CN109280199B - Crystalline anion exchange membrane with microphase separation structure and preparation method thereof - Google Patents
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Abstract
The invention relates to a crystal anion exchange membrane with a microphase separation structure and a preparation method thereof, wherein SBS elastomer is taken as a starting material, and is subjected to normal pressure catalytic hydrogenation reaction to prepare crystal SEBS, and then halogen groups are introduced on benzene rings to prepare a functionalized polyolefin copolymer; the membrane is prepared into a uniform solution, a solution coating process is adopted to prepare the membrane, and hydroxide ions are introduced into the obtained membrane material through quaternization and alkalization to prepare the high-performance anion exchange membrane. The anion exchange membrane has the following advantages: 1) the hydrogenation of the SBS elastomer converts its polybutadiene chains into polyethylene chains while retaining its polystyrene blocks, thus combining the advantages of thermoplastic elastomers and polyolefins. 2) After the star SBS is hydrogenated, the molecular weight of the polyolefin block can be greatly improved on the premise of ensuring good solubility, a high molecular weight polyolefin copolymer anion exchange membrane with excellent film forming performance is obtained, and the system is endowed with good processability, mechanical strength and dimensional stability.
Description
Technical Field
The invention relates to a crystalline anion exchange membrane with a microphase separation structure and a preparation method thereof, belonging to the field of anion exchange membrane fuel cells.
Background
In recent years, increasingly serious global energy and environmental crisis have raised higher requirements for the development of clean energy technologies, and among them, Anion Exchange Membrane Fuel Cells (AEMFCs) exhibit wide application prospects by virtue of the advantages of high electrode reaction efficiency, low fuel leakage rate, use of non-noble metal catalysts, wide fuel selection range, low cost and the like. As a key component of AEMFCs, Anion Exchange Membranes (AEMs) are both separators for oxidant and fuel and OH-The chemical and mechanical stability and ion transport properties of the conductors under strongly alkaline conditions directly determine the life and performance of the AEMFCs. Up to now, various aromatic polymers and aliphatic polymers have been used in succession in the field of anion exchange membranes, such as polyphenylene ethers, polyfluorenes, polyarylethersulfones, polyaryletherketones, polystyrenes, thermoplastic elastomers, polyolefins and other polymers.
Among various polymer systems, polystyrene-b- (ethylene-co-butylene) -b-polystyrene (SEBS) thermoplastic elastomers are receiving attention because of their abundant raw materials, low cost, good microphase separation structure and chemical stability. Their Polystyrene (PS) blocks are covalently bound to thermodynamically incompatible intermediate soft blocks, establishing the physical network responsible for their mechanical properties (d.wang, s.fujinami, h.liu, k.nakajima, t.nishi, Macromolecules,43,9049; x.han, j.hu, h.l.liu, y.hu, Langmuir,22,3428.). When SEBS is used as the polymer backbone of AEMs, the PS block needs to be chemically modified (i.e., chloromethylated and quaternized) (QH Zeng, QL Liu, I Broadwell, AM Zhu, Y Xiong, XP Tu, J.Membr.Sci.2010,349, 237; R Vinodh, A Ilakkiya, S Elamathi, D Sangetetha, Mater.Sci.Eng.B 2010,167, 43; L Sun, J Guo, J Zhou, Q Xu, D Chu, R Chen, J.Power Source 2012,202, 70; J Zhou, J Guo, D Chu, R n, J.Power Source 2012,219,272.) to provide a transport channel for hydroxyl ions. Theoretically, the highest possible degree of PS functionalization is required for the preparation of high-performance SEBS-based AEMs. However, an excessively high degree of functionalization can severely increase the water absorption (WU) and the swelling capacity (SR) of the AEMs and thus can lead to a severe deterioration of their mechanical properties. Moreover, commercial SEBS copolymers were originally designed for use as elastomers, with the mid-soft block not contributing to mechanical stability, making it difficult to meet the use requirements of AEMs. Therefore, the invention aims to perform hydrogenation reduction on the polystyrene-b-polybutadiene-b-polystyrene (SBS) copolymer with high 1, 4-butadiene unit content by a normal pressure hydrogenation method, combine the advantages of the thermoplastic elastomer and the polyolefin and invent the crystalline anion exchange membrane with a microphase separation structure.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a crystalline anion exchange membrane with a microphase separation structure and a preparation method thereof, and the main process is as follows: firstly, SBS is taken as a starting material, and the crystallization SEBS is prepared by normal pressure catalytic hydrogenation; secondly, introducing a halogen-containing functional group on a benzene ring through functional modification to prepare a functional crystalline SEBS; and finally, hydroxyl ions are introduced through quaternization and alkalization to prepare the high-performance crystalline anion exchange membrane.
The technical scheme of the invention is as follows:
a crystalline anion exchange membrane with a microphase separation structure is characterized in that a main chain mainly comprises a polystyrene block and a polyethylene block, the polystyrene block and the polyethylene block form the microphase separation structure, wherein the polystyrene block loads a functional group, and the polyethylene block provides good mechanical properties for a system by forming the crystalline structure. The structural formula of the film is as follows:
the preparation method of the crystalline anion-exchange membrane with the microphase separation structure is characterized by comprising the following steps:
the method comprises the following steps: dissolving SBS in an organic solvent under an inert gas atmosphere, stirring uniformly, adding 1-3 times of p-toluenesulfonic acid and 0.5-2 times of tri-n-propylamine in the molar amount of double bonds in SBS, and heating and refluxing for 4-8 h when the temperature is raised to 135-140 ℃. And after the reaction liquid is cooled, pouring the reaction liquid into an ethanol solution acidified by hydrochloric acid, stirring overnight, repeatedly washing the product obtained after filtration by using ethanol and deionized water in sequence, and performing vacuum drying at 50 ℃ for 12 hours.
Step two: dissolving the product obtained in the step one in an organic solvent, stirring uniformly, adding a catalyst with the molar weight of 0.5-2 times that of a styrene unit in a polymer and a functionalized reagent with the molar weight of 8-12 times that of the catalyst, reacting at 50-60 ℃ for 6-12 h, pouring into ethanol for precipitation to obtain a crude product, dissolving the crude product with the organic solvent, precipitating in ethanol again to obtain a required product, and vacuum drying at 35 ℃ for 12 h.
Step three: and (3) fully dissolving the product obtained in the step two in an organic solvent, coating by adopting a solution casting method, standing for 24 hours at 70-90 ℃, removing the film, and drying in a vacuum oven at 80 ℃ overnight to remove the residual solvent. And then sequentially immersing the membrane sample into an ammonium reagent and an alkalization reagent for 48 hours respectively to obtain the crystalline anion-exchange membrane with the microphase separation structure.
In the first step and the third step of the invention, the organic solvent is toluene, xylene, p-xylene, m-xylene and o-xylene, and the organic solvent in the second step is tetrahydrofuran, chloroform, toluene, xylene, chlorobenzene, dichlorobenzene, N-dimethylformamide or carbon tetrachloride. The catalyst is anhydrous tin tetrachloride, anhydrous zinc chloride and anhydrous titanium tetrachloride; the functional reagent is chloromethyl methyl ether, chloromethyl ethyl ether and 1, 4-dichloromethoxybutane; the ammonification reagent is trimethylamine or triethylamine; the alkalizing agent is NaOH or KOH.
The invention has the advantages that: firstly, the polybutadiene molecular chain is converted into the polyethylene chain by the hydrogenation of the SBS elastomer, and meanwhile, the polystyrene block is reserved, so that the advantages of the thermoplastic elastomer and the polyolefin are combined. And secondly, the star SBS hydrogenated product can greatly improve the molecular weight of the polyolefin block on the premise of ensuring good solubility, so that the high molecular weight polyolefin copolymer anion exchange membrane with excellent film forming property is obtained, and the system is endowed with good processability, mechanical strength and dimensional stability.
Drawings
FIG. 1 shows the IR spectra of SBS (A), hydrogenated SBS (B), hydrogenated SBS chloromethyl functionalization (C) and prepared anion exchange membrane (D).
FIG. 2 is a graph showing the change of ion conductivity of an anion exchange membrane with temperature.
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:
230mL of toluene was charged into a 500mL three-necked round-bottomed flask containing 4g of linear SBS in an inert gas atmosphere, and after complete dissolution of SBS, 22g of p-toluenesulfonic acid (2 times the molar amount of the double bond in SBS) and 17g of tri-n-propylamine (1 time the molar amount of p-toluenesulfonic acid) were added thereto in this order, and the mixture was heated to 135 ℃ and refluxed for 4 hours. And after the reaction liquid is cooled, pouring the reaction liquid into an ethanol solution containing 10% hydrochloric acid, stirring overnight, repeatedly washing the product obtained after filtering by using ethanol and deionized water in sequence until the filtrate is neutral, and placing the filtrate at 50 ℃ for vacuum drying for 12 hours to obtain the crystalline SEBS.
2g of crystalline SEBS was added to 60mL of chlorobenzene and stirred at 70 ℃ to homogenize, and then 1.13mL of anhydrous tin tetrachloride (1 time the molar amount of styrene unit) was added at 30 ℃ to stir for 30 minutes, and then 6.2g of chloromethyl methyl ether (8 times the molar amount of catalyst) was slowly added dropwise thereto and reacted at 60 ℃ for 6 hours. The reaction solution is poured into ethanol for precipitation to obtain a crude product, then tetrahydrofuran is added again for dissolution, ethanol precipitation is carried out, washing is carried out for a plurality of times, and then vacuum drying is carried out for 12 hours at 35 ℃.
Weighing 0.3g of the product, dissolving the product with 10ml of dimethylbenzene at 100 ℃, casting the product on a polytetrafluoroethylene plate, and standing the product at 90 ℃ for 24 hours; after finishing, the film is taken off and put into a vacuum oven at 80 ℃ for drying for 12h to remove residual solvent. And then sequentially soaking the membrane sample in 30 wt% of trimethylamine aqueous solution and 1M NaOH solution for 48 hours to obtain the anion exchange membrane.
FIG. 1 is an infrared spectrum of a polymer film at various stages in this example. As can be seen from the figure, 1640cm-1C ═ C stretching vibration absorption peak and 911cm-1And 967cm-1The absorption peaks corresponding to the trans 1,2 and 1,4 structures both disappeared after the hydrogenation reaction, indicating that SBS had been successfully hydrogenated. After the hydrogenation of SBS chloromethylation reaction, its product is 1265cm-1The characteristic absorption peak of chloromethyl group appeared, which indicated that chloromethyl group had been successfully introduced. And 1265cm in the subsequent quaternization and basification reactions-1The absorption peak gradually disappeared, and at the same time, 1640cm-1And 3400cm-1Then the stretching vibration and OH respectively corresponding to C-N appear-1The absorption peak of (a) can prove that chloromethyl has been successfully quaternized and basified.
The anion-exchange membrane prepared in this example had an ion-exchange capacity of 0.97 mmol/g.
As shown in FIG. 2, curve a is the ionic conductivity versus temperature curve for the membrane prepared in this example, and it can be seen that the ionic conductivity is 27.86mS/cm at 30 ℃.
Example 2:
230mL of xylene was added to a 500mL three-necked round bottom flask containing 4g of linear SBS under an inert gas atmosphere, after SBS was completely dissolved, 11g of p-toluenesulfonic acid (1 time the molar amount of the double bond in SBS) and 8.5g of tri-n-propylamine (1 time the molar amount of p-toluenesulfonic acid) were added thereto in this order, and the mixture was heated to 136 ℃ and refluxed for 5 hours. And after the reaction liquid is cooled, pouring the reaction liquid into an ethanol solution containing 10% hydrochloric acid, stirring overnight, repeatedly washing the product obtained after filtering by using ethanol and deionized water in sequence until the filtrate is neutral, and placing the filtrate at 50 ℃ for vacuum drying for 12 hours to obtain the crystalline SEBS.
2g of crystalline SEBS was added to 60mL of dichlorobenzene and stirred at 70 ℃ to homogeneity, and then 0.86mL of anhydrous tin tetrachloride (0.5 time the molar amount of styrene units) was added at 30 ℃ and after stirring for 30 minutes, 12.4g of 1, 4-dichloromethoxybutane (9 times the molar amount of the catalyst) was slowly added dropwise thereto and reacted at 55 ℃ for 8 hours. The reaction solution was poured into ethanol to precipitate a crude product, and then chloroform was added again to dissolve it, and after precipitation with ethanol and repeated washing several times, vacuum drying was carried out at 35 ℃ for 12 hours.
Weighing 0.3g of the product, dissolving the product with 10ml of toluene at 90 ℃, casting the product on a polytetrafluoroethylene plate, and standing the product at 80 ℃ for 24 hours; after finishing, the film is taken off and put into a vacuum oven at 80 ℃ for drying for 12h to remove residual solvent. And then sequentially soaking the membrane sample in 30 wt% of trimethylamine aqueous solution and 1M NaOH solution for 48 hours to obtain the anion exchange membrane.
The anion-exchange membrane prepared in this example had an ion-exchange capacity of 1.39 mmol/g.
As shown in FIG. 2, curve b is the ionic conductivity versus temperature curve of the membrane prepared in this example, and it can be seen that the ionic conductivity is 27.46mS/cm at 30 ℃.
Example 3:
230mL of p-xylene was added to a 500mL three-necked round-bottomed flask containing 4g of linear SBS under an inert gas atmosphere, after SBS was completely dissolved, 33g of p-toluenesulfonic acid (3 times the molar amount of the double bond in SBS) and 13g of tri-n-propylamine (0.5 times the molar amount of p-toluenesulfonic acid) were added thereto in this order, and the mixture was heated to 137 ℃ and refluxed for 6 hours. And after the reaction liquid is cooled, pouring the reaction liquid into an ethanol solution containing 10% hydrochloric acid, stirring overnight, repeatedly washing the product obtained after filtering by using ethanol and deionized water in sequence until the filtrate is neutral, and placing the filtrate at 50 ℃ for vacuum drying for 12 hours to obtain the crystalline SEBS.
2g of crystalline SEBS was added to 60mL of carbon tetrachloride and stirred at 60 ℃ uniformly, and then 1.53mL of anhydrous titanium tetrachloride (2 times the molar amount of styrene units) was added at 30 ℃ and stirred for 30 minutes, and then 13.2g of chloromethyl ether (10 times the molar amount of the catalyst) was slowly added dropwise thereto and reacted at 50 ℃ for 12 hours. The reaction solution is poured into ethanol for precipitation to obtain a crude product, then toluene is added again for dissolution, ethanol precipitation is carried out, washing is carried out for a plurality of times, and then vacuum drying is carried out for 12 hours at 35 ℃.
Weighing 0.3g of the product, dissolving the product with 10ml of m-xylene at 80 ℃, casting the product on a polytetrafluoroethylene plate, and standing the product at 70 ℃ for 24 hours; after finishing, the film is taken off and put into a vacuum oven at 80 ℃ for drying for 12h to remove residual solvent. And then sequentially soaking the membrane sample in 30 wt% of triethylamine aqueous solution and 1M KOH solution for 48h to obtain the anion exchange membrane.
The anion-exchange membrane prepared in this example had an ion-exchange capacity of 1.34 mmol/g.
As shown in FIG. 2, curve c is the ionic conductivity versus temperature curve for the membrane prepared in this example, and it can be seen that the ionic conductivity is 30.81mS/cm at 30 ℃.
Example 4:
230mL of o-xylene was added to a 500mL three-necked round bottom flask containing 4g of star SBS under an inert gas atmosphere, after SBS was completely dissolved, 22g of p-toluenesulfonic acid (2 times the molar amount of the double bond in SBS) and 34g of tri-n-propylamine (2 times the molar amount of p-toluenesulfonic acid) were added thereto in this order, and the mixture was heated to 138 ℃ and refluxed for 7 h. And after the reaction liquid is cooled, pouring the reaction liquid into an ethanol solution containing 10% hydrochloric acid, stirring overnight, repeatedly washing the product obtained after filtering by using ethanol and deionized water in sequence until the filtrate is neutral, and placing the filtrate at 50 ℃ for vacuum drying for 12 hours to obtain the crystalline SEBS.
2g of crystalline SEBS was added to 60mL of dichlorobenzene and stirred at 70 ℃ to homogeneity, and then 1.36mL of anhydrous titanium tetrachloride (1.5 times the molar amount of styrene units) was added at 30 ℃ and stirred for 30 minutes, after which 25.5g of 1, 4-dichloromethoxybutane (11 times the molar amount of catalyst) was slowly added dropwise thereto and reacted at 60 ℃ for 7 hours. The reaction solution is poured into ethanol for precipitation to obtain a crude product, then xylene is added again for dissolution, ethanol precipitation is carried out, washing is carried out for a plurality of times, and then vacuum drying is carried out for 12 hours at 35 ℃.
Weighing 0.3g of the product, dissolving the product with 10ml of p-xylene at 90 ℃, casting the dissolved product on a polytetrafluoroethylene plate, and standing the product at 80 ℃ for 24 hours; after finishing, the film is taken off and put into a vacuum oven at 80 ℃ for drying for 12h to remove residual solvent. And then sequentially soaking the membrane sample in 30 wt% of trimethylamine aqueous solution and 1M KOH solution for 48h to obtain the anion exchange membrane.
The anion exchange membrane prepared in this example had an ion exchange capacity of 0.98 mmol/g.
As shown in FIG. 2, a curve d is a graph of ionic conductivity versus temperature for the membrane prepared in this example, and it can be seen that the ionic conductivity is 23.57mS/cm at 30 ℃.
Example 5:
under an inert gas atmosphere, 230mL of m-xylene is added into a 500mL three-neck round-bottom flask containing 4g of star SBS, after SBS is completely dissolved, 17g of p-toluenesulfonic acid (2 times of the molar amount of double bond in SBS) and 20g of tri-n-propylamine (1.5 times of the molar amount of p-toluenesulfonic acid) are added into the flask in sequence, and the temperature is raised to 140 ℃ and heated and refluxed for 8 h. And after the reaction liquid is cooled, pouring the reaction liquid into an ethanol solution containing 10% hydrochloric acid, stirring overnight, repeatedly washing the product obtained after filtering by using ethanol and deionized water in sequence until the filtrate is neutral, and placing the filtrate at 50 ℃ for vacuum drying for 12 hours to obtain the crystalline SEBS.
2g of crystalline SEBS was added to 60mL of carbon tetrachloride and stirred at 60 ℃ uniformly, and then 1.63mL of anhydrous zinc chloride (2 times the molar amount of styrene units) was added at 30 ℃ and stirred for 30 minutes, and then 33.6g of chloromethyl methyl ether (12 times the molar amount of the catalyst) was slowly added dropwise thereto and reacted at 55 ℃ for 10 hours. The reaction solution is poured into ethanol for precipitation to obtain a crude product, then N, N-dimethylformamide is added again for dissolution, ethanol precipitation is carried out, washing is carried out for a plurality of times, and vacuum drying is carried out for 12 hours at 35 ℃.
Weighing 0.3g of the product, dissolving the product with 10ml of o-xylene at 90 ℃, casting the product on a polytetrafluoroethylene plate, and standing the product at 80 ℃ for 24 hours; after finishing, the film is taken off and put into a vacuum oven at 80 ℃ for drying for 12h to remove residual solvent. And then sequentially soaking the membrane sample in 30 wt% of triethylamine aqueous solution and 1M NaOH solution for 48h to obtain the anion exchange membrane.
The anion-exchange membrane prepared in this example had an ion-exchange capacity of 1.69 mmol/g.
As shown in FIG. 2, curve e is the ionic conductivity versus temperature curve for the membrane prepared in this example, and it can be seen that the ionic conductivity is 33.60mS/cm at 30 ℃.
Claims (8)
1. A preparation method of a crystalline anion exchange membrane with a microphase separation structure is characterized in that a main chain of the crystalline anion exchange membrane mainly comprises a polystyrene block and a polyethylene block which form the microphase separation structure, wherein the polystyrene block loads a functional group, and the polyethylene block provides good mechanical property for a system by forming the crystalline structure;
the structural formula of the membrane is as follows:
Wherein: r is-CH3or-CH2CH3；
The preparation method comprises the following steps:
the method comprises the following steps: dissolving SBS in an organic solvent under an inert gas atmosphere, stirring uniformly, adding 1-3 times of p-toluenesulfonic acid and 0.5-2 times of tri-n-propylamine in the molar amount of double bonds in SBS, and heating and refluxing for 4-8 h when the temperature is raised to 135-140 ℃; after the reaction liquid is cooled, pouring the reaction liquid into an ethanol solution acidified by hydrochloric acid, stirring overnight, repeatedly washing products obtained after filtering by using ethanol and deionized water in sequence, and carrying out vacuum drying treatment;
step two: dissolving the product obtained in the step one in an organic solvent, stirring uniformly, adding a catalyst with the molar weight of 0.5-2 times that of a styrene unit in a polymer and a functionalized reagent with the molar weight of 8-12 times that of the catalyst, reacting at 50-60 ℃ for 6-12 h, pouring into ethanol for precipitation to obtain a crude product, dissolving the crude product with the organic solvent, precipitating in ethanol again to obtain a required product, and vacuum-drying at 35 ℃ for 12 h;
step three: fully dissolving the product obtained in the step two in an organic solvent, coating by adopting a solution casting method, standing for 24 hours at 70-90 ℃, removing the film, and placing the film in a vacuum oven to remove the residual solvent; and then sequentially immersing the membrane sample into an ammonium reagent and an alkalization reagent for 48 hours respectively to obtain the crystalline anion-exchange membrane with the microphase separation structure.
2. The method according to claim 1, wherein the catalyst in step two is anhydrous stannic chloride, anhydrous zinc chloride, anhydrous titanium tetrachloride, and the functionalizing agent is chloromethyl methyl ether, chloromethyl ethyl ether, or 1, 4-dichloromethoxybutane.
3. The method according to claim 1 or 2, wherein the ammonium agent in step three is trimethylamine or triethylamine, and the alkalizing agent is NaOH or KOH.
4. The method according to claim 1 or 2, wherein the organic solvent in step one or step three is toluene, xylene, p-xylene, m-xylene, o-xylene, and the organic solvent in step two is tetrahydrofuran, chloroform, toluene, xylene, chlorobenzene, dichlorobenzene, N-dimethylformamide, or carbon tetrachloride.
5. The method according to claim 3, wherein the organic solvent in step one and step three is toluene, xylene, p-xylene, m-xylene, o-xylene, and the organic solvent in step two is tetrahydrofuran, chloroform, toluene, xylene, chlorobenzene, dichlorobenzene, N-dimethylformamide, or carbon tetrachloride.
6. The method according to claim 1,2 or 5, wherein the vacuum drying treatment temperature in the first step is 50 ℃ and the time is 12 hours; the temperature of the vacuum oven in the third step is 80 ℃.
7. The method according to claim 3, wherein the vacuum drying treatment temperature in the first step is 50 ℃ and the time is 12 hours; the temperature of the vacuum oven in the third step is 80 ℃.
8. The method according to claim 4, wherein the vacuum drying treatment temperature in the first step is 50 ℃ and the time is 12 hours; the temperature of the vacuum oven in the third step is 80 ℃.
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