CN106268381A - A kind of anion exchange membrane of resistance to alkaline hydrolysis material and its preparation method and application - Google Patents
A kind of anion exchange membrane of resistance to alkaline hydrolysis material and its preparation method and application Download PDFInfo
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- CN106268381A CN106268381A CN201610792970.9A CN201610792970A CN106268381A CN 106268381 A CN106268381 A CN 106268381A CN 201610792970 A CN201610792970 A CN 201610792970A CN 106268381 A CN106268381 A CN 106268381A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The present invention discloses anion exchange membrane material of a kind of resistance to alkaline hydrolysis and its preparation method and application: this novel anionic exchange membrane material has the structure as shown in (1);The present invention selects the omethylated polymers containing different degree of substitution to be polymer basic framework, by carrying out quaterisation with diamantane (obsolete) tertiary amine, then carries out ion exchange, obtains anion exchange membrane material based on diamantane (obsolete) quaternary ammonium salt.Cheaper starting materials used by the present invention is easy to get, and preparation method is simple, is suitable for large-scale industrial production, has the many advantages such as chemical stability good, ionic conductance is high, excellent in mechanical performance based on the anion exchange membrane prepared by this anion exchange membrane material.
Description
Technical field
The invention belongs to ion exchange membrane material field, be specifically related to one using diamantane (obsolete) quaternary ammonium salt as function cation
Anion exchange membrane material and its preparation method and application.
Background technology
Anion exchange membrane is that a class is with fixing cation group, the optional polymer dielectric material by anion
Material, is made up of anion three part moveable on polymer backbone, the functional group of charge positive charge and functional group.Due to
It is in the extensive application of the industrial circles such as fuel cell barrier film, basic industry barrier film, water process, and its exploitation and performance optimization are at material
Material and chemical industrial field are constantly subjected to pay close attention to widely.
The functional group of charge positive charge is to be connected on polymer backbone by chemical bond, also referred to as ion-exchange group, cloudy
The ion exchanging function of ion exchange membrane is determined by it.At present, quaternary ammonium salt is the most sufficiently ion-exchange group of research, but
Owing to the chemical stability of anion exchange membrane based on conventional quaternary ammonium salts is inadequate, quaternary ammonium can occur the most in the basic conditions
The decomposition of cation, it is impossible to meet requirement (the J.R.Varcoe and of anion exchange membrane life-time service in the basic conditions
R.C.T.Slade,Fuel Cells,2005,5,187-200.)。
Therefore, design and synthesize the ion-exchange group with superior chemical stability, and prepare based on this and meet fuel
The high performance anion-exchange membrane material of battery applications is the key issue needing solution at present badly.
Summary of the invention
It is an object of the invention to be for the deficiencies in the prior art, it is provided that a kind of anion based on diamantane (obsolete) quaternary ammonium salt
Exchange membrane material and its preparation method and application, to be solved technical problem is that makes this anion exchange membrane material of gained have
Excellent alkali resistance and relatively high ion conductivity, so that it is in alkaline fuel cell barrier film, chlorine industry, film electrolysis, electrodialysis
Etc. association area, there is preferable application prospect.
Technical scheme is as follows:
Shown in the structural formula such as formula (1) of the anion exchange membrane material based on diamantane (obsolete) quaternary ammonium salt that the present invention provides:
It has a diamantane (obsolete) quaternary ammonium salt structure as shown in formula (2):
R in its Chinese style (1) and (2)1, R2It is each independently selected from the aliphatic substitution that carbon number is 1~16, or carbon
Atomic number is the aromatic substituents of 6~24;X is anion, at least one in Cl, Br.
Shown in the structure such as formula (3) of the polymer backbone in formula (1), formula (4), formula (5) or formula (6):
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)
Just alkane quaternary ammonium salt;
In formula (4): 1≤h1+i1+j1+k1≤4, and it it is integer;X=0.01~0.99;N is between 10 to 1000
Integer;Q refers to the diamantane (obsolete) quaternary ammonium salt as shown in formula (2);R3One or more in following structure:
In formula (5): 1≤h2+i2+j2+k2≤4, and it it is integer;X=0.01~0.99;N is between 10 to 1000
Integer;Q refers to the diamantane (obsolete) quaternary ammonium salt as shown in formula (2);R4One or more in following structure:
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)
Just alkane quaternary ammonium salt.
In the present invention, the preparation method of anion exchange membrane material based on diamantane (obsolete) quaternary ammonium salt, mainly includes walking as follows
Rapid:
The polymer of halomethylation is dissolved in organic solvent, according to halomethyl mole contained by omethylated polymers
1~10 times addition diamantane (obsolete) tertiary amine compound, at 0~60 DEG C react 1~48h;After reaction terminates, precipitate in precipitant
Separate out, separate, wash, after drying, obtain anion exchange membrane material based on diamantane (obsolete) quaternary ammonium salt.
Wherein: shown in the general structure of the polymer of described 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 in3Refer to identical;R4With R in formula (5)4Refer to identical;N is the integer between 10 to 1000;Y is Cl or Br.
The general structure of described diamantane (obsolete) tertiary amine compounds isWherein R1、R2Refer to formula (1) and
(2) referring in is identical;Described organic solvent is preferably polar non-solute, such as dimethyl sulfoxide, N-Methyl pyrrolidone, N,
Dinethylformamide, DMAC N,N' dimethyl acetamide;Described precipitant is selected from water, methanol, ethanol, acetone or ether at least
A kind of.
Invention further provides the preparation method of anion exchange membrane based on above-mentioned anion exchange membrane material, table
State as follows:
Anion exchange membrane material based on diamantane (obsolete) quaternary ammonium salt is dissolved in organic solvent, it is thus achieved that based on diamantane (obsolete) season
The polymer solution of the anion exchange membrane material of ammonium salt;The polymer solution film on matrix or reinforced fabric that will obtain,
After removing solvent, obtain the anion exchange membrane that anion is chloride ion or bromide ion.Carry out hydroxide radical anion friendship further
Changing, i.e. obtaining anion is hydroxide ion anion exchange membrane.
The preparation method of above-mentioned anion exchange membrane, also has a characteristic that
Described organic solvent selected from polar non-solute (such as DMF, N,N-dimethylacetamide,
N-Methyl pyrrolidone, dimethyl sulfoxide, gamma-butyrolacton etc.) or chloroform, sym.-tetrachloroethane, acetonitrile in one or
Their mixed solvent;Described matrix is selected from glass plate or polyfluortetraethylene plate;Described reinforced fabric select polyethylene cloth, poly-third
Alkene cloth, woven dacron, nylon cloth or polrvinyl chloride cloth;The method of described film can be solution-cast film forming, spin-coating, scrape
Film, it is cast or impregnates;The method of described removal solvent can be selected for room temperature volatilization or at 30~200 DEG C of heating, dryings.
Above-mentioned anion is that the anion in the anion exchange membrane of halogen atom can change into other the moon as required
Ion, will be converted to other required ion by halide ion, such as by the X in formula (1):
The anion exchange membrane that described anion is halide ion is immersed in the NaOH water that concentration is 0.01~10mol/L
Solution or KOH aqueous solution that concentration is 0.01~10mol/L carry out anion exchange, it is thus achieved that anion is hydroxide ion
Anion exchange membrane (will the structural formula of anion exchange membrane material based on diamantane (obsolete) quaternary ammonium salt in X be converted to OH).
The anion exchange membrane that the present invention is obtained can be applied in multiple barrier film field, is particularly suitable for use as alkalescence combustion
The anion exchange membrane of material battery.
Compared with existing anion exchange membrane material structure, the moon based on diamantane (obsolete) quaternary ammonium salt provided by the present invention from
Proton exchange membrane material raw material sources are extensive, preparation method is simple;It addition, obtain based on diamantane (obsolete) quaternary ammonium salt anion exchange membrane
There is chemical stability and the ionic conductance of excellence, it is possible to meet the application demand of fuel cell field, there is good answering
Use prospect.
Accompanying drawing explanation
Fig. 1 is the NMR (Nuclear Magnetic Resonance) spectrum figure (DMSO-d of the anion exchange membrane prepared by embodiment 16);
Fig. 2 is the Cl of the anion exchange membrane prepared by embodiment 1ˉElectrical conductivity variation with temperature curve;
Fig. 3 be the anion exchange membrane prepared by embodiment 1 at 1M NaOH (aq), alkaline hydrolysis under the conditions of 60 DEG C, after alkaline hydrolysis
ClˉElectrical conductivity is with alkaline hydrolysis time-varying relationship.
Detailed description of the invention
The present invention is described in further detail with embodiment below in conjunction with accompanying drawing.
Embodiment 1
In the present embodiment, anion exchange membrane based on diamantane (obsolete) quaternary ammonium salt has a structural formula shown in formula (11):
Concrete preparation method is:
The brominated polyphenylether that 0.5g methyl bromide degree is 40% is dissolved in 10mL N-Methyl pyrrolidone, then adds
Enter 0.4g N, N-dimethyladamantane tertiary amine, be warming up to 50 DEG C of reaction 24h.After reaction terminates, reaction system is slowly dropped to
A large amount of ether separate out, filters, fully wash with fresh ether, dry in 60 DEG C of vacuum drying ovens, obtain based on diamantane (obsolete)
The polyphenylene oxide of quaternary ammonium salt.
Being dissolved in N-Methyl pyrrolidone by the polyphenylene oxide based on diamantane (obsolete) quaternary ammonium salt of preparation, obtaining mass fraction is
The polymer solution of 10%.After filtration, by the tape casting, this solution is coated on the glass plate of cleaning, glass plate is placed on 80
DEG C drying baker in be dried overnight, to remove major part solvent, be then transferred in 80 DEG C of vacuum drying ovens fully to remove molten
Agent.After temperature is down to room temperature, takes out glass plate, is placed on demoulding in deionized water, then after fully washing with deionized water,
Thin film is placed in drying baker drying, obtains the anion exchange membrane that anion is bromide ion.
This thin film is placed in 2mol/L KOH solution immersion 48h, more fully washs thin film with deionized water, i.e. can obtain
It is OH to anion-Anion exchange membrane.
After measured, the ion exchange capacity of this thin film is 2.02mmol/g.Water absorption rate under room temperature is 21%;Film is at 40 DEG C
Under electrical conductivity (surveyed electrical conductivity by OH by 13.9mS/cmˉIt is exchanged into ClˉThe Cl of rear testˉElectrical conductivity, institute in example below
The electrical conductivity referred to is ClˉElectrical conductivity.).
This anion exchange membrane is placed in 60 DEG C, 1M NaOH (aq) carries out alkaline hydrolysis stability test, measure its ClˉElectricity
Conductance is with the variation relation of alkaline hydrolysis time.
Embodiment 2
In the present embodiment, anion exchange membrane material based on diamantane (obsolete) quaternary ammonium salt has a structural formula shown in formula (12):
Concrete preparation method is:
The chloromethylation polyether sulfone that 1.00g chloromethylation substitution value is 50% is dissolved in 10mL N, N-dimethyl formyl
In amine, it is subsequently adding 0.40g N-methyl--V-pentyl diamantane (obsolete) tertiary amine, is warming up to 45 DEG C of reaction 48h.After reaction terminates, by body
Tie up to ether precipitates, wash, filter, obtain polyether sulfone based on diamantane (obsolete) quaternary ammonium salt after drying.
The polyether sulfone based on diamantane (obsolete) quaternary ammonium salt of preparation is dissolved in DMF, obtains mass fraction
It it is the polymer solution of 15%.After filtration, by the tape casting, this solution is coated on the glass plate of cleaning, glass plate is placed on
The drying baker of 80 DEG C is dried overnight, to remove major part solvent, is then transferred in 80 DEG C of vacuum drying ovens fully remove
Solvent.After temperature is down to room temperature, takes out glass plate, is placed on demoulding in deionized water, after fully washing with deionized water,
Thin film is placed in drying baker drying, obtains the anion exchange membrane that anion is chloride ion.
This film is placed in 1mol/L KOH solution immersion 48h, more clean with deionized water, i.e. can obtain cloudy from
Son is OH-Anion exchange membrane.
After measured, the ion exchange capacity of this thin film is 0.86mmol/g.Water absorption rate under room temperature is 8%;Film is at 40 DEG C
Under electrical conductivity be 9.6mS/cm.
Embodiment 3
In the present embodiment, anion exchange membrane based on diamantane (obsolete) quaternary ammonium salt has a structural formula shown in formula (13):
Concrete preparation method is:
The brominated polyphenylether that 0.5g methyl bromide degree is 30% is dissolved in 10mL N-Methyl pyrrolidone, then adds
Enter 0.2g N-ethyl-N-propyl group diamantane (obsolete) tertiary amine, be warming up to 50 DEG C of reaction 48h.After reaction terminates, reaction system is slowly dripped
It is added in a large amount of ether separate out, filters, fully wash with fresh ether, dry in 60 DEG C of vacuum drying ovens, obtain based on gold
The just polyphenylene oxide of alkane quaternary ammonium salt.
Being dissolved in N-Methyl pyrrolidone by the polyphenylene oxide based on diamantane (obsolete) quaternary ammonium salt of preparation, obtaining mass fraction is
The polymer solution of 10%.After filtration, by the tape casting, this solution is coated on the glass plate of cleaning, glass plate is placed on 80
DEG C drying baker in be dried overnight, to remove major part solvent, be then transferred in 80 DEG C of vacuum drying ovens fully to remove molten
Agent.After temperature is down to room temperature, takes out glass plate, is placed on demoulding in deionized water, after fully washing with deionized water, thin
Film is placed in drying baker drying, obtains the anion exchange membrane that anion is bromide ion.
This film is placed in 2mol/L KOH solution immersion 48h, more clean with deionized water, i.e. can obtain cloudy from
Son is OH-Anion exchange membrane.
After measured, the ion exchange capacity of this thin film is 1.57mmol/g.Water absorption rate under room temperature is 13%;Film is at 40 DEG C
Under electrical conductivity be 10.2mS/cm.
Embodiment 4
In the present embodiment, anion exchange membrane based on diamantane (obsolete) quaternary ammonium salt has a structural formula shown in formula (14):
Concrete preparation method is:
By molten for the copolymer (p-chloromethyl styrene molar content is 30%) of 1.00g styrene and p-chloromethyl styrene
Solution, in 10mL N,N-dimethylacetamide, is subsequently adding 0.70g N-methyl-N-isopropyl diamantane (obsolete) tertiary amine, is warming up to 40
DEG C reaction 48h.After reaction terminates, by polymer solution Precipitation in a large amount of ether, wash, obtain containing diamantane (obsolete) after drying
The polystyrene of quaternary ammonium salt.
Being dissolved in N-Methyl pyrrolidone by the polystyrene of the preparation quaternary ammonium salt containing diamantane (obsolete), obtaining mass fraction is
The polymer solution of 10%.After filtration, by the tape casting, this solution is coated on the glass plate of cleaning, glass plate is placed on 80
DEG C drying baker in be dried overnight, to remove major part solvent, be then transferred in 80 DEG C of vacuum drying ovens fully to remove molten
Agent.After temperature is down to room temperature, takes out glass plate, is placed on demoulding in deionized water, after fully washing with deionized water, thin
Film is placed in vacuum drying oven drying, obtains the anion exchange membrane that anion is chloride ion.
This film is placed in 2mol/L KOH solution immersion 48h, more clean with deionized water, i.e. can obtain cloudy from
Son is OH-Anion exchange membrane.
After measured, the ion exchange capacity of this thin film is 1.71mmol/g.Water absorption rate under room temperature is 17%;Film is at 40 DEG C
Under electrical conductivity be 15.2mS/cm.
Embodiment 5
In the present embodiment, anion exchange membrane based on diamantane (obsolete) quaternary ammonium salt has a structural formula shown in formula (15):
Concrete preparation method is:
The chloromethylation polyether sulfone that 1.00g chloromethylation substitution value is 40% is dissolved in 20mL N, N-dimethyl formyl
In amine, it is subsequently adding 0.35g N, N-dimethyladamantane tertiary amine, and system is warming up to 45 DEG C of reaction 48h.After reaction terminates,
System is precipitated in ether, washs, filter, obtain after drying the polyether sulfone of quaternary ammonium salt containing diamantane (obsolete).
The polyether sulfone of the quaternary ammonium salt containing diamantane (obsolete) of preparation is dissolved in DMF, obtains mass fraction
It it is the polymer solution of 15%.After filtration, by the tape casting, this solution is coated on the glass plate of cleaning, glass plate is placed on
The drying baker of 80 DEG C is dried overnight, to remove major part solvent, is then transferred in 80 DEG C of vacuum drying ovens fully remove
Solvent.After temperature is down to room temperature, takes out glass plate, is placed on demoulding in deionized water, after fully washing with deionized water,
Thin film is placed in vacuum drying oven drying, obtains the anion exchange membrane that anion is chloride ion.
This film is placed in 1mol/L KOH solution immersion 48h, more clean with deionized water, i.e. can obtain cloudy from
Son is OH-Anion exchange membrane.
After measured, the ion exchange capacity of this thin film is 0.83mmol/g.Water absorption rate under room temperature is 6%;Film is at 40 DEG C
Under electrical conductivity be 8.6mS/cm.
Claims (10)
1. the anion exchange membrane material of a resistance to alkaline hydrolysis, it is characterised in that as shown in formula (1) using diamantane (obsolete) quaternary ammonium salt as
The anion exchange membrane material of function cation:
2. anion exchange membrane material as claimed in claim 1, it is characterised in that containing the diamantane (obsolete) quaternary ammonium as shown in formula (2)
Salt structure:
3. the anion exchange membrane material based on diamantane (obsolete) quaternary ammonium salt as described in claim 1 and 2, it is characterised in that:
In formula (1) and (2): R1, R2It is each independently selected from the aliphatic substitution that carbon number is 1~16, or carbon number is
The aromatic substituents of 6~24;X is anion, at least one in Cl, Br.
4. anion exchange membrane material based on diamantane (obsolete) quaternary ammonium salt as claimed in claim 1, it is characterised in that: in formula (1)
The structure such as formula (3) of polymer backbone, formula (4), formula (5) or formula (6) shown in:
In formula (3): x=0.01~0.99;N is the integer between 10 to 1000;Q refers to the diamantane (obsolete) as shown in formula (2)
Quaternary ammonium salt;
In formula (4): 1≤h1+i1+j1+k1≤4, and it it is integer;X=0.01~0.99;N is whole between 10 to 1000
Number;Q refers to the diamantane (obsolete) quaternary ammonium salt as shown in formula (2);R3One or more in following structure:
In formula (5): 1≤h2+i2+j2+k2≤4, and it it is integer;X=0.01~0.99;N is whole between 10 to 1000
Number;Q refers to the diamantane (obsolete) quaternary ammonium salt as shown in formula (2);R4One or more in following structure:
In formula (6): x=0.01~0.99;N is the integer between 10 to 1000;Q refers to the diamantane (obsolete) as shown in formula (2)
Quaternary ammonium salt.
5. the preparation method of the anion exchange membrane material based on diamantane (obsolete) quaternary ammonium salt described in claim 1, its feature exists
In carrying out as follows:
The polymer of halomethylation is dissolved in organic solvent, according to contained by omethylated polymers the 1 of halomethyl mole
~10 times of addition diamantane (obsolete) tertiary amine compounds, at 0~60 DEG C, react 1~48h;After reaction terminates, precipitation analysis in precipitant
Go out, separate, wash, after drying, obtain anion exchange membrane material based on diamantane (obsolete) quaternary ammonium salt.
The preparation method of anion exchange membrane material based on diamantane (obsolete) quaternary ammonium salt the most according to claim 5, its feature
It is:
Shown in the general structure of the polymer of described halomethylation such as formula (7), formula (8), formula (9) or formula (10), in formula: x=
0.01~0.99;1≤h1+i1+j1+k1≤4, and be integer;1≤h2+i2+j2+k2≤4, and be integer;R3With R in formula (4)3
Refer to identical;R4With R in formula (5)4Refer to identical;N is the integer between 10 to 1000;Y is Cl or Br;
The general structure of described diamantane (obsolete) tertiary amine compound isWherein R1、R2Refer to and formula (1) refer to phase
With;
Described organic solvent is polar non-solute;
At least one in water, methanol, ethanol, acetone or ether of described precipitant.
7. a preparation method for anion exchange membrane based on the anion exchange membrane material described in claim 1, its feature
It is:
Anion exchange membrane material based on diamantane (obsolete) quaternary ammonium salt is dissolved in organic solvent, it is thus achieved that based on diamantane (obsolete) quaternary ammonium salt
The polymer solution of anion exchange membrane material;The polymer solution film on matrix or reinforced fabric that will obtain, removes
After solvent, obtain the anion exchange membrane that anion is chloride ion or bromide ion.Carry out hydroxide radical anion exchange further, i.e.
Obtaining anion is hydroxide ion anion exchange membrane.
The preparation method of anion exchange membrane the most according to claim 7, it is characterised in that: described organic solvent is selected from
Polar non-solute (such as DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide,
Gamma-butyrolacton etc.) or chloroform, 1,1,2,2-sym-tetrachloroethane, acetonitrile in a kind of or their mixed solvent;Described film side
Method is solution-cast film forming, spin-coating, knifing, dipping or casting film-forming.
The preparation method of anion exchange membrane the most according to claim 7, it is characterised in that: it is chlorine by the anion of preparation
The anion exchange membrane of ion or bromide ion be immersed in NaOH aqueous solution that concentration is 0.01~10mol/L or concentration be 0.01~
Carrying out anion exchange in the KOH aqueous solution of 10mol/L, obtaining corresponding anion is anion exchange membrane hydroxy.
10. the application of anion exchange membrane obtained by preparation method as described in claim 7,8 and 9, it is characterised in that: preferably
For the anion exchange membrane as alkaline fuel cell.
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CN108232225A (en) * | 2018-01-02 | 2018-06-29 | 泰顺永庆电力技术有限公司 | A kind of diaphragm of vanadium cell containing adamantane structure and preparation method thereof |
CN114507350A (en) * | 2022-01-17 | 2022-05-17 | 北京化工大学 | Polyphosphazene anion exchange membrane loaded with adamantyl quaternary phosphonium cation unit and preparation method thereof |
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