CN106268381B - A kind of alkaline hydrolysis-resistant anion exchange membrane material and preparation method and application thereof - Google Patents
A kind of alkaline hydrolysis-resistant anion exchange membrane material and preparation method and application thereof Download PDFInfo
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- CN106268381B CN106268381B CN201610792970.9A CN201610792970A CN106268381B CN 106268381 B CN106268381 B CN 106268381B CN 201610792970 A CN201610792970 A CN 201610792970A CN 106268381 B CN106268381 B CN 106268381B
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000005904 alkaline hydrolysis reaction Methods 0.000 title claims description 11
- ORILYTVJVMAKLC-UHFFFAOYSA-N Adamantane Natural products C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims abstract description 46
- -1 adamantane quaternary ammonium salt Chemical class 0.000 claims abstract description 40
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 150000001450 anions Chemical group 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229940006460 bromide ion Drugs 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 238000005349 anion exchange Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 238000005266 casting Methods 0.000 claims 2
- 238000000576 coating method Methods 0.000 claims 2
- 239000003880 polar aprotic solvent Substances 0.000 claims 2
- 239000011248 coating agent Substances 0.000 claims 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 claims 1
- 125000004970 halomethyl group Chemical group 0.000 claims 1
- 230000003014 reinforcing effect Effects 0.000 claims 1
- 238000007790 scraping Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 238000005342 ion exchange Methods 0.000 abstract description 10
- 238000006467 substitution reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000005956 quaternization reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- 239000011521 glass Substances 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 239000004695 Polyether sulfone Substances 0.000 description 6
- 229920006393 polyether sulfone Polymers 0.000 description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000010345 tape casting Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 4
- 238000007265 chloromethylation reaction Methods 0.000 description 4
- 229920006380 polyphenylene oxide Polymers 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229940102396 methyl bromide Drugs 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920004934 Dacron® Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
本发明公开一种耐碱解的阴离子交换膜材料及其制备方法和应用：该新型阴离子交换膜材料具有如(1)所示的结构；本发明选用含不同取代度的卤甲基化聚合物为聚合物基本骨架，通过与金刚烷叔胺进行季铵化反应，再进行离子交换，得到基于金刚烷季铵盐的阴离子交换膜材料。本发明所用的原料廉价易得，制备方法简单，适合大规模工业化生产，基于该阴离子交换膜材料所制备的阴离子交换膜具有化学稳定性好、离子传导率高、力学性能优异等诸多优势。 The invention discloses an anion exchange membrane material resistant to alkali hydrolysis, a preparation method and application thereof: the novel anion exchange membrane material has the structure shown in (1); the present invention selects halomethylated polymers with different degrees of substitution As the basic skeleton of the polymer, the anion exchange membrane material based on adamantane quaternary ammonium salt is obtained by performing quaternization reaction with adamantane tertiary amine and then performing ion exchange. The raw materials used in the invention are cheap and easy to obtain, the preparation method is simple, and is suitable for large-scale industrial production.
Description
Technical field
The invention belongs to ion exchange membrane material fields, and in particular to a kind of using adamantane quaternary ammonium salt as function cation
Anion exchange membrane material and its preparation method and application.
Background technique
Anion-exchange membrane is a kind of with fixed cation group, the polymer electrolytic material that may be selected through anion
Material, by polymer backbone, charge positive charge functional group and functional group on moveable anion three parts form.Due to
It is in the extensive use of the industrial circles such as fuel cell barrier film, basic industry diaphragm, water process, and exploitation and performance optimization are in material
Material and chemical industrial field are constantly subjected to widely pay close attention to.
The functional group of charge positive charge is connected on polymer backbone by chemical bond, also referred to as ion-exchange group, yin
The ion exchanging function of amberplex is determined by it.Currently, quaternary ammonium salt is the ion-exchange group the most sufficient of research, still
Since the chemical stability of the anion-exchange membrane based on conventional quaternary ammonium salts is inadequate, quaternary ammonium can especially occur under alkaline condition
The decomposition of cation, is unable to satisfy requirement (the J.R.Varcoe and that anion-exchange membrane is used for a long time under alkaline condition
R.C.T.Slade,Fuel Cells,2005,5,187-200.)。
Therefore, design and synthesis have the ion-exchange group of superior chemical stability, and are prepared based on this and meet fuel
The high performance anion-exchange membrane material of battery applications is the critical issue of current urgent need to resolve.
Summary of the invention
The purpose of the present invention is be to provide a kind of anion based on adamantane quaternary ammonium salt in view of the deficiencies of the prior art
Membrane material and its preparation method and application is exchanged, the technical problem to be solved is that have the gained anion exchange membrane material
Excellent alkali resistance and compared with high ion conductivity, so that it is in alkaline fuel cell diaphragm, chlorine industry, film electrolysis, electrodialysis
Etc. related fieldss with good application prospect.
Technical scheme is as follows:
Shown in the structural formula such as formula (1) of anion exchange membrane material provided by the invention based on adamantane quaternary ammonium salt:
It has the adamantane quaternary ammonium salt structure as shown in formula (2):
Wherein R in formula (1) and (2)1, R2It is each independently selected from aliphatic substitution or carbon that carbon atom number is 1~16
The aromatic substituents that atomicity is 6~24；X is anion, selected from least one of Cl, Br.
Structure such as formula (3), formula (4), formula (5) or the formula (6) of polymer backbone in formula (1) are shown:
In formula (3): x=0.01~0.99；N is the integer between 10 to 1000；Q refers to the gold as shown in formula (2)
Rigid alkane quaternary ammonium salt；
In formula (4): 1≤h1+i1+j1+k1≤4, and be integer；X=0.01~0.99；N is between 10 to 1000
Integer；Q refers to the adamantane quaternary ammonium salt as shown in formula (2)；R3Selected from one of such as flowering structure or a variety of:
In formula (5): 1≤h2+i2+j2+k2≤4, and be integer；X=0.01~0.99；N is between 10 to 1000
Integer；Q refers to the adamantane quaternary ammonium salt as shown in formula (2)；R4Selected from one of such as flowering structure or a variety of:
In formula (6): x=0.01~0.99；N is the integer between 10 to 1000；Q refers to the gold as shown in formula (2)
Rigid alkane quaternary ammonium salt.
The preparation method of anion exchange membrane material in the present invention based on adamantane quaternary ammonium salt, main includes following step
It is rapid:
In organic solvent by the polymer dissolution of halomethylation, according to halogen methyl mole contained by omethylated polymers
1~10 times of addition adamantane tertiary amine compound, at 0~60 DEG C react 1~48h；After reaction, it is precipitated in precipitating reagent
It is precipitated, after separation, washing, drying, obtains the anion exchange membrane material based on adamantane quaternary ammonium salt.
Wherein: shown in the general structure of the polymer of the halomethylation such as formula (7), formula (8), formula (9) or formula (10), formula
In: x=0.01~0.99；1≤h1+i1+j1+k1≤4, and be integer；1≤h2+i2+j2+k2≤4, and be integer；R3With formula
(4) R in3It refers to identical；R4With R in formula (5)4It refers to identical；N is the integer between 10 to 1000；Y is Cl or Br.
The general structure of the adamantane tertiary amine compounds isWherein R1、R2Reference and formula (1) and
(2) reference in is identical；The organic solvent is preferably polar non-solute, such as dimethyl sulfoxide, N-Methyl pyrrolidone, N,
Dinethylformamide, DMAC N,N' dimethyl acetamide；The precipitating reagent in water, methanol, ethyl alcohol, acetone or ether at least
It is a kind of.
Invention further provides the preparation method of the anion-exchange membrane based on above-mentioned anion exchange membrane material, tables
It states as follows:
Anion exchange membrane material based on adamantane quaternary ammonium salt is dissolved in organic solvent, obtains and is based on adamantane season
The polymer solution of the anion exchange membrane material of ammonium salt；Obtained polymer solution in matrix or is enhanced into film on fabric,
After removing solvent, the anion-exchange membrane that anion is chloride ion or bromide ion is obtained.Further progress hydroxide radical anion is handed over
It changes to get being hydroxide ion anion-exchange membrane to anion.
The preparation method of above-mentioned anion-exchange membrane, also has a characteristic that
The organic solvent be selected from polar non-solute (such as n,N-Dimethylformamide, n,N-dimethylacetamide,
N-Methyl pyrrolidone, dimethyl sulfoxide, gamma-butyrolacton etc.) or chloroform, 1, one of 1,2,2- tetrachloroethanes, acetonitrile or
Their mixed solvent；Described matrix is selected from glass plate or polyfluortetraethylene plate；The enhancing fabric selects polyethylene cloth, poly- third
Alkene cloth, woven dacron, nylon cloth or polyvinyl chloride cloth；The method of the film can be solution-cast film forming, spin-coating, scrape
Film, curtain coating or dipping；The method of the removal solvent can be selected room temperature volatilization or in 30~200 DEG C of heating, drying.
Above-mentioned anion can according to need for the anion in the anion-exchange membrane of halogen atom and be converted to other yin
X in formula (1) is converted to other required ions by halide ion by ion, such as:
The anion-exchange membrane that the anion is halide ion is immersed in the NaOH water that concentration is 0.01~10mol/L
Anion exchange is carried out in the KOH aqueous solution that solution or concentration are 0.01~10mol/L, obtaining anion is hydroxide ion
X in the structural formula of anion exchange membrane material based on adamantane quaternary ammonium salt (is converted to OH) by anion-exchange membrane.
Present invention anion-exchange membrane obtained can be applied in a variety of diaphragm fields, and alkaline combustion is particularly suitable for use as
Expect the anion-exchange membrane of battery.
Compared with existing anion-exchange membrane material structure, it is provided by the present invention based on adamantane quaternary ammonium salt yin from
Proton exchange membrane material raw material sources are extensive, preparation method is simple；In addition, obtain based on adamantane quaternary ammonium salt anion-exchange membrane
With excellent chemical stability and ionic conductivity, the application demand of fuel cell field can satisfy, there is good answer
Use prospect.
Detailed description of the invention
Fig. 1 is the NMR spectrum figure (DMSO-d of anion-exchange membrane prepared by embodiment 16)；
Fig. 2 is the Cl of anion-exchange membrane prepared by embodiment 1ˉConductivity variation with temperature curve；
Fig. 3 is anion-exchange membrane alkaline hydrolysis under the conditions of 1M NaOH (aq), 60 DEG C prepared by embodiment 1, after alkaline hydrolysis
ClˉConductivity is with alkaline hydrolysis time-varying relationship.
Specific embodiment
Below in conjunction with attached drawing, present invention is further described in detail with embodiment.
Embodiment 1
In the present embodiment, the anion-exchange membrane based on adamantane quaternary ammonium salt has structural formula shown in formula (11):
It is specific the preparation method comprises the following steps:
By 0.5g methyl bromide degree be 40% brominated polyphenylether be dissolved in 10mL N-Methyl pyrrolidone, then plus
Enter 0.4g N, N- dimethyladamantane tertiary amine is warming up to 50 DEG C of reactions for 24 hours.After reaction, reaction system is slowly dropped to
It is precipitated in a large amount of ether, filters, sufficiently washed with fresh ether, dried in 60 DEG C of vacuum drying ovens, obtained based on adamantane
The polyphenylene oxide of quaternary ammonium salt.
The polyphenylene oxide based on adamantane quaternary ammonium salt of preparation is dissolved in N-Methyl pyrrolidone, obtaining mass fraction is
10% polymer solution.After filtering, the solution is coated on clean glass plate with the tape casting, glass plate is placed on 80
DEG C drying box in be dried overnight, to remove most of solvent, be then transferred to molten sufficiently to remove in 80 DEG C of vacuum ovens
Agent.It is cooled to room temperature taking-up glass plate to temperature, places it in demoulding in deionized water, then after sufficiently being washed with deionized water,
Film is placed in drying box and dries, and obtains the anion-exchange membrane that anion is bromide ion.
The film is placed in 2mol/L KOH solution and impregnates 48h, then sufficiently washs film with deionized water, it can
It is OH to anion-Anion-exchange membrane.
After measured, the ion exchange capacity of the film is 2.02mmol/g.Water absorption rate at room temperature is 21%；Film is at 40 DEG C
Under conductivity conductivity (is surveyed for OH by 13.9mS/cmˉIt is exchanged into ClˉThe Cl tested afterwardsˉConductivity, institute in following example
The conductivity of finger is ClˉConductivity.).
The anion-exchange membrane is placed in 60 DEG C, the middle progress alkaline hydrolysis stability test of 1M NaOH (aq), measures its ClˉElectricity
Conductance with the alkaline hydrolysis time variation relation.
Embodiment 2
In the present embodiment, the anion exchange membrane material based on adamantane quaternary ammonium salt has structural formula shown in formula (12):
It is specific the preparation method comprises the following steps:
The chloromethylation polyether sulfone that 1.00g chloromethylation degree of substitution is 50% is dissolved in 10mL N, N- dimethyl formyl
In amine, 0.40g N- methyl -- V-pentyl adamantane tertiary amine is then added, is warming up to 45 DEG C of reaction 48h.After reaction, by body
Tie up in ether and precipitate, wash, filter, dry after obtain the polyether sulfone based on adamantane quaternary ammonium salt.
The polyether sulfone based on adamantane quaternary ammonium salt of preparation is dissolved in n,N-Dimethylformamide, mass fraction is obtained
For 15% polymer solution.After filtering, the solution is coated on clean glass plate with the tape casting, glass plate is placed on
It is dried overnight in 80 DEG C of drying box, to remove most of solvent, is then transferred in 80 DEG C of vacuum ovens sufficiently to remove
Solvent.It is cooled to room temperature taking-up glass plate to temperature, places it in demoulding in deionized water, after sufficiently being washed with deionized water,
Film is placed in drying box and dries, and obtains the anion-exchange membrane that anion is chloride ion.
The film is placed in 1mol/L KOH solution and impregnates 48h, then with deionized water sufficiently clean, it can obtain yin from
Son is OH-Anion-exchange membrane.
After measured, the ion exchange capacity of the film is 0.86mmol/g.Water absorption rate at room temperature is 8%；Film is at 40 DEG C
Under conductivity be 9.6mS/cm.
Embodiment 3
In the present embodiment, the anion-exchange membrane based on adamantane quaternary ammonium salt has structural formula shown in formula (13):
It is specific the preparation method comprises the following steps:
By 0.5g methyl bromide degree be 30% brominated polyphenylether be dissolved in 10mL N-Methyl pyrrolidone, then plus
Enter 0.2g N- ethyl-N- propyl adamantane tertiary amine, is warming up to 50 DEG C of reaction 48h.After reaction, reaction system is slowly dripped
It is added in a large amount of ether and is precipitated, filter, sufficiently washed with fresh ether, dried in 60 DEG C of vacuum drying ovens, obtain based on gold
The polyphenylene oxide of rigid alkane quaternary ammonium salt.
The polyphenylene oxide based on adamantane quaternary ammonium salt of preparation is dissolved in N-Methyl pyrrolidone, obtaining mass fraction is
10% polymer solution.After filtering, the solution is coated on clean glass plate with the tape casting, glass plate is placed on 80
DEG C drying box in be dried overnight, to remove most of solvent, be then transferred to molten sufficiently to remove in 80 DEG C of vacuum ovens
Agent.It is cooled to room temperature taking-up glass plate to temperature, places it in demoulding in deionized water, it is thin after sufficiently being washed with deionized water
Film is placed in drying box and dries, and obtains the anion-exchange membrane that anion is bromide ion.
The film is placed in 2mol/L KOH solution and impregnates 48h, then with deionized water sufficiently clean, it can obtain yin from
Son is OH-Anion-exchange membrane.
After measured, the ion exchange capacity of the film is 1.57mmol/g.Water absorption rate at room temperature is 13%；Film is at 40 DEG C
Under conductivity be 10.2mS/cm.
Embodiment 4
In the present embodiment, the anion-exchange membrane based on adamantane quaternary ammonium salt has structural formula shown in formula (14):
It is specific the preparation method comprises the following steps:
The copolymer (p-chloromethyl styrene molar content is 30%) of 1.00g styrene and p-chloromethyl styrene is molten
Then solution is added 0.70g N- methyl-N-isopropyl adamantane tertiary amine, is warming up to 40 in 10mL n,N-dimethylacetamide
DEG C reaction 48h.After reaction, by polymer solution, Precipitation, washing are obtained after drying containing adamantane in a large amount of ether
Quaternary ammonium salt polystyrene.
The polystyrene for preparing the quaternary ammonium salt containing adamantane is dissolved in N-Methyl pyrrolidone, obtaining mass fraction is
10% polymer solution.After filtering, the solution is coated on clean glass plate with the tape casting, glass plate is placed on 80
DEG C drying box in be dried overnight, to remove most of solvent, be then transferred to molten sufficiently to remove in 80 DEG C of vacuum ovens
Agent.It is cooled to room temperature taking-up glass plate to temperature, places it in demoulding in deionized water, it is thin after sufficiently being washed with deionized water
Film is placed in a vacuum drying oven drying, obtains the anion-exchange membrane that anion is chloride ion.
The film is placed in 2mol/L KOH solution and impregnates 48h, then with deionized water sufficiently clean, it can obtain yin from
Son is OH-Anion-exchange membrane.
After measured, the ion exchange capacity of the film is 1.71mmol/g.Water absorption rate at room temperature is 17%；Film is at 40 DEG C
Under conductivity be 15.2mS/cm.
Embodiment 5
In the present embodiment, the anion-exchange membrane based on adamantane quaternary ammonium salt has structural formula shown in formula (15):
It is specific the preparation method comprises the following steps:
The chloromethylation polyether sulfone that 1.00g chloromethylation degree of substitution is 40% is dissolved in 20mL N, N- dimethyl formyl
In amine, 0.35g N, N- dimethyladamantane tertiary amine is then added, and system is warming up to 45 DEG C of reaction 48h.After reaction,
System is precipitated in ether, wash, filter, dry after obtain the polyether sulfone of the quaternary ammonium salt containing adamantane.
The polyether sulfone of the quaternary ammonium salt containing adamantane of preparation is dissolved in n,N-Dimethylformamide, mass fraction is obtained
For 15% polymer solution.After filtering, the solution is coated on clean glass plate with the tape casting, glass plate is placed on
It is dried overnight in 80 DEG C of drying box, to remove most of solvent, is then transferred in 80 DEG C of vacuum ovens sufficiently to remove
Solvent.It is cooled to room temperature taking-up glass plate to temperature, places it in demoulding in deionized water, after sufficiently being washed with deionized water,
Film is placed in a vacuum drying oven drying, obtains the anion-exchange membrane that anion is chloride ion.
The film is placed in 1mol/L KOH solution and impregnates 48h, then with deionized water sufficiently clean, it can obtain yin from
Son is OH-Anion-exchange membrane.
After measured, the ion exchange capacity of the film is 0.83mmol/g.Water absorption rate at room temperature is 6%；Film is at 40 DEG C
Under conductivity be 8.6mS/cm.
Claims (9)
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| CN107383406B (en) * | 2017-08-14 | 2020-08-07 | 合肥工业大学 | Anion exchange membrane material with excellent mechanical property and preparation method and application thereof |
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| CN104817714A (en) * | 2015-03-25 | 2015-08-05 | 沈阳化工大学 | Adamantane structure-containing polyarylether anion-exchange membrane and preparation method thereof |
| CN105504284A (en) * | 2016-01-04 | 2016-04-20 | 中国科学院长春应用化学研究所 | Polymer containing quaternary ammonium group, anion exchange membrane and preparation method thereof |
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| CN105504284A (en) * | 2016-01-04 | 2016-04-20 | 中国科学院长春应用化学研究所 | Polymer containing quaternary ammonium group, anion exchange membrane and preparation method thereof |
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