CN103467396A - Compound containing 1,2,4-triazole ring, polymer proton exchange membrane (PEM) containing 1,2,4-triazole ring and preparation methods - Google Patents
Compound containing 1,2,4-triazole ring, polymer proton exchange membrane (PEM) containing 1,2,4-triazole ring and preparation methods Download PDFInfo
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Abstract
The invention provides a compound containing 1,2,4-triazole ring, a polymer proton exchange membrane (PEM) containing 1,2,4-triazole ring and preparation methods, belonging to the field of macromolecular polymer PEMs and preparation methods thereof and solving the problems of complex preparation methods and costly raw materials of existing monomers containing triazole and low proton conductivity of existing PEMs under the condition of medium and high temperatures. The compound, the PEM and the preparation methods have the beneficial effects that the compound containing 1,2,4-triazole ring reacts with sulfonated monomers and introduces conjugated triazole rings into sulfonated aromatic main polymer chains; by utilizing heterocyclic structures in the sulfonated monomers and the hydrogen-bond interaction of sulfonic groups, jump points and transmission channels of protons can be formed and then the problem of proton conductivity reduction caused by water loss of the membrane under the condition of low humidity or high temperature is solved and the defect that the degree of sulfonation in the post sulfonation method is not easy to control is simultaneously avoided; the proton conductivity of the PEM at 100 DEG C can reach 0.91-1.12S/cm.
Description
Technical field
The invention belongs to polymer chemistry and Proton Exchange Membrane Fuel Cells field, be specifically related to a kind of compound that contains 1,2,4-triazole ring, containing proton exchange polymer membrane and the preparation method of 1,2,4-triazole ring.
Background technology
At present, energy problem is the great difficult problem that the mankind have to face, and developing the little but also green energy resource that have the high-energy transformation efficiency concurrently of a kind of not only environmental pollution becomes people's problem demanding prompt solution.Fuel cell is as a kind of 21 century high-tech product battery, and the dream of the renewable resources of pursuing for the mankind has been brought hope, and Proton Exchange Membrane Fuel Cells is considered to that a new generation is efficient, environmental protection, free of contamination clean energy.Proton exchange membrane is Proton Exchange Membrane Fuel Cells " heart ", different from the barrier film in general chemical power source, and it not only can isolate fuel and oxygenant, prevents that them from directly reacting, and plays electrolytical effect.The quality of its performance will directly have influence on the application and development of fuel cell.The at present more still combustion of application is perfluoro sulfonic acid membrane (as the Nafion film), but its drawbacks limit such as proton conductivity descends under low humidity or high temperature, methanol permeability is high and involve great expense its further application.Therefore many investigators have thrown into sight on the aromatic polymer that development has good thermostability and higher intensity, conjugacy because of nitrogen heterocyclic makes nitrogen-atoms have the characteristics to body and acceptor of proton concurrently again, can not exclusively rely on water and transmit proton, therefore in the aromaticity mould material, introduce the study hotspot that nitrogen heterocyclic also becomes numerous investigators.Yet simple physical doping, as the imidazoles doping, be easy to cause come off.For avoiding this phenomenon, can nitrogen heterocyclic be fixed in main polymer chain by modes such as condensation polymerizations, and work out so a kind of with supplying the nitrogen heterocyclic of the end group of polymerization to become key.
Publication number is the preparation that discloses two hydroxyl triazole ring monomers and polymkeric substance thereof in US5182356, and its preparation process requires very high to experimental installation and reaction raw materials is also comparatively expensive, implements comparatively difficulty.The people such as KennethR.Carter have also prepared two fluorine end group triazole ring monomers, but will complete through three steps, and it is raw materials used not only expensive and be difficult to obtain.
Summary of the invention
The objective of the invention is that the existing preparation method containing the triazole ring monomer is complicated, raw material is expensive and existing proton exchange membrane low problem of proton conductivity under middle hot conditions in order to solve, contain 1 and provide a kind of, 2, the compound of 4-triazole ring, preparation method reach containing 1, the proton exchange polymer membrane of 2,4-triazole ring and preparation method.
At first the present invention provides a kind of compound that contains 1,2,4-triazole ring, and structural formula is suc as formula shown in I:
R is-OH or-F, be substituted radical arbitrarily on phenyl ring.
The present invention also provides a kind of preparation method who contains the compound of 1,2,4-triazole ring, comprises as follows:
In reaction vessel, benzoic acid compounds, hydrazonium sulfate and polyphosphoric acid are mixed, react 4～6h under 150～160 ℃, add aniline after being warming up to 180～200 ℃ in reaction vessel, reaction 1～3h, obtain containing 1, the compound of 2,4-triazole ring, described benzoic acid compounds is hydroxy-benzoic acid or fluorinated acid.
Preferably, the mol ratio of described benzoic acid compounds, hydrazonium sulfate, polyphosphoric acid and aniline is (0.1～0.15): (0.05～0.08): (0.5～0.8): (0.05～0.08).
The present invention also provides containing a kind of proton exchange polymer membrane that contains 1,2,4-triazole ring, and structural formula is suc as formula shown in II:
In the formula II, 0.5≤m<1.0,0<n≤0.5, m+n=1; The proton exchange film thickness is 50～100 μ m, and sulfonation degree is 20%～100%, at 100 ℃ of lower proton conductivities, is 0.91～1.12S/cm.
X and Y independently are selected from
The present invention also provides containing a kind of preparation method who contains the sulfonated polymer proton exchange membrane of 1,2,4-triazole ring, comprises as follows:
Step 1: will mix in organic solvent containing the compound of 1,2,4-triazole ring, the monomer that contains the X structure, the monomer that contains the Y structure, sulfonation chlorine end group monomer, salt of wormwood, and under protection of inert gas, under 170～200 ℃, react 20～30h, and obtain product;
Step 2: product in step 2 is poured in acetone and precipitated, and filtration, washing, drying obtain the polymkeric substance sterling;
Step 3: the polymkeric substance sterling that step 2 is obtained is dissolved in organic solvent, obtain polymers soln, by the polymer dissolution casting film-forming, dry 12～18h under 60～80 ℃, dry 12～18h under 100～120 ℃ again, be cooled to room temperature, the demoulding in water, be placed in hydrochloric acid soln by film and carry out proton exchange 12～24h, use again the deionized water repetitive scrubbing until PH=6～7, obtain the sulfonated polymer proton exchange membrane containing 1,2,4-triazole ring;
The monomer of the described X of containing structure is selected from
The monomer of the described Y of containing structure is selected from
Preferably, the described mol ratio that contains the compound of 1,2,4-triazole ring, the monomer that contains the X structure, the monomer that contains the Y structure and sulfonation chlorine end group monomer is (0.5～0.9): (0.5～0.9): (0.1～0.5): (0.1～0.5).
Preferably, the sulfonation chlorine end group monomer of described step 1 is the sulfonation dichloro diphenyl sulfone.
Preferably, the concentration of the hydrochloric acid soln of described step 3 is 2mol/L.
Preferably, described organic solvent is selected from one or both mixtures in N-Methyl pyrrolidone or N-cyclohexyl pyrrolidone.
Preferably, in described mixture, the volume ratio of N-Methyl pyrrolidone and N-cyclohexyl pyrrolidone is 1:1.
Beneficial effect of the present invention
At first the present invention provides a kind of and contains 1, 2, the compound of 4-triazole ring, structural formula is suc as formula shown in I, should be containing 1, 2, the compound of 4-triazole ring reacts with sulfonated monomers, and the triazole ring of conjugation is introduced in the aromatic sulfonated polymer main chain, utilize heterocycle structure (C=N) and sulfonic hydrogen bond action in sulfonated polymer, can form jump and the transmission path of proton, then solve the problem that film dehydration under low humidity or high temperature causes proton conductivity to descend, also avoided the uppity shortcoming of rear method of sulfonating sulfonation degree simultaneously, sulfonation degree can be controlled in 20%～100% scope.
The present invention also provides a kind of preparation method who contains the compound of 1,2,4-triazole ring, with prior art, compares, and preparation method of the present invention is simple, and cost is low, and the compound containing 1,2,4-triazole ring prepared can be applied in Proton Exchange Membrane Fuel Cells.
The present invention also provides a kind of and contains 1,2, the sulfonated polymer proton exchange membrane of 4-triazole ring, this proton exchange membrane is utilized the interaction of sulfonic acid group and nitrogen heterocyclic, set up new proton transport passage, being conducive to proton is transmitted according to " Grotthuss " mechanism, simultaneously because the N atom becomes the transition point in proton transfer, also be conducive to proton according to " Vehicle " and " Surface " mechanism transmission, the synergy by three kind of proton transporting mechanisms improves the proton conductivity of proton exchange membrane when high temperature jointly.Experimental result shows: proton exchange membrane of the present invention can reach 0.91～1.12S/cm at 100 ℃ of lower proton conductivities.
The present invention also provides a kind of preparation method who contains the sulfonated polymer proton exchange membrane of 1,2,4-triazole ring, and this preparation method is simple, and raw material is easy to get, and the proton exchange membrane prepared at high temperature has higher proton conductivity.
The accompanying drawing explanation
Fig. 1 is the infrared spectrogram containing the compound of 1,2,4-triazole ring that the embodiment of the present invention 1 prepares.
The infrared spectrogram of the sulfonated polymer proton exchange membrane containing 1,2,4-triazole ring that Fig. 2 is the embodiment of the present invention 5 preparations.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these are described is the restriction for further illustrating the features and advantages of the present invention rather than patent of the present invention being required.
At first the present invention provides a kind of compound that contains 1,2,4-triazole ring, and structural formula is suc as formula shown in I:
R is-OH or-F, be substituted radical arbitrarily on phenyl ring.
The present invention also provides a kind of preparation method who contains the compound of 1,2,4-triazole ring, comprises as follows:
In reaction vessel, benzoic acid compounds, hydrazonium sulfate and polyphosphoric acid are mixed, react 4～6h under 150～160 ℃, add aniline after being warming up to 180～200 ℃ in reaction vessel, reaction 1～3h, discharging, in the cold NaOH aqueous solution, is filtered the washing final vacuum and is dried, obtain containing 1, the compound of 2,4-triazole ring, product is white floss.Described benzoic acid compounds is hydroxy-benzoic acid or fluorinated acid, and described hydroxy-benzoic acid is P-hydroxybenzoic acid, m-Salicylic acid or salicylic acid, and fluorinated acid is parafluorobenzoic acid, m-fluorobenzoic acid or o-fluorobenzoic acid.The mol ratio of described benzoic acid compounds, hydrazonium sulfate, polyphosphoric acid and aniline is preferably (0.1～0.15): (0.05～0.08): (0.5～0.8): (0.05～0.08).
Concrete reaction process is as follows:
The present invention also provides containing a kind of sulfonated polymer proton exchange membrane that contains 1,2,4-triazole ring, and structural formula is suc as formula shown in II:
In the formula II, 0.5≤m<1.0,0<n≤0.5, m+n=1; The proton exchange film thickness is 50～100 μ m, and sulfonation degree is 20%～100%, at 100 ℃ of lower proton conductivities, is 0.91～1.12Scm
-1.
X and Y independently are selected from
The present invention also provides containing a kind of preparation method who contains the sulfonated polymer proton exchange membrane of 1,2,4-triazole ring, comprises as follows:
Step 1: will mix in organic solvent containing the compound of 1,2,4-triazole ring, the monomer that contains the X structure, the monomer that contains the Y structure, sulfonation chlorine end group monomer, salt of wormwood, and under protection of inert gas, under 170～200 ℃, react 20～30h, and obtain product;
Step 2: product in step 2 is poured in acetone and precipitated, and filtration, washing, drying obtain the polymkeric substance sterling;
Step 3: the polymkeric substance sterling that step 2 is obtained is dissolved in organic solvent, obtain polymers soln, by the polymer dissolution casting film-forming, dry 12～18h under 60～80 ℃, dry 12～18h under 100～120 ℃ again, be cooled to room temperature, the demoulding in water, be placed in hydrochloric acid soln by film and carry out proton exchange 12～24h, use again the deionized water repetitive scrubbing until PH=6～7, obtain the sulfonated polymer proton exchange membrane containing 1,2,4-triazole ring;
The monomer of the described X of containing structure is selected from
The monomer of the described Y of containing structure is selected from
Reaction process is as follows:
In step 1 of the present invention, in the described compound that contains 1,2,4-triazole ring R be-during OH, the monomer of the described X of containing structure is selected from
the monomer that contains the Y structure is selected from
in the described compound that contains 1,2,4-triazole ring R be-during F, the monomer of the described X of containing structure is selected from
the monomer that contains the Y structure is selected from
The sulfonation chlorine end group monomer of step 1 of the present invention is the sulfonation dichloro diphenyl sulfone, and structural formula is
The mol ratio that contains the compound of 1,2,4-triazole ring, the monomer that contains the X structure, the monomer that contains the Y structure and sulfonation chlorine end group monomer of the present invention is (0.5～0.9): (0.5～0.9): (0.1～0.5): (0.1～0.5).
Specifically, contain 1 when described, 2, in the compound of 4-triazole ring R be-during F, need to meet (containing 1, the compound of 2,4-triazole ring+sulfonation chlorine end group monomer): (monomer that contains the X structure+contain the Y structure monomer) mol ratio is 1:1, and the monomer that contains the X structure and the monomer that contains the Y structure can be the same or different; In the described compound that contains 1,2,4-triazole ring R be-during OH, need to meet (containing the monomer of the compound of 1,2,4-triazole ring+contain the Y structure): (monomer that contains the X structure+sulfonation chlorine end group monomer) mol ratio is 1: 1.
1.0～1.5 times of the mole number that the salt of wormwood consumption of step 1 of the present invention is sulfonation chlorine end group monomer.
The concentration of the hydrochloric acid soln of step 3 of the present invention is preferably 2mol/L.
Organic solvent of the present invention is preferably selected from n-formyl sarcolysine base pyrrolidone, dimethyl sulfoxide (DMSO), tetramethylene sulfone, dimethyl formamide or N,N-DIMETHYLACETAMIDE, more preferably one or both mixtures in N-Methyl pyrrolidone or N-cyclohexyl pyrrolidone.In described mixture, the volume ratio of N-Methyl pyrrolidone and N-cyclohexyl pyrrolidone is preferably 1: 1.
Embodiment 1
In reaction vessel, 0.1mol parafluorobenzoic acid, 0.05mol hydrazonium sulfate and 0.5mol polyphosphoric acid are mixed, react 6h under 150 ℃, add 0.05mol aniline after being warming up to 180 ℃ in reaction vessel, reaction 3h, discharging, in the cold NaOH aqueous solution, is filtered the washing final vacuum and is dried, obtain containing 1, the compound of 2,4-triazole ring, product is white floss.
The mol ratio of described benzoic acid compounds, hydrazonium sulfate, polyphosphoric acid and aniline is preferably (0.1～0.15): (0.05～0.08): (0.5～0.8): (0.05～0.08).
Fig. 1 is the infrared spectrogram containing the compound of 1,2,4-triazole ring that the embodiment of the present invention 1 prepares, as we know from the figure, and 1607cm
-1the stretching vibration peak of the C=N of 1,2,4-triazole ring, 1229cm
-1be the stretching vibration peak of the C-N of 1,2,4-triazole ring, the compound containing 1,2,4-triazole ring that synthesized of success of the present invention is described.
Embodiment 2
In reaction vessel, 0.15mol P-hydroxybenzoic acid, 0.08mol hydrazonium sulfate and 0.8mol polyphosphoric acid are mixed, react 4h under 160 ℃, add 0.08mol aniline after being warming up to 200 ℃ in reaction vessel, reaction 1h, discharging, in the cold NaOH aqueous solution, is filtered the washing final vacuum and is dried, obtain containing 1, the compound of 2,4-triazole ring, product is white floss.
Embodiment 3
In reaction vessel, 0.14mol m-fluorobenzoic acid compound, 0.07mol hydrazonium sulfate and 0.7mol polyphosphoric acid are mixed, react 5h under 155 ℃, add 0.07mol aniline after being warming up to 190 ℃ in reaction vessel, reaction 2h, discharging, in the cold NaOH aqueous solution, is filtered the washing final vacuum and is dried, obtain containing 1, the compound of 2,4-triazole ring, product is white floss.
Embodiment 4
In reaction vessel, 0.12mol m-Salicylic acid compound, 0.06mol hydrazonium sulfate and 0.6mol polyphosphoric acid are mixed, react 5h under 155 ℃, add 0.06mol aniline after being warming up to 190 ℃ in reaction vessel, reaction 2h, discharging, in the cold NaOH aqueous solution, is filtered the washing final vacuum and is dried, obtain containing 1, the compound of 2,4-triazole ring, product is white floss.
Embodiment 5
Under protection of inert gas, the fluorine end group triazole ring monomer 0.06mol that embodiment 1 is obtained, with the 0.1mol dihydroxyphenyl propane, 0.04mol the sulfonation dichloro diphenyl sulfone adds in reactor, take 0.05mol salt of wormwood as salt forming agent, under nitrogen protection, take N-Methyl pyrrolidone as solvent, toluene is the band aqua, band water 2h, then after steaming toluene, be warmed up to 200 ℃ of reaction 20h, obtain reaction product, product precipitates in acetone, filter, wash five times, dry, the polymkeric substance sterling obtained, the polymkeric substance sterling is dissolved in DMF, casting film-forming, at 60 ℃ of dry 12h, dry 12h under 120 ℃ of hollows, after being cooled to room temperature, the demoulding in water.The HCL that film is placed in to 2M carries out proton exchange 12h, then uses the deionized water repetitive scrubbing until PH=6～7 obtain the sulfonated polyether sulphone proton exchange membrane containing triazole ring.Through test, thickness is 60 μ m, and sulfonation degree is 80%, and in the time of 100 ℃, its proton conductivity is up to 1.04S/cm.
Fig. 2 is the infrared spectrogram containing the sulfonated polymer of 1,2,4-triazole ring that the embodiment of the present invention 5 prepares, as we know from the figure, and 1606cm
-1the stretching vibration peak of the C=N of 1,2,4-triazole ring, 1229cm
-1the stretching vibration peak of the C-N of 1,2,4-triazole ring, 1019cm
-1the stretching vibration peak of S=O in sulfonic acid group, 1072cm
-1the characteristic peak of O=S=O in sodium group, illustrate our success introducing triazole ring and sulfonic acid group.
Embodiment 6
Under protection of inert gas, two hydroxyl triazole ring monomer 0.05mol that embodiment 2 is obtained, with the 0.05mol difluoro benzophenone, 0.05mol dihydroxyphenyl propane, 0.05mol the sulfonation dichloro diphenyl sulfone adds in reactor, take 0.065mol salt of wormwood as salt forming agent, under nitrogen protection, take N-Methyl pyrrolidone as solvent, toluene is the band aqua, band water 2h, then after steaming toluene, be warmed up to 170 ℃ of reaction 30h, obtain reaction product, product precipitates in acetone, filter, wash five times, dry, the polymkeric substance sterling obtained, the polymkeric substance sterling is dissolved in DMF, casting film-forming, at 80 ℃ of dry 18h, dry 18h under 100 ℃ of hollows, after being cooled to room temperature, the demoulding in water, the HCL that film is placed in to 2M carries out proton exchange 24h, use again the deionized water repetitive scrubbing until PH=6～7, obtain the sulfonated polyether sulphone proton exchange membrane containing triazole ring.Through test, thickness is 65 μ m, and sulfonation degree is 100%, and in the time of 100 ℃, its proton conductivity is up to 1.12S/cm.
Embodiment 7
Under protection of inert gas, two fluorine end group triazole ring monomer 0.08mol that embodiment 3 is obtained, with 0.1mol fluoro dihydroxyphenyl propane, 0.02mol the sulfonation dichloro diphenyl sulfone adds in reactor, take 0.025mol salt of wormwood as salt forming agent, under nitrogen protection, take N-Methyl pyrrolidone as solvent, toluene is the band aqua, band water 2h, then after steaming toluene, be warmed up to 190 ℃ of reaction 24h, obtain reaction product, product precipitates in acetone, filter, wash five times, dry, the polymkeric substance sterling obtained, the polymkeric substance sterling is dissolved in DMF, casting film-forming, at 70 ℃ of dry 15h, dry 16h under 110 ℃ of hollows, after being cooled to room temperature, the demoulding in water, the HCL that film is placed in to 2M carries out proton exchange 15h, use again the deionized water repetitive scrubbing until PH=6～7, obtain the sulfonated polyether sulphone proton exchange membrane containing triazole ring.Through test, thickness is 55 μ m, and sulfonation degree is 40%, and in the time of 100 ℃, its proton conductivity is up to 0.97S/cm.
Embodiment 8
Under protection of inert gas, two fluorine end group triazole ring monomer 0.09mol that embodiment 1 is obtained, with 0.1mol parazon diphenol, 0.01mol the sulfonation dichloro diphenyl sulfone adds in reactor, take 0.0125mol salt of wormwood as salt forming agent, under nitrogen protection, take N-Methyl pyrrolidone as solvent, toluene is the band aqua, band water 2h, then after steaming toluene, be warmed up to 190 ℃ of reaction 24h, obtain reaction product, product precipitates in acetone, filter, wash five times, dry, the polymkeric substance sterling obtained, the polymkeric substance sterling is dissolved in DMF, casting film-forming, at 70 ℃ of dry 15h, dry 16h under 110 ℃ of hollows, after being cooled to room temperature, the demoulding in water, the HCL that film is placed in to 2M carries out proton exchange 15h, use again the deionized water repetitive scrubbing until PH=6～7, obtain the sulfonated polyether sulphone proton exchange membrane containing triazole ring.Through test, thickness is 70 μ m, and sulfonation degree is 20%, and in the time of 100 ℃, its proton conductivity is up to 0.91S/cm.
Embodiment 9
Under protection of inert gas, two hydroxyl triazole ring monomer 0.07mol that embodiment 4 is obtained, with the two fluorine S of 0.07mol, 0.03mol para hydroxybenzene phenol, 0.03mol the sulfonation dichloro diphenyl sulfone adds in reactor, take 0.04mol salt of wormwood as salt forming agent, under nitrogen protection, take N-Methyl pyrrolidone as solvent, toluene is the band aqua, band water 2h, then after steaming toluene, be warmed up to 170 ℃ of reaction 30h, obtain reaction product, product precipitates in acetone, filter, wash five times, dry, the polymkeric substance sterling obtained, the polymkeric substance sterling is dissolved in DMF, casting film-forming, at 80 ℃ of dry 18h, dry 18h under 100 ℃ of hollows, after being cooled to room temperature, the demoulding in water, the HCL that film is placed in to 2M carries out proton exchange 24h, use again the deionized water repetitive scrubbing until PH=6～7, obtain the sulfonated polyether sulphone proton exchange membrane containing triazole ring.Through test, thickness is 73 μ m, and sulfonation degree is 60%, and in the time of 100 ℃, its proton conductivity is up to 1.06S/cm.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof; should be understood that; for those skilled in the art; under the premise without departing from the principles of the invention; can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (10)
1. the compound containing 1,2,4-triazole ring, structural formula is suc as formula shown in I:
R is-OH or-F, be substituted radical arbitrarily on phenyl ring.
2. a kind of preparation method who contains the compound of 1,2,4-triazole ring according to claim 1, is characterized in that, comprises as follows:
In reaction vessel, benzoic acid compounds, hydrazonium sulfate and polyphosphoric acid are mixed, react 4～6h under 150～160 ℃, add aniline after being warming up to 180～200 ℃ in reaction vessel, reaction 1～3h, obtain containing 1, the compound of 2,4-triazole ring, described benzoic acid compounds is hydroxy-benzoic acid or fluorinated acid.
3. according to claim 2ly a kind ofly contain 1,2, the preparation method of the compound of 4-triazole ring, it is characterized in that, the mol ratio of described benzoic acid compounds, hydrazonium sulfate, polyphosphoric acid and aniline is (0.1～0.15): (0.05～0.08): (0.5～0.8): (0.05～0.08).
4. the proton exchange polymer membrane containing 1,2,4-triazole ring, structural formula is suc as formula shown in II:
In the formula II, 0.5≤m<1.0,0<n≤0.5, m+n=1; The proton exchange film thickness is 50～100 μ m, and sulfonation degree is 20%～100%, at 100 ℃ of lower proton conductivities, is 0.91～1.12S/cm.
X and Y independently are selected from
5. a kind of preparation method who contains the proton exchange polymer membrane of 1,2,4-triazole ring according to claim 4, is characterized in that, comprises as follows:
Step 1: will mix in organic solvent containing the compound of 1,2,4-triazole ring, the monomer that contains the X structure, the monomer that contains the Y structure, sulfonation chlorine end group monomer, salt of wormwood, and under protection of inert gas, under 170～200 ℃, react 20～30h, and obtain product;
Step 2: product in step 2 is poured in acetone and precipitated, and filtration, washing, drying obtain the polymkeric substance sterling;
Step 3: the polymkeric substance sterling that step 2 is obtained is dissolved in organic solvent, obtain polymers soln, by the polymer dissolution casting film-forming, dry 12～18h under 60～80 ℃, dry 12～18h under 100～120 ℃ again, be cooled to room temperature, the demoulding in water, be placed in hydrochloric acid soln by film and carry out proton exchange 12～24h, use again the deionized water repetitive scrubbing until PH=6～7, obtain the proton exchange polymer membrane containing 1,2,4-triazole ring;
The monomer of the described X of containing structure is selected from
The monomer of the described Y of containing structure is selected from
6. according to claim 5ly a kind ofly contain 1,2, the preparation method of the proton exchange polymer membrane of 4-triazole ring, it is characterized in that, describedly contain 1, the mol ratio of the compound of 2,4-triazole ring, the monomer that contains the X structure, the monomer that contains the Y structure and sulfonation chlorine end group monomer is (0.5～0.9): (0.5～0.9): (0.1～0.5): (0.1～0.5).
7. a kind of preparation method who contains the proton exchange polymer membrane of 1,2,4-triazole ring according to claim 5, is characterized in that, the sulfonation chlorine end group monomer of described step 1 is the sulfonation dichloro diphenyl sulfone.
8. a kind of preparation method who contains the proton exchange polymer membrane of 1,2,4-triazole ring according to claim 5, is characterized in that, the concentration of the hydrochloric acid soln of described step 3 is 2mol/L.
9. a kind of preparation method who contains the proton exchange polymer membrane of 1,2,4-triazole ring according to claim 5, is characterized in that, described organic solvent is selected from one or both mixtures in N-Methyl pyrrolidone or N-cyclohexyl pyrrolidone.
10. a kind of preparation method who contains the proton exchange polymer membrane of 1,2,4-triazole ring according to claim 9, is characterized in that, in described mixture, the volume ratio of N-Methyl pyrrolidone and N-cyclohexyl pyrrolidone is 1: 1.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103880718A (en) * | 2014-03-21 | 2014-06-25 | 北京理工大学 | Wholly aromatic side-chain-type sulfonated dichloro monomer and preparation method thereof |
| CN107828007A (en) * | 2017-11-19 | 2018-03-23 | 湖南辰砾新材料有限公司 | A kind of low-temperature protonic exchange membrane and preparation method thereof |
| US10003096B2 (en) | 2014-03-28 | 2018-06-19 | Kolon Industries, Inc. | Polymer electrolyte membrane, membrane-electrode assembly comprising the same and fuel cell comprising the same |
| CN111682209A (en) * | 2020-05-22 | 2020-09-18 | 浙江中科玖源新材料有限公司 | Binder for lithium ion battery, preparation method of binder and lithium ion battery |
| CN112838252A (en) * | 2019-11-25 | 2021-05-25 | 嘉应学院 | Proton exchange membrane with high proton conductivity for fuel cell and preparation method and application thereof |
| US11581487B2 (en) | 2017-04-26 | 2023-02-14 | Oti Lumionics Inc. | Patterned conductive coating for surface of an opto-electronic device |
| US11730012B2 (en) | 2019-03-07 | 2023-08-15 | Oti Lumionics Inc. | Materials for forming a nucleation-inhibiting coating and devices incorporating same |
| US11751415B2 (en) | 2018-02-02 | 2023-09-05 | Oti Lumionics Inc. | Materials for forming a nucleation-inhibiting coating and devices incorporating same |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880718A (en) * | 2014-03-21 | 2014-06-25 | 北京理工大学 | Wholly aromatic side-chain-type sulfonated dichloro monomer and preparation method thereof |
| US10003096B2 (en) | 2014-03-28 | 2018-06-19 | Kolon Industries, Inc. | Polymer electrolyte membrane, membrane-electrode assembly comprising the same and fuel cell comprising the same |
| US11581487B2 (en) | 2017-04-26 | 2023-02-14 | Oti Lumionics Inc. | Patterned conductive coating for surface of an opto-electronic device |
| CN107828007A (en) * | 2017-11-19 | 2018-03-23 | 湖南辰砾新材料有限公司 | A kind of low-temperature protonic exchange membrane and preparation method thereof |
| CN107828007B (en) * | 2017-11-19 | 2019-11-05 | 湖南辰砾新材料有限公司 | A kind of low-temperature protonic exchange membrane and preparation method thereof |
| US11751415B2 (en) | 2018-02-02 | 2023-09-05 | Oti Lumionics Inc. | Materials for forming a nucleation-inhibiting coating and devices incorporating same |
| US11730012B2 (en) | 2019-03-07 | 2023-08-15 | Oti Lumionics Inc. | Materials for forming a nucleation-inhibiting coating and devices incorporating same |
| CN112838252A (en) * | 2019-11-25 | 2021-05-25 | 嘉应学院 | Proton exchange membrane with high proton conductivity for fuel cell and preparation method and application thereof |
| CN111682209A (en) * | 2020-05-22 | 2020-09-18 | 浙江中科玖源新材料有限公司 | Binder for lithium ion battery, preparation method of binder and lithium ion battery |
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