CN110527088A - A kind of bicyclic ammonium ion polybenzimidazoles and anion-exchange membrane and its preparation method and application - Google Patents
A kind of bicyclic ammonium ion polybenzimidazoles and anion-exchange membrane and its preparation method and application Download PDFInfo
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- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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Abstract
The invention discloses a kind of bicyclic ammonium ion polybenzimidazoles and anion-exchange membrane preparation method and applications, belong to polyelectrolyte and ion exchange membrane technology field.Halogenated loop coil ammonium is then introduced on polybenzimidazoles strand by graft reaction, synthesizes bicyclic ammonium ion polybenzimidazoles, exchange by basic ion, prepare bicyclic ammonium ion polybenzimidazole anion exchange membrane by synthesizing halogen loop coil ammonium salt first.The bicyclic ammonium ion polybenzimidazole anion exchange membrane prepared according to the method for the present invention, polymer film forming is good, ionic conductivity is high, mechanical performance and alkali stability significantly improve, good dimension stability is widely used in fuel cell, flow battery, water electrolysis and electrodialysis, sea water desalination plasma exchange membrane related fields.
Description
Technical field
The invention belongs to polyelectrolyte and ion exchange membrane technology field, it is related to a kind of bicyclic ammonium ion polyphenyl and miaow
Azoles and anion-exchange membrane and its preparation method and application.
Background technique
In recent years, energy crisis, resource exhaustion have caused the urgent need of every profession and trade and the people's livelihood to clean energy resource, and the world is each
The exploitation of state's renewed attention clean energy resource.Fuel cell because its is environmentally protective, energy transformation ratio is high etc., got over by series of advantages
Carry out the concern of more scientific research personnel, while fuel cell also achieves a series of significant progresses.Alkaline anion-exchange membrane
The one kind of fuel cell as fuel cell, have the advantages that make catalyst, water management without noble metal it is simple, while also face from
The challenge that sub- conductivity is not high, alkali stability is bad, this is also that the present invention puts forth effort the place improved.
Polybenzimidazoles as a kind of excellent special engineering plastics, show excellent mechanical stability, heat resistance and
Alkali resistance has attracted the concern of more and more scientific research personnel, the fields such as fuel cell, energy-storage battery ionic membrane apply by
Concern.Currently, polybenzimidazoles is chiefly used in high temperature proton membrane, patent [Wang Lei etc., patent publication No.: CN 106684415
A] disclose a kind of PBI doping phosphoric acid high temperature proton membrane preparation, patent [Lu Jinbo etc., patent publication No.: CN
107887626 A] compound high temperature proton membrane of a kind of crosslinking and preparation method thereof is disclosed, here patent [knows bright etc., patent disclosure
Number: 107674417 A of CN] disclose a kind of non-ionic hydrophilic side chain polybenzimidazoles and preparation method thereof.However, will gather
Open source literature of the benzimidazole for alkaline anion-exchange membrane is less, patent [Zhu Xiuling etc., patent publication No.: CN
108623806 A] disclose a kind of polyphenyl imidazoles with pendant amine groups and its anion-exchange membrane and preparation method.
Summary of the invention
For current basic anionic resin and its amberplex, that there are ionic conductivities is not high, alkali stability is bad
The problem of, the present invention provides a kind of with good mechanical property, alkali resistance is high and the bicyclic ammonium ion polyphenyl of good stability of the dimension
And imidazoles and its anion-exchange membrane and preparation method.
Realization that the present invention adopts the following technical solutions:
A kind of bicyclic ammonium ion polybenzimidazoles, which is characterized in that have a structure that
Wherein, n=0~0.8；
Z is Cl-,Br-, or OH-Ion, preferably OH-Ion；
A is singly-bound, methylene-CH2, ehter bond-O- or carbonyl-CO-, preferably A are singly-bound or methylene-CH2-；
X is aliphatic structure:Wherein, 2≤n '≤18；It is preferred that X is 2≤n '≤12；
Y has a structure that
It is preferred that Y is (a), (c), (e) and (f)；
G is loop coil ammonium ion, and structure is as follows:
G preferred structure is (Gb), (Gd).
The integer of 0≤y≤12, the preferably integer of 2≤y≤6；The integer of 0 q≤12 <, preferably 2≤q≤6 is whole
Number；
A kind of preparation method of bicyclic ammonium ion polybenzimidazole anion exchange membrane, is characterized in that comprising the steps of:
Step 1, the synthesis of polybenzimidazoles
The polybenzimidazoles is to be synthesized by tetramine monomers (II) and diacid monomer (III) by solution polycondensation reaction.
The structure of the tetramine monomers (II) is as follows:
Wherein, A is singly-bound, methylene-CH2, ehter bond-O- or carbonyl-CO-, preferably A are singly-bound or methylene-CH2-；
The structure of the diacid monomer (III) is as follows:
HOOC-X-COOH and HOOC-Y-COOH
Wherein, X is aliphatic structure:Wherein 2≤n '≤18, preferably X are 2≤n '≤12；
Y has a structure that
It is preferred that Y is (a), (c), (e) and (f)；
Polyphosphoric acids is added in the reactor with stirring, in N2Under protection, tetramine monomers (II) and equimolar ratio is added
Diacid monomer (III) HOOC-X-COOH and HOOC-Y-COOH, stirring and dissolving, make the total concentration 1 of monomer II and III~
20wt%.It is warming up to 90~140 DEG C and is stirred to react 0.5~10h, be warming up to 140~160 DEG C and be stirred to react 0.5~10h, heat up
To 160~190 DEG C of 8~30h of reaction.Polymerization reaction terminates, and product is poured into a large amount of deionized waters, and excess NaHCO is added3,
It is stirred overnight.Polymer is washed with deionized water until neutral in filtering.Product is dry, obtains polybenzimidazoles.
Step 2-1, the synthesis of halogenated loop coil ammonium salt (IV)
A certain amount of piperazine or thyl-piperazin are added in the solvent 1 of dibromo pentane, alkali compounds 2 is added, is warming up to
30~90 DEG C are stirred to react 6~72h.Reaction terminates, and filtering obtains N.
The N of a certain amount of above-mentioned synthesis is added to a certain amount of saturated dihalide P- (CH2)w- P (P is Cl or Br atom, 0 < w≤
12 integer, preferably 2≤w≤8) in the solution of solvent 1, alkali compounds 2 is added and reacts 4~100h at 30~90 DEG C,
Reaction terminates filtering, and product centrifugal drying obtains IV.
Step 2-2, the synthesis of halogenated loop coil ammonium salt (V)
By a certain amount of 1, ω-two piperidines alkane (M) is added to a certain amount of saturated dihalide P- (CH2)m(P is Cl or Br former to-P
Son) in the solution of solvent 1, alkali compounds 2 is added and reacts 4~100h at 30~90 DEG C, reaction terminates to filter, dry
To M '；A certain amount of M ' is added to a certain amount of P- (CH2)m(P is Cl or Br atom, the integer of 0 m≤12 <, preferably 2≤m to-P
≤ 8) in the solution of solvent 2,6~100h is reacted at 30~90 DEG C, reaction terminates revolving solvent, and filtering is dried to obtain V.
Step 3, the synthesis of bicyclic ammonium ion polybenzimidazoles (I)
The polybenzimidazoles of a certain amount of synthesis is dissolved by heating in solvent 2 and obtains 0.5~10wt% solution, is added halogenated
Loop coil ammonium salt (IV) or halogenated loop coil ammonium salt (V), in 30~150 DEG C of 8~100h of reaction.Reaction terminates, and pours into precipitating reagent 1, mistake
Filter, filter cake are washed with deionized water 3 times, and product is dry, obtain I.I is dissolved in solvent 1,0.5~15% solution is made, obtained
Bicyclic ammonium ion polybenzimidazoles.
Further, in the above-mentioned technical solutions, the solvent 2 is toluene, methylene chloride, tetrahydrofuran, methanol, second
One or more of alcohol, n,N-dimethylacetamide, dimethyl sulfoxide, n,N-Dimethylformamide, N-Methyl pyrrolidone
Mixture；
The solvent 3 is methylene chloride, acetone, methanol, ethyl alcohol, n,N-dimethylacetamide, dimethyl sulfoxide, N, N- bis-
The mixture of one or more of methylformamide, N-Methyl pyrrolidone.
Further, in the above-mentioned technical solutions, in step 2-1, the molar ratio of piperazine or thyl-piperazin and dibromo pentane
It is 0.05~1:1, the molar ratio of piperazine or thyl-piperazin and alkali compounds 2 is 0.1~1:1, preferably 0.2~1:1；N with
Saturated dihalide P- (CH2)wThe molar ratio of-P is 0.05~1:1, preferably 0.1~0.5:1；
In step 2-2,1, ω-two piperidines alkane (M) and saturated dihalide P- (CH2)5The molar ratio of-P is 1:1~0.1, excellent
It is selected as 1:0.5~1, M ' and P- (CH2)mThe molar ratio of-P is 0.05~1:1, preferably 0.1~0.5:1；1, ω-two piperidines alkane
The molar ratio of hydrocarbon (M) and alkali compounds 2 is 0.1~1:1, preferably 0.2~1:1.
Polybenzimidazoles and IV molar ratio are 0.1~2:1 in step 3, preferably 0.2~1:1.
Further, in the above-mentioned technical solutions, the precipitating reagent 1 is methanol, ethyl alcohol, ether, ethyl acetate, dichloromethane
The mixture of one or more of alkane, tetrahydrofuran, acetone and water.
Further, in the above-mentioned technical solutions, the alkali compounds 2 can be sodium bicarbonate, saleratus, carbonic acid
Sodium, potassium carbonate, cesium carbonate, one or more of sodium hydride, lithium hydride.
Further, in the above-mentioned technical solutions, the viscosity average molecular weigh of polybenzimidazoles is 10,000~450,000g/
Mol, polymerization degree n are 20~1200.
The present invention provides a kind of preparation method of bicyclic ammonium ion polybenzimidazole anion exchange membrane, by above-mentioned bicyclic ammonium
Ion polybenzimidazoles I dissolves in solvent 1 prepares 1~15wt% solution, and filtrate is cast in clean plate upper berth by filtering
Film is transferred to oven drying.By film obtained, it is put into 24~48h in 1M NaOH or 1M KOH aqueous solution, is soaked in water after taking-up
For 24 hours, drying is taken out, bicyclic ammonium ion polybenzimidazole anion exchange membrane is obtained.
Further, the solvent 1 is selected from toluene, methanol, ethyl alcohol, methylene chloride, tetrahydro furan in the above-mentioned technical solutions
It mutters, acetonitrile, acetone, ethyl acetate, n,N-dimethylacetamide, dimethyl sulfoxide, n,N-Dimethylformamide, N- methylpyrrole
The mixture of one or more of alkanone.
The present invention provides above-mentioned bicyclic ammonium ion polybenzimidazoles as electrolyte in fuel cell, flow battery, water power
Solution, electrodialysis and the application in UF membrane field.
It is a further object of the present invention to provide the bicyclic ammonium ion polybenzimidazoles anion friendships that above-mentioned preparation method obtains
Film is changed in the application of the related fieldss such as fuel cell, flow battery, water electrolysis and electrodialysis, sea water desalination and UF membrane.
Compared with prior art, the present invention has the advantage that according to bicyclic ammonium ion polyphenyl prepared by the present invention and miaow
Azoles and its anion-exchange membrane, polymer film forming is good, and ionic conductivity is high, and film toughness and alkali stability are high, in fuel electricity
Pond, flow battery, electrolysis and electrodialysis, sea water desalination plasma film related fields are widely used.
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic spectrogram of bromo piperazine loop coil ammonium prepared by embodiment 4；
Fig. 2 is the hydrogen nuclear magnetic spectrogram that methyl piperazine loop coil prepared by embodiment 4 is grafted PBI anion-exchange membrane；
Fig. 3 is the hydrogen nuclear magnetic spectrogram that two piperidines loop coil ammoniums prepared by embodiment 7 are grafted PBI anion-exchange membrane；
Fig. 4 is the photo that two piperidines loop coil ammoniums prepared by embodiment 7 are grafted PBI anion-exchange membrane.
Specific embodiment
A kind of bicyclic ammonium ion polybenzimidazoles anion exchange of the present invention in detail is further illustrated by the following examples
Film and preparation method and application, but be not used in and limit the scope of the invention, unless otherwise specified, involved in the present inventionization
It learns reagent and drug is commercially available, unless otherwise specified, related method is conventional method.
Test method involved in embodiment:
Ion exchange capacity (IEC) test method: 3 parts of single ammonium ion polybenzimidazoles 0.1g or so are taken, are separately immersed in
In the NaOH of 100ml, 1M for 24 hours, then neutrality is impregnated for 24 hours and is washed to 100ml deionized water respectively, 60 degree of vacuum drying oven are dried
It is dry, it is dipped into the HCl of 0.02002M respectively for 24 hours.A few drop phenolphthalein are added, become pink with the NaOH titration of 0.0182M
Color, the dosage of NaOH needed for recording.NaOH molal quantity is subtracted again divided by 0.1 (g), as IEC with HCl molal quantity.
Test equipment involved in embodiment:
Conductivity test: electrochemical workstation used is produced by Shanghai Chen Hua Instrument Ltd., model: chi660c.
Nuclear-magnetism test: nuclear magnetic resonance chemical analyser used is that VARIAN Oncology Systems produces, and model is Bruker Avance
II 400.In nuclear magnetic spectrogram, two kinds of salt are all to use D2For O as solvent, be grafted post-consumer polymer is DMSO-d6 as solvent.
Table 1 is the chemical structure of bicyclic ammonium ion polybenzimidazoles used in the examples.
Table 1
Embodiment 1
Polyphosphoric acids is added in the reactor with stirring, in N2Under protection, biphenyl tetramine and succinic acid and biphenyl is added
Diacid (molal quantity that the total mole number of succinic acid and biphenyl acid is equal to biphenyl tetramine), heating stirring dissolution make the total matter of monomer
Amount concentration is 10wt%.It is warming up to 110 DEG C and is stirred to react 1h, then 130 DEG C of reaction 1h are warming up to 170 DEG C of reaction 8h, until body
It is that viscosity is not further added by.Polymerization terminates, and product is poured into a large amount of deionized waters, and excess NaHCO is added3, it is stirred overnight.It crosses
Polymer is washed with deionized water until neutral in filter.Product is dry, obtains polybenzimidazoles.
The methyl piperazine of equimolar ratio and dibromo pentane are added in acetone, 30 DEG C is warming up to and is stirred to react 15h.Reaction
Terminate, filtering obtains product N.The above-mentioned product N of 10mol is added in the dichloroethanes of 100mol dibromo-hexane, at 30 DEG C
React 12h.Reaction terminates filtering, and product centrifugal drying obtains product IV.
The polybenzimidazoles of 10mol synthesis is dissolved by heating in N-Methyl pyrrolidone (NMP) and obtains 7wt% solution,
The above-mentioned product IV of 10mol is added, in 40 DEG C of reaction 15h.Reaction terminates, and pours into ethyl alcohol, and filtering, filter cake is washed with deionized water 3 times,
Product is dry, obtains double ammonium ion PBI.
Double ammonium ion PBI of above-mentioned synthesis are dissolved in preparation 5wt% solution in NMP, 0.5h is vacuumized, filters, will filter
Liquid casts in plastic film mulch on clean plate, is transferred to 60 DEG C of oven dryings.By film obtained, immerses in 1M NaOH solution for 24 hours, take out
After be soaked in water for 24 hours, take out drying, obtain double ammonium ion PBI anionic membranes.
After tested, 80 DEG C when double ammonium ion PBI anionic membranes OH-Conductivity is 53mS/cm, the ion film toughness
It is good, after impregnating 1300h in the KOH solution of 80 DEG C of 1M, OH-Ionic conductivity keeps 85%.
Embodiment 2
Polyphosphoric acids is added in the reactor with stirring, in N2Under protection, biphenyl tetramine and succinic acid and biphenyl is added
Diacid (molal quantity that the total mole number of succinic acid and biphenyl acid is equal to biphenyl tetramine), heating stirring dissolution make the total matter of monomer
Amount concentration is 15wt%.It being warming up to 100 DEG C and is stirred to react 5h, then 140 DEG C of reaction 0.5h are warming up to 170 DEG C of reaction 8h, until
System viscosity is not further added by.Polymerization terminates, and product is poured into a large amount of deionized waters, and excess NaHCO is added3, it is stirred overnight.It crosses
Polymer is washed with deionized water until neutral in filter.Product is dry, obtains polybenzimidazoles.
The methyl piperazine of equimolar ratio and dibromo pentane are added in acetone, 50 DEG C is warming up to and is stirred to react 12h.Reaction
Terminate, filtering obtains product N.The above-mentioned product N of 10mol is added in the dichloroethanes of 120mol dibromo-hexane, at 50 DEG C
React 20h.Reaction terminates filtering, and product centrifugal drying obtains product IV.
The polybenzimidazoles of 10mol synthesis is dissolved by heating in N-Methyl pyrrolidone (NMP) and obtains 7wt% solution,
The above-mentioned product IV of 12mol is added, in 40 DEG C of reaction 15h.Reaction terminates, and pours into ethyl alcohol, and filtering, filter cake is washed with deionized water 3 times,
Product is dry, obtains double ammonium ion PBI.
Double ammonium ion PBI of above-mentioned synthesis are dissolved in n,N-dimethylacetamide (DMAc) and prepare 7wt% solution, are taken out
Vacuum 0.5h, filtering, casts in plastic film mulch on clean plate for filtrate, is transferred to 60 DEG C of oven dryings.By film obtained, 1M is immersed
In NaOH solution for 24 hours, it is soaked in water after taking-up for 24 hours, takes out drying, obtain double ammonium ion PBI anionic membranes.
After tested, 80 DEG C when double ammonium ion PBI anionic membranes OH-Conductivity is 45mS/cm, the ion film toughness
It is good, after impregnating 1200h in the KOH solution of 80 DEG C of 1M, OH-Ionic conductivity keeps 85%.
Embodiment 3
Polyphosphoric acids is added in the reactor with stirring, in N2Under protection, be added benzhydryl tetramine and ethanedioic acid and
Isophthalic acid (molal quantity that the total mole number of ethanedioic acid and isophthalic acid is equal to benzhydryl tetramine), heating stirring dissolution make
Monomer gross mass concentration is 10wt%.It is warming up to 130 DEG C and is stirred to react 2h, then 150 DEG C of reaction 4h are warming up to 190 DEG C of reactions
6h, until system viscosity is not further added by.Polymerization terminates, and product is poured into a large amount of deionized waters, and excess NaHCO is added3, stirring
Overnight.Polymer is washed with deionized water until neutral in filtering.Product is dry, obtains polybenzimidazoles.
1,6-, the bis- piperidines hexane and dibromo pentane of equimolar ratio are added in acetone, are stirred to react for 24 hours at 40 DEG C.
Reaction terminates filtering, is dried to obtain product M '；The above-mentioned product M ' of 10mol is added to the acetonitrile solution of the dibromobutane of 20mol
In, 10h is reacted at 50 DEG C.Reaction terminates to rotate out solvent, filters, is dried to obtain product IV.
The 10mol polybenzimidazoles synthesized is dissolved by heating in NMP and obtains 8wt% solution, the above-mentioned product of 20mol is added
IV, it is reacted for 24 hours at 50 DEG C.Reaction terminates, and pours into acetone, and filtering, filter cake is washed with deionized water 3 times, and product is dry, obtains double ammoniums
Ion PBI.
Double ammonium ion PBI of above-mentioned synthesis are dissolved in n,N-Dimethylformamide (DMF) and prepare 1wt% solution, are taken out
Vacuum 0.5h, filtering, casts in plastic film mulch on clean plate for filtrate, is transferred to 60 DEG C of oven dryings.By film obtained, 1M is immersed
In NaOH solution for 24 hours, it is soaked in water after taking-up for 24 hours, takes out drying, obtain double ammonium ion PBI anionic membranes.
After tested, 80 DEG C when double ammonium ion PBI anionic membranes OH-Conductivity is 46mS/cm, the ion film toughness
It is good, after impregnating 1100h in the KOH solution of 80 DEG C of 1M, OH-Ionic conductivity keeps 84%.
Embodiment 4
Polyphosphoric acids is added in the reactor with stirring, in N2Under protection, biphenyl tetramine and ethanedioic acid and hexichol is added
Ether diacid (molal quantity that the total mole number of ethanedioic acid and diphenyl ether diacid is equal to biphenyl tetramine), heating stirring dissolution make monomer
Total mass concentration is 10wt%.It being warming up to 120 DEG C and is stirred to react 3h, then 145 DEG C of reaction 2h are warming up to 180 DEG C of reaction 25h,
Until system viscosity is not further added by.Polymerization terminates, and product is poured into a large amount of deionized waters, and excess NaHCO is added3, stirred
Night.Polymer is washed with deionized water until neutral in filtering.Product is dry, obtains polybenzimidazoles.
10mol methyl piperazine and 80mol dibromo pentane are added in acetone, 60 DEG C is warming up to and is stirred to react 15h.Reaction
Terminate, filtering obtains product N.The above-mentioned product N of 10mol is added in the dichloroethanes of 30mol dibromo-hexane, at 50 DEG C
React 12h.Reaction terminates filtering, and product centrifugal drying obtains product IV.
The polybenzimidazoles of 10mol synthesis is dissolved by heating in N-Methyl pyrrolidone (NMP) and obtains 7wt% solution,
The above-mentioned product IV of 10mol is added, in 70 DEG C of reaction 15h.Reaction terminates, and pours into ethyl alcohol, and filtering, filter cake is washed with deionized water 3 times,
Product is dry, obtains double ammonium ion PBI.
Double ammonium ion PBI of above-mentioned synthesis are dissolved in preparation 10wt% solution in DMSO, 0.5h is vacuumized, filters, it will
Filtrate casts in plastic film mulch on clean plate, is transferred to 60 DEG C of oven dryings.By film obtained, immerses in 1M NaOH solution for 24 hours, take
It is soaked in water after out for 24 hours, takes out drying, obtain double ammonium ion PBI anionic membranes.
After tested, 80 DEG C when double ammonium ion PBI anionic membranes OH-Conductivity is 50mS/cm, the ion film toughness
It is good, after impregnating 1400h in the KOH solution of 80 DEG C of 1M, OH-Ionic conductivity keeps 84%.
Polyphosphoric acids is added in the reactor with stirring in embodiment 5, in N2Under protection, equimolar biphenyl tetramine is added
With diphenyl-methane diacid, heating stirring dissolution makes monomer gross mass concentration 5wt%.It is warming up to 110 DEG C and is stirred to react 8h, 160
DEG C reaction 5h, is then warming up to 175 DEG C of reaction 15h, is not further added by up to system viscosity.Polymerization terminates, and product is poured into largely
In deionized water, excess NaHCO is added3, it is stirred overnight.Polymer is washed with deionized water until neutral in filtering.Product is dry,
Obtain polybenzimidazoles.
- two piperidines butane of Isosorbide-5-Nitrae and 12mol dibromo pentane of 10mol are added in acetone, are stirred to react at 40 DEG C
10h.Reaction terminates filtering, is dried to obtain product M '；The above-mentioned product M ' of 10mol is added to the acetone of the dibromobutane of 20mol
In solution, 8h is reacted at 90 DEG C.Reaction terminates to rotate out solvent, filters, is dried to obtain product IV.
The 10mol polybenzimidazoles synthesized is dissolved by heating in NMP and obtains 5wt% solution, the above-mentioned product of 10mol is added
IV, in 80 DEG C of reaction 8h.Reaction terminates, and pours into acetone, and filtering, filter cake is washed with deionized water 3 times, and product is dry, obtains double ammoniums
Ion PBI.
Double ammonium ion PBI of above-mentioned synthesis are dissolved in preparation 6wt% solution in DMAc, 0.5h is vacuumized, filters, will filter
Liquid casts in plastic film mulch on clean plate, is transferred to 60 DEG C of oven dryings.By film obtained, immerses in 1M NaOH solution for 24 hours, take out
After be soaked in water for 24 hours, take out drying, obtain double ammonium ion PBI anionic membranes.
After tested, 80 DEG C when double ammonium ion PBI anionic membranes OH-Conductivity is 45mS/cm, the ion film toughness
It is good, after impregnating 1200h in the KOH solution of 80 DEG C of 1M, OH-Ionic conductivity keeps 80%.
Embodiment 6
Polyphosphoric acids is added in the reactor with stirring, in N2Under protection, biphenyl tetramine and pimelic acid and hexichol is added
Ether diacid (molal quantity that the total mole number of pimelic acid and diphenyl ether diacid is equal to biphenyl tetramine), heating stirring dissolution make monomer
Total mass concentration is 10wt%.It being warming up to 140 DEG C and is stirred to react 1h, then 160 DEG C of reaction 1h are warming up to 185 DEG C of reaction 12h,
Until system viscosity is not further added by.Polymerization terminates, and product is poured into a large amount of deionized waters, and excess NaHCO is added3, stirred
Night.Polymer is washed with deionized water until neutral in filtering.Product is dry, obtains polybenzimidazoles.
10mol methyl piperazine and 30mol dibromo pentane are added in acetone, 70 DEG C is warming up to and is stirred to react 12h.Reaction
Terminate, filtering obtains product N.The above-mentioned product N of 10mol is added in the tetrahydrofuran of 50mol dibromo-hexane, at 70 DEG C
React 15h.Reaction terminates filtering, and product centrifugal drying obtains IV.
The 10mol polybenzimidazoles synthesized is dissolved by heating in NMP and obtains 7wt% solution, the above-mentioned product of 20mol is added
IV, in 90 DEG C of reaction 16h.Reaction terminates, and pours into ethyl alcohol, and filtering, filter cake is washed with deionized water 3 times, and product is dry, obtains double ammoniums
Ion PBI.
Double ammonium ion PBI of above-mentioned synthesis are dissolved in preparation 5wt% solution in DMSO, 0.5h is vacuumized, filters, will filter
Liquid casts in plastic film mulch on clean plate, is transferred to 60 DEG C of oven dryings.By film obtained, immerses in 1M NaOH solution for 24 hours, take out
After be soaked in water for 24 hours, take out drying, obtain double ammonium ion PBI anionic membranes.
After tested, 80 DEG C when double ammonium ion PBI anionic membranes OH-Conductivity is 50mS/cm, the ion film toughness
It is good, after impregnating 1200h in the KOH solution of 80 DEG C of 1M, OH-Ionic conductivity keeps 81%.
Embodiment 7
Polyphosphoric acids is added in the reactor with stirring, in N2Under protection, biphenyl tetramine and adipic acid and hexichol is added
Ether diacid (molal quantity that the total mole number of adipic acid and diphenyl ether diacid is equal to biphenyl tetramine), heating stirring dissolution make monomer
Total mass concentration is 8wt%.It is warming up to 130 DEG C and is stirred to react 8h, then 150 DEG C of reaction 3h are warming up to 170 DEG C of reaction 14h, directly
It is not further added by system viscosity.Polymerization terminates, and product is poured into a large amount of deionized waters, and excess NaHCO is added3, it is stirred overnight.
Polymer is washed with deionized water until neutral in filtering.Product is dry, obtains polybenzimidazoles.
1, the 2- dipiperidinoethane of 10mol and 80mol dibromo pentane are added in acetone, are stirred to react at 55 DEG C
8h.Reaction terminates filtering, is dried to obtain product M '；The above-mentioned product M ' of 10mol is added to the dichloroethanes of 30mol dibromo-hexane
In solution, 16h is reacted at 55 DEG C.Reaction terminates to rotate out solvent, filters, is dried to obtain product IV.
The 10mol polybenzimidazoles synthesized is dissolved by heating in NMP and obtains 8wt% solution, the above-mentioned product of 10mol is added
IV, in 100 DEG C of reaction 12h.Reaction terminates, and pours into acetone, and filtering, filter cake is washed with deionized water 3 times, and product is dry, obtains double
Ammonium ion PBI.
Double ammonium ion PBI of above-mentioned synthesis are dissolved in preparation 5wt% solution in DMAc, 0.5h is vacuumized, filters, will filter
Liquid casts in plastic film mulch on clean plate, is transferred to 60 DEG C of oven dryings.By film obtained, immerses in 1M NaOH solution for 24 hours, take out
After be soaked in water for 24 hours, take out drying, obtain double ammonium ion PBI anionic membranes.
After tested, 80 DEG C when double ammonium ion PBI anionic membranes OH-Conductivity is 65mS/cm, the ion film toughness
It is good, after impregnating 1500h in the KOH solution of 80 DEG C of 1M, OH-Ionic conductivity keeps 80%.
Embodiment 8
Polyphosphoric acids is added in the reactor with stirring, in N2Under protection, benzhydryl tetramine and diphenyl-methane is added
Diacid (molal quantity that the total mole number of diphenyl-methane diacid is equal to benzhydryl tetramine), heating stirring dissolution make the total matter of monomer
Amount concentration is 8wt%.It is warming up to 130 DEG C and is stirred to react 2h, then 150 DEG C of reaction 4h are warming up to 190 DEG C of reaction 6h, until body
It is that viscosity is not further added by.Polymerization terminates, and product is poured into a large amount of deionized waters, and excess NaHCO is added3, it is stirred overnight.It crosses
Polymer is washed with deionized water until neutral in filter.Product is dry, obtains polybenzimidazoles.
1, the 2- dipiperidinoethane of 10mol and 10mol dibromo pentane are added in acetone, are stirred to react at 50 DEG C
12h.Reaction terminates filtering, is dried to obtain product M '；The above-mentioned product M ' of 10mol is added to the acetone of the dibromobutane of 30mol
In solution, 12h is reacted at 40 DEG C.Reaction terminates to rotate out solvent, filters, is dried to obtain product IV.
The 10mol polybenzimidazoles synthesized is dissolved by heating in NMP and obtains 2wt% solution, the above-mentioned product of 10mol is added
IV, in 50 DEG C of reaction 30h.Reaction terminates, and pours into acetone, and filtering, filter cake is washed with deionized water 3 times, and product is dry, obtains double ammoniums
Ion PBI.
Double ammonium ion PBI of above-mentioned synthesis are dissolved in preparation 4wt% solution in DMSO, 0.5h is vacuumized, filters, will filter
Liquid casts in plastic film mulch on clean plate, is transferred to 60 DEG C of oven dryings.By film obtained, immerses in 1M NaOH solution for 24 hours, take out
After be soaked in water for 24 hours, take out drying, obtain double ammonium ion PBI anionic membranes.
After tested, 80 DEG C when double ammonium ion PBI anionic membranes OH-Conductivity is 50mS/cm, the ion film toughness
It is good, after impregnating 1300h in the KOH solution of 80 DEG C of 1M, OH-Ionic conductivity keeps 82%.
Embodiment 9
Polyphosphoric acids is added in the reactor with stirring, in N2Under protection, biphenyl tetramine and ethanedioic acid and hexichol is added
Ether diacid (molal quantity that the total mole number of ethanedioic acid and diphenyl ether diacid is equal to biphenyl tetramine), heating stirring dissolution make monomer
Total mass concentration is 17wt%.It being warming up to 120 DEG C and is stirred to react 5h, then 145 DEG C of reaction 2h are warming up to 170 DEG C of reaction 30h,
Until system viscosity is not further added by.Polymerization terminates, and product is poured into a large amount of deionized waters, and excess NaHCO is added3, stirred
Night.Polymer is washed with deionized water until neutral in filtering.Product is dry, obtains polybenzimidazoles.
- two piperidines butane of Isosorbide-5-Nitrae and 8mol dibromo pentane of 10mol are added in acetonitrile, are stirred to react at 20 DEG C
30h.Reaction terminates filtering, is dried to obtain product M '；The acetonitrile that the above-mentioned product M ' of 10mol is added to 30mol dibromo pentane is molten
In liquid, 20h is reacted at 40 DEG C.Reaction terminates to rotate out solvent, filters, is dried to obtain product IV.
The 10mol polybenzimidazoles synthesized is dissolved by heating in NMP and obtains 10wt% solution, the above-mentioned production of 15mol is added
Object IV reacts for 24 hours at 50 DEG C.Reaction terminates, and pours into ethyl alcohol, and filtering, filter cake is washed with deionized water 3 times, and product is dry, obtains double
Ammonium ion PBI.
Double ammonium ion PBI of above-mentioned synthesis are dissolved in preparation 15wt% solution in DMSO, 0.5h is vacuumized, filters, it will
Filtrate casts in plastic film mulch on clean plate, is transferred to 60 DEG C of oven dryings.By film obtained, immerses in 1M NaOH solution for 24 hours, take
It is soaked in water after out for 24 hours, takes out drying, obtain double ammonium ion PBI anionic membranes.
After tested, 80 DEG C when double ammonium ion PBI anionic membranes OH-Conductivity is 45mS/cm, the ion film toughness
It is good, after impregnating 1200h in the KOH solution of 80 DEG C of 1M, OH-Ionic conductivity keeps 81%.
Embodiment 10
Polyphosphoric acids is added in the reactor with stirring, in N2Under protection, be added benzhydryl tetramine and succinic acid and
Diphenyl-methane diacid (molal quantity that the total mole number of succinic acid and diphenyl-methane diacid is equal to benzhydryl tetramine), heating stirring
Dissolution, makes monomer gross mass concentration 3wt%.It is warming up to 130 DEG C and is stirred to react 2h, then 150 DEG C of reaction 4h are warming up to 180
DEG C reaction 6h, until system viscosity is not further added by.Polymerization terminates, and product is poured into a large amount of deionized waters, is added excessive
NaHCO3, it is stirred overnight.Polymer is washed with deionized water until neutral in filtering.Product is dry, obtains polybenzimidazoles.
10mol methyl piperazine and 15mol dibromo pentane are added in dichloroethanes, 40 DEG C is warming up to and is stirred to react 15h.
Reaction terminates, and filtering obtains product N.The above-mentioned product N of 10mol is added in the dichloroethanes of 30mol dibromo-hexane, 40
12h is reacted at DEG C.Reaction terminates filtering, and product centrifugal drying obtains product IV.
The polybenzimidazoles of 10mol synthesis is dissolved by heating in N-Methyl pyrrolidone (NMP) and obtains 10wt% solution,
The above-mentioned product IV of 15mol is added, in 40 DEG C of reaction 15h.Reaction terminates, and pours into methanol, and filtering, filter cake is washed with deionized water 3 times,
Product is dry, obtains double ammonium ion PBI.
Double ammonium ion PBI of above-mentioned synthesis are dissolved in NMP) in prepare 5wt% solution, vacuumize 0.5h, filter, will filter
Liquid casts in plastic film mulch on clean plate, is transferred to 60 DEG C of oven dryings.By film obtained, immerses in 1M NaOH solution for 24 hours, take out
After be soaked in water for 24 hours, take out drying, obtain double ammonium ion PBI anionic membranes.
After tested, 80 DEG C when double ammonium ion PBI anionic membranes OH-Conductivity is 50mS/cm, the ion film toughness
It is good, after impregnating 1300h in the KOH solution of 80 DEG C of 1M, OH-Ionic conductivity keeps 82%.
Embodiment 11
Polyphosphoric acids is added in the reactor with stirring, in N2Under protection, biphenyl tetramine and adipic acid and hexichol is added
Ether diacid (molal quantity that the total mole number of adipic acid and diphenyl ether diacid is equal to biphenyl tetramine), heating stirring dissolution make monomer
Total mass concentration is 15wt%.It being warming up to 130 DEG C and is stirred to react 1h, then 160 DEG C of reaction 1h are warming up to 190 DEG C of reaction 15h,
Until system viscosity is not further added by.Polymerization terminates, and product is poured into a large amount of deionized waters, and excess NaHCO is added3, stirred
Night.Polymer is washed with deionized water until neutral in filtering.Product is dry, obtains polybenzimidazoles.
1,3-, the bis- piperidines propane and 100mol dibromo pentane of 10mol are added in acetone, are stirred to react at 50 DEG C
24h.Reaction terminates filtering, is dried to obtain product M '；The above-mentioned product M ' of 10mol is added to the tetrahydro furan of 100mol dibromo-hexane
It mutters in solution, is reacted for 24 hours at 60 DEG C.Reaction terminates to rotate out solvent, filters, is dried to obtain product IV.
The 10mol polybenzimidazoles synthesized is dissolved by heating in NMP and obtains 8wt% solution, the above-mentioned product of 30mol is added
IV, it is reacted for 24 hours at 70 DEG C.Reaction terminates, and pours into acetone, and filtering, filter cake is washed with deionized water 3 times, and product is dry, obtains double ammoniums
Ion PBI.
Double ammonium ion PBI of above-mentioned synthesis are dissolved in preparation 5wt% solution in DMSO, 0.5h is vacuumized, filters, will filter
Liquid casts in plastic film mulch on clean plate, is transferred to 60 DEG C of oven dryings.By film obtained, immerses in 1M NaOH solution for 24 hours, take out
After be soaked in water for 24 hours, take out drying, obtain double ammonium ion PBI anionic membranes.
After tested, 80 DEG C when double ammonium ion PBI anionic membranes OH-Conductivity is 50mS/cm, the ion film toughness
It is good, after impregnating 1200h in the KOH solution of 80 DEG C of 1M, OH-Ionic conductivity keeps 83%.
Embodiment 12
Polyphosphoric acids is added in the reactor with stirring, in N2Under protection, biphenyl tetramine and ethanedioic acid and biphenyl is added
Diacid (molal quantity that the total mole number of ethanedioic acid and biphenyl acid is equal to biphenyl tetramine), heating stirring dissolution make the total matter of monomer
Amount concentration is 12wt%.It being warming up to 100 DEG C and is stirred to react 7h, then 150 DEG C of reaction 3h are warming up to 170 DEG C of reaction 30h, until
System viscosity is not further added by.Polymerization terminates, and product is poured into a large amount of deionized waters, and excess NaHCO is added3, it is stirred overnight.It crosses
Polymer is washed with deionized water until neutral in filter.Product is dry, obtains polybenzimidazoles.
10mol methyl piperazine and 10mol dibromo pentane are added in acetone, 30 DEG C is warming up to and is stirred to react 15h.Reaction
Terminate, filtering obtains product N.The above-mentioned product N of 10mol is added in the dichloroethanes of 20mol dibromobutane, at 50 DEG C
React 10h.Reaction terminates filtering, and product centrifugal drying obtains product IV.
The 10mol polybenzimidazoles synthesized is dissolved by heating in NMP and obtains 7wt% solution, the above-mentioned product of 60mol is added
IV, in 40 DEG C of reaction 15h.Reaction terminates, and pours into methanol, and filtering, filter cake is washed with deionized water 3 times, and product is dry, obtains double ammoniums
Ion PBI.
Double ammonium ion PBI of above-mentioned synthesis are dissolved in preparation 8wt% solution in NMP, 0.5h is vacuumized, filters, will filter
Liquid casts in plastic film mulch on clean plate, is transferred to 60 DEG C of oven dryings.By film obtained, immerses in 1M NaOH solution for 24 hours, take out
After be soaked in water for 24 hours, take out drying, obtain double ammonium ion PBI anionic membranes.
After tested, 80 DEG C when double ammonium ion PBI anionic membranes OH-Conductivity is 45mS/cm, the ion film toughness
It is good, after impregnating 1200h in the KOH solution of 80 DEG C of 1M, OH-Ionic conductivity keeps 82%.
The proton magnetic spectrum map analysis of Fig. 1:
Fig. 1 is the hydrogen nuclear magnetic spectrogram of bromomethyl piperazine loop coil ammonium, and nuclear-magnetism frequency is 400MHZ, solvent D2O。
Characteristic peak is the-CH that is connected with-Br at 3.478ppm2The chemical shift of upper H1；At 3.276ppm characteristic peak be with N just
Ion (- N+) connected-CH3The chemical shift of upper H2；Characteristic peak is side chain piperazine at 3.802ppm, 3.683ppm, 3.559ppm
In piperazine loop coil with-N+Connected-CH2The chemical shift of upper H3, H4, H5；Characteristic peak is piperazine spiral shell at 1.897ppm, 1.690ppm
- N in ring+Meta position, contraposition-CH2The chemical shift of upper H6, H7；Characteristic peak is that ring is outer with-N at 3.599ppm+Be connected-
CH2The chemical shift of upper H8；Characteristic peak is long side chain-CH at 1.835ppm, 1.749ppm, 1.455ppm, 1.396ppm2Upper H9,
The chemical shift of H10, H11, H12.It can thus be appreciated that successfully synthesizing bromo piperazine loop coil ammonium.
The proton magnetic spectrum map analysis of Fig. 2:
Fig. 2 is the hydrogen nuclear magnetic spectrogram of methyl piperazine loop coil grafting PBI, and nuclear-magnetism frequency is 400MHZ, solvent DMSO-d6。
The characteristic peak of no PBI benzimidazole ring N-H at 11~15ppm illustrates the reaction hair of PBI grafting piperazine loop coil
It is raw.Characteristic peak is proximate to the chemical shift of H2 on ehter bond-O- phenyl ring at 8.286ppm；Characteristic peak is separate at 7.312ppm
The chemical shift of H1 on the phenyl ring of ehter bond；At 7.990ppm, 7.850ppm and 7.626ppm characteristic peak be H3, H4 on phenyl ring,
The chemical shift of H5；Characteristic peak is after with PBI graft reaction occurs for N methyl piperazine loop coil ammonium, with PBI benzo miaow at 2.545ppm
Connected-the CH of double bond N in azoles ring2The chemical shift of upper H6；Characteristic peak is that N methyl piperazine loop coil ammonium and PBI occur at 2.384ppm
After graft reaction ,-the CH that is connected with PBI benzimidazole ring N atom2The chemical shift of upper H7.By being analyzed above it is found that N methyl
Piperazine loop coil is grafted on PBI strand, to be successfully prepared the PBI anion exchange with methyl piperazine loop coil ammonium side chain
Film.
The proton magnetic spectrum map analysis of Fig. 3:
Fig. 3 is the hydrogen nuclear magnetic spectrogram of ionic membrane after two piperidines loop coil ammoniums grafting PBI, and nuclear-magnetism frequency is 400MHZ, solvent
It is DMSO-d6.It can be seen from figure 3 that not occurring the characteristic peak of N-H in imidazole ring between 11-15ppm, illustrate the N-H in imidazole ring
Substitution reaction has occurred.It is the characteristic peak of H on phenyl ring at 7-9ppm, is direct with ehter bond-O- at 8.33ppm and 7.41ppm
The characteristic peak of H2, H1, at 8.14ppm, 8.02ppm, 7.87ppm are connected directly on phenyl ring with imidazole ring on connected phenyl ring
The characteristic peak of H3, H4, H5.It is to be connected directly CH with N at 2.54ppm and 2.40ppm2The characteristic peak of upper H6, H7.3.82ppm and
It is the CH that piperidines loop coil is connected with N cation at 3.20ppm2The characteristic peak of upper H9, H8.It is piperidines at 1.97ppm and 1.57ppm
Meta position, contraposition CH in loop coil in N cation2The characteristic peak of upper H10, H11.By being analyzed above it is found that two piperidines loop coil ammoniums
It has been grafted on PBI strand, to be successfully prepared the PBI anion-exchange membrane of two piperidines loop coil ammonium side chain of band.
Claims (10)
1. a kind of bicyclic ammonium ion polybenzimidazoles, which is characterized in that have following general formula (I) structure:
Wherein, in (I), n=0~0.8；
Z is Cl-,Br-, or OH-Ion；
A is singly-bound, methylene-CH2, ehter bond-O- or carbonyl-CO-；
X is aliphatic structure:Wherein, wherein 2≤n '≤18；
Y has a structure that
G is loop coil ammonium ion, and structure is as follows:
The integer of 0≤y≤12, the integer of 0 q≤12 <.
2. the preparation method of bicyclic ammonium ion polybenzimidazoles as described in claim 1, is characterized in that comprising the steps of:
Step 1, the synthesis of polybenzimidazoles
The polybenzimidazoles is to be synthesized by tetramine monomers (II) and diacid monomer (III) by solution polycondensation reaction；
The structure of the tetramine monomers (II) is as follows:
Wherein, A is singly-bound, methylene-CH2, ehter bond-O- or carbonyl-CO-；
The structure of the diacid monomer (III) is as follows:
HOOC-X-COOH and HOOC-Y-COOH
Wherein, X is aliphatic structure:Wherein, wherein 2≤n '≤18；
Y has a structure that
Polyphosphoric acids is added in the reactor with stirring, in N2Under protection, the diacid of tetramine monomers (II) and equimolar ratio is added
Monomer (III) HOOC-X-COOH and HOOC-Y-COOH, stirring and dissolving, make the total mass concentration 1 of monomer II and III~
20wt%；It is warming up to 90~140 DEG C and is stirred to react 0.5~10h, be then warming up to 140~160 DEG C and be stirred to react 0.5~10h,
It is warming up to 160~190 DEG C of 8~30h of reaction；Polymerization reaction terminates, and product is poured into a large amount of deionized waters, is added excessive
NaHCO3, it is stirred overnight；Polymer is washed with deionized water until neutral in filtering；Product is dry, obtains polybenzimidazoles；
Step 2-1, the synthesis of halogenated loop coil ammonium salt (IV)
A certain amount of piperazine or thyl-piperazin are added in the solvent 1 of dibromo pentane, alkali compounds 2 is added, it is warming up to 30~
90 DEG C are stirred to react 6~72h；Reaction terminates, and filtering obtains N；
The N of a certain amount of above-mentioned synthesis is added to a certain amount of saturated dihalide P- (CH2)wAlkalinity is added in the solution of solvent 1 in-P
Compound 2 reacts 4~100h at 30~90 DEG C, and reaction terminates filtering, and product centrifugal drying obtains IV；Wherein, P is selected from Cl
Or Br atom, the integer of 0 w≤12 <；
Step 2-2, the synthesis of halogenated loop coil ammonium salt (V)
By a certain amount of 1, ω-two piperidines alkane (M) is added to a certain amount of saturated dihalide P- (CH2)5- P (P is Cl or Br atom) In
In the solution of solvent 1, alkali compounds 2 is added and reacts 4~100h at 30~90 DEG C, reaction terminates filtering, is dried to obtain M '；
A certain amount of M ' is added to a certain amount of P- (CH2)m- P reacts 6~100h, instead in the solution of solvent 2 at 30~90 DEG C
It should terminate to rotate solvent, filtering is dried to obtain V；Wherein, P is selected from Cl or Br atom, and m is the integer of 0 m≤12 <,
Step 3, the synthesis of bicyclic ammonium ion polybenzimidazoles (I)
A certain amount of polybenzimidazoles is dissolved by heating in solvent 2 and obtains 0.5~10wt% solution, halogenated loop coil ammonium salt is added
(IV) or halogenated loop coil ammonium salt (V), in 30~150 DEG C of 8~100h of reaction；Reaction terminates, and pours into precipitating reagent 1, filtering, filter cake
It is washed with deionized water, product is dry, obtains I；I is dissolved in solvent 1,0.5~15% solution is made, obtains bicyclic ammonium ion
Polybenzimidazole electrolyte matter solution.
3. preparation method according to claim 2, is characterized in that, the solvent 2 be toluene, methylene chloride, tetrahydrofuran,
One of methanol, ethyl alcohol, n,N-dimethylacetamide, dimethyl sulfoxide, n,N-Dimethylformamide, N-Methyl pyrrolidone
Or several mixture；
The solvent 3 is methylene chloride, acetone, methanol, ethyl alcohol, n,N-dimethylacetamide, dimethyl sulfoxide, N, N- dimethyl
The mixture of one or more of formamide, N-Methyl pyrrolidone.
4. preparation method according to claim 2, which is characterized in that in step 2-1, piperazine or thyl-piperazin and dibromo
The molar ratio of pentane is 0.05~1:1, piperazine or thyl-piperazin and the molar ratio of alkali compounds 2 is 0.1~1:1；N and two
Alkyl halide P- (CH2)wThe molar ratio of-P is 0.05~1:1,2≤w≤8；
In step 2-2,1, ω-two piperidines alkane M and saturated dihalide P- (CH2)mThe molar ratio of-P is 1:1~0.1, M ' and P-
(CH2)mThe molar ratio of-P is 0.05~1:1；The molar ratio of 1, ω-two piperidines alkane M and alkali compounds 2 is 0.1~1:1；
Polybenzimidazoles and IV molar ratio are 0.1~2:1 in step 3.
5. preparation method according to claim 2 is it is characterized in that, the precipitating reagent 1 is methanol, ethyl alcohol, ether, acetic acid
The mixture of one or more of ethyl ester, methylene chloride, tetrahydrofuran, acetone and water；
The alkali compounds 2 is in sodium bicarbonate, saleratus, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride, lithium hydride
One or more.
6. polybenzimidazoles or preparation method as claimed in claim 2 according to claim 1, are characterized in that, polyphenyl and miaow
The viscosity average molecular weigh of azoles is 10,000~450,000g/mol, and polymerization degree n is 20~1200.
7. a kind of preparation method of bicyclic ammonium ion polybenzimidazole anion exchange membrane, is characterized in that: will be double in claim 1
Cycloaminium ion polybenzimidazoles I dissolves in solvent 1 prepares 1~15wt% solution, and filtering casts in filtrate on clean plate
Plastic film mulch is transferred to oven drying；By film obtained, it is put into 24~48h in 1M NaOH or 1M KOH aqueous solution and carries out OH-Ion is handed over
It changes, takes out the 24~48h that is soaked in water, take the film out drying, obtain bicyclic ammonium ion polybenzimidazole anion exchange membrane.
8. the preparation method according to claim 2 or 7, is characterized in that, the solvent 1 is selected from toluene, methanol, ethyl alcohol, two
Chloromethanes, tetrahydrofuran, acetonitrile, acetone, ethyl acetate, n,N-dimethylacetamide, dimethyl sulfoxide, N, N- dimethyl formyl
The mixture of one or more of amine, N-Methyl pyrrolidone.
9. the 2 bicyclic ammonium ion polybenzimidazoles are as electrolyte in fuel cell, flow battery, water power such as claim 1
Solution, electrodialysis and the application in UF membrane field.
10. the bicyclic ammonium ion polybenzimidazole anion exchange membrane that the preparation method as described in claim 7 or 8 obtains is in fuel
Battery, flow battery, water electrolysis, electrodialysis and the application in UF membrane field.
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| CN111748096A (en) * | 2020-07-08 | 2020-10-09 | 吉林大学 | Preparation and application of polybenzimidazole based single-ion polymer gel electrolyte |
| WO2020238731A1 (en) * | 2019-05-28 | 2020-12-03 | 大连理工大学 | Bicyclic ammonium ion polybenzimidazole, anion exchange membrane, preparation method therefor and use thereof |
| CN113527685A (en) * | 2021-06-10 | 2021-10-22 | 中国科学院山西煤炭化学研究所 | Polybenzimidazole ion solvent membrane and preparation method and application thereof |
| CN116606438A (en) * | 2022-02-08 | 2023-08-18 | 大连理工大学 | Preparation method and application of polybenzimidazole with spiro-ammonified main chain, anion exchange membrane and ionomer solution thereof |
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| CN109742428A (en) * | 2019-01-28 | 2019-05-10 | 太原理工大学 | A kind of blending anion-exchange membrane based on N- spiro quaternary ammonium salt polymer |
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| WO2020238731A1 (en) * | 2019-05-28 | 2020-12-03 | 大连理工大学 | Bicyclic ammonium ion polybenzimidazole, anion exchange membrane, preparation method therefor and use thereof |
| CN111748096A (en) * | 2020-07-08 | 2020-10-09 | 吉林大学 | Preparation and application of polybenzimidazole based single-ion polymer gel electrolyte |
| CN113527685A (en) * | 2021-06-10 | 2021-10-22 | 中国科学院山西煤炭化学研究所 | Polybenzimidazole ion solvent membrane and preparation method and application thereof |
| CN116606438A (en) * | 2022-02-08 | 2023-08-18 | 大连理工大学 | Preparation method and application of polybenzimidazole with spiro-ammonified main chain, anion exchange membrane and ionomer solution thereof |
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| WO2020238731A1 (en) | 2020-12-03 |
| CN110527088B (en) | 2020-08-14 |
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