CN102295291B - Method for preparing mesoporous silicon dioxide - Google Patents
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- CN102295291B CN102295291B CN 201110218650 CN201110218650A CN102295291B CN 102295291 B CN102295291 B CN 102295291B CN 201110218650 CN201110218650 CN 201110218650 CN 201110218650 A CN201110218650 A CN 201110218650A CN 102295291 B CN102295291 B CN 102295291B
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Abstract
The invention relates to a method for preparing mesoporous silicon dioxide, the method is characterized in that mercapto-vinyl can be used for a free radical addition reaction, organo-silicone containing a mercapto group and polybutadiene block of triblock copolymer of styrene-butadiene-styrene are reacted, an organo-siloxane modified styrene-butadiene-styrene triblock copolymer can be obtained, then the organo-siloxane modified styrene-butadiene-styrene triblock copolymer is carried out a sol-gel reaction with a silicon source under the acidic or alkaline condition to form gel, the mesoporous silicon dioxide is obtained after cracking the gel. Compared with the prior art, the mesoporous silicon dioxide material has the average pore diameter of 5-18nm, the pore volume of 0.24-0.30 cm<3>/g, the specific surface area of 418-480 cm<2>/g, and has the advantages of cheap raw material and easy raw material acquisition, mild reaction condition, simple and high efficient preparation process, safety and environmental protection, and is convenient for large scale production.
Description
Technical field
The present invention relates to a kind of preparation method of inorganic materials, especially relate to a kind of method for preparing mesoporous silicon oxide.
Background technology
Mesoporous silicon oxide has larger nano level aperture, is applicable to the multiple uses such as macromole separation, catalysis, microreactor.Yet, for synthesizing of mesoporous silicon oxide, still lack simple and practical method.
Chinese patent CN 1872684A has reported a kind of preparation method of mesoporous silicon oxide, and template and water-soluble polymers is water-soluble, adds acid the pH value is adjusted between the 0.3-0.4; Add again silicon ester and obtain reaction solution, at room temperature stir reactor that hydrolysis changed autogenous pressure in 4-20 hour in 80-120 ℃ of crystallization 24 hours, leach, washing, drying, at last in retort furnace in 550 ℃ of roastings 6 hours, obtain mesoporous silicon oxide.The used template of the method mainly is expensive oxygen ethene-oxypropylene-oxygen ethene triblock copolymer, need simultaneously to use water-soluble polymers, and reaction needed is carried out under the condition of High Temperature High Pressure.
Chinese patent CN 1435373A has reported a kind of preparation method of mesoporous silicon oxide, at first organosilane or small molecules organic compound, water, hydrochloric acid and ethanol is pressed the certain mol proportion reaction; Add again a kind of or mixing blocked nonionogenic tenside homodisperse solution in ethanol; Behind strong stirring, add inorganic silicon source reaction for some time, and in air, placing under the room temperature, make solvent evaporates complete; Then use the methods such as organic solvent reflux extraction or high-temperature roasting with removal of surfactant, thereby obtain mesoporous silicon oxide.The method of this solvent flashing is that resulting colloidal sol is transferred in furnace pot, crucible or the porcelain boat, perhaps use " dip coating " or " spin-coating method " directly to be coated onto on the carriers such as sheet glass, silicon chip, plastics, solvent evaporates efficient is low and easily also there is potential safety hazard in process of production in environment.Described blocked nonionic surface active agent is also all expensive.
SBS (SBS) is a kind of commercial macromolecular material of widespread use.SBS mainly obtains by sequence anionoid polymerization.Can regulate the ratio of divinyl 1,2 and Isosorbide-5-Nitrae structure in the polymerization process by regulating solvent polarity.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of raw material cheap and easy to get for the defective that overcomes above-mentioned prior art existence, and reaction conditions is gentle, and preparation process is simple efficiently, the method for preparing mesoporous silicon oxide of safety and environmental protection.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of method for preparing mesoporous silicon oxide, adopted sulfydryl-Vinyl radical addition reaction will contain organo-siloxane and the reaction of the polybutadiene block in the SBS of mercapto groups, obtain organic siloxane modified SBS, then sol gel reaction formation gel is occured in organic siloxane modified SBS and silicon source under acidity or alkaline condition, microphase-separated occurs in organic siloxane modified SBS in gel, gel obtains mesoporous silicon oxide after cracking, this preparation method obtains mean pore size at 5-18nm, and pore volume is at 0.24-0.30cm
3/ g, specific surface area is at 418-480cm
2The Metaporous silicon dioxide material of/g.
The method specifically may further comprise the steps:
A kind of method for preparing mesoporous silicon oxide is characterized in that, the method may further comprise the steps:
(1) with organic solvent, SBS and contain the organo-siloxane stirring and dissolving of mercapto groups, add radical initiator, be warming up to 45-90 ℃, begin to carry out the graft modification reaction, reaction times 0.5-24h, adding dehydrated alcohol to polymkeric substance all precipitates after reacting end, and suction filtration and drying obtain organic siloxane modified SBS;
(2) under 10-45 ℃ of agitation condition, the organic siloxane modified SBS that step (1) is prepared and silicon come from the organic solvent and dissolve, add deionized water and acid solution or alkaline solution, carry out sol gel reaction, 10-45 ℃ of lower the maintenance 2-14 days, form gel, then washing and dry rear in 500-600 ℃ of cracking 3-5 hour namely obtains a kind of mesoporous silicon oxide.
The mass ratio of the organic solvent described in the step (1) and SBS is 20-100, containing sulfydryl in the organo-siloxane of mercapto groups and the mol ratio of the two keys in the SBS is 1-20, and containing sulfydryl in the organo-siloxane of mercapto groups and the mol ratio of radical initiator is 10-500.
The preferred 40-60 of mass ratio of the organic solvent described in the step (1) and SBS, contain sulfydryl in the organo-siloxane of mercapto groups and the preferred 5-12 of mol ratio of the two keys in the SBS, contain sulfydryl in the organo-siloxane of mercapto groups and the preferred 80-120 of mol ratio of radical initiator.
The mass ratio of the organic solvent described in the step (1) and SBS is 44-55 more preferably, the mol ratio that contains sulfydryl in the organo-siloxane of mercapto groups and the two keys in the SBS is 9-10 more preferably, and the mol ratio that contains sulfydryl in the organo-siloxane of mercapto groups and radical initiator is 90-110 more preferably.
Organic solvent described in the step (1) is selected from 1,2-ethylene dichloride, 1, one or more in 2-methylene dichloride, normal hexane, chloroform, benzene, tetrahydrofuran (THF), dioxane, tetracol phenixin, toluene or the dimethylbenzene; The described organo-siloxane that contains mercapto groups is mercaptopropyl trimethoxysilane or mercaptopropyltriethoxysilane; The number-average molecular weight scope of described SBS is 1000-30000, and the massfraction of the 1，2-butadiene that wherein contains is 20-80%; Described radical initiator is selected from a kind of in dibenzoyl peroxide, dilauroyl peroxide, di-cyclohexylperoxy dicarbonate, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), methyl vinyl ketone, st-yrax, dimethoxybenzoin, benzophenone or the eosin.
The mass ratio of the silicon source described in the step (2) and organic siloxane modified SBS is 0-10, contained siloxy total amount and the mol ratio of deionized water are 0.1-10 in silicon source and the organic siloxane modified SBS, contained siloxy total amount and the mol ratio of acid or alkali are 0.5-10 in silicon source and the organic siloxane modified SBS, and the concentration range of described acid solution or alkaline solution is 0.1-5mol/L.
The preferred 1.5-9 of mass ratio of the silicon source described in the step (2) and organic siloxane modified SBS, contained siloxy total amount and the preferred 0.8-1.2 of mol ratio of deionized water in silicon source and the organic siloxane modified SBS, contained siloxy total amount and the preferred 0.8-1.2 of mol ratio of acid or alkali in silicon source and the organic siloxane modified SBS, the preferred 0.5-2mol/L of the concentration range of described acid solution or alkaline solution.
The mass ratio of the silicon source described in the step (2) and organic siloxane modified SBS more preferably 4, the mol ratio of contained siloxy total amount and deionized water more preferably 1 in silicon source and the organic siloxane modified SBS, the mol ratio of contained siloxy total amount and acid or alkali more preferably 1 in silicon source and the organic siloxane modified SBS, and the concentration range of described acid solution or alkaline solution is 1mol/L more preferably.
Silicon source described in the step (2) is selected from one or more in methyl silicate, tetraethoxy, positive silicic acid propyl ester, butyl silicate, water glass or the silicon sol.
Acid solution described in the step (2) is selected from a kind of in the aqueous solution of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acid or glacial acetic acid, and described alkaline solution is ammoniacal liquor.
The preparation method's of mesoporous silicon oxide chemical equation is as follows:
The principle for preparing the method for mesoporous silicon oxide is, contain the intermediate that sulfydryl in the organo-siloxane of mercapto groups and the vinyl generation Radical Addition in the SBS form vinyl thioether form, thus this intermediate rapidly with the organo-siloxane that contains mercapto groups in another sulfydryl reaction form thioether product and obtain organic siloxane modified SBS.Siloxanes in the organic siloxane modified SBS again with the silicon source in siloxanes sol gel reaction occurs under acidity or alkaline condition forms gel, microphase-separated occurs in organic siloxane modified SBS in gel, gel obtains a kind of mesoporous silicon oxide after cracking.Compare with background technology, the present invention has following advantage:
(1) raw material is cheap and easy to get, and all raw materials used in the present invention are cheap industrialization product, and employed segmented copolymer price is all higher in the background technology;
(2) the reaction conditions temperature with, temperature of reaction of the present invention is lower and do not need condition of high voltage, and Chinese patent CN 1872684A needs high-temperature and high-pressure conditions;
(3) preparation process is simply efficient, and it is complete that Chinese patent CN 1435373A requires to be placed to solvent evaporates under the room temperature, and this is very time-consuming, and there is not this problem in the present invention;
(4) safety and environmental protection, the solvent-free volatilization step of the present invention, and the solvent evaporates step of Chinese patent CN 1435373A pollutes the environment and have potential safety hazard;
(5) be convenient to scale operation, raw material used in the present invention is the general industry product, and reaction conditions all possesses the large-scale industrial production requirement;
(6) the present invention prepares mean pore size at 5-18nm, and pore volume is at 0.24-0.30cm
3/ g, specific surface area is at 418-480cm
2The Metaporous silicon dioxide material of/g, have raw material cheap and easy to get, reaction conditions is gentle, and preparation process is simple efficiently, the characteristics of safety and environmental protection, be convenient to scale operation, product has broad application prospects at aspects such as catalysis, sensor, macromole separation, microreactor, biochips.
Description of drawings
Fig. 1 is the proton nmr spectra of the organic siloxane modified SBS of embodiment 1 gained and pure styrene-butadiene-styrene triblock copolymer;
Fig. 2 is the nitrogen adsorption-desorption curve and pore size distribution curve figure of embodiment 1 gained mesoporous silicon oxide;
Fig. 3 is the transmission electron microscope photo of the mesoporous silicon oxide for preparing of embodiment 4.
Embodiment
The present invention is described in detail below in conjunction with accompanying drawing and specific embodiment.
The employed SBS of following examples is provided by Balin Branch Corp. SINOPEC, number-average molecular weight is 178000, molecular weight distribution 1.02, the vinylbenzene massfraction is 43.75%, 1 of divinyl, the massfraction of 2 structures is 36.36%, and the massfraction of the Isosorbide-5-Nitrae structure of divinyl is 19.89%.
(1) 1g SBS and 24.79g mercaptopropyltriethoxysilane are dissolved in the dioxane of 48mL, under 10-45 ℃, stir; Then add the 0.17g Diisopropyl azodicarboxylate and be uniformly dispersed, be warming up to gradually 60 ℃ of reactions 1 day.Through precipitation, suction filtration, drying, obtain organic siloxane modified SBS;
(2) under 10-45 ℃ of condition, in encloses container that 0.2010g is organic siloxane modified SBS and 1.8015g tetraethoxy are dissolved in the 5mL tetrahydrofuran (THF) and continuous the stirring, dropwise add again 0.6544g deionized water and 0.6568g 1M hydrochloric acid, along with the carrying out that stirs, the generation of sol gel reaction so that system viscosity rise gradually; Approximately stop after 25 minutes stirring, keep 10-45 ℃ of reactor to descend airtight 14 days; Thereby then in tube furnace, its high temperature degradation is removed polymkeric substance and obtain a kind of mesoporous silicon oxide.Its mean pore size 12nm.Fig. 1 and Fig. 2 are respectively organic siloxane modified SBS and proton nmr spectra and nitrogen adsorption-desorption curve and the pore size distribution curve figure of pure styrene-butadiene-styrene triblock copolymer, as seen from Figure 1, contain sulfydryl in the organo-siloxane that contains mercapto groups of mercapto groups and successfully add on the two keys of butadiene block in the SBS, successfully obtain organic siloxane modified SBS; As seen from Figure 2, the BET value of this mesoporous silicon oxide reaches 418m
2/ g, pore volume 0.24cm
3/ g.
(1) 1g SBS and 24.79g mercaptopropyltriethoxysilane are dissolved in the dioxane of 48mL, under 10-45 ℃, stir; Then add the 0.17g Diisopropyl azodicarboxylate and be uniformly dispersed, be warming up to gradually 60 ℃ of reactions 1 day.Through precipitation, suction filtration, drying, obtain organic siloxane modified SBS;
(2) under 10-45 ℃ of condition, in encloses container that 0.4002g is organic siloxane modified SBS and 1.6039g tetraethoxy are dissolved in the 5mL tetrahydrofuran (THF) and continuous the stirring, dropwise add again 0.6175g deionized water and 0.6300g 1M hydrochloric acid, along with the carrying out that stirs, the generation of sol gel reaction so that system viscosity rise gradually; Approximately stop after 15 minutes stirring, keep 10-45 ℃ of reactor to descend airtight 14 days; Thereby then in tube furnace, its high temperature degradation is removed polymkeric substance and obtain a kind of mesoporous silicon oxide.Its BET value reaches 450m
2/ g, mean pore size 18nm, pore volume 0.29cm
3/ g.
Embodiment 3
(1) 1g SBS and 24.79g mercaptopropyltriethoxysilane are dissolved in the dioxane of 48mL, under 10-45 ℃, stir; Then add the 0.17g Diisopropyl azodicarboxylate and be uniformly dispersed, be warming up to gradually 60 ℃ of reactions 1 day.Through precipitation, suction filtration, drying, obtain organic siloxane modified SBS;
(2) under 10-45 ℃ of condition, in encloses container that 0.6024g is organic siloxane modified SBS and 1.4080g tetraethoxy are dissolved in the 5mL tetrahydrofuran (THF) and continuous the stirring, dropwise add again 0.5807g deionized water and 0.5764g 1M hydrochloric acid, along with the carrying out that stirs, the generation of sol gel reaction so that system viscosity rise gradually; Approximately stop after 8 minutes stirring, keep 10-45 ℃ of reactor to descend airtight 14 days; Thereby then in tube furnace, its high temperature degradation is removed polymkeric substance and obtain a kind of mesoporous silicon oxide.Its BET value reaches 480m
2/ g, mean pore size 8nm, pore volume 0.30cm
3/ g.
Embodiment 4
(1) 1g SBS and 24.79g mercaptopropyltriethoxysilane are dissolved in the dioxane of 48mL, under 10-45 ℃, stir; Then add the 0.17g Diisopropyl azodicarboxylate and be uniformly dispersed, be warming up to gradually 60 ℃ of reactions 1 day.Through precipitation, suction filtration, drying, obtain organic siloxane modified SBS;
(2) under 10-45 ℃ of condition, in encloses container that 0.8001g is organic siloxane modified SBS and 1.2025g tetraethoxy are dissolved in the 5mL tetrahydrofuran (THF) and continuous the stirring, dropwise add again 0.5438g deionized water and 0.5496g 1M hydrochloric acid, along with the carrying out that stirs, the generation of sol gel reaction so that system viscosity rise gradually; Approximately stop after 8 minutes stirring, keep 10-45 ℃ of reactor to descend airtight 14 days; Thereby then in tube furnace, its high temperature degradation is removed polymkeric substance and obtain a kind of mesoporous silicon oxide.Its BET value reaches 425m
2/ g, pore volume 0.29cm
3/ g.Fig. 3 is the transmission electron microscope photo of this mesoporous silicon oxide, and as seen from Figure 3, the mean pore size of this mesoporous silicon oxide is 5nm.
Embodiment 5
(1) 1g SBS and 24.79g mercaptopropyltriethoxysilane are dissolved in the dioxane of 48mL, under 10-45 ℃, stir; Then add the 0.17g Diisopropyl azodicarboxylate and be uniformly dispersed, be warming up to gradually 60 ℃ of reactions 1 day.Through precipitation, suction filtration, drying, obtain organic siloxane modified SBS;
(2) under 10-45 ℃ of condition, the SBS that 1.1802g is organic siloxane modified is dissolved in the 5mL tetrahydrofuran (THF) and constantly and stirs in encloses container, dropwise add again 0.5209g deionized water and 0.5496g 1M hydrochloric acid, along with the carrying out that stirs, the generation of sol gel reaction so that system viscosity rise gradually; Approximately stop after 8 minutes stirring, keep 10-45 ℃ of reactor to descend airtight 14 days; Thereby then in tube furnace, its high temperature degradation is removed polymkeric substance and obtain a kind of mesoporous silicon oxide.Its BET value reaches 445m
2/ g, mean pore size 8nm, pore volume 0.29cm
3/ g.
Embodiment 6
A kind of method for preparing mesoporous silicon oxide, adopted sulfydryl-Vinyl radical addition reaction will contain organo-siloxane and the reaction of the polybutadiene block in the SBS of mercapto groups, obtain organic siloxane modified SBS, then sol gel reaction formation gel is occured in organic siloxane modified SBS and silicon source under acidic conditions, microphase-separated occurs in organic siloxane modified SBS in gel, gel obtains mesoporous silicon oxide after cracking.
The method specifically may further comprise the steps:
(1) with organic solvent, SBS and the organo-siloxane stirring and dissolving that contains mercapto groups, add radical initiator, be warming up to 45 ℃, begin to carry out the graft modification reaction, reaction times 24h, adding dehydrated alcohol to polymkeric substance after reaction finishes all precipitates, suction filtration and drying obtain organic siloxane modified SBS, wherein, the mass ratio of organic solvent and SBS is 20, containing sulfydryl in the organo-siloxane of mercapto groups and the mol ratio of the two keys in the SBS is 1, containing sulfydryl in the organo-siloxane of mercapto groups and the mol ratio of radical initiator is 10, in the present embodiment, organic solvent is 1,2-one ethylene dichloride, the organo-siloxane that contains mercapto groups is mercaptopropyl trimethoxysilane, the number-average molecular weight of SBS is 1000, wherein the massfraction of 1，2-butadiene is 20%; Radical initiator is dibenzoyl peroxide;
(2) under 10 ℃ of agitation conditions, the organic siloxane modified SBS that step (1) is prepared dissolves in organic solvent, adds deionized water and acid solution, carries out sol gel reaction, 10 ℃ of lower maintenances 14 days, form gel; Then washing and dry rear in 500 ℃ of cracking 4 hours, namely obtain mesoporous silicon oxide, wherein, contained siloxy total amount and the mol ratio of deionized water are 0.1 in silicon source and the organic siloxane modified SBS, contained siloxy total amount is 0.5 with the mol ratio of acid in silicon source and the organic siloxane modified SBS, the silicon source is siloxane solvent, and acid solution is the hydrochloric acid soln of 0.1mol/L.
Embodiment 7
A kind of method for preparing mesoporous silicon oxide specifically may further comprise the steps:
(1) with organic solvent, SBS and the organo-siloxane stirring and dissolving that contains mercapto groups, add radical initiator, be warming up to 50 ℃, begin to carry out the graft modification reaction, reaction times 6h, adding dehydrated alcohol to polymkeric substance after reaction finishes all precipitates, suction filtration and drying obtain organic siloxane modified SBS, wherein, the mass ratio of organic solvent and SBS is 40, containing sulfydryl in the organo-siloxane of mercapto groups and the mol ratio of the two keys in the SBS is 5, containing sulfydryl in the organo-siloxane of mercapto groups and the mol ratio of radical initiator is 80, the organic solvent that adopts in the present embodiment is the mixture of chloroform and tetracol phenixin, and the organo-siloxane that contains mercapto groups is mercaptopropyltriethoxysilane; The number-average molecular weight of SBS is 5000, and wherein the massfraction of 1，2-butadiene is 30%; Radical initiator is di-cyclohexylperoxy dicarbonate;
(2) under 25 ℃ of agitation conditions, the organic siloxane modified SBS that step (1) is prepared and silicon come from the organic solvent and dissolve, add deionized water and acid solution, carry out sol gel reaction, 25 ℃ of lower maintenances 7 days, form gel; Then washing and dry rear in 500 ℃ of cracking 5 hours, namely obtain mesoporous silicon oxide, wherein, the mass ratio of silicon source and organic siloxane modified SBS is 1.5, contained siloxy total amount and the mol ratio of deionized water are 0.8 in silicon source and the organic siloxane modified SBS, contained siloxy total amount is 0.8 with the mol ratio of acid in silicon source and the organic siloxane modified SBS, the silicon source is water glass, and acid solution is the sulfuric acid of 1mol/L.
Embodiment 8
A kind of method for preparing mesoporous silicon oxide specifically may further comprise the steps:
(1) with organic solvent, SBS and the organo-siloxane stirring and dissolving that contains mercapto groups, add radical initiator, be warming up to 80 ℃, begin to carry out the graft modification reaction, reaction times 12h, adding dehydrated alcohol to polymkeric substance after reaction finishes all precipitates, suction filtration and drying obtain organic siloxane modified SBS, wherein, the mass ratio of organic solvent and SBS is 60, containing sulfydryl in the organo-siloxane of mercapto groups and the mol ratio of the two keys in the SBS is 12, containing sulfydryl in the organo-siloxane of mercapto groups and the mol ratio of radical initiator is 120, the organic solvent that adopts is the mixture of toluene and dimethylbenzene, the organo-siloxane that contains mercapto groups is mercaptopropyl trimethoxysilane, the number-average molecular weight of SBS is 10000, wherein the massfraction of 1，2-butadiene is 60%; Radical initiator is methyl vinyl ketone;
(2) under 30 ℃ of agitation conditions, the organic siloxane modified SBS that step (1) is prepared and silicon come from the organic solvent and dissolve, add deionized water and alkaline solution, carry out sol gel reaction, 30 ℃ of lower maintenances 5 days, form gel; Then washing and dry rear in 600 ℃ of cracking 4 hours, namely obtain mesoporous silicon oxide, wherein, the mass ratio of silicon source and organic siloxane modified SBS is 9, contained siloxy total amount and the mol ratio of deionized water are 1.2 in silicon source and the organic siloxane modified SBS, contained siloxy total amount and the mol ratio of alkali are 1.2 in silicon source and the organic siloxane modified SBS, the silicon source is tetraethoxy and positive silicic acid propyl ester, and alkaline solution is the ammoniacal liquor of 0.8mol/L.
Embodiment 9
A kind of method for preparing mesoporous silicon oxide specifically may further comprise the steps:
(1) with organic solvent, SBS and the organo-siloxane stirring and dissolving that contains mercapto groups, add radical initiator, be warming up to 80 ℃, begin to carry out the graft modification reaction, reaction times 12h, adding dehydrated alcohol to polymkeric substance after reaction finishes all precipitates, suction filtration and drying obtain organic siloxane modified SBS, wherein, the mass ratio of organic solvent and SBS is 44, containing sulfydryl in the organo-siloxane of mercapto groups and the mol ratio of the two keys in the SBS is 9, containing sulfydryl in the organo-siloxane of mercapto groups and the mol ratio of radical initiator is 90, the organic solvent that adopts is tetracol phenixin, the organo-siloxane that contains mercapto groups is mercaptopropyl trimethoxysilane, the number-average molecular weight of described SBS is 10000, wherein the massfraction of 1，2-butadiene is 60%; Radical initiator is Diisopropyl azodicarboxylate;
(2) under 30 ℃ of agitation conditions, the organic siloxane modified SBS that step (1) is prepared and silicon come from the organic solvent and dissolve, add deionized water and alkaline solution, carry out sol gel reaction, 30 ℃ of lower maintenances 5 days, form gel; Then washing and dry rear in 600 ℃ of cracking 4 hours, namely obtain mesoporous silicon oxide, wherein, the mass ratio of silicon source and organic siloxane modified SBS is 4, contained siloxy total amount and the mol ratio of deionized water are 1 in silicon source and the organic siloxane modified SBS, contained siloxy total amount and the mol ratio of alkali are 1 in silicon source and the organic siloxane modified SBS, the silicon source is tetraethoxy, and alkaline solution is the ammoniacal liquor of 2mol/L.
Embodiment 10
A kind of method for preparing mesoporous silicon oxide specifically may further comprise the steps:
(1) with organic solvent, SBS and the organo-siloxane stirring and dissolving that contains mercapto groups, add radical initiator, be warming up to 80 ℃, begin to carry out the graft modification reaction, reaction times 12h, adding dehydrated alcohol to polymkeric substance after reaction finishes all precipitates, suction filtration and drying obtain organic siloxane modified SBS, wherein, the mass ratio of organic solvent and SBS is 55, containing sulfydryl in the organo-siloxane of mercapto groups and the mol ratio of the two keys in the SBS is 10, containing sulfydryl in the organo-siloxane of mercapto groups and the mol ratio of radical initiator is 110, the organic solvent that adopts is tetracol phenixin, the organo-siloxane that contains mercapto groups is mercaptopropyl trimethoxysilane, the number-average molecular weight of described SBS is 10000, wherein the massfraction of 1，2-butadiene is 60%; Radical initiator is methyl vinyl ketone;
(2) under 30 ℃ of agitation conditions, the organic siloxane modified SBS that step (1) is prepared and silicon come from the organic solvent and dissolve, add deionized water and alkaline solution, carry out sol gel reaction, 30 ℃ of lower maintenances 5 days, form gel; Then washing and dry rear in 600 ℃ of cracking 4 hours, namely obtain mesoporous silicon oxide, wherein, the mass ratio of silicon source and organic siloxane modified SBS is 4, contained siloxy total amount and the mol ratio of deionized water are 1 in silicon source and the organic siloxane modified SBS, contained siloxy total amount and the mol ratio of alkali are 1 in silicon source and the organic siloxane modified SBS, the silicon source is tetraethoxy, and alkaline solution is the ammoniacal liquor of 1mol/L.
Embodiment 11
A kind of method for preparing mesoporous silicon oxide, adopted sulfydryl-Vinyl radical addition reaction will contain organo-siloxane and the reaction of the polybutadiene block in the SBS of mercapto groups, obtain organic siloxane modified SBS, then sol gel reaction formation gel is occured in organic siloxane modified SBS and silicon source under acidity or alkaline condition, microphase-separated occurs in organic siloxane modified SBS in gel, gel obtains mesoporous silicon oxide after cracking.
The method specifically may further comprise the steps:
(1) with organic solvent, SBS and the organo-siloxane stirring and dissolving that contains mercapto groups, add radical initiator, be warming up to 90 ℃, begin to carry out the graft modification reaction, reaction times 0.5h, adding dehydrated alcohol to polymkeric substance after reaction finishes all precipitates, suction filtration and drying obtain organic siloxane modified SBS, wherein, the mass ratio of organic solvent and SBS is 100, containing sulfydryl in the organo-siloxane of mercapto groups and the mol ratio of the two keys in the SBS is 20, containing sulfydryl in the organo-siloxane of mercapto groups and the mol ratio of radical initiator is 500, the organic solvent that uses is dimethylbenzene, the organo-siloxane that contains mercapto groups is mercaptopropyltriethoxysilane, the number-average molecular weight of SBS is 30000, wherein 1, the massfraction of 2-divinyl is 80%, and radical initiator is benzophenone;
(2) under 45 ℃ of agitation conditions, the organic siloxane modified SBS that step (1) is prepared and silicon come from the organic solvent and dissolve, add deionized water and alkaline solution, carry out sol gel reaction, 45 ℃ of lower maintenances 2 days, form gel; Then washing and dry rear in 600 ℃ of cracking 3 hours, namely obtain mesoporous silicon oxide, wherein the mass ratio of silicon source and organic siloxane modified SBS is 10, contained siloxy total amount and the mol ratio of deionized water are 10 in silicon source and the organic siloxane modified SBS, contained siloxy total amount and the mol ratio of alkali are 10 in silicon source and the organic siloxane modified SBS, the silicon source is methyl silicate, tetraethoxy, the mixture of positive silicic acid propyl ester, alkaline solution is the ammoniacal liquor of 5mol/L.
Claims (7)
1. a method for preparing mesoporous silicon oxide is characterized in that, the method may further comprise the steps:
(1) with organic solvent, SBS and contain the organo-siloxane stirring and dissolving of mercapto groups, add radical initiator, be warming up to 45-90 ℃, begin to carry out the graft modification reaction, reaction times 0.5-24h, adding dehydrated alcohol to polymkeric substance all precipitates after reacting end, and suction filtration and drying obtain organic siloxane modified SBS;
(2) under 10-45 ℃ of agitation condition, the organic siloxane modified SBS that step (1) is prepared and silicon come from the organic solvent and dissolve, add deionized water and acid solution or alkaline solution, carry out sol gel reaction, 10-45 ℃ of lower the maintenance 2-14 days, form gel, then washing and dry rear in 500-600 ℃ of cracking 3-5 hour namely obtains a kind of mesoporous silicon oxide;
The mass ratio of the organic solvent described in the step (1) and SBS is 20-100, containing sulfydryl in the organo-siloxane of mercapto groups and the mol ratio of the two keys in the SBS is 1-20, and containing sulfydryl in the organo-siloxane of mercapto groups and the mol ratio of radical initiator is 10-500;
Described organic solvent is selected from 1,2-ethylene dichloride, 1, one or more in 2-methylene dichloride, normal hexane, chloroform, benzene, tetrahydrofuran (THF), dioxane, tetracol phenixin, toluene or the dimethylbenzene; The described organo-siloxane that contains mercapto groups is mercaptopropyl trimethoxysilane or mercaptopropyltriethoxysilane; The number-average molecular weight scope of described SBS is 1000-30000, and the massfraction of the 1，2-butadiene that wherein contains is 20-80%; Described radical initiator is selected from a kind of in dibenzoyl peroxide, dilauroyl peroxide, di-cyclohexylperoxy dicarbonate, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), methyl vinyl ketone, st-yrax, dimethoxybenzoin, benzophenone or the eosin;
The mass ratio of the silicon source described in the step (2) and organic siloxane modified SBS is 0-10, contained siloxy total amount and the mol ratio of deionized water are 0.1-10 in silicon source and the organic siloxane modified SBS, contained siloxy total amount and the mol ratio of acid or alkali are 0.5-10 in silicon source and the organic siloxane modified SBS, and the concentration range of described acid solution or alkaline solution is 0.1-5mol/L.
2. a kind of method for preparing mesoporous silicon oxide according to claim 1, it is characterized in that, the preferred 40-60 of mass ratio of the organic solvent described in the step (1) and SBS, contain sulfydryl in the organo-siloxane of mercapto groups and the preferred 5-12 of mol ratio of the two keys in the SBS, contain sulfydryl in the organo-siloxane of mercapto groups and the preferred 80-120 of mol ratio of radical initiator.
3. a kind of method for preparing mesoporous silicon oxide according to claim 1, it is characterized in that, the mass ratio of the organic solvent described in the step (1) and SBS is 44-55 more preferably, the mol ratio that contains sulfydryl in the organo-siloxane of mercapto groups and the two keys in the SBS is 9-10 more preferably, and the mol ratio that contains sulfydryl in the organo-siloxane of mercapto groups and radical initiator is 90-110 more preferably.
4. a kind of method for preparing mesoporous silicon oxide according to claim 1, it is characterized in that, the preferred 1.5-9 of mass ratio of the silicon source described in the step (2) and organic siloxane modified SBS, contained siloxy total amount and the preferred 0.8-1.2 of mol ratio of deionized water in silicon source and the organic siloxane modified SBS, contained siloxy total amount and the preferred 0.8-1.2 of mol ratio of acid or alkali in silicon source and the organic siloxane modified SBS, the preferred 0.5-2mol/L of the concentration range of described acid solution or alkaline solution.
5. a kind of method for preparing mesoporous silicon oxide according to claim 1, it is characterized in that, the mass ratio of the silicon source described in the step (2) and organic siloxane modified SBS more preferably 4, the mol ratio of contained siloxy total amount and deionized water more preferably 1 in silicon source and the organic siloxane modified SBS, the mol ratio of contained siloxy total amount and acid or alkali more preferably 1 in silicon source and the organic siloxane modified SBS, and the concentration range of described acid solution or alkaline solution is 1mol/L more preferably.
6. according to claim 1 or 4 or 5 described a kind of methods that prepare mesoporous silicon oxide, it is characterized in that, the silicon source described in the step (2) is selected from one or more in methyl silicate, tetraethoxy, positive silicic acid propyl ester, butyl silicate, water glass or the silicon sol.
7. according to claim 1 or 4 or 5 described a kind of methods that prepare mesoporous silicon oxide, it is characterized in that, acid solution described in the step (2) is selected from a kind of in the aqueous solution of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acid or glacial acetic acid, and described alkaline solution is ammoniacal liquor.
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| CN1618735A (en) * | 2003-11-19 | 2005-05-25 | 中国科学院金属研究所 | Synthesis method of monodispersed nano-mesopore silicon dioxide material |
| CN1872684A (en) * | 2006-06-16 | 2006-12-06 | 清华大学 | Method for synthesizing microspheres of high ordered mesoporous silicon dioxide |
| CN101387019A (en) * | 2008-10-24 | 2009-03-18 | 上海应用技术学院 | Method for preparing mesoporous silica molecular sieve fiber |
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| CN1618735A (en) * | 2003-11-19 | 2005-05-25 | 中国科学院金属研究所 | Synthesis method of monodispersed nano-mesopore silicon dioxide material |
| CN1872684A (en) * | 2006-06-16 | 2006-12-06 | 清华大学 | Method for synthesizing microspheres of high ordered mesoporous silicon dioxide |
| CN101387019A (en) * | 2008-10-24 | 2009-03-18 | 上海应用技术学院 | Method for preparing mesoporous silica molecular sieve fiber |
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