CN109265715A - A kind of polystyrene thermoplastic elastomer/polystyrene composite membrane and preparation method - Google Patents
A kind of polystyrene thermoplastic elastomer/polystyrene composite membrane and preparation method Download PDFInfo
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Abstract
The present invention relates to a kind of polystyrene thermoplastic elastomer/polystyrene composite membrane and preparation methods.The membrane material, by solution blending in varing proportions after the two functionalization, is film-made using polystyrene thermoplastic elastomer and polystyrene as matrix after crosslinking agent is added, and a series of anion-exchange membranes are made after quaternary amine salinization and alkalization under heterogeneous state.1) prepared polystyrene thermoplastic elastomer/polystyrene composite membrane, which has the advantages that, carries out Effective Regulation to the micro phase separation structure in film by simple and easy physics complex technique, to significantly improve ion transmission efficiency.2) high intensity of the toughness of polystyrene thermoplastic elastomer and polystyrene is wanted to combine, the good mechanical property of composite membrane and dimensional stability can be assigned.
Description
Technical field
The present invention relates to a kind of polystyrene thermoplastic elastomer/polystyrene composite membrane and preparation methods, belong to quaternary ammonium salt
Type anion-exchange membrane alkaline fuel cell field.
Background technique
As a kind of efficient, clean energy conversion device, anion-exchange membrane fuel cells have electrode reaction efficiency
It is high, use the plurality of advantages such as non-precious metal catalyst, fuel permeability be low.As its critical component, anion-exchange membrane is both
The separator of yin-yang the two poles of the earth fuel and oxidant, and be OH-Conductor, performance directly decides anion-exchange membrane fuel
The superiority and inferiority of battery.
In recent years, polystyrene thermoplastic elastomer is used for anion exchange by unique structure and performance advantage
Film introduces quaternary ammonium salt cationic by styrene block (PS) functional modification, obtains the microfacies point for being conducive to ion transmission
From structure, there is good flexibility, machinery and chemical stability under basic conditions, especially eliminated by hydrogenation
The polystyrene thermoplastic elastic of unsaturated double-bond has better stability, and such as s-B-S three block is total
Hydride (SEBS) and the hydride (SEPS) of styrene-isoprene-styrene triblock copolymer of polymers etc..People are logical
Often by guiding to quaternary ammonium salt cationic on PS phenyl ring, corresponding polystyrene thermoplastic elastomer base anion-exchange membrane is prepared.
Since the initial design object of polystyrene thermoplastic elastomer is not used to prepare anion-exchange membrane, presently commercially available material exists
It is difficult to give full play to the due efficiency of polystyrene thermoplastic elastomer in terms of mechanical stability and ion transmission performance.With styrene
It is thermoplastic elastomer difference, the whole strand of polystyrene all has phenyl ring, fits through above-mentioned functionalization process and obtains continuously
Ion transmission channel, be theoretically particularly suited for preparing anion-exchange membrane, still, polystyrene lacking toughness, correspond to
Thin-film material it is easily broken, it is damaged that swelling is easy to happen after functionalization.
In order to improve the mechanical stability and ion transmission performance of anion-exchange membrane, the present invention is directed to compound by physics
Technology together by the blend of predominance of both polystyrene thermoplastic elastomer and polystyrene prepares a kind of high-performance styrene
Thermoplastic elastomer/polystyrene composite membrane.
Summary of the invention
For deficiency existing for existing polystyrene thermoplastic elastomer and polystyrene, the present invention provides a kind of polystyrene
Thermoplastic elastomer/polystyrene composite membrane and preparation method.
Technical scheme is as follows:
A kind of polystyrene thermoplastic elastomer/polystyrene composite membrane, main chain is by polystyrene thermoplastic elastomer and gathers
Styrene is constituted, and when polystyrene molecular weight is lower, main function is the microfacies knot for adjusting polystyrene thermoplastic elastomer
Structure；When polystyrene molecular weight is higher, it is mainly used as ion transmission channel, and polystyrene thermoplastic elastomer is then to it
Carry out toughening.Using SEBS and PS as raw material, its chemical structural formula of the composite membrane of synthesis are as follows:
Wherein, SEBS could alternatively be SBS, SIS, SEPS or derivatives thereof.
A kind of preparation method of the polystyrene thermoplastic elastomer/polystyrene composite membrane, it is characterised in that step is such as
Under:
Step 1: in organic solvent by the dissolution of polystyrene thermoplastic elastomer, after mixing evenly to it, successively thereto
The catalyst of 0.8~2 times of styrene units mole and the functional modification reagent of 2~6 times of catalyst moles is added,
And poured into dilute hydrochloric acid after being stirred 24 hours at 15~25 DEG C, to remove catalyst.Then the emulsion of lower layer is poured into greatly
Crude product is obtained in amount ethyl alcohol, uses ethanol precipitation to get functionalization polystyrene thermoplastic elastic again after dissolving crude product with solvent
Body, and be dried in vacuo 12 hours in 35 DEG C.
Step 2: in organic solvent by polystyrene dissolution, after mixing evenly to it, 0.4~1 is successively added thereto
Times catalyst of styrene units mole and the functional modification reagent of 2~6 times of catalyst moles, and in 15~25
It is poured into dilute hydrochloric acid after being stirred 24 hours at DEG C, to remove catalyst.Then the emulsion of lower layer is poured into a large amount of ethyl alcohol and is obtained
Crude product is obtained, uses ethanol precipitation to get functional polystyrene again after dissolving crude product with solvent, and be dried in vacuo 12 in 35 DEG C
Hour.
Step 3: functionalization polystyrene thermoplastic elastomer and functional polystyrene is molten with mass ratio 10:0~1:9
Cross-linking reagent and at room temperature casting film are added under fast stirring, is set after standing 24 hours in organic solvent for solution
In 60 DEG C of vacuum drying ovens 12 hours to remove remaining solvent.
Step 4: at room temperature, above-mentioned composite membrane is impregnated into ammonium reagent and alkalizing agent 48 hours respectively to get styrene
It is thermoplastic elastomer/polystyrene composite membrane.
The polystyrene thermoplastic elastomer that the present invention selects is SBS, SIS, SEBS, SEPS or derivatives thereof；The polyphenyl
Ethylene molecule amount is 2000~300000；It is described Step 1: in step 2 organic solvent be tetrahydrofuran, chloroform, methylene chloride,
Chlorobenzene, dichloro-benzenes or carbon tetrachloride, organic solvent is tetrahydrofuran, chloroform, methylene chloride, toluene, dimethylbenzene, four in step 3
Chlorination carbon or N,N-dimethylformamide；The catalyst is anhydrous stannic chloride, anhydrous zinc chloride or anhydrous titanium tetrachloride；Institute
Stating functional modification reagent is chloromethyl methyl ether (CME), chloromethyl ether (CEE) or Isosorbide-5-Nitrae-dichloro methyl butyl ether (BCMB)；
The cross-linking reagent is 4-methyl hexamethylene diamine (TMHDA), 4-methyl-diaminopropane (TMPDA) or tetramethylethylenediamine (TMEDA)；Institute
Stating ammonium reagent is trimethylamine or triethylamine；The alkalizing agent is NaOH or KOH.
Effect and benefit of the invention: 1) by simple and easy physics complex technique to the micro phase separation structure in film into
Row Effective Regulation, to significantly improve ion transmission efficiency.2) by the toughness of polystyrene thermoplastic elastomer and polystyrene
High intensity is wanted to combine, and can assign the good mechanical property of composite membrane and dimensional stability.
Detailed description of the invention
Fig. 1 is the anion-exchange membrane of chloromethylation SEBS and chloromethylation PS composite membrane (A) and preparation in embodiment 2
(B) infrared spectrum.
Fig. 2 is anion-exchange membrane 2M NaOH solution intermediate ion conductivity and soaking time at 60 DEG C in embodiment 9
Relation curve.
Specific embodiment
It is right with reference to embodiments in order to show the purpose of the present invention, technical solution and advantage more clearly from
The present invention is further described.Following embodiment is merely illustrative, and is not limited the scope of the invention in any way.
Embodiment 1:
2g SEBS (6mmol styrene units) is added in the three-necked flask equipped with magnetic stir bar, and by 30mL tetra-
Chlorination carbon is added thereto.After it is dissolved at 35 DEG C, 0.56mL (4.8mmol) anhydrous stannic chloride is added under ice-water bath
It is stirred 30 minutes into above-mentioned solution.1.8g (9.6mmol) BCMB is added dropwise in the solution later, and is reacted at 18 DEG C
24 hours.After reaction, reaction solution is poured into dilute hydrochloric acid solution to remove catalyst, is then poured into ethyl alcohol and obtains
Crude product is dissolved in after tetrahydrofuran again with ethanol precipitation, and with second alcohol and water rinse up in solution without chloride ion after
It is dried in vacuo 12 hours at 35 DEG C.
Weigh 0.5g chloromethylation SEBS, dissolved at room temperature with 10ml chloroform, it is to be dissolved completely after under ice-water bath plus
Enter 0.079mL TMHDA and be vigorously stirred and cast on polyfluortetraethylene plate after five minutes, stands 24 hours at room temperature；
After film taken off be put into 60 DEG C of vacuum drying ovens dry 12 hours to remove residual solvent.The film of preparation is put respectively later
Enter in 30wt% trimethylamine solution and 1M NaOH solution each 48 hours to get polystyrene thermoplastic elastomer group compound film.
The ion exchange capacity of the composite membrane be 0.89mmol/g, water absorption rate 6.80%, swellbility 1.52%, 30 DEG C
Lower ionic conductivity is 9.05mS/cm.
Embodiment 2:
2g SEBS (6mmol styrene units) is added in the three-necked flask equipped with magnetic stir bar, and by 30mL tetra-
Chlorination carbon is added thereto.After it is dissolved at 35 DEG C, 0.70mL (6mmol) anhydrous stannic chloride is added under ice-water bath
It is stirred 30 minutes in above-mentioned solution.3.4g (18mmol) BCMB is added dropwise in the solution later, and reacts 24 at 18 DEG C
Hour.After reaction, reaction solution is poured into remove catalyst in dilute hydrochloric acid solution, is then poured into ethyl alcohol and obtains slightly
Product is dissolved in after toluene again with ethanol precipitation, and with second alcohol and water rinse up in solution without after chloride ion in 35 DEG C
Lower vacuum drying 12 hours.
By 2gPS (Mn=11000) (20mmol styrene units) are added in the three-necked flask equipped with magnetic stir bar,
And 60mL carbon tetrachloride is added thereto.After it is dissolved at 35 DEG C, by 0.94mL (8mmol) anhydrous stannic chloride in ice water
It is added in above-mentioned solution and stirs 30 minutes under bath.4.5g (24mmol) BCMB is added dropwise in the solution later, and 18
It is reacted 24 hours at DEG C.After reaction, reaction solution is poured into dilute hydrochloric acid solution to remove catalyst, is then poured into second
Obtain crude product in alcohol, be dissolved in after toluene again with ethanol precipitation, and with second alcohol and water rinse up in solution without chlorine from
It is dried in vacuo 12 hours at 35 DEG C after son.
0.45g chloromethylation SEBS and 0.05g chloromethylation PS is weighed, is dissolved at room temperature with 10ml tetrahydrofuran, to
0.091mL TMHDA is added after dissolution completely under ice-water bath and is vigorously stirred and is cast in polyfluortetraethylene plate after five minutes
On, it reacts 24 hours at room temperature；After film is taken off be put into 60 DEG C of vacuum drying ovens dry to remove residual solvent.Later
The film of preparation is respectively put into 30wt% trimethylamine solution and 1M NaOH solution each 48 hours to get polystyrene thermoplastic bullet
Property body group compound film.
Fig. 1 is IR Characterization result.Wherein A represents chloromethylation SEBS and chloromethylation PS composite membrane；B represents final institute
The anion-exchange membrane obtained.From the figure we can see that 1265cm in A-1Place is-CH2The stretching vibration absworption peak of Cl, but this
One characteristic peak completely disappears in B, and in 3360cm-1And 1640cm-1Occur new corresponding respectively to the flexible of O-H and C-N
Vibration absorption peak.These results show the successful preparation of anion-exchange membrane.
The ion exchange capacity of the composite membrane be 1.35mmol/g, water absorption rate 7.09%, swellbility 2.27%, 30 DEG C
Lower ionic conductivity is 11.66mS/cm.
Embodiment 3:
2g SEBS (6mmol styrene units) is added in the three-necked flask equipped with magnetic stir bar, and by 30mL tetra-
Chlorination carbon is added thereto.After it is dissolved at 35 DEG C, 0.84mL (7.2mmol) anhydrous stannic chloride is added under ice-water bath
It is stirred 30 minutes into above-mentioned solution.5.4g (28.8mmol) BCMB is added dropwise in the solution later, and anti-at 18 DEG C
It answers 24 hours.After reaction, reaction solution is poured into dilute hydrochloric acid solution to remove catalyst, is then poured into ethyl alcohol and obtains
Crude product, be dissolved in after dimethylbenzene again with ethanol precipitation, and with second alcohol and water rinse up in solution without chloride ion after
It is dried in vacuo 12 hours at 35 DEG C.
By 2gPS (Mn=8000) (20mmol styrene units) are added in the three-necked flask equipped with magnetic stir bar, and
60mL carbon tetrachloride is added thereto.After it is dissolved at 35 DEG C, by 1.40mL (12mmol) anhydrous stannic chloride in ice water
It is added in above-mentioned solution and stirs 30 minutes under bath.9.0g (48mmol) BCMB is added dropwise in the solution later, and 18
It is reacted 24 hours at DEG C.After reaction, reaction solution is poured into dilute hydrochloric acid solution to remove catalyst, is then poured into second
Crude product is obtained in alcohol, is dissolved in after dimethylbenzene using ethanol precipitation again, and rinsed with second alcohol and water until without chlorine in solution
It is dried in vacuo 12 hours at 35 DEG C after ion.
0.4g chloromethylation SEBS and 0.1g chloromethylation PS is weighed, is dissolved at room temperature with 10ml chloroform, it is to be dissolved complete
0.103mL TMHDA is added after complete under ice-water bath and is vigorously stirred and is cast on polyfluortetraethylene plate after five minutes, in room
Temperature lower reaction 24 hours；After film is taken off be put into 60 DEG C of vacuum drying ovens dry to remove residual solvent.It later will preparation
Film be respectively put into 30wt% trimethylamine solution and 1MNaOH solution each 48 hours it is multiple to get polystyrene thermoplastic elastomer base
Close film.The ion exchange capacity of the composite membrane is 1.48mmol/g, water absorption rate 10.03%, swellbility 2.78%, at 30 DEG C
Ionic conductivity is 14.83mS/cm.
Embodiment 4:
2g SEBS (6mmol styrene units) is added in the three-necked flask equipped with magnetic stir bar, and by 30mL tetra-
Chlorination carbon is added thereto.After it is dissolved at 35 DEG C, 0.84mL (7.2mmol) anhydrous stannic chloride is added under ice-water bath
It is stirred 30 minutes into above-mentioned solution.4.04g (21.6mmol) BCMB is added dropwise in the solution later, and anti-at 18 DEG C
It answers 24 hours.After reaction, reaction solution is poured into dilute hydrochloric acid solution to remove catalyst, is then poured into ethyl alcohol and obtains
Crude product is obtained, is dissolved in after tetrahydrofuran using ethanol precipitation again, and rinsed with second alcohol and water until without chloride ion in solution
It is dried in vacuo 12 hours at 35 DEG C afterwards.
By 2g PS (Mn=5000) (20mmol styrene units) are added in the three-necked flask equipped with magnetic stir bar,
And 60mL carbon tetrachloride is added thereto.After it is dissolved at 35 DEG C, by 1.87mL (16mmol) anhydrous stannic chloride in ice
It is added in above-mentioned solution and stirs 30 minutes under water-bath.9.0g (48mmol) BCMB is added dropwise in the solution later, and
It is reacted 24 hours at 18 DEG C.After reaction, reaction solution is poured into dilute hydrochloric acid solution to remove catalyst, is then poured into
Crude product is obtained in ethyl alcohol, is dissolved in after tetrahydrofuran using ethanol precipitation again, and rinsed with second alcohol and water until in solution
It is dried in vacuo 12 hours at 35 DEG C after no chloride ion.
0.35g chloromethylation SEBS and 0.15g chloromethylation PS is weighed, is dissolved at room temperature with 10ml chloroform, it is to be dissolved
0.115mL TMHDA is added after completely under ice-water bath and is vigorously stirred and is cast on polyfluortetraethylene plate after five minutes,
It reacts 24 hours at room temperature；After film is taken off be put into 60 DEG C of vacuum drying ovens dry to remove residual solvent.It later will system
Standby film is respectively put into 30wt% trimethylamine solution and 1MNaOH solution each 48 hours to get polystyrene thermoplastic elastomer base
The ion exchange capacity of the composite membrane composite membrane be 1.73mmol/g, water absorption rate 13.49%, swellbility 3.86%, 30 DEG C
Lower ionic conductivity is 17.35mS/cm.
Embodiment 5:
2g SEBS (6mmol styrene units) is added in the three-necked flask equipped with magnetic stir bar, and by 30mL tetra-
Chlorination carbon is added thereto.After it is dissolved at 35 DEG C, 1.12mL (9.6mmol) anhydrous stannic chloride is added under ice-water bath
It is stirred 30 minutes into above-mentioned solution.9.0g (48mmol) BCMB is added dropwise in the solution later, and is reacted at 18 DEG C
24 hours.After reaction, reaction solution is poured into dilute hydrochloric acid solution to remove catalyst, is then poured into ethyl alcohol and obtains
Crude product is dissolved in after toluene again with ethanol precipitation, and with second alcohol and water rinse up in solution without after chloride ion in 35
It is dried in vacuo 12 hours at DEG C.
By 2g PS (Mn=2000) (20mmol styrene units) are added in the three-necked flask equipped with magnetic stir bar,
And 60mL carbon tetrachloride is added thereto.After it is dissolved at 35 DEG C, 1.40mL (12mmol) anhydrous stannic chloride is in ice water
It is added in above-mentioned solution and stirs 30 minutes under bath.11.22g (60mmol) BCMB is added dropwise in the solution later, and
It is reacted 24 hours at 18 DEG C.After reaction, reaction solution is poured into dilute hydrochloric acid solution to remove catalyst, is then poured into
Crude product is obtained in ethyl alcohol, is dissolved in after toluene using ethanol precipitation again, and rinsed with second alcohol and water until without chlorine in solution
It is dried in vacuo 12 hours at 35 DEG C after ion.
0.3g chloromethylation SEBS and 0.2g chloromethylation PS is weighed, is dissolved at room temperature with 10ml carbon tetrachloride, to molten
0.127mL TMHDA is added after solution is complete under ice-water bath and is vigorously stirred and is cast on polyfluortetraethylene plate after five minutes,
It reacts 24 hours at room temperature；After film is taken off be put into 60 DEG C of vacuum drying ovens dry to remove residual solvent.Later will
The film of preparation is respectively put into 30wt% trimethylamine solution and 1M NaOH solution each 48 hours to get polystyrene thermoplastic elastic
Body group compound film.The ion exchange capacity of the composite membrane be 1.78mmol/g, water absorption rate 18.82%, swellbility 4.37%,
Ionic conductivity is 22.45mS/cm at 30 DEG C.
Embodiment 6:
2g SEPS (6mmol styrene units) is added in the three-necked flask equipped with magnetic stir bar, and by 35mL chlorine
It is imitative to be added thereto.After it is dissolved at 35 DEG C, 0.51mL (10.8mmol) anhydrous zinc chloride is added under ice-water bath
It states in solution and stirs 30 minutes.5.22g (64.8mmol) CME is added dropwise in the solution later, and reacts 24 at 15 DEG C
Hour.After reaction, reaction solution is poured into remove catalyst in dilute hydrochloric acid solution, is then poured into ethyl alcohol and obtains slightly
Product is dissolved in after tetrahydrofuran again with ethanol precipitation, and with second alcohol and water rinse up in solution without after chloride ion in
It is dried in vacuo 12 hours at 35 DEG C.
By 2g PS (Mn=300000) (20mmol styrene units) are added to the three-necked flask equipped with magnetic stir bar
In, and 65mL chloroform is added thereto.After it is dissolved at 35 DEG C, by 0.75mL (16mmol) anhydrous zinc chloride in ice-water bath
Under be added in above-mentioned solution and stir 30 minutes.7.73g (96mmol) CME is added dropwise in the solution later, and at 15 DEG C
Lower reaction 24 hours.After reaction, reaction solution is poured into dilute hydrochloric acid solution to remove catalyst, is then poured into ethyl alcohol
Middle acquisition crude product is dissolved in after tetrahydrofuran using ethanol precipitation again, and is rinsed with second alcohol and water until without chlorine in solution
It is dried in vacuo 12 hours at 35 DEG C after ion.
0.15g chloromethylation SEPS and 0.35g chloromethylation PS is weighed, is dissolved at room temperature with 10ml toluene, it is to be dissolved
0.127mL TMEDA is added after completely under ice-water bath and is vigorously stirred and is cast on polyfluortetraethylene plate after five minutes,
It reacts 24 hours at room temperature；After film is taken off be put into 60 DEG C of vacuum drying ovens dry to remove residual solvent.It later will system
Standby film is respectively put into 30wt% triethylamine solution and 1MKOH solution each 48 hours to get polystyrene thermoplastic elastomer base
Composite membrane.The ion exchange capacity of the composite membrane be 1.84mmol/g, water absorption rate 24.86%, swellbility 5.88%, 30 DEG C
Lower ionic conductivity is 18.56mS/cm.
Embodiment 7:
2g SBS (4mmol styrene units) is added in the three-necked flask equipped with magnetic stir bar, and by 25mL bis-
Chloromethanes is added thereto.After it is dissolved at 35 DEG C, 0.70mL (6.4mmol) anhydrous titanium tetrachloride is added under ice-water bath
It is stirred 30 minutes into above-mentioned solution.1.2g (12.8mmol) CEE is added dropwise in the solution later, and is reacted at 25 DEG C
24 hours.After reaction, reaction solution is poured into dilute hydrochloric acid solution to remove catalyst, is then poured into ethyl alcohol and obtains
Crude product is dissolved in after n,N-Dimethylformamide using ethanol precipitation again, and is rinsed with second alcohol and water up to nothing in solution
It is dried in vacuo 12 hours at 35 DEG C after chloride ion.
By 2gPS (Mn=200000) (20mmol styrene units) are added in the three-necked flask equipped with magnetic stir bar,
And 50mL methylene chloride is added thereto.After it is dissolved at 35 DEG C, by 2.20mL (20mmol) anhydrous titanium tetrachloride in ice
It is added in above-mentioned solution and stirs 30 minutes under water-bath.3.78g (40mmol) CEE is added dropwise in the solution later, and
It is reacted 24 hours at 25 DEG C.After reaction, reaction solution is poured into dilute hydrochloric acid solution to remove catalyst, is then poured into
Crude product is obtained in ethyl alcohol, is dissolved in after n,N-Dimethylformamide using ethanol precipitation again, and rinsed directly with second alcohol and water
Into solution without being dried in vacuo 12 hours at 35 DEG C after chloride ion.
0.1g chloromethyl SBS and 0.4g chloromethylation PS are weighed, with 10mlN, dinethylformamide is molten at room temperature
Solution, it is to be dissolved completely after 0.115mL TMPDA is added under ice-water bath and is vigorously stirred and is cast in polytetrafluoroethyl-ne after five minutes
On alkene plate, react 24 hours at room temperature；After film is taken off be put into 60 DEG C of vacuum drying ovens dry to remove residual solvent.
The film of preparation is respectively put into 30wt% triethylamine solution and 1M KOH solution each 48 hours to get polystyrene thermoplastic later
Elastomer group compound film.The ion exchange capacity of the composite membrane is 0.82mmol/g, and water absorption rate 30.98%, swellbility is
10.97%, ionic conductivity is 8.02mS/cm at 30 DEG C.
Embodiment 8:
2g SIS (7.7mmol styrene units) is added in the three-necked flask equipped with magnetic stir bar, and by 40mL
Carbon tetrachloride is added thereto.After it is dissolved at 35 DEG C, by 1.80mL (15.4mmol) anhydrous stannic chloride under ice-water bath
It is added in above-mentioned solution and stirs 30 minutes.5.82g (61.6mmol) CEE is added dropwise in the solution later, and at 20 DEG C
Lower reaction 24 hours.After reaction, reaction solution is poured into dilute hydrochloric acid solution to remove catalyst, is then poured into ethyl alcohol
Middle acquisition crude product is dissolved in after chloroform using ethanol precipitation again, and is rinsed with second alcohol and water until without chloride ion in solution
It is dried in vacuo 12 hours at 35 DEG C afterwards.
By 2gPS (Mn=100000) (20mmol styrene units) are added in the three-necked flask equipped with magnetic stir bar,
And 70mL carbon tetrachloride is added thereto.After it is dissolved at 35 DEG C, by 2.34mL (20mmol) anhydrous stannic chloride in ice
It is added in above-mentioned solution and stirs 30 minutes under water-bath.7.56g (80mmol) CEE is added dropwise in the solution later, and
It is reacted 24 hours at 20 DEG C.After reaction, reaction solution is poured into dilute hydrochloric acid solution to remove catalyst, is then poured into
Crude product is obtained in ethyl alcohol, is dissolved in after chloroform using ethanol precipitation again, and rinsed with second alcohol and water until without chlorine in solution
It is dried in vacuo 12 hours at 35 DEG C after ion.
0.05g chloromethylation SIS and 0.45g chloromethylation PS is weighed, is dissolved at room temperature with 10ml tetrahydrofuran, to molten
0.103mL TMHDA is added after solution is complete under ice-water bath and is vigorously stirred and is cast on polyfluortetraethylene plate after five minutes,
It reacts 24 hours at room temperature；After film is taken off be put into 60 DEG C of vacuum drying ovens dry to remove residual solvent.Later will
The film of preparation is respectively put into 30wt% triethylamine solution and 1M KOH solution each 48 hours to get polystyrene thermoplastic elastomer
Group compound film.The ion exchange capacity of the composite membrane be 1.27mmol/g, water absorption rate 29.86%, swellbility 9.34%, 30
Ionic conductivity is 10.33mS/cm at DEG C.
Embodiment 9:
The anion-exchange membrane prepared in Example 5 carries out alkali resistance test as sample.It, will under the conditions of 60 DEG C
The membrane sample is immersed in the 2M NaOH solution full of inert gas, is drawn off afterwards at regular intervals, anti-with deionized water
Multiple flushing tests its ionic conductivity at 60 DEG C after removing lye remained on surface.Test results are shown in figure 2, the film sample
Only there is slight reduction in product ionic conductivity after alkali resistance is tested, this shows polystyrene thermoplastic prepared by the present invention
Elastomer group compound film has good chemical stability.
Claims (10)
1. a kind of polystyrene thermoplastic elastomer/polystyrene composite membrane, which is characterized in that the polystyrene thermoplastic elastic
Body/polystyrene composite membrane main chain is made of polystyrene thermoplastic elastomer and polystyrene；Using SEBS and PS as raw material, close
At composite membrane its chemical structural formula are as follows:
Wherein, SEBS could alternatively be SBS, SIS, SEPS or derivatives thereof.
2. a kind of preparation method of polystyrene thermoplastic elastomer/polystyrene composite membrane described in claim 1, feature exist
In steps are as follows:
Step 1: the polystyrene thermoplastic elastomer of functionalization is prepared
In organic solvent by the dissolution of polystyrene thermoplastic elastomer, after mixing evenly to it, 0.8~2 is successively added thereto
Times catalyst of styrene units mole and the functional modification reagent of 2~6 times of catalyst moles, and in 15~25
It is poured into dilute hydrochloric acid after being stirred 24 hours at DEG C, removes catalyst；The emulsion of lower layer is poured into and obtains crude product in ethyl alcohol, is used
Solvent uses ethanol precipitation after dissolving crude product again, obtains the polystyrene thermoplastic elastomer of functionalization after vacuum drying treatment；
Step 2: the polystyrene of functionalization is prepared
In organic solvent by polystyrene dissolution, after mixing evenly to it, 0.4~1 times of styrene is successively added thereto
The functional modification reagent of the catalyst of unit mole and 2~6 times of catalyst moles, and 24 are stirred at 15~25 DEG C
It is poured into dilute hydrochloric acid after hour, to remove catalyst；Then the emulsion of lower layer is poured into a large amount of ethyl alcohol and obtains crude product, used
Solvent uses ethanol precipitation after dissolving crude product again, obtains functional polystyrene after vacuum drying treatment；
Step 3: the functionalized polystyrene that the polystyrene thermoplastic elastomer for the functionalization that step 1 obtains and step 2 are obtained
Alkene is dissolved in organic solvent with mass ratio 10:0~1:9, and cross-linking reagent is added under fast stirring and is cast at room temperature
Film places it in vacuum drying oven after standing 24 hours and removes remaining solvent；
Step 4: at room temperature, above-mentioned composite membrane is impregnated into ammonium reagent and alkalizing agent 48 hours respectively, obtains obtaining polystyrene
Thermoplastic elastomer/polystyrene composite membrane.
3. preparation method according to claim 2, which is characterized in that polystyrene thermoplastic elastomer described in step 1 is
SBS, SIS, SEBS, SEPS or derivatives thereof.
4. preparation method according to claim 3, which is characterized in that polystyrene molecular weight described in step 2 is 2000
~300000.
5. the preparation method according to claim 4, which is characterized in that catalyst described in step 1 is anhydrous four chlorination
Tin, anhydrous zinc chloride or anhydrous titanium tetrachloride, catalyst described in step 2 are anhydrous stannic chloride, anhydrous zinc chloride or anhydrous
Titanium tetrachloride.
6. preparation method according to claim 5, which is characterized in that functional modification reagent described in step 1 is chloromethane
Base methyl ether, chloromethyl ether or Isosorbide-5-Nitrae-dichloro methyl butyl ether, functional modification reagent described in step 2 are chloromethyl methyl ether,
Chloromethyl ether or 1,4- dichloro methyl butyl ether.
7. preparation method according to claim 6, which is characterized in that cross-linking reagent described in step 3 be tetramethyl oneself two
Amine, 4-methyl-diaminopropane or tetramethylethylenediamine.
8. preparation method according to claim 6, which is characterized in that ammonium reagent described in step 3 is trimethylamine or three
Ethamine, the alkalizing agent are NaOH or KOH.
9. preparation method according to claim 8, which is characterized in that in the step one and step 2 at vacuum drying
Managing temperature is 35 DEG C, and the time is 12 hours；Vacuum drying oven temperature in the step three is 60 DEG C, and standing time is 12 small
When.
10. preparation method according to claim 9, which is characterized in that Step 1: organic solvent described in step 2 is
Tetrahydrofuran, chloroform, methylene chloride, chlorobenzene, dichloro-benzenes or carbon tetrachloride；Organic solvent described in step 3 be tetrahydrofuran,
Chloroform, methylene chloride, toluene, dimethylbenzene, carbon tetrachloride or N,N-dimethylformamide.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054792A (en) * | 2019-05-15 | 2019-07-26 | 常州大学 | A kind of anion-exchange membrane and preparation method thereof based on SBS |
| CN110408040A (en) * | 2019-07-17 | 2019-11-05 | 大连理工大学 | A kind of functionalization polystyrene thermoplastic elastomer is epoxy resin toughened and preparation method thereof |
| CN112760991A (en) * | 2021-01-25 | 2021-05-07 | 福州大学 | Method for preparing anion exchange membrane in green manner |
| WO2021204890A1 (en) * | 2020-04-07 | 2021-10-14 | Enapter S.r.l. | Ion exchange membrane and method of manufacturing an ion exchange membrane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101896540B (en) * | 2007-12-11 | 2012-11-28 | 伯斯有限公司 | Fuel cell polymer electrolyte membrane |
| CN105642136A (en) * | 2014-11-18 | 2016-06-08 | 北京化工大学 | A copolymer quaternization crosslinking type anion-exchange membrane containing soft and hard segments and a preparing method thereof |
| CN108084302A (en) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | A kind of preparation method of alkalescence anion-exchange resin |
-
2018
- 2018-09-06 CN CN201811036178.6A patent/CN109265715B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101896540B (en) * | 2007-12-11 | 2012-11-28 | 伯斯有限公司 | Fuel cell polymer electrolyte membrane |
| CN105642136A (en) * | 2014-11-18 | 2016-06-08 | 北京化工大学 | A copolymer quaternization crosslinking type anion-exchange membrane containing soft and hard segments and a preparing method thereof |
| CN108084302A (en) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | A kind of preparation method of alkalescence anion-exchange resin |
Non-Patent Citations (2)
| Title |
|---|
| BANERJEE, RITIMA ET AL: ""Microstructure Development and Its Influence on the Properties of Styrene-Ethylene-Butylene-Styrene/Polystyrene Blends"", 《POLYMERS》 * |
| ZHOU, JIE ET AL: ""Impacts of anion-exchange-membranes with various ionic exchange capacities on the performance of H2/O2 fuel cells"", 《JOURNAL OF POWER SOURCES》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054792A (en) * | 2019-05-15 | 2019-07-26 | 常州大学 | A kind of anion-exchange membrane and preparation method thereof based on SBS |
| CN110054792B (en) * | 2019-05-15 | 2021-11-02 | 常州大学 | SBS-based anion exchange membrane and preparation method thereof |
| CN110408040A (en) * | 2019-07-17 | 2019-11-05 | 大连理工大学 | A kind of functionalization polystyrene thermoplastic elastomer is epoxy resin toughened and preparation method thereof |
| WO2021204890A1 (en) * | 2020-04-07 | 2021-10-14 | Enapter S.r.l. | Ion exchange membrane and method of manufacturing an ion exchange membrane |
| JP2023521327A (en) * | 2020-04-07 | 2023-05-24 | エナプター エス．アール．エル． | Ion-exchange membrane and method for producing ion-exchange membrane |
| CN112760991A (en) * | 2021-01-25 | 2021-05-07 | 福州大学 | Method for preparing anion exchange membrane in green manner |
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