CN1511786A - Process for continuously preparing meso visual ordered hybridization silicon dioxide fiber - Google Patents
Process for continuously preparing meso visual ordered hybridization silicon dioxide fiber Download PDFInfo
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Abstract
The present invention relates to meso visual ordered hybridized silicon dioxide fiber, and is especially sol-gel process of continuously spinning meso visual ordered hybridized silicon dioxide fiber with high strength and great specific surface area and the process of compounding derivative with optical, electric and magnetic characteristic and catalytic activity. The present invention combines solvent evaporating, surfactant self-organization inducing and silica sol-gel process, continuous spinning process to prepare hybridized silicon dioxide fiber, and high temperature sintering or solvent extracting to eliminate surfactant and to obtain meso visual ordered hybridized silicon dioxide fiber. Via controlling the molecular structure and concentration of surfactant, the continuous regulation of meso visual structure and size may be realized. The fiber of the present invention has excellent mass transferring performance as well as high strength and high size stability.
Description
Technical field
The present invention relates to a kind of Jie and see orderly hydridization silica fiber, be particularly related to Jie who has high strength, high-specific surface area in conjunction with the continuous spinning of sol-gel technique and see orderly hydridization silica fiber, and the method for the derivative of complex light, electricity, magnetic properties and catalytic active substance.
Background technology
The sight Ordered Materials that is situated between is an important research direction of nano material, be meant with the tensio-active agent to be template, utilize physical and chemical processes such as sol/gel, emulsification or microemulsified, by the interface interaction between organism and inorganics assembling and work in coordination with a class aperture that chemical reaction generates between 1.3-30nm, pore size distribution is narrow and porous material with regular hole path structure.Be situated between and see Ordered Materials except the character that possesses nano material, also carry out chemical modification and Heterogeneous Composite easily, obtain functional material.The researchist of Mobil company in 1992 has successfully synthesized MCM-41 type Jie and has seen the ordered molecular sieve, the aperture can be adjusted between 1.5-10nm, its single pore size distribution, high specific surface area and porosity have caused extensive concern (C.T.Kresge, M.E.Leonowicz, W.J.Roth, J.C.Vartuli, J.S.Beck, " Ordered mesoporousmolecular sieves synthesized by a liquid crystal templatemechanism ", Nature 1992,359,710).People not only can utilize segmented copolymer or small molecules tensio-active agent to make the size (D.Zhao of template control punch now, J.Feng, Q.Huo, N.Melosh, G.H.Fredrickson, B.F.Chmelka, G.D.Stucky, " Triblock copolymer syntheses of mcsoporous silica with periodic50 to 300 angstrom pores ", Science 1998,279, and 548), and can be processed into certain shape be situated between seeing Ordered Materials, studying more at present is film and microballoon.People such as Lu have prepared the porous silica film (Y.Lu of 2-dimensional mesoscopic ordered structure in conjunction with the immersion coating technology by the self-organization of solvent evaporation induced surface promoting agent, R.Ganguli, C.A.Drewien, M.T.Anderson, C.J.Brinker, W.Gong, Y.Guo, H.Soyez, B.Dunn, M.H.Huang, J.I.Zink, " Continuous formation of supported cubicand hexagonal mesoporous films by sol-gel dip-coating ", Nature1997,389,364).Adopt tensio-active agent self-organization and aerosol deposition technology to combine, the silicon dioxide gel system can be made zero dimension Jie and see orderly sub-micro ball.If in colloidal sol, add function ingredients such as golden nanometer particle, organic dye, organic polymer, then can obtain having the nano composite material (Y.Lu of specific function, H.Fan, A.Stump, T.L.Ward, T.Rieker, C.J.Brinker, " Aerosol-assisted self-assembly of mesostructuredspherical nanoparticles ", Nature 1999,398,223).In addition, regulate the composition in silicon source, in the inorganics skeleton, introduce organic fragment, then can improve the network affinity and the network strength of film or microballoon, reduce specific inductivity (Y.Lu, H.Fan, N.Doke, D.A.Loy, R.A.Assink, D.A.Lavan, C.J.Brinker, " Evaporation-inducedself-assembly of hybrid bridged silsesquioxane film andparticulate mesophases with integral organic functionality ", J.Am.Chem.Soc.2000,122,5258).Yet it is less at present one dimension Jie to be seen orderly fiber research, and bigger specific surface area and the good mass transfer performances of fiber makes it have more application prospects at aspects such as absorption, catalysis, sensing and optical waveguides.People such as Huo use the spontaneous process of growth after the organosilicon source hydrolysis to prepare to be situated between in oil/water two-phase reaction system and see orderly silica fiber, and length can reach 5cm (Q.Huo, D.Zhao, J.Feng, K.Weston, S.K.Buratto, G.D.Stucky, S.Schacht, F.Schuth, " Room temperaturegrowth of mesoporous silica fibcrs:a new high-surface-areaoptical waveguide ", Adv.Mater.1997,9,974).People such as Yang have prepared the orderly silica fiber of the sight (P.Yang that is situated between by sol-gel process with the glass stick wire drawing, D.Zhao, B.F.Chmelka, G.D.Stucky, " Triblock-copolymer-directedsyntheses of large-pore mesoporous silica fibers " .Chem.Mater.1998,10,2033).Recently, the method for usefulness centrifugal spinnings such as Jung has prepared to be situated between sees orderly silica fiber, and length can reach 3～10cm.(K.T.Jung，Y.H.Chu，S.Haam，Y.G.Shul，“Synthesis?of?mesoporous?silica?fiber?using?spinningmethod”，J.Non-Cryst.Solids，2002，298，193)。But this several method all can not the continuous production silica fiber.Matsuzaki etc. once carried out spinning with the dry-spinning method to the silicon-dioxide pre-gelled, obtained the successive silica fiber, but not existing to be situated between, this fiber do not see ordered structure (K.Matsuzaki, D.Arai, N.Taneda, T.Mukaiyama, M.Ikemura, " Continuous silica glass fiber produced by sol-gel process ", J.Non-Cryst.Solids 1989,112,437).The similar method of employings such as Baskaran has prepared to be situated between sees orderly silica fiber, but need to add polymkeric substance (as polyoxyethylene) to improve the viscosity (P.J.Bruinsma of spinning solution, A.Y.Kim, J.Liu, S.Baskaran, " Mesoporous silica synthesized by solvent evaporation:spunfibers and spray-dried hollow spheres ", Chem.Mater.1997,9,2507).How to adopt sol-gel technique to prepare Jie continuously and see ordered fiber, and the controllable adjustment of implementation structure feature, and all kinds of active substances of assembling in fiber surface or duct how, make it have special light, electricity and magnetic property, and these materials are applied to molectronics, nonlinear optics, energy storage and aspects such as conversion, chemical sensor, significance is arranged.
Summary of the invention
The purpose of this invention is to provide a kind of constitutional features controllable adjustment, and can assemble all kinds of active substances in fiber surface or duct, Jie with special light, electricity and magnetic property sees the continuous preparation method of orderly hydridization silica fiber.
Another object of the present invention provides a kind of Jie and sees the purposes of orderly hydridization silica fiber.
The present invention is in conjunction with promoting agent self-organization of solvent evaporation induced surface and silica sol-gel process, method by continuous spinning has prepared successive hydridization silica fiber, and high temperature sintering or solvent extraction are removed organic surface active agent and obtained being situated between the orderly hydridization silica fiber of sight.By the molecular structure and the concentration of control surface promoting agent, can realize the continuous adjusting of mesoscopic structure and size.Fiber of the present invention not only has excellent mass transferring performance, also has the good intensity and the stability of hole dimension.Because method of the present invention has good consistency with nanoparticles such as various metals, oxide compound etc. in preparation process, in preparation process functional system introduce to be situated between is seen in the ordered structure fiber as the system with katalysis or photoelectromagnetism characteristic, to see orderly hydridization silica fiber functional thereby give Jie of the present invention.
The present invention relates to select different organosilicon source instead of part silicate class Si (OR)
4, organic composition is introduced the network of silicon-dioxide or the surface in hole, make the skeleton in hole become the hybrid body, improve the physical and chemical performance and the affine selectivity of skeleton.
The present invention relates to sol-gel process and continuous spinning process.The silicon-dioxide pre-gelled that makes is extruded by spinning jet, through static traction or mechanical stretching traction, drying makes the successive silica fiber, and high temperature sintering or solvent extraction are removed tensio-active agent and obtained Jie's sight ordered structure, realizes the orderly hydridization silica fiber process of preparation Jie sight continuously.
Jie of the present invention sees the continuous preparation method of orderly hydridization silica fiber, and step comprises:
(1). the preparation of silicon dioxide gel: with the silicon source of 208 weight parts, the ethanol of 130～230 weight parts, the water of 18～36 weight parts, the tensio-active agent of the acid catalyst of 0.005～5 weight part and 48～60 weight parts mixes, 50～70 ℃ of backflows, obtain transparent silicon dioxide gel;
(2). the preparation of pre-gelled: the silicon dioxide gel that step (1) is made places 40～80 ℃ of water-baths to heat, along with the alcoholic acid volatilization, surfactant concentrations reaches micelle-forming concentration, the process of self-organization of tensio-active agent takes place, generating is situated between sees ordered structure, and characteristic dimension is in nanometer scale; The continuation volatilization of solvent causes the viscosity of silicon dioxide gel to increase gradually, forms pre-gelled.The ratio of the present invention by control silicon source and water makes and forms linear macromolecule after the hydrolysis of silicon source, thereby the pre-gelled that makes has spinning property.
(3). the continuous preparation of hybridized fiber: the pre-gelled that step (2) obtains is extruded (aperture of spinning jet is at the 10-500 mu m range) through the porous spinning jet, stretch with machinery or electrostatic field acceleration form, follow ethanol volatilization induced surface promoting agent self-organization and further sol-gel process simultaneously, obtain continuous hydridization silica fiber, the silica stationary that the orderly mesoscopic structure that the tensio-active agent self-organization forms is formed in the sol-gel process is got off.By regulating aperture, draw speed or the strength of electric field of spinning jet, obtaining diameter is the controlled hydridization silica fiber of 0.2～100 μ m.
(4). be situated between and see the preparation of orderly hydridization silica fiber: the continuous hydridization silica fiber that step (3) is obtained places in the sintering oven, and blowing air, be warming up to 300～700 ℃ of (preferred 450 ℃) calcinations 0.2～3 hour with 0.1～10 ℃/minute speed; The continuous hydridization silica fiber that perhaps step (3) is obtained uses alcohol solvent to carry out extracting, removes organic surface active agent; The orderly hydridization silica fiber of sight obtains being situated between.If desired, the polymerization single polymerization monomer that can add 20～50 weight parts carries out polymerization, as CH
3(CH
2)
11C ≡ C-C ≡ C-(CH
2)
8CO-(OCH
2CH
2)
5-OH or (C
2H
5O)
3Si-(CH
2)
6-CH=CH
2Deng fiber reinforcement being carried out modification, adding polymerization single polymerization monomer should be before removing tensio-active agent.
(5). the fiber production of metal ion: Jie that step (4) is obtained sees orderly hydridization silica fiber and further is immersed in and contains in the respective metal ionic salts solution, as cupric nitrate, vanadylic sulfate, Silver Nitrate or ferric chloride Solution, repeat to contain in fiber for several times the metal ion content of design, Jie who obtains containing metal ion sees orderly hydridization silica fiber.
In the transparent silicon dioxide gel system that step (1) obtains, can further add the function monomer of 20～50 weight parts and the initiator of 0.02～0.5 weight part, or add the function nano metal or 5～30 weight part nanometer metal oxide microparticles of 5～30 weight parts, obtain functional nanometer silicon dioxide composite material.In addition, Jie that step (4) is obtained sees orderly hydridization silica fiber and is immersed in the aqueous solution of 1～10 weight part biological enzyme, and heterogeneous Jie who obtains biologically active after the taking-up sees orderly hydridization silica fiber.
Monomer, vinyl-containing monomers, organic fragment hydridization siloxanes, alkyl that alkoxyl group can be selected to contain in described silicon source replace siloxanes, coupling agent one type of silane or their any mixture.
The described monomer that contains alkoxyl group comprises Si (OCH
3)
4, Si (OCH
2CH
3)
4, Si{OCH (CH
3)
2}
4Or Si (OCH
2CH
2CH
2CH
3)
4Deng, preferred Si (OCH
2CH
3)
4Or Si{OCH (CH
3)
24, best Si (OCH
2CH
3)
4
Described vinyl-containing monomers comprises CH
2=CHSi (OC
2H
5)
3, CH
2=CH (CH
2)
2Si (OC
2H
5)
3Or CH
2=CH-(CH
2)
6-Si (OC
2H
5)
3Deng, preferred CH
2=CH-(CH
2)
6-Si (OC
2H
5)
3
Described organic fragment hydridization siloxanes comprises (CH
3CH
2O)
3Si-CH
2-Si (OCH
2CH
3)
3, (C
2H
5O)
3Si-CH
2CH=CHCH
2-Si (OC
2H
5)
3, (CH
3CH
2O)
3Si-C
6H
4-Si (OCH
2CH
3)
3Or (CH
3CH
2O)
3Si-CH
2CH
2-Si (OCH
2CH
3)
3Deng, preferred (C
2H
5O)
3Si-C
6H
4-Si (OC
2H
5)
3Or (CH
3CH
2O)
3Si-CH
2CH
2-Si (OCH
2CH
3)
3
Described alkyl replaces siloxanes and comprises (C
2H
5O)
3Si-CH
3, (C
2H
5O)
3Si-(CH
2)
4CH
3Or CF
3(CF
2)
5CH
2CH
2Si (OC
2H
5)
3Deng, preferred CF
3(CF
2)
5CH
2CH
2Si (OC
2H
5)
3
Described coupling agent one type of silane comprises NH
2CH
2Si (OCH
2CH
3)
3, CH
2=C (CH
3) COO (CH
2)
3Si (OCH
3)
3, (CH
3O)
3Si-(CH
2)
3-SH, C
6H
5NHCH
2Si (OCH
3)
3Or (C
2H
5O)
3SiCH
2S
4CH
2Si (OC
2H
5)
3Deng, preferred (CH
3O)
3Si-(CH
2)
3-SH or CH
2=C (CH
3) COO (CH
2)
3Si (OCH
3)
3
Described tensio-active agent can be selected small molecules tensio-active agent or copolymer surfactants.Wherein, the small molecules tensio-active agent comprises cats product such as Trimethyllaurylammonium bromide, cetyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride or lauric acid dimethylamino-ethanol ester benzyl ammonium chloride etc., preferred cetyl trimethylammonium bromide or octadecyl trimethyl ammonium chloride; Nonionogenic tenside such as fatty alcohol-polyoxyethylene ether, by pears alcohol mono-laurate, Brij-56{CH
3(CH
2)
15(OCH
2CH
2)
10OH}, Brij-58{CH
3(CH
2)
15(OCH
2CH
2)
20OH}, OP-10 or Span-20 etc., preferred Brij-56 or Brij-58; Copolymer surfactants comprises oxygen ethene-oxypropylene multipolymer such as Pluronic-123 (PEO
20-PPO
70-PEO
20), Pluronic-127 (PEO
20-PPO
106-PEO
20), vinylbenzene-oxygen ethylene copolymer, toxilic acid-methyl acrylate copolymer or ethyl propenoate-vinylformic acid-acrylonitrile copolymer etc., preferred Pluronic-123 or Pluronic-127.
Described catalyzer can be selected any one in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid or the Hydrogen bromide, preferred hydrochloric acid or nitric acid, preferably nitric acid.
Described function monomer comprises and contains two keys or triple-linked monomer such as C
6H
4CH=CH
2, CH
2=CHCOO (CH
2)
11CH
3, CH
3(CH
2)
11C ≡ C-C ≡ C-(CH
2)
8CO-(OCH
2CH
2)
5-OH, CH
2=C (CH
3) COOCH
3Or CH
2=C (CH
3) COOCH
2-CH=CH
2Deng, make the initiator of these monomer polymerizations comprise Diisopropyl azodicarboxylate, benzoyl peroxide or ditertiary butyl peroxide etc.
Described metal is gold and silver, copper or nickel etc.; Described metal oxide is titanium dioxide, Vanadium Pentoxide in FLAKES, cupric oxide, Manganse Dioxide or ferric oxide etc.
Described biological enzyme is any one in glucose oxidase, ascorbate salt oxydase or the N,O-Diacetylmuramidase.
Preparation method of the present invention and products characteristics are as follows:
● raw material is very cheap, for common chemical reagent, and as nitric acid, ethanol, the positive tetraethyl orthosilicate in common molecule silicon source etc.
● experimental implementation is easy.
● can prepare continuously to be situated between by sol-gel technique and see orderly hydridization silica fiber.
● be aided with the high-voltage electrostatic spinning technology, can obtain than the thinner fiber of conventional spinning products obtained therefrom, its diameter can reach nanometer～submicron order.
● select the spinning jet of different hole shapes for use, can obtain the different profile fibre of cross section shapes.
● by control surface active agent molecule concentration, can control is situated between sees ordered structure form such as nanoporous, stratiform or co-continuous.By changing the kind of surfactant molecule, and add organic solvent, can realize the continuous adjusting of mesoscopic structure and size, as for nanometer its aperture of fiber of structure can in 2～30nm scope, regulate.
● by regulating silicon source The Nomenclature Composition and Structure of Complexes, add function component and auxilliary different post processing modes outward, realize that in wide range having Jie sees the controlled of ordered structure fiber form and function.With the organic fragment difference that introduce in the silicon source, can regulate fibre network affinity and network strength, complexation of metal ions is regulated specific inductivity, improves mechanical property and thermal characteristics etc.
● in sol system, introduce functional surface promoting agent or monomer (as two alkynes class tensio-active agents or vinyl monomer), by obtaining nano-complex with silicon source cocondensation or monomer post polymerization, at catalyzer, bionics, drug controllable release, aspects such as functional materials have the important application meaning.
● be equipped with the sight ordered fiber that is situated between with the sol/gel legal system, not only raw material is pure, and the control of gel time is simple and direct, effective.Product has high-specific surface area, high strength and good hole dimension stability, is good support of the catalyst.
Jie of the present invention sees orderly hydridization silica fiber and can be used for synthetic sorbing material, support of the catalyst, photoelectric functional material, and other functional material, as electro-conductive material, optical material, nonlinear optical material, biomaterial, orderly magneticsubstance, molecular device etc.
Description of drawings
Fig. 1. the transmission electron microscope picture of the embodiment of the invention 1.
Fig. 2. the transmission electron microscope picture of the embodiment of the invention 2.
Fig. 3. the transmission electron microscope picture of the embodiment of the invention 3.
Fig. 4. the transmission electron microscope picture of the embodiment of the invention 4.
Fig. 5. the transmission electron microscope picture of the embodiment of the invention 5.
Fig. 6. the transmission electron microscope picture of the embodiment of the invention 8.
Embodiment
Embodiment 1: be situated between and see the continuous preparation of orderly silica fiber
With positive tetraethyl orthosilicate 208 weight parts, ethanol 156 weight parts, water 36 weight parts, nitric acid 0.63 weight part, cetyl trimethylammonium bromide 55 weight parts mix, and in 50 ℃ of backflow 90min, obtain faint yellow transparent silicon dioxide gel under the induction stirring.The silicon dioxide gel that makes is uncovered to place 70 ℃ of water-baths to heat 2.5 hours to the viscosity increase, forms pre-gelled.The silicon-dioxide pre-gelled is extruded (bore dia is 20 μ m) through the porous spinning jet, applies 2 * 10 simultaneously
5The high tension electrostatic field of V/m stretches, and obtains the successive silica fiber after the drying, and fiber is placed in the sintering oven, and blowing air, rise to 450 ℃ of calcinations 3 hours with 1 ℃/minute speed, remove tensio-active agent, obtain being situated between and see orderly nanoporous silica fiber, Fibre diameter 400nm.X-ray diffraction and transmission electron microscope results show that ordered nano hole is six sides to be arranged, and hole dimension is 2nm, and the nitrogen absorption result shows the long-pending 1250m of being of specific fiber surface
2/ g.Increase strength of electric field, can prepare the thinner fiber of diameter.As shown in Figure 1.
Embodiment 2: be situated between and see the continuous preparation of orderly silica fiber
With positive tetraethyl orthosilicate 208 weight parts, ethanol 180 weight parts, water 30 weight parts, nitric acid 0.48 weight part, Brij-58{CH
3(CH
2)
15(OCH
2CH
2)
20The OH}52 weight part mixes, and in 60 ℃ of backflow 90min, obtains water white silicon dioxide gel under the induction stirring.Step according to embodiment 1 prepares silica fiber, The hole diameter of spinneret 1O μ m, Fibre diameter 320nm.X-ray diffraction and transmission electron microscope results show that ordered nano hole is a cube arrangement, and hole dimension is 4nm, and the nitrogen absorption result shows the long-pending 710m of being of specific fiber surface
2/ g.As shown in Figure 2.
Embodiment 3: be situated between and see the continuous preparation of orderly silica fiber
With positive tetraethyl orthosilicate 208 weight parts, ethanol 230 weight parts, water 18 weight parts, nitric acid 0.6 weight part, Pluronic-123{PEO
20-PPO
70-PEO
2048 weight parts mix, and in 60 ℃ of backflow 90min, obtain water white silicon dioxide gel under the induction stirring.Be situated between according to the preparation of the step of embodiment 1 and see orderly silica fiber, but added electric field not, but forming fiber by the mechanical stretching effect, The hole diameter of spinneret 100 μ m, rate of extension 30cm/min, Fibre diameter are 5 μ m.X-ray diffraction and transmission electron microscope results show that ordered nano hole is a cube arrangement, and hole dimension is 4nm, and the nitrogen absorption result shows the long-pending 620m of being of specific fiber surface
2/ g.As shown in Figure 3.
Embodiment 4: be situated between and see the continuous preparation of orderly silica fiber
With positive tetraethyl orthosilicate 208 weight parts, ethanol 130 weight parts, water 36 weight parts, nitric acid 0.63 weight part, Pluronic-127{PEO
20-PPO
106-PEO
2048 weight parts mix, and in 60 ℃ of backflow 90min, obtain water white silicon dioxide gel under the induction stirring.Step preparation Jie according to embodiment 3 sees orderly silica fiber, The hole diameter of spinneret 500 μ m, Fibre diameter 70 μ m.X-ray diffraction and transmission electron microscope results show that ordered nano hole is six sides to be arranged, and hole dimension is 6nm, and the nitrogen absorption result shows the long-pending 480m of being of specific fiber surface
2/ g.As shown in Figure 4.
Embodiment 5: be situated between and see the continuous preparation of orderly silica fiber
As different from Example 4, add 36 weight part organic solvents 1,3 in the silicon dioxide gel system, the 5-trimethylbenzene is because it to the micellar solublization, makes the size of ordered nano hole significantly improve, gained Fibre diameter 70 μ m.X-ray diffraction and transmission electron microscope results show, order mesoporously is six sides and arranges, and hole dimension is 30nm, and the nitrogen absorption result shows that specific fiber surface is long-pending and is 350m
2/ g.The kind of reconciliation statement surface-active agent and the amount of organic solvent can make hole dimension regulate continuously between 2～30nm.As shown in Figure 5.
Embodiment 6: be situated between and see the continuous preparation of orderly silica fiber
As different from Example 3, tensio-active agent is not to remove by the agglomerating method, but makes solvent with ethanol, and extracting is removed in apparatus,Soxhlet's, and Fibre diameter is 5 μ m.X-ray diffraction and transmission electron microscope results show that ordered nano hole is a cube arrangement, and hole dimension is 4nm, and the nitrogen absorption result shows the long-pending 750m of being of specific fiber surface
2/ g.
Embodiment 7: be situated between and see the continuous preparation of orderly silicon-dioxide profile fibre
As different from Example 1, the hole ovalize of spinning jet, pre-gelled is extruded the back and is formed fiber by the mechanical stretching effect, rate of extension 15cm/min, fiber cross section ovalize, X-ray diffraction and transmission electron microscope results show that ordered nano hole is six sides and arranges, hole dimension is 2nm, and the nitrogen absorption result shows the long-pending 580m of being of specific fiber surface
2/ g.Use difform spinning jet, can prepare the profile fibre that comes in every shape.
Embodiment 8: be situated between and see the continuous preparation of orderly silicon-dioxide concentric tube
With positive tetraethyl orthosilicate 208 weight parts, ethanol 170 weight parts, water 36 weight parts, nitric acid 0.5 weight part, Pluronic-123{PEO
20-PPO
70-PEO
2056 weight parts mix, and in 60 ℃ of backflow 90min, obtain water white silicon dioxide gel under the induction stirring.Step according to embodiment 1 prepares silica fiber, Fibre diameter 500nm.Because tensio-active agent organizes themselves into laminate structure, the transmission electron microscope observing fiber cross section finds that fiber is that concentric tube is formed, and the pipe interlamellar spacing is 5nm.The nitrogen absorption result shows the long-pending 580m of being of specific fiber surface
2/ g.As shown in Figure 6.
Embodiment 9: functionalization is situated between and sees the continuous preparation of orderly silica fiber
With positive tetraethyl orthosilicate 104 weight parts, (CH
3CH
2O)
3Si-CH
2CH
2-Si (OCH
2CH
3)
3177 weight parts, ethanol 160 weight parts, water 54 weight parts, nitric acid 0.63 weight part, cetyl trimethylammonium bromide 30 weight parts mix, and in 60 ℃ of backflow 90min, obtain faint yellow transparent silicon dioxide gel under the induction stirring.Step according to embodiment 3 prepares silica fiber, The hole diameter of spinneret 200 μ m, draw speed 15cm/min.Fiber is placed in the sintering oven, and logical nitrogen, be warming up to 350 ℃ of calcinations 3 hours with 1 ℃/minute speed, remove tensio-active agent, the orderly silica fiber of sight that obtains being situated between, Fibre diameter 20 μ m.X-ray diffraction and transmission electron microscope results show that ordered nano hole is six sides to be arranged, and hole dimension is 2nm, and the nitrogen absorption result shows the long-pending 970m of being of specific fiber surface
2/ g.Because organic fragment-Si-CH
2CH
2The introducing of-Si-, the lipophilicity and the network strength of inorganic matter fiber network increase.Regulate positive tetraethyl orthosilicate and (CH
3CH
2O)
3Si-CH
2CH
2-Si (OCH
2CH
3)
3Ratio, can obtain the order mesoporous fiber of different affinities.
Embodiment 10: functionalization is situated between and sees the continuous preparation of orderly silica fiber
With positive tetraethyl orthosilicate 104 weight parts, (CH
3CH
2O)
3Si-C
6H
4-Si (OCH
2CH
3)
3201 weight parts, ethanol 156 weight parts, water 50 weight parts, nitric acid 0.54 weight part, cetyl trimethylammonium bromide 30 weight parts mix, and in 60 ℃ of backflow 90min, obtain faint yellow transparent silicon dioxide gel under the induction stirring.Step preparation Jie according to embodiment 9 sees orderly silica fiber, Fibre diameter 20 μ m.X-ray diffraction and transmission electron microscope results show that ordered nano hole is six sides to be arranged, and hole dimension is 2nm, and the nitrogen absorption result shows the long-pending 950m of being of specific fiber surface
2/ g.Contain phenyl ring in this fiber reinforcement.Phenyl ring is carried out modification, then can realize the functionalization of product.
Embodiment 11: functionalization is situated between and sees the continuous preparation of orderly silica fiber
It is in the 95-98% vitriol oil that fiber among the embodiment 10 immerses concentration, is warming up to 85 ℃, reacts 3 hours, reduces to room temperature then.Reacted product is under agitation dropped in the cold water, cool off washing.This fiber can swelling in water, illustrates that the phenyl ring in the fiber reinforcement has been sulfonated modification, for further preparation functional fiber provides condition.
Embodiment 12: functionalization is situated between and sees the continuous preparation of orderly silica fiber
It is 3% that product among the embodiment 11 immerses concentration, and pH is the hydrochloric acid soln of 1～2 aniline, through long-time the immersion aniline solution is penetrated in the silica fiber, water flushing fiber surface, then drop into 3% ammonium persulfate solution immediately, reacted 3 hours, obtain cyan conjugated fibre.Gained fiber water soaks repeatedly, and flushing places the vacuum drying oven drying at room temperature.Infrared Characterization shows the polyaniline that has generated the emeraldine salt form in the silica fiber, and its room-temperature conductivity can reach 4.76 * 10
-4S/cm.Have hydrogen ion on the sulfonic group in the fiber, can produce bonding force, play the auto-doping effect simultaneously with the aniline molecule.
Embodiment 13: functionalization is situated between and sees the continuous preparation of orderly silica fiber
With positive tetraethyl orthosilicate 104 weight parts, (CH
3O)
3Si-CH
2CH
2CH
2-SH98 weight part, ethanol 200 weight parts, water 34 weight parts, nitric acid 0.63 weight part, Pluronic-123{PEO
20-PPO
70-PEO
2048 weight parts mix, and in 60 ℃ of backflow 90min, obtain water white silicon dioxide gel under the induction stirring.Step preparation Jie according to embodiment 9 sees orderly silica fiber, Fibre diameter 20 μ m.X-ray diffraction and transmission electron microscope results show that ordered nano hole is a cube arrangement, and hole dimension is 4nm, and the nitrogen absorption result shows the long-pending 720m of being of specific fiber surface
2/ g.Contain sulfydryl in the skeleton of this method synthetic Jie sight ordered structure fiber, have complexing noble metal such as Ag, Au, effects such as Hg form metal/silica nanometer hole conjugated fibre, are with a wide range of applications at catalytic field.
Embodiment 14: functionalization is situated between and sees the continuous preparation of orderly silica fiber
With positive tetraethyl orthosilicate 188 weight parts, CF
3(CF
2)
5CH
2CH
2Si (OC
2H
5)
352 weight parts, ethanol 156 weight parts, water 36 weight parts, nitric acid 0.63 weight part, cetyl trimethylammonium bromide 55 weight parts mix, and in 70 ℃ of backflow 90min, obtain faint yellow transparent silicon dioxide gel under the induction stirring.Step preparation Jie according to embodiment 9 sees orderly silica fiber, Fibre diameter 17 μ m.X-ray diffraction and transmission electron microscope results show that ordered nano hole is six sides to be arranged, and hole dimension is 2.5nm, and the nitrogen absorption result shows the long-pending 900m of being of specific fiber surface
2/ g.Contain hydrophobic grouping in the skeleton of this method synthetic Jie sight ordered structure fiber, can obtain the hole material of low-k, have good machinery and thermal properties, significant aspect the microelectronic device of a new generation.In addition, this material can detect the underwater trace organism, and is not subjected to the influence of water, and it is fast to have the reaction times, characteristics such as sensitivity height.
Embodiment 15: functionalization is situated between and sees the continuous preparation of orderly silica fiber
With positive tetraethyl orthosilicate 208 weight parts, ethanol 156 weight parts, water 36 weight parts, nitric acid 0.63 weight part has surface-active couple of alkynes molecule CH
3(CH
2)
11C ≡ C-C ≡ C-(CH
2)
8CO-(OCH
2CH
2)
5-OH30 weight part mixes, and in 60 ℃ of backflow 90min, obtains water white silicon dioxide gel under the induction stirring.Step according to embodiment 9 prepares silica fiber, Fibre diameter 22 μ m.Be incorporated in 350 ℃ of following sintering 3h with the two alkynes of benzoyl peroxide initiation of 0.3 weight part are poly-, obtain organic/inorganic Jie and see orderly composite functional fiber, this functional fibre rotaversion owing to conjugated double bond under action of ultraviolet light presents the color transition characteristic.
Embodiment 16: functionalization is situated between and sees the continuous preparation of orderly silica fiber
With positive tetraethyl orthosilicate 206 weight parts, (C
2H
5O)
3Si-(CH
2)
6-CH=CH
23 weight parts, organic monomer CH
2=CHCOO (CH
2)
11CH
32.4 weight part, linking agent (CH
2=CHCOO)
2(CH
2)
41 weight part, ethanol 156 weight parts, water 36 weight parts, nitric acid 0.63 weight part, Pluronic-123{PEO
20-PPO
70-PEO
2056 weight parts mix, and in 6O ℃ of backflow 90min, obtain water white silicon dioxide gel under the induction stirring.Step continuous spinning according to embodiment 1.Tensio-active agent is with the mode self-organization of lamella mesomorphic phase in this example, fiber is placed in the sintering oven, and logical nitrogen, be warming up to 350 ℃ of calcinations 3 hours with 1 ℃/minute speed, remove tensio-active agent, the double-bond polymerization that brings out simultaneously in the skeleton is crosslinked, form organic/inorganic alternative laminated composites, interlamellar spacing is 2nm, and this similar is in the laminate structure of shell, simulate the biomineralization process, can significantly improve the intensity and the toughness of fiber.
Embodiment 17: Jie of containing metal oxide compound sees the continuous preparation of orderly silica fiber
Add the aluminium oxide nano particulate of 12 parts of diameter 30nm as different from Example 1 in colloidal sol, pre-gelled is extruded through spinning jet, makes fiber under the mechanical stretching effect, rate of extension 20cm/min, drying, sintering obtain being situated between and see orderly silica fiber, and Fibre diameter is 10 μ m.This fiber surface contains the aluminum oxide composition, is expected to be applied at catalytic field.
This method is equally applicable to preparation and contains nanoparticles such as nano metal particulate such as gold and silver, oxide compound such as zinc oxide, and ferric oxide, Jie of titanium dioxide sees the ordered structure silica fiber.
Embodiment 18: Jie of containing metal oxide compound sees the continuous preparation of orderly silica fiber
Jie that embodiment 1 is made sees in the vanadylic sulfate solution that the ordered structure silica fiber is immersed in 2mol/L, makes nanoporous absorption vanadium ion.The said process triplicate, each 3 hours, the fiber after the absorption placed tube furnace, and blowing air in 550 ℃ of following sintering 6 hours, naturally cools to room temperature then.X-ray photoelectron spectroscopy is the result show, there is Vanadium Pentoxide in FLAKES in the silica nanometer hole surface.By concentration and the immersion number of times of regulating vanadylic sulfate, the content of energy adjustment hole surface Vanadium Pentoxide in FLAKES.
Embodiment 19: metallic Jie sees the continuous preparation of orderly silica fiber
Jie that embodiment 4 is made sees in the copper nitrate solution that the ordered structure silica fiber is immersed in 2mol/L, makes mesoporous fiber absorbing copper ion.The said process triplicate, each 3 hours, and be about 7～8 with less ammonia adjusting pH all at every turn.With absorbing copper ionic fiber vacuum drying, place tube furnace, blowing air is warming up to 600 ℃ and kept 5 hours with 3 ℃ of/minute speed programs, naturally cools to room temperature then, and the product outward appearance is a black.X-ray photoelectron spectroscopy is the result show, there is cupric oxide in the silica nanometer hole surface.This product is used down hydrogen reducing half an hour at 600 ℃, keeping under the condition of hydrogen then, be cooled to room temperature.X-ray photoelectron spectroscopy is the result show, there is copper in gained fiber nanoporous surface.
This method is equally applicable to preparation and contains ferric oxide, iron-cobalt magneticsubstance, and silver, manganese, Jie of metals such as nickel sees orderly silica fiber.
Claims (10)
1. one kind is situated between and sees the preparation method of orderly hydridization silica fiber, and step comprises:
(1). the preparation of silicon dioxide gel: with the silicon source of 208 weight parts, the ethanol of 130～230 weight parts, the water of 18～36 weight parts, the tensio-active agent of the acid catalyst of 0.005～5 weight part and 48～60 weight parts mixes, 50～70 ℃ of backflows, obtain transparent silicon dioxide gel;
(2). the preparation of pre-gelled: the silicon dioxide gel that step (1) is made places 40～80 ℃ of water-baths to heat, and along with the alcoholic acid volatilization, tensio-active agent organizes themselves into ordered structure, and characteristic dimension is in nanometer scale; Continue solvent flashing, cause the viscosity of silicon dioxide gel to increase gradually, form pre-gelled;
(3). the continuous preparation of hybridized fiber: the pre-gelled that step (2) obtains is extruded through the porous spinning jet, stretched, obtain continuous hydridization silica fiber with machinery or electrostatic field acceleration form;
(4). be situated between and see the preparation of orderly hydridization silica fiber: the continuous hydridization silica fiber that step (3) is obtained places in the sintering oven, and blowing air, is warming up to 300～700 ℃ of calcinations with 0.1～10 ℃/minute speed; The continuous hydridization silica fiber that perhaps step (3) is obtained uses alcohol solvent to carry out extracting, removes organic surface active agent; The orderly hydridization silica fiber of sight obtains being situated between.
2. the method for claim 1, it is characterized in that: in the transparent silicon dioxide gel system that step (1) obtains, further add the function monomer of 20～50 weight parts and the initiator of 0.02～0.5 weight part, or add the function nano metal or 5～30 weight part nanometer metal oxide microparticles of 5～30 weight parts, obtain functional nanometer silicon dioxide composite material.
3. the method for claim 1, it is characterized in that: Jie that described step (4) obtains sees orderly hydridization silica fiber and further is immersed in and contains in the respective metal ionic salts solution, repeat to contain in fiber for several times the metal ion content of design, Jie who obtains the implication metal ion sees orderly hydridization silica fiber;
Or Jie of obtaining of described step (4) sees in the aqueous solution that orderly hydridization silica fiber further is immersed in biological enzyme, and heterogeneous Jie who obtains biologically active sees orderly hydridization silica fiber.
4. method as claimed in claim 3 is characterized in that: the salts solution of described metal ion is cupric nitrate, vanadylic sulfate, Silver Nitrate or ferric chloride Solution.
5. the method for claim 1 is characterized in that: add polymerization single polymerization monomer 20～50 weight parts that fiber reinforcement is carried out modification except that tensio-active agent takes a step forward in step (4);
Described polymerization single polymerization monomer is CH
3(CH
2)
11C ≡ C-C ≡ C-(CH
2)
8CO-(OCH
2CH
2)
5-OH or (C
2H
5O)
3Si-(CH
2)
6-CH=CH
2
6. the method for claim 1 is characterized in that: monomer, vinyl-containing monomers, organic fragment hydridization siloxanes, alkyl that alkoxyl group is selected to contain in described silicon source replace siloxanes, coupling agent one type of silane or their any mixture;
The described monomer that contains alkoxyl group comprises Si (OCH
3)
4, Si (OCH
2CH
3)
4, Si{OCH (CH
3)
2}
4Or Si (OCH
2CH
2CH
2CH
3)
4
Described vinyl-containing monomers comprises CH
2=CHSi (OC
2H
5)
3, CH
2=CH (CH
2)
2Si (OC
2H
5)
3Or CH
2=CH-(CH
2)
6-Si (OC
2H
5)
3
Described organic fragment hydridization siloxanes comprises (CH
3CH
2O)
3Si-CH
2-Si (OCH
2CH
3)
3, (C
2H
5O)
3Si-CH
2CH=CHCH
2-Si (OC
2H
5)
3, (CH
3CH
2O)
3Si-C
6H
4-Si (OCH
2CH
3)
3Or (CH
3CH
2O)
3Si-CH
2CH
2-Si (OCH
2CH
3)
3
Described alkyl replaces siloxanes and comprises (C
2H
5O)
3Si-CH
3, (C
2H
5O)
3Si-(CH
2)
4CH
3Or CF
3(CF
2)
5CH
2CH
2Si (OC
2H
5)
3
Described coupling agent one type of silane comprises NH
2CH
2Si (OCH
2CH
3)
3, CH
2=C (CH
3) COO (CH
2)
3Si (OCH
3)
3, (CH
3O)
3Si-(CH
2)
3-SH, C
6H
5NHCH
2Si (OCH
3)
3Or (C
2H
5O)
3SiCH
2S
4CH
2Si (OC
2H
5)
3
7. the method for claim 1, it is characterized in that: described tensio-active agent is Trimethyllaurylammonium bromide, cetyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride, lauric acid dimethylamino-ethanol ester benzyl ammonium chloride, fatty alcohol-polyoxyethylene ether, sorbitan monolaurate, Brij-56{CH
3(CH
2)
15(OCH
2CH
2)
10OH}, Brij-58{CH
3(CH
2)
15(OCH
2CH
2)
20OH}, OP-10, Span-20, Pluronic-123 (PEO
20-PPO
70-PEO
20), Pluronic-127 (PEO
20-PPO
106-PEO
20), vinylbenzene-oxygen ethylene copolymer, toxilic acid-methyl acrylate copolymer or ethyl propenoate-vinylformic acid-acrylonitrile copolymer;
Described catalyzer is sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid or Hydrogen bromide.
8. method as claimed in claim 2 is characterized in that: described function monomer comprises C
6H
4CH=CH
2, CH
2=CHCOO (CH
2)
11CH
3, CH
3(CH
2)
11C ≡ C-C ≡ C-(CH
2)
8CO-(OCH
2CH
2)
5-OH, CH
2=C (CH
3) COOCH
3Or CH
2=C (CH
3) COOCH
2-CH=CH
2
Described initiator is Diisopropyl azodicarboxylate, benzoyl peroxide or ditertiary butyl peroxide;
Described metal is gold and silver, copper or nickel; Described metal oxide is titanium dioxide, Vanadium Pentoxide in FLAKES, cupric oxide, Manganse Dioxide or ferric oxide.
9. method as claimed in claim 3 is characterized in that: described biological enzyme is glucose oxidase, ascorbate salt oxydase or N,O-Diacetylmuramidase.
10. the method for claim 1, it is characterized in that: the aperture of described spinning jet is 10-500 μ m.
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|---|---|---|---|
| CN 02159683 CN1278931C (en) | 2002-12-30 | 2002-12-30 | Process for continuously preparing meso visual ordered hybridization silicon dioxide fiber |
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