WO2016095237A1 - N1位取代的咪唑化合物与碱性阴离子交换膜及制备 - Google Patents

N1位取代的咪唑化合物与碱性阴离子交换膜及制备 Download PDF

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WO2016095237A1
WO2016095237A1 PCT/CN2014/094471 CN2014094471W WO2016095237A1 WO 2016095237 A1 WO2016095237 A1 WO 2016095237A1 CN 2014094471 W CN2014094471 W CN 2014094471W WO 2016095237 A1 WO2016095237 A1 WO 2016095237A1
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anion exchange
exchange membrane
basic anion
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孙公权
杨丛荣
王素力
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F12/00—Homopolymers and 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 aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons
    • C08F12/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/24—Haloalkylation
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention belongs to the field of polymer compounds and basic anion exchange membranes, and in particular relates to an alkyl substituted imidazole at the N1 position and a substituted imidazole type basic anion exchange membrane at the N1 position and a preparation method thereof.
  • the alkaline anion exchange membrane fuel cell Compared with the traditional proton exchange membrane fuel cell, the alkaline anion exchange membrane fuel cell has the advantages of fast electrode reaction kinetics and weak corrosive environment, so the electrode of the alkaline anion exchange membrane fuel cell can use non-precious metal as a catalyst. The cost is greatly reduced; compared with the alkaline fuel cell, the basic anion exchange membrane fuel cell can avoid the problems of electrolyte loss and carbonation caused by the liquid electrolyte. Therefore, at present, researchers in various fields of research on basic anion exchange membrane fuel cells have devoted a lot of work. However, the basic anion exchange membrane fuel cell is not widely available for production and application.
  • the limiting factor is that the performance of the basic anion exchange membrane (especially the conductivity and stability) is far from meeting the requirements of the basic anion exchange membrane fuel cell. Therefore, the development of research on basic anion exchange membranes for fuel cells has become a hot spot and focus of researchers.
  • the functional groups used in the basic anion exchange membrane are studied more in the quaternary ammonium salt structure, and are also more in-depth.
  • the conductivity of the membrane has been greatly improved.
  • 10 -2 Scm -1 is increased to 10 -1 Scm -1 or above (see: Energy Environ. Sci., 2014, 7, 354-360; ChemSusChem 2013, 6, 1376 - 1383).
  • the first type is OH - attacking ⁇ -C, which causes quaternary ammonium group degradation by nucleophilic substitution reaction;
  • the second type is OH - ion attacking ⁇ -H, Hofmann elimination reaction occurs, resulting in functional group degradation;
  • the third type is OH - The ions attack ⁇ -H and then rearrange through Stevens and Sommelet-Hauser to cause the quaternary ammonium group to lose its ability to conduct ions.
  • the modified imidazole (especially 2-methylimidazole) is a basic anion exchange membrane that conducts OH - ion functional groups, which can maintain certain chemical stability in alkali, and other properties of the membrane are better.
  • J. Mater. Chem., 2011, 21, 12744-12724; Chem. Mater. 2013, 25, 1858-1867 showing that such membranes have certain application prospects in alkaline fuel cells.
  • imidazole-type basic anion exchange membranes with different alkyl substitutions at the N1 position has not been a related study of imidazole-type basic anion exchange membranes with different alkyl substitutions at the N1 position.
  • an object of the present invention is to provide an imidazole-type basic anion exchange membrane substituted with an alkyl group at the N1 position and a preparation method thereof.
  • R 1 is a C 1 -C 10 linear alkane
  • R 2 is a C 1 -C 9 chain alkane, or a C 3 -C 6 cycloalkane, or a phenyl group or a biphenyl group.
  • N1 substituted imidazole compound Preparation method for adding in solvent Strong base reagent and R 1 -X, after reacting for a period of time, extracting and drying the reaction solution to obtain an imidazole compound substituted at the N1 position
  • R1 is a C 1 -C 10 linear alkane
  • R 2 is a C 1 -C 9 chain alkane, or a C 3 -C 6 cycloalkane, or a phenyl group or a biphenyl group
  • It is one or two of Cl and Br.
  • the solvent is one or more selected from the group consisting of acetonitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone.
  • the strong base reagent is one or more selected from the group consisting of NaOH, KOH, NaH, KH, LiH, potassium t-butoxide, and butyl lithium.
  • the concentration in the solvent is 0.05-0.33 g/mL;
  • the mass ratio to the strong base reagent is 1:1 to 1:4;
  • the ratio of the mass of the substance to R 1 -X is 1:1 to 1:3;
  • the reaction temperature is 0 ° C to 75 ° C; and the reaction time is not less than 12 h.
  • the extraction process is carried out using one of ethyl acetate, diethyl ether, n-hexane, and n-pentane.
  • a basic anion exchange membrane comprising a halomethylated polymer backbone and a molecular formula An alkyl substituted alkyl imidazole branch at the N1 position;
  • the polymer main chain is one of polyether sulfone, polyether ketone, polyphenylene sulfone, polystyrene, polyaryl ether sulfone ketone, polyphenylene ether; the alkyl group substituted imidazole at the N1 position
  • R 1 is a C 1 -C 10 linear alkane
  • R 2 is a C 1 -C 9 chain alkane, or a C 3 -C 6 cycloalkane, either a phenyl group or a biphenyl group.
  • the N3 position is linked to the methylene group of the halomethylated polyethersulfone, polyether ketone, polyphenylene sulfone, polyaryl ether sulfone ketone, polyphenylene ether, and the methylene group after removal of the halogen element; or
  • the methylene group after removal of the halogen element in the N3 position and the para-halomethylated polystyrene is bonded by a CN chemical bond.
  • a preparation method of the basic anion exchange membrane comprising the following steps,
  • R 1 is a C 1 -C 10 linear alkane
  • R 2 is a C 1 -C 9 chain alkane, or a C 3 -C 6 cycloalkane, or a phenyl group or a biphenyl group
  • X is one or two of Cl, Br;
  • halomethylated polymer backbone a high molecular polymer, a halomethylating agent and a catalyst are added to a second solvent and reacted at a temperature below 20 ° C for a period of time and then mixed with a third solvent to precipitate a polymerization.
  • N1-position alkyl-substituted imidazole-type anion exchange membrane adding the halomethylated high molecular polymer obtained in the step (2) and the N1-position alkyl-substituted imidazole obtained in the step (1) to the fourth solvent, stirring and After the reaction for a while, the mixture was filtered, and the obtained transparent solution was cast by a solvent evaporation method to obtain an N1-position alkyl-substituted imidazole-type basic anion exchange membrane.
  • the method further comprises the step of subjecting the obtained N1-position alkyl-substituted imidazole-type basic anion exchange membrane to a potassium hydroxide or sodium hydroxide solution for a period of time for ion exchange.
  • the total concentration of the potassium hydroxide and/or sodium hydroxide is from 0.1 to 3 mol/L; and the solution temperature is from room temperature to 40 °C.
  • the step (1) further comprises the steps of extracting and drying the obtained N1-position alkyl substituted imidazole solution
  • the step (2) further includes a step of obtaining a halomethylated polymer and then washing it with one or more of water, methanol, ethanol, isopropanol, and acetone.
  • the first solvent in the step (1) is acetonitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, One or more of N-methylpyrrolidone;
  • the strong base reagent is one or more selected from the group consisting of NaOH, KOH, KH, NaH, LiH, potassium t-butoxide, and butyl lithium;
  • the concentration in the first solvent is 0.05-0.33 g/mL;
  • the mass ratio to the strong base reagent is 1:1 to 1:4;
  • the ratio of the mass to the mass of R 1 -X is 1:1 to 1:3.
  • the catalyst in the step (2) is one or more of anhydrous tin tetrachloride, zinc chloride, trifluoroacetic acid and concentrated sulfuric acid;
  • the halogen methylation reagent is chloromethyl ether and chloromethylbutyl One or more of ether, chloromethyl hexyl ether, 1,4-dichloromethoxybutane, and N-bromosuccinimide;
  • the second solvent in the step (2) is concentrated sulfuric acid, carbon tetrachloride, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, dichloromethane, chloroform, dichloro One or more of ethane;
  • the third solvent is one or more of water, methanol, ethanol, isopropanol, acetone;
  • the mass of the high molecular polymer added to the second solvent in the step (2) is 0.017-0.067 g/mL; the mass ratio of the polymer to the catalyst added is 200:1 to 1:5; The volume ratio of the mass of the polymer to be added to the halomethylating agent is from 1:1 to 1:10.
  • the fourth solvent in the step (3) is one or more of dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone; and the fourth solvent is added.
  • the mass of the halomethylated polymer is 0.02-0.067 g/mL; the mass ratio of the halomethylated polymer to the alkyl substituted imidazole at the N1 position in the step (3) is 10:1 to 1:2.
  • the organic reagent used in the extraction process is one of ethyl acetate, diethyl ether, n-hexane, and n-pentane.
  • the reaction temperature in the step (1) is from 0 ° C to 75 ° C; and the reaction time is not less than 12 h.
  • the reaction time described in the step (2) is not less than 0.5 h.
  • the reaction temperature in the step (3) ranges from room temperature to 90 ° C; the reaction time is not less than 12 h; the casting film temperature is 40-70 ° C, and the casting time is not less than 4 h.
  • the N1-position alkyl-substituted imidazole, the N1-position alkyl-substituted imidazole-type basic anion exchange membrane and the preparation method thereof have the following advantages:
  • the prepared N1-position alkyl-substituted imidazole compound has good stability, non-toxicity, moderate molecular weight, and easy OH - conduction;
  • the prepared N1-position alkyl-substituted imidazole-type basic anion exchange membrane has a uniform, smooth and compact surface, and the conductivity of the N1-position alkyl-substituted imidazole-type anion exchange membrane film in deionized water is >15 mS/cm at 60 ° C, It shows that such membranes have good ability to conduct ions;
  • the prepared N1-position alkyl-substituted imidazole-type basic anion exchange membrane has good thermodynamic stability, and its glass transition temperature is above 150 ° C, which can satisfy the operating temperature of the battery;
  • the prepared N1-position alkyl-substituted imidazole-type basic anion exchange membrane has good mechanical strength, and the tensile strength is above 40 MPa, which is higher than the tensile strength of the commercial Nafion-117 membrane;
  • Figure 1 is a dynamic thermodynamic analysis curve (DMA) of the chloromethylated polyether ketone obtained in Examples 1 and 2;
  • Example 3 is a N1-methyl-2-methylimidazole type polyether ketone basic anion exchange membrane obtained in Example 1 in deionized water. The conductivity of the curve as a function of temperature;
  • Example 4 is a dynamic thermodynamic analysis curve (DMA) of the N1-methyl-2-methylimidazole type polyether ketone basic anion exchange membrane obtained in Example 1;
  • DMA dynamic thermodynamic analysis curve
  • Figure 5 is a graph showing the conductivity versus temperature of a N1-mercapto-2-isopropylimidazole type polyetherketone basic anion exchange membrane in deionized water of Example 2;
  • Figure 6 is a schematic diagram showing the chemical structure of N1-hexyl-2-butylimidazole type polystyrene
  • Figure 7 is a graph showing the conductivity versus temperature of the N1-hexyl-2-butylimidazole type polystyrene basic anion exchange membrane of Example 3;
  • Figure 8 is a graph showing the conductivity versus temperature of the N1-octyl-2-methylimidazole type basic anion exchange membrane of Example 4.
  • Figure 9 is a graph showing changes in conductivity, size, and ion exchange capacity (IEC) values of the N1-octyl-2-methylimidazole-type basic anion exchange membrane of Example 4 before and after immersion in 1 M KOH at 60 °C;
  • IEC ion exchange capacity
  • Figure 10 is a discharge curve of the assembly of a single cell using an N1-octyl-2-methylimidazole type basic anion exchange membrane in Example 4;
  • Figure 11 is a chemical structural formula of an imidazole-type basic anion exchange membrane substituted with a halogenated methylated polyphenylene ether as a main chain at the N1 position;
  • Figure 12 is a chemical structural formula of an imidazole-type basic anion exchange membrane substituted with a halogenated methylated polyethersulfone as a main chain at the N1 position;
  • Figure 13 is a chemical structural formula of an imidazole-type basic anion exchange membrane substituted with a halogenated methylated polyphenylenesulfone as a main chain at the N1 position;
  • Fig. 14 is a chemical structural formula of an imidazole-type basic anion exchange membrane substituted with a halogenated methylated polyaryl ether sulfone ketone as a main chain at the N1 position.
  • the mechanical strength test of the 1,2-dimethylimidazole type polyether ketone as the main chain film was carried out by TA Corporation's Q800.
  • the stretch mode was chosen using a linear stretch rate of 5%.
  • Thermodynamic dynamic analysis was performed using TA's DMA test.
  • the heating rate is 3 ° C min -1 and the temperature range is from room temperature to 350 ° C.
  • the frequency is 1 Hz and the amplitude used is 20 ⁇ m. It can be seen from the data structure analysis of Fig. 4 and Table 5 that the mechanical strength and thermodynamic properties of such films are good.
  • the conductivity of the basic anion exchange membrane of the 1,2-dimethylimidazole type polyether ketone as the main chain was tested by an alternating current impedance method.
  • the formula for calculating the conductivity is:
  • ⁇ is the conductivity (S/cm) of the film
  • L is the distance between the two electrodes (cm)
  • W is the width (cm) of the film
  • T is the thickness (cm) of the film
  • R is the resistance of the film ( ⁇ ).
  • Fig. 2 is a schematic view showing the chemical structure of a polymer of the N1-methyl-2-methylimidazole type polyether ketone obtained in Example 1 as a main chain.
  • Fig. 3 is a graph showing the electrical conductivity of a film cast from a polymer of the N1-methyl-2-methylimidazole type polyether ketone obtained in Example 1 as a main chain in deionized water as a function of temperature.
  • the abscissa is the temperature (°C)
  • the ordinate is the conductivity (mScm -1 ); as shown in Fig. 3, the conductance of the film of the N1-methyl-2-methylimidazole type polyether ketone as the main chain The rate varies significantly with temperature.
  • DMA dynamic thermodynamic analysis curve
  • the abscissa is the temperature (°C)
  • the ordinate on the left side is the storage modulus (MPa)
  • the ordinate on the right side is the loss modulus (MPa).
  • the temperature corresponding to the peak in the loss modulus curve is the glass transition temperature of the film. From the results of dynamic thermodynamic analysis, the initial storage modulus of this type of film can reach 1950MPa, and the glass transition temperature is above 200 °C, indicating that its thermodynamic performance is better, which can meet the requirements of fuel cell working conditions.
  • Table 1 is a comparison of the mechanical strength of the film of the N1-methyl-2-methylimidazole type polyether ketone obtained in Example 1 as a main chain with the commercial Nafion-117 film. It can be found from the table that although the elongation at break of the film is much lower than the value of the commercial Nafion film, the tensile strength and elastic modulus are greater than those of the commercial Nafion film, indicating that the film has poor elasticity, but mechanical The strength is better.
  • the conductivity of the basic anion exchange membrane having the 1-mercapto-2-isopropyl imidazole type polyether ketone as the main chain was also tested by the alternating current impedance method. It can be seen from the test results that the conductivity of such a film changes with temperature similarly to the change of the conductivity of the film in Example 1, and the change in conductivity is relatively large when the temperature is raised from 25 ° C to 60 ° C.
  • the conductivity of such a film is smaller than that of the film of Example 1, and the reason is that the addition of a long substituent increases the molecular weight of the polymer and lowers the ion exchange capacity (i.e., IEC value) of the film, while the film
  • the ion exchange capacity is closely related to the conductivity of the membrane. Off, so the ionic conductivity of the membrane is lowered.
  • Figure 1 is a dynamic thermodynamic analysis curve (DMA) of the chloromethylated polyether ketone obtained in Examples 1 and 2.
  • DMA dynamic thermodynamic analysis curve
  • the abscissa is the temperature (°C)
  • the ordinate on the left side is the storage modulus (MPa)
  • the ordinate on the right side is the loss modulus (MPa).
  • the temperature corresponding to the peak in the loss modulus curve is the glass transition temperature of the polymer. From the results of dynamic thermodynamic analysis, the glass transition temperature of chloromethylated polyether ketone is above 150 °C, indicating that its thermodynamic properties are good and can meet the requirements of fuel cell operating conditions.
  • Figure 5 is a graph showing the conductivity versus temperature of a film of N1-mercapto-2-isopropylimidazole type polyether ketone as the main chain in Example 2 in deionized water.
  • the abscissa is the temperature (°C)
  • the ordinate is the conductivity (mScm -1 ); as can be seen from Fig. 5, the conductivity of such a film changes with temperature, but the change trend does not have a N1 position as a methyl group. The trend of change is obvious, indicating that its conductivity is not affected by temperature, probably because its mechanism of conducting ions is different from that of N1.
  • Fig. 6 is a schematic diagram showing the chemical structure of a polymer of N1-hexyl-2-butylimidazole type polystyrene as a main chain in Example 3.
  • Fig. 7 is a graph showing the electrical conductivity versus temperature of a film cast from a polymer of N1-hexyl-2-butylimidazole type polystyrene as a main chain in Example 3.
  • the abscissa is the temperature (°C)
  • the ordinate is the conductivity (mScm -1 ); as can be seen from Fig. 8, when the temperature is raised from 40 ° C to 60 ° C, the conductivity of the film changes significantly, possibly It is the increase in temperature that causes the internal phase structure of the membrane to change, so that the way in which ions are conducted changes, and the conductivity changes accordingly.
  • the synthesis process of 1-octyl-2-methylimidazole type polymer is as follows: adding 0.5 g of chloromethylated polystyrene to 10 mL of dimethyl sulfoxide, dissolving it at 60 ° C and adding 0.3 g of 1-octine Base-2-methylimidazole, magnetically stirred at 80 ° C for 24 h. The reaction solution was returned to room temperature for filtration, dried in a blast oven at 50 ° C for 2 h, and dried at 70 ° C overnight to cast a film. The prepared membrane was thoroughly washed with deionized water and stored in sealed deionized water for testing.
  • the basic anion exchange membrane of the 1-octyl-2-methylimidazole type polystyrene as a main chain was subjected to conductivity test. At room temperature, the conductivity of such membranes in deionized water is 11.1 mScm -1 , which can meet the requirements of fuel cells.
  • the basic anion exchange membrane of the 1-octyl-2-methylimidazole type polystyrene as a main chain was subjected to a thermal alkali stability test.
  • the chemical stability of the membrane was examined by measuring the change in conductivity, size and ion exchange capacity of the membrane before and after alkali treatment. It can be seen from the data analysis that the conductivity, size and ion exchange capacity of these membranes remain basically unchanged before and after alkali treatment, indicating that the stability of such membranes in hot alkali is good.
  • the prepared basic anion exchange membrane of 1-octyl-2-methylimidazole type polystyrene as a main chain was assembled into a single cell for testing.
  • the anode used was a PtRu/C catalyst having a metal loading of 2.6 mg cm-2
  • the cathode was a Pt/C catalyst having a metal loading of 2 mg cm-2.
  • the ionomers used in the anode and the anode are Nafion and 1-octyl-2-methylimidazole type polystyrene as the main chain polymer, and the mass fraction is 20%.
  • the instrument used for the test was Arbin's fuel cell test system.
  • the test temperature was 60 ° C
  • the anode feed was 1 M MeOH + 1 M KOH
  • the flow rate was 1 mL min -1
  • the cathode was oxygen and the flow rate was 80 sccm.
  • the single cell discharge data shows that the single cell assembled with such a membrane as a solid electrolyte has better performance (power density up to 44 mWcm -2 ).
  • Figure 8 is a graph showing the electrical conductivity as a function of temperature for the N1-octyl-2-methylimidazole-type basic anion exchange membrane of Example 4.
  • the abscissa is the temperature (°C)
  • the ordinate is the conductivity (mScm -1 ); as can be seen from Fig. 8, the conductivity of the film at room temperature is >10 mScm -1 , which can satisfy the alkaline fuel cell. Test requirements.
  • Figure 9 is a graph showing the changes in conductivity, size, and ion exchange capacity (IEC) values of the N1-octyl-2-methylimidazole-type basic anion exchange membrane of Example 4 before and after immersion in 1 M KOH at 60 °C. It can be seen from Fig. 9 that the conductivity, size and IEC value of the film have no obvious change before and after the hot alkali treatment, indicating that the film has good stability in the hot alkali and can satisfy the basic anion exchange with the alkaline fuel cell. The requirements for chemical stability of the membrane indicate that such membranes have certain application prospects in alkaline fuel cells.
  • IEC ion exchange capacity
  • Figure 10 is a graph showing the discharge of a single cell in which a N1-octyl-2-methylimidazole type basic anion exchange membrane was assembled in Example 4.
  • the abscissa is the current density (mAcm -2 )
  • the left ordinate is the potential (V)
  • the right ordinate is the power density (mWcm -2 ). It can be seen from Fig.
  • N1-octyl-2-methylimidazole basic anion exchange membrane is a solid electrolyte assembled single cell with a high open circuit voltage >0.8V, indicating that the noble metal is used as a catalyst, N1-octyl-2 -
  • the methylimidazole type basic anion exchange membrane has a small polarization of the single cell assembled by the solid electrolyte; at the same time, the maximum power density of the single cell is close to 44 mWcm -2 , and the corresponding current density is 121 mAcm -2 .
  • the field of alkaline direct methanol is relatively high, indicating that such membranes have good application value in alkaline fuel cells.

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Abstract

一种N1位取代的咪唑化合物，其中R 1为C 1-C 10的直链烷烃；R 2为C 1-C 9的链状烷烃，或为C 3-C 6的环烷烃，或为苯基、或为联苯基。一种碱性阴离子交换膜及其制备方法，包括卤甲基化的高分子聚合物主链和分子式为的N1位烷基取代的咪唑支链；所述高分子聚合物主链为聚醚砜、聚醚酮、聚亚苯基砜、聚苯乙烯、聚芳醚砜酮、聚苯醚中的一种。所述N1位烷基取代咪唑可在碱性燃料电池中应用。

Description

N1位取代的咪唑化合物与碱性阴离子交换膜及制备 技术领域
本发明属于高分子化合物领域和碱性阴离子交换膜领域，具体的说涉及N1位烷基取代咪唑和N1位烷基取代咪唑型碱性阴离子交换膜及制备方法。
背景技术
相比于传统的质子交换膜燃料电池，碱性阴离子交换膜燃料电池具有电极反应动力学快，腐蚀环境较弱等优势，所以碱性阴离子交换膜燃料电池的电极就可以采用非贵金属作为催化剂，大大降低了成本；而与碱性燃料电池相比，碱性阴离子交换膜燃料电池又可以避免液体电解质引起的电解质流失以及碳酸盐化等问题。所以目前关于碱性阴离子交换膜燃料电池的研究各领域科研工作者倾注了大量的工作。然而，碱性阴离子交换膜燃料电池尚不能大范围内生产、应用的限制因素为碱性阴离子交换膜的性能(尤其是电导率以及稳定性)还远不能满足碱性阴离子交换膜燃料电池的要求，因此开发研究燃料电池用碱性阴离子交换膜成为了研究者关注的热点与重点。
目前，碱性阴离子交换膜中所采用的官能团以季铵盐结构研究的较多，而且也比较深入。通过研究者对季铵盐型碱性阴离子交换膜的深入研究与改进(包括增加IEC值、改变膜的相分离结构等方式)，目前这种膜的电导率有了很大程度的提高，从10-2Scm-1提升到了10-1Scm-1或以上(参见：Energy Environ.Sci.,2014,7,354–360；ChemSusChem 2013,6,1376–1383)。然而季铵基团在碱中的化学稳定性仍存在一定的问题。有研究者认为季铵盐型官能团在高温、高浓度碱条件下处理化学性质不稳定，容易被OH-离子攻击，从而发生降解，通常认为季铵基团的降解分为三类。第一类是OH-攻击α-C，发生亲核取代反应造成季铵基团的降解；第二类是OH-离子攻击β-H，发生Hofmann消除反应，从而造成官能团降解；第三类是OH-离子攻击α-H，然后通过Stevens和Sommelet-Hauser重排从而造成季铵基团失去传导离子的能力。最近有人提出了一些可取代季铵盐官能团的基团，比如胍基(参见：Chem.Commun.2010,46,7495–7497)、哌嗪(参见：J.Mater.Chem.,2011,21,6158–6160)、金属阳离子型(参见：J.Am.Chem.Soc.2012,134,4493-4496)、季膦型(参见：J.Am.Chem.Soc.2012,134,18161-18164)、咪唑型(参见：Macromolecules 2014,47,208-216)等。其中以咪唑型为官能团的研究最多。而且目前的研究结果表明以修饰的咪唑(尤其是2-甲基咪唑)为传导OH-离子官能团的碱性阴离子交换膜在碱中能够保持一定的化学稳定性，而且膜的其他性能也较好(J.Mater.Chem.,2011,21,12744–12752；Chem.Mater.2013,25,1858-1867)，显示这类膜在碱性燃料电池中具有一定的应用前景。然而，还没有出现在N1位上进行不同烷基取代的咪唑型碱性阴离子交换膜的相关研究。
发明内容
针对现有技术存在的问题，本发明的目的在于提供一种N1位烷基取代的咪唑型碱性阴离子交换膜及其制备方法。
一种N1位取代的咪唑化合物R1为C1-C10的直链烷烃；R2为C1-C9的链状烷烃，或为C3-C6的环烷烃，或为苯基、或为联苯基。
所述N1位取代的咪唑化合物
Figure PCTCN2014094471-appb-000002
的制备方法，为于溶剂中加入
Figure PCTCN2014094471-appb-000003
强碱试剂和R1-X，反应一段时间后对反应溶液进行萃取并干燥，得N1位取代的咪唑化合物
Figure PCTCN2014094471-appb-000004
其中，R1为C1-C10的直链烷烃；R2为C1-C9的链状烷烃，或为C3-C6的环烷烃，或为苯基、或为联苯基；X为Cl，Br中的一种或两种。
所述溶剂为乙腈、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮中的一种或两种以上。
所述强碱试剂为NaOH、KOH、NaH、KH、LiH、叔丁醇钾、丁基锂中的一种或两种以上。
所述
Figure PCTCN2014094471-appb-000005
于溶剂中的浓度为0.05-0.33g/mL；所述
Figure PCTCN2014094471-appb-000006
与强碱试剂的物质量比为1:1-1:4；所述
Figure PCTCN2014094471-appb-000007
与R1-X的物质量之比为1:1～1:3；所述反应温度为0℃-75℃；所述反应时间不小于12h。
所述萃取过程采用乙酸乙酯、乙醚、正己烷、正戊烷中的一种进行。
一种碱性阴离子交换膜，包括卤甲基化的高分子聚合物主链和分子式为
Figure PCTCN2014094471-appb-000008
的N1位烷基取代的咪唑支链；
所述高分子聚合物主链为聚醚砜、聚醚酮、聚亚苯基砜、聚苯乙烯、聚芳醚砜酮、聚苯醚中的一种；所述N1位烷基取代的咪唑中R1为C1-C10的直链烷烃；R2为C1-C9的链状烷烃，或为C3-C6的环烷烃，或为苯基、或为联苯基。
所述碱性阴离子交换膜中，
Figure PCTCN2014094471-appb-000009
的N3位与卤甲基化的聚醚砜、聚醚酮、聚亚苯基砜、聚芳醚砜酮、聚苯醚中去掉卤元素后的亚甲基以C-N化学键连接；或
Figure PCTCN2014094471-appb-000010
的N3位与对位卤甲基化的聚苯乙烯中去掉卤元素后的亚甲基以C-N化学键连接。
一种所述碱性阴离子交换膜的制备方法，包括以下步骤，
(1)N1位烷基取代咪唑的合成：于第一溶剂中加入
Figure PCTCN2014094471-appb-000011
强碱试剂和R1-X反应一段时间后得N1位烷基取代咪唑溶液；
其中，R1为C1-C10的直链烷烃；R2为C1-C9的链状烷烃，或为C3-C6的环烷烃，或为苯基、或为联苯基；X为Cl，Br中的一种或两种；
(2)卤甲基化高分子聚合物主链的制备：于第二溶剂中加入高分子聚合物、卤甲基化试剂和催化剂并于20℃以下反应一段时间后与第三溶剂混合析出聚合物，即得卤甲基化高分子聚合物；
(3)N1位烷基取代咪唑型阴离子交换膜的制备：于第四溶剂中加入步骤(2)所得卤甲基化高分子聚合物和步骤(1)所得N1位烷基取代咪唑，搅拌并反应一段时间后过滤，对得到的透明溶液采用溶剂挥发法铸膜，得N1位烷基取代咪唑型碱性阴离子交换膜。
所述方法还包括将所得N1位烷基取代咪唑型碱性阴离子交换膜置于氢氧化钾或氢氧化钠溶液中浸泡一段时间进行离子交换的步骤。所述的氢氧化钾和/或氢氧化钠的总浓度为0.1-3mol/L；所述溶液温度为室温-40℃。
所述步骤(1)还包括对得到的N1位烷基取代咪唑溶液进行萃取并干燥的步骤；
所述步骤(2)还包括得到卤甲基化高分子聚合物后采用水、甲醇、乙醇、异丙醇、丙酮中的一种或两种以上进行清洗的步骤。
步骤(1)中所述第一溶剂为乙腈、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、 N-甲基吡咯烷酮中的一种或两种以上；所述强碱试剂为NaOH、KOH、KH、NaH、LiH、叔丁醇钾、丁基锂中的一种或两种以上；
步骤(1)中所述
Figure PCTCN2014094471-appb-000012
于第一溶剂的中的浓度为0.05-0.33g/mL；所述
Figure PCTCN2014094471-appb-000013
与强碱试剂的物质量比为1:1-1:4；所述
Figure PCTCN2014094471-appb-000014
与R1-X的物质量之比为1:1～1:3。
步骤(2)所述催化剂为无水四氯化锡、氯化锌、三氟乙酸、浓硫酸中的一种或两种以上；所述卤甲基化试剂为氯甲醚、氯甲基丁醚、氯甲基己醚、1,4-二氯甲氧基丁烷、N-溴代丁二酰亚胺中的一种或两种以上；
步骤(2)所述第二溶剂为浓硫酸、四氯化碳、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮、二氯甲烷、氯仿、二氯乙烷中的一种或两种以上；所述第三溶剂为水、甲醇、乙醇、异丙醇、丙酮中的一种或两种以上；
步骤(2)中于第二溶剂中加入所述高分子聚合物的质量为0.017-0.067g/mL；所述加入的高分子聚合物与催化剂的质量比为200:1-1:5；所述加入的高分子聚合物的质量与卤甲基化试剂的体积比为1:1-1:10。
步骤(3)所述第四溶剂为二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮中的一种或两种以上；于第四溶剂中加入所述卤甲基化聚合物的质量为0.02-0.067g/mL；步骤(3)中所述卤甲基化聚合物与N1位烷基取代咪唑的质量之比为10:1-1:2。
所述萃取过程采用的有机试剂为乙酸乙酯、乙醚、正己烷、正戊烷中的一种。
步骤(1)所述反应温度为0℃-75℃；反应时间为不小于12h。
步骤(2)所述的反应时间不小于0.5h。
步骤(3)中所述反应温度范围为室温-90℃；所述反应时间为不小于12h；所述的铸膜温度为40-70℃,所述铸膜时间不小于4h。
本发明所述N1位烷基取代咪唑、N1位烷基取代咪唑型碱性阴离子交换膜及制备方法具有如下优点：
1)制备方法环境友好，工艺简单；
2)制备得到的N1位烷基取代咪唑化合物具有稳定性好、无毒、分子量适中，易于OH-传导；
2)制备得到的N1位烷基取代咪唑型碱性阴离子交换膜表面均匀、平滑、紧凑，在60℃，去离子水中N1位烷基取代咪唑型阴离子交换膜膜的电导率>15mS/cm，表明这类膜具备较好的传导离子的能力；
3)制备得到的N1位烷基取代咪唑型碱性阴离子交换膜具有较好的热力学稳定性，其玻璃态转化温度在150℃以上，能够满足电池是工作温度；
4)制备得到的N1位烷基取代咪唑型碱性阴离子交换膜具有较好的机械强度，其抗拉强度在40MPa以上，高于商品的Nafion-117膜的抗拉强度；
5)将制备得到的N1位烷基取代咪唑型碱性阴离子交换膜组装成单池进行测试，在碱性直接甲醇燃料电池中的最大功率密度可达到40mWcm-2，表明这类碱性阴离子交换膜在碱性燃料电池中具有良好的应用价值。
附图说明
图1为实施例1、2所得的氯甲基化聚醚酮的动态热力学分析曲线(DMA)；
图2为以卤甲基化的聚醚酮为主链的N1位烷基取代的咪唑型碱性阴离子交换膜的化学结构式；
图3为实施例1所得的N1-甲基-2-甲基咪唑型聚醚酮碱性阴离子交换膜在去离子水 中的电导率随温度变化曲线；
图4为实施例1所得的N1-甲基-2-甲基咪唑型聚醚酮碱性阴离子交换膜的动态热力学分析曲线(DMA)；
图5是实施例2中N1-癸基-2-异丙基咪唑型聚醚酮碱性阴离子交换膜在去离子水中电导率随温度变化曲线；
图6是N1-己基-2-丁基咪唑型聚苯乙烯的化学结构简图；
图7是实施例3中N1-己基-2-丁基咪唑型聚苯乙烯碱性阴离子交换膜的电导率随温度变化曲线；
图8是实施例4中N1-辛基-2-甲基咪唑型碱性阴离子交换膜的电导率随温度变化曲线；
图9是实施例4中N1-辛基-2-甲基咪唑型碱性阴离子交换膜的电导率、尺寸及离子交换容量(IEC)值在60℃的1M KOH中浸泡前后的变化曲线；
图10是实施例4中采用N1-辛基-2-甲基咪唑型碱性阴离子交换膜组装单池进行测试的放电曲线；
图11以卤甲基化的聚苯醚为主链的N1位烷基取代的咪唑型碱性阴离子交换膜的化学结构式；
图12以卤甲基化的聚醚砜为主链的N1位烷基取代的咪唑型碱性阴离子交换膜的化学结构式；
图13以卤甲基化的聚亚苯基砜为主链的N1位烷基取代的咪唑型碱性阴离子交换膜的化学结构式；
图14以卤甲基化的聚芳醚砜酮为主链的N1位烷基取代的咪唑型碱性阴离子交换膜的化学结构式。
具体实施方式
实施例1
于50mL CCl4中加入2g聚醚酮聚合物，40℃冷凝循环磁力搅拌使之溶解。在冰水浴的条件下，加入0.5g三氟乙酸，搅拌10min后，慢慢滴入10mL氯甲醚，15～17℃搅拌4h。将反应物倒入无水乙醇中析出固体，得到氯甲基化聚醚酮聚合物，然后用乙醇充分洗涤后用去离子水洗涤多次，40℃真空干燥待用。于10mL二甲基乙酰胺中加入0.5g氯甲基化聚醚酮聚合物，70℃磁力搅拌使之溶解后加入0.096g 1,2-二甲基咪唑，70℃磁力搅拌反应24h。待反应液恢复至室温过滤，50℃鼓风干燥箱内采用挥发溶剂的方法铸膜。将制备好的膜用去离子水充分洗涤后，在密封的去离子水中保存。
对1,2-二甲基咪唑型聚醚酮为主链膜的机械强度测试采用的是TA公司的Q800。选择的是拉伸模式，采用的是5％的线性拉伸速率。热力学动态分析采用的是TA公司的DMA测试。升温速率为3℃min-1，温度范围为室温～350℃。频率为1Hz，采用的振幅为20μm。从图4和表5的数据结构分析可以看出，这类膜的机械强度和热力学性能较好。
对所述1,2-二甲基咪唑型聚醚酮为主链的碱性阴离子交换膜电导率采用交流阻抗法进行测试。电导率的计算公式为：
Figure PCTCN2014094471-appb-000015
式中б为膜的电导率(S/cm),L为两电极之间的距离(cm)，W为膜的宽度(cm)，T为膜的厚度(cm)，R为膜的电阻(Ω)。
测试前将Cl-型碱性阴离子交换膜剪一长方形(1*4cm2)膜样品夹于带有银丝的聚四氟乙烯模具中间，将其放入去离子水中平衡后测量交流阻抗。实验仪器采用SolartronAC1260阻抗分析仪和1287电化学工作站，扫描频率范围为1-106Hz。对膜的电导率进 行多次测量取平均值。在去离子水中，当温度从25℃升到60℃时，碱性阴离子交换膜电导率变化比较明显(从5.7mScm-1增加到13.5mScm-1)，原因可能是温度的升高改变了膜的微观结构，从而改变了离子的传输途径，从而使得电导率提高。
表1N1-甲基-2-甲基咪唑型聚醚酮碱性阴离子交换膜与商品Nafion-117膜机械强度对比
Figure PCTCN2014094471-appb-000016
图2为实施例1所得的N1-甲基-2-甲基咪唑型聚醚酮为主链的聚合物的化学结构简图。
图3为实施例1所得的N1-甲基-2-甲基咪唑型聚醚酮为主链的聚合物铸成的膜在去离子水中的电导率随温度变化曲线。在图3中，横坐标为温度(℃)，纵坐标为电导率(mScm-1)；由图3可知，N1-甲基-2-甲基咪唑型聚醚酮为主链的膜的电导率随温度变化比较明显。
图4为实施例1所得的N1-甲基-2-甲基咪唑型聚醚酮为主链的膜的动态热力学分析曲线(DMA)。在图4中，横坐标为温度(℃)，左边一侧纵坐标为储存模量(MPa)，右边一侧纵坐标为损失模量(MPa)。其中，损失模量曲线中的峰值对应的温度为膜的玻璃态转化温度。从动态热力学分析结果可知，这类膜的起始储存模量能达到1950MPa，而且玻璃态转化温度在200℃以上，说明其热力学性能较好，能满足燃料电池工况的要求。
表1为实施例1所得的N1-甲基-2-甲基咪唑型聚醚酮为主链的膜的机械强度与商品Nafion-117膜的对比数据。从表中可以发现此类膜虽然断裂伸长率要远低于商品Nafion膜的值，但其抗拉强度与弹性模量要大于商品Nafion膜的值，说明这类膜弹性较差，但机械强度比较好。
实施例2
于80mL CCl4中加入2g聚醚酮聚合物，60℃冷凝循环磁力搅拌使之溶解。在冰水浴的条件下，加入10g四氯化锡，然后慢慢滴入10mL1,4-二氯甲氧基丁烷，15℃反应7h。将反应物倒入去离子水中析出固体，得到氯甲基化聚醚酮聚合物，然后用去离子水充分洗涤，45℃真空干燥待用。于10mL乙腈中加入4g(约40mmol)2-异丙基咪唑，磁力搅拌使其溶解。在冰水浴的条件下，加入4g 60％NaH/煤油固体(100mmol)，搅拌10min后加入17.2mL(约72mmol)溴代正癸烷，室温下搅拌过夜。将反应液倒入水中，然后用乙酸乙酯萃取分离，得上层有机物，将有机物用无水MgSO4干燥后采用柱层析色谱进行分离纯化得到1-癸基2-异丙基咪唑，最后将其置于常温氮气箱中待用。于10mL二甲基乙酰胺中加入0.5g氯甲基化聚醚酮聚合物，70℃磁力搅拌使之溶解后加入0.28g(1mmol)1-癸基-2-异丙基咪唑，70℃磁力搅拌反应24h。待反应液恢复至室温过滤，40℃鼓风干燥箱内干燥4h，70℃干燥过夜进行铸膜。将制备好的膜用去离子水充分洗涤后，在密封的去离子水中保存，待测。
对所述1-癸基-2-异丙基咪唑型聚醚酮为主链的碱性阴离子交换膜电导率同样采用交流阻抗法进行测试。从测试结果可以看出此类膜的电导率随温度变化与实施例1中膜的电导率变化类似，当温度从25℃升到60℃时，电导率的变化比较大。而且这类膜的电导率比实施例1中膜的电导率小，猜测原因为长取代基的加入使得聚合物的分子量增大，降低了膜的离子交换容量(即IEC值)，而膜的离子交换容量与膜的电导率密切相 关，所以使得膜的离子电导率降低。
图1为实施例1、2所得的氯甲基化聚醚酮的动态热力学分析曲线(DMA)。在图1中，横坐标为温度(℃)，左边一侧纵坐标为储存模量(MPa)，右边一侧纵坐标为损失模量(MPa)。在图1中，损失模量曲线中的峰值对应的温度为聚合物的玻璃态转化温度。从动态热力学分析结果可知，氯甲基化聚醚酮的玻璃态转化温度在150℃以上，说明其热力学性能较好，能满足燃料电池工况的要求。
图5是实施例2中N1-癸基-2-异丙基咪唑型聚醚酮为主链的膜在去离子水中电导率随温度变化曲线。在图5中，横坐标为温度(℃)，纵坐标为电导率(mScm-1)；由图5可知，这类膜的电导率随温度发生变化，但是其变化趋势没有N1位为甲基的变化趋势明显，说明其电导率受温度影响不是很明显，可能是由于其传导离子的机理与N1位为甲基的不同。
实施例3
于50mL CCl4中加入2g聚苯乙烯，40℃冷凝循环磁力搅拌使之溶解。在冰水浴的条件下(17℃)，加入2.23g四氯化锡，然后慢慢滴入10mL1,4-二氯甲氧基丁烷，室温下反应4h。将反应物倒入去离子水中析出固体，得到氯甲基化聚苯乙烯，然后用去离子水充分洗涤，45℃真空干燥待用。于10mL二甲基甲酰胺中加入4g(约29mmol)2-丁基咪唑，磁力搅拌使其溶解。在冰水浴的条件下，加入6.7g叔丁醇钾(60mmol)，搅拌10min后加入10.0mL(约72mmol)溴代正己烷，室温下搅拌过夜。将反应液倒入水中，然后用乙酸乙酯萃取分离，得上层有机物，将有机物用无水MgSO4干燥后采用柱层析色谱进行分离纯化得到1-己基2-丁基咪唑，最后将其置于常温氮气箱中待用。于10mL二甲基亚砜中加入0.5g氯甲基化聚苯乙烯，80℃磁力搅拌使之溶解后加入0.22g1-己基-2-丁基咪唑，80℃磁力搅拌反应15h。待反应液恢复至室温过滤，50℃鼓风干燥箱内干燥过夜进行铸膜。将制备好的膜用去离子水充分洗涤后，在密封的去离子水中保存。
对所述1-己基-2-丁基咪唑型聚苯乙烯为主链的碱性阴离子交换膜电导率进行测试。在室温下，交换膜在去离子水中电导率为8.7mScm-1，原因可能是聚苯乙烯的氯甲基化程度较低，从而使得官能团化较小，造成电导率低。但是这类膜在40℃以上的温度时电导率都在10-2Scm-1以上，能满足燃料电池的要求。
图6是实施例3中N1-己基-2-丁基咪唑型聚苯乙烯为主链的聚合物的化学结构简图。
图7是实施例3中N1-己基-2-丁基咪唑型聚苯乙烯为主链的聚合物铸成的膜的电导率随温度变化曲线。在图7中，横坐标为温度(℃)，纵坐标为电导率(mScm-1)；由图8可知，当温度从40℃升到60℃时，膜的电导率变化比较明显，可能原因是温度的升高使膜的内部相结构发生了变化，从而使得传导离子的方式发生了变化，电导率随之发生了变化。
实施例4
于60mL CCl4中加入2g聚苯乙烯，30℃冷凝循环磁力搅拌使之溶解。在冰水浴的条件下(约7-17℃)，加入4g四氯化锡，然后慢慢滴入20mL1,4-二氯甲氧基丁烷，15℃反应7h。将反应物倒入去离子水中析出固体，得到氯甲基化聚苯乙烯，然后用去离子水充分洗涤，45℃真空干燥待用。然后合成N1-辛基-2-甲基咪唑。于10mL二甲基甲酰胺中加入4g(约29mmol)2-甲基咪唑，磁力搅拌使其溶解。在冰水浴的条件下，加入7.2g叔丁醇钾(61mmol)，搅拌10min后加入12.6mL(约72mmol)溴代正辛烷，室温下搅拌反应24h。将反应液倒入水中，然后用乙酸乙酯萃取分离，得上层有机物，将有机物用无水MgSO4干燥后采用柱层析色谱进行分离纯化得到1-辛基2-甲基咪唑，60℃真空干燥12h。1-辛基-2-甲基咪唑型聚合物的合成过程为：于10mL二甲 基亚砜中加入0.5g氯甲基化聚苯乙烯，60℃磁力搅拌使之溶解后加入0.3g1-辛基-2-甲基咪唑，80℃磁力搅拌反应24h。待反应液恢复至室温过滤，50℃鼓风干燥箱内干燥2h，70℃干燥过夜进行铸膜。将制备好的膜用去离子水充分洗涤后，在密封的去离子水中保存待测。
对所述1-辛基-2-甲基咪唑型聚苯乙烯为主链的碱性阴离子交换膜进行电导率测试。在常温下，此类膜在去离子水中电导率为11.1mScm-1，能满足燃料电池的要求。
对所述1-辛基-2-甲基咪唑型聚苯乙烯为主链的碱性阴离子交换膜进行热碱中稳定性测试。通过测量碱处理前后膜的电导率、尺寸及离子交换容量的变化，考察膜的化学稳定性。通过数据分析可以看出此类膜在碱处理前后电导率、尺寸及离子交换容量基本维持不变，说明此类膜在热碱中的稳定性良好。
将所制备的1-辛基-2-甲基咪唑型聚苯乙烯为主链的碱性阴离子交换膜组装成单池进行测试。所采用的阳极为金属载量为2.6mgcm-2的PtRu/C催化剂，阴极为金属载量为2mgcm-2的Pt/C催化剂。其中阴、阳极中所用的离聚物分别为Nafion和1-辛基-2-甲基咪唑型聚苯乙烯为主链聚合物，质量分数为20％。测试采用的仪器为Arbin公司的燃料电池测试系统。测试温度为60℃，阳极进料为1M MeOH+1M KOH，流量为1mLmin-1；阴极为氧气，流量为80sccm。单池放电数据结果显示，采用此类膜为固体电解质组装的单池的性能较好(功率密度可达44mWcm-2)。
图8是实施例4中N1-辛基-2-甲基咪唑型碱性阴离子交换膜的电导率随温度变化曲线。在图8中，横坐标为温度(℃)，纵坐标为电导率(mScm-1)；由图8可知，此类膜在室温条件下的电导率>10mScm-1,能满足碱性燃料电池的测试需求。
图9是实施例4中N1-辛基-2-甲基咪唑型碱性阴离子交换膜的电导率、尺寸及离子交换容量(IEC)值在60℃的1M KOH中浸泡前后的变化曲线。由图9可知，此类膜的电导率、尺寸及IEC值在热碱处理前后没有明显的变化，说明此类膜在热碱中的稳定性良好，能够满足碱性燃料电池随碱性阴离子交换膜化学稳定性的要求，说明此类膜在碱性燃料电池中存在一定的应用前景。
图10是实施例4中采用N1-辛基-2-甲基咪唑型碱性阴离子交换膜组装单池进行测试的放电曲线。在图10中,横坐标为电流密度(mAcm-2),左边纵坐标为电势(V)，右边纵坐标为功率密度(mWcm-2)。由图10可知，以N1-辛基-2-甲基咪唑型碱性阴离子交换膜为固体电解质组装单池具有较高的开路电压>0.8V，说明以贵金属为催化剂，N1-辛基-2-甲基咪唑型碱性阴离子交换膜为固体电解质组装的单池的极化较小；同时此单池的最大功率密度接近44mWcm-2,对应的电流密度为121mAcm-2，这一电池性能在碱性直接甲醇领域属于较高的，说明此类膜在碱性燃料电池中具有较好的应用价值。

Claims (19)

  1. [根据细则26改正01.06.2015]　
    N1位取代的咪唑化合物，其特征在于：结构式为
    Figure WO-DOC-FIGURE-
    R1为C1-C10的直链烷烃；R2为C1-C9的链状烷烃，或为C3-C6的环烷烃，或为苯基、或为联苯基。
  2. [根据细则26改正01.06.2015]　
    如权利要求1所述N1位取代的咪唑化合物
    Figure WO-DOC-CHEMICAL-1
    的制备方法，其特征在于：于溶剂中加入
    Figure WO-DOC-CHEMICAL-2
    、强碱试剂和R1-X，反应后对反应溶液进行萃取并干燥，得N1位取代的咪唑化合物
    Figure WO-DOC-CHEMICAL-1
    其中，R1为C1-C10的直链烷烃；R2为C1-C9的链状烷烃，或为C3-C6的环烷烃，或为苯基、或为联苯基；X为Cl，Br中的一种或两种。
  3. 如权利要求2所述制备方法，其特征在于：所述溶剂为乙腈、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮中的一种或两种以上。
  4. 如权利要求2所述制备方法，其特征在于：所述强碱试剂为NaOH、KOH、KH、NaH、LiH、叔丁醇钾、丁基锂中的一种或两种以上。
  5. [根据细则26改正01.06.2015]　
    如权利要求2所述制备方法，其特征在于：所述
    Figure WO-DOC-CHEMICAL-2
    于溶剂中的浓度为0.05-0.33g/mL；所述
    Figure WO-DOC-CHEMICAL-2
    与强碱试剂的物质量比为1:1-1:4；所述
    Figure WO-DOC-CHEMICAL-2
    与R1-X的物质量之比为1:1～1:3；所述反应温度为0℃-75℃；所述反应时间不小于12h。
  6. 如权利要求2所述制备方法，其特征在于：所述萃取过程采用乙酸乙酯、乙醚、正己烷、正戊烷中的一种进行。
  7. [根据细则26改正01.06.2015]　
    一种碱性阴离子交换膜，其特征在于：包括卤甲基化的高分子聚合物主链和分子式为
    Figure WO-DOC-CHEMICAL-1
    的N1位烷基取代的咪唑支链；
    所述高分子聚合物主链为聚醚砜、聚醚酮、聚亚苯基砜、聚苯乙烯、聚芳醚砜酮、聚苯醚中的一种；所述N1位烷基取代的咪唑中R1为C1-C10的直链烷烃；R2为C1-C9的链状烷烃，或为C3-C6的环烷烃，或为苯基、或为联苯基。
  8. [根据细则26改正01.06.2015]　
    如权利要求7所述碱性阴离子交换膜，其特征在于：
    Figure WO-DOC-CHEMICAL-1
    的N3位与卤甲基化的聚醚砜、聚醚酮、聚亚苯基砜、聚芳醚砜酮、聚苯醚中卤甲基去掉卤元素后的亚甲基以C-N化学键连接；或
    Figure WO-DOC-CHEMICAL-1
    的N3位与对位卤甲基化的聚苯乙烯中卤甲基去掉卤元素后的亚甲基以C-N化学键连接。
  9. [根据细则26改正01.06.2015]　
    一种权利要求7或8所述碱性阴离子交换膜的制备方法，其特征在于：包括以下步骤，
    (1)N1位烷基取代咪唑的合成：于第一溶剂中加入
    Figure WO-DOC-CHEMICAL-2
    强碱试剂和R1-X反应一段时间后得N1位烷基取代咪唑溶液；
    其中，R1为C1-C10的直链烷烃；R2为C1-C9的链状烷烃，或为C3-C6的环烷烃，或为苯基、或为联苯基；X为Cl，Br中的一种或两种；
    (2)卤甲基化高分子聚合物主链的制备：于第二溶剂中加入高分子聚合物、卤甲基化试剂和催化剂并于20℃以下反应后与第三溶剂混合析出聚合物，即得卤甲基化高分子聚合物；
    (3)N1位烷基取代咪唑型阴离子交换膜的制备：于第四溶剂中加入步骤(2)所得卤甲基化高分子聚合物和步骤(1)所得N1位烷基取代咪唑，搅拌并反应一段时间后过滤，对得到的透明溶液采用溶剂挥发法铸膜，得N1位烷基取代咪唑型碱性阴离子交换膜。
  10. 如权利要求9所述碱性阴离子交换膜的制备方法，其特征在于：还包括将所得N1位烷基取代咪唑型碱性阴离子交换膜置于氢氧化钾或氢氧化钠溶液中浸泡一段时间进行离子交换的步骤。
  11. 如权利要求9所述碱性阴离子交换膜的制备方法，其特征在于：
    所述步骤(1)还包括对得到的N1位烷基取代咪唑溶液进行萃取并干燥的步骤；
    所述步骤(2)还包括得到卤甲基化高分子聚合物后采用水、甲醇、乙醇、异丙醇、丙酮中的一种或两种以上进行清洗的步骤。
  12. [根据细则26改正01.06.2015]　
    如权利要求9所述碱性阴离子交换膜的制备方法，其特征在于：
    步骤(1)中所述第一溶剂为乙腈、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮中的一种或两种以上；所述强碱试剂为NaOH、KOH、KH、NaH、LiH、叔丁醇钾、丁基锂中的一种或两种以上；
    步骤(1)中所述
    Figure WO-DOC-CHEMICAL-2
    于第一溶剂的中的浓度为0.05-0.33g/mL；所述
    Figure WO-DOC-CHEMICAL-2
    与强碱试剂的物质量比为1:1-1:4；所述
    Figure WO-DOC-CHEMICAL-2
    与R1-X的物质量之比为1:1～1:3。
  13. 如权利要求9所述碱性阴离子交换膜的制备方法，其特征在于：
    步骤(2)所述催化剂为无水四氯化锡、氯化锌、三氟乙酸、浓硫酸中的一种或两种以上；所述卤甲基化试剂为氯甲醚、氯甲基丁醚、氯甲基己醚、1,4-二氯甲氧基丁烷、N-溴代丁二酰亚胺的中一种或两种以上；
    步骤(2)所述第二溶剂为浓硫酸、四氯化碳、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮、二氯甲烷、氯仿、二氯乙烷中的一种或两种以上；所述第三溶剂为水、甲醇、乙醇、异丙醇、丙酮中的一种或两种以上；
    步骤(2)中于第二溶剂中加入所述高分子聚合物的质量为0.017-0.067g/mL；所述加入的高分子聚合物与催化剂的质量比为200:1-1:5；所述加入的高分子聚合物的质量与卤甲基化试剂的体积比为1:1-1:10。
  14. 如权利要求9所述碱性阴离子交换膜的制备方法，其特征在于：
    步骤(3)所述第四溶剂为二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮中的一种或两种以上；于第四溶剂中加入所述卤甲基化聚合物的质量为0.02-0.067g/mL；步骤(3)中所述卤甲基化聚合物与N1位烷基取代咪唑的质量之比为10:1-1:2。
  15. 如权利要求11所述碱性阴离子交换膜的制备方法，其特征在于：所述萃取过程采用的有机试剂为乙酸乙酯、乙醚、正己烷、正戊烷中的一种。
  16. 如权利要求9所述碱性阴离子交换膜的制备方法，其特征在于：步骤(1)所述反应温度为0℃-75℃；反应时间为不小于12h。
  17. 如权利要求9所述碱性阴离子交换膜的制备方法，其特征在于：步骤(2)所述的反应时间不小于0.5h。
  18. 如权利要求9所述碱性阴离子交换膜的制备方法，其特征在于：步骤(3)中所述反应温度范围为室温-90℃；所述反应时间为不小于12h；所述的铸膜温度为40-70℃,所述铸膜时间不小于4h。
  19. 如权利要求10所述碱性阴离子交换膜的制备方法，其特征在于：所述的氢氧化钾和/或氢氧化钠的总浓度为0.1-3mol/L；所述溶液温度为室温-40℃。
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CN108075161B (zh) * 2016-11-18 2020-08-04 中国科学院大连化学物理研究所 一种n1-长链烷烃取代-4,5-二甲基咪唑型碱性阴离子交换膜的制备方法
CN108461790B (zh) * 2016-12-13 2020-10-02 中国科学院大连化学物理研究所 一种长侧链sebs基碱性聚合物电解质膜及其制备和应用
CN108232260B (zh) * 2016-12-13 2020-06-09 中国科学院大连化学物理研究所 一种长侧链sebs基碱性聚合物电解质膜及其制备方法和应用
CN107579270B (zh) * 2017-08-01 2020-01-24 大连理工大学 一种多支链聚芳醚酮阴离子交换膜及其制备方法
CN108666602B (zh) * 2018-05-17 2020-07-24 北京化工大学 一种负载取代咪唑单元的耐碱性阴离子交换膜及其制备方法
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CN112316988A (zh) * 2020-10-23 2021-02-05 天津市大陆制氢设备有限公司 一种高效的阴离子交换膜及其制备方法

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