CN1743378A - A kind of organic/inorganic nano composite proton electro-conductive material and preparation method thereof - Google Patents
A kind of organic/inorganic nano composite proton electro-conductive material and preparation method thereof Download PDFInfo
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- CN1743378A CN1743378A CN 200510028253 CN200510028253A CN1743378A CN 1743378 A CN1743378 A CN 1743378A CN 200510028253 CN200510028253 CN 200510028253 CN 200510028253 A CN200510028253 A CN 200510028253A CN 1743378 A CN1743378 A CN 1743378A
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Abstract
The invention belongs to the functional composite material technical field, be specially organic/inorganic nano composite proton electro-conductive material of a kind of POSS of containing and preparation method thereof.Its preparation method is: by organosilane monomer and the synthetic a kind of double bond containing POSS of monomeric partial hydrolysis one angle-sealing method of active organosilicon, with itself and double bond containing reactive monomer copolymerization, be prepared into the organic/inorganic nano composite proton electro-conductive material that contains POSS again.The adding of POSS has significantly improved the electric conductivity of matrix material, and makes polymkeric substance have higher physical strength and certain film-forming properties.This electro-conductive material is under 200 ℃ of temperature condition, and its specific conductivity reaches 2 * 10
-3, reach more than 70% at the light transmission rate of visible region.The inventive method is simple to operate, production efficiency is higher, and the thermostability and the chemical stability of prepared organic/inorganic nano composite material are good, the proton fuel cell field of high temperature non-aqueous system in can being widely used in.
Description
Technical field
The invention belongs to matrix material and technical field of function materials, be specifically related to organic/inorganic nano composite proton electro-conductive material of a kind of POSS of containing and preparation method thereof.
Background technology
Organic is a kind of novel organic/inorganic composite material that development in recent years is got up, it is with the addition polymerization in inorganic chemistry and the polymer subject, the combination dexterously of chemical reactions such as polycondensation, make formed matrix material possess simple organism or the not available performance of inorganics, its performance is between traditional organic materials (as polymer) and inorganic materials (as pottery), both had the good processibility of organic materials, toughness is with low-cost, it is heat-resisting to keep inorganic materials again, resistance to oxidation and excellent mechanical property have become the important means for preparing the performance function material at present.
The method for preparing Organic mainly contains 4 kinds of coupling agent pack, in-situ inserted polymerization, sol-gel method and functionalization polyhedral oligomeric silsesquioxane (POSS) modification composite algorithms etc.The coupling agent pack is difficult to solve inorganic nano-particle because of the high difficult problem of easily reuniting of surface energy, the limitation of intercalation compounding is the inorganic materials that is only applicable to the characteristics hierarchical structure, and though sol-gel method is simple, efficient and reappears, its thermostability and chemical stability are still waiting improvement.POSS then is a kind of novel material of developing in recent years, the advantage that has traditional Organic based on the matrix material of POSS, the shortcoming of but not having traditional Organic, but it not only can be by the nanoparticle of the functionalization of purchasing, make polymkeric substance and inorganic nano material reach truly Chemical bond, simultaneously, the POSS molecule can also connect various functional group, prepare novel organic and inorganic complex light, electricity, magnetic, even biomaterial etc.
Summary of the invention
The objective of the invention is to propose a kind of thermostability and chemical stability is good, can be applied to the organic/inorganic nano composite proton electro-conductive material and preparation method thereof of the novel POSS of containing in the proton fuel cell field of high temperature non-aqueous system.
The organic/inorganic nano composite proton electro-conductive material that contains POSS that the present invention proposes by organosilane monomer and the synthetic a kind of double bond containing POSS of the monomeric partial hydrolysis-angle-sealing method of active organosilicon, prepares it earlier again with containing the double bond monomer copolymerization, wherein:
Organosilane monomer is METHYL TRICHLORO SILANE, ethyl trichlorosilane, propyltrichlorosilan, phenyl-trichloro-silicane, vinyl trichloro silane, methyl ethylene trichlorine siloxanes or γ-chloropropyl trichlorine siloxanes etc., preferable methyl trichlorine siloxanes and phenyl trichlorine siloxanes;
The active organosilicon monomer is vinyl trichloro silane, methyl ethylene trichlorine siloxanes, γ-chloropropyl trichlorine siloxanes, vinyltrimethoxy silane, vinyltriethoxysilane, γ-acryloxy Trimethoxy silane or γ-acryloxy triethoxyl silane etc., preferred vinyl Trimethoxy silane and γ-acryloxy Trimethoxy silane;
Containing double bond monomer is vinylbenzene, vinylformic acid, methacrylic acid, methyl methacrylate, vinyl carbazole, ethene imidazoles, V-Pyrol RC, vinylpyridine, vinyl cyanide or vinyl acetate etc., optimal ethylene imidazoles, vinyl carbazole and V-Pyrol RC.
The preparation method of the above-mentioned organic/inorganic nano composite proton electro-conductive material that contains POSS is as follows:
(1) in the there-necked flask that reflux condensate device and agitator are housed, adds the total machine solvent of 5～25mL organosilane monomer, 5～50mL distilled water and 25～150mL, 30～80 ℃ stirred in water bath 12～72 hours, collection is obtained white solid, filter with total machine solvent wash, vacuum-drying is more than 12 hours under 30～60 ℃ of conditions, product is handled with the alkali organic solvent of 5～30 times of weight, again it is poured in the mixture of isopyknic hydrochloric acid and ice, filter and be washed to neutrality then, vacuum-drying is more than 12 hours under 40～80 ℃ of conditions.Thoroughly extract with ether again, obtain unmodified POSS;
(2) be that dropwise Dropwise 5～25ml concentration is the active organosilicon monomer solution of 0.025g/ml, reacts 12～72 hours in 30～50 ℃ of water-baths in the mixed organic solvents of above-mentioned POSS of 0.025g/ml in 5～50ml concentration.Product poured in 5～20 times frozen water and the hydrochloric acid mixed solution leave standstill more than 12 hours, the precipitate with deionized water washing that obtains is till filtrate is neutrality.Filter the white solid of collecting, vacuum-drying promptly obtained the POSS with two key groups more than 12 hours under 30～60 ℃ of conditions;
(3) in the there-necked flask of reflux condensate device is housed, the above-mentioned POSS of 0.5～5g is dissolved in 10～50ml organic solvent, slow Dropwise 5～25ml contains the organic solvent solution of double bond monomer and initiator under 60-70 ℃ of condition, initiator amount is the 0.5-1.5% of monomer weight, dropwise the back and continue reaction 6～24 hours, behind the stopped reaction, the methanol extraction that adds 5～20 times, after centrifuging and the purification process, 60～100 ℃ of vacuum-dryings promptly obtain containing the organic/inorganic nano composite proton electro-conductive material of POSS more than 12 hours (as 12-18 hour).
Organic/inorganic nano composite proton electro-conductive material and the organic solvent of the above-mentioned POSS of containing are heated to dissolving fully, making concentration is the organic/inorganic nano composite proton electro-conductive material solution that contains POSS of 5～30% (weight ratios), in this solution, add protonic acid (for example doping level is 0.1～10.0) then, the back casting film stirs, freeze-day with constant temperature 12～48h in vacuum drying oven, so that remove solvent residual in the composite membrane and water fully, prepare the organic/inorganic nano composite proton conducting film that contains POSS at last, the thickness of this composite membrane is generally 2～10 μ m.
Among the present invention, organosilane monomer can be METHYL TRICHLORO SILANE, ethyl trichlorosilane, propyltrichlorosilan, phenyl-trichloro-silicane, vinyl trichloro silane, methyl ethylene trichlorosilane or γ-chloropropyl trichloro-silane etc.
Among the present invention, the active organosilicon monomer can be vinyl trichloro silane, methyl ethylene trichlorine siloxanes, vinyltrimethoxy silane, vinyltriethoxysilane, γ-acryloxy Trimethoxy silane or γ-acryloxy triethoxyl silane etc.
Among the present invention, the monomer of two keys can be vinyl carbazole, ethene imidazoles, V-Pyrol RC, vinylpyridine, vinyl cyanide, vinylformic acid, methacrylic acid, methyl methacrylate or vinyl acetate etc.
Among the present invention, initiator can be benzoyl peroxide, peroxidized t-butyl perbenzoate, peroxidation-3,5, the 5-trimethylacetic acid tert-butyl ester, peroxide-2-ethyl hexanoic acid tert-butyl, dilauroyl peroxide, tert-butyl peroxy acetate, Diisopropyl azodicarboxylate, 1, the peroxidation-3 of 1-dual-tert-butyl, 3,5 trimethyl-cyclohexanes, isopropyl benzene hydroperoxide, tertbutyl peroxide, ditertiary butyl peroxide, tert-pentyl peroxide 2-ethylhexanoate, 2,5-dimethyl-2,5 di-t-butyl peroxy hexane etc.
Among the present invention, total machine solvent can be acetone, butanone, tetrahydrofuran (THF), dioxane, dimethyl formamide or N,N-DIMETHYLACETAMIDE etc.
Among the present invention, alkali organic solvent can be pyridine, picoline, ethylpyridine, ethamine, diethylamine, triethylamine, dimethyl formamide or N,N-DIMETHYLACETAMIDE etc.
Among the present invention, mixed organic solvents can be two kinds or the mixture of above solvent in tetrahydrofuran (THF), trichloromethane, methylene dichloride, dioxane, acetone, butanone, pimelinketone, benzene,toluene,xylene, pyridine, picoline, ethylpyridine, ethamine, diethylamine, triethylamine, dimethyl formamide or the N,N-DIMETHYLACETAMIDE.
Among the present invention, protonic acid can be phosphoric acid, sulfuric acid, hydrochloric acid or heteropolyacid etc.
Advantage of the present invention is: adopt functionalization polyhedral oligomeric silsesquioxane (POSS) modification composite algorithm, POSS is carried out polyreaction with the monomer that contains ethene, prepare the organic/inorganic nano composite proton electro-conductive material of a kind of novel POSS of containing.The adding of inorganic components POSS not only can improve the electric conductivity of composite membrane, and the adding of POSS can make polymkeric substance have higher physical strength and certain film-forming properties, in addition, the thermal stability of this organic/inorganic nano composite proton electro-conductive material is good, chemical stability is higher.The electric conductivity of this novel organic/inorganic nano composite proton electro-conductive material is under 200 ℃ of temperature condition, and its specific conductivity can reach 2 * 10
-3, the organic/inorganic nano composite proton electro-conductive material of this novel POSS of containing can be applied to the proton fuel cell of middle high temperature non-aqueous system, gathers around to have broad application prospects and use value.
Description of drawings
Fig. 1 is the field emission scanning electron microscope figure that contains the organic/inorganic nano composite proton electro-conductive material of POSS.
Fig. 2 is the graph of a relation of the electric conductivity of the organic/inorganic nano composite proton conducting film (phosphate-doped degree is 1) that contains POSS to temperature.
Fig. 3 is the ultraviolet-visible light transmission rate that contains the organic/inorganic nano composite proton electro-conductive material of POSS.
Embodiment
The above-mentioned organic/inorganic nano composite proton electro-conductive material that contains POSS, its preparation method is at first to add 5～25mL organosilane monomer in the there-necked flask that reflux condensate device and agitator are housed, 5～50ml distilled water and 25～150mL have the machine solvent, 20～80 ℃ stirred in water bath 12～72 hours, the white solid that after reaction finishes collection is obtained filters back vacuum-drying under 30～60 ℃ of conditions with total machine solvent wash and spends the night, product spends the night with the alkali organic solvent suspension and the stirring of 5～30 times of weight, this solution is poured in the mixture of isopyknic concentrated hydrochloric acid and ice, collecting precipitation is washed with water to neutrality then, and vacuum-drying is spent the night under 40～80 ℃ of conditions.Thoroughly extract with ether again, can obtain unmodified POSS.
Be that dropwise Dropwise 5～25ml concentration is the active organosilicon monomer solution of 0.025g/ml, reacts 12～72 hours in 30～50 ℃ of water-baths in the mixed organic solvents of above-mentioned POSS of 0.025g/ml in 5～50ml concentration then.Pour product in 5～20 times frozen water and concentrated hydrochloric acid mixing solutions standing over night, the precipitate with deionized water that obtains is washed till filtrate is neutrality.Filter white solid vacuum-drying under 30～60 ℃ of conditions of collecting and promptly obtain POSS more than 12 hours with two key groups.
Then in the there-necked flask of reflux condensate device is housed, the POSS of the above-mentioned band active group of 0.5～5g is dissolved in 10～50ml organic solvent, slow Dropwise 5～25ml contains the organic solvent solution of double bond monomer and an amount of initiator under 60-70 ℃ of temperature condition, dropwise the back and continue reaction 6～24 hours, behind the stopped reaction, the methanol extraction that adds 5～20 times, after centrifuging and the purification process, 60～100 ℃ of vacuum-dryings promptly obtained containing the organic/inorganic nano composite proton electro-conductive material of POSS more than 12 hours.
At last with a certain amount of above-mentioned organic/inorganic nano composite proton electro-conductive material and the organic solvent that contains POSS, after heating is dissolved fully, making concentration is the organic/inorganic nano composite proton electro-conductive material solution that contains POSS of 5～30% (weight ratios), in this solution, add protonic acid (for example doping level is 0.1～10.0) then, the back casting film stirs, freeze-day with constant temperature 12～48h in vacuum drying oven, so that remove solvent residual in the composite membrane and water fully, prepare the organic/inorganic nano composite proton conducting film that contains POSS at last, the thickness of this composite membrane is generally 2～10 μ m.
Organosilane is METHYL TRICHLORO SILANE, ethyl trichlorosilane, propyltrichlorosilan, phenyl-trichloro-silicane, vinyl trichloro silane, methyl ethylene trichlorine siloxanes or γ-chloropropyl trichlorine siloxanes etc., preferable methyl trichlorine siloxanes and phenyl trichlorine siloxanes.The active organosilicon monomer is vinyl trichloro silane, methyl ethylene trichlorine siloxanes, γ-chloropropyl trichlorine siloxanes, vinyltrimethoxy silane, vinyltriethoxysilane, γ-acryloxy Trimethoxy silane or γ-acryloxy triethoxyl silane etc., preferred vinyl Trimethoxy silane and γ-acryloxy Trimethoxy silane.Total machine solvent can be acetone, butanone, tetrahydrofuran (THF), dioxane, dimethyl formamide or N,N-DIMETHYLACETAMIDE etc., preferred acetone, butanone and dioxane etc.Alkali organic solvent can be pyridine, picoline, ethylpyridine, ethamine, diethylamine, triethylamine, dimethyl formamide or N,N-DIMETHYLACETAMIDE etc., preferred pyridine and dimethyl formamide etc.Mixed organic solvents can be in tetrahydrofuran (THF), trichloromethane, methylene dichloride, dioxane, acetone, butanone, pimelinketone, benzene,toluene,xylene, pyridine, picoline, ethylpyridine, ethamine, diethylamine, triethylamine, dimethyl formamide or the N,N-DIMETHYLACETAMIDE two kinds or more than, preferred tetrahydrofuran (THF)/triethylamine and tetrahydrofuran (THF)/dimethyl formamide etc.Double bond containing monomer is vinylbenzene, vinylformic acid, methacrylic acid, methyl methacrylate, vinyl carbazole, ethene imidazoles, V-Pyrol RC, vinylpyridine, vinyl cyanide or vinyl acetate etc., optimal ethylene imidazoles, vinyl carbazole and V-Pyrol RC.Initiator is benzoyl peroxide, peroxidized t-butyl perbenzoate, peroxidation-3,5, the 5-trimethylacetic acid tert-butyl ester, peroxide-2-ethyl hexanoic acid tert-butyl, dilauroyl peroxide, tert-butyl peroxy acetate, Diisopropyl azodicarboxylate, 1, the peroxidation-3 of 1-dual-tert-butyl, 3,5 trimethyl-cyclohexanes, isopropyl benzene hydroperoxide, tertbutyl peroxide, ditertiary butyl peroxide, tert-pentyl peroxide 2-ethylhexanoate, 2,5-dimethyl-2,5 di-t-butyl peroxy hexanes etc., preferred benzoyl peroxide and Diisopropyl azodicarboxylate.
The present invention will be described in detail below in conjunction with embodiment.Do not violating under the purport of the present invention, the present invention should be not limited to the content that following experimental example is specifically expressed.
Embodiment 1
In the there-necked flask that reflux condensate device and agitator are housed, careful 17.7mL distilled water is added in 10mL trichloromethyl silane and the 60mL acetone under agitation condition, 50 ℃ stirred in water bath reactions 48 hours, the white solid that after reaction finishes collection is obtained filters back vacuum-drying under 45 ℃ of conditions with washing with acetone and spends the night, product spends the night with the pyridine suspension and the stirring of 20 times of weight, again this pyridine solution is poured in the mixture of isopyknic concentrated hydrochloric acid and ice, be washed with water to neutrality then, vacuum-drying is more than 12 hours under 60 ℃ of conditions.Thoroughly extract with ether again, can obtain unmodified POSS.Be triethylamine/tetrahydrofuran (THF) (1: 100 of the above-mentioned POSS of 0.025g/ml then in 15ml concentration, volume ratio) in the mixing solutions, dropwise dripping 20ml concentration is the tetrahydrofuran solution of γ-acryloxy Trimethoxy silane of 0.025g/ml, and reaction is 72 hours in 35 ℃ of water-baths.Pour product in 10 times frozen water and concentrated hydrochloric acid mixing solutions standing over night, the precipitate with deionized water that obtains washing several times are till filtrate is neutrality.It is dry more than 12 hours under 60 ℃ of vacuum to filter the white solid of collecting, and promptly obtains the POSS with two key groups.Then in the there-necked flask of reflux condensate device is housed, with the POSS ultrasonic dissolution of the two keys of the above-mentioned band of 1.0g in the 15ml tetrahydrofuran (THF), the tetrahydrofuran solution of slow Dropwise 5 ml ethene imidazoles monomer and 1% benzoyl peroxide under 65 ℃ of temperature condition, drip the back and continue reaction 10 hours, behind the stopped reaction, add 10 times methanol extraction, after centrifuging and the purification process, 65 ℃ of vacuum-dryings promptly obtained containing the organic/inorganic nano composite proton electro-conductive material of POSS more than 12 hours.At last with a certain amount of above-mentioned organic/inorganic nano composite proton electro-conductive material and the dioxane solvent that contains POSS, after heating is dissolved fully, making concentration is the organic/inorganic nano composite proton electro-conductive material solution that contains POSS of 25% (weight ratio), in this solution, add a certain amount of phosphoric acid or sulfuric acid (doping level is 1) then, the back casting film stirs, put into 80 ℃ of dry 48h of vacuum drying oven constant temperature at last, so that remove solvent residual in the composite membrane fully, prepare the organic/inorganic nano composite proton conducting film that contains POSS, the thickness of this composite membrane is 5 μ m.Fig. 1 is this electron micrograph that contains the organic/inorganic nano composite proton electro-conductive material of POSS, in this figure just as can be seen the POSS particle size about 100nm, in addition, can see that from this figure these organic/inorganic nano composite particles great majority are the bilayer structure of coated.Fig. 2 is the graph of a relation of the electric conductivity of the organic/inorganic nano composite proton conducting film (phosphate-doped degree is 1) that contains POSS to temperature, as can be seen from the figure the electric conductivity of this organic/inorganic nano composite proton conducting film enlarges markedly along with the rising of temperature, under 200 ℃ temperature condition, its specific conductivity can reach 2 * 10
-3Fig. 3 be contain POSS organic/inorganic nano composite proton electro-conductive material visible light transmissivity, this organic/inorganic nano composite proton conducting film all is improved largely in the transmitance of visible light and UV-light part, especially in the visible light part, transmitance reaches more than 70%.
Embodiment 2
Identical with embodiment 1, but trichloromethyl silane changes trichlorophenyl silane into, γ-acryloxy Trimethoxy silane changes methyl ethylene trichlorine siloxanes into, and concentration and consumption are constant.
Embodiment 3
Identical with embodiment 1, but trichloromethyl silane changes vinyl trichloro silane into, and consumption becomes 6mL.
Embodiment 4
Identical with embodiment 1, but the quantitative change of water is 14mL.
Embodiment 5
Identical with embodiment 1, but the quantitative change of water is 26mL.
Embodiment 6
Identical with embodiment 1, but the monomeric quantitative change of ethene imidazoles is 10ml, and initiator concentration becomes 0.5%.
Embodiment 7
Identical with embodiment 1, but the monomeric quantitative change of ethene imidazoles is 15ml, and initiator concentration becomes 1.5%.
Embodiment 8
Identical with embodiment 1, but the doping level of phosphoric acid becomes 2.
Embodiment 9
Identical with embodiment 1, but the doping level of phosphoric acid becomes 4.
Embodiment 10
Identical with embodiment 1, but ethene imidazoles monomer changes vinyl carbazole into, and consumption is constant.
Embodiment 11
Identical with embodiment 1, but ethene imidazoles monomer changes vinylpyridine into, and consumption becomes 10mL.
Embodiment 12
Identical with embodiment 1, but γ-acryloxy Trimethoxy silane changes vinyltrimethoxy silane into, and consumption and concentration become 10mL and 0.05g/mL respectively.
Embodiment 13
Identical with embodiment 1, but γ-acryloxy Trimethoxy silane changes ethyl trichlorosilane into, and other remains unchanged.
The organic/inorganic nano composite proton electro-conductive material that contains POSS that the foregoing description 2-13 is prepared, its structure and performance and embodiment 1 come to the same thing or similar, all have good thermostability and chemical stability, and under middle hot conditions, have higher proton conductivity and an optical transmittance, be a kind of good organic/inorganic nano composite functional material, the fields such as proton fuel cell of high temperature non-aqueous system in can be applicable to.
Claims (7)
1, a kind of organic/inorganic nano composite proton electro-conductive material that contains POSS, it is characterized in that, by organosilane monomer and the synthetic a kind of double bond containing POSS of the monomeric partial hydrolysis-angle-sealing method of active organosilicon, again it is prepared with containing the double bond monomer copolymerization earlier, wherein:
Organosilane monomer is METHYL TRICHLORO SILANE, ethyl trichlorosilane, propyltrichlorosilan, phenyl-trichloro-silicane, vinyl trichloro silane, methyl ethylene trichlorine siloxanes or γ-chloropropyl trichlorine siloxanes;
The active organosilicon monomer is vinyl trichloro silane, methyl ethylene trichlorine siloxanes, γ-chloropropyl trichlorine siloxanes, vinyltrimethoxy silane, vinyltriethoxysilane, γ-acryloxy Trimethoxy silane or γ-acryloxy triethoxyl silane;
Containing double bond monomer is vinylbenzene, vinylformic acid, methacrylic acid, methyl methacrylate, vinyl carbazole, ethene imidazoles, V-Pyrol RC, vinylpyridine, vinyl cyanide or vinyl acetate.
2, a kind of preparation method who contains the organic/inorganic nano composite proton electro-conductive material of POSS as claimed in claim 1 is characterized in that concrete steps are:
(1) in the there-necked flask that reflux condensate device and agitator are housed, adds the total machine solvent of 5～25mL organosilane monomer, 5～50mL distilled water and 25～150mL, 30～80 ℃ stirred in water bath 12～72 hours; Collection obtains white solid, filters with total machine solvent wash again, and vacuum-drying is more than 12 hours under 30～60 ℃ of conditions; Product is handled with the alkali organic solvent of 5～30 times of weight, it is poured in the mixture of isopyknic hydrochloric acid and ice again, filters and be washed to neutrality then, and vacuum-drying is more than 12 hours under 40～80 ℃ of conditions; Thoroughly extract with ether again, obtain unmodified POSS;
(2) be that Dropwise 5～25ml concentration is the active organosilicon monomer solution of 0.025g/ml, reacts 12～72 hours in 30～50 ℃ of water-baths in the mixed organic solvents of above-mentioned POSS of 0.025g/ml in 5～50ml concentration; Product poured in 5～20 times frozen water and the concentrated hydrochloric acid mixing solutions leave standstill more than 12 hours, the precipitate with deionized water washing that obtains is till filtrate is neutrality; Filter the white solid of collecting, vacuum-drying promptly obtained the POSS with two key groups more than 12 hours under 30～60 ℃ of conditions;
(3) in the there-necked flask of reflux condensate device is housed, the above-mentioned POSS of 0.5～5g is dissolved in 10～50ml organic solvent, Dropwise 5～25ml contains the organic solvent solution of double bond monomer and initiator under 60-70 ℃ of temperature condition, initiator amount is the 0.5-1.5% of monomer weight, dropwises the back and continues reaction 6～24 hours; Behind the stopped reaction, add 5～20 times methanol extraction, after centrifuging and the purification process, 60～100 ℃ of vacuum-dryings promptly obtained containing the organic/inorganic nano composite proton electro-conductive material of POSS more than 12 hours.
3, preparation method according to claim 2, its feature is heated to dissolving fully in organic/inorganic nano composite proton electro-conductive material and the organic solvent with the described POSS of containing, make weight concentration and be 5～30% the organic/inorganic nano composite proton electro-conductive material solution that contains POSS, in this solution, add doping level then and be 0.1～10.0 protonic acid, the back casting film stirs, freeze-day with constant temperature 12～48h in vacuum drying oven, remove solvent residual in the composite membrane and water fully, obtain containing the organic/inorganic nano composite proton conducting film of POSS.
4, according to claim 2 or 3 described preparation methods, it is characterized in that said initiator is benzoyl peroxide, peroxidized t-butyl perbenzoate, peroxidation-3,5, the 5-trimethylacetic acid tert-butyl ester, peroxide-2-ethyl hexanoic acid tert-butyl, dilauroyl peroxide, tert-butyl peroxy acetate, Diisopropyl azodicarboxylate, 1, the peroxidation-3 of 1-dual-tert-butyl, 3,5 trimethyl-cyclohexanes, isopropyl benzene hydroperoxide, tertbutyl peroxide, ditertiary butyl peroxide, tert-pentyl peroxide 2-ethylhexanoate or 2,5-dimethyl-2,5 di-t-butyl peroxy hexane.
5,, it is characterized in that said total machine solvent is acetone, butanone, tetrahydrofuran (THF), dioxane, dimethyl formamide or N,N-DIMETHYLACETAMIDE according to claim 2 or 3 described preparation methods.
6,, it is characterized in that said alkali organic solvent is pyridine, picoline, ethylpyridine, ethamine, diethylamine, triethylamine, dimethyl formamide or N,N-DIMETHYLACETAMIDE according to claim 2 or 3 described preparation methods.
7,, it is characterized in that said mixed organic solvents is made up of two or more mixing in tetrahydrofuran (THF), trichloromethane, methylene dichloride, dioxane, acetone, butanone, pimelinketone, benzene,toluene,xylene, pyridine, picoline, ethylpyridine, ethamine, diethylamine, triethylamine, dimethyl formamide or the N,N-DIMETHYLACETAMIDE according to claim 2 or 3 described preparation methods.
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| CN103113505A (en) * | 2013-02-04 | 2013-05-22 | 厦门大学 | Triazole-based polyhedral oligomeric silsesquioxane copolymer and preparation method thereof |
| CN104282428A (en) * | 2013-07-10 | 2015-01-14 | 天津工业大学 | Method for preparing magnetic POSS |
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| CN101974118B (en) * | 2010-11-10 | 2012-08-22 | 上海交通大学 | Solvent thermal polymerization method of styrene-silane copolymer |
| CN103113505A (en) * | 2013-02-04 | 2013-05-22 | 厦门大学 | Triazole-based polyhedral oligomeric silsesquioxane copolymer and preparation method thereof |
| CN103113505B (en) * | 2013-02-04 | 2015-05-13 | 厦门大学 | Triazole-based polyhedral oligomeric silsesquioxane copolymer and preparation method thereof |
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| CN104356284A (en) * | 2014-11-04 | 2015-02-18 | 江南大学 | Epoxy functional group containing nano-reinforcer for hybrid polymer epoxy resin |
| CN111909409A (en) * | 2020-08-11 | 2020-11-10 | 河北工业大学 | Preparation method of azole ring-containing oligosiloxane composite proton exchange membrane |
| CN111909409B (en) * | 2020-08-11 | 2022-07-05 | 河北工业大学 | Preparation method of azole ring-containing oligosiloxane composite proton exchange membrane |
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