CN112201827B - Preparation method of novel composite proton exchange membrane material - Google Patents
Preparation method of novel composite proton exchange membrane material Download PDFInfo
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- 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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
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- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0286—Chemical after-treatment
- C08G75/029—Modification with organic compounds
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H01M8/1041—Polymer electrolyte composites, mixtures or blends
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- 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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
- H01M8/1088—Chemical modification, e.g. sulfonation
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- 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
Abstract
The invention discloses a preparation method of a novel composite proton exchange membrane material, which sequentially comprises the following steps: a) a sulfonated polyphenyl ether preparation step; b) preparing chloromethylation sulfonated polyphenyl ether; c) preparing azido sulfonated polyphenylene ether; d) 6-tosyl-beta cyclodextrin preparation; e) preparing alkynyl beta-cyclodextrin; f) preparing alkynylated beta cyclodextrin @ graphene oxide; g) and (3) preparing a proton composite membrane material. Compared with the existing SPPO membrane, the proton conductivity at a high temperature of 80 ℃ is improved by 1-1.5 times, the methanol permeability is reduced by more than 150 times, and the stability is also obviously improved; compared with the existing nafion membrane, the methanol permeability is reduced by more than 20 times, and the stability is obviously improved.
Description
Technical Field
The present invention belongs to the preparation process of proton exchange membrane material, and is especially the preparation process of proton exchange membrane material for fuel cell.
Background
The fuel cell has the advantages of zero emission, environmental friendliness, high energy conversion efficiency, good durability, high specific energy and the like. The improvement of the comprehensive performance of the proton exchange membrane as a core component is always a difficult problem. At present, Nafion series membranes of the DuPont company, the XUS-B204 membranes of the Dow chemical company, the Aciplex membranes of the Asahi chemical company and the like are industrialized, wherein the Nafion series membranes belonging to the DuPont company are popularized most successfully and are widely applied at home and abroad. Although Nafion membrane has so many advantages, its high price and high methanol leakage rate limit its further promotion.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a proton exchange membrane material with low methanol leakage rate.
The technical scheme for solving the technical problem is as follows: a preparation method of a novel composite proton exchange membrane material sequentially comprises the following steps: a) a sulfonated polyphenyl ether preparation step; b) preparing chloromethylation sulfonated polyphenyl ether; c) preparing azido sulfonated polyphenylene ether; d) 6-tosyl-beta cyclodextrin preparation; e) preparing alkynyl beta-cyclodextrin; f) preparing alkynylated beta cyclodextrin @ graphene oxide; g) and (3) preparing a proton composite membrane material.
The preparation step of the a) sulfonated polyphenyl ether comprises the following steps:
completely dissolving polyphenyl ether with the number average molecular weight of 2 w-1000 w in CHCl under the condition of mechanical stirring3In, HSO is added dropwise3Cl and Si (CH)3)3Mixture of Cl in N2Reacting at 35-40 deg.C for 12-14h under atmosphere, adding CH3ONa, and continuing to react for 1-2h until white particles appear; alternately washing the white particles with anhydrous methanol and deionized water for 2-3 times, and vacuum drying at 70-80 deg.C to constant weight to obtain sulfonated polyphenylene oxide (SPPO);
polyphenylene ether with CHCl3The weight/volume ratio of the (B) is 1:8-10 g/ml;
polyphenylene ether, HSO3Cl、Si(CH3)3Cl、CH3The weight ratio of ONa is 100: 170-340:200-400:400-700.
b) Preparation step of chloromethylated sulfonated polyphenylene ether
Dissolving the sulfonated polyphenylene oxide (SPPO) obtained in the step a in 1, 2-dichloroethane, adding anhydrous zinc chloride and chloromethyl ether, heating to 35-40 ℃, reacting for 4-6h, cooling to room temperature, settling the polymer with anhydrous methanol for 2-3 times, washing with deionized water for 2-3 times, putting into a vacuum drying oven with the temperature of 50-55 ℃, and drying in vacuum to constant weight to obtain chloromethylated sulfonated polyphenylene oxide (SPPO-CH)2Cl)；
The weight/volume ratio of the sulfonated polyphenylene ether (SPPO) to the 1, 2-dichloroethane is 1:5-10 g/ml;
the weight ratio of the sulfonated polyphenyl ether, the anhydrous zinc chloride and the chloromethyl ether is 100: 10-20: 40-50;
c) preparation step of azido sulfonated polyphenylene ether
Taking the SPPO-CH obtained in the step b2Dissolving Cl and sodium azide in dimethyl sulfoxide (DMSO) solvent, heating to 70-75 ℃, reacting for no less than 48h, cooling to room temperature, precipitating the polymer with a mixed solvent of anhydrous methanol and deionized water for 2-3 times, filtering, placing in a vacuum drying oven at 30-35 ℃, drying to constant weight to obtain the product SPPO-CH2N3；
SPPO-CH2The weight ratio of Cl to sodium azide is 10: 1-1.5,
SPPO-CH2the weight/volume ratio of the Cl to the dimethyl sulfoxide solution is 1:5-10g/ml,
the volume ratio of the anhydrous methanol to the deionized water is 3.8-4.2: 1;
the following steps:
d) preparation step of 6-p-toluenesulfonyl-beta cyclodextrin
e) Preparing alkynyl beta-cyclodextrin;
reference is made to Synthesis, chromatographic evaluation and hydrolytic interaction/reversed-phase mixed-mode scanner of a "Click beta-cycle" static phase. J chromatograph A,2009.1216(2): p.257-63.
f) Preparation step of alkynylated beta cyclodextrin @ graphene oxide
Adding Graphene Oxide (GO) into a DMF solution, wherein the weight/volume ratio of the Graphene Oxide (GO) to the DMF is 1: carrying out ultrasonic treatment for 5-8h at a concentration of 50-75g/ml to obtain a stable dispersed GO/DMF solution; adding SOCl2Heating to 70-75 deg.C, reacting for 24-28 hr to obtain GO-Cl, and removing excessive SOCl with rotary evaporator2And then adding DMF for dissolution to obtain a GO-Cl/DMF solution, wherein the weight/volume ratio of GO-Cl to DMF is 1: adding 200g/ml of the alkynylated beta cyclodextrin 6-beta-CD-C ≡ CH obtained in the step e, heating to 95-100 ℃, reacting for 48-60 hours, cooling to room temperature, filtering, and drying in a vacuum oven at 70-75 ℃ to constant weight to obtain the alkynylated beta cyclodextrin @ graphene oxide (CH ≡ C-beta-CD @ GO);
graphene Oxide (GO) and SOCl2In a weight/volume ratio of 1: 150-200 g/ml;
the weight ratio of Graphene Oxide (GO) to alkynylated beta cyclodextrin 6-beta-CD-C ≡ CH is 1: 10-20.
The graphene oxide GO is prepared by a modified Hummers method, refer to the W.S.hummers Jr article (J.Am.chem.Soc.,1958,80,1339.)
g) Preparation of proton composite membrane material
Taking the alkynylated beta cyclodextrin @ graphene oxide obtained in the step f, and adding SPPO-CH2N3Adding N, N-Dimethylformamide (DMF) for dissolving, injecting N, N, N '-N' -Pentamethyldiethylenetriamine (PMDETA) and cuprous bromide under the argon atmosphere, introducing argon for 15-20 minutes, sealing a reaction container, reacting at 35-75 ℃ for 12-48 hours, cooling to room temperature, settling for 2-3 times by using absolute methanol, washing by using deionized water, putting into a vacuum drying oven at 25-40 ℃, drying to constant weight, and preparing the polymer SPPO/beta-CD @ GO;
alkynylated beta cyclodextrin @ graphene oxide, SPPO-CH2N3And the weight ratio of N, N, N' -pentamethyldiethylenetriamine to cuprous bromide is 1: 20-200: 1.3-9.6: 1.4-8;
the weight/volume ratio of the alkynylated beta cyclodextrin @ graphene oxide to DMF is 1: 400-800 g/ml;
in the preparation process of the sulfonated polyphenylene oxide (SPPO) in the step a of the invention:
compared with the traditional concentrated sulfuric acid sulfonation and chlorosulfonic acid method, the sulfonation degree is not required to be controlled by reaction time, the reaction condition is milder, and the success rate is higher.
Steps b and c of the present invention are intended to attach the azido group to the polyphenylene ether and to provide a cushion for the subsequent click chemistry reaction.
Step f of the invention;
the method is characterized in that no literature report exists before a two-dimensional layered structure of graphene oxide is grafted with beta-cyclodextrin, graphene oxide is subjected to acyl chlorination, then acyl chlorinated graphene oxide reacts with hydroxyl on cyclodextrin to generate ester bonds, and alkynyl beta-cyclodextrin is grafted on the surface of a graphene oxide sheet through the ester bonds.
Step g of the invention;
using CuICatalyzing click chemical reaction between alkyne and azide to prepare the composite proton exchange membrane. The preparation method is characterized in that alkynylated beta cyclodextrin @ graphene oxide and azido sulfonated polyphenylene oxide are reacted to obtain sulfonated polyphenylene oxide/beta cyclodextrin @ graphene oxide (SPPO/beta-CD @ GO), the beta cyclodextrin @ graphene oxide is fixed on the sulfonated polyphenylene oxide, and the preparation method is different from a traditional physical doping mode, and the mode of bonding connection is utilized to enable the stability of the composite membrane to be higher.
Sulfonated polyphenylene ether (SPPO) is the most similar polymer to the Nafion series membrane structure. The sulfonated polyphenyl ether has hydrophobic 1, 4-methyl and hydrophilic sulfonated groups on the benzene ring of the main chain, and flexible ether beside the benzene ring of the main chain.
The sulfonation degree of the polyphenyl ether is determined, and the proton transport capacity is improved under the condition of ensuring good stability of the polyphenyl ether. The beta-cyclodextrin has the characteristics of hydrophilic two ends and hydrophobic inner cavity, and the unique property can enable the beta-cyclodextrin and various organic molecules to form a host-guest inclusion compound, so that the beta-cyclodextrin can improve the dispersibility of functional materials and enhance the compatibility of a composite film. The graphene oxide has the characteristics of excellent mechanical property, thermal stability and oxygen-containing functional groups. Polyphenylene oxide is combined with beta-CD @ GO by a click chemistry method. Therefore, the stability, the proton conductivity and the power density of the whole material are improved.
Compared with the existing SPPO membrane, the proton conductivity at a high temperature of 80 ℃ is improved by 1-1.5 times, the methanol permeability is reduced by more than 150 times, and the stability is also obviously improved;
compared with the existing nafion membrane, the methanol permeability is reduced by more than 20 times, and the stability is obviously improved.
Drawings
Fig. 1 is a scanning electron micrograph of graphene oxide.
Fig. 2 is a scanning electron microscope image of beta cyclodextrin uniformly loaded on graphene oxide.
Fig. 3 is a scanning electron microscope image of beta cyclodextrin uniformly loaded on graphene oxide.
FIG. 4 is an infrared spectrum of graphene oxide, SPPO/beta-CD @ GO.
1 is graphene oxide; 2 is SPPO/beta-CD @ GO.
Detailed Description
The technical solution of the present invention is further specifically described below by way of examples.
Example 1
A preparation method of a novel composite proton exchange membrane material sequentially comprises the following steps: a) a sulfonated polyphenyl ether preparation step; b) preparing chloromethylation sulfonated polyphenyl ether; c) preparing azido sulfonated polyphenylene ether; d) 6-tosyl-beta cyclodextrin preparation; e) preparing alkynyl beta-cyclodextrin; f) preparing alkynylated beta cyclodextrin @ graphene oxide; g) preparing a proton composite membrane material;
said
a) The preparation method of the sulfonated polyphenylene oxide comprises the following steps:
50g PPO (number average molecular weight 2 w-1000 w) was completely dissolved in 500mL CHCl under mechanical stirring3In the reaction solution, 50ml of HSO is added dropwise3Cl and 100gSi (CH)3)3And (4) Cl. At 35 ℃ N2After reacting for 12h under the atmosphere, 200gCH is added3ONa, continue the reaction for 1h until white particles appear. And alternately washing the particles for 2 times by using methanol and deionized water, and drying the particles in vacuum at the temperature of 80 ℃ to constant weight to prepare the sulfonated polyphenylene oxide (SPPO).
b) Preparation step of chloromethylated sulfonated polyphenylene ether
B, dissolving 50g of sulfonated polyphenylene oxide (SPPO) obtained in the step a in 250mL of 1, 2-dichloroethane, putting the dissolved sulfonated polyphenylene oxide (SPPO) into a round-bottom flask connected with a reflux condensing device and a stirring device, then adding 5.0g of anhydrous zinc chloride and 20g of chloromethyl ether, heating a reaction system to 40 ℃, reacting for 4 hours, cooling to room temperature, settling the polymer for 2 times by using anhydrous methanol, washing for 2 times by using deionized water, putting the washed polymer into a vacuum drying oven, setting the temperature to be 50 ℃, and drying in vacuum to constant weight to prepare SPPO-CH2Cl。
c) Preparation step of azido sulfonated polyphenylene ether
Taking 30g of SPPO-CH obtained in step b2Cl and 3g of sodium azide are dissolved in 200mL of dimethyl sulfoxide (DMSO), heated to 70 ℃, reacted for 48 hours and cooled toSettling the polymer for three times at room temperature by using a mixed solvent of anhydrous methanol and deionized water, wherein the volume ratio of the anhydrous methanol to the deionized water is 3.8:1, filtering, putting the polymer into a vacuum drying oven, setting the temperature to be 30 ℃, and drying in vacuum to constant weight to obtain a product SPPO-CH2N3And (5) standby.
d) Preparation step of 6-p-toluenesulfonyl-beta cyclodextrin
Adding 6g of beta-CD (beta-cyclodextrin) into a 500mL dry single-neck flask, then adding 120mL of NaOH solution with the concentration of 0.75moL/L, stirring to completely dissolve the beta-CD, controlling the temperature at 0-5 ℃, slowly adding 1.2g of paratoluensulfonyl chloride under stirring after cyclodextrin is completely dissolved, controlling the temperature at 0-5 ℃ all the time to react for 5 hours, filtering to remove unreacted raw materials, adjusting the filtrate to be neutral by using dilute hydrochloric acid, placing the neutral filtrate into a refrigerator to be refrigerated overnight, filtering to obtain a crude product, dissolving the obtained crude product into hot water, filtering while the hot crude product is hot, placing the filtrate into the refrigerator to be overnight, and filtering to obtain the product. The precipitation is repeated for 3 times, and vacuum drying is carried out until the weight is constant, so as to obtain the 6-TsO-beta-CD.
e) Preparation step of alkynylated beta-cyclodextrin
And d, adding 10.0g of 6-TsO-beta-CD obtained in the step d into 20mL of propynylamine, heating the mixed solution to 65 ℃ under the nitrogen atmosphere, and reacting for 24 h. The mixture was then poured into 100mL of acetonitrile to give the solid product 6- β -CD-C ≡ CH.
f) Preparation step of alkynylated beta cyclodextrin @ graphene oxide
Adding 200mg GO into 15mL of DMF solution, carrying out ultrasonic treatment for 5h to obtain stable dispersed GO/DMF solution, adding 30mL of SOCl2The temperature is raised to 70 ℃, the reaction is refluxed for 24 hours, and when the reaction is finished, the excessive SOCl is removed by a rotary evaporator2And d, dissolving GO-Cl into 22mL of DMF solution, adding 6-beta-CD-C [ identical to ] CH (6-beta-CD-C [ identical to ] CH) obtained in the step e, uniformly mixing, heating, reacting at 100 ℃ for 48 hours, cooling to room temperature, filtering, and drying in a vacuum oven at 70 ℃ to constant weight to obtain the alkynyl beta-cyclodextrin @ graphene oxide (CH [ identical to ] C-beta-CD @ GO).
g) The preparation method of the proton composite membrane material comprises the following steps:
taking 0.05gCH ≡ C-beta-CD @ GO and 10g SPPO-CH2N3(0.5 wt.%) dissolving the polymer in 20mL of N, N-Dimethylformamide (DMF) in a Schlenk bottle, filling the mixture in an argon atmosphere after three times of pumping, injecting 0.58mL of N, N, N' -Pentamethyldiethylenetriamine (PMDETA) and 0.4g of cuprous bromide, introducing argon for 15min, sealing the reaction vessel, reacting for 48h at 35 ℃, cooling to room temperature, settling the product for 3 times by using absolute methanol, washing by using deionized water, putting the product in a vacuum drying oven at 25 ℃, and drying in vacuum to constant weight to prepare the polymer SPGO/beta-CD @ from the product.
As shown in fig. 1: fig. 1 shows the state of graphene oxide under a scanning electron microscope, which is a layer with a smooth surface.
Fig. 2 is a graph of beta cyclodextrin loaded on the surface of graphene oxide, and shows that the loading of beta cyclodextrin makes the surface of graphene oxide rough, and uniform scattering indicates successful loading.
Fig. 3 is a cross-sectional state captured when graphene oxide is in a stacked state, and shows that β cyclodextrin is supported on not only the surface but also the cross-section of graphene oxide, thereby verifying the success of the loading again.
As shown in fig. 4:
1 is graphene oxide: 1723cm-1And 1623cm-1Stretching vibration of C ═ O and C ═ C in graphene oxide;
2 is SPPO/β -CD @ GO: 1626cm-1Is the stretching vibration of C ═ C in graphene oxide, 1433cm-1Is the C-OH stretching vibration peak of beta-cyclodextrin, 1040cm-1Is the vibration of the antisymmetric glycoside C-O-C in the beta-cyclodextrin, and therefore, the beta-cyclodextrin is successfully loaded.
Example 2
A preparation method of a novel composite proton exchange membrane material sequentially comprises the following steps: a) a sulfonated polyphenyl ether preparation step; b) preparing chloromethylation sulfonated polyphenyl ether; c) preparing azido sulfonated polyphenylene ether; d) 6-tosyl-beta cyclodextrin preparation; e) preparing alkynyl beta-cyclodextrin; f) preparing alkynylated beta cyclodextrin @ graphene oxide; g) preparing a proton composite membrane material;
said
a) The preparation method of the sulfonated polyphenylene oxide comprises the following steps:
50g PPO (number average molecular weight 2 w-1000 w) was completely dissolved in 500mL CHCl under mechanical stirring3In the reaction solution, 50ml of HSO is added dropwise3Cl and 150gSi (CH)3)3And (4) Cl. At 35 ℃ N2After reacting for 12h under the atmosphere, 250gCH is added3ONa, continue the reaction for 1h until white particles appear. And alternately washing the particles for 2 times by using methanol and deionized water, and drying the particles in vacuum at the temperature of 80 ℃ to constant weight to prepare the sulfonated polyphenylene oxide (SPPO).
b) Preparation step of chloromethylated sulfonated polyphenylene ether
B, dissolving 50g of sulfonated polyphenylene oxide (SPPO) obtained in the step a in 300mL of 1, 2-dichloroethane, putting the dissolved sulfonated polyphenylene oxide (SPPO) into a round-bottom flask connected with a reflux condensing device and a stirring device, then adding 6.0g of anhydrous zinc chloride and 22g of chloromethyl ether, heating a reaction system to 40 ℃, reacting for 4 hours, cooling to room temperature, settling the polymer for 2 times by using anhydrous methanol, washing for 2 times by using deionized water, putting the washed polymer into a vacuum drying oven, setting the temperature to be 50 ℃, and drying in vacuum to constant weight to prepare SPPO-CH2Cl。
c) Preparation step of azido sulfonated polyphenylene ether
Taking 30g of SPPO-CH obtained in step b2Dissolving Cl and 3.6g of sodium azide in 220mL of dimethyl sulfoxide (DMSO), heating to 70 ℃, reacting for 48 hours, cooling to room temperature, settling the polymer for three times by using a mixed solvent of anhydrous methanol and deionized water, wherein the volume ratio of the anhydrous methanol to the deionized water is 3.9:1, filtering, putting the polymer into a vacuum drying oven, setting the temperature to be 30 ℃, and drying in vacuum to constant weight to obtain a product SPPO-CH2N3And (5) standby.
d) Preparation step of 6-p-toluenesulfonyl-beta cyclodextrin
Adding 6g of beta-CD (beta-cyclodextrin) into a 500mL dry single-neck flask, then adding 120mL of NaOH solution with the concentration of 0.75moL/L, stirring to completely dissolve the beta-CD, controlling the temperature at 0-5 ℃, slowly adding 1.2g of paratoluensulfonyl chloride under stirring after cyclodextrin is completely dissolved, controlling the temperature at 0-5 ℃ all the time to react for 5 hours, filtering to remove unreacted raw materials, adjusting the filtrate to be neutral by using dilute hydrochloric acid, placing the neutral filtrate into a refrigerator to be refrigerated overnight, filtering to obtain a crude product, dissolving the obtained crude product into hot water, filtering while the hot crude product is hot, placing the filtrate into the refrigerator to be overnight, and filtering to obtain the product. The precipitation is repeated for 3 times, and vacuum drying is carried out until the weight is constant, so as to obtain the 6-TsO-beta-CD.
e) Preparation step of alkynylated beta-cyclodextrin
And d, adding 10.0g of 6-TsO-beta-CD obtained in the step d into 20mL of propynylamine, heating the mixed solution to 65 ℃ under the nitrogen atmosphere, and reacting for 24 h. The mixture was then poured into 100mL of acetonitrile to give the solid product 6- β -CD-C ≡ CH.
f) Preparation step of alkynylated beta cyclodextrin @ graphene oxide
Adding 200mg GO into 16mL of DMF solution, carrying out ultrasonic treatment for 6h to obtain stable dispersed GO/DMF solution, adding 34mL of SOCl2The temperature is raised to 72 ℃, the reaction is refluxed for 36 hours, and when the reaction is finished, the excessive SOCl is removed by a rotary evaporator2And d, dissolving GO-Cl into 24mL of DMF solution, adding 6-beta-CD-C [ identical to ] CH (3.6 g) obtained in the step e, uniformly mixing, heating, reacting at 90 ℃ for 52h, cooling to room temperature, filtering, and drying in a vacuum oven at 75 ℃ to constant weight to obtain alkynyl beta-cyclodextrin @ graphene oxide (CH [ identical to ] C-beta-CD @ GO).
g) The preparation method of the proton composite membrane material comprises the following steps:
taking 0.1gCH ≡ C-beta-CD @ GO and 10g SPPO-CH2N3(1 wt.%) dissolving the product in 20mL of N, N-Dimethylformamide (DMF) in a Schlenk bottle, pumping three times, injecting 0.58mL of N, N, N' -Pentamethyldiethylenetriamine (PMDETA) and 0.4g of cuprous bromide under the argon atmosphere, introducing argon for 15min, sealing the reaction vessel, reacting for 48h at 40 ℃, cooling to room temperature, settling the product with anhydrous methanol for 3 times, washing with deionized water, putting in a vacuum drying oven at 25 ℃, and drying in vacuum to constant weight to prepare the polymer SPPO/beta-CD @ GO.
Example 3
A preparation method of a novel composite proton exchange membrane material sequentially comprises the following steps: a) a sulfonated polyphenyl ether preparation step; b) preparing chloromethylation sulfonated polyphenyl ether; c) preparing azido sulfonated polyphenylene ether; d) 6-tosyl-beta cyclodextrin preparation; e) preparing alkynyl beta-cyclodextrin; f) preparing alkynylated beta cyclodextrin @ graphene oxide; g) preparing a proton composite membrane material;
said
a) The preparation method of the sulfonated polyphenylene oxide comprises the following steps:
50g PPO (number average molecular weight 2 w-1000 w) was completely dissolved in 500mL CHCl under mechanical stirring3In the reaction solution, 100ml of HSO is added dropwise3Cl and 150gSi (CH)3)3And (4) Cl. At 35 ℃ N2After reacting for 12h under the atmosphere, 300gCH is added3ONa, continue the reaction for 1h until white particles appear. And alternately washing the particles for 2 times by using methanol and deionized water, and drying the particles in vacuum at the temperature of 80 ℃ to constant weight to prepare the sulfonated polyphenylene oxide (SPPO).
b) Preparation step of chloromethylated sulfonated polyphenylene ether
B, dissolving 50g of sulfonated polyphenylene ether (SPPO) obtained in the step a in 400mL of 1, 2-dichloroethane, putting the dissolved sulfonated polyphenylene ether (SPPO) into a round-bottom flask connected with a reflux condensing device and a stirring device, then adding 7.0g of anhydrous zinc chloride and 23g of chloromethyl ether, heating a reaction system to 40 ℃, reacting for 4 hours, cooling to room temperature, settling the polymer for 2 times by using anhydrous methanol, washing for 2 times by using deionized water, putting the washed polymer into a vacuum drying oven, setting the temperature to be 50 ℃, and drying in vacuum to constant weight to prepare SPPO-CH2Cl。
c) Preparation step of azido sulfonated polyphenylene ether
Taking 30g of SPPO-CH obtained in step b2Dissolving Cl and 4g of sodium azide in 240mL of dimethyl sulfoxide (DMSO), heating to 70 ℃, reacting for 48 hours, cooling to room temperature, settling the polymer for three times by using a mixed solvent of anhydrous methanol and deionized water, wherein the volume ratio of the anhydrous methanol to the deionized water is 4:1, filtering, putting into a vacuum drying oven, setting the temperature to be 30 ℃, and drying in vacuum to constant weight to obtain a product SPPO-CH2N3And (5) standby.
d) Preparation step of 6-p-toluenesulfonyl-beta cyclodextrin
Adding 6g of beta-CD (beta-cyclodextrin) into a 500mL dry single-neck flask, then adding 120mL of NaOH solution with the concentration of 0.75moL/L, stirring to completely dissolve the beta-CD, controlling the temperature at 0-5 ℃, slowly adding 1.2g of paratoluensulfonyl chloride under stirring after cyclodextrin is completely dissolved, controlling the temperature at 0-5 ℃ all the time to react for 5 hours, filtering to remove unreacted raw materials, adjusting the filtrate to be neutral by using dilute hydrochloric acid, placing the neutral filtrate into a refrigerator to be refrigerated overnight, filtering to obtain a crude product, dissolving the obtained crude product into hot water, filtering while the hot crude product is hot, placing the filtrate into the refrigerator to be overnight, and filtering to obtain the product. The precipitation is repeated for 3 times, and vacuum drying is carried out until the weight is constant, so as to obtain the 6-TsO-beta-CD.
e) Preparation step of alkynylated beta-cyclodextrin
And d, adding 10.0g of 6-TsO-beta-CD obtained in the step d into 20mL of propynylamine, heating the mixed solution to 65 ℃ under the nitrogen atmosphere, and reacting for 24 h. The mixture was then poured into 100mL of acetonitrile to give the solid product 6- β -CD-C ≡ CH.
f) Preparation step of alkynylated beta cyclodextrin @ graphene oxide
Adding 200mg GO into 13mL of DMF solution, carrying out ultrasonic treatment for 8h to obtain stable dispersed GO/DMF solution, adding 36mL of SOCl2The temperature is raised to 70 ℃, the reaction is refluxed for 36 hours, and when the reaction is finished, the excessive SOCl is removed by a rotary evaporator2And d, dissolving GO-Cl into 26mL of DMF solution, adding 6-beta-CD-C [ identical to ] CH (3.2 g) obtained in the step e, uniformly mixing, heating, reacting at 100 ℃ for 48 hours, cooling to room temperature, filtering, and drying in a vacuum oven at 70 ℃ to constant weight to obtain alkynyl beta-cyclodextrin @ graphene oxide (CH [ identical to ] C-beta-CD @ GO).
g) The preparation method of the proton composite membrane material comprises the following steps:
taking 0.2gCH ≡ C-beta-CD @ GO and 10g SPPO-CH2N3(2 wt.%) dissolving the product in 20mL of N, N-Dimethylformamide (DMF) in a Schlenk bottle, pumping three times, injecting 0.58mL of N, N, N' -Pentamethyldiethylenetriamine (PMDETA) and 0.4g of cuprous bromide under the argon atmosphere, introducing argon for 15min, sealing the reaction vessel, reacting at 35 ℃ for 48h, cooling to room temperature, settling the product with anhydrous methanol for 3 times, washing with deionized water, putting in a vacuum drying oven at 25 ℃, and drying in vacuum to constant weight to prepare the polymer SPPO/beta-CD @ GO.
Example 4
A preparation method of a novel composite proton exchange membrane material sequentially comprises the following steps: a) a sulfonated polyphenyl ether preparation step; b) preparing chloromethylation sulfonated polyphenyl ether; c) preparing azido sulfonated polyphenylene ether; d) 6-tosyl-beta cyclodextrin preparation; e) preparing alkynyl beta-cyclodextrin; f) preparing alkynylated beta cyclodextrin @ graphene oxide; g) preparing a proton composite membrane material;
said
a) The preparation method of the sulfonated polyphenylene oxide comprises the following steps:
50g PPO (number average molecular weight 2 w-1000 w) was completely dissolved in 400mL CHCl under mechanical stirring3In the process, 80ml of HSO is added dropwise3Cl and 140gSi (CH)3)3And (4) Cl. At 35 ℃ N2After reacting for 12h under the atmosphere, 200gCH is added3ONa, continue the reaction for 1h until white particles appear. And alternately washing the particles for 2 times by using methanol and deionized water, and drying the particles in vacuum at the temperature of 80 ℃ to constant weight to prepare the sulfonated polyphenylene oxide (SPPO).
b) Preparation step of chloromethylated sulfonated polyphenylene ether
B, dissolving 50g of sulfonated polyphenylene oxide (SPPO) obtained in the step a in 450mL of 1, 2-dichloroethane, putting the dissolved sulfonated polyphenylene oxide (SPPO) into a round-bottom flask connected with a reflux condensing device and a stirring device, then adding 8.0g of anhydrous zinc chloride and 24g of chloromethyl ether, heating a reaction system to 40 ℃, reacting for 4 hours, cooling to room temperature, settling the polymer for 2 times by using anhydrous methanol, washing for 2 times by using deionized water, putting the washed polymer into a vacuum drying oven, setting the temperature to be 50 ℃, and drying in vacuum to constant weight to prepare SPPO-CH2Cl。
c) Preparation step of azido sulfonated polyphenylene ether
B, dissolving 50g of sulfonated polyphenylene oxide (SPPO) obtained in the step a in 500mL of 1, 2-dichloroethane, putting the dissolved sulfonated polyphenylene oxide (SPPO) into a round-bottom flask connected with a reflux condensing device and a stirring device, then adding 10.0g of anhydrous zinc chloride and 25g of chloromethyl ether, heating a reaction system to 35 ℃, reacting for 6 hours, cooling to room temperature, settling the polymer for 3 times by using anhydrous methanol, washing for 3 times by using deionized water, putting the washed polymer into a vacuum drying oven, setting the temperature to be 55 ℃, and drying in vacuum to constant weight to prepare SPPO-CH2Cl。
d) Preparation step of 6-p-toluenesulfonyl-beta cyclodextrin
Adding 6g of beta-CD (beta-cyclodextrin) into a 500mL dry single-neck flask, then adding 120mL of NaOH solution with the concentration of 0.75moL/L, stirring to completely dissolve the beta-CD, controlling the temperature at 0-5 ℃, slowly adding 1.2g of paratoluensulfonyl chloride under stirring after cyclodextrin is completely dissolved, controlling the temperature at 0-5 ℃ all the time to react for 5 hours, filtering to remove unreacted raw materials, adjusting the filtrate to be neutral by using dilute hydrochloric acid, placing the neutral filtrate into a refrigerator to be refrigerated overnight, filtering to obtain a crude product, dissolving the obtained crude product into hot water, filtering while the hot crude product is hot, placing the filtrate into the refrigerator to be overnight, and filtering to obtain the product. The precipitation is repeated for 3 times, and vacuum drying is carried out until the weight is constant, so as to obtain the 6-TsO-beta-CD.
e) Preparation step of alkynylated beta-cyclodextrin
And d, adding 10.0g of 6-TsO-beta-CD obtained in the step d into 20mL of propynylamine, heating the mixed solution to 65 ℃ under the nitrogen atmosphere, and reacting for 24 h. The mixture was then poured into 100mL of acetonitrile to give the solid product 6- β -CD-C ≡ CH.
f) Preparation step of alkynylated beta cyclodextrin @ graphene oxide
Adding 200mg GO into 10mL of DMF solution, carrying out ultrasonic treatment for 5h to obtain stable dispersed GO/DMF solution, adding 40mL of SOCl2The temperature is raised to 70 ℃ and the reaction is refluxed for 48 hours, and when the reaction is finished, the excess SOCl is removed by a rotary evaporator2And d, dissolving GO-Cl into 33mL of DMF solution, adding 6-beta-CD-C [ identical to ] CH (6-beta-CD-C [ identical to ] CH) obtained in the step e, uniformly mixing, heating, reacting at 100 ℃ for 60 hours, cooling to room temperature, filtering, and drying in a vacuum oven at 70 ℃ to constant weight to obtain the alkynyl beta-cyclodextrin @ graphene oxide (CH [ identical to ] C-beta-CD @ GO).
g) The preparation method of the proton composite membrane material comprises the following steps:
taking 0.5gCH ≡ C-beta-CD @ GO and 10g SPPO-CH2N3(5 wt.%) dissolving the product in 20mL of N, N-Dimethylformamide (DMF), vacuumizing for three times, injecting 0.58mL of N, N, N' -Pentamethyldiethylenetriamine (PMDETA) and 0.4g of cuprous bromide under argon atmosphere, introducing argon for 15min, sealing the reaction vessel, reacting at 35 ℃ for 48h, cooling to room temperature, settling the product with anhydrous methanol for 3 times, washing with deionized water, placing in a vacuum drying oven at 25 ℃, and drying in vacuum to constant weight to obtain the productThe polymer SPPO/β -CD @ GO.
Example 5
A preparation method of a novel composite proton exchange membrane material sequentially comprises the following steps: a) a sulfonated polyphenyl ether preparation step; b) preparing chloromethylation sulfonated polyphenyl ether; c) preparing azido sulfonated polyphenylene ether; d) 6-tosyl-beta cyclodextrin preparation; e) preparing alkynyl beta-cyclodextrin; f) preparing alkynylated beta cyclodextrin @ graphene oxide; g) preparing a proton composite membrane material;
removing g) a preparation step of the proton composite membrane material:
1.5gCH ≡ C-beta-CD @ GO and 10g SPPO-CH are taken2N3(15 wt.%), except that, the same as example 4.
Example 6
Dissolving 1g of the proton composite membrane material (SPPO/beta-CD @ GO) prepared in examples 1-5 in 8.4ml of DMF, preparing 12 wt.% solution, heating to 25 ℃, keeping the temperature for 1h, cooling to room temperature, standing for more than 12h to obtain polymer solution, coating the polymer solution on a glass plate, drying in an oven at 70 ℃ for 12h to prepare composite membranes 1,2, 3, 4 and 5, wherein the results are shown in Table 1
Methanol Permeability of the invention (10)-7cm2S) according to Yang, T.and C.Liu, SPEEK/sulfonated cyclic extension blend membrane for direct conversion of hydrocarbon Energy,2011.36(9): p.5666-5674. Standard
Proton conductivity (10)-3S/cm) according to Yang, T.and C.Liu, SPEEK/sulfonated cyclic extension blend membrane for direct methanol fuel cell, 2011.36(9): p.5666-5674. Standard
Water absorption (%) test according to the Gong, C.L., et al, A new Strategy for designing high-performance sulfonated poly (ether ketone) polymer electrolyte membranes using inorganic proton conductor-functional carbon nanotubes, journal of Power Source, 2016.325: p.453-464. Standard
TABLE 1
Claims (8)
1. A preparation method of a composite proton exchange membrane material is characterized by comprising the following steps: the method sequentially comprises the following steps: a) a sulfonated polyphenyl ether preparation step; b) preparing chloromethylation sulfonated polyphenyl ether; c) preparing azido sulfonated polyphenylene ether; d) 6-tosyl-beta cyclodextrin preparation; e) preparing alkynyl beta-cyclodextrin; f) preparing alkynylated beta cyclodextrin @ graphene oxide; g) preparing a proton composite membrane material;
the f) preparation step of the alkynyl beta-cyclodextrin @ graphene oxide comprises the following steps:
adding graphene oxide GO into DMF, wherein the weight-volume ratio of graphene oxide GO to DMF is 1: carrying out ultrasonic treatment for 5-8h at a concentration of 50-75g/ml to obtain a stable dispersed GO/DMF solution; adding SOCl2Heating to 70-75 deg.C, reacting for 24-28 hr to obtain GO-Cl, and removing excessive SOCl with rotary evaporator2And then adding DMF for dissolution to obtain a GO-Cl/DMF solution, wherein the weight to volume ratio of GO-Cl to DMF is 1: 100 and 200g/ml, adding the alkynylated beta cyclodextrin 6-beta-CD-C ≡ CH obtained in the step e, heating to 95-100 ℃, reacting for 48-60 hours, cooling to room temperature, filtering, and drying in a vacuum oven at 70-75 ℃ to constant weight to obtain the alkynylated beta cyclodextrin @ graphene oxide CH ≡ C-beta-CD @ GO;
the g) proton composite membrane material preparation step:
taking the alkynylated beta cyclodextrin @ graphene oxide obtained in the step f, and adding the azido sulfonated polyphenylene ether SPPO-CH obtained in the step c2N3And then adding N, N-dimethylformamide DMF (dimethyl formamide) for dissolving, injecting N, N, N' -pentamethyl diethylenetriamine PMDETA and cuprous bromide under the argon atmosphere, introducing argon for 15-20 minutes, sealing a reaction container, reacting at 35-75 ℃ for 12-48 hours, cooling to room temperature, settling for 2-3 times by using anhydrous methanol, washing by using deionized water, putting into a vacuum drying oven at 25-40 ℃, drying to constant weight, and preparing the sulfonated polyphenylene oxide/beta cyclodextrin @ graphene oxide SPPO/beta-CD @ GO polymer.
2. The method for preparing a composite proton exchange membrane material according to claim 1, wherein:
the preparation step of the a) sulfonated polyphenyl ether comprises the following steps:
completely dissolving polyphenyl ether with the number average molecular weight of 2 w-1000 w in CHCl under the condition of mechanical stirring3In, HSO is added dropwise3Cl and Si (CH)3)3Mixture of Cl in N2Reacting at 35-40 deg.C for 12-14h under atmosphere, adding CH3ONa, and continuing to react for 1-2h until white particles appear; alternately washing the white particles with anhydrous methanol and deionized water for 2-3 times, and vacuum drying at 70-80 ℃ to constant weight to prepare sulfonated polyphenylene oxide (SPPO);
polyphenylene ether with CHCl3The weight to volume ratio of (1): 8-10 g/ml;
polyphenylene ether, HSO3Cl、Si(CH3)3Cl、CH3The weight ratio of ONa is 100: (170-340):(200-400): (400-700).
3. The method for preparing a composite proton exchange membrane material according to claim 1, wherein:
the b) chloromethylation sulfonated polyphenylene oxide preparation step comprises:
dissolving the sulfonated polyphenylene oxide SPPO obtained in the step a in 1, 2-dichloroethane, then adding anhydrous zinc chloride and chloromethyl ether, heating to 35-40 ℃, reacting for 4-6h, cooling to room temperature, settling the polymer prepared by the reaction with anhydrous methanol for 2-3 times, washing with deionized water for 2-3 times, putting into a vacuum drying oven with the temperature of 50-55 ℃, and drying in vacuum to constant weight to obtain chloromethylated sulfonated polyphenylene oxide SPPO-CH2Cl；
The weight-volume ratio of the sulfonated polyphenylene ether SPPO to the 1, 2-dichloroethane is 1:5-10 g/ml;
the weight ratio of the sulfonated polyphenyl ether, the anhydrous zinc chloride and the chloromethyl ether is 100: (10-20): (40-50).
4. The method for preparing a composite proton exchange membrane material according to claim 1, wherein:
the c) azido sulfonated polyphenylene oxide preparation step comprises:
taking chloromethylation sulfonated polyphenyl ether SPPO-CH obtained in the step b2Dissolving Cl and sodium azide in dimethyl sulfoxide, heating to 70-75 ℃, cooling to room temperature after reaction for not less than 48h, settling the polymer prepared by the reaction for 2-3 times by using a mixed solvent of anhydrous methanol and deionized water, filtering, putting into a vacuum drying oven at 30-35 ℃, and drying to constant weight to obtain a product, namely the azido sulfonated polyphenylene ether SPPO-CH2N3；
SPPO-CH2The weight ratio of Cl to sodium azide is 10: 1-1.5,
SPPO-CH2the weight to volume ratio of Cl to dimethylsulfoxide was 1:5-10g/ml of the mixture,
the volume ratio of the anhydrous methanol to the deionized water is 3.8-4.2: 1.
5. the method for preparing a composite proton exchange membrane material according to claim 1, wherein:
graphene oxide GO and SOCl2The weight to volume ratio of (1): 150-200 g/ml.
6. The method for preparing a composite proton exchange membrane material according to claim 1, wherein:
the weight ratio of graphene oxide GO to alkynylated beta cyclodextrin 6-beta-CD-C ≡ CH is 1: 10-20.
7. The method for preparing a composite proton exchange membrane material according to claim 1, wherein:
the alkynylated beta cyclodextrin @ graphene oxide and SPPO-CH2N3N, N, N' -pentamethyldiethylenetriamine and cuprous bromide in the weight ratio of 1: (20-200): (1.3-9.6): (1.4-8).
8. The method for preparing a composite proton exchange membrane material according to claim 1, wherein:
the weight-volume ratio of the alkynyl beta-cyclodextrin @ graphene oxide to DMF in the g) preparation step of the proton composite membrane material is 1: 400-800 g/ml.
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