CN101337975B - Polyhedral silsesquioxane nano-wires - Google Patents
Polyhedral silsesquioxane nano-wires Download PDFInfo
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- CN101337975B CN101337975B CN2007100248416A CN200710024841A CN101337975B CN 101337975 B CN101337975 B CN 101337975B CN 2007100248416 A CN2007100248416 A CN 2007100248416A CN 200710024841 A CN200710024841 A CN 200710024841A CN 101337975 B CN101337975 B CN 101337975B
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Abstract
The invention discloses a novel polyhedral silsesquioxane nano-wire, the diameter of which is 10 to 100 nanometers, and the length thereof is 100 to 500 nanometers. The invention further discloses a method for simply preparing polyhedral silsesquioxane nano-wire, and obtains polyhedral silsesquioxane nano-wire with the novel special morphology. The special linear structure is suitable for researching the characteristic of polyhedral silsesquioxane material in one-dimensional direction under light, electricity and field and the change of the mechanical property caused by the scaling-down, is excellent candidate material of a electronic device, a photoelectronic device and a mechanical transmission device with nano-size, and has wide application prospect in the fields of electron, photology, magnetic storage material, catalytic action, ceramics, machine work, biomedicine, etc.
Description
Technical field
The invention belongs to the material technology field, be specifically related to a kind of nano level polyhedral silsesquioxane line with and preparation method thereof.
Background technology
Polyhedral silsesquioxane (polyhedral oligomeric silsesquioxane is called for short POSS) is that U.S. Hybrid Plastics company is towards novel molecular decentralized nanometer strengthener global development, that be used for the development of high molecule plastic regeneration product.Than other inorganic nano particle modified dose like nano level clay, silicon-dioxide, titanium oxide, lime carbonate etc.; Polyhedral silsesquioxane nanoparticle with cage structure has not only that monodispersity is good, density is low, Heat stability is good and do not contain advantages such as trace metal impurities, and polymeric matrix nonpolar or that polarity is little is had the good interface consistency; In addition, at the different reactive functional groups of polyhedral silsesquioxane surface bond, also can give the multifunctionality of polyhedral silsesquioxane nanoparticle and highly reactive through chemical process.
But these researchs focus mostly on to the improvement of its functional group and further with polymeric matrix copolymerization or blend on, and seldom to the applied research of polyhedral silsesquioxane itself.The invention provides the simple method for preparing polyhedral silsesquioxane nano-wires, obtained a kind of polyhedral silsesquioxane material with novel special appearance.This special nanowire-type structure is suitable for studying the polyhedral silsesquioxane material in light, electricity, the character on the one dimension direction after the match; And the variation of the mechanical property brought of dimension shrinks; Be electron device, the opto-electronic device of nano-scale, the good candidate material of mechanical drive, all have broad application prospects in fields such as electronics, optics, magnetic memory materials, catalysis, pottery, mechanical workout, biomedicines.
Summary of the invention
The objective of the invention is the application of polyhedral silsesquioxane itself is studied, a kind of nano level polyhedral silsesquioxane line of novel special appearance is provided.
Another object of the present invention provides a kind of preparation method of above-mentioned polyhedral silsesquioxane line.
The object of the invention can reach through following measure:
A kind of novel polyhedral silsesquioxane nano-wires, this polyhedral silsesquioxane nano-wires are that diameter is the wire of 10～100nm; Wherein this polyhedral silsesquioxane nano-wires is processed by the polyhedral silsesquioxane of following formula: [(RSiO
1.5)
m(XSiO
1.5)
n] or [(RSiO
(1.5p-0.5q)/p)
p(OH)
q]
Wherein:
M ≧ 1, n ≧ 0, m+n ≧ 4, and m+n is an even number; P ≧ q ≧ 1, q=2 or 3, p+q ≧ 4, and p+q is an even number;
R is a Wasserstoffatoms, or alkyl, naphthenic base, fluoroalkyl, alkenyl, cycloalkenyl group, aryl, epoxy group(ing), siloyl group, ether, propenoate or the methacrylic ester of substituting group or unsubstituted are arranged;
X is hydroxyl, epoxy group(ing), carboxyl, halogen, fluoroalkyl, propenoate, methacrylic ester, ether, itrile group, amino, perhaps contains the R group of above-mentioned group (hydroxyl, epoxy group(ing), carboxyl, halogen, fluoroalkyl, propenoate, methacrylic ester, ether, itrile group, amino).
Polyhedral silsesquioxane is preferably: [(RSiO
1.5)
m(XSiO
1.5)
n]
Wherein:
M ≧ 3, n ≧ 0,12 ≧ m+n ≧ 6, and m+n is an even number;
R is a Wasserstoffatoms, or alkyl, naphthenic base, fluoroalkyl, alkenyl, aryl, epoxy group(ing), ether, propenoate or the methacrylic ester of substituting group or unsubstituted are arranged;
X is hydroxyl, epoxy group(ing), halogen, fluoroalkyl, ether, propenoate, methacrylic ester, perhaps contains the R group of above-mentioned group (hydroxyl, epoxy group(ing), halogen, fluoroalkyl, ether, propenoate, methacrylic ester).
The polyhedral silsesquioxane another kind is preferably: [(RSiO
(1.5p-0.5q)/p)
p(OH)
q]
Wherein:
P ≧ 3, q=2 or 3,12 ≧ p+q ≧ 6, and p+q is an even number;
R is a Wasserstoffatoms, or alkyl, naphthenic base, alkenyl, aryl, ether, propenoate or the methacrylic ester of substituting group or unsubstituted are arranged.
" substituting group " in " substituting group or unsubstituted being arranged " among the present invention is the cycloalkenyl group, aryl, epoxy group(ing), siloyl group, hydroxyl, carboxyl, halogen, itrile group, amino etc. of alkenyl, C3～6 of naphthenic base, C2～6 of the alkyl that refers to C1～10, C3～10 if this vocabulary does not have in addition explanation here.
" alkyl " be not if this vocabulary has to explain in addition the alkyl that is meant C1～10 here, like methyl, ethyl, sec.-propyl, iso-octyl etc.
" naphthenic base " be not if there is to explain in addition the naphthenic base that is meant C3～6 here, like cyclopropyl, cyclopentyl etc.
" alkenyl " is not meant vinyl, propenyl, butadienyl etc. if explain in addition here.
" cycloalkenyl group " is not meant cyclobutene base, cyclopentenyl, cyclohexenyl etc. if explain in addition here.
" aryl " be not if there is to explain in addition the alkyl phenyl that is meant phenyl or C1～6 here, like aminomethyl phenyl, p-methylphenyl, an aminomethyl phenyl, ethylphenyl etc.
" epoxy group(ing) " is not meant Oxyranyle, propylene oxide base, epoxy hexyl etc. if explain in addition here.
" siloyl group " is not meant Trimethoxy silane base, vinyl-dimethyl base silane base etc. if explain in addition here.
" halogen " explanation is not meant chlorine, fluorine, bromine, iodine and the substituting group that contains halogen if having in addition here, like the third amino chlorine, benzene chlorine etc.
" fluoroalkyl " is not meant trifluoro propane, trifluoromethane, HFC-143a etc. if explain in addition here.
" itrile group " or " nitrile " is not meant propionitrile base etc. if explain in addition here.
" ether " if there is not in addition explanation to be meant the ether of C2～12 here, like the alkoxyalkyl of C2～12, aryloxyalkyl group, oxirane oxyalkyl, alkoxy aromatic yl, aryl aryloxycarboxylic etc.
A kind of method for preparing above-mentioned various body silsesquioxane nano-wires prepares as the masterplate molecule with mesoporous molecular sieve SBA-15, implements according to following steps:
1) <under the vacuum of 5KPa, 240～260 ℃ of following constant temperature were removed air and moisture content in the masterplate molecule in 1～3 hour at pressure with the masterplate molecule; Then be cooled to room temperature, under vacuum condition, add polyhedral silsesquioxane solution, keep vacuum state, at room temperature stir 30～50 hours after, drain solvent, obtain pulverous SBA-15 and polyhedral silsesquioxane composite particles;
2) get SBA-15 and polyhedral silsesquioxane powder, add the HF aqueous solution, react 15 seconds～48 hours, treat that SBA-15 is decomposed by HF after, behind the thin up, the reaction solution bottom have disperse tiny as thread thread, be the nano wire of polyhedral silsesquioxane.
Said mesoporous molecular sieve SBA-15 is spheroidal particle according to patent CN1206159C self-control, and its median size is 50-100nm, and the aperture is 4-30nm, hole wall 2-7nm, and specific surface area is 500-2000m
2/ g, pore volume is 0.7-2.3cm
3/ g.The preparation method of concrete mesoporous molecular sieve SBA-15 is following:
(purchase obtains with 20g polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer; Commodity are called Pluronics P123) and the 2g cetyl trimethylammonium bromide be dissolved in the 150g water, then add 450g hydrochloric acid soln (2mol/kg), process the solution of a clear 35～40 ℃ of stirrings; Then add the positive tetraethyl orthosilicate of 58g; Stirring reaction is 24 hours under 40 ℃ of temperature, obtains a gelating soln, transfers in the polypropylene container; 80 ℃ of following hydro-thermal reaction 70h, washing, filtering and drying obtain the powder of white.Be placed on 580 ℃ of heating 6h down, can obtain described mesoporous molecular sieve SBA-15.
Above-mentioned polyhedral silsesquioxane solution is that to be dissolved in the concentration that forms in the solvent be 0.01～10g/ml (solution of preferred 0.01～1g/ml) to polyhedral silsesquioxane; According to the deliquescent difference of different types of polyhedral silsesquioxane, its concentration range has than big-difference.Wherein solvent adopts water, ethanol, methyl alcohol, hexane, methylene dichloride, acetone, THF, chloroform, N-NMF, N-methylacetamide or DMSO 99.8MIN..The add-on of the solution of polyhedral silsesquioxane solution has than big-difference according to the ratio of SBA-15 in the deliquescent difference of different types of polyhedral silsesquioxane and the required SBA-15+ polyhedral silsesquioxane composite particles and polyhedral silsesquioxane is different.
In SBA-15 and the polyhedral silsesquioxane composite particles, the mass ratio of SBA-15 and polyhedral silsesquioxane is 1:0.01～1:1.
The concentration of the HF aqueous solution is 0.05～0.5g/ml.The consumption of the HF aqueous solution is 5:1～1000:1ml/g with the ratio of SBA-15 and polyhedral silsesquioxane composite particles.
The object of the invention specifically can reach through following measure:
The present invention prepares the method for polyhedral silsesquioxane nano-wires, may further comprise the steps:
1) SBA-15 is added three mouthfuls of round-bottomed flasks, <under the vacuum of 5KPa, preferred 250 ℃ of following constant temperature 2 hours are with air in the system of removing and moisture content at pressure; After then removing heating source and treating that SBA-15 is chilled to room temperature, under vacuum condition, the solution of the polyhedral silsesquioxane for preparing is in advance injected among the round-bottomed flask; Keep vacuum state, at room temperature preferably stir 44 hours after, utilize Rotary Evaporators that solvent is drained, can obtain pulverous SBA-15+ polyhedral silsesquioxane;
2) the SBA-15+ polyhedral silsesquioxane powder that takes a morsel; Place plastic centrifuge tube, add an amount of HF aqueous solution, reacted 15 seconds～48 hours; After treating that SBA-15 is decomposed by HF; Thin up is also poured solution in the glass cylinder into, and have the thread of paucidisperse tiny as silk at the solution bottom this moment, is the nano wire of polyhedral silsesquioxane.
In order to obtain being easy to isolating polyhedral silsesquioxane nano-wires; Can use appropriate solvent that the SBA-15+ polyhedral silsesquioxane composite powder that obtains in the step 1) is washed, separates, to remove the outer residual polyhedral silsesquioxane that does not get into the duct of SBA-15.
The solvent that polyhedral silsesquioxane solution adopted in the step 1) can be: water, ethanol, methyl alcohol, hexane, methylene dichloride, acetone, THF, chloroform, N-NMF, N-methylacetamide or DMSO 99.8MIN. etc.
The strength of solution that polyhedral silsesquioxane solution is adopted in the step 1) is 0.01～10g/ml, and according to the deliquescent difference of different types of polyhedral silsesquioxane, its solvent species and concentration range have than big-difference.
The add-on of polyhedral silsesquioxane solution is 1～500ml in the step 1), has than big-difference according to the ratio of SBA-15 in the deliquescent difference of different types of polyhedral silsesquioxane and the required SBA-15+ polyhedral silsesquioxane composite particles and polyhedral silsesquioxane is different.
In the step 1) in the SBA-15+ polyhedral silsesquioxane composite particles ratio of SBA-15 and polyhedral silsesquioxane be 1:0.01～1:1 (mass ratio).
Step 2) consumption of SBA-15+ polyhedral silsesquioxane composite particles can be selected as requested in, is generally 0.001～1g.
Step 2) the HF concentration of aqueous solution that adds in is 0.05～0.5g/ml.
The consumption of the HF aqueous solution that adds step 2) and the ratio of SBA-15+ polyhedral silsesquioxane composite particles are 5:1～1000:1ml/g.
The structure and the pattern of the polyhedral silsesquioxane nano-wires of the present invention's preparation can adopt means such as ESEM or transmission electron microscope to observe.The diameter of the polyhedral silsesquioxane nano-wires that obtains between 10～100 nanometers, length (length through using the nano wire that different types of masterplate molecule obtains or can continue to prolong) between 100～500 nanometers.
The present invention to existing research to silsesquioxane focus mostly on to the improvement of its functional group and further with polymeric matrix copolymerization or blend on, and seldom to the applied research of polyhedral silsesquioxane itself.The invention provides a kind of method of easy manufacture polyhedral silsesquioxane nano-wires, obtained a kind of polyhedral silsesquioxane material with novel special appearance.This special linear structure is suitable for studying the polyhedral silsesquioxane material in light, electricity, the character on the one dimension direction after the match; And the variation of the mechanical property brought of dimension shrinks; Be electron device, the opto-electronic device of nano-scale, the good candidate material of mechanical drive, all have broad application prospects in fields such as electronics, optics, magnetic memory materials, catalysis, pottery, mechanical workout, biomedicines.
Description of drawings
Fig. 1 is the transmission electron microscope photo of eight iso-octyl silsesquioxane nano-wires of the embodiment of the invention 1 resulting complete condensation.
Fig. 2 is the transmission electron microscope photo of the cyclopentyl silsesquioxane trivalent alcohol nano wire of the embodiment of the invention 8 resulting incomplete condensations.
Embodiment
The present invention can obtain further elaboration through the embodiment of following preferred embodiment, but these embodiment only are to illustrate, and scope of the present invention is not made and being defined.
Embodiment 1: the nano wire of eight iso-octyl silsesquioxanes of condensation preparation fully
1) buy the eight iso-octyl silsesquioxanes (Hybrid Plastics company) that obtained having regular hexahedron structure, have following structure:
2) 1.0gSBA-15 is added three mouthfuls of round-bottomed flasks, <under the vacuum of 5KPa, 250 ℃ of following constant temperature 2 hours is with air in the system of removing and moisture content at pressure; After then removing heating source and treating that SBA-15 is chilled to room temperature, under vacuum condition, the concentration that 1ml is prepared in advance is that the acetone soln of the eight iso-octyl silsesquioxanes of 0.01g/>ml injects among the round-bottomed flask; Keep vacuum state, at room temperature stir 44 hours after, utilize Rotary Evaporators that solvent is drained, can obtain pulverous SBA-15+0.01 eight iso-octyl silsesquioxanes;
3) get 0.005gSBA-15+0.01 eight iso-octyl silsesquioxane powder; Place plastic centrifuge tube, add the 1ml0.1g/ml HF aqueous solution, reacted 3 hours; After treating that SBA-15 is decomposed by HF; Thin up is also poured solution in the glass cylinder into, and have the thread of paucidisperse tiny as silk at the solution bottom this moment, is the nano wire of eight iso-octyl silsesquioxanes.
Synthetic eight iso-octyl silsesquioxane nano-wires diameters are between 10～100 nanometers, and length is between 100～400 nanometers.
Embodiment 2: the nano wire of 12 trifluoropropyl alkyl silsesquioxanes of condensation preparation fully
1) buy the 12 trifluoropropyl alkyl base silsesquioxanes (HybridPlastics company) that obtained having octahedral structure, have following structure:
2) 1.0gSBA-15 is added three mouthfuls of round-bottomed flasks, <under the vacuum of 5KPa, 250 ℃ of following constant temperature 2 hours is with air in the system of removing and moisture content at pressure; After then removing heating source and treating that SBA-15 is chilled to room temperature, under vacuum condition, the concentration that 5ml is prepared in advance is that the chloroformic solution of the 12 trifluoropropyl alkyl silsesquioxanes of 0.01g/>ml injects among the round-bottomed flask; Keep vacuum state, at room temperature stir 44 hours after, utilize Rotary Evaporators that solvent is drained, can obtain pulverous SBA-15+0.05 12 trifluoropropyl alkyl silsesquioxanes;
3) get 0.005gSBA-15+0.05 12 trifluoropropyl alkyl silsesquioxane powder; Place plastic centrifuge tube, add the 1ml0.2g/ml HF aqueous solution, reacted 3 hours; After treating that SBA-15 is decomposed by HF; Thin up is also poured solution in the glass cylinder into, and have the thread of paucidisperse tiny as silk at the solution bottom this moment, is the nano wire of 12 trifluoropropyl alkyl silsesquioxanes.
Synthetic 12 trifluoropropyl alkyl silsesquioxane nano-wires diameters are between 10～100 nanometers, and length is between 100～300 nanometers.
Embodiment 3: the nano wire of the methylacrylic acid isobutyl-silsesquioxane of condensation preparation fully
1) buy the methylacrylic acid sec.-butyl silsesquioxane (Hybrid Plastics company) that has obtained having regular hexahedron structure, have following structure:
2) 1.0gSBA-15 is added three mouthfuls of round-bottomed flasks, <under the vacuum of 5KPa, 250 ℃ of following constant temperature 2 hours is with air in the system of removing and moisture content at pressure; After then removing heating source and treating that SBA-15 is chilled to room temperature, under vacuum condition, the concentration that 10ml is prepared in advance is that the hexane solution of the methylacrylic acid isobutyl-silsesquioxane of 0.01g/>ml injects among the round-bottomed flask; Keep vacuum state, at room temperature stir 44 hours after, utilize Rotary Evaporators that solvent is drained, can obtain pulverous SBA-15+0.1 methylacrylic acid isobutyl-silsesquioxane;
3) get 0.005gSBA-15+0.1 methylacrylic acid isobutyl-silsesquioxane powder; Place plastic centrifuge tube, add the 1ml0.2g/ml HF aqueous solution, reacted 3 hours; After treating that SBA-15 is decomposed by HF; Thin up is also poured solution in the glass cylinder into, and have the thread of paucidisperse tiny as silk at the solution bottom this moment, is the nano wire of methylacrylic acid isobutyl-silsesquioxane.
Synthetic methylacrylic acid isobutyl-silsesquioxane nano-wires diameter is between 10～80 nanometers, and length is between 200～400 nanometers.
Embodiment 4: the nano wire of the octahydro base silsesquioxane of condensation preparation fully
1) buy the octahydro base silsesquioxane (HybridPlastics company) that has obtained having regular hexahedron structure, have following structure:
2) 1.0gSBA-15 is added three mouthfuls of round-bottomed flasks, <under the vacuum of 5KPa, 250 ℃ of following constant temperature 2 hours is with air in the system of removing and moisture content at pressure; After then removing heating source and treating that SBA-15 is chilled to room temperature, under vacuum condition, the concentration that 1ml is prepared in advance is that the dichloromethane solution of the octahydro base silsesquioxane of 0.02g/>ml injects among the round-bottomed flask; Keep vacuum state, at room temperature stir 44 hours after, utilize Rotary Evaporators that solvent is drained, can obtain pulverous SBA-15+0.02 octahydro base silsesquioxane;
3) get 0.005gSBA-15+10% octahydro base silsesquioxane powder; Place plastic centrifuge tube, add the 1ml0.5g/ml HF aqueous solution, reacted 3 hours; After treating that SBA-15 is decomposed by HF; Thin up is also poured solution in the glass cylinder into, and have the thread of paucidisperse tiny as silk at the solution bottom this moment, is the nano wire of octahydro base silsesquioxane.
Synthetic octahydro base silsesquioxane nano-wires diameter is between 10～100 nanometers, and length is between 100～500 nanometers.
Embodiment 5: the nano wire of the glycidyl phenyl silsesquioxane of condensation preparation fully
1) buy glycidyl silsesquioxane or the glycidyl phenyl silsesquioxane (Hybrid Plastics company) that has obtained having regular hexahedron structure, have following structure:
2) 1.0gSBA-15 is added three mouthfuls of round-bottomed flasks, <under the vacuum of 5KPa, 250 ℃ of following constant temperature 2 hours is with air in the system of removing and moisture content at pressure; After then removing heating source and treating that SBA-15 is chilled to room temperature, under vacuum condition, the concentration that 10ml is prepared in advance is that the tetrahydrofuran solution of the glycidyl phenyl silsesquioxane of 0.01g/>ml injects among the round-bottomed flask; Keep vacuum state, at room temperature stir 44 hours after, utilize Rotary Evaporators that solvent is drained, can obtain pulverous SBA-15+0.1 glycidyl phenyl silsesquioxane;
3) get 0.005gSBA-15+0.1 glycidyl phenyl silsesquioxane powder; Place plastic centrifuge tube, add the 1ml0.2g/ml HF aqueous solution, reacted 3 hours; After treating that SBA-15 is decomposed by HF; Thin up is also poured solution in the glass cylinder into, and have the thread of paucidisperse tiny as silk at the solution bottom this moment, is the nano wire of glycidyl phenyl silsesquioxane.
Synthetic glycidyl phenyl silsesquioxane nanowire diameter is between 10～100 nanometers, and length is between 200～400 nanometers.
Embodiment 6: the nano wire of the vinyl silsesquioxane of condensation preparation fully
1) buy vinyl silsesquioxane or the sec.-butyl vinyl silsesquioxane (Hybrid Plastics company) that has obtained having regular hexahedron structure, have following structure, wherein R and X are identical or different:
2) 1.0gSBA-15 is added three mouthfuls of round-bottomed flasks, <under the vacuum of 5KPa, 250 ℃ of following constant temperature 2 hours is with air in the system of removing and moisture content at pressure; After then removing heating source and treating that SBA-15 is chilled to room temperature, under vacuum condition, the concentration that 10ml is prepared in advance is that the methyl alcohol or the tetrahydrofuran solution of the vinyl silsesquioxane of 0.01g/>ml injects among the round-bottomed flask; Keep vacuum state, at room temperature stir 44 hours after, utilize Rotary Evaporators that solvent is drained, can obtain pulverous SBA-15+0.1 vinyl silsesquioxane;
3) get 0.05gSBA-15+0.1 vinyl silsesquioxane powder; Place plastic centrifuge tube, add the 1ml0.2g/ml HF aqueous solution, reacted 3 hours; After treating that SBA-15 is decomposed by HF; Thin up is also poured solution in the glass cylinder into, and have the thread of paucidisperse tiny as silk at the solution bottom this moment, is the nano wire of vinyl silsesquioxane.
Synthetic vinyl silsesquioxane nano-wires diameter is between 10～100 nanometers, and length is between 100～400 nanometers.
Embodiment 7: the nano wire of the isopropyl chloride silsesquioxane of condensation preparation fully
1) buy the isopropyl chloride silsesquioxane (Hybrid Plastics company) that has obtained having regular hexahedron structure, have following structure:
2) 1.0gSBA-15 is added three mouthfuls of round-bottomed flasks, <under the vacuum of 5KPa, 250 ℃ of following constant temperature 2 hours is with air in the system of removing and moisture content at pressure; After then removing heating source and treating that SBA-15 is chilled to room temperature, under vacuum condition, the concentration that 10ml is prepared in advance is that the chloroformic solution of the isopropyl chloride silsesquioxane of 0.05g/>ml injects among the round-bottomed flask; Keep vacuum state, at room temperature stir 44 hours after, utilize Rotary Evaporators that solvent is drained, can obtain pulverous SBA-15+0.5 isopropyl chloride silsesquioxane;
3) get 0.002gSBA-15+0.5 isopropyl chloride silsesquioxane powder; Place plastic centrifuge tube, add the 1ml0.2g/ml HF aqueous solution, reacted 3 hours; After treating that SBA-15 is decomposed by HF; Thin up is also poured solution in the glass cylinder into, and have the thread of paucidisperse tiny as silk at the solution bottom this moment, is the nano wire of isopropyl chloride silsesquioxane.
Synthetic isopropyl chloride silsesquioxane nano-wires diameter is between 10～100 nanometers, and length is between 200～500 nanometers.
Embodiment 8: the not exclusively preparation of the cyclopentyl silsesquioxane trivalent alcohol nano wire of condensation
1) be raw material with the cyclopentyl trichlorosilane, according to Feher (method 10:2526) has made through hydrolytic condensation and has had the not complete cyclopentyl silsesquioxane trivalent alcohol of condensation of trihydroxy-, has following structure for Organometallics, 199l:
2) 1.0gSBA-15 is added three mouthfuls of round-bottomed flasks, <under the vacuum of 5KPa, 250 ℃ of following constant temperature 2 hours is with air in the system of removing and moisture content at pressure; After then removing heating source and treating that SBA-15 is chilled to room temperature, under vacuum condition, the concentration that 40ml is prepared in advance be 0.0125g/>ml not fully the tetrahydrofuran solution of the cyclopentyl silsesquioxane trivalent alcohol of condensation inject among the round-bottomed flask; Keep vacuum state, at room temperature stir 44 hours after, under the normal temperature solvent is drained, can obtain pulverous SBA-15+0.5 cyclopentyl silsesquioxane trivalent alcohol;
3) get 0.01gSBA-15+0.5 cyclopentyl silsesquioxane trivalent alcohol powder; Place plastic centrifuge tube, add the 2ml0.1g/ml HF aqueous solution, reacted 0.5 hour; After treating that SBA-15 is decomposed by HF; Thin up is also poured solution in the glass cylinder into, and have the thread of paucidisperse tiny as silk at the solution bottom this moment, is the nano wire of the cyclopentyl silsesquioxane trivalent alcohol of incomplete condensation.
The nanowire diameter of the cyclopentyl silsesquioxane trivalent alcohol of the incomplete condensation of synthetic is between 10～100 nanometers, and length is between 100～500 nanometers.
Embodiment 9: the not exclusively preparation of the sec.-propyl silsesquioxane divalent alcohol nano wire of condensation
1) buy the sec.-butyl silsesquioxane divalent alcohol (HybridPlastics company) that has obtained having regular hexahedron structure, have following structure:
2) 1.0gSBA-15 is added three mouthfuls of round-bottomed flasks, <under the vacuum of 5KPa, 250 ℃ of following constant temperature 2 hours is with air in the system of removing and moisture content at pressure; After then removing heating source and treating that SBA-15 is chilled to room temperature, under vacuum condition, the concentration that 50ml is prepared in advance be 0.02g/>ml not fully the chloroformic solution of the sec.-propyl silsesquioxane divalent alcohol of condensation inject among the round-bottomed flask; Keep vacuum state, at room temperature stir 44 hours after, under the normal temperature solvent is drained, can obtain pulverous SBA-15+100 sec.-propyl silsesquioxane divalent alcohol;
3) get 0.01gSBA-15+100 sec.-propyl silsesquioxane divalent alcohol powder; Place plastic centrifuge tube, add the 2ml0.5g/ml HF aqueous solution, reacted 0.5 hour; After treating that SBA-15 is decomposed by HF; Thin up is also poured solution in the glass cylinder into, and have the thread of paucidisperse tiny as silk at the solution bottom this moment, is the nano wire of the sec.-propyl silsesquioxane divalent alcohol of incomplete condensation.
The nanowire diameter of the sec.-propyl silsesquioxane divalent alcohol of the incomplete condensation of synthetic is between 10～100 nanometers, and length is between 200～500 nanometers.
Claims (6)
1. a polyhedral silsesquioxane nano-wires is characterized in that this polyhedral silsesquioxane nano-wires is that diameter is the wire of 10～100nm; Wherein this polyhedral silsesquioxane nano-wires is processed by the polyhedral silsesquioxane of following formula:
[(RSiO
1.5)
m(XSiO
1.5)
n] or [(RSiO
(1.5p-0.5q)/p)
p(OH)
q]
Wherein:
M >=3, n >=0,12 >=m+n >=6, and m+n is an even number; P >=3, q=2 or 3,12 >=p+q >=6, and p+q is an even number;
R is a Wasserstoffatoms, or alkyl, naphthenic base, fluoroalkyl, alkenyl, aryl or the epoxy group(ing) of substituting group or unsubstituted are arranged;
X is hydroxyl, epoxy group(ing), halogen, propenoate, perhaps contains the R group of above-mentioned group;
Wherein, alkyl is meant the alkyl of C1～10; Naphthenic base is meant the naphthenic base of C3～6; Fluoroalkyl is meant trifluoro propane, trifluoromethane or HFC-143a; Alkenyl is meant vinyl, propenyl or butadienyl; Aryl is meant the alkyl phenyl of phenyl or C1～6; Epoxy group(ing) is meant Oxyranyle, propylene oxide base or cyclohexene oxide groups; Halogen is meant chlorine, fluorine, bromine or iodine;
Above-mentioned substituting group refers to the alkyl of C1～10 or the naphthenic base of C3～10.
2. a method for preparing the polyhedral silsesquioxane nano-wires described in the claim 1 is characterized in that preparing as the masterplate molecule with mesoporous molecular sieve SBA-15, implements according to following steps:
1) with the masterplate molecule under the vacuum of pressure＜5KPa, 240～260 ℃ of following constant temperature were removed air and moisture content in the masterplate molecule in 1～3 hour; Then be cooled to room temperature, under vacuum condition, add polyhedral silsesquioxane solution, keep vacuum state, at room temperature stir 30～50 hours after, drain solvent, obtain pulverous SBA-15 and polyhedral silsesquioxane composite particles;
2) get SBA-15 and polyhedral silsesquioxane powder, add the HF aqueous solution, react 15 seconds～48 hours, treat that SBA-15 is decomposed by HF after, behind the thin up, the reaction solution bottom have disperse tiny as thread thread, be the nano wire of polyhedral silsesquioxane;
Used polyhedral silsesquioxane has formula:
[(RSiO
1.5)
m(XSiO
1.5)
n] or [(RSiO
(1.5p-0.5q)/p)
p(OH)
q]
Wherein:
M >=3, n >=0,12 >=m+n >=6, and m+n is an even number; P >=3, q=2 or 3,12 >=p+q >=6, and p+q is an even number;
R is a Wasserstoffatoms, or alkyl, naphthenic base, fluoroalkyl, alkenyl, aryl or the epoxy group(ing) of substituting group or unsubstituted are arranged;
X is hydroxyl, epoxy group(ing), halogen, propenoate, perhaps contains the R group of above-mentioned group;
Wherein, alkyl is meant the alkyl of C1～10; Naphthenic base is meant the naphthenic base of C3～6; Fluoroalkyl is meant trifluoro propane, trifluoromethane, HFC-143a; Alkenyl is meant vinyl, propenyl, butadienyl; Aryl is meant the alkyl phenyl of phenyl or C1～6; Epoxy group(ing) is meant Oxyranyle, propylene oxide base, cyclohexene oxide groups; Halogen is meant chlorine, fluorine, bromine or iodine;
Above-mentioned substituting group refers to the alkyl of C1～10, the naphthenic base of C3～10.
3. method according to claim 2; It is characterized in that described polyhedral silsesquioxane solution be polyhedral silsesquioxane to be dissolved in the concentration that forms in the solvent be the solution of 0.01～10g/ml, wherein solvent adopts water, ethanol, methyl alcohol, hexane, methylene dichloride, acetone, THF, chloroform, N-NMF, N-methylacetamide or DMSO 99.8MIN..
4. method according to claim 2 is characterized in that in SBA-15 and the polyhedral silsesquioxane composite particles, the mass ratio of SBA-15 and polyhedral silsesquioxane is 1: 0.01～1: 1.
5. method according to claim 2, the concentration that it is characterized in that the described HF aqueous solution is 0.05～0.5g/ml.
6. method according to claim 2 is characterized in that the consumption of the described HF aqueous solution and the ratio of SBA-15 and polyhedral silsesquioxane composite particles are 5: 1～1000: 1ml/g.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1844126A (en) * | 1931-01-21 | 1932-02-09 | Grayson Heat Control Inc | Thermostatically controlled gas valve |
| US6972312B1 (en) * | 1999-08-04 | 2005-12-06 | Hybrid Plastics Llc | Process for the formation of polyhedral oligomeric silsesquioxanes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1844126A (en) * | 1931-01-21 | 1932-02-09 | Grayson Heat Control Inc | Thermostatically controlled gas valve |
| US6972312B1 (en) * | 1999-08-04 | 2005-12-06 | Hybrid Plastics Llc | Process for the formation of polyhedral oligomeric silsesquioxanes |
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