CN112521535A - Anion exchange membrane with high alkali stability and preparation method thereof - Google Patents

Anion exchange membrane with high alkali stability and preparation method thereof Download PDF

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CN112521535A
CN112521535A CN202011501472.7A CN202011501472A CN112521535A CN 112521535 A CN112521535 A CN 112521535A CN 202011501472 A CN202011501472 A CN 202011501472A CN 112521535 A CN112521535 A CN 112521535A
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张轩
桂广辉
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Nanjing University of Science and Technology
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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    • C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
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    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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Abstract

The invention relates to a high-alkali-stability anion exchange membrane and a preparation method thereof, wherein a polymerizable monomer with an active group is synthesized through Friedel-crafts reaction, and then a polyvinyl ketone polymer is synthesized through free radical polymerization; then synthesizing a polyvinyl ketone polymer with quaternizable reactive sites through bromination reaction; then synthesizing polyvinyl polymers with different side chains through Menshutkin reaction and reduction reaction respectively, converting the polyvinyl polymers into a film through a solvent pouring method under a semi-closed condition, and performing ion exchange to obtain the side chain type polyethylene anion exchange membrane. According to the invention, by changing the side chain structure, the electron-withdrawing group is removed and long-chain branches with different lengths are introduced, so that the ion conductivity and the alkali resistance stability of the anion exchange membrane are improved.

Description

Anion exchange membrane with high alkali stability and preparation method thereof
Technical Field
The invention belongs to the technical field of anion exchange membranes, and relates to an anion exchange membrane and a preparation method thereof.
Background
Near tableOver ten years, the problems of environmental pollution and energy shortage are increasingly serious, and the development of novel clean alternative energy is urgently needed in the face of the severe environmental energy crisis when China is used as a country with large energy consumption. Unlike conventional batteries, Fuel cells (Fuel cells) are not limited by the carnot cycle, can directly convert chemical energy stored in Fuel and oxidant into electrical energy, and the only byproduct is water, which is a highly efficient and clean green energy source, thus making Fuel cells stand out of numerous ways to solve environmental and energy problems. The fuel cell is an electrochemical power generation device, isothermal and electrochemical directly converts chemical energy into electric energy without a heat engine process, so that the fuel cell has high energy conversion efficiency, no noise and no pollution, and is becoming an ideal energy utilization mode. Fuel cells are largely divided into two categories: proton Exchange Membrane Fuel Cells (PEMFCs) and Anion Exchange Membrane Fuel Cells (AEMFCs). Proton exchange membrane fuel cells, also known as polymer electrolyte membrane fuel cells, have the advantages of high energy conversion rate, high power density, low operating temperature, fast start-up, long service life, and the like, but the expensive price makes people turn their eyes to alkaline anion exchange membrane fuel cells. The anion exchange membrane is used as the core component of the AEMFC, plays the role of a catalyst support body, provides environment for electrode reaction, isolates gas or fuel, and is OH-The provision of a transmission channel has been a hot spot in the field of fuel cell research.
Currently, researches on preparing AEM by taking aromatic as a polymer main chain are more, such as polyphenyl ether, polyether ketone, polyether sulfone and the like, but hydrolysis is serious under alkaline, especially high-temperature conditions. While fully or semi-aliphatic backbones, such as polystyrene and polyethylene, have good alkali stability, but poor mechanical properties and relatively complicated synthesis methods (organometallic catalysis, radiation, etc.) still need to be solved.
Disclosure of Invention
The invention aims to provide an anion exchange membrane and a preparation method thereof, which effectively improve the ionic conductivity and the alkali resistance stability of a polymer membrane and can be used as an anion exchange membrane material.
The technical scheme of the invention is as follows: a polyethylene-based polymer M having the structure:
Figure BDA0002843612120000021
wherein p is the number of carbon atoms, and p is 0-15; n is the polymerization degree and is an integer which is more than or equal to 100 and less than or equal to 200.
The preparation method of the polyvinyl polymer M comprises the steps of synthesizing a polymerized monomer (VTK) by a Friedel-crafts reaction through the reaction of toluene and acryloyl chloride; synthesizing a polyvinyl Polymer (PVTK) using VTK by radical polymerization; then synthesizing brominated polyvinyl polymer (PVBK-Br) through bromination reaction; finally, polymers with different side chain structures are synthesized by a Moxiujin reaction, and the method comprises the following specific steps:
step 1, preparation of polymerized monomer (VTK):
slowly dripping a dichloromethane solution of acryloyl chloride into dichloromethane of toluene, adding aluminum chloride as a catalyst, reacting at 0 ℃, and extracting with dichloromethane to obtain a polymerized monomer;
step 2, polyvinyl Ketone Polymer (PVTK)n) The preparation of (1):
dissolving the dry and pure polymerized monomer in toluene, adding an initiator Azobisisobutyronitrile (AIBN), reacting at 60 ℃, and separating out after the reaction is finished to obtain a polyvinyl ketone polymer;
step 3, preparation of brominated polyvinyl ketone polymer (PVBK-Br):
mixing PVTKnDissolving N-bromosuccinamide (NBS) in tetrachloroethane, adding AIBN as an initiator, reacting at 80 ℃ to obtain a brominated polymer, and separating out to obtain a brominated polyvinyl ketone polymer;
step 4, preparation of brominated polyvinyl polymer (PAB-Br):
dissolving PVBK-Br, Triethylsilane (TES) and trifluoroacetic acid (TFA) in 1, 2-dichloroethane, and obtaining a brominated polyvinyl polymer at room temperature;
step 5, preparation of polyvinyl polymer:
and dissolving the PAB-Br and the monomer x in dimethylacetamide (DMAc), and separating out after the reaction is finished to obtain the polyvinyl polymer.
Preferably, the reaction is carried out at 60 ℃ for 2-4 hours.
Preferably, the monomer x is
Figure BDA0002843612120000031
p＝0-15。
The invention also provides a polyethylene anion exchange membrane, which is prepared by dissolving the polymer M in an organic solvent to prepare a homogeneous solution with a certain concentration; degassing the solution at 70-90 deg.C; and after degassing, pouring the solution into a clean container according to the required volume, and casting at the temperature of 70-90 ℃ by using the solution to obtain the anion exchange membrane.
Compared with the prior art, the invention has the following remarkable advantages:
(1) the invention synthesizes the anion exchange membrane with the main aliphatic chain through simple free radical polymerization reaction, and has the characteristics of simple synthesis process, uniform and compact membrane material and the like.
(2) The invention synthesizes four anion exchange membranes with different side chain structures through Friedel-crafts reaction, free radical polymerization reaction, bromination reaction and Menxiu reaction, and aims to improve the alkali stability of the anion exchange membranes by changing different side chain structures.
In summary, the invention can prepare the novel anion exchange membrane by a simple process, and meets the requirements of related fields, especially fuel cells, chlor-alkali process and other related fields.
Drawings
FIG. 1 shows the NMR spectrum of example 6.
FIG. 2 shows the NMR spectrum of example 9.
FIG. 3 is a graph of the conductivity performance of the membrane of example 12.
FIG. 4 is a graph of the base stability performance of the film of example 13.
Detailed Description
According to the polymer side chainPrinciple of degradation of radicals, OH-The attack quaternary ammonium group is mainly nucleophilic attack, so that the degradation of the quaternary ammonium group is accelerated by an electron-withdrawing group near the quaternary ammonium group. The quaternary ammonium group has a long-chain branch chain, so that the alkali stability of the anion exchange membrane can be greatly improved, and meanwhile, because the introduction of a long chain can increase the hydrophilic-hydrophobic phase separation, an ion transmission channel is better formed, and the ion conductivity of the anion exchange membrane is favorably improved. Different side chain groups are designed according to the method, and the ion conductivity and the alkali resistance stability of the anion exchange membrane are improved by removing the electron-withdrawing group and introducing the long-chain branch.
According to the invention, a double bond is introduced through a Friedel-crafts reaction, a primary polymer is generated through a free radical polymerization reaction, a bromomethyl group is introduced through a bromination reaction, and finally a quaternary ammonium type polymer is generated through a Menxiu-Au reaction. The polymers of different side chains were then converted into films by solution casting. Finally, the anion exchange membrane with ion conduction capability is obtained through ion exchange.
The synthetic route of the polyethylene-based polymer of the invention is as follows:
Figure BDA0002843612120000041
example 1 preparation of polymerized monomer (VTK):
to a 250mL three-necked flask equipped with a magnetic stirrer were added aluminum chloride (9.130g, 68.47mmol), dichloromethane (70.0mL) and toluene (5.096g, 55.307 mmol). Acryloyl chloride (4.767g, 52.668mmol) diluted with 10.0mL of methylene chloride was added from a constant pressure addition funnel. The reaction was carried out in an ice bath for 2 hours, and then transferred to a 10% hydrochloric acid solution. The organic phase was extracted repeatedly with dichloromethane, washed with deionized water until neutral, and then with anhydrous MgSO4And (5) drying.
Example 2 polyvinyl Ketone Polymer (PVTK)100) The preparation of (1):
Figure BDA0002843612120000042
dissolving the dry pure polymerized monomer in toluene, adding an initiator Azobisisobutyronitrile (AIBN), reacting at 60-70 ℃ for 2 hours, pouring the product into a methanol solution, and washing with methanol to obtain the target polymer.
Example 3 polyvinyl Ketone Polymer (PVTK)200) The preparation of (1):
Figure BDA0002843612120000043
dissolving the dry pure polymerized monomer in toluene, adding an initiator Azobisisobutyronitrile (AIBN), reacting for 4 hours at 60-70 ℃, pouring the product into a methanol solution, and washing with methanol to obtain the target polymer.
Example 4 preparation of brominated polyvinyl ketone Polymer (PVBK-Br):
Figure BDA0002843612120000051
into a three-neck flask equipped with a magnetic stirrer, PVTK was added200(2.0g, 13.41mmol), NBS (2.922g, 16.42mmol) and 1,1,2, 2-tetrachloroethane (10.0 mL). After complete dissolution of PVTK and NBS, AIBN (0.054g, 0.33mmol) was added. The reaction was held at 80 ℃ for 4 hours until a dark brown solution was obtained. After cooling to room temperature, the product was isolated in 300mL of methanol, then washed thoroughly with fresh methanol and dried under vacuum.
Example 5 preparation of brominated polyvinyl Polymer (PAB-Br):
Figure BDA0002843612120000052
to a three-necked flask equipped with a magnetic stirrer were added PVBK-Br (1.31g,5.8173mmol), TFA (43.211mL, 581.73mmol), 1.2-dichloroethane (74mL), followed by TES (9.2917mL, 58.1731 mmol). After 24 hours at 100 ℃ the product was isolated in 300mL of methanol, washed thoroughly with fresh methanol and dried under vacuum.
Example 6 preparation of a polyethylene-based Polymer (PAB-1 DMA):
Figure BDA0002843612120000053
a two-necked flask equipped with a magnetic stirrer was charged with PAB-Br (0.323g, 1.5304mmol) and DMAc (3.0 mL). After PVBK-Br was completely dissolved, aqueous TMA (0.3618g, 6.1215mmol) was added to the flask. After 24 hours of reaction at 30 ℃, the mixture was poured into a large amount of water to isolate the product. The brown polymer was then collected by filtration and dried under vacuum at 60 ℃ overnight. A polymer was obtained. FIG. 1 shows the nuclear magnetization of the polymer, demonstrating the successful synthesis of the polymer.
Example 7 preparation of a long side chain polyethylene-based polymer (PAB-4 DMA):
Figure BDA0002843612120000061
a two-necked flask equipped with a magnetic stirrer was charged with PAB-Br (0.1g,0.4738mmol) and DMAc (2.0 mL). After the PVBK-Br was completely dissolved, 4DMA (0.4g, 0.4mmol) was added to the flask. After 24 hours of reaction at 30 ℃, the mixture was poured into a large amount of water to isolate the product. The brown polymer was then collected by filtration and dried under vacuum at 60 ℃ overnight.
Example 8 preparation of a long side chain polyethylene-based polymer (PAB-8 DMA):
Figure BDA0002843612120000062
a three-necked flask equipped with a magnetic stirrer was charged with PAB-Br (0.5g,3.953mmol) and DMAc (4 mL). After the PVBK-Br was completely dissolved, 8DMA (1.25g,7.947mmol) was added, the reaction was carried out at room temperature for 48 hours, and the mixture was poured into a mixed solution of acetone and water (1:1) to precipitate, which was then washed to colorless and dried under vacuum at 60 ℃ overnight.
Example 9 preparation of a long side chain polyethylene-based polymer (PAB-12 DMA):
Figure BDA0002843612120000071
a three-necked flask equipped with a magnetic stirrer was charged with PAB-Br (0.4162g,1.9707mmol) and DMAc (3 mL). After PVBK-Br was completely dissolved, 12DMA (1.0514g,4.9268mmol) was added, the reaction was carried out at room temperature for 48 hours, and the mixture was poured into a mixed solution of acetone and water (1:1) to precipitate, which was then washed to colorless and dried under vacuum at 60 ℃ overnight. FIG. 2 shows the nuclear magnetization of the polymer, demonstrating the successful synthesis of the polymer.
Example 10 preparation of a long side chain polyethylene-based polymer (PAB-16 DMA):
Figure BDA0002843612120000072
a three-necked flask equipped with a magnetic stirrer was charged with PAB-Br (0.5g,3.953mmol) and DMAc (4 mL). After PVBK-Br was completely dissolved, 16DMA (1.25g,4.638mmol) was added, the reaction was carried out at room temperature for 48 hours, the mixture was poured into a mixed solution of acetone and water (1:1) to precipitate, which was then washed to colorless and dried under vacuum at 60 ℃ overnight.
EXAMPLE 11 preparation of five anion exchange membranes
Respectively weighing PAB-TMA, PAB-4DMA, PAB-8DMA, PAB-12DMA and PAB-16DMA, dissolving in 2mL of dimethylformamide, filtering by an organic filter head to remove impurities, and then placing the liquid at 70 ℃ for degassing; after degassing, the solution was poured into a clean container and converted into a film by solution casting at a temperature of 70 ℃. Finally, the anion exchange membrane is obtained through ion exchange.
Example 12 determination of membrane conductivity:
the resistance value of the hydroxide was estimated using an impedance analyzer in a frequency range of 0.1kHz to 100 kHz. The membrane was placed in a two-point probe conductivity cell equipped with two Pt plate electrodes. The cells were then placed in deionized water for 1 hour under different test conditions prior to each measurement. Specific membrane conductivity data are shown in figure 3.
Example 13 alkaline stability test:
the alkali stability of the membrane was evaluated by measuring its conductivity. The membrane samples were immersed in a 1M NaOH solution at 60 ℃. At fixed times per day, the membranes were removed, rinsed thoroughly with deionized water, and mounted in a mold for membrane conductivity measurements. And then the alkaline stability of different side-chain fuel cell membranes was evaluated. Specific base stability performance is shown in figure 4.
Experiments show that the conductivity of the anion exchange membrane is greatly improved due to the introduction of the long chain, and the alkali resistance stability is also greatly improved.

Claims (5)

1. A polyethylene-based polymer characterized by the structure:
Figure FDA0002843612110000011
wherein p is the number of carbon atoms, and p is 0-15; n is the polymerization degree, and n is more than or equal to 100 and less than or equal to 200.
2. The process for preparing a polyethylene-based polymer according to claim 1, comprising the specific steps of:
step 1, preparation of polymerized monomers:
slowly dripping a dichloromethane solution of acryloyl chloride into dichloromethane of toluene, adding aluminum chloride as a catalyst, reacting at 0 ℃, and extracting with dichloromethane to obtain a polymerized monomer;
step 2, preparation of polyvinyl ketone polymer:
dissolving the dry and pure polymerized monomer in toluene, adding an initiator azobisisobutyronitrile, reacting at 60 ℃, and separating out after the reaction is finished to obtain a polyvinyl ketone polymer;
step 3, preparation of brominated polyvinyl ketone polymer PVBK-Br:
dissolving polyvinyl ketone polymer and N-bromosuccinamide in tetrachloroethane, adding azobisisobutyronitrile as an initiator, reacting at 80 ℃ to obtain brominated polymer, and separating out to obtain brominated polyvinyl ketone polymer;
step 4, preparation of brominated polyvinyl polymer:
dissolving brominated polyvinyl ketone polymer, triethylsilane and trifluoroacetic acid in 1, 2-dichloroethane, and obtaining brominated polyvinyl polymer at room temperature;
step 5, preparation of polyvinyl polymer:
mixing a brominated polyvinyl polymer; and dissolving a monomer x in dimethylacetamide, and separating out after the reaction is finished to obtain the polyvinyl polymer.
3. The method of claim 2, wherein the reaction is carried out at 60 ℃ for 2 to 4 hours.
4. The method of claim 2, wherein monomer x is
Figure FDA0002843612110000012
p＝0-15。
5. A polyethylene anion exchange membrane prepared by dissolving the polymer of claim 1 in an organic solvent to form a homogeneous solution of a certain concentration; degassing the solution at 70-90 deg.C; and after degassing, pouring the solution into a clean container according to the required volume, and casting at the temperature of 70-90 ℃ by using the solution to obtain the anion exchange membrane.
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