CN104311857B - A kind of preparation method of pair of quaternary ammonium side long chain type anion-exchange membrane - Google Patents
A kind of preparation method of pair of quaternary ammonium side long chain type anion-exchange membrane Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of pair of quaternary ammonium side long chain type anion-exchange membrane, it is characterised in that：Nucleophilic substitution is carried out to the main polymer chain containing active benzyl bromine, benzyl chloride or chlorine carboxyl groups by the bi-functional monomer simultaneous with tertiary amine group and quaternary ammonium group, double quaternary ammonium sides long chain type anion-exchange membrane is obtained.The present invention is raw materials used cheap and easy to get, and preparation technology is simple, is adapted to large-scale industrial production.Prepared anion-exchange membrane has many advantages such as high ion-conductivity, service life length, mechanical performance are excellent, dissolubility is good.
Description
Technical field
The invention belongs to technical field of membrane, more particularly to be a kind of high anionic conduction double quaternary ammonium sides long chain type it is cloudy
Amberplex and preparation method thereof.
Background technology
Anion-exchange membrane has a very wide range of applications in terms of metallurgy, chemical industry, biology and the energy, is used as a variety of electricity
The key component of chemical technology such as film electrolysis, electrodialysis, pressure difference dialysis and fuel cell etc., in recent years its research and development, prepare and change
Enter and increasingly paid close attention to by people.
Britain《Energy and environment science》(Energy Environ.Sci., 2013,6,2912) reports a kind of pair of quaternary ammonium
The preparation method of side long chain type anion-exchange membrane, i.e., it is 2,3- epoxypropyltrimethylchloride chlorides (GTMC) and dimethylamine is anti-
Should, prepare 3- (dimethylamino) -2- hydroxypropyls-N, N, N- trimethyl ammonium chloride (DHTC).This functional group one end
With tertiary amine group, the other end carries quaternary ammonium group.Nucleophilic displacement of fluorine is carried out to the polysulfones of chloromethylation using this functional group
Reaction, that is, obtain the anion-exchange membrane containing double quaternary ammonium functional groups in side chain.But the raw material that this preparation technology is used
2,3- epoxypropyltrimethylchloride chloride prices costly, are not suitable for large-scale commercial Application.And due to two in side chain
Individual quaternary ammonium group shares a β-hydrogen, causes its side chain to be easier to occur hoffman degradation reaction.In addition, the quaternary ammonium of side chain terminal
Only have three atom separations between group and main chain, cause the locomitivity of side chain poor, this causes such a anion exchange
The microcosmic hydrophilic-hydrophobic phase separation ability of film is poor, so as to limit the anionic conduction performance of such a anion-exchange membrane, separately
On the one hand, also cause the pliability of its anion-exchange membrane poor.
The content of the invention
To avoid the weak point present in above-mentioned prior art, a kind of technique of present invention offer is simple, raw material is inexpensively easy
, it is adapted to the preparation method of the anion-exchange membrane of large-scale industrial production, and prepared anion-exchange membrane has conductance
The many advantages such as height, service life length, mechanical performance are excellent, dissolubility is good.
The present invention solves technical problem, adopts the following technical scheme that：
The invention discloses a kind of preparation method of high conductance anion-exchange membrane, its feature is：With containing simultaneously
The bi-functional monomer of tertiary amine group and quaternary ammonium group enters to the main polymer chain containing active benzyl bromine, benzyl chloride or chlorine carboxyl groups
Row nucleophilic substitution, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
The preparation method of a kind of pair of quaternary ammonium side long chain type anion-exchange membrane of the invention, its feature is lain also in：
Shown in the general structure such as formula (1) of the bi-functional monomer simultaneously containing tertiary amine group and quaternary ammonium group, n in formula
=1~22, m=2~6；
The compound for meeting structural formula (1) is preferred：6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyls ammonium bromide,
6- (dimethylamino) hexyl-N, N- dimethyl-N -s butylammonium bromide, 6- (dimethylamino) hexyl-N, N- dimethyl-N-ten
Eight alkyl bromination ammoniums.
The polymer containing active benzyl bromine, benzyl chloride or chlorine carboxyl groups is brominated polyphenylether (BPPO), chloromethyl
Change polysulfones (CPES), chloromethylation polyether sulfone (CPSU), chloromethylation polyether-ketone (CPEK), chloromethylation polyphenylene oxide (CPPO),
Chlorine is acylated polyphenylene oxide (CAPPO), chloromethylated polystyrene (CPSt) etc..
The preparation method is that carrying out as follows：
(1) preparation of the bi-functional monomer simultaneously containing tertiary amine group and quaternary ammonium group：Di-tertiary amine monomer is dissolved in molten
In agent, brominated alkanes are then added, 6h-48h is reacted at 20~60 DEG C, after reaction terminates, rotary evaporation is removed after solvent, plus
Enter proper amount of acetone or acetonitrile, be filtered to remove precipitation, the processing of filtrate rotary evaporation removes after acetone or acetonitrile, adds appropriate second
Ether or ethyl acetate washing, filtering, that is, obtain the bi-functional monomer containing tertiary amine group and quaternary ammonium group simultaneously；
The solvent is ethanol, methanol, acetonitrile, isopropanol chloroform or tetrahydrofuran；The brominated alkanes and described couple of uncle
The ratio between mole of amine monomers is 0.1-1：1；The di-tertiary amine monomer be N, N, N', N'- tetramethyl -1,2- ethylenediamines, N, N,
N', N'- tetramethyl-Putriscine, N, N, N', N'- tetramethyl -1,3- butanediamine, N, N, N', N'- tetramethyls -1,6- oneself two
Amine.The brominated alkanes are that 1- bromoethanes, 1- N-Propyl Bromides, 1- NBBs, 1- bromo pentane silanes, hexyl bromide 1 bromohexane, 1- heptyl bromides, 1- bromines are pungent
Alkane, 1- bromononanes, 1- bromo-decanes, 1- bromo-n-11s, 1- bromo-dodecanes, 1- bromine 13s alkane, 1- bromo-tetradecanes, pe-ntadecyl bromide,
1- bromines hexadecane, 1- bromines heptadecane, 1- bromo-octadecanes, 1- bromines eicosane, 1- bromine docosane.
(2) preparation of double quaternary ammonium side long chain type anion-exchange membranes：Active benzyl bromine, benzyl chloride or chlorine carboxyl groups will be contained
Polymer be dissolved in be configured in aprotic polar solvent mass concentration be 5%-50% homogeneous solution；Then add thereto
Enter the bi-functional monomer containing tertiary amine group and quaternary ammonium group simultaneously, 1~72h is reacted at 20~60 DEG C, uniform casting solution is obtained；
By the casting solution after cladding process film forming, 6-48h is soaked in deionized water, that is, obtains double quaternary ammonium sides long chain type anion
Exchange membrane；The bi-functional monomer simultaneously containing tertiary amine group and quaternary ammonium group with it is described containing active benzyl bromine, benzyl chloride or
The ratio between mole of polymer of chlorine carboxyl groups is 1~5:1.
The aprotic polar solvent is METHYLPYRROLIDONE, N,N-dimethylformamide, dimethyl sulfoxide or N, N-
Dimethyl acetamide.
Shown in the structural formula of the brominated polyphenylether such as formula (2), x is defined as the bromination degree of brominated polyphenylether in formula：
The chlorine is acylated shown in the structural formula such as formula (3) of polyphenylene oxide, and y is defined as the function that chlorine is acylated polyphenylene oxide in formula
Degree：
Shown in the structural formula such as formula (4) of the chloromethylation polyphenylene oxide, z is defined as the function of chloromethylation polyphenylene oxide in formula
Degree：
Shown in the structural formula of the chloromethyl polysulphone such as formula (5), t is defined as the functionality of chloromethyl polysulphone in formula：
Shown in the structural formula such as formula (6) of the chloromethylation polyether-ketone, u is defined as the function of chloromethylation polyether-ketone in formula
Degree：
Shown in the structural formula such as formula (7) of the chloromethylation polyether sulfone, v is defined as the function of chloromethylation polyether sulfone in formula
Degree：
Shown in the structural formula of the chloromethylated polystyrene such as formula (8), w is defined as chloromethylated polystyrene in formula
Functionality：
By the tertiary amine group in the bi-functional monomer with tertiary amine group and quaternary ammonium group simultaneously to containing active benzyl chloride, Bian
The polymer of bromine or chlorine carboxyl groups carries out nucleophilic substitution, has prepared double quaternary ammonium side long chain type anion-exchange membranes.And
And prepared double quaternary ammonium side long chain type amberplexes have containing two quaternary ammonium groups on overlength side chain and side chain, this causes
The side chain of such a anion-exchange membrane keep high charge density while with suitable flexibility, with extraordinary microcosmic parent
Water hydrophobic phase separating capacity, so as to reach very high conductance.
Compared with prior art, beneficial effects of the present invention are embodied in：
1st, by the present invention in that with the polymer of difference in functionality degree, can accurately control prepared anion-exchange membrane from
The performances such as sub- exchange capacity, anionic conduction, moisture content；
2nd, the polymer-based film with benzyl bromine or benzyl chloride functional group is immersed in trimethylamine by the present invention different from traditional
In technical method, using the method for homogeneous reaction, thus in the absence of be used for a long time during hydraulic performance decline the problem of, extend
The service life of film；
3rd, present invention short-side chain anion-exchange membrane different from the past, longer side chain has stronger mobility,
And the formation that can largely promote the microcosmic hydrophilic-hydrophobic of amberplex to be separated, substantially increase anion friendship
Change the ionic conduction performance of film；
4th, the maximum advantage of the present invention, has exactly prepared the anion-exchange membrane that side chain contains two quaternary ammonium groups, this
Plant structure and substantially increase the density of quaternary ammonium group in anion transmission channel, so that the conductance of superelevation is obtained, and original used
Material is cheap, and synthesis step is easy, it is easy to industrialize.
Brief description of the drawings
Fig. 1 is the core of gained 6- (dimethylamino) hexyl-N, N- the dimethyl-N-ethyl ammonium bromides of the embodiment of the present invention 1
Magnetic resonance hydrogen is composed；
Fig. 2 is able to the double quaternary ammonium side long chain type anion-exchange membranes and bromine that polyphenylene oxide is main chain by the embodiment of the present invention 1
Change the proton nmr spectra of polyphenylene oxide；
Fig. 3 is the core of gained 6- (dimethylamino) hexyl-N, N- the dimethyl-N-decyl ammonium bromides of the embodiment of the present invention 23
Magnetic resonance hydrogen is composed；
Fig. 4 is able to the core for double quaternary ammonium side long chain type anion-exchange membranes that polyphenylene oxide is main chain by the embodiment of the present invention 23
Magnetic resonance hydrogen is composed.
Embodiment
The present invention is further described below by specific embodiment.
Embodiment 1
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：By 1mL N, N, N', N'- tetra-
Methyl isophthalic acid, 6- hexamethylene diamines are dissolved in 19mL ethanol, are configured to the solution of 5% volume fraction, add the 1- bromine second of 1 times of mole
Alkane, reacts 48h at room temperature.Rotary evaporation removes ethanol, adds proper amount of acetone, is filtered to remove precipitation, and filtrate rotary evaporation is handled,
Remove after acetone, washed with ether for several times, filtering obtains 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl brominations
Ammonium.
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：0.3g brominations degree is dissolved for 0.084 brominated polyphenylether
In 3mL (2.92g) METHYLPYRROLIDONE, 0.084g 6- (dimethylamino) hexyl-N, N- dimethyl-N -s are added
Ethyl phosphonium bromide ammonium, stirs 12h and obtains uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, at 60 DEG C
12h is dried, 12h is then soaked in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
6- (dimethylamino) hexyl-N, the N- dimethyl-N-ethyls ammonium bromide obtained to the present embodiment carries out nuclear-magnetism
Resonate hydrogen analysis of spectrum, as a result as shown in figure 1, as can be seen from the figure successfully having prepared the 6- (two of high-purity using this method
Methylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromide.
The double quaternary ammonium side long chain type anion-exchange membranes obtained to the present embodiment carry out hydrogen nuclear magnetic resonance analysis of spectrum, as a result
As shown in Fig. 2 as can be seen from the figure successfully having prepared the anion friendship that side chain contains two quaternary ammonium groups using this method
Change film.
Show through water content and ion exchange capacity test, the water content of prepared anion-exchange membrane in the present embodiment
For 8.9%, anion-exchange capacity is 1.14mmol.g-1；The OH of the film-Conductance is 16.5mS.cm-1, tensile strength is
26.3MPa, shows that the homogeneous-phase anion exchange film prepared in the present embodiment has higher ionic conductivity, suitable water content
And ion exchange capacity, good mechanical strength, possess the condition applied in a fuel cell.
Embodiment 2
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：Be the same as Example 1
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：0.3g brominations degree is dissolved for 0.093 brominated polyphenylether
In 3mL (2.92g) METHYLPYRROLIDONE, 0.092g 6- (dimethylamino) hexyl-N, N- dimethyl-N -s are added
Ethyl phosphonium bromide ammonium, stirs 12h and obtains uniform casting solution, at 60 DEG C by above-mentioned casting solution even application on a glass at room temperature
12h is dried, 12h is then soaked in deionized water, that is, obtains double quaternary ammonium sides long chain type type anion-exchange membrane.
Show through water content and ion exchange capacity test, the water content of prepared anion-exchange membrane in the present embodiment
For 18.2%, anion-exchange capacity is 1.24mmol.g-1；The OH of the film-Conductance is 21.6mS.cm-1, tensile strength is
33.0MPa, shows the anionic conduction that the homogeneous-phase anion exchange film prepared in the present embodiment has had, suitable water content
And ion exchange capacity, good mechanical strength, possess the condition applied in a fuel cell.
Embodiment 3
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：Be the same as Example 1
The preparation of double quaternary ammonium side long chain anionic exchange membranes：0.3g brominations degree is dissolved in for 0.13 brominated polyphenylether
In 3mL (2.92g) METHYLPYRROLIDONE, 0.126g 6- (dimethylamino) hexyl-N, N- dimethyl-N-second is added
Base ammonium bromide, stirs 12h and obtains uniform casting solution, dried at 60 DEG C by above-mentioned casting solution even application on a glass at room temperature
Dry 12h, then soaks 12h in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Show through water content and ion exchange capacity test, the water content of prepared anion-exchange membrane in the present embodiment
For 42.5%, anion-exchange capacity is 1.60mmol.g-1；The OH of the film-Conductance is 36.3mS.cm-1, tensile strength is
14.9MPa, shows the anionic conduction that the homogeneous-phase anion exchange film prepared in the present embodiment has had, suitable water content
And ion exchange capacity, good mechanical strength, possess the condition applied in a fuel cell.
Embodiment 4
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：Be the same as Example 1
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：0.3g brominations degree is dissolved in for 0.21 brominated polyphenylether
In 3mL (2.92g) METHYLPYRROLIDONE, 0.19g 6- (dimethylamino) hexyl-N, N- dimethyl-N-second is added
Base ammonium bromide, stirs 12h and obtains uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, dried at 60 DEG C
Dry 12h, then soaks 12h in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Show through water content and ion exchange capacity test, the water content of prepared anion-exchange membrane in the present embodiment
For 120.4%, anion-exchange capacity is 2.13mmol.g-1；The OH of the film-Conductance is 53mS.cm-1, tensile strength is
19.2MPa, shows that the anion-exchange membrane that is prepared in the present embodiment has a very high anionic conduction, suitable water content and
Ion exchange capacity, good mechanical strength possesses the condition applied in a fuel cell.
Embodiment 5
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：Be the same as Example 1
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：0.3g brominations degree is dissolved in for 0.28 brominated polyphenylether
In 3mL (2.92g) METHYLPYRROLIDONE, 0.25g 6- (dimethylamino) hexyl-N, N- dimethyl-N-second is added
Base ammonium bromide, stirs 12h and obtains uniform casting solution, dried at 60 DEG C by above-mentioned casting solution even application on a glass at room temperature
Dry 12h, then soaks 12h in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Show through water content and ion exchange capacity test, the water content of prepared anion-exchange membrane in the present embodiment
For 311.3%, anion-exchange capacity is 2.56mmol.g-1；The OH of the film-Conductance is 32.0mS.cm-1, tensile strength is
3MPa。
Embodiment 6
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：Be the same as Example 1
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：0.3g functionalities is molten for 0.06 chloromethylation polyphenylene oxide
Solution in 3mL (2.92g) METHYLPYRROLIDONE, add 0.07g 6- (dimethylamino) hexyl-N, N- dimethyl-
N- ethyl phosphonium bromide ammoniums, stir 12h and obtain uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, 60 DEG C
Lower drying 12h, then soaks 12h in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Ion exchange capacity test shows that the anion-exchange capacity of prepared anion-exchange membrane is in the present embodiment
0.87mmol.g-1；The OH of the film-Conductance is 10mS.cm-1。
Embodiment 7
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：Be the same as Example 1
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：0.3g functionalities is molten for 0.19 chloromethylation polyphenylene oxide
Solution adds 0.2g 6- (dimethylamino) hexyl-N, N- dimethyl-N -s in 3mL (2.92g) METHYLPYRROLIDONE
Ethyl phosphonium bromide ammonium, stirs 12h and obtains uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, at 60 DEG C
12h is dried, 12h is then soaked in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Show through ion exchange capacity test, the anion-exchange capacity of prepared anion-exchange membrane in the present embodiment
For 2.04mmol.g-1；The OH of the film-Conductance is 51.3mS.cm-1。
Embodiment 8
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：Be the same as Example 1
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：0.3g functionalities is molten for 0.25 chloromethylation polyphenylene oxide
Solution in 3mL (2.92g) METHYLPYRROLIDONE, add 0.25g 6- (dimethylamino) hexyl-N, N- dimethyl-
N- ethyl phosphonium bromide ammoniums, stir 12h and obtain uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, 60 DEG C
Lower drying 12h, then soaks 12h in deionized water.Obtain double quaternary ammonium sides long chain type anion-exchange membrane.
Show through ion exchange capacity test, the anion-exchange capacity of prepared anion-exchange membrane in the present embodiment
For 2.46mmol.g-1；The OH of the film-Conductance is 23mS.cm-1。
Embodiment 9
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：Be the same as Example 1
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：0.3g functionalities is molten for 0.06 chlorine acylation polyphenylene oxide
Solution in 3mL (2.92g) METHYLPYRROLIDONE, add 0.06g 6- (dimethylamino) hexyl-N, N- dimethyl-
N- ethyl phosphonium bromide ammoniums, stir 12h and obtain uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, 60 DEG C
Lower drying 12h, then soaks 12h in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Show through ion exchange capacity test, the anion-exchange capacity of prepared anion-exchange membrane in the present embodiment
For 0.8mmol.g-1；The OH of the film-Conductance is 12.2mS.cm-1。
Embodiment 10
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：Be the same as Example 1
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：0.3g functionalities is molten for 0.22 chlorine acylation polyphenylene oxide
Solution in 3mL (2.92g) METHYLPYRROLIDONE, add 0.22g 6- (dimethylamino) hexyl-N, N- dimethyl-
N- ethyl phosphonium bromide ammoniums, stir 12h and obtain uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, 60 DEG C
Lower drying 12h, then soaks 12h in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Show through ion exchange capacity test, the anion-exchange capacity of prepared anion-exchange membrane in the present embodiment
For 2.1mmol.g-1；The OH of the film-Conductance is 54.2mS.cm-1。
Embodiment 11
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：Be the same as Example 1
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：0.3g functionalities is molten for 0.29 chlorine acylation polyphenylene oxide
Solution in 3mL (2.92g) METHYLPYRROLIDONE, add 0.26g 6- (dimethylamino) hexyl-N, N- dimethyl-
N- ethyl phosphonium bromide ammoniums, stir 12h and obtain uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, 60 DEG C
Lower drying 12h, then soaks 12h in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Show through ion exchange capacity test, the anion-exchange capacity of prepared anion-exchange membrane in the present embodiment
For 2.61mmol.g-1；The OH of the film-Conductance is 21.1mS.cm-1。
Embodiment 12
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：Be the same as Example 1
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：0.3g functionalities are dissolved for 0.25 chloromethyl polysulphone
In 3mL (2.92g) METHYLPYRROLIDONE, 0.07g 6- (dimethylamino) hexyl-N, N- dimethyl-N -s are added
Ethyl phosphonium bromide ammonium, stirs 12h and obtains uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, at 60 DEG C
12h is dried, 12h is then soaked in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Show through ion exchange capacity test, the anion-exchange capacity of prepared anion-exchange membrane in the present embodiment
For 0.95mmol.g-1；The OH of the film-Conductance is 13.3mS.cm-1。
Embodiment 13
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：Be the same as Example 1
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：0.3g functionalities are dissolved for 0.73 chloromethyl polysulphone
In 3mL (2.92g) METHYLPYRROLIDONE, 0.2g 6- (dimethylamino) hexyl-N, N- dimethyl-N-second is added
Base ammonium bromide, stirs 12h and obtains uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, dried at 60 DEG C
Dry 12h, then soaks 12h in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Show through ion exchange capacity test, the anion-exchange capacity of prepared anion-exchange membrane in the present embodiment
For 2.16mmol.g-1；The OH of the film-Conductance is 55.2mS.cm-1。
Embodiment 14
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：Be the same as Example 1
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：0.3g functionalities are dissolved for 0.91 chloromethyl polysulphone
In 3mL (2.92g) METHYLPYRROLIDONE, 0.24g 6- (dimethylamino) hexyl-N, N- dimethyl-N -s are added
Ethyl phosphonium bromide ammonium, stirs 12h and obtains uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, at 60 DEG C
12h is dried, 12h is then soaked in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Show through ion exchange capacity test, the anion-exchange capacity of prepared anion-exchange membrane in the present embodiment
For 2.41mmol.g-1；The OH of the film-Conductance is 19.2mS.cm-1。
Embodiment 15
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：Be the same as Example 1
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：0.3g functionalities is molten for 0.21 chloromethylation polyether-ketone
Solution in 3mL (2.92g) METHYLPYRROLIDONE, add 0.06g 6- (dimethylamino) hexyl-N, N- dimethyl-
N- ethyl phosphonium bromide ammoniums, stir 12h and obtain uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, 60 DEG C
Lower drying 12h, then soaks 12h in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Show through ion exchange capacity test, the anion-exchange capacity of prepared anion-exchange membrane in the present embodiment
For 0.85mmol.g-1；The OH of the film-Conductance is 9.8mS.cm-1。
Embodiment 16
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：Be the same as Example 1
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：0.3g functionalities is molten for 0.87 chloromethylation polyether-ketone
Solution in 3mL (2.92g) METHYLPYRROLIDONE, add 0.25g 6- (dimethylamino) hexyl-N, N- dimethyl-
N- ethyl phosphonium bromide ammoniums, stir 12h and obtain uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, 60 DEG C
Lower drying 12h, then soaks 12h in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Show through ion exchange capacity test, the anion-exchange capacity of prepared anion-exchange membrane in the present embodiment
For 2.48mmol.g-1；The OH of the film-Conductance is 21.3mS.cm-1。
Embodiment 17
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：Be the same as Example 1
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：0.3g functionalities is molten for 0.17 chloromethylation polyether sulfone
Solution in 3mL (2.92g) METHYLPYRROLIDONE, add 0.07g 6- (dimethylamino) hexyl-N, N- dimethyl-
N- ethyl phosphonium bromide ammoniums, stir 12h and obtain uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, 60 DEG C
Lower drying 12h, then soaks 12h in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Show through ion exchange capacity test, the anion-exchange capacity of prepared anion-exchange membrane in the present embodiment
For 0.92mmol.g-1；The OH of the film-Conductance is 12.8mS.cm-1。
Embodiment 18
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：Be the same as Example 1
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：0.3g functionalities is molten for 0.48 chloromethylation polyether sulfone
Solution in 3mL (2.92g) METHYLPYRROLIDONE, add 0.18g 6- (dimethylamino) hexyl-N, N- dimethyl-
N- ethyl phosphonium bromide ammoniums, stir 12h and obtain uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, 60 DEG C
Lower drying 12h, then soaks 12h in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Show through ion exchange capacity test, the anion-exchange capacity of prepared anion-exchange membrane in the present embodiment
For 2.16mmol.g-1；The OH of the film-Conductance is 43.2mS.cm-1。
Embodiment 19
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：Be the same as Example 1
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：0.3g functionalities is molten for 0.64 chloromethylation polyether sulfone
Solution in 3mL (2.92g) METHYLPYRROLIDONE, add 0.24g 6- (dimethylamino) hexyl-N, N- dimethyl-
N- ethyl phosphonium bromide ammoniums, stir 12h and obtain uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, 60 DEG C
Lower drying 12h, then soaks 12h in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Show through ion exchange capacity test, the anion-exchange capacity of prepared anion-exchange membrane in the present embodiment
For 2.51mmol.g-1；The OH of the film-Conductance is 19.7mS.cm-1。
Embodiment 20
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：Be the same as Example 1
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：By the chloromethylated polystyrene that 0.3g functionalities are 0.06
It is dissolved in 3mL (2.92g) METHYLPYRROLIDONE, adds 0.07g 6- (dimethylamino) hexyl-N, N- diformazans
Base-N- ethyl phosphonium bromide ammoniums, stir 12h and obtain uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, 60
12h is dried at DEG C, 12h is then soaked in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Show through ion exchange capacity test, the anion-exchange capacity of prepared anion-exchange membrane in the present embodiment
For 1.1mmol.g-1；The OH of the film-Conductance is 17.2mS.cm-1。
Embodiment 21
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：Be the same as Example 1
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：By the chloromethylated polystyrene that 0.3g functionalities are 0.15
It is dissolved in 3mL (2.92g) METHYLPYRROLIDONE, adds 0.17g 6- (dimethylamino) hexyl-N, N- diformazans
Base-N- ethyl phosphonium bromide ammoniums, stir 12h and obtain uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, 60
12h is dried at DEG C, 12h is then soaked in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Show through ion exchange capacity test, the anion-exchange capacity of prepared anion-exchange membrane in the present embodiment
For 2.01mmol.g-1；The OH of the film-Conductance is 50.1mS.cm-1。
Embodiment 22
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-ethyl ammonium bromides：Be the same as Example 1
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：By the chloromethylated polystyrene that 0.3g functionalities are 0.19
It is dissolved in 3mL (2.92g) METHYLPYRROLIDONE, adds 0.22g 6- (dimethylamino) hexyl-N, N- diformazans
Base-N- ethyl phosphonium bromide ammoniums, stir 12h and obtain uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, 60
12h is dried at DEG C, 12h is then soaked in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Show through ion exchange capacity test, the anion-exchange capacity of prepared anion-exchange membrane in the present embodiment
For 2.37mmol.g-1；The OH of the film-Conductance is 25.6mS.cm-1。
Embodiment 23
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-decyl ammonium bromides：By 1mL N, N, N', N'- tetra-
Methyl isophthalic acid, 6- hexamethylene diamines are dissolved in 19mL ethanol, are configured to the solution of 5% volume fraction.Add the 1- bromine last of the ten Heavenly stems of 1 times of mole
Alkane, reacts 8h at 60 DEG C.Rotary evaporation removes ethanol, adds proper amount of acetone, is filtered to remove precipitation, and filtrate rotary evaporation is handled,
Remove after acetone, washed with ether for several times, filtering obtains 6- (dimethylamino) hexyl-N, N- dimethyl-N-decyl brominations
Ammonium.
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：By the chloromethylated polystyrene that 0.3g functionalities are 0.16
It is dissolved in 3mL (2.92g) METHYLPYRROLIDONE, adds 0.18g 6- (dimethylamino) hexyl-N, N- diformazans
Base-N- decyl ammonium bromides, stir 12h and obtain uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, 60
12h is dried at DEG C, 12h is then soaked in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
6- (dimethylamino) hexyl-N, the N- dimethyl-N-decyls ammonium bromide obtained to the present embodiment carries out nuclear-magnetism
Resonate hydrogen analysis of spectrum, as a result as shown in figure 3, as can be seen from the figure successfully having prepared the 6- (two of high-purity using this method
Methylamino) hexyl-N, N- dimethyl-N-decyl ammonium bromide.
The double quaternary ammonium side long chain type anion-exchange membranes obtained to the present embodiment carry out hydrogen nuclear magnetic resonance analysis of spectrum, as a result
As shown in figure 4, as can be seen from the figure successfully having prepared the anion friendship that side chain contains two quaternary ammonium groups using this method
Change film.
Show through ion exchange capacity test, the anion-exchange capacity of prepared anion-exchange membrane in the present embodiment
For 1.88mmol.g-1；The OH of the film-Conductance is 41.3mS.cm-1。
Embodiment 24
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-octadecyl base ammonium bromides：By 1mL N, N, N',
N'-1,6- 4-methyl hexamethylene diamine are dissolved in 19mL ethanol, are configured to the solution of 5% volume fraction.Add the 1- of 1 times of mole
Bromo-octadecane, reacts 8h at 60 DEG C.Rotary evaporation removes ethanol, adds proper amount of acetone, is filtered to remove precipitation, filtrate rotary evaporation
Processing, is removed after acetone, is washed with ether for several times, and filtering obtains 6- (dimethylamino) hexyl-N, N- dimethyl-N-ten
Eight alkyl bromination ammoniums.
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：0.3g brominations degree is dissolved in for 0.23 brominated polyphenylether
In 3mL (2.92g) METHYLPYRROLIDONE, 0.25g 6- (dimethylamino) hexyl-N, N- dimethyl-N-ten is added
Eight alkyl bromination ammoniums, stir 12h and obtain uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, 60 DEG C
Lower drying 12h, then soaks 12h in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Show through ion exchange capacity test, the anion-exchange capacity of prepared anion-exchange membrane in the present embodiment
For 1.77mmol.g-1；The OH of the film-Conductance is 38.2mS.cm-1。
Embodiment 25
The preparation of 2- (dimethylamino) ethyl-N, N- dimethyl-N-ethyl ammonium bromides：By 1mL N, N, N', N'-1,
2- tetramethylethylenediamines are dissolved in 19mL ethanol, are configured to the solution of 5% volume fraction.The bromoethane of 1 times of mole is added,
48h is reacted at room temperature.Rotary evaporation removes ethanol, adds proper amount of acetone, is filtered to remove precipitation, and the processing of filtrate rotary evaporation is removed
Go after acetone, washed with ether for several times, filtering obtains 2- (dimethylamino) ethyl-N, N- dimethyl-N-ethyl brominations
Ammonium.
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：By the chloromethylated polystyrene that 0.3g functionalities are 0.16
It is dissolved in 3mL (2.92g) METHYLPYRROLIDONE, adds 0.18g 2- (dimethylamino) ethyl-N, N- diformazans
Base-N- ethyl phosphonium bromide ammoniums, stir 12h and obtain uniform casting solution at room temperature.By above-mentioned casting solution even application on a glass, 60
12h is dried at DEG C, 12h is then soaked in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Show through ion exchange capacity test, the anion-exchange capacity of prepared anion-exchange membrane in the present embodiment
For 1.98mmol.g-1；The OH of the film-Conductance is 51.3mS.cm-1。
Embodiment 26
The preparation of 6- (dimethylamino) hexyl-N, N- dimethyl-N-docosyl ammonium bromides：By 1mL N, N, N',
N'-1,6- 4-methyl hexamethylene diamine are dissolved in 19mL chloroforms, are configured to the solution of 5% volume fraction.0.1 times of mole of addition
1- bromine docosane, reacts 8h at 60 DEG C.Rotary evaporation removes chloroform, and ether is washed for several times, and filtering obtains 6- (dimethyl
Amino) hexyl-N, N- dimethyl-N-docosyl ammonium bromide.
The preparation of double quaternary ammonium side long chain type anion-exchange membranes：By the chloromethylated polystyrene that 0.3g functionalities are 0.21
It is dissolved in 3mL (2.92g) METHYLPYRROLIDONE, adds 0.24g 6- (dimethylamino) hexyl-N, N- diformazans
Base-N- docosyl ammonium bromides, stir 36h and obtain uniform casting solution at room temperature.By above-mentioned casting solution even application in glass
On plate, 12h is dried at 60 DEG C, 12h is then soaked in deionized water, that is, obtains double quaternary ammonium sides long chain type anion-exchange membrane.
Show through ion exchange capacity test, the anion-exchange capacity of prepared anion-exchange membrane in the present embodiment
For 1.88mmol.g-1；The OH of the film-Conductance is 41.3mS.cm-1。
Claims (2)
1. the preparation method of a kind of pair of quaternary ammonium side long chain type anion-exchange membrane, it is characterised in that：By containing tertiary amine group simultaneously
Nucleophilic is carried out with the bi-functional monomer of quaternary ammonium group to the main polymer chain containing active benzyl bromine, benzyl chloride or chlorine carboxyl groups to take
Generation reaction, obtains double quaternary ammonium sides long chain type anion-exchange membrane；
Shown in the general structure such as formula (1) of the bi-functional monomer simultaneously containing tertiary amine group and quaternary ammonium group, n=1 in formula
~22, m=2~6；
The polymer containing active benzyl bromine, benzyl chloride or chlorine carboxyl groups is brominated polyphenylether, chloromethyl polysulphone, chloromethane
Base polyether sulfone, chloromethylation polyether-ketone, chloromethylation polyphenylene oxide, chlorine are acylated polyphenylene oxide or chloromethylated polystyrene；
Specifically carry out as follows：
(1) preparation of the bi-functional monomer simultaneously containing tertiary amine group and quaternary ammonium group：Di-tertiary amine monomer is dissolved in solvent,
Brominated alkanes are then added, 6h-48h is reacted at 20~60 DEG C, after reaction terminates, rotary evaporation is removed after solvent, are added suitable
Measure acetone or acetonitrile, be filtered to remove after precipitation, the processing of filtrate rotary evaporation, removing acetone or acetonitrile, add appropriate ether or
Ethyl acetate washing, filtering, that is, obtain the bi-functional monomer containing tertiary amine group and quaternary ammonium group simultaneously；
The solvent is ethanol, methanol, acetonitrile, isopropanol chloroform or tetrahydrofuran；The brominated alkanes and the di-tertiary amine list
The ratio between mole of body is 0.1-1：1；
(2) preparation of double quaternary ammonium side long chain type anion-exchange membranes：Will be poly- containing active benzyl bromine, benzyl chloride or chlorine carboxyl groups
Compound is dissolved in the homogeneous solution for being configured to that mass concentration is 5%-50% in aprotic polar solvent；Then add thereto same
The bi-functional monomer of Shi Hanyou tertiary amine groups and quaternary ammonium group, 1~72h is reacted at 20~60 DEG C, uniform casting solution is obtained；By institute
Casting solution is stated after cladding process film forming, 6-48h is soaked in deionized water, that is, obtains double quaternary ammonium side long chain type anion exchanges
Film；The bi-functional monomer simultaneously containing tertiary amine group and quaternary ammonium group contains active benzyl bromine, benzyl chloride or chlorine acyl with described
The ratio between mole of polymer of base group is 1~5:1.
2. preparation method according to claim 1, it is characterised in that：The di-tertiary amine monomer is N, N, N', N'- tetramethyls
Base -1,2- ethylenediamine, N, N, N', N'- tetramethyls-Putriscine, N, N, N', N'- tetramethyl -1,3- butanediamine, N, N, N',
N'- tetramethyl -1,6- hexamethylene diamines；The brominated alkanes are 1- bromoethanes, 1- N-Propyl Bromides, 1- NBBs, 1- bromo pentane silanes, 1- bromines
Hexane, 1- heptyl bromides, 1- bromooctanes, 1- bromononanes, 1- bromo-decanes, 1- bromo-n-11s, 1- bromo-dodecanes, 1- bromine 13s alkane, 1-
Bromo-tetradecane, pe-ntadecyl bromide, 1- bromines hexadecane, 1- bromines heptadecane, 1- bromo-octadecanes, 1- bromines eicosane, 1- bromine docosane；
The aprotic polar solvent is METHYLPYRROLIDONE, N,N-dimethylformamide, dimethyl sulfoxide or N, N- diformazan
Yl acetamide.
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| KR102031823B1 (en) | 2018-01-18 | 2019-10-14 | 인천대학교 산학협력단 | Conductive polymer and preparation method of polymer electrolyte membrane using the same |
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