The preparation method of phosphorylation sulfonated polyether-ether-ketone and Nano particles of silicon dioxide composite membraneTechnical field
The invention belongs to technical field of polymer composite materials, and in particular to a kind of phosphorylation sulfonated polyether-ether-ketone and dioxyThe preparation method of SiClx nanoparticle composite membrane.
Background technique
Proton exchange membrane is one of the core component of Proton Exchange Membrane Fuel Cells and direct alcohol fuel cell, effectIt is: (1) separates anode and cathode, fuel and air (oxygen) directly mixing is prevented to chemically react；(2) proton conducting, matterElectron conductivity is higher, and the internal resistance of film is smaller, and the efficiency of fuel cell is higher；(3) electrical insulator prevents electronics from conducting in film,Electronics, by outside line road direction cathode flow, it is for people to use to generate foreign current by anode.In general, fuel cell PEM materialIt must meet the following requirement: (1) inexpensive；(2) high proton conductivity；(3) good mechanical strength (anti-swelling) and size are steadyIt is qualitative；(4) excellent chemical stability and electrochemical stability；(5) very low gas or methanol permeability；(6) and catalystLayer matching；(7) it is used for a long time and stablizes.
A kind of macromolecule of the sulfonated polyether-ether-ketone as glassy state has good thermal stability and mechanical strength, gasInfiltration coefficient it is lower.In gas separation process, usually with the presence of vapor, and most of membrane material water-resistant stability byLimitation, and sulfonated polyether-ether-ketone has excellent water resistance, can be used as the high-molecular matrix material in hybridized film.
Summary of the invention
The purpose of the present invention is to provide a kind of phosphorylation sulfonated polyether-ether-ketones and Nano particles of silicon dioxide composite membranePreparation method.
The technical solution adopted by the present invention to solve the technical problems is: phosphorylation sulfonated polyether-ether-ketone is received with silicaThe preparation method of rice corpuscles composite membrane, comprising the following steps:
1) N is added in phosphorylation sulfonated polyether-ether-ketone, in N '-dimethyl formamide, mechanical stirring 1-2h must be uniformly dispersedConcentration be 5-10wt% polymer solution；
2) Nano particles of silicon dioxide is added N, in N '-dimethyl formamide, ultrasonic disperse 30-60min obtains titanium dioxideThen silicon dispersion liquid is added graphene oxide and chitosan, is ultrasonically treated to obtain mixed liquor；
3) polymer solution of step 1) is added in the mixed liquor of step 2), is then added silane coupling agent, 40-65 DEG CMechanical stirring 4-6h, is cooled to room temperature, and is coated on clean glass plate, is dried in vacuo 12-24h, is immersed in 1mol/L after demouldingSulfuric acid solution in for 24 hours, then use deionized water soaking and washing, it is dry after up to phosphorylation sulfonated polyether-ether-ketone and silicaNanoparticle composite membrane.
Specifically, Nano particles of silicon dioxide in the step 2), graphene oxide, chitosan mass ratio be 3-8:5-10:5-10。
Specifically, in the step 3 phosphorylation sulfonated polyether-ether-ketone, Nano particles of silicon dioxide, silane coupling agent matterAmount is than being 10-20:3-8:1-2；The silane coupling agent is 3-aminopropyltriethoxysilane, 3- (2- aminoethyl)-ammonia thirdOne of base trimethoxy silane and 3- TSL 8330.
Specifically, the preparation step of the phosphorylation sulfonated polyether-ether-ketone is as follows:
1) sulfonated polyether-ether-ketone is added in organic solvent and is dispersed with stirring uniformly, chloromethyl is added in concentration 10-20wt%Octyl Ether is stirred to react 1-2h, and the mass ratio of sulfonated polyether-ether-ketone and chloromethyl Octyl Ether is 1-5:20-35, after reaction willSolution pours into ice water, filters, is washed till neutrality repeatedly with deionized water, then washs several times product with ethyl alcohol, removes chloromethaneBase Octyl Ether, 40 DEG C of vacuum drying for 24 hours, obtain chloromethylation sulfonated polyether-ether-ketone；The organic solvent be dimethyl sulfoxide, N,One of N '-dimethyl formamide, dehydrated alcohol；
2) chloromethylation sulfonated polyether-ether-ketone is dissolved in NMP, is configured to the dispersion liquid that concentration is 1-3wt%, be added sub-The mass ratio of triethyl phosphate, triethyl phosphite and chloromethylation sulfonated polyether-ether-ketone is 3-5:1-3, anti-in 100-120 DEG C10h is answered, is evaporated under reduced pressure to remove remaining triethyl phosphite, washed product, suction filtration are dried in vacuo repeatedly with deionized waterPhosphate is obtained for 24 hours replaces sulfonated polyether-ether-ketone；
3) replace sulfonated polyether-ether-ketone that back flow reaction 12h in concentrated hydrochloric acid is added phosphate, phosphate replaces sulfonated polyetherThe mass ratio of ether ketone and concentrated hydrochloric acid is 3-7:80-120, is washed till neutrality, 60-80 DEG C of vacuum drying 20- with a large amount of deionized watersFor 24 hours, phosphorylation sulfonated polyether-ether-ketone is obtained.
The invention has the following advantages: the present invention first to sulfonated polyether-ether-ketone carry out phosphorylation, then with titanium dioxideComposite membrane is made by casting film-forming in silicon nano, graphene oxide, chitosan, silane coupling agent, the composite membrane have compared withGood proton-conducting reduces methanol permeability.Due to introducing Nano particles of silicon dioxide, it can also enhance the moisture absorption energy of composite membranePower makes composite membrane also be able to maintain certain proton conductivity when compared with low humidity.
Specific embodiment
The following is specific embodiments of the present invention, is described further to technical solution of the present invention, but of the inventionProtection scope is not limited to these examples.It is all to be included in the present invention without departing substantially from the change of present inventive concept or equivalent substituteProtection scope within.
Embodiment 1
Sulfonated polyether-ether-ketone is added in dimethyl sulfoxide and is dispersed with stirring uniformly, it is pungent that chloromethyl is added in concentration 15wt%Base ether is stirred to react 1h, and sulfonated polyether-ether-ketone and the mass ratio of chloromethyl Octyl Ether are 2:35, after reaction pours into solutionIt in ice water, filters, is washed till neutrality repeatedly with deionized water, then product is washed several times with ethyl alcohol, removes chloromethyl Octyl Ether,40 DEG C of vacuum drying for 24 hours, obtain chloromethylation sulfonated polyether-ether-ketone；
Chloromethylation sulfonated polyether-ether-ketone is dissolved in NMP, the dispersion liquid that concentration is 3wt% is configured to, phosphorous acid is addedThe mass ratio of triethyl, triethyl phosphite and chloromethylation sulfonated polyether-ether-ketone is 3:2, and in 110 DEG C of reaction 10h, decompression is steamedIt evaporates to remove remaining triethyl phosphite, with deionized water, washed product, suction filtration, vacuum drying obtain phosphate for 24 hours repeatedlyReplace sulfonated polyether-ether-ketone；
Replace sulfonated polyether-ether-ketone that back flow reaction 12h in concentrated hydrochloric acid is added phosphate, phosphate replaces sulfonated polyether etherThe mass ratio of ketone and concentrated hydrochloric acid is 5:110, is washed till neutrality with a large amount of deionized waters, 60 DEG C of vacuum drying 20h obtain phosphorylation sulfonationPolyether-ether-ketone.
The preparation method of phosphorylation sulfonated polyether-ether-ketone and Nano particles of silicon dioxide composite membrane, comprising the following steps:
1) N is added in phosphorylation sulfonated polyether-ether-ketone, in N '-dimethyl formamide, mechanical stirring 2h obtains finely dispersedConcentration is the polymer solution of 7wt%；
2) Nano particles of silicon dioxide is added N, in N '-dimethyl formamide, ultrasonic disperse 40min obtains silica pointThen graphene oxide and chitosan is added in dispersion liquid, be ultrasonically treated to obtain mixed liquor, Nano particles of silicon dioxide, graphene oxide,The mass ratio of chitosan is 8:7:5；
3) polymer solution of step 1) is added in the mixed liquor of step 2), silane coupling agent 3- aminopropan is then addedEthyl triethoxy silicane alkane, phosphorylation sulfonated polyether-ether-ketone, Nano particles of silicon dioxide, silane coupling agent mass ratio be 15:7:2,50 DEG C of mechanical stirring 5h, are cooled to room temperature, and are coated on clean glass plate, are dried in vacuo 18h, are immersed in 1mol/L after demouldingSulfuric acid solution in for 24 hours, then use deionized water soaking and washing, it is dry after up to phosphorylation sulfonated polyether-ether-ketone and silicaNanoparticle composite membrane.
Embodiment 2
N is added in sulfonated polyether-ether-ketone, is dispersed with stirring in N '-dimethyl formamide uniformly, chlorine is added in concentration 20wt%Methyl Octyl Ether is stirred to react 1h, and the mass ratio of sulfonated polyether-ether-ketone and chloromethyl Octyl Ether is 1:20, after reaction will be moltenLiquid pours into ice water, filters, is washed till neutrality repeatedly with deionized water, then washs several times product with ethyl alcohol, removes chloromethylOctyl Ether, 40 DEG C of vacuum drying for 24 hours, obtain chloromethylation sulfonated polyether-ether-ketone；
Chloromethylation sulfonated polyether-ether-ketone is dissolved in NMP, the dispersion liquid that concentration is 2wt% is configured to, phosphorous acid is addedThe mass ratio of triethyl, triethyl phosphite and chloromethylation sulfonated polyether-ether-ketone is 5:2, and in 100 DEG C of reaction 10h, decompression is steamedIt evaporates to remove remaining triethyl phosphite, with deionized water, washed product, suction filtration, vacuum drying obtain phosphate for 24 hours repeatedlyReplace sulfonated polyether-ether-ketone；
Replace sulfonated polyether-ether-ketone that back flow reaction 12h in concentrated hydrochloric acid is added phosphate, phosphate replaces sulfonated polyether etherThe mass ratio of ketone and concentrated hydrochloric acid is 3:80, is washed till neutrality with a large amount of deionized waters, 70 DEG C of vacuum drying for 24 hours, obtain phosphorylation sulfonationPolyether-ether-ketone.
The preparation method of phosphorylation sulfonated polyether-ether-ketone and Nano particles of silicon dioxide composite membrane, comprising the following steps:
1) N is added in phosphorylation sulfonated polyether-ether-ketone, in N '-dimethyl formamide, mechanical stirring 1.5h must be uniformly dispersedConcentration be 5wt% polymer solution；
2) Nano particles of silicon dioxide is added N, in N '-dimethyl formamide, ultrasonic disperse 30min obtains silica pointThen graphene oxide and chitosan is added in dispersion liquid, be ultrasonically treated to obtain mixed liquor, Nano particles of silicon dioxide, graphene oxide,The mass ratio of chitosan is 4:5:10；
3) polymer solution of step 1) is added in the mixed liquor of step 2), silane coupling agent 3- aminopropan is then addedBase trimethoxy silane, phosphorylation sulfonated polyether-ether-ketone, Nano particles of silicon dioxide, silane coupling agent mass ratio be 10:5:0 DEG C of mechanical stirring 4h of Isosorbide-5-Nitrae, is cooled to room temperature, and is coated on clean glass plate, is dried in vacuo 12h, is immersed in 1mol/L after demouldingSulfuric acid solution in for 24 hours, then use deionized water soaking and washing, it is dry after up to phosphorylation sulfonated polyether-ether-ketone and silicaNanoparticle composite membrane.
Embodiment 3
Sulfonated polyether-ether-ketone is added to absolute ethanol and is dispersed with stirring uniformly, chloromethyl octyl is added in concentration 10wt%Ether is stirred to react 2h, and sulfonated polyether-ether-ketone and the mass ratio of chloromethyl Octyl Ether are 3:25, and solution is poured into ice after reactionIt in water, filters, is washed till neutrality repeatedly with deionized water, then washed product several times with ethyl alcohol, removing chloromethyl Octyl Ether, 40DEG C vacuum drying for 24 hours, obtain chloromethylation sulfonated polyether-ether-ketone；
Chloromethylation sulfonated polyether-ether-ketone is dissolved in NMP, the dispersion liquid that concentration is 1wt% is configured to, phosphorous acid is addedThe mass ratio of triethyl, triethyl phosphite and chloromethylation sulfonated polyether-ether-ketone is 4:3, and in 120 DEG C of reaction 10h, decompression is steamedIt evaporates to remove remaining triethyl phosphite, with deionized water, washed product, suction filtration, vacuum drying obtain phosphate for 24 hours repeatedlyReplace sulfonated polyether-ether-ketone；
Replace sulfonated polyether-ether-ketone that back flow reaction 12h in concentrated hydrochloric acid is added phosphate, phosphate replaces sulfonated polyether etherThe mass ratio of ketone and concentrated hydrochloric acid is 6:100, is washed till neutrality with a large amount of deionized waters, 80 DEG C of vacuum drying 22h obtain phosphorylation sulfonationPolyether-ether-ketone.
The preparation method of phosphorylation sulfonated polyether-ether-ketone and Nano particles of silicon dioxide composite membrane, comprising the following steps:
1) N is added in phosphorylation sulfonated polyether-ether-ketone, in N '-dimethyl formamide, mechanical stirring 1h obtains finely dispersedConcentration is the polymer solution of 10wt%；
2) Nano particles of silicon dioxide is added N, in N '-dimethyl formamide, ultrasonic disperse 50min obtains silica pointThen graphene oxide and chitosan is added in dispersion liquid, be ultrasonically treated to obtain mixed liquor, Nano particles of silicon dioxide, graphene oxide,The mass ratio of chitosan is 3:8:7；
3) polymer solution of step 1) is added in the mixed liquor of step 2), silane coupling agent 3- (2- ammonia is then addedEthyl)-aminopropyl trimethoxysilane, the quality of phosphorylation sulfonated polyether-ether-ketone, Nano particles of silicon dioxide, silane coupling agentThan being cooled to room temperature for 20:3:2,65 DEG C of mechanical stirring 6h, it is coated on clean glass plate, vacuum drying for 24 hours, is soaked after demouldingBubble for 24 hours, then uses deionized water soaking and washing, up to phosphorylation sulfonated polyether-ether-ketone after drying in the sulfuric acid solution of 1mol/LWith Nano particles of silicon dioxide composite membrane.
Embodiment 4
N is added in sulfonated polyether-ether-ketone, is dispersed with stirring in N '-dimethyl formamide uniformly, chlorine is added in concentration 18wt%Methyl Octyl Ether is stirred to react 2h, and the mass ratio of sulfonated polyether-ether-ketone and chloromethyl Octyl Ether is 5:31, after reaction will be moltenLiquid pours into ice water, filters, is washed till neutrality repeatedly with deionized water, then washs several times product with ethyl alcohol, removes chloromethylOctyl Ether, 40 DEG C of vacuum drying for 24 hours, obtain chloromethylation sulfonated polyether-ether-ketone；
Chloromethylation sulfonated polyether-ether-ketone is dissolved in NMP, the dispersion liquid that concentration is 2wt% is configured to, phosphorous acid is addedThe mass ratio of triethyl, triethyl phosphite and chloromethylation sulfonated polyether-ether-ketone is 3:1, and in 110 DEG C of reaction 10h, decompression is steamedIt evaporates to remove remaining triethyl phosphite, with deionized water, washed product, suction filtration, vacuum drying obtain phosphate for 24 hours repeatedlyReplace sulfonated polyether-ether-ketone；
Replace sulfonated polyether-ether-ketone that back flow reaction 12h in concentrated hydrochloric acid is added phosphate, phosphate replaces sulfonated polyether etherThe mass ratio of ketone and concentrated hydrochloric acid is 7:120, is washed till neutrality with a large amount of deionized waters, 70 DEG C of vacuum drying for 24 hours, obtain phosphorylation sulfonationPolyether-ether-ketone.
The preparation method of phosphorylation sulfonated polyether-ether-ketone and Nano particles of silicon dioxide composite membrane, comprising the following steps:
1) N is added in phosphorylation sulfonated polyether-ether-ketone, in N '-dimethyl formamide, mechanical stirring 2h obtains finely dispersedConcentration is the polymer solution of 8wt%；
2) Nano particles of silicon dioxide is added N, in N '-dimethyl formamide, ultrasonic disperse 60min obtains silica pointThen graphene oxide and chitosan is added in dispersion liquid, be ultrasonically treated to obtain mixed liquor, Nano particles of silicon dioxide, graphene oxide,The mass ratio of chitosan is 6:10:9；
3) polymer solution of step 1) is added in the mixed liquor of step 2), silane coupling agent 3- (2- ammonia is then addedEthyl)-aminopropyl trimethoxysilane, the quality of phosphorylation sulfonated polyether-ether-ketone, Nano particles of silicon dioxide, silane coupling agentThan being cooled to room temperature for 17:8:1,60 DEG C of mechanical stirring 4h, it is coated on clean glass plate, is dried in vacuo 20h, is soaked after demouldingBubble for 24 hours, then uses deionized water soaking and washing, up to phosphorylation sulfonated polyether-ether-ketone after drying in the sulfuric acid solution of 1mol/LWith Nano particles of silicon dioxide composite membrane.