CN110752398A - Star topology structure polyolefin anion exchange membrane, preparation method and application - Google Patents
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Abstract
The invention discloses a star topology structure polyolefin anion exchange membrane, a preparation method and application, and belongs to the technical field of alkaline anion exchange membranes. The star topological structure polyolefin block main chain membrane material with good solubility and stability is synthesized by an anion polymerization mode, a benzyl site is brominated by catalytic hydrogenation and a bromination reagent, and an ion conduction group is grafted by a Menshu gold reaction to obtain the star topological structure polyolefin membrane material and prepare the membrane. The prepared membrane has good alkali stability and high ionic conductivity, and can be applied to alkaline fuel cells.
Description
Technical Field
The invention belongs to the technical field of alkaline anion exchange membranes, and relates to a star topology structure polyolefin anion exchange membrane, a preparation method and application thereof.
Background
With the increasing severity of global environment and energy problems, fuel cells as a new power generation device have drawn attention due to the advantages of wide fuel source, high efficiency, low or even zero emission. The alkaline anion exchange membrane fuel cell is one of the fuel cells, and compared with the mature proton exchange membrane fuel cell studied at present, the alkaline anion exchange membrane fuel cell has the advantages of high oxidation speed, low fuel permeation speed, contribution to water balance, relatively low cost and the like. The advantage of low cost (Varcoe, j.r.; ataassov, p.; Dekel, d.r.; Herring, a.m.; Hickner, m.a.; Kohl, p.a.; Kucernak, a.r.; musain, w.e.; Nijmeijer, k.; Scott, k.; Xu, t.w.; Zhuang, l.energy environ.sci.,2014,7,3135 @) stems from the fact that alkaline anion exchange membrane fuel cells can use non-noble metals as catalysts, which is one of their most main advantages.
The alkaline anion exchange membrane is a core component of the alkaline anion exchange membrane fuel cell and plays a role in selectively transferring hydroxide ions and separating two polar chambers. Such functions require that the alkaline anion exchange membrane not only have good ability to transfer hydroxide ions, but also maintain stable performance in an alkaline environment. (Wu, L.; Zhou, G.F.; Liu, X.; Zhang, Z.H.; Li, C.R.; Xu, T.W.J.Membr.Sci.,2011,371, 155-162.) polymers such as polysulfone, polyether ether ketone, polyphenylene oxide and the like are commonly used as main chains in current membrane materials, and usually a modification grafting method is adopted to graft ion conduction groups to prepare the target polymer anion exchange membrane. (Chinese patent CN 106543459A; CN 106432744A; however, because the distribution of the ion conduction groups is not controllable due to post-modification grafting modification, the formation of ion conduction channels in the membrane is restricted, and the ion conductivity is limited; in addition, due to the heteroatom structure in the main chain of the polymer, the main chain of most membrane materials can be attacked by hydroxide radicals in an alkaline environment, and the membrane materials are degraded, so that the service life of the membrane materials is seriously influenced. ChulsungBae et al successfully synthesized a polystyrene-b-poly (ethylene-co-butadiene) -b-polystyrene crystalline-amorphous triblock polyolefin copolymer by living polymerization, and the membrane material still had good chemical stability after being soaked in 1M NaOH solution at 60 ℃ and 80 ℃ for four weeks, and the polymer main chain structure and the ionic group still had stability after the fuel cell life test at 60 ℃ for 110 hours. (Angela D. Mohanty, Chang Y. Ryu, Yu Seung Kim. et al; Macromolecules 2015,48, 7085-.
Disclosure of Invention
The invention aims to provide a preparation method of a polyolefin anion exchange membrane with a star topology structure, so as to achieve the aim of improving the alkali resistance stability and the hydroxyl transfer performance of an alkaline anion exchange membrane. Synthesizing a star topology structure polyolefin block main chain membrane material with good solubility and stability in an anionic polymerization mode, brominating a benzyl site by catalyzing through hydrogenation and a brominating reagent, then adding a crosslinking agent for crosslinking, and introducing an ion conduction functional group to obtain the star topology structure polyolefin membrane material and prepare the membrane. The prepared membrane has good alkali stability and high ionic conductivity, and can be applied to alkaline fuel cells.
The technical scheme of the invention is as follows:
a star topology structure polyolefin anion exchange membrane has the following structure:
wherein x/(x + y) is 0.1-0.6, and y/(x + y) is 0.4-0.9; x-Is OH-、HCO3 -、Cl-、Br-Or I-；FG+The ion-conducting functional group is 1-methylimidazolium cation, 1, 2-dimethylimidazolium cation, N-methylmorpholine quaternary ammonium salt, N-methylpiperidine quaternary ammonium salt, N-methylpyrrolidine quaternary ammonium salt, trimethyl quaternary ammonium salt, triethyl quaternary ammonium salt, tripropyl quaternary ammonium salt, triisopropyl quaternary ammonium salt, tri-N-butyl quaternary ammonium salt, trihexyl quaternary ammonium salt or trioctyl quaternary ammonium salt.
A preparation method of a star topology structure polyolefin anion exchange membrane comprises the following steps:
(1) synthesizing a star topology polyolefin main chain: carrying out polymerization reaction under the protection of inert gas, adding isoprene and cyclohexane, adding organic lithium, and stirring1The method comprises the following steps of (1) taking minutes; after the reaction is finished, adding p-methylstyrene, and continuously stirring t2The method comprises the following steps of (1) taking minutes; after the reaction is finished, adding a cross-linking agent and stirring t3After minutes, adding a chain terminator to stop the reaction; settling the reaction solution by using a solvent A to separate out a solid polymer, filtering, washing and drying; obtaining the polyolefin main chain membrane material with the star topology structure.
The organic lithium is one of methyl lithium, n-butyl lithium, isobutyl lithium, tert-butyl lithium, n-hexyl lithium, n-octyl lithium and phenyl lithium;
the solvent A is one or more of acetone, methanol, ether, ethanol, ethyl acetate and water;
the chain terminator is one or a mixture of more than two of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-hexanol, cyclohexanol and n-octanol;
the cross-linking agent is divinylbenzene or silicon tetrachloride;
the molar ratio of the organic lithium to the cross-linking agent is 1: 1-1: 10;
the molar ratio of the organic lithium to the isoprene is 1: 100-1: 3000A;
the mole ratio of isoprene to p-methylstyrene is 5: 1-1: 5;
the stirring time t1Is 30-1500 min, whereinPreferably 180-600 min;
the stirring time t260-1500 min, preferably 180-600 min;
the stirring time t360-1500 min, preferably 180-600 min;
the w/v of the isoprene in the cyclohexane is 5-20%, and the unit of the w/v is g/ml;
the w/v of the p-methylstyrene in the cyclohexane is 5 to 20 percent, and the unit of the w/v is g/ml;
the polymerization reaction temperature is 20-50 ℃;
(2) synthesizing a star topology structure polyolefin anion exchange membrane: dissolving a star topology polyolefin main chain membrane material in a solvent B, brominating a benzyl site by catalytic hydrogenation and a bromination reagent, settling reaction liquid by using a solvent C, separating out a solid polymer, filtering, washing and drying to prepare a saturated polyolefin material modified by benzyl bromide; dissolving the prepared benzyl bromide modified saturated polyolefin in a solvent B, reacting with a nitrogen-containing group through Menshu gold, grafting an ion conducting group, settling a polymer reaction solution by using a solvent C, separating out a solid polymer, filtering, washing and drying; and then preparing the obtained polymer into a casting film solution, casting the casting film solution to form a film, soaking the film in alkali liquor, and soaking the film in deionized water until the film is neutral to obtain the star topology structure polyolefin anion exchange film.
The solvent B is one of N, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone;
the solvent C is one of ethyl acetate, dichloromethane, diethyl ether, ethanol, methanol and water;
the w/v of the star topology structure polyolefin membrane material in a solvent B is 3-10%, and the unit of the w/v is g/ml;
the catalytic hydrogenation reaction time is 5-170 h;
the temperature of the catalytic hydrogenation reaction is 30-150 ℃;
the nitrogen-containing group is one of 1-methylimidazole, 2-methylimidazole, 1, 2-dimethylimidazole, N-methylmorpholine, N-methylpiperidine, N-methylpyrrolidine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine and trioctylamine;
the w/v of the casting solution is 3-10%, and the unit of the w/v is g/ml.
And (3) mixing alkali liquor in the step (2) with one or more than two of aqueous solutions of sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, calcium hydroxide, strontium hydroxide and barium hydroxide, and soaking for 24-48 h.
The hydrogenation catalyst used in the catalytic hydrogenation reaction in the step (2) is Raney nickel or palladium carbon.
The reaction time of the Shujin reaction in the step (2) is 3-120 h; the reaction temperature is 30-150 ℃.
The number of arms of the polyolefin with the star topology structure is 3-12.
The polyolefin anion exchange membrane with the star topology structure is used as an anion exchange membrane of an alkaline fuel cell.
The invention has the beneficial effects that:
(1) the polyolefin main chain with the star topological structure does not contain other heteroatoms, and is beneficial to improving the chemical stability and the mechanical strength.
(2) The hydrophilic groups of the polyolefin membrane material with the star topology structure are effectively arranged and gathered, the micro-phase separation in the membrane is promoted, a continuous ion transfer channel is constructed, and the swelling is reduced.
Drawings
FIG. 1 shows the nuclear magnetic spectrum of the brominated polymer.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) Synthesizing a star topology polyolefin main chain: under the protection of inert gas, adding isoprene (2g 29.3mmol) and 20mL cyclohexane into a reaction bottle, adding n-butyllithium (40uL 1.6M), stirring for 6h, adding p-methylstyrene (3.45g 29.3mmol), continuing stirring for 6h, adding divinylbenzene (0.028g 0.21mmol), stirring for 6h, adding methanol, and stopping the reaction; settling the reaction solution by using ethanol, separating out a solid polymer, filtering, washing and drying; obtaining the polyolefin main chain membrane material with the star topology structure.
(2) Synthesizing a star topology structure polyolefin anion exchange membrane: in a flask, 3g of star topology polyolefin main chain membrane material is dissolved in 100ml of dimethyl sulfoxide, raney nickel is added for catalysis, the reaction is carried out for 3 days at 120 ℃, ethanol is separated out, the ethanol is washed for three times, and the vacuum drying is carried out until the constant weight is achieved, so as to obtain the membrane material polymer. And dissolving the polymer in dimethyl sulfoxide, adding a bromization reagent, reacting for 48 hours, separating out ethanol, washing with ethanol for three times, and drying in vacuum until the weight is constant. Weighing 0.2g of polymer, dissolving in 10ml of dimethyl sulfoxide polymer, adding 0.5g of 1, 2-dimethyl imidazole, heating for reaction for 12 hours, settling reaction liquid by using ethanol, separating out solid polymer, filtering, washing and drying; and then preparing the polymer into a casting solution, casting the casting solution into a membrane, soaking the membrane in 1mol/L alkali liquor for 48 hours, and soaking the membrane in deionized water to be neutral to obtain the star topology structure polyolefin anion exchange membrane.
The anion-exchange membrane obtained in this example had the following structure:
tests show that the ionic conductivity of the polyolefin anion-exchange membrane with the block structure prepared in the embodiment at 20 ℃ is 30mS cm-1The water absorption rate is 32 percent, the swelling degree is 12 percent, the membrane is not obviously degraded after being soaked in 1mol/L KOH solution for 300 hours at the temperature of 60 ℃, and the membrane shows more excellent performance.
Example 2
(1) Synthesizing a star topology polyolefin main chain: under the protection of inert gas, adding isoprene (2g 29.3mmol) and 20mL of cyclohexane into a reaction bottle, adding tert-butyl lithium (40uL 1.6M), stirring for 8h, adding p-methylstyrene (2.31g 19.5mmol), continuing stirring for 8h, adding silicon tetrachloride (0.036g 0.21mmol), stirring for 8h, and adding ethanol to stop the reaction; precipitating the reaction solution by using acetone to separate out a solid polymer, filtering, washing and drying; obtaining the polyolefin main chain membrane material with the star topology structure.
(2) Synthesizing a star topology structure polyolefin anion exchange membrane: in a flask, 3g of star topology polyolefin main chain membrane material is dissolved in 100ml of N-methyl pyrrolidone, palladium carbon is added for catalysis, reaction is carried out for 4 days at 120 ℃, ethyl acetate is separated out, the ethyl acetate is washed for three times, and vacuum drying is carried out until the weight is constant, so as to obtain the membrane material polymer. And dissolving the polymer in N-methyl pyrrolidone, adding a bromization reagent, reacting for 36 hours, separating out ethyl acetate, washing the ethyl acetate for three times, and drying in vacuum until the weight is constant. Weighing 0.2g of polymer, dissolving in 10ml of N-methylpyrrolidone, adding 0.5g N-methylpiperidine, heating for reaction for 24 hours, settling reaction liquid by using ethyl acetate, separating out solid polymer, filtering, washing and drying; and then preparing the polymer into a casting solution, casting the casting solution into a membrane, soaking the membrane in 2mol/L alkali liquor for 36h, and soaking the membrane in deionized water to be neutral to obtain the star topology structure polyolefin anion exchange membrane.
The anion-exchange membrane obtained in this example had the following structure:
tests show that the ionic conductivity of the polyolefin anion-exchange membrane with the block structure prepared in the embodiment at 20 ℃ is 32mS cm-1The water absorption rate is 35 percent, the swelling degree is 15 percent, the membrane is not obviously degraded after being soaked in 1mol/L KOH solution for 300 hours at the temperature of 60 ℃, and the membrane shows more excellent performance.
Example 3
(1) Synthesizing a star topology polyolefin main chain: under the protection of inert gas, adding isoprene (2g 29.3mmol) and 20mL of cyclohexane into a reaction bottle, adding n-octyl lithium (40uL 1.6M), stirring for 10h, adding p-methylstyrene (1.48g 12.5mmol), continuing stirring for 10h, adding potassium persulfate (0.057g 0.21mmol), stirring for 10h, and adding n-propanol to stop the reaction; settling the reaction solution by using ether to separate out a solid polymer, filtering, washing and drying; obtaining the polyolefin main chain membrane material with the star topology structure.
(2) Synthesizing a star topology structure polyolefin anion exchange membrane: in a flask, 3g of polyolefin main chain membrane material with a star topology structure is dissolved in 100ml of dimethylacetamide, raney nickel is added for catalysis, the reaction lasts for 5 days at 120 ℃, dichloromethane is separated out, dichloromethane is washed for three times, and the membrane material polymer is obtained by vacuum drying to constant weight. And dissolving the polymer in dimethylacetamide, adding a bromization reagent, reacting for 24 hours, separating out dichloromethane, washing with dichloromethane for three times, and drying in vacuum until the weight is constant. Weighing 0.2g of polymer, dissolving in 10ml of dimethylacetamide, adding 0.5g N-methylmorpholine, heating for reaction for 36 hours, settling reaction liquid by dichloromethane, separating out solid polymer, filtering, washing and drying; and then preparing the polymer into a casting solution, casting the casting solution into a membrane, soaking the membrane in 3mol/L alkali liquor for 12 hours, and soaking the membrane in deionized water to be neutral to obtain the star topology structure polyolefin anion exchange membrane.
The anion-exchange membrane obtained in this example had the following structure:
tests show that the ionic conductivity of the polyolefin anion-exchange membrane with the block structure prepared in the embodiment at 20 ℃ is 38mS cm-1The water absorption rate is 36 percent, the swelling degree is 18 percent, the membrane is not obviously degraded after being soaked in 1mol/L KOH solution for 300 hours at the temperature of 60 ℃, and the membrane shows more excellent performance.
Claims (10)
1. The star topology structure polyolefin anion exchange membrane is characterized in that the structure of the star topology structure polyolefin anion exchange membrane is as follows:
wherein x/(x + y) is 0.1-0.6, and y/(x + y) is 0.4-0.9; x-Is OH-、HCO3 -、Cl-、Br-Or I-；FG+The ion-conducting functional group is 1-methylimidazolium cation, 1, 2-dimethylimidazolium cation, N-methylmorpholine quaternary ammonium salt, N-methylpiperidine quaternary ammonium salt, N-methylpyrrolidine quaternary ammonium salt, trimethyl quaternary ammonium salt, triethyl quaternary ammonium salt, tripropyl quaternary ammonium salt, triisopropyl quaternary ammonium salt, tri-N-butyl quaternary ammonium salt, trihexyl quaternary ammonium salt or trioctyl quaternary ammonium salt.
2. A preparation method of a star topology structure polyolefin anion exchange membrane is characterized by comprising the following steps:
(1) synthesizing a star topology polyolefin main chain: carrying out polymerization reaction under the protection of inert gas, adding isoprene and cyclohexane, adding organic lithium, and stirring1The method comprises the following steps of (1) taking minutes; after the reaction is finished, adding p-methylstyrene, and continuously stirring t2The method comprises the following steps of (1) taking minutes; after the reaction is finished, adding a cross-linking agent and stirring t3After minutes, adding a chain terminator to stop the reaction; settling the reaction solution by using a solvent A to separate out a solid polymer, filtering, washing and drying; obtaining a polyolefin main chain membrane material with a star topological structure;
the organic lithium is one of methyl lithium, n-butyl lithium, isobutyl lithium, tert-butyl lithium, n-hexyl lithium, n-octyl lithium and phenyl lithium;
the solvent A is one or more of acetone, methanol, ether, ethanol, ethyl acetate and water;
the chain terminator is one or a mixture of more than two of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-hexanol, cyclohexanol and n-octanol;
the cross-linking agent is divinylbenzene or silicon tetrachloride;
the molar ratio of the organic lithium to the cross-linking agent is 1: 1-1: 10;
the molar ratio of the organic lithium to the isoprene is 1: 100-1: 3000A;
the mole ratio of isoprene to p-methylstyrene is 5: 1-1: 5;
the stirring time t1Is 30-1500 min;
the stirring time t260-1500 min;
the stirring time t360-1500 min;
the w/v of the isoprene in the cyclohexane is 5-20%, and the unit of the w/v is g/ml;
the w/v of the p-methylstyrene in the cyclohexane is 5 to 20 percent, and the unit of the w/v is g/ml;
the polymerization reaction temperature is 20-50 ℃;
(2) synthesizing a star topology structure polyolefin anion exchange membrane: dissolving a star topology polyolefin main chain membrane material in a solvent B, brominating a benzyl site by catalytic hydrogenation and a bromination reagent, settling reaction liquid by using a solvent C, separating out a solid polymer, filtering, washing and drying to prepare a saturated polyolefin material modified by benzyl bromide; dissolving the prepared benzyl bromide modified saturated polyolefin in a solvent B, reacting with a nitrogen-containing group through Menshu gold, grafting an ion conducting group, settling a polymer reaction solution by using a solvent C, separating out a solid polymer, filtering, washing and drying; then preparing the obtained polymer into a casting film solution, casting the casting film solution to form a film, soaking the film in alkali liquor, and soaking the film in deionized water until the film is neutral to obtain the star topology structure polyolefin anion exchange film;
the solvent B is one of N, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone;
the solvent C is one of ethyl acetate, dichloromethane, diethyl ether, ethanol, methanol and water;
the w/v of the star topology structure polyolefin membrane material in a solvent B is 3-10%, and the unit of the w/v is g/ml;
the catalytic hydrogenation reaction time is 5-170 h;
the temperature of the catalytic hydrogenation reaction is 30-150 ℃;
the nitrogen-containing group is one of 1-methylimidazole, 2-methylimidazole, 1, 2-dimethylimidazole, N-methylmorpholine, N-methylpiperidine, N-methylpyrrolidine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine and trioctylamine;
the w/v of the casting solution is 3-10%, and the unit of the w/v is g/ml.
3. The preparation method according to claim 2, wherein the alkali solution in the step (2) is one or more of an aqueous solution of sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, calcium hydroxide, strontium hydroxide and barium hydroxide, and the soaking time is 24-48 h.
4. The process according to claim 2 or 3, wherein the hydrogenation catalyst used in the catalytic hydrogenation in step (2) is Raney nickel or palladium on carbon.
5. The preparation method according to claim 2 or 3, wherein the reaction time of the Menshujin reaction in the step (2) is 3-120 h; the reaction temperature is 30-150 ℃.
6. The preparation method according to claim 4, wherein the polymer functionalization reaction time in the step (2) is 3-120 h; the reaction temperature is 30-150 ℃.
7. The method according to claim 2, 3 or 6, wherein the number of arms of the polyolefin having the star topology is 3 to 12.
8. The method according to claim 4, wherein the number of arms of the polyolefin having the star topology is 3 to 12.
9. The method according to claim 5, wherein the number of arms of the polyolefin having the star topology is 3 to 12.
10. The star topology polyolefin anion exchange membrane of claim 1 used as an anion exchange membrane for alkaline fuel cells.
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| CN111725549A (en) * | 2020-06-24 | 2020-09-29 | 常州大学 | Polymer electrolyte membrane based on polyvinyl alcohol and preparation method thereof |
| CN111725549B (en) * | 2020-06-24 | 2021-05-25 | 常州大学 | Polymer electrolyte membrane based on polyvinyl alcohol and preparation method thereof |
| CN111793156A (en) * | 2020-07-24 | 2020-10-20 | 安徽大学 | Block anion exchange membrane and preparation method thereof |
| CN111793156B (en) * | 2020-07-24 | 2023-04-07 | 安徽大学 | Block anion exchange membrane and preparation method thereof |
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