacuum drying oven, vacuum drying at 50~80 DEG C, until matter Until amount no longer changes, the first block PVBC is obtainedx；
The preparation of step 2, the second block: by 4- fluorobenzene ethene 4FS, the first block PVBCx, initiator azodiisobutyronitrile AIBN Mix and be put into magnetic rotor, the molar ratio range of Chain transfer agent and initiator additional amount is 10~5,4- fluorobenzene ethene 4FS and the first block PVBCxMolar ratio be 500~900, and suitable N-Methyl pyrrolidone is added by PVBCxIt is completely molten Solution, air in bottle is removed, be subsequently placed in 70~85 DEG C of oil bath pans and heat using freeze-thaw pump circulation method three times, reaction 24 ~48 hours；
It is quenched after reaction with liquid nitrogen, again with methanol is precipitated after being dissolved product with tetrahydrofuran THF, the polymerization that will be settled out Object passes through filtered on buchner funnel, cleans the polymer polymerizeing three times repeatedly；
It after polymer is placed the long period at room temperature, is then transferred in vacuum drying oven, vacuum drying at 50~80 DEG C, until matter Until amount no longer changes, the second block polymer PVBC is obtainedx-b-P4FSy, structural formula are as follows:
Step 3: by the second block polymer PVBCx-b-P4FSyBe dissolved in obtained in NMP mass ratio be 20% solution, and to its The middle tetrahydrofuran solution that trimethylamine is added, the additional amount of trimethylamine are five times of equivalents of benzyl chloride group and instillation one in polymer Polymer of the quantitative methanol after amination can just dissolve, and reaction be sufficiently stirred at room temperature 24~48 hours；It is added three The concentration of the tetrahydrofuran solution of methylamine is 30wt%
It is described after reaction to drip this solution solidifying 24~48 on plate glass and under the conditions of being put into baking oven at 70~80 DEG C Hour, then 12~24 hours are handled under 50~80 DEG C of vacuum conditions to remove extra solvent；
Gained film is immersed in 24~48h in the NaOH solution of 1M, fluorine-containing two are finally obtained after being rinsed well with deionized water Block polymer anion fuel cell membranes PVBCx-b-P4FSy- OH, structural formula are as follows:
4. according to the method described in claim 3, it is characterized by: in the preparation of second block of step 2, with 2,3,4,5,6- Pentafluorostyrene PFS replaces 4- fluorobenzene ethene 4FS, obtains the second block section polymer P VBCx-b-PPFSy, structural formula are as follows:
Then to the second block section polymer P VBCx-b-PPFSyImplementation steps 3 obtain fluorine-containing diblock polymer anion combustion Expect battery membranes PVBCx-b-PPFSy- OH, structural formula are as follows:
CN201711200069.9A 2017-11-27 2017-11-27 A kind of fluorine-containing diblock polymer anion fuel cell membranes and preparation method Expired - Fee Related CN108039441B (en)

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