CN1129641C - Prepn of ordered porous material comprising ordered polymer and inorganic heterocomplex and its derivative - Google Patents
Prepn of ordered porous material comprising ordered polymer and inorganic heterocomplex and its derivative Download PDFInfo
- Publication number
- CN1129641C CN1129641C CN 01100392 CN01100392A CN1129641C CN 1129641 C CN1129641 C CN 1129641C CN 01100392 CN01100392 CN 01100392 CN 01100392 A CN01100392 A CN 01100392A CN 1129641 C CN1129641 C CN 1129641C
- Authority
- CN
- China
- Prior art keywords
- ordered
- gel
- orderly
- resin
- gel resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Silicon Compounds (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a preparation method of an ordered high polymer/inorganic hybrid and an ordered porous material of a derivative of the ordered high polymer/inorganic hybrid. The material prepared with the method of the present invention has the advantages of favorable mass transfer performance, high strength and high pore size stability. In addition, the size, the form and the connectivity of pores are adjustable. Since the method has high compatibility with various metallic salts, various complex compounds, etc. in the preparation process, functional systems, such as systems performing catalytic action or optical characteristics, electric characteristics, magnetic characteristics, etc., are led into the inorganic porous material in the preparation process to endow the composite porous system with high functionality.
Description
The present invention relates to the preparation of a kind of novel orderly superpolymer gel resin/inorganic hybrid and derivative three-dimensional ordered inorganic porous material thereof, be particularly related to high strength with two kinds of homogeneous pore size distributions, the inorganic materials of high-ratio surface, and have the catalyzer derivative of potential catalytic activity and simple and effective preparation method thereof.
Zeolite is common poromerics, it is big that it has specific surface area, duct size uniform and ordered, Heat stability is good, therefore advantages such as the chemical environment in the hole (acid-basicity on the power of electrostatic field and surface) is controlled have very important use at absorption, separation and catalytic field.At present, the application of zeolite is from traditional absorption, separation and catalytic field, and gradually to environment protection and improvement, high-tech areas such as biotechnology and photoelectric functional material are expanded.Mesopore molecular sieve is meant with the tensio-active agent to be template, utilize physical and chemical processes such as collosol and gel, emulsification or micro emulsion, a class aperture that generates by the interface interaction between organism and inorganics assembling and collaborative chemical reaction between 1.3-30nm, pore size distribution is narrow and inorganic porous material with regular pore canal structure.The people such as Kreoge of Mobil company in 1992 have successfully synthesized MCM-41 type molecular sieve, and its aperture can be adjusted between 1.5-10nm, have caused attention and interest that people are general.(C.T.Kresge，M.E.Leonowicz，W.J.Roth，J.C.Vartuli，J.S.Beck，“Ordered?mesoporous?molecular?sievessynthesized?by?a?liqiud?crystal?template”，Nature?1992，359，710)。People such as R.Ryoo had synthesized the unordered mesopore molecular sieve of KIT type in 1996, and this material has good hydrothermal stability, high specific surface and is better than the mass-transfer performance of MCM series, has very application prospects.(R.Ryoo, J.M.Kim, C.H.Ko, C.H.Shin, " Disordered molecular sieve withbranched mesoporous channel network ", J.Phys.Chem.1996,100,17718) the synthetic and functionalization of mesoporous material also has important use in fields such as the separating of macromolecular catalysis, biomolecules, molecular electronic devices.Because its hole dimension is big, plays the irreplaceable effect of zeolite molecular sieve in actual applications.Yet in this field, still there are many brand-new problems to need to solve.For example, how in mesopore molecular sieve surface or duct, to assemble all kinds of active substances by molecule, make it have special light, electricity and magnetic property, and these materials are made can be for the actual device that uses, being applied to molectronics, nonlinear optics, energy storage and aspects such as conversion, chemical sensor, has been pendulum problem as incentive in face of people.Under many occasions, the reactant size is bigger such as working as, and can not enter the duct of zeolite or mesopore molecular sieve, and therefore the preparation of larger sized ordered porous material just has realistic meaning.
People (O.D.Velev such as O.D.Velev in 1997, T.A.Jede, R.F.Lobo, A.M.Lenhoff, " Porous silica via colloidal crystallization ", Nature 1997,389,447) and people (B.T.Holland such as A.Stein in 1998, C.F.Blanford, A.Stein, " Synthesis ofmacroporous minerals with highly ordered three-dimensional arrays ofspherical voids ", Science 1998,281,538) be template with the polystyrene colloid crystalline substance, use different silicon sources respectively, prepared the aperture at the adjustable three-dimensional ordered macroporous molecular sieve of 200-1000 nanometer range.But it is very low that the distinct disadvantage of this type of material is an intensity, causes the orderly pore volume of gained easily to cave in.
The present invention adopts this breadboard patented product ordered gel resin (Yang Zhenzhong etc., in the patent application, 2000), with improved so-gel technology, prepares orderly high polymer/inorganic hybrid, and by sintering organism is removed and to be obtained inorganic hole material.Constitutional features by control superpolymer gel resin can realize the continuous adjusting of inorganic pore structure and size.Therefore, it is little to have solved existing mesoporous material aperture, is unfavorable for the problem of reactant mass transfer; Also improved simultaneously the problem of the intensity difference of existing macropore Ordered Materials.So this material not only has excellent mass transferring performance, also has the good intensity and the stability of hole dimension.Because this method has good consistency with various metallic salts, complex compound etc. in preparation process, in preparation process, will have functional system and be incorporated in the material of inorganic hole, will give more powerful of this composite holes system as system with katalysis or photoelectromagnetism characteristic.
The present invention relates to carry out hydrophilicity-imparting treatment, obtain ordered gel resin containing aromatic nucleus polymeric colloid crystal template, and further adsorption function system such as metal-salt; To improve sol-gel processing, prepare orderly high polymer/inorganic hybrid; High temperature sintering is removed organic constituents such as gel template, obtains the Heterogeneous Composite body or the orderly inorganic hole material that form with ergasia.
At least contain a kind of aromatic nucleus polymkeric substance in the polymeric colloid crystalline substance, aromatic nucleus comprises phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, terphenyl ring, anthracene nucleus, phenanthrene ring, pyrene ring, cool ring; Be preferably phenyl ring, naphthalene nucleus, cyclohexyl biphenyl; Preferential phenyl ring, i.e. polystyrene and the polydivinylbenezene selected.
In the ordered gel resin between microballoon, microballoon contains hydrophilic radical and crosslinked group; Hydrophilic radical is preferably sulfonic group, carboxylic acid group, amide group, hydroxyl, preferentially selects sulfonic group; Crosslinked group is preferably sulfuryl, ester group, methylene radical, preferentially selects sulfuryl.
Ordered gel resin can be complete processed ordered gel resin, also can be the ordered nucleus/shell gel resin of partially disposed.
Affinity groups in the ordered gel resin can be in conjunction with each metal ion species.
The sol/gel process reference literature Wang C. of modification, Zhang Y, Lu Y, Wei Y., J.Mater.Res., 1999,14 (10): 4098-4102, in this process, can apply electric field with the ellipsoid that the shape of regulating particulate obtains having different major-minor axis ratios to gel, further obtain having difform hole.Preparation method of the present invention generally carries out in the following order:
1. template preparation in order: prepare single dispersion resin parent microballoon by means such as letex polymerization, micro-emulsion polymerization or suspension polymerizations.The composition of parent particulate can be homopolymerization or the multipolymer that contains polystyrene, the mixture that is coated by the homopolymerization of polystyrene or multipolymer.The orderly accumulation of monodisperse polymer particulate can be passed through the centrifugal or sedimentation with the monodisperse polymer emulsion, and methods such as drying obtain.
2. the preparation of ordered gel resin: with above-mentioned orderly template and the vitriol oil or oleum by mass ratio 100: 1-1: mix between 100, p-poly-phenyl ethene carries out the sulfonation processing under 20-150 ℃ (being preferably 20-99 ℃), generate sulfonic group and sulfuryl, simultaneously between microballoon, also there are sulfuryl and sulfonic group, make former orderly template become ordered gel resin.Gel resin obtains orderly (water) gel with water or other solvent soaking.Because sulfuryl is between microballoon, crosslinkedly between molecular chain become insoluble reticulated structure, make gel resin swelling can not dissolve.Be reduced to gel resin behind gel dehydration or other solvent.
3. the ordered gel resin of metal ion preparation: in the ordered gel resin and after, be immersed in and contain in the respective metal ionic salts solution, make metal ion exchanged in ordered gel resin, repeat in orderly resin, to contain for several times the metal ion content of design.
4. the preparation of high polymer/inorganic hybrid in order: with 30-70% tetraethoxy (TEOS), 15-50% tetrahydrofuran (THF) (THF), 5-20%H
2The O and the 0.5-5%2M HCI aqueous solution are mixed, 60 ℃ of hydrolysis 3 hours, extract the initial viscosity of part tetrahydrofuran (THF) with control colloidal sol with hexanaphthene then, obtain silicon dioxide gel at last.Ordered gel resin or orderly hydrogel are immersed in the above-mentioned silicon dioxide gel, and room temperature ageing 1-3 days is steadily carried out gelation process, obtains orderly high polymer/inorganic hybrid.
5. the preparation of orderly inorganic hole material: above-mentioned hybrid is placed in the sintering oven, and blowing air, rise to 350-800 ℃ of calcination 0.5-10 hour with 1-10 ℃/minute speed, remove organic formwork, obtain orderly porous silica material.
Preparation method of the present invention and products characteristics are as follows:
● raw material is very cheap, is general polymer monomer (as vinylbenzene, acrylate etc.) sulfuric acid, water glass, common molecule silicon source tetraethoxy etc.; The experiment required equipment is simple, simple to operate.
● the superpolymer mean particle dia can be 10
1-10
4Regulate in the nm scope, its dispersion coefficient should be at 0.01-11%.By the control template particle grain size, can regulate the intravital organic phase size of hydridization, and then the size of regulating inorganic hole material.
● can be by changing kind, concentration and the reaction times of sulphonating agent, the constitutional features of regulating ordered gel resin is as complete sulfonated ordered gel resin and core/shell type ordered gel resin.
● ordered gel resin suction or other polar solvent (as ethanol) after form gel, are reduced to gel resin behind gel dehydration or other solvent, and this process is reversible; Particulate in the gel can deformation under outfield (as electric field) effect, has created condition for preparing non-spherical pore material.
● the common polystyrene colloid crystalline substance of the strength ratio of the porous silica material of gained improves greatly for the strength of materials of template gained.Simultaneously by control sulfonation degree, the porous silica material that can obtain having two kinds of distribution of sizes.This material with high-ratio surface, high strength and good hole dimension stability is good support of the catalyst.
● present method has universality.Can use different molecular precursor, obtain containing such as TiO
2, Al
2O
3, Fe
2O
3, inorganic oxides such as CuO, CdS ordered porous material.
● prepare Ordered Materials with fast sol/gel method, not only raw material is pure, and simple and direct, effective for the control of condition such as initial viscosity, gel time in the process of osmosis.In addition, can be the silicon source also with other inorganics precursor such as water glass, raw material is cheap, and preparation cost is cheap.
The present invention can be used for synthetic sorbing material, support of the catalyst, and other functional material, and photoelectric functional material, as electro-conductive material, optical material, nonlinear optical material; Matrix material, as biomaterial, orderly magneticsubstance; Molecular device etc.
EXAMPLE Example 1: the preparation of ordered gel resin
The monodisperse polystyrene mean particle dia is 10
1-10
4The nm scope is adjustable, and its dispersed index is between 0.1-11%.Wherein, 10
1-10
2The particle of nm prepares with microemulsion polymerization method; 10
2-10
3The particle of nm prepares with emulsion polymerization; 10
3-10
4The particle of nm is with dynamic swelling emulsion or suspension polymerization preparation.Above-mentioned emulsion can under the effect of centrifugal force, obtain the structure of single disperse particles ordered arrangement at gravity by nature or slow drying.This structure can generate gel resin under vitriol oil effect.As obtain the monodisperse emulsion of 250nm with the seeded emulsion polymerization method, seasoning obtains the film that orderly ps particle is piled up formation in air.The adding of 8g film is filled in the reaction flask of the 75g vitriol oil (concentration is 95-98%), be warming up to 85 ℃ under the stirring state, reacted 3 hours.Reduce to room temperature then, reacted product is under agitation dropped in the cold water, cool off washing.The very fast expansion of gel resin suction becomes transparent aquagel, illustrates that polystyrene has all obtained modification in the case.In addition, this hydrogel has bright-colored, and this color changes with the variation of viewing angle, presents different colours such as red, green, indigo plant respectively.This is the diameter of particle homogeneous in the hydrogel, arranges the Bragg scattering result who produces in order, and has obtained scanning electron microscope result's proof.Be brown after hydrogel dries, volumetric shrinkage expands after the water swelling more again, and this process is reversible.Embodiment 2: the preparation of ordered gel resin
Obtain the monodisperse emulsion of 500nm with the seeded emulsion polymerization method, seasoning obtains orderly ps particle and piles up the film that forms in air.The adding of 8g film is filled 75g oleum (free SO
3Concentration is 20-25%) reaction flask in, be warming up to 70 ℃ under the stirring state, reacted 3 hours.Reduce to room temperature then, reacted product is under agitation dropped in the cold water, cool off washing.The very fast expansion of gel resin suction becomes transparent aquagel, illustrates that polystyrene has all obtained modification in the case.In addition, this hydrogel has bright-colored, and this color changes with the variation of viewing angle, presents different colours such as red, green, indigo plant respectively.This is the diameter of particle homogeneous in the hydrogel, arranges the Bragg scattering result who produces in order, and has obtained scanning electron microscope result's proof.Be brown after hydrogel dries, volumetric shrinkage expands after the water swelling more again, and this process is reversible.Embodiment 3: the preparation of silicon-dioxide hole material in order
With 51% tetraethoxy (TEOS), 35% tetrahydrofuran (THF) (THF), 13%H
2O and 1%2M aqueous hydrochloric acid are mixed, 60 ℃ of hydrolysis 3 hours, extract the initial viscosity of part tetrahydrofuran (THF) with control colloidal sol with a certain amount of hexanaphthene then, obtain silicon dioxide gel.
Ordered gel resin among the embodiment 1 is soaked in the silicon dioxide gel, in air slowly ageing 1-3 days, make it gelation after, obtain orderly superpolymer/SiO 2 hybrid body.This hybrid has the toughness of polymkeric substance and the hardness of inorganics concurrently, and transparent bright-colored is arranged, and shows its order.This hybrid is placed tube furnace, and blowing air is warming up to 600 ℃ and kept 5 hours with 3 ℃ of/minute speed programs, naturally cools to room temperature then, obtains having the higher porous silica material of intensity.The fracture of this material presents the color with dependence of angle, shows the order of porous silica material.The result of scanning electron microscope proves that this material connects into orderly integral body in the space by the silicon-dioxide entity by the porous silica microballoon of homogeneous, the microballoon in the lucky corresponding hydrogel template of porous silica.Transmission electron microscope and nitrogen adsorption experiment result show that the average cell size of porous silica is 4nm, and specific surface area is 150m
2/ g.Embodiment 4: the preparation of silicon-dioxide large pore material in order
As different from Example 3, polystyrene moulding is unprocessed, carries out same sol-gel process, obtains orderly superpolymer/SiO 2 hybrid body.This hybrid has bright-colored, and its order is described.This hybrid is placed tube furnace, and blowing air is warming up to 600 ℃ and kept 5 hours with 3 ℃ of/minute speed programs, naturally cools to room temperature then, removes organic formwork, obtains the porous silica material, and this material breaks easily.The result of fracture scanning electron microscope proves that this material is made up of the homogeneous macropore, and hole wall is a silicon-dioxide.Big hole dimension is suitable with the polystyrene microsphere size, is about 250nm.The nitrogen adsorption experiment proves that its specific surface area is 98m
2/ g.Embodiment 5: the preparation of porous silica material in order
It is 12 that sodium silicate aqueous solution with 15% is regulated pH value with hydrochloric acid, mixes drying at room temperature ageing 2 days with ordered gel resin template among the embodiment 2, carry out fully until gelation, obtain orderly superpolymer/water glass hybrid, this hybrid has bright-colored, shows its order.Hybrid is placed in the tubular type sintering oven, and blowing air is warming up to 600 ℃ and kept 3 hours with 3 ℃ of/minute speed programs, naturally cools to room temperature then, removes organic formwork, has obtained having the porous material of the water glass of certain intensity.Morphological analysis is the result show, this material has 2 same structures with embodiment.The nitrogen absorption result shows that its pore size is at 5nm, and specific surface area is 170m
2/ g.Embodiment 6: the preparation of silicon-dioxide hole material in order
With 59% tetraethoxy (TEOS), 35% tetrahydrofuran (THF) (THF), 5%H
2O and 1%2M aqueous hydrochloric acid are mixed, 60 ℃ of hydrolysis 3 hours, extract the initial viscosity of part tetrahydrofuran (THF) with control colloidal sol with a certain amount of hexanaphthene then, obtain silicon dioxide gel.
50 volts of/centimetre electric fields are fixed and imposed at the two ends of the dried ordered gel resin among the embodiment 1 with electrode, be immersed in the silicon dioxide gel.Keep under the electric field situation, in air slowly ageing 1-3 days, make it gelation after, remove voltage, just obtain a kind of novel orderly superpolymer/SiO 2 hybrid body.This hybrid has the toughness of polymkeric substance and the hardness of inorganics concurrently, and in addition, it is transparent and bright-colored is arranged, and its order is described.This hybrid is placed tube furnace, and blowing air is warming up to 600 ℃ and kept 5 hours with 3 ℃ of/minute speed programs, turns off power supply then and naturally cools to room temperature, removes organic formwork, obtains having the porous silica material of relatively good intensity.The fracture of this material presents the color with dependence of angle, the order of this explanation porous silica material.The result of fracture scanning electron microscope proves, this material is connected to orderly integral body in the space by silicon-dioxide by the porous silica microballoon of homogeneous, microballoon has obtained the ellipsoid structure in a certain direction generation deformation, major axis is 1.5: 1 with the ratio of minor axis, the orientation of microballoon under electric field action in this lucky corresponding gel template.Transmission electron microscope and nitrogen adsorption experiment result show that the average cell size of porous silica is 4nm, and specific surface area is 140m
2/ g.Embodiment 7: the preparation of silicon-dioxide hole material in order
Repeat the experiment among the embodiment 6, different is that strength of electric field is changed to 100 volts/centimetre.Orderly superpolymer/SiO 2 hybrid the body that obtains still has the toughness of polymkeric substance and the hardness of inorganics concurrently, and in addition, it is transparent and bright-colored is arranged, and its order is described.The result of the fracture scanning electron microscope of the hole material that obtains behind the sintering proves, this material is connected to orderly integral body in the space by silicon-dioxide by the porous silica microballoon of homogeneous, microballoon has obtained the ellipsoid structure in a certain direction generation deformation, major axis is 3: 1 with the ratio of minor axis, the orientation of microballoon under electric field action in this lucky corresponding gel template.Transmission electron microscope and nitrogen adsorption experiment result show that the average cell size of porous silica is 4nm, and specific surface area is 120m
2/ g.Embodiment 8: the preparation of silicon-dioxide diplopore material in order
With the undressed monodisperse polystyrene template among the embodiment 4, under 20 ℃ of room temperatures, be dipped in the 95-98% vitriol oil.After 48 hours, take out the template of handling and be washed till neutrality with a large amount of distilled water.In the silicon dioxide gel among the dry template adding embodiment 3.And repeat gelation and sintering process among the embodiment 3, obtain the porous silica material of three-dimensional order.This Fracture Profile in Metallic Materials still presents the color with dependence of angle, shows that this material three-dimensional is orderly, and has obtained scanning electron microscope result's proof.Compare with embodiment 3, the ordered porous materials hole wall in this example is thick, and big hole dimension is reduced to 180nm.The hole wall of this hole material is made up of two portions: amorphous silica that obtains in microballoon and microballoon gap and the mesoporous silicon oxide that is obtained by microballoon sulfonation skin.The nitrogen absorption result shows that its aperture is between the 2-3 nanometer.The kernel of particulate unsulfonated has stayed macropore after being burnt mistake.This structure has improved the intensity of hole material on the one hand, and the specific channel of material transfer and reaction is provided on the other hand.The nitrogen adsorption experiment is the result show, the specific surface area of this porous material is 180m
2/ g.Embodiment 9: the preparation of silicon-dioxide diplopore material in order
Be not both processed 115 hours of template with embodiment 8.The porous silica Fracture Profile in Metallic Materials that obtains three-dimensional order still presents the color with dependence of angle, shows that this material three-dimensional is orderly, and has obtained scanning electron microscope result's proof.Compare with embodiment 8, the ordered porous materials hole wall in this example becomes thicker, and big hole dimension is reduced to 40nm.The hole wall of this hole material is made up of two portions: amorphous silica that obtains in microballoon and microballoon gap and the mesoporous silicon oxide that is obtained by microballoon sulfonation skin.The nitrogen absorption result shows that its aperture is between the 2-3 nanometer.The kernel of particulate unsulfonated has stayed macropore after being burnt mistake.This structure has improved the intensity of hole material on the one hand, and the specific channel of material transfer and reaction is provided on the other hand.The nitrogen adsorption experiment is the result show, the specific surface area of this porous material is 250m
2/ g.Embodiment 10: the preparation of silicon-dioxide diplopore material in order
Be not both processed 162 hours of template with embodiment 8.Compare with embodiment 8, the ordered porous materials hole wall in this example becomes thicker, and macropore almost disappears.The hole wall of this hole material is made up of two portions: amorphous silica that obtains in microballoon and microballoon gap and the mesoporous silicon oxide that is obtained by microballoon sulfonation skin.The nitrogen absorption result shows that its aperture is between the 2-3 nanometer.The particulate kernel also almost all is sulfonated, so macropore almost disappears.This structure has improved the intensity of hole material on the one hand, is a kind of novel mesoporous material on the other hand.The nitrogen adsorption experiment is the result show, the specific surface area of this porous material is 320m
2/ g.Embodiment 11: the preparation of silicon-dioxide three hole materials in order
Be not both with embodiment 8, used silicon dioxide gel contains a kind of cats product.On the silicon dioxide gel basis that embodiment 1 prepares, add the cetyl trimethylammonium bromide that is equivalent to silicon dioxide gel quality 15%, heating for dissolving, whole colloidal sol is faint yellow transparence, and is stand-by.The porous silica material mouth that obtains three-dimensional order still presents the color with dependence of angle, shows that this material three-dimensional is orderly, and has obtained scanning electron microscope result's proof.Pore wall thickness and big hole dimension all do not change.The hole wall of this hole material is made up of two portions: the mesoporous silicon oxide that obtains mesoporous silicon oxide and obtained by microballoon sulfonation skin in microballoon and microballoon gap.The nitrogen absorption result shows that its aperture is between the 2-10 nanometer.The kernel of particulate unsulfonated has stayed macropore after being burnt mistake.This structure has improved the intensity of hole material on the one hand, and the specific channel of material transfer and reaction is provided on the other hand.The nitrogen adsorption experiment is the result show, the specific surface area of this porous material is 370m
2/ g.This is that microballoon-microballoon gap inner gel contains cetyl trimethylammonium bromide, is removed under the high temperature sintering situation, leaves another mesoporous cause.The specific surface area of porous material and mesoporous pore size distribution experimental fact such as broaden has all illustrated this point.Embodiment 12: the preparation of the orderly inorganics porous material of containing metal oxide compound
Similar with embodiment 5, water glass with 75% mixes with 25% aluminum chloride, be mixed with 15% aqueous solution, regulating pH value with hydrochloric acid is 12, mixes drying at room temperature ageing 2 days with ordered gel resin template among the embodiment 3, carry out fully until gelation, obtain orderly superpolymer/water glass hybrid, this hybrid has bright-colored, shows its order.Hybrid is placed in the tubular type sintering oven, and blowing air is warming up to 600 ℃ and kept 3 hours with 3 ℃ of/minute speed programs, turns off power supply then and makes sintering oven naturally cool to room temperature, removes organic formwork, has obtained having the porous material of the water glass of certain intensity.Morphological analysis is the result show, this material has 3 same structures with embodiment.The nitrogen absorption result shows that its pore size is at 5nm, and specific surface area is 170m
2/ g.Different is that the meso-porous titanium dioxide silicon face contains the alchlor composition, will be as acid sites, for Application of Catalyst creates conditions.Embodiment 13: the preparation of the orderly silicon-dioxide of containing metal oxide compound hole material
With the copper nitrate solution of the ordered gel resin among the embodiment 4 and 50%, mix by 20: 80 weight ratios, make gel resin absorbing copper ion.The said process triplicate is 3 hours at every turn, and is about 7-8 with less ammonia adjusting PH all at every turn.Absorbing copper ionic gel resin still can present color in water, illustrate that the ordered structure in the gel resin is existed.With absorbing copper ionic gel resin, vacuum drying is standby.With the gel resin among the gel resin replacement embodiment 4 that has adsorbed cupric ion, and the step that responds.Similar among structure that obtains and the embodiment 4.Its outward appearance is a black.X-ray photoelectron spectroscopy is the result show, there is cupric oxide in the mesoporous SiO 2 surface.By concentration and the immersion number of times of regulating cupric nitrate, can regulate the content of mesoporous copper oxide surface.Embodiment 14: the preparation of the orderly silicon-dioxide of containing metal copper hole material
Product among the embodiment 13 reduces half an hour down at 600 ℃ with hydrogen, is keeping under the condition of hydrogen then, is cooled to room temperature.Similar among structure that obtains and the embodiment 13.But its outward appearance is yellow.X-ray photoelectron spectroscopy is the result show, there is copper in the mesoporous SiO 2 surface.Embodiment 15: the preparation of the orderly silicon-dioxide of containing metal iron hole material
Repeat the corresponding steps among the embodiment 13 and 14, but used salt is iron nitrate, rather than cupric nitrate.Similar among structure that obtains and the embodiment 14.But its outward appearance is a black.X-ray photoelectron spectroscopy is the result show, there is iron in the mesoporous SiO 2 surface.Embodiment 16: the preparation of the orderly silicon-dioxide of nickel metal hole material
Repeat the corresponding steps of embodiment 15, similar among structure that obtains and the embodiment 14.But its outward appearance is a black.X-ray photoelectron spectroscopy is the result show, there is nickel in the mesoporous SiO 2 surface.Embodiment 17: the preparation of silicon-dioxide hole material in order of containing metal silver
Repeat the corresponding steps of embodiment 13, used salt is not a cupric nitrate, but Silver Nitrate.To structure and embodiment 13 in similar.Its outward appearance is a black.X-ray photoelectron spectroscopy is the result show, there is silver in the mesoporous SiO 2 surface.
Claims (5)
1. the preparation method of orderly high polymer/inorganic hybrid and derivative ordered porous materials thereof comprises:
A. prepare single dispersion resin parent microballoon, homopolymerization that the consisting of of parent microballoon contains polystyrene or multipolymer or the mixture that coats by the homopolymerization or the multipolymer of polystyrene;
B. by the centrifugal or sedimentation with the monodisperse polymer emulsion, drying obtains the orderly packed structures of monodisperse polymer particulate, i.e. template in order;
C. with above-mentioned orderly template and the vitriol oil or oleum by mass ratio 100: 1-1: mix between 100, carry out sulfonation at 20-150 ℃ of following p-poly-phenyl ethene and handle, obtain gel resin;
D. gel resin obtains orderly (water) gel with solvent soaking, and gel is reduced to gel resin after losing solvent;
E. ordered gel resin is immersed in the salts solution that contains required metal ion, makes metal ion exchanged in gel resin;
F. with the 30-70% tetraethoxy, 15-50% tetrahydrofuran (THF), 5-20%H
2The O and the 0.5-5%2M HCl aqueous solution are mixed, at 30-60 ℃ of following hydrolysis 1-3 hour, extract the part tetrahydrofuran (THF) with hexanaphthene then, obtain silicon dioxide gel;
G. ordered gel resin or orderly hydrogel are immersed in the above-mentioned silicon dioxide gel, obtain orderly high polymer/inorganic hybrid;
H. above-mentioned hybrid is placed calcination in the sintering oven, obtain orderly porous silica material.
2. in accordance with the method for claim 1, wherein, in step g, with ordered gel resin or after in order hydrogel is immersed in silicon dioxide gel, room temperature ageing 1-3 days.
3. in accordance with the method for claim 1, wherein, single dispersion resin parent microballoon is by letex polymerization, micro-emulsion polymerization or suspension polymerization.
4. in accordance with the method for claim 1, wherein, described calcination is at bubbling air, rises to 1-10 ℃/minute speed and carries out in 350-800 ℃ of calcination 0.5-10 hour.
5. in accordance with the method for claim 1, wherein, the sulfonation of polystyrene is handled and is carried out at 20-99 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01100392 CN1129641C (en) | 2001-01-04 | 2001-01-04 | Prepn of ordered porous material comprising ordered polymer and inorganic heterocomplex and its derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01100392 CN1129641C (en) | 2001-01-04 | 2001-01-04 | Prepn of ordered porous material comprising ordered polymer and inorganic heterocomplex and its derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1362442A CN1362442A (en) | 2002-08-07 |
| CN1129641C true CN1129641C (en) | 2003-12-03 |
Family
ID=4651553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01100392 Expired - Fee Related CN1129641C (en) | 2001-01-04 | 2001-01-04 | Prepn of ordered porous material comprising ordered polymer and inorganic heterocomplex and its derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1129641C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100410301C (en) * | 2006-02-21 | 2008-08-13 | 武汉化工学院 | Method for preparation of ordered porous conductive polymer by suction filtration / immersion method |
| CN102050955B (en) * | 2009-10-28 | 2012-07-18 | 北京化工大学 | Preparation method of polystyrene-based mesoporous silica film |
| WO2016094777A1 (en) * | 2014-12-12 | 2016-06-16 | Exxonmobil Research And Engineering Company | Organosilica materials |
| CN110542683B (en) * | 2019-09-25 | 2022-03-11 | 东南大学 | Photopolymerisable gel capable of realizing color self-feedback hardness distribution, preparation method and application |
-
2001
- 2001-01-04 CN CN 01100392 patent/CN1129641C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1362442A (en) | 2002-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhou et al. | Grafting of thermo-responsive polymer inside mesoporous silica with large pore size using ATRP and investigation of its use in drug release | |
| Chen et al. | Synthesis of monodispersed mesoporous silica spheres (MMSSs) with controlled particle size using gemini surfactant | |
| Yamada et al. | Synthesis of monodispersed super-microporous/mesoporous silica spheres with diameters in the low submicron range | |
| Zhang et al. | Utilization of NaP zeolite synthesized with different silicon species and NaAlO2 from coal fly ash for the adsorption of Rhodamine B | |
| Wang et al. | Synthesis of length controllable mesoporous SBA-15 rods | |
| CA2835154C (en) | Mesoporous silica and organosilica materials and process for their preparation | |
| CN1511785A (en) | Silicon dioxide mesoporous material and its preparing method | |
| CN101143724A (en) | Method for synthesizing silicon dioxide hollow sphere with mesoporous channel controlled by dodecyl sulfonic acid sodium salt | |
| WO2006052917A2 (en) | Silica mesoporous materials | |
| CN1129641C (en) | Prepn of ordered porous material comprising ordered polymer and inorganic heterocomplex and its derivative | |
| Lyu et al. | Hierarchically porous TiO 2 monolith prepared using a cellulose monolith as a template | |
| CN101817530A (en) | Method for preparing hollow silicon dioxide microspheres | |
| US9822233B2 (en) | Use of self-assembled nanoporous glass colloids for prolongation of plasticity of polymeric materials | |
| Liu et al. | Porous TiO 2 Assembled from Monodispersed Nanoparticles | |
| Jin et al. | A two-step route to synthesis of small-pored and thick-walled SBA-16-type mesoporous silica under mildly acidic conditions | |
| CN108862304B (en) | Hydrophobic hybrid silicon-aluminum molecular sieve containing organic groups and having micro-nano hierarchical structure and preparation method thereof | |
| CN100500564C (en) | Method for preparing mesoporous material by non-surface activator process | |
| CN1176961C (en) | Sensitive ordered porous polymer gel and its preparing process | |
| CN109279622A (en) | A kind of periodic mesoporous organic silicon oxide material of structure-controllable and preparation method thereof | |
| Ranjit et al. | A review of the chemical manipulation of nanomaterials using solvents: Gelation dependent structures | |
| Yang et al. | The synthesis of mesoporous silica film using multi-templates directing and the effects of inorganic acids | |
| Zhang et al. | Synthesis and characterization of hollow mesoporous silica spheres with tunable shell thicknesses and its application in ibuprofen delivery | |
| Qin et al. | Synthesis of polymer/zirconium hydroxide core–shell microspheres and the hollow porous zirconium oxide microspheres | |
| CN112520744B (en) | Preparation of nano SiO by using silica sol 2 Method (2) | |
| Li et al. | Synthesis of titania/polymer core-shell hybrid microspheres |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |