CN109265715B - Styrene thermoplastic elastomer/polystyrene composite film and preparation method thereof - Google Patents
Styrene thermoplastic elastomer/polystyrene composite film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a styrene thermoplastic elastomer/polystyrene composite film and a preparation method thereof. The membrane material takes styrene thermoplastic elastomer and polystyrene as a matrix, the styrene thermoplastic elastomer and the polystyrene are functionalized and then mixed with solutions in different proportions, a cross-linking agent is added to prepare a membrane, and a series of anion exchange membranes are prepared by quaternization and alkalization under a heterogeneous state. The prepared styrene thermoplastic elastomer/polystyrene composite film has the following advantages: 1) the microphase separation structure in the membrane is effectively regulated and controlled by a simple and easy physical composite technology, so that the ion transmission efficiency is obviously improved. 2) The toughness of the styrene thermoplastic elastomer and the high strength of the polystyrene are combined, so that the composite film has good mechanical property and dimensional stability.
Description
Technical Field
The invention relates to a styrene thermoplastic elastomer/polystyrene composite membrane and a preparation method thereof, belonging to the field of quaternary ammonium salt type anion exchange membrane alkaline fuel cells.
Background
As an efficient and clean energy conversion device, the anion exchange membrane fuel cell has the advantages of high electrode reaction efficiency, use of a non-noble metal catalyst, low fuel permeability and the like. As a key part, the anion exchange membrane is not only a separator of anode and cathode fuel and oxidant, but also OH-The performance of the conductor directly determines the quality of the anion exchange membrane fuel cell.
In recent years, styrene thermoplastic elastomers are used for anion exchange membranes by virtue of unique structural and performance advantages, quaternary ammonium salt cations are introduced through styrene block (PS) functional modification, a microphase separation structure beneficial to ion transmission is obtained, the styrene thermoplastic elastomers have good flexibility, mechanical and chemical stability under a strong alkaline condition, and particularly, styrene thermoplastic elastomers with unsaturated double bonds eliminated through hydrogenation reaction have better stability, such as hydrides of styrene-butadiene-styrene triblock copolymers (SEBS), hydrides of styrene-isoprene-styrene triblock copolymers (SEPS) and the like. One typically prepares the corresponding styrenic thermoplastic elastomer based anion exchange membranes by introducing quaternary ammonium cations onto the PS benzene rings. Since the original design goal of the styrene-based thermoplastic elastomer is not to prepare an anion exchange membrane, it is difficult for the current commercial materials to fully exert the required performance of the styrene-based thermoplastic elastomer in terms of mechanical stability and ion transmission performance. Different from styrene thermoplastic elastomers, polystyrene has benzene rings in the whole molecular chain, is suitable for obtaining a continuous ion transmission channel through the functionalization process, and is theoretically more suitable for preparing an anion exchange membrane, but polystyrene lacks toughness, a corresponding film material is easy to break, and swelling and damage are easy to occur after functionalization.
In order to improve the mechanical stability and ion transmission performance of an anion exchange membrane, the invention aims to prepare a high-performance styrene thermoplastic elastomer/polystyrene composite membrane by combining the advantages of a styrene thermoplastic elastomer and polystyrene through a physical composite technology.
Disclosure of Invention
Aiming at the defects of the prior styrene thermoplastic elastomer and polystyrene, the invention provides a styrene thermoplastic elastomer/polystyrene composite film and a preparation method thereof.
The technical scheme of the invention is as follows:
a styrene thermoplastic elastomer/polystyrene composite membrane, its main chain is formed by styrene thermoplastic elastomer and polystyrene, when the polystyrene molecular weight is lower, its main function is to adjust the microphase structure of the styrene thermoplastic elastomer; when the molecular weight of the polystyrene is higher, the polystyrene is mainly used as an ion transmission channel, and the styrene thermoplastic elastomer is used for toughening the polystyrene. SEBS and PS are used as raw materials, and the synthesized composite membrane has a chemical structural formula as follows:
wherein, SEBS can be replaced by SBS, SIS, SEPS or derivatives thereof.
A preparation method of the styrene thermoplastic elastomer/polystyrene composite film is characterized by comprising the following steps:
the method comprises the following steps: dissolving a styrene thermoplastic elastomer in an organic solvent, after uniformly stirring, sequentially adding a catalyst in an amount which is 0.8-2 times of the molar weight of a styrene unit and a functionalized modification reagent in an amount which is 2-6 times of the molar weight of the catalyst, stirring at 15-25 ℃ for 24 hours, and then pouring into dilute hydrochloric acid to remove the catalyst. Then pouring the emulsion at the lower layer into a large amount of ethanol to obtain a crude product, dissolving the crude product with a solvent, then precipitating with ethanol to obtain the functionalized styrene thermoplastic elastomer, and drying in vacuum at 35 ℃ for 12 hours.
Step two: dissolving polystyrene in an organic solvent, after uniformly stirring, sequentially adding a catalyst with the molar weight of 0.4-1 time of that of a styrene unit and a functional modification reagent with the molar weight of 2-6 times of that of the catalyst, stirring at 15-25 ℃ for 24 hours, and then pouring into dilute hydrochloric acid to remove the catalyst. And then pouring the emulsion at the lower layer into a large amount of ethanol to obtain a crude product, dissolving the crude product by using a solvent, then precipitating by using ethanol to obtain the functionalized polystyrene, and drying for 12 hours in vacuum at 35 ℃.
Step three: dissolving a functionalized styrene thermoplastic elastomer and functionalized polystyrene in an organic solvent according to a mass ratio of 10: 0-1: 9, adding a crosslinking reagent under rapid stirring, casting at room temperature to form a film, standing for 24 hours, and then placing in a vacuum oven at 60 ℃ for 12 hours to remove residual solvent.
Step four: and respectively soaking the composite membrane in an ammonium agent and an alkalization agent for 48 hours at room temperature to obtain the styrene thermoplastic elastomer/polystyrene composite membrane.
The styrene thermoplastic elastomer selected by the invention is SBS, SIS, SEBS, SEPS or derivatives thereof; the molecular weight of the polystyrene is 2000-300000; the organic solvent in the first step and the second step is tetrahydrofuran, chloroform, dichloromethane, chlorobenzene, dichlorobenzene or carbon tetrachloride, and the organic solvent in the third step is tetrahydrofuran, chloroform, dichloromethane, toluene, xylene, carbon tetrachloride or N, N-dimethylformamide; the catalyst is anhydrous tin tetrachloride, anhydrous zinc chloride or anhydrous titanium tetrachloride; the functional modification reagent is Chloromethyl Methyl Ether (CME), Chloromethyl Ethyl Ether (CEE) or 1, 4-dichloromethoxybutane (BCMB); the crosslinking reagent is Tetramethylhexamethylenediamine (TMHDA), Tetramethylpropylenediamine (TMPDA) or Tetramethylethylenediamine (TMEDA); the ammonification reagent is trimethylamine or triethylamine; the alkalizing agent is NaOH or KOH.
The invention has the advantages that: 1) the microphase separation structure in the membrane is effectively regulated and controlled by a simple and easy physical composite technology, so that the ion transmission efficiency is obviously improved. 2) The toughness of the styrene thermoplastic elastomer and the high strength of the polystyrene are combined, so that the composite film has good mechanical property and dimensional stability. .
Drawings
FIG. 1 is an infrared spectrum of chloromethylated SEBS and chloromethylated PS composite membrane (A) and prepared anion-exchange membrane (B) in example 2.
FIG. 2 is a graph showing the relationship between the ion conductivity and the soaking time of the anion exchange membrane in a 2M NaOH solution at 60 ℃ in example 9.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly appear, the present invention is further described in detail with reference to the following embodiments. The following examples are illustrative only and do not limit the scope of the invention in any way.
Example 1:
2g of SEBS (6mmol of styrene units) were introduced into a three-necked flask equipped with a magnetic stirrer, and 30mL of carbon tetrachloride were added thereto. After it was dissolved at 35 ℃, 0.56mL (4.8mmol) of anhydrous tin tetrachloride was added to the above solution under ice water bath and stirred for 30 minutes. Thereafter, 1.8g (9.6mmol) of BCMB was added dropwise to the solution and reacted at 18 ℃ for 24 hours. After the reaction was completed, the reaction solution was poured into a dilute hydrochloric acid solution to remove the catalyst, and then poured into ethanol to obtain a crude product, which was dissolved in tetrahydrofuran, precipitated again with ethanol, washed with ethanol and water until the solution was free of chloride ions, and then vacuum-dried at 35 ℃ for 12 hours.
Weighing 0.5g of chloromethylated SEBS, dissolving the SEBS with 10mL of chloroform at room temperature, adding 0.079mL of TMHDA in an ice water bath after complete dissolution, violently stirring for 5 minutes, casting the SEBS on a polytetrafluoroethylene plate, and standing for 24 hours at room temperature; after completion, the film was removed and dried in a vacuum oven at 60 ℃ for 12 hours to remove the residual solvent. Then the prepared membranes are respectively put into 30 wt% trimethylamine solution and 1M NaOH solution for 48 hours respectively, and the styrene thermoplastic elastomer based composite membrane is obtained.
The ion exchange capacity of the composite membrane is 0.89mmol/g, the water absorption rate is 6.80%, the swelling degree is 1.52%, and the ionic conductivity at 30 ℃ is 9.05 mS/cm.
Example 2:
2g of SEBS (6mmol of styrene units) were introduced into a three-necked flask equipped with a magnetic stirrer, and 30mL of carbon tetrachloride were added thereto. After it was dissolved at 35 ℃, 0.70mL (6mmol) of anhydrous tin tetrachloride was added to the above solution under ice water bath and stirred for 30 minutes. Thereafter, 3.4g (18mmol) of BCMB was added dropwise to the solution and reacted at 18 ℃ for 24 hours. After the reaction was completed, the reaction solution was poured into a dilute hydrochloric acid solution to remove the catalyst, and then it was poured into ethanol to obtain a crude product, which was dissolved in toluene, precipitated again with ethanol, washed with ethanol and water until the solution was free of chloride ions, and then vacuum-dried at 35 ℃ for 12 hours.
2gPS (M)n11000) (20mmol of styrene units) was charged into a three-necked flask equipped with a magnetic stirrer, and 60mL of carbon tetrachloride was added thereto. After it was dissolved at 35 ℃, 0.94mL (8mmol) of anhydrous tin tetrachloride was added to the above solution under ice water bath and stirred for 30 minutes. Thereafter, 4.5g (24mmol) of BCMB was added dropwise to the solution and reacted at 18 ℃ for 24 hours. After the reaction was completed, the reaction solution was poured into a dilute hydrochloric acid solution to remove the catalyst, and then it was poured into ethanol to obtain a crude product, which was dissolved in toluene, precipitated again with ethanol, washed with ethanol and water until the solution was free of chloride ions, and then vacuum-dried at 35 ℃ for 12 hours.
Weighing 0.45g of chloromethylated SEBS and 0.05g of chloromethylated PS, dissolving the SEBS and the PS in 10mL of tetrahydrofuran at room temperature, adding 0.091mL of TMHDA in ice-water bath after the SEBS and the PS are completely dissolved, violently stirring the mixture for 5 minutes, then casting the mixture on a polytetrafluoroethylene plate, and reacting the mixture for 24 hours at room temperature; after the completion of the process, the film was removed and dried in a vacuum oven at 60 ℃ to remove the residual solvent. Then the prepared membranes are respectively put into 30 wt% trimethylamine solution and 1M NaOH solution for 48 hours respectively, and the styrene thermoplastic elastomer based composite membrane is obtained.
FIG. 1 shows the results of infrared characterization. Wherein A represents a chloromethylated SEBS and a chloromethylated PS composite membrane; b represents the finally obtained anion-exchange membrane. As can be seen from the figure, 1265cm in A-1Is represented by-CH2A peak was absorbed by Cl in the stretching vibration, but this characteristic peak was completely disappeared in B and was 3360cm-1And 1640cm-1New stretching vibrations corresponding to O-H and C-N, respectively, appearedDynamic absorption peak. These results all indicate the successful preparation of anion exchange membranes.
The ion exchange capacity of the composite membrane is 1.35mmol/g, the water absorption is 7.09%, the swelling degree is 2.27%, and the ionic conductivity at 30 ℃ is 11.66 mS/cm.
Example 3:
2g of SEBS (6mmol of styrene units) were introduced into a three-necked flask equipped with a magnetic stirrer, and 30mL of carbon tetrachloride were added thereto. After it was dissolved at 35 ℃, 0.84mL (7.2mmol) of anhydrous tin tetrachloride was added to the above solution under ice water bath and stirred for 30 minutes. Thereafter, 5.4g (28.8mmol) of BCMB was added dropwise to the solution and reacted at 18 ℃ for 24 hours. After the reaction was completed, the reaction solution was poured into a dilute hydrochloric acid solution to remove the catalyst, and then poured into ethanol to obtain a crude product, which was dissolved in xylene, precipitated again with ethanol, washed with ethanol and water until the solution was free of chloride ions, and then vacuum-dried at 35 ℃ for 12 hours.
2gPS (M)n8000) (20mmol styrene units) was charged to a three-necked flask equipped with a magnetic stirrer, and 60mL of carbon tetrachloride was added thereto. After it was dissolved at 35 ℃, 1.40mL (12mmol) of anhydrous tin tetrachloride was added to the above solution under an ice water bath and stirred for 30 minutes. Thereafter, 9.0g (48mmol) of BCMB was added dropwise to the solution and reacted at 18 ℃ for 24 hours. After the reaction was completed, the reaction solution was poured into a dilute hydrochloric acid solution to remove the catalyst, and then poured into ethanol to obtain a crude product, which was dissolved in xylene, precipitated again with ethanol, washed with ethanol and water until the solution was free of chloride ions, and then vacuum-dried at 35 ℃ for 12 hours.
Weighing 0.4g of chloromethylated SEBS and 0.1g of chloromethylated PS, dissolving the SEBS and the PS at room temperature by using 10mL of chloroform, adding 0.103mL of TMHDA in ice-water bath after complete dissolution, violently stirring the mixture for 5 minutes, casting the mixture on a polytetrafluoroethylene plate, and reacting the mixture for 24 hours at room temperature; after the completion of the process, the film was removed and dried in a vacuum oven at 60 ℃ to remove the residual solvent. Then the prepared film is respectively put into 30 wt% trimethylamine solution and 1M NaOH solution for 48 hours respectively, and the styrene thermoplastic elastomer base composite film is obtained. The ion exchange capacity of the composite membrane is 1.48mmol/g, the water absorption rate is 10.03%, the swelling degree is 2.78%, and the ionic conductivity at 30 ℃ is 14.83 mS/cm.
Example 4:
2g of SEBS (6mmol of styrene units) were introduced into a three-necked flask equipped with a magnetic stirrer, and 30mL of carbon tetrachloride were added thereto. After it was dissolved at 35 ℃, 0.84mL (7.2mmol) of anhydrous tin tetrachloride was added to the above solution under ice water bath and stirred for 30 minutes. Thereafter, 4.04g (21.6mmol) of BCMB was added dropwise to the solution, and reacted at 18 ℃ for 24 hours. After the reaction was completed, the reaction solution was poured into a dilute hydrochloric acid solution to remove the catalyst, and then poured into ethanol to obtain a crude product, which was dissolved in tetrahydrofuran, precipitated again with ethanol, washed with ethanol and water until the solution was free of chloride ions, and then vacuum-dried at 35 ℃ for 12 hours.
2g of PS (M)n5000) (20mmol of styrene units) was charged into a three-necked flask equipped with a magnetic stirrer, and 60mL of carbon tetrachloride was added thereto. After it was dissolved at 35 ℃, 1.87mL (16mmol) of anhydrous tin tetrachloride was added to the above solution under ice water bath and stirred for 30 minutes. Thereafter, 9.0g (48mmol) of BCMB was added dropwise to the solution and reacted at 18 ℃ for 24 hours. After the reaction was completed, the reaction solution was poured into a dilute hydrochloric acid solution to remove the catalyst, and then poured into ethanol to obtain a crude product, which was dissolved in tetrahydrofuran, precipitated again with ethanol, washed with ethanol and water until the solution was free of chloride ions, and then vacuum-dried at 35 ℃ for 12 hours.
Weighing 0.35g of chloromethylated SEBS and 0.15g of chloromethylated PS, dissolving the SEBS and the PS at room temperature by using 10mL of chloroform, adding 0.115mL of TMHDA in ice-water bath after complete dissolution, violently stirring the mixture for 5 minutes, casting the mixture on a polytetrafluoroethylene plate, and reacting the mixture for 24 hours at room temperature; after the completion of the process, the film was removed and dried in a vacuum oven at 60 ℃ to remove the residual solvent. And then respectively putting the prepared membrane into 30 wt% of trimethylamine solution and 1M NaOH solution for 48 hours respectively to obtain the styrene thermoplastic elastomer based composite membrane, wherein the ion exchange capacity of the composite membrane is 1.73mmol/g, the water absorption rate is 13.49%, the swelling degree is 3.86%, and the ionic conductivity at 30 ℃ is 17.35 mS/cm. .
Example 5:
2g of SEBS (6mmol of styrene units) were introduced into a three-necked flask equipped with a magnetic stirrer, and 30mL of carbon tetrachloride were added thereto. After it was dissolved at 35 ℃, 1.12mL (9.6mmol) of anhydrous tin tetrachloride was added to the above solution under ice water bath and stirred for 30 minutes. Thereafter, 9.0g (48mmol) of BCMB was added dropwise to the solution and reacted at 18 ℃ for 24 hours. After the reaction was completed, the reaction solution was poured into a dilute hydrochloric acid solution to remove the catalyst, and then it was poured into ethanol to obtain a crude product, which was dissolved in toluene, precipitated again with ethanol, washed with ethanol and water until the solution was free of chloride ions, and then vacuum-dried at 35 ℃ for 12 hours.
2g of PS (M)n2000) (20mmol styrene units) was charged to a three-necked flask equipped with a magnetic stirrer, and 60mL of carbon tetrachloride was added thereto. After it was dissolved at 35 ℃, 1.40mL (12mmol) of anhydrous tin tetrachloride was added to the above solution under an ice water bath and stirred for 30 minutes. Thereafter, 11.22g (60mmol) of BCMB was added dropwise to the solution and reacted at 18 ℃ for 24 hours. After the reaction was completed, the reaction solution was poured into a dilute hydrochloric acid solution to remove the catalyst, and then it was poured into ethanol to obtain a crude product, which was dissolved in toluene, precipitated again with ethanol, washed with ethanol and water until the solution was free of chloride ions, and then vacuum-dried at 35 ℃ for 12 hours.
Weighing 0.3g of chloromethylated SEBS and 0.2g of chloromethylated PS, dissolving the SEBS and the PS at room temperature by using 10mL of carbon tetrachloride, adding 0.127mL of TMHDA in ice-water bath after complete dissolution, violently stirring the mixture for 5 minutes, casting the mixture on a polytetrafluoroethylene plate, and reacting the mixture for 24 hours at room temperature; after the completion of the process, the film was removed and dried in a vacuum oven at 60 ℃ to remove the residual solvent. Then the prepared membranes are respectively put into 30 wt% trimethylamine solution and 1M NaOH solution for 48 hours respectively, and the styrene thermoplastic elastomer based composite membrane is obtained. The ion exchange capacity of the composite membrane is 1.78mmol/g, the water absorption rate is 18.82%, the swelling degree is 4.37%, and the ionic conductivity at 30 ℃ is 22.45 mS/cm.
Example 6:
2g of SEPS (6mmol of styrene units) are introduced into a three-necked flask equipped with a magnetic stirrer and 35mL of chloroform are added thereto. After it was dissolved at 35 ℃, 0.51mL (10.8mmol) of anhydrous zinc chloride was added to the above solution under ice water bath and stirred for 30 minutes. Thereafter, 5.22g (64.8mmol) of CME was added dropwise to the solution, and reacted at 15 ℃ for 24 hours. After the reaction was completed, the reaction solution was poured into a dilute hydrochloric acid solution to remove the catalyst, and then poured into ethanol to obtain a crude product, which was dissolved in tetrahydrofuran, precipitated again with ethanol, washed with ethanol and water until the solution was free of chloride ions, and then vacuum-dried at 35 ℃ for 12 hours.
2g of PS (M)n300000) (20mmol of styrene units) was added to a three-necked flask equipped with a magnetic stirrer, and 65mL of chloroform was added thereto. After it was dissolved at 35 ℃, 0.75mL (16mmol) of anhydrous zinc chloride was added to the above solution under ice-water bath and stirred for 30 minutes. Thereafter, 7.73g (96mmol) of CME was added dropwise to the solution, and reacted at 15 ℃ for 24 hours. After the reaction was completed, the reaction solution was poured into a dilute hydrochloric acid solution to remove the catalyst, and then poured into ethanol to obtain a crude product, which was dissolved in tetrahydrofuran, precipitated again with ethanol, washed with ethanol and water until the solution was free of chloride ions, and then vacuum-dried at 35 ℃ for 12 hours.
Weighing 0.15g of chloromethylated SEPS and 0.35g of chloromethylated PS, dissolving the SEPS and the PS in 10mL of toluene at room temperature, adding 0.127mL of TMEDA in an ice water bath after the SEPS and the PS are completely dissolved, violently stirring the SEPS and the PS for 5 minutes, casting the SEPS and the PS on a polytetrafluoroethylene plate, and reacting the SEPS and the PS at room temperature for 24 hours; after the completion of the process, the film was removed and dried in a vacuum oven at 60 ℃ to remove the residual solvent. And then respectively putting the prepared film into 30 wt% of triethylamine solution and 1MKOH solution for 48 hours respectively to obtain the styrene thermoplastic elastomer-based composite film. The ion exchange capacity of the composite membrane is 1.84mmol/g, the water absorption rate is 24.86%, the swelling degree is 5.88%, and the ionic conductivity at 30 ℃ is 18.56 mS/cm.
Example 7:
2g SBS (4mmol styrene units) was added to a three-necked flask equipped with a magnetic stirrer bar and 25mL methylene chloride was added thereto. After it was dissolved at 35 ℃, 0.70mL (6.4mmol) of anhydrous titanium tetrachloride was added to the above solution under an ice water bath and stirred for 30 minutes. Thereafter, 1.2g (12.8mmol) of CEE was added dropwise to the solution, and reacted at 25 ℃ for 24 hours. After the reaction was completed, the reaction solution was poured into a dilute hydrochloric acid solution to remove the catalyst, and then poured into ethanol to obtain a crude product, which was dissolved in N, N-dimethylformamide and precipitated again with ethanol, washed with ethanol and water until the solution was free of chloride ions, and then vacuum-dried at 35 ℃ for 12 hours.
2gPS (M)n200000) (20mmol of styrene units) was charged in a three-necked flask equipped with a magnetic stirrer, and 50mL of dichloromethane was added thereto. After it was dissolved at 35 ℃, 2.20mL (20mmol) of anhydrous titanium tetrachloride was added to the above solution under an ice water bath and stirred for 30 minutes. Thereafter, 3.78g (40mmol) of CEE was added dropwise to the solution, and reacted at 25 ℃ for 24 hours. After the reaction was completed, the reaction solution was poured into a dilute hydrochloric acid solution to remove the catalyst, and then poured into ethanol to obtain a crude product, which was dissolved in N, N-dimethylformamide and precipitated again with ethanol, washed with ethanol and water until the solution was free of chloride ions, and then vacuum-dried at 35 ℃ for 12 hours.
Weighing 0.1g of chloromethylated SBS and 0.4g of chloromethylated PS, dissolving the materials by using 10mL of N, N-dimethylformamide at room temperature, adding 0.115mL of TMPDA in an ice-water bath after the materials are completely dissolved, violently stirring the mixture for 5 minutes, casting the mixture on a polytetrafluoroethylene plate, and reacting the mixture for 24 hours at room temperature; after the completion of the process, the film was removed and dried in a vacuum oven at 60 ℃ to remove the residual solvent. And then respectively putting the prepared film into 30 wt% of triethylamine solution and 1M KOH solution for 48 hours respectively to obtain the styrene thermoplastic elastomer-based composite film. The ion exchange capacity of the composite membrane is 0.82mmol/g, the water absorption rate is 30.98%, the swelling degree is 10.97%, and the ionic conductivity at 30 ℃ is 8.02 mS/cm.
Example 8:
2g of SIS (7.7mmol of styrene units) were charged into a three-necked flask equipped with a magnetic stirrer, and 40mL of carbon tetrachloride were added thereto. After it was dissolved at 35 ℃, 1.80mL (15.4mmol) of anhydrous tin tetrachloride was added to the above solution under ice water bath and stirred for 30 minutes. Thereafter, 5.82g (61.6mmol) of CEE was added dropwise to the solution, and reacted at 20 ℃ for 24 hours. After the reaction was completed, the reaction solution was poured into a dilute hydrochloric acid solution to remove the catalyst, and then it was poured into ethanol to obtain a crude product, which was dissolved in chloroform and precipitated again with ethanol, washed with ethanol and water until the solution was free of chloride ions, and then vacuum-dried at 35 ℃ for 12 hours.
2gPS (M)n100000) (20mmol of styrene units) was added to a three-necked flask equipped with a magnetic stirrer, and 70mL of carbon tetrachloride was added thereto. After it was dissolved at 35 ℃, 2.34mL (20mmol) of anhydrous tin tetrachloride was added to the above solution under an ice water bath and stirred for 30 minutes. Thereafter, 7.56g (80mmol) of CEE was added dropwise to the solution, and reacted at 20 ℃ for 24 hours. After the reaction was completed, the reaction solution was poured into a dilute hydrochloric acid solution to remove the catalyst, and then it was poured into ethanol to obtain a crude product, which was dissolved in chloroform and precipitated again with ethanol, washed with ethanol and water until the solution was free of chloride ions, and then vacuum-dried at 35 ℃ for 12 hours.
Weighing 0.05g of chloromethylated SIS and 0.45g of chloromethylated PS, dissolving with 10mL of tetrahydrofuran at room temperature, adding 0.103mL of TMHDA in an ice water bath after complete dissolution, violently stirring for 5 minutes, casting the mixture on a polytetrafluoroethylene plate, and reacting for 24 hours at room temperature; after the completion of the process, the film was removed and dried in a vacuum oven at 60 ℃ to remove the residual solvent. And then respectively putting the prepared film into 30 wt% of triethylamine solution and 1M KOH solution for 48 hours respectively to obtain the styrene thermoplastic elastomer-based composite film. The ion exchange capacity of the composite membrane is 1.27mmol/g, the water absorption rate is 29.86%, the swelling degree is 9.34%, and the ionic conductivity at 30 ℃ is 10.33 mS/cm.
Example 9:
the anion-exchange membrane prepared in example 5 was used as a sample to conduct an alkali resistance test. Soaking the membrane sample in 2M NaOH solution filled with inert gas at 60 ℃, taking out the membrane sample at intervals, repeatedly washing the membrane sample with deionized water to remove residual alkali liquor on the surface, and testing the ionic conductivity of the membrane sample at 60 ℃. The test result is shown in fig. 2, the ion conductivity of the film sample is only slightly reduced after the alkali resistance test, which shows that the styrenic thermoplastic elastomer-based composite film prepared by the invention has good chemical stability.
Claims (9)
1. A method for preparing a styrene thermoplastic elastomer/polystyrene composite film is characterized in that the main chain of the styrene thermoplastic elastomer/polystyrene composite film is composed of a styrene thermoplastic elastomer and polystyrene; SEBS and PS are used as raw materials, and the synthesized composite membrane has a chemical structural formula as follows:
the preparation method comprises the following steps:
the method comprises the following steps: preparation of functionalized styrenic thermoplastic elastomers
Dissolving a styrene thermoplastic elastomer in an organic solvent, after uniformly stirring, sequentially adding a catalyst in an amount which is 0.8-2 times of the molar weight of a styrene unit and a functionalized modification reagent in an amount which is 2-6 times of the molar weight of the catalyst, stirring at 15-25 ℃ for 24 hours, then pouring into dilute hydrochloric acid, and removing the catalyst; pouring the emulsion at the lower layer into ethanol to obtain a crude product, dissolving the crude product by using a solvent, then precipitating by using ethanol, and performing vacuum drying treatment to obtain a functionalized styrene thermoplastic elastomer;
step two: preparation of functionalized polystyrene
Dissolving polystyrene in an organic solvent, after uniformly stirring, sequentially adding a catalyst with the molar weight of 0.4-1 time of that of a styrene unit and a functionalized modifying reagent with the molar weight of 2-6 times of that of the catalyst, stirring at 15-25 ℃ for 24 hours, and then pouring into dilute hydrochloric acid to remove the catalyst; then pouring the emulsion at the lower layer into a large amount of ethanol to obtain a crude product, dissolving the crude product by using a solvent, then precipitating by using ethanol, and performing vacuum drying treatment to obtain the functionalized polystyrene;
step three: dissolving the functionalized styrene thermoplastic elastomer obtained in the step one and the functionalized polystyrene obtained in the step two in an organic solvent according to a mass ratio of 10: 0-1: 9, adding a crosslinking reagent under rapid stirring, casting at room temperature to form a film, standing for 24 hours, and then placing in a vacuum oven to remove residual solvent;
step four: and respectively soaking the composite membrane in an ammonium agent and an alkalization agent for 48 hours at room temperature to obtain the styrene thermoplastic elastomer/polystyrene composite membrane.
2. The method as claimed in claim 1, wherein the styrenic thermoplastic elastomer of step one is SBS, SIS, SEBS, SEPS or their derivatives.
3. The method according to claim 2, wherein the polystyrene in the second step has a molecular weight of 2000 to 300000.
4. The method according to claim 3, wherein the catalyst in the first step is anhydrous tin tetrachloride, anhydrous zinc chloride or anhydrous titanium tetrachloride, and the catalyst in the second step is anhydrous tin tetrachloride, anhydrous zinc chloride or anhydrous titanium tetrachloride.
5. The method according to claim 4, wherein the functional modification reagent in the first step is chloromethyl methyl ether, chloromethyl ethyl ether or 1, 4-dichloromethoxybutane, and the functional modification reagent in the second step is chloromethyl methyl ether, chloromethyl ethyl ether or 1, 4-dichloromethoxybutane.
6. The method according to claim 5, wherein the crosslinking reagent in the third step is tetramethylhexamethylenediamine, tetramethylpropylenediamine or tetramethylethylenediamine.
7. The method according to claim 5, wherein the ammonium agent in step three is trimethylamine or triethylamine, and the alkalizing agent is NaOH or KOH.
8. The method according to claim 7, wherein the temperature of the vacuum drying treatment in the first and second steps is 35 ℃ and the time is 12 hours; the temperature of the vacuum oven in the third step is 60 ℃, and the standing time is 12 hours.
9. The method according to claim 8, wherein the organic solvent used in the first and second steps is tetrahydrofuran, chloroform, dichloromethane, chlorobenzene, dichlorobenzene or carbon tetrachloride; in the third step, the organic solvent is tetrahydrofuran, chloroform, dichloromethane, toluene, xylene, carbon tetrachloride or N, N-dimethylformamide.
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