CN1483861A - Method for preparing self-assembiling colloid crystal by vertical double base piece - Google Patents
Method for preparing self-assembiling colloid crystal by vertical double base piece Download PDFInfo
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Abstract
The present invention relates to a method for preparing self-assembled colloidal crystal using vertical two substrates, including two steps of preparing polymer microsphere and preparing colloidal crystal body between vertical two substrates. In the aqueous solution of polyethylene or methyl methacrylate monomer adding function monomer, cross-linking agent, initiator and buffering agent, stirring them in 100-400 rpm and in the water bath with 60-85 deg.C and making soapless emulsion copolymerization reaction, after 20 hr. obtaining the surface-functionated monodisperse cross-linking polymer microsphere with 60-800 nm. and placing the treated two substrates which are mutually closed into the 1-5 ml of monodisperse cross-linking polymer microsphere emulsion whose microsphere mass concentration is 0.5-3%.
Description
Technical field
The present invention relates to a kind ofly prepare the method for three-dimensional order colloidal crystal, particularly relate to a kind of method of utilizing the three-dimensional order colloidal crystal that vertical double-basis sheet method preparation is made up of mono-dispersion microballoon or silicon dioxide microsphere with mono-dispersion microballoon or silicon dioxide microsphere.
Background technology
Single dispersoid microsphere system is in Materials science, and the application in the chemistry and biology has become an important goal of colloid science.Mono-dispersion microballoon organizes themselves into colloidal crystal and people can be accessed have periodically long-range be situated between to see ordered structure, and can access the functional structure material of using value.The orderly assembling that colloid micro ball forms can be used as the optics microprism in imaging process; Can be used as the physical template of evaporation or response type ion etching structure micron or nano-structural ordered assembling; Also can be used as the formwork structure that is used for soft lithography elasticity seal designsization.At present, the three-dimensional order colloidal crystal made of mono-dispersion microballoon is the important directions that mono-dispersion microballoon is used aspect infant industry materials such as photoelectric material.Optical diffraction and optical band gap character that the common three-dimensional order colloidal crystal of being made by monodisperse polymer micro-sphere or silicon dioxide microsphere has because of its ordered 3 D structure, so they are base mateirals of making the diffraction element of optical filter, transmodulator, biological and chemical transmitter and photonic crystal or other optics and electro-optical device.Simultaneously, they can be used as the mould material of orderly large pore material of structure and high-strength ceramic.And regulation and control monodisperse polymer micro-sphere or the silicon dioxide microsphere preparation condition when preparation three-dimensional order colloidal crystal is an important link in the preparation colloidal crystal.Methods such as the self-assembly under gravity field deposition, the physical restriction, electrophoretic deposition are commonly used to prepare colloidal crystal.United States Patent (USP) 4,803,688 disclose a kind of utilization leaves standstill the method that sedimentation prepares colloidal crystal, United States Patent (USP) 5,139,611 also utilize similar methods to prepare colloidal crystal, but require extraneous noiseless.United States Patent (USP) 6,123,845 and 6,325,957 also disclose the correlation method of preparation colloidal crystal, the just device that preparation process is comparatively loaded down with trivial details or needs are more special.In the application of reality, surface patterning in order is needed in the relevant practical devices of preparation, thereby colloidal crystal also needs to be configured various different ordered micro structures in practical devices is used simultaneously.
Summary of the invention
The purpose of this invention is to provide and a kind ofly utilize vertical double-basis sheet method to prepare the method for three-dimensional order colloidal crystal, provide a kind of simultaneously and utilize vertical double-basis sheet method to prepare the method for patterned surface three-dimensional order colloidal crystal by monodisperse polymer micro-sphere or silicon dioxide microsphere.
Purpose of the present invention can be achieved through the following technical solutions: the present invention utilizes vertical double-basis sheet method to prepare the three-dimensional order colloidal crystal of being made up of monodisperse polymer micro-sphere or silicon dioxide microsphere between two substrates with the surface-functionalized monodisperse cross-linked polymer microspheres of emulsifier-free emulsion polymerization preparation and the monodisperse silica microspheres of precipitator method preparation then.
Method of the present invention comprises two steps:
1. the preparation of monodisperse cross-linked polymer microspheres: with distilled water is dispersion medium, the vinylbenzene or the methyl methacrylate monomer that in every 100ml distilled water, add the 5-20 gram, and (methyl) vinylformic acid that adds monomer mass 0-20%, 2-hydroxyethyl methacrylate, function monomers such as 4-Sodium styrene sulfonate or ethylene benzyl Trimethylamine hydrochloride, add 4 of monomer mass 0-20% simultaneously, 4 '-dimethyl allene acyloxy-2,2 '-diphenyl propane or Vinylstyrene are as linking agent, the Potassium Persulphate of monomer mass 0.1-2%, ammonium persulphate or 2,2 '-two (2-methyl-prop amidine) dihydrochloride comes initiated polymerization, the sodium bicarbonate of monomer mass 0-5% is as buffer reagent, general mechanical stirring speed can be regulated in 100-400 rev/min of scope, in 60-85 ℃ water-bath, carry out the soap-free emulsion copolymerization, make surface-functionalized monodisperse cross-linked polymer microspheres after 20 hours, microballoon is of a size of 60 to 800 nanometers, and the mass content in emulsion is 3-15%.
2. substrate was handled 15 minutes to 24 hours with the mixing solutions of 98% vitriol oil and 30% hydrogen peroxide, and the consumption volume ratio of two kinds of solution normally 2: 8 to 4: 6 is through dry under nitrogen or air atmosphere after the rinsed with deionized water.Two substrates handling are vertically put into and contained the container that 1-5 milliliter mass percentage concentration is 0.5--3% monodisperse cross-linked polymer microspheres emulsion (low microballoon concentration is diluted with distilled water and obtained) near back (distance between two substrates is the 0.05-1 millimeter) mutually, 4 ℃-75 ℃ volatilizations down, just can in the middle of two substrates, obtain the three-dimensional order colloidal crystal of forming by monodisperse cross-linked polymer microspheres after 6 hours-96 hours then.
In the aforesaid method, between two substrates, form the colloidal crystal of three-dimensional order with vertical double-basis sheet method.Colloidal crystal is mainly made to the monodisperse polymer micro-sphere or the silicon dioxide microsphere of 800 nanometers by 60 nanometers.
In the aforesaid method, two substrates in the vertical double-basis sheet method generally are sheet glass, silicon chip, quartz plate, polydimethylsiloxane substrate, or the wherein combination of two kinds of substrates.
In the aforesaid method, the surface has the preparation of colloidal crystal of the three-dimensional order of orderly pattern and generally uses the polydimethylsiloxane substrate of patterning and other substrate (sheet glass, silicon chip, quartz plate) combination to obtain.
In the aforesaid method, be that the substrate of base material can be prepared to the substrate that the surface has different size and shape pattern with the polydimethylsiloxane, thereby can obtain the three-dimensional order colloidal crystal that the surface has different pattern.Dimethyl siloxane performed polymer and solidifying agent is even by the mixed of 20: 1 to 5: 1 (mass ratio), irritate after the vacuum outgas in the mould of forming by the photoresist sheet of two silicon chips or silicon chip and patterned surface, 40 ℃ to 80 ℃ solidified 8～10 hours.After the cooling polymeric film that is cured is taken off on silicon chip or photoresist sheet carefully, thereby obtained polydimethylsiloxane substrate surfacing or patterned surface, the thickness of substrate is 50 microns to 1.5 millimeters usually.The photoresist sheet of patterned surface can utilize the light of different size and shape to cover plate, and the pattern of light being covered on the plate by photoetching technique copies on the photoresist sheet, obtains the photoresist sheet of patterned surface.(Y.N.Xia，E.Kim，X.M.Zhao，J.A.Rogers，M.Prentiss，G.M.Whitesides，Science1996，273，347.Y.N.Xia，G.M.Whitesides，Angew.Chem.Int.Ed.Engl.1998，37，550.)。
In the aforesaid method, with the close mutually placement of two substrates handling, distance is the 0.05--1 millimeter, (preparation method of silicon dioxide microsphere is referring to W.St ber for silicon dioxide microsphere emulsion that vertically to put into 1 milliliter of microspheres quality concentration be 0.5--3%, A.Fink, J.ColloidInterface Sci.1968,26,62), descend volatilization just can in the middle of two substrates, obtain the three-dimensional order colloidal crystal of forming by silicon dioxide microsphere after 6-96 hour at 4-75 ℃ then.
In the aforesaid method, two substrates in the vertical double-basis sheet method can also be nonplanar or piped, make in the tubular substrate such as the fiber rod is inserted, and put into the emulsion that contains polymer microballoon or silicon dioxide microsphere then, form colloidal crystal.Tubular substrate can be glass or quartz, also can be polymkeric substance, and their diameter can be variable in 1 micron to 1 millimeter scope.
In the present invention, utilize the colloidal crystal of the three-dimensional order that simple and effective vertical double-basis sheet method prepares and the colloidal crystal that the surface has orderly pattern between two substrates, colloidal crystal by the preparation of different-grain diameter Nano microsphere has different ultraviolet absorption peaks, by the stack of multilayer colloid crystal, can form combination colloidal crystal with a plurality of ultraviolet absorption peaks; Further, by rotation to certain one deck colloidal crystal in-plane in the combination colloidal crystal, the corresponding uv-absorbing of assembly adhesive body crystalline peak position is changed, thereby can make colloidal crystal of the present invention be widely used in the preparation and the aspects such as photoswitch or light-filter of three-dimensional ordered polyporous material and photonic crystal.
Description of drawings
Fig. 1: vertical double-basis sheet prepares the self-organized colloidal crystal synoptic diagram;
Fig. 2 (a): the surface is the three-dimensional order colloidal crystal synoptic diagram that the wide straight-line groove of micron order is arranged;
Its partial enlarged drawing of Fig. 2 (b): Fig. 2 (a) synoptic diagram;
Fig. 3: the colloidal crystal sem photograph between fiber and glass or the polymer pipe inwall;
Fig. 4: the uv-absorbing figure that forms the three-dimensional order colloidal crystal with the polymer microballoon of 188 nanometers;
Fig. 5: the uv-absorbing figure that forms the three-dimensional order colloidal crystal with 220 nanometer polymer microballoons;
Fig. 6: the uv-absorbing figure that forms the three-dimensional order colloidal crystal with the polymer microballoon of 238 nanometers;
Fig. 7: the uv-absorbing figure that forms the three-dimensional order colloidal crystal with the polymer microballoon of 270 nanometers;
Fig. 8: use 188 nanometers respectively, 220 nanometer polymer microballoons are formed the uv-absorbing figure of three-dimensional order colloidal crystal combination;
Fig. 9: use 188 nanometers respectively, 220 nanometers and 238 nanometer polymer microballoons are formed the uv-absorbing figure of three-dimensional order colloidal crystal combination;
Figure 10: use 188 nanometers respectively, 220 nanometers and 238 nanometer polymer microballoons are formed the uv-absorbing figure of three-dimensional order colloidal crystal combination, and wherein two of 220 nanometer three-dimensional order colloidal crystals are rotated 20 degree;
Figure 11: the stack synoptic diagram of the pairing colloidal crystal of Fig. 9;
Figure 12: the stack synoptic diagram of the pairing colloidal crystal of Figure 10, the colloidal crystal plane in its middle layer is with respect to stack plane rotation 20 degree;
Figure 11 is the synergetic structural representation of a plurality of colloidal crystals (corresponding embodiment 13) of preparation: 1,2,3rd, and quartz plate; 4 is three-dimensional colloidal crystals that 188 Nano microspheres form; 5 is three-dimensional colloidal crystals that 220 Nano microspheres form; 6 is three-dimensional colloidal crystals that 238 Nano microspheres form.
Figure 12 is the synergetic structural representation of a plurality of colloidal crystals (corresponding embodiment 14) of preparation: 1,2,3rd, and quartz plate; 4 is three-dimensional colloidal crystals that 188 Nano microspheres form; 5 is three-dimensional colloidal crystals that 220 Nano microspheres form; 6 is three-dimensional colloidal crystals that 238 Nano microspheres form.
Embodiment
The present invention is further elaborated below in conjunction with embodiment, rather than will limit the invention with this.
Embodiment 1:
Under nitrogen protection; with 100 milliliters distilled water is dispersion medium; with 10 gram vinylbenzene; 0.5 4 of gram, 4 '-dimethyl allene acyloxy-2,2 '-diphenyl propane; 1.2 (methyl) vinylformic acid of gram and 0.08 gram Potassium Persulphate or ammonium persulphate; 0.24 the sodium bicarbonate of gram adds and is equipped with in the reactor of mechanical stirrer and reflux condensing tube, mechanical stirring speed is at 300 rev/mins.In 70 ℃ water-bath, carry out the emulsifier-free emulsion polymerization reaction, need not add any tensio-active agent and dispersion agent herein, react the emulsion that obtains stablizing the monodisperse cross-linked polystyrene microsphere of oyster white after 24 hours, diameter of micro ball is 220 nanometers, and the emulsion solid content of polystyrene microsphere is 5.0% (mass percent).
Sheet glass and quartz plate volume ratio are that 3: 7 98% vitriol oil and the mixing solutions of 30% hydrogen peroxide are handled, through dry under nitrogen or air atmosphere after the rinsed with deionized water.With two blocks of substrate (sheet glass handling, quartz plate) mutually vertically puts into and contain 1 milliliter near back (distance between two substrates is 0.05 millimeter), the concentration of polymer microballoon is in the container of emulsion of monodisperse cross-linked polymer microspheres of 2% (mass percent), then 40 ℃ of down volatilizations, just can obtain the colloidal crystal of the three-dimensional order in the middle of two substrates, formed after 12 hours by monodisperse cross-linked polymer microspheres.Its operational path as shown in Figure 1.
Embodiment 2:
1. the preparation of monodisperse cross-linked polymer microspheres and substrate (sheet glass, silicon chip, quartz plate) are handled as described in the embodiment 1.
2. the preparation of polydimethylsiloxane substrate, dimethyl siloxane performed polymer and solidifying agent is even by 10: 1 (mass ratio) mixed, irritate after the vacuum outgas in the silicon chip mould, 60 ℃ solidify 10h.The polymeric film that will be cured after the cooling is taken off from silicon chip carefully, obtains the polydimethylsiloxane substrate of surfacing, and the thickness of substrate is 1.0 millimeters.
3. the polydimethylsiloxane substrate carries out supersound process after 1 minute with chloroform and dehydrated alcohol respectively, through drying up at nitrogen after the dehydrated alcohol rinsing.A substrate of handling (sheet glass, silicon chip or quartz plate) and polydimethylsiloxane substrate are vertically put into and contained 1 milliliter near back (distance between two substrates is 0.1 millimeter), the concentration of polymer microballoon is in the container of emulsion of monodisperse cross-linked polymer microspheres of 3% (mass percent), then 40 ℃ of down volatilizations, just can in the middle of two substrates, obtain the colloidal crystal of the three-dimensional order formed by monodisperse cross-linked polymer microspheres after 12 hours.Remove the polydimethylsiloxane substrate,, can obtain the three-dimensional order colloidal crystal of surfacing on the substrate of silicon chip or quartz plate at sheet glass.
Embodiment 3:
1. the preparation of monodisperse cross-linked polymer microspheres and substrate are handled as described in the embodiment 1.
2. Biao Mian pattern is the polydimethylsiloxane substrate preparation that arrange in micron order diameter round platform four directions, dimethyl siloxane performed polymer and solidifying agent is even by 10: 1 (mass ratio) mixed, after the degassing, it is that arrange in the photoresist sheet mould in micron order diameter round platform four directions that filling advances to have picture on surface, and 60 ℃ solidify 9h.The polymeric film that will be cured after the cooling is taken off from photoresist sheet carefully, cuts away pattern-free zone, four limits, obtains picture on surface and is all and has micron order diameter round platform four directions and arrange the polydimethylsiloxane substrate, and the height of round platform is 1.0 microns.
3. be after the cubic polydimethylsiloxane substrate of arranging of micron order diameter round platform is handled with chloroform and dehydrated alcohol respectively with picture on surface, again with a substrate (sheet glass of handling, silicon chip, quartz plate) and surface polydimethylsiloxane substrate that micron order diameter round platform four directions Pareto diagram arranged vertically put into and contain 1 milliliter near back (distance between two substrates is 0.05 millimeter), the concentration of polymer microballoon is in the container of emulsion of monodisperse cross-linked polymer microspheres of 1% (mass percent), then 40 ℃ of volatilizations down, the colloidal crystal that just can obtain the three-dimensional order be made up of monodisperse cross-linked polymer microspheres after 12 hours in the middle of two substrates is removed the polydimethylsiloxane substrate, at sheet glass, can obtain the colloidal crystal of surface on the substrate of silicon chip or quartz plate for the three-dimensional order of micrometer grade hole pattern.
Embodiment 4:
1. the preparation of monodisperse cross-linked polymer microspheres and substrate are handled as described in the embodiment 1.
2. Biao Mian pattern is the preparation of the polydimethylsiloxane substrate of the wide straight-line groove arrangement of micron order, dimethyl siloxane performed polymer and solidifying agent is even by 10: 1 (mass ratio) mixed, after the degassing, irritating picture on surface is that 60 ℃ solidify 8～10h in the photoresist sheet mould of the wide straight-line groove arrangement of micron order.The polymeric film that will be cured after the cooling is taken off from photoresist sheet carefully, cuts away pattern-free zone, four limits, and the pattern that obtains the surface is all the polydimethylsiloxane substrate that the wide straight-line groove of micron order is arranged, and the width of groove is 8 microns, and the degree of depth is 1.2 microns.
3. be after polydimethylsiloxane substrate that the wide straight-line groove of micron order is arranged is handled with chloroform and dehydrated alcohol with the pattern on surface, again with a substrate (sheet glass of handling, silicon chip, quartz plate) and surface polydimethylsiloxane substrate that the wide straight-line groove Pareto diagram of micron order arranged vertically put into and contain 1.0 milliliters near back (distance between two substrates is 0.1 millimeter), the concentration of polymer microballoon is that 1% (mass percent) and microsphere diameter are in the container of emulsion of polymer microballoon of 238 nanometers, 40 ℃ of volatilizations down, just can obtain the three-dimensional order colloidal crystal of in the middle of two substrates, forming after 12 hours then by monodisperse cross-linked polymer microspheres.Remove the polydimethylsiloxane substrate,, can obtain the three-dimensional order colloidal crystal that arrange for the wide straight-line groove of micron order on the surface on the substrate of silicon chip or quartz plate, shown in accompanying drawing 2 (a) and Fig. 2 (b) at sheet glass.
Embodiment 5:
The preparation of monodisperse cross-linked polymer microspheres and substrate handle and the colloidal crystal preparation as described in the embodiment 1.
2. regulating two distances between the substrate is 0.5 millimeter, two that handled vertically put into contain 2 milliliters, the concentration of polymer microballoon is in the emulsion container of monodisperse cross-linked polymer microspheres of 3% (mass percent), 60 ℃ of volatilizations down, just can in the middle of two substrates, obtain the three-dimensional order colloidal crystal of forming by monodisperse cross-linked polymer microspheres after 8 hours then.Compare colloidal crystal among the embodiment 1, thickness is significantly increased, but not variation of order can obtain thicker three-dimensional order colloidal crystal like this.
Embodiment 6:
1. the preparation of monodisperse cross-linked polymer microspheres and substrate are handled as described in the embodiment 1.
2. be diameter that to insert internal diameter be in 600 microns the glass or polymer pipe for 180 microns Fiber glass rod, vertically put into then and contain 2 milliliters, the concentration of polymer microballoon is in the emulsion container of monodisperse cross-linked polymer microspheres of 3% (mass percent), 25 ℃ of volatilizations down, just can between fiber and glass or polymer pipe inwall, obtain the three-dimensional order colloidal crystal formed by monodisperse cross-linked polymer microspheres after 48 hours, as shown in Figure 3.
Embodiment 7:
Utilize the silicon dioxide microsphere of precipitator method preparation, utilize method purifying such as centrifugal, redispersion and dialysis.The diameter of the silicon dioxide microsphere of preparation is in 100 nanometers to 1 micron, and concentration is 2.0% to 10% (mass percent).The processing of substrate and three-dimensional colloidal crystal preparation process arrive as described in the embodiment 6 as embodiment 1.Two substrates handling (distance between two substrates is 0.1 millimeter) are vertically put into and contained 1 milliliter, concentration is that 2% (mass percent) microsphere diameter is in the container of monodisperse silica microspheres emulsion of 400 nanometers, 40 ℃ of volatilizations down, just can in the middle of two substrates, obtain forming three-dimensional order colloidal crystal after 12 hours then with different surfaces structure by monodisperse silica microspheres.
Embodiment 8:
The preparation of monodisperse cross-linked polymer microspheres and quartz or glass substrate are handled, and the colloidal crystal preparation is as described in the embodiment 1.The polymer microballoon of 188 nanometers is as preparation as described in the embodiment 1; its concrete processing parameter is: under nitrogen protection; with 100 milliliters distilled water is dispersion medium; with 9.0 gram vinylbenzene, 4 of 0.5 gram, 4 '-dimethyl allene acyloxy-2; 2 '-diphenyl propane; 1.0 (methyl) vinylformic acid of gram and 0.08 gram Potassium Persulphate or ammonium persulphate, the sodium bicarbonate of 0.20 gram, mechanical stirring speed is at 300 rev/mins.In 70 ℃ water-bath, carry out emulsifier-free emulsion polymerization reaction 24 hours.Utilize the polymer microballoon of 188 nanometers to prepare the three-dimensional order colloidal crystal again, because Bragg diffraction (Xia, the Y.N. of three-dimensional order colloidal crystal as construction unit; Gates, B.; Yin, Y.D.; Lu, Y.Adv.Mater.2000,12,693-713), in 420 nanometers tangible ultraviolet absorption peak is arranged, as shown in Figure 4.Zhi Bei three-dimensional order colloidal crystal just has better stability like this, such as repeating to fill the aqueous solution and organic solution, and then dry, the ordered 3 D structure of colloidal crystal keeps not being destroyed, for the further application of colloidal crystal provides stable system.Simultaneously they also can be directly used in and filter 420 nano-devices or in the preparation of the light shutter device of 420 nanometers.
Embodiment 9:
The preparation of monodisperse cross-linked polymer microspheres and quartz or glass substrate are handled, and the colloidal crystal preparation is as described in the embodiment 1.The polymer microballoon of 220 nanometers is as preparation as described in the embodiment 1, utilize the polymer microballoon of 220 nanometers to prepare the three-dimensional order colloidal crystal again as construction unit, because the Bragg diffraction of three-dimensional order colloidal crystal has tangible ultraviolet absorption peak in 516 nanometers, as shown in Figure 5.Zhi Bei three-dimensional order colloidal crystal just has better stability like this, such as repeating to fill the aqueous solution and organic solution, and then the exsiccant process, the ordered 3 D structure of colloidal crystal keeps not being destroyed, for the further application of colloidal crystal provides stable system.Simultaneously they can be directly used in and filter 516 nano-devices or in the preparation of the light shutter device of 516 nanometers.
Embodiment 10:
The preparation of monodisperse cross-linked polymer microspheres and quartz or glass substrate are handled, and the colloidal crystal preparation is as described in the embodiment 1.The polymer microballoon of 238 nanometers is as preparation as described in the embodiment 1; its concrete processing parameter is: under nitrogen protection; with 100 milliliters distilled water is dispersion medium, with 9.0 gram vinylbenzene, 4 of 0.6 gram; 4 '-dimethyl allene acyloxy-2; 2 '-diphenyl propane, (methyl) vinylformic acid of 1.2 grams and 0.08 gram Potassium Persulphate or ammonium persulphate, the sodium bicarbonate of 0.24 gram; mechanical stirring speed is carried out emulsifier-free emulsion polymerization reaction 24 hours at 300 rev/mins in 70 ℃ water-bath.Utilize the polymer microballoon of 238 nanometers to prepare the three-dimensional order colloidal crystal again, because the Bragg diffraction of three-dimensional order colloidal crystal has tangible ultraviolet absorption peak (accompanying drawing six) in 550 nanometers as construction unit.Zhi Bei three-dimensional order colloidal crystal just has better stability like this, such as repeating to fill the aqueous solution and organic solution, and then the exsiccant process, the ordered 3 D structure of colloidal crystal keeps not being destroyed, for the further application of colloidal crystal provides stable system.Simultaneously they can be directly used in and filter 550 nano-devices or in the preparation of the light shutter device of 550 nanometers.
Embodiment 11:
The preparation of monodisperse cross-linked polymer microspheres and quartz or glass substrate are handled, and the colloidal crystal preparation is as described in the embodiment 1.The polymer microballoon of 270 nanometers is as preparation as described in the embodiment 1; its concrete processing parameter is: under nitrogen protection; with 100 milliliters distilled water is dispersion medium, with 12 gram vinylbenzene, 4 of 0.6 gram; 4 '-dimethyl allene acyloxy-2; 2 '-diphenyl propane, (methyl) vinylformic acid of 0.8 gram and 0.09 gram Potassium Persulphate or ammonium persulphate, the sodium bicarbonate of 0.20 gram; mechanical stirring speed is carried out emulsifier-free emulsion polymerization reaction 24 hours at 300 rev/mins in 70 ℃ water-bath.Utilize the polymer microballoon of 270 nanometers to prepare the three-dimensional order colloidal crystal again, because the Bragg diffraction of three-dimensional order colloidal crystal has tangible ultraviolet absorption peak (accompanying drawing seven) in 629 nanometers as construction unit.Zhi Bei three-dimensional order colloidal crystal just has better stability like this, such as repeating to fill the aqueous solution and organic solution, and then the exsiccant process, the ordered 3 D structure of colloidal crystal keeps not being destroyed, for the further application of colloidal crystal provides stable system.Simultaneously they can be directly used in and filter 629 nano-devices or in the preparation of the light shutter device of 629 nanometers.
Embodiment 12:
The preparation of monodisperse cross-linked polymer microspheres and quartz or glass substrate are handled, and the colloidal crystal preparation is as described in the embodiment 1.Polymer microballoon with 188 nanometers and 238 nanometers prepares the three-dimensional order colloidal crystal respectively, and the substrate at colloidal crystal two ends is selected with the kind substrate.188 nanometers that substrate and the three-dimensional order colloidal crystal between them are formed and two colloidal crystal systems of 238 nanometers are superimposed and form the combination colloidal crystal then.The colloidal crystal of combination has tangible ultraviolet absorption peak respectively in 418 nanometers and 550 nanometers, as shown in Figure 8.Such system has stability preferably, can be directly used in the light-filter spare that filters 418 nanometers and 550 nanometers simultaneously or in 418 nanometers and 550 nanometers photoswitch character preparation of devices be arranged simultaneously.
Embodiment 13:
The preparation of monodisperse cross-linked polymer microspheres and quartz or glass substrate are handled, and the colloidal crystal preparation is as described in the embodiment 1.Use 188 nanometers respectively, the polymer microballoon of 220 nanometers and 238 nanometers prepares the three-dimensional order colloidal crystal, and the substrate at colloidal crystal two ends is selected with the kind substrate.Then 188 nanometers, 220 nanometers and three colloidal crystal systems of 238 nanometers of substrate and the composition of the three-dimensional order colloidal crystal between them are superimposed and form the combination colloidal crystal, as shown in Figure 11.The colloidal crystal of combination has tangible ultraviolet absorption peak respectively in 418 nanometers, 516 nanometers and 550 nanometers, as shown in Figure 9.Such system has preferably stability, can be directly used in the device that filters 418 nanometers, 516 nanometers and 550 nanometers simultaneously or simultaneously in 418 nanometers, 516 nanometers and 550 nanometers have photoswitch character preparation of devices.
Embodiment 14:
The preparation of monodisperse cross-linked polymer microspheres and quartz or glass substrate are handled, and the colloidal crystal preparation is as described in the embodiment 1.Use 188 nanometers respectively, the polymer microballoon of 220 nanometers and 238 nanometers prepares the three-dimensional order colloidal crystal, and the substrate at colloidal crystal two ends is selected with the kind substrate.Then 188 nanometers, 220 nanometers and three colloidal crystal systems of 238 nanometers of substrate and the composition of the three-dimensional order colloidal crystal between them are superimposed and form the combination colloidal crystal, simultaneously two substrates of the three-dimensional order colloidal crystal of being made up of 220 nanometer polymer microballoons are rotated 20 degree along combined planar, as shown in Figure 12.This system has tangible ultraviolet absorption peak respectively in 418 nanometers, 480 nanometers and 550 nanometers, as shown in Figure 10.Such system has stability preferably, can be directly used in the device that filters 418 nanometers, 480 nanometers and 550 nanometers simultaneously or in 418 nanometers, 480 nanometers and 550 nanometers photoswitch character preparation of devices be arranged simultaneously.We can regulate different the combination number of plies and angle simultaneously, can obtain the optical system of different uv-absorbing character, particularly can obtain in a certain wavelength band, light being advanced the device of regulation and control, significant aspect light-filter and photoswitch.
Claims (10)
1, vertical double-basis sheet prepares the method for self-organized colloidal crystal, and two steps of preparation of colloidal crystal between the preparation that comprises monodisperse cross-linked polymer microspheres and vertical double-basis sheet is characterized in that:
(1) with water is dispersion medium, the vinylbenzene or the methyl methacrylate monomer that in every 100ml water, add the 5-20 gram, and (methyl) vinylformic acid that adds monomer mass 0-20%, 2-hydroxyethyl methacrylate, 4-Sodium styrene sulfonate or ethylene benzyl Trimethylamine hydrochloride function monomer, 4 of 0-20%, 4 '-dimethyl allene acyloxy-2,2 '-diphenyl propane or Vinylstyrene are as linking agent, the Potassium Persulphate of 0.1-2%, ammonium persulphate or 2,2 '-two (2-methyl-prop amidine) dihydrochloride comes initiated polymerization, the sodium bicarbonate of 0-5% is as buffer reagent, general mechanical stirring speed can be regulated in 100-400 rev/min of scope, in 60-85 ℃ water-bath, carry out the soap-free emulsion copolymerization, make surface-functionalized monodisperse cross-linked polymer microspheres after 20 hours, microballoon is of a size of 60 to 800 nanometers, and the quality percentage composition in emulsion is 3-15%;
(2) two substrates will handling are mutually near placing, distance is the 0.05--1 millimeter, vertically put into the 1-5 milliliter, microspheres quality concentration is the monodisperse cross-linked polymer microspheres emulsion of 0.5--3%, then 4-75 ℃ down volatilization just can in the middle of two substrates, obtain the three-dimensional order colloidal crystal formed by monodisperse cross-linked polymer microspheres after 6-96 hour.
2, vertical double-basis sheet as claimed in claim 1 prepares the method for self-organized colloidal crystal, it is characterized in that: two substrates will handling are mutually near placing, distance is the 0.05--1 millimeter, vertically put into the 1-5 milliliter, microspheres quality concentration is the silicon dioxide microsphere emulsion of 0.5--3%, then 4-75 ℃ down volatilization just can in the middle of two substrates, obtain the three-dimensional order colloidal crystal formed by silicon dioxide microsphere after 6-96 hour.
3, vertical double-basis sheet as claimed in claim 1 or 2 prepares the method for self-organized colloidal crystal, it is characterized in that: two substrates generally are sheet glass, silicon chip, quartz plate, polydimethylsiloxane substrate, or the wherein combination of two kinds of substrates, substrate can be made plane, on-plane surface or piped.
4, vertical double-basis sheet as claimed in claim 1 or 2 prepares the method for self-organized colloidal crystal, it is characterized in that: substrate was handled 15 minutes to 24 hours with the mixing solutions of 98% vitriol oil and 30% hydrogen peroxide, the consumption volume ratio of two kinds of solution is 2: 8-4: 6, and through dry under nitrogen or air atmosphere after the rinsed with deionized water.
5, vertical double-basis sheet as claimed in claim 1 or 2 prepares the method for self-organized colloidal crystal, it is characterized in that: a substrate in the double-basis sheet can also be prepared the self-organized colloidal crystal of patterned surface with surperficial polydimethylsiloxane substrate with pattern.
6, vertical double-basis sheet as claimed in claim 1 or 2 prepares the method for self-organized colloidal crystal, it is characterized in that: a plurality of colloidal crystals of preparation can be superimposed, thereby obtain having the combination colloidal crystal of a plurality of ultraviolet absorption peaks.
7, vertical double-basis sheet as claimed in claim 6 prepares the method for self-organized colloidal crystal, it is characterized in that: in the combination colloidal crystal between a certain group of substrate the colloidal crystal plane that superposes relatively rotate the change that a certain angle can realize the uv-absorbing peak position.
8, by the self-organized colloidal crystal of claim 1 or the preparation of 2 described methods in the application aspect three-dimensional ordered polyporous material, photonic crystal, nanofiltration device and nanometer light shutter device.
9, by the self-organized colloidal crystal of the described method of claim 6 preparation in the application aspect three-dimensional ordered polyporous material, photonic crystal, nanofiltration device and nanometer light shutter device.
10, as the self-organized colloidal crystal of method preparation as described in the claim 7 in the application aspect three-dimensional ordered polyporous material, photonic crystal, nanofiltration device and nanometer light shutter device.
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