CN1916056A - Photon crystal membrane of polymer colloid with controllable wet ability, prepartion method and application - Google Patents
Photon crystal membrane of polymer colloid with controllable wet ability, prepartion method and application Download PDFInfo
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- CN1916056A CN1916056A CN 200510086237 CN200510086237A CN1916056A CN 1916056 A CN1916056 A CN 1916056A CN 200510086237 CN200510086237 CN 200510086237 CN 200510086237 A CN200510086237 A CN 200510086237A CN 1916056 A CN1916056 A CN 1916056A
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Abstract
This invention relates to a method for preparing infiltration-controllable polymer colloidal protonic crystal film and its application in waterproof coating. The method comprises: covering a flat substrate with an emulsion of mono-dispersed polymer latex particles with hard core/soft shell structure, and volatilizing the liquid to obtain the film formed from the mono-dispersed polymer latex particles. The mono-dispersed polymer latex particles with diameters of 100-300 nm can realize phase inversion at 30-90 deg.C. The thickness of the shell is 20-50 nm; while the polydispersity is lower than 0.005. The film has compact structure, and can be used as UV-resistant and waterproof color coating material.
Description
Technical field
The invention belongs to the preparation and the applied technical field of colloid photonic crystal film, relate in particular to photon crystal membrane of polymer colloid, and this have the preparation method and the purposes aspect water-proof coating of the photon crystal membrane of polymer colloid of controllable immersing with controllable immersing.
Background technology
The surface wettability of solid material is an extremely important performance.Natural lotus leaf is subjected to the influence of lotus leaf surface micro-nano compound structure according to the super-hydrophobicity realization automatically cleaning on surface and the effect of self-protection, and many methods are used to adjust the wetting property of solid material surface.As sol-gel process, or the low-surface-energy material surface roughening, or adopt the mould extruding to make certain polymer molecule in solvent, realize being separated.Disclosed as CN:00103573.8, realize hydrophobic, oleophobic property at the super two fluorine-containing organosilicone compounds of (hydrophobic, oleophobic) treatment agent of dredging of material surface utilization; CN:01120628.4 is disclosed, utilizes nano-form, and polymers soln is extruded from template, obtains nano polymer fibre, realizes super-hydrophobic; CN:02121555.3 carries out preoxidation and carbonization (900～1600 ℃) with nanofiber and handles, and realizes super-hydrophobicly, dredges acid, the surface of thin alkali; CN:200310121809.1 is disclosed, utilizes the aperture to roll back and forth at polymer surfaces from the alumina formwork of 30～300nm, produces nanostructure at material surface, realizes the super-hydrophobic of surface of polymer material; CN:200310115722.3 is disclosed, adopts the phase inversion process of solvent-precipitation agent, obtains the polychloroethylene film of porosity and looseness, has realized super-hydrophobic; CN:01110291.8 is disclosed, adopts chemical vapour deposition to obtain having the film of array structure, adopts concentrated acid then, hydrophobic alcohol and ultrapure water, and thermal treatment obtains based superhydrophobic thin films; CN:01118387.X is disclosed, adopt the method for chemical vapour deposition and thermofixation, nano level low surface energy powder, dispersion agent stirred in nano-photo catalytic binding agent and organic solvent mixed atmosphere resolve into emulsion, on 40～380 purpose metal fibre interlacement, obtain having the super lipophilicity/super-hydrophobicity nano-interface separating net of self-cleaning function successively with technologies such as spraying, dry setting treatment.The common ground of above-mentioned these methods all is based on or adopts the material of low surface energy or makes uneven surface, realizes the super-hydrophobicity of material surface.
The colloidal photon crystal material is realized special regulation and control to light with the formed periodic structure of the regular arrangement of single dispersed latex grain to the refraction of light or diffraction.According to the size difference of periodic arrangement, regulate and control the light wavelength difference.The Application Areas difference of corresponding prepared colloid photonic crystal film.In common patent documentation, colloid photonic crystal film is mainly used in wave filter (as CN:01105105.1, CN:98110990.X), photoswitch (CN:02160207.7), optical waveguides (CN:02804125.9, CN:99810798, CN:01132293.4, CN:02811132.X), optical fiber (CN:00803964.X, CN:00803960.7, aspect such as CN:03127694.6).
The present invention is based on the document basis of front, on the photonic crystal basis, realized a kind of infiltrating method of solid material surface of more simply regulating and control, only need by adjusting the assembling temperature, just can realize very hydrophilic (contact angle is less than 15 °), hydrophilic, hydrophobic and, not change with the photon band gap of time crystalline substance near the preparation of the brilliant material of super-hydrophobic light.
The present invention is based on the inventor at preceding patent application (number of patent application: CN:200510011219.2, CN:200510012021.6, CN:200510012047.0) the single dispersed latex grain of easy manufacture, and big area prepares the colloid photonic crystal film of visible and ultraviolet region fast, and it is applied in decorative paint, the basis of preventing ultraviolet coating and makeup and strengthening photo luminescent devices, and in conjunction with the super-hydrophobic working foundation of this group and regulate and control the wetting property of light epitaxial, to widen the Application Areas of photon crystal film.
Different with the method for aforementioned documents and patent report, the present invention does not need template and special device, do not need low-surface-energy material yet, only need to be coated with film temperature by regulation and control, just single dispersed latex grain of same particle diameter can be obtained very hydrophilic (water contact angle is lower than 15 °), or hydrophobic, or near the brilliant film of the light of super-hydrophobic (water contact angle is 145 °), the photon band gap of brilliant film remains unchanged with the time.This method is not appeared in the newspapers in document or patent.
Summary of the invention
One of purpose of the present invention provides a kind of photon crystal membrane of polymer colloid with controllable immersing; this film is to have the photon crystal membrane of polymer colloid of large size photon band gap in ultraviolet and visibility region; and this colloid photonic crystal film is with low cost, and this film has automatically cleaning and self-shield performance.
Two of purpose of the present invention provides a kind of preparation method with photon crystal membrane of polymer colloid of controllable immersing, this method neither needs by specific device, and need not carry out low-surface-energy material on the film surface handles, just by being controlled to film temperature, the wetting property of film just can be from hydrophilic (water contact angle is lower than 15 °) to carrying out a series of transformations near super-hydrophobic (water contact angle is 145 °).It is simple that this method has technology, with low cost, equipment do not had characteristics such as particular requirement.
Three of the object of the invention provides the photon crystal membrane of polymer colloid purposes with controllable immersing of purpose one, to widen this application with adjustable infiltrating photon band gap at the photon crystal membrane of polymer colloid of ultraviolet and visibility region.
The present invention is based on the inventor on preceding patent application (number of patent application: CN:200510011219.2, basis CN:200510012021.6).The method by preceding patent application at first, take the batch method letex polymerization,, can single stage method prepare emulsion particle with nuclear-shell structure by suitable adjustment emulsion polymerization technique, its particle size range is 100～300nm, and polydispersity index is less than or equal to 0.005.The photon band gap of prepared colloid photonic crystal film is distributed in 200～800nm, and the emulsion particle that obtains does not need any purification just can realize that single dispersion index is less than or equal to 0.005.
Photon crystal membrane of polymer colloid with controllable immersing of the present invention is to be piled up with face-centered cubic by the monodisperse polymer emulsion particle with hard core-soft core structure to form, and phase reversion in various degree can take place under 30～90 ℃ of temperature conditionss the monodisperse polymer emulsion particle; Thick 20～the 50nm of the shell of monodisperse polymer emulsion particle, monodisperse polymer latex particle size scope is 100～300nm, polydispersity index is less than or equal to 0.005; Described film has dense structure.
The photon band gap of described colloid photonic crystal film is distributed in ultraviolet and the full visibility region of 200～800nm; Along with the descending variation of latex particle size, the peak generation blue shift of the reflection spectrum of resulting colloid photonic crystal film.
Colloid photonic crystal film of the present invention can be realized the infiltrating adjustment of light epitaxial, and the wetting property of film can be from hydrophilic (water contact angle is lower than 15 °) to approaching super-hydrophobic (water contact angle be 145 °).
Preparation method with photon crystal membrane of polymer colloid of controllable immersing of the present invention may further comprise the steps:
(1) under the normal temperature monodisperse polymer emulsion particle is dispersed in the water, then resulting monodisperse polymer emulsion particle emulsion is evenly covered on the flat substrates, wherein the concentration of monodisperse polymer emulsion particle emulsion is 5～30wt%.
(2) temperature (30～90 ℃) of the monodisperse polymer emulsion particle solvent evaporates that obtains of set-up procedure (1), make the aqueous solvent volatilization, the monodisperse polymer emulsion particle is piled up with face-centered cubic on base material, behind dried coating film, film is peeled off from base material, can obtain having the colloid photonic crystal film of photon band gap in ultraviolet and full visibility region, this film can be realized hydrophilic, hydrophobic or approaching super-hydrophobic regulation and control.
According to adjusting dispersion liquid evaporable temperature, the hydrophilic and hydrophobic difference of gained film can realize that the colloidal crystal film is from hydrophilic, hydrophobic and approaching super-hydrophobic infiltrating adjustment.
Single dispersion index of described monodisperse polymer emulsion particle is less than or equal to 0.005, and particle size range is 100～300nm.Reduce the photon band gap generation blue shift of gained crystal film with photon from 300 to 100nm with latex particle size.
Described base material comprises glass, silicon chip, paper or stainless steel plate etc.
Photon crystal membrane of polymer colloid with controllable immersing of the present invention can be used as water-proof coating material, waterproof printing material or the water resistant cosmetic coloured coating of UV resistant.
The preparation that the present invention has the monodisperse polymer emulsion particle of nucleocapsid structure is to adopt one step of batch method letex polymerization to realize that the typical preparation method who is adopted is:
With the monomer 1 that wetting ability increases successively, monomer 2, monomer 3 blending dispersion are in the aqueous solution that contains pH buffer reagent and emulsifying agent; Is 300～800rpm with resulting emulsion polymerization systems at rotating speed, be preferably under the rotating speed of 500rpm and mix, and be heated to 65～85 ℃ (preferred temperature are 78 ℃), the initiator that adds initiator total amount 1/2 makes reaction begin to carry out, react the initiator that adds initiator total amount 1/4 after 2～4.5 hours again, remaining initiator is continuing reaction adding after 2～4.5 hours, and the 0.2wt%～1wt% of the suitable total monomer weight of the total consumption of described initiator is preferably 0.3wt%.Reaction continues end in 1～3 hour subsequently, obtains single dispersion index and is less than or equal to 0.005, and particle size range is the monodisperse polymer emulsion particle with hard core-soft core structure of 100～300nm.
Wherein, the total consumption of monomer is that (consumption of monomer 1 is 88～94wt% of total monomer weight in the emulsion polymerization systems for 11～17wt% of emulsion polymerization systems gross weight, monomer 2 is 3～6wt%, monomer 3 is 3～6wt%), the concentration of pH buffer reagent in emulsion polymerization systems is 0.02～0.99wt%, the concentration of emulsifying agent in emulsion polymerization systems is that (weight ratio 0～0.5wt%) of monomer total amount in emulsifying agent consumption and the polymerization system, the concentration of initiator in emulsion polymerization systems is 0.02～0.99wt% to 0～0.067wt%.
The realization of the nucleocapsid structure of monodisperse polymer emulsion particle does not need special technological process, just according to reaction monomers in the polymerization system and the hydrophilic difference of phase emergencing copolymer, hydrophilic radical progressively moves to the top layer in polymerization process, and lipophilic group partly moves to stratum nucleare, finally realizes hard core-soft core structure.
The reaction times that preparation has the monodisperse polymer emulsion particle of nucleocapsid structure is 5～12 hours, and the preferred reaction time is 10～11 hours.
Described reaction monomers is the compound that contains at least one ethylene linkage in the molecule, and its wetting ability increases successively, and monomer 1 is the relatively poor reaction monomers of wetting ability, as vinylbenzene, vinyl toluene or their mixture; And monomer 2 is a wetting ability monomer relatively preferably, as esters of acrylic acid, vinyl acetate or their mixture etc., described esters of acrylic acid is selected from methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, isobutyl acrylate or their any mixture; Monomer 3 is the very strong water-soluble reaction monomer of wetting ability, as vinylformic acid, methacrylic acid, acrylamide, propylene cyanogen or their any mixture etc.The introducing of minor amount of water dissolubility reaction monomers 3 is in order to increase the stability of system.And selecting for use of the different successively reaction monomers of wetting ability is for spontaneous formation nucleocapsid structure in polymerization process.
Described initiator is selected from alkali metal sulfates, ammonium persulphate or their mixture.Wherein initiator is that form with the aqueous solution is incorporated in the polymerization system, and its strength of solution is 2～5wt%.
Described basic metal is selected from potassium or sodium.
The emulsifying agent of the size of the final gained emulsion particle of described adjusting is selected from one or more the mixture etc. in sodium laurylsulfonate, sodium lauryl sulphate, the Sodium dodecylbenzene sulfonate.
Described pH buffer reagent is selected from one or more the mixture etc. in bicarbonate of ammonia, sodium bicarbonate, the sodium hydrogen phosphate.
For guaranteeing effective realization of emulsion particle monodispersity, strict control stir speed (S.S.) is fed in raw material and heating schedule, to avoid the appearance of secondary nucleation in the polymerization process.
Along with emulsifying agent consumption difference in the monodisperse polymer emulsion particle polymerization system with nucleocapsid structure, the particle diameter difference of gained emulsion particle, cause final colloid photonic crystal film photon band gap position difference,, just present distinct colors when photon band gap drops on the visible region; Emulsifying agent is in the mode introducing system by solution among the present invention.For example, the weight ratio of monomer total amount is respectively 0.0214%, 0.0267% in emulsifying agent consumption and the polymerization system, and 0.0299%, 0.0342%, 0.0427%, 0.0577%, 0.0641% o'clock, preparation-obtained latex particle size is followed successively by 284nm, 253nm, 245nm, 230nm, 211nm, 190nm, 170nm, the color of corresponding colloid photonic crystal film is red, orange, Huang is green, green grass or young crops, indigo plant, purple; The weight ratio of monomer total amount is respectively 0.238%, 0.214% in emulsifying agent consumption and polymerization system, and 0.19%, 0.119%, 0.095%, 0.071%, 0.048% o'clock, preparation-obtained latex particle size was followed successively by 100nm, 115nm, 120nm, 125nm, 130nm, 150nm, 160nm, the photon band gap position of corresponding colloid photonic crystal film is respectively: 253nm, 281nm, 300nm, 319nm, 327nm, 345nm, 380nm.
The resulting photon band gap of the present invention can be applicable to colored, water-repellent coating, fields such as makeup and printing at the photon crystal membrane of polymer colloid with controllable immersing of full visible region.Wherein, full-color colloid photonic crystal film mainly substitutes pigment/dye composition wherein, and also is used as membrane-forming agent in coloured coating and printed matter.The photon crystal membrane of polymer colloid with controllable immersing of the resulting photon band gap of the present invention in the ultraviolet region can be used as the ultraviolet material of prevention or can be used as the material that prevents in the ultraviolet makeup, or with UV light absorber or the membrane-forming agent of latex crystal film with photon as pre-antiultraviolet coating; Or be applied in the association area of other pre-antiultraviolet product.
Become the difference of film base material according to colloidal photon crystal, resulting coating can be used on the different substrate materials.
Colored newborn epitaxial be owing to can produce beautiful color, the harm of avoiding conventional dyes/pigment simultaneously and being had to human body and environment, and be applied to effect pigment.Its this performance can make its base-material with Clear paint or makeup mix, and shows the coloured pigment effect.
Photon crystal membrane of polymer colloid with controllable immersing of the present invention and other Clear paint blended application process mutually can be undertaken by following operation:
Photon crystal membrane of polymer colloid with controllable immersing of the present invention is peeled off from base material, be crushed to the micro-size particles size, mix with Clear paint and solvent phase, colloid photonic crystal film can show pigment effect, wherein colloid photonic crystal film is 1～10wt% in the mixed solution, Clear paint is 50～70wt%, and solvent is 20～40wt%.
Described Clear paint is selected from one or more the mixture etc. in acrylic varnish, polyurethane lacquer, 582-2 melamine resin, the zapon varnish.
Described solvent is an ethanol, one or more mixing in ethyl acetate or the butylacetate.
Photon band gap does not have harm at the photon crystal membrane of polymer colloid with controllable immersing of visible region to human body and environment, can be applicable to makeup, and especially color make-up series resembles lipstick, eye shadow, nail wet goods.Concrete application process is as follows:
Photon crystal membrane of polymer colloid with controllable immersing of the present invention is peeled off from base material, be crushed to the micro-size particles size, mix mutually with the base-material of makeup.Panchromatic crystal film with photon mainly replaces the coloring components in the makeup.
The photon crystal membrane of polymer colloid that wherein has controllable immersing in the mixed system is 1～10wt%.The base-material of makeup comprises: pigment extender (4～12wt%), film form agent (0～25wt%), the solvent part (comprise the oiliness part (38～70wt%), water-based part (3～12wt%) and other auxiliary agent (0～5wt%)).
Described pigment extender is TiO
2, in kaolin or the talcum powder one or more mix etc.
The described formation agent of filming is one or more mixing in soluble cotton, Synolac, sulfonamide resin or the acrylic resin etc.
Described oiliness partly comprises wax component, synthetic oil part and oil-based solvent.Wherein wax component is that in gama wax, solid paraffin, beeswax or the carnauba wax one or more mix etc.; Synthetic oil mostly is glyceryl ester, particularly tri-glyceride, ricinoleic acid octyl group dodecane ester or their mixture; Oil-based solvent is Viscotrol C and some solubility promoters, resembles butyl stearate, ethyl sebacate, tetrahydrofurfuryl alcohol and acetic ester thereof.
Described water-based partly comprises one or more mixing in water, glycerine, propylene glycol, glycol or the polyoxyethylene glycol etc.
Described other auxiliary agent comprises nonionogenic tenside, softening agent etc.Wherein nonionogenic tenside mostly is the epoxy ethane-epoxy propane embedding and forges multipolymer, as polyoxyethylene (25) polyoxypropylene (202) tetradecane ether; Softening agent is in citric acid acetyl tri-n-butyl, the camphor or their mixture etc.
When the present invention is used for multicolor printing, be as starting raw material with the monodisperse polymer emulsion particle.Monodisperse polymer emulsion particle wherein is both as membrane-forming agent or tamanori, again as wherein dyes/pigments part.The well matched side of one is:
(5～10wt%), (0.5～2wt%), all the other are deionized water to wetting Agent for Printing Inks to monodisperse polymer emulsion particle emulsion, and after above-mentioned three was fully mixed, the print cartridge that injects color printer was stand-by.
Wetting Agent for Printing Inks wherein is an ethylene glycol, propylene glycol, one or more mixing in the polyoxyethylene glycol etc.
Self-assembly preparation with photon crystal membrane of polymer colloid of controllable immersing of the present invention, adopt a kind of simple method to realize: evenly to cover certain density single dispersed latex grain on the flat substrates, after treating that wherein dispersion liquid volatilization is done, just form the orderly three-D photon crystal film of periodic arrangement.Temperature difference when volatilizing according to dispersion liquid, can realize wetting property by hydrophilic to hydrophobic adjustment.This method is simple, and required equipment is simple, helps realizing having the mass preparation of the photon crystal membrane of polymer colloid of controllable immersing.According to the difference of used single dispersed latex grain particle diameter, the photon crystal membrane of polymer colloid that gained of the present invention has a controllable immersing can present by red to purple shades of colour or have the ultraviolet coating of prevention.
The single dispersed latex grain shell in self assembling process with hard core-soft core structure that aforementioned one step of employing emulsion polymerization prepared obtains deforms, and forms fine and close structure, helps improving the mechanical stability of film.
The photon crystal membrane of polymer colloid with controllable immersing that this method prepares is owing to be polymeric film, when beautiful color is provided, can avoid of the harm of the dyes/pigments of routine to environment and human body, and be widely used in coloured coating, printing and cosmetic field, and the photon crystal membrane of polymer colloid with controllable immersing of photon band gap in the ultraviolet region can be applied in the ultraviolet coating of prevention.
Because the used material of photon crystal membrane of polymer colloid with controllable immersing is functional adjustable polymkeric substance, has good agglutinating value(of coal) between the feasible like this and various base materials.
The invention will be further described below in conjunction with accompanying drawing and by embodiment.
Description of drawings
Fig. 1. the embodiment of the invention 1 has the transmission electron microscope picture of poly-(vinylbenzene-methyl methacrylate-vinylformic acid) emulsion particle of terpolymer of nucleocapsid structure.
Fig. 2. the variation (being designated as the particle diameter of mono-dispersed latex grain among the figure) of the contact angle of poly-(vinylbenzene-methyl methacrylate-vinylformic acid) film of the embodiment of the invention 2 resulting terpolymers of different assembling temperature.
Fig. 3. and the SEM of the resulting colloidal photon crystal assembling film of the embodiment of the invention 2 different assembling temperature and the contact angle of corresponding membrane (a, 50 ℃, 11 ° of contact angles, b, 60 ℃, contact angle is 35.5 °, c, 90 ℃, contact angle is 139.9 °).
Fig. 4. the variation of the photon band gap position of the resultant film of the embodiment of the invention 2 different assembling temperature.(a, particle diameter are that single dispersed latex grain of 100nm is respectively 50,60 in the assembling temperature, 80,90 ℃ of gained light epitaxial UV-Vis reflection spectrograms; B, particle diameter are that single dispersed latex grain of 150nm is respectively 50,60 in the assembling temperature, the UV-Vis reflection spectrogram of 70,90 ℃ of resulting smooth epitaxials; C, particle diameter are that single dispersed latex grain of 170nm is respectively 50,60 in the assembling temperature, the UV-Vis reflection spectrogram of 70,80,90 ℃ of resultant smooth epitaxials.
Fig. 5. emulsion particle generation phase reversion before and after the assembling in the embodiment of the invention 2; (a) nucleocapsid structure changes synoptic diagram before and after the assembling; (b) be microcell molecule segment change in orientation synoptic diagram before and after the assembling; (c) the assembling temperature is 30 degree gained films 5 ° x-ray photoelectron power spectrum; (d) the assembling temperature is 90 degree gained films 5 ° x-ray photoelectron power spectrum.
Fig. 6. (particle diameter is respectively 100nm to different-grain diameter in the embodiment of the invention 3,150nm, 170nm, 230nm, single dispersed latex grain 298nm) is at the wetting property of difference assembling temperature gained film situation (a, 50 ℃ over time, b, is designated as the particle diameter of mono-dispersed latex ball by 90 ℃ among the figure).
Embodiment
Embodiment 1 has the preparation of the photon crystal membrane of polymer colloid of controllable immersing
Under the room temperature, with concentration is that (particle diameter is 170nm for single dispersed latex grain of the terpolymer poly-(vinylbenzene-methyl methacrylate-vinylformic acid) for preparing of the described method of employing aforementioned patent applications of 5wt%, has tangible nucleocapsid structure, its stratum nucleare is hard polystyrene, shell is that soft and whippy polymethylmethacrylate and polyacrylic acid are formed, thick 20～25 nanometers of the shell of monodisperse polymer emulsion particle are seen Fig. 1) emulsion, evenly cover the glass of cleaning, on silicon chip or the stainless steel plate base material, the base material of filming is put in certain temperature (35～90 ℃), after treating that wherein dispersion liquid moisture evaporation is done, just form the orderly three-D photon crystal film of periodic arrangement, monodisperse polymer emulsion particle with hard core-soft core structure is piled up with face-centered cubic and is formed, and the polydispersity index of monodisperse polymer emulsion particle grain is less than or equal to 0.005.
According to dispersion liquid evaporation of water temperature difference, the wetting property result of prepared film as shown in Figure 2.Under the room temperature, with concentration is single dispersed latex grain emulsion of the terpolymer poly-(vinylbenzene-methyl methacrylate-vinylformic acid) for preparing of the described method of employing aforementioned patent applications of 10wt%, evenly cover on the glass baseplate of cleaning, the particle diameter of polyalcohol emulsion particle is respectively 100nm, 150nm, 170nm, 230nm (thick 20～25 nanometers of the shell of monodisperse polymer emulsion particle), moisture is 50 ℃ in temperature, 60 ℃, 70 ℃, 80 ℃, after volatilization was done under 90 ℃ the situation, the variation of the contact angle of the film that assembling obtains on glass baseplate improved with the assembling temperature as shown in Figure 2, the contact angle of film increases gradually, the film of different-grain diameter changes different with its wetting property of assembling temperature variation, the less emulsion particle of particle diameter just can be realized hydrophilic to hydrophobic variation at lesser temps, and greater particle size could be realized the variation of wetting property from hydrophilic to hydrophobic at comparatively high temps.It is that the single dispersed latex grain of terpolymer poly-(vinylbenzene-methyl methacrylate-vinylformic acid) of 170nm is at the stereoscan photograph of the light epitaxial of difference assembling temperature that Fig. 3 has listed particle diameter.From figure as can be seen, emulsion particle still keeps the face-centred cubic structure of closely piling up, this has determined the photon band gap invariant position of the light epitaxial that its differing temps assembling obtains (to see Fig. 4, being respectively particle diameter is 100nm, 150nm, single dispersed latex grain of the terpolymer of 170nm poly-(vinylbenzene-methyl methacrylate-vinylformic acid) is at the reflection spectrogram of differing temps assembling film).
Emulsion particle is at a certain temperature in assembling process for poly-(vinylbenzene-methyl methacrylate-vinylformic acid) colloid photonic crystal film of terpolymer, phase reversion takes place, and the emulsion particle that is enriched in shell by the hydrophilic radical that begins becomes hydrophilic radical to internal contraction.Fig. 5 (a) (b) is respectively the morphology change of assembling front and back emulsion particle and microcell.This phase reversion phenomenon is by x-ray photoelectron power spectrum be confirmed (Fig. 5 (c), (d)).
Fig. 5 (c), (d) be respectively particle diameter be 170 nanometers monodisperse ternary multipolymer poly-(vinylbenzene-methyl methacrylate-vinylformic acid) have film that single dispersed latex grain that hard styrene core-soft polymethylmethacrylate and polyacrylic acid segment form obtains 30 ℃ and 90 ℃ (humidity is 70%) assembling a test result 5 ° of x-ray photoelectron power spectrums, as seen from the figure, enrichment carbonyl on the film surface that obtains 30 ℃ of assemblings, carboxyl or ester group that is to say the polymethylmethacrylate of possess hydrophilic property group and the polyacrylic acid segment still is distributed in bead when 30 degree assemblings surface.And on the film surface that 90 ℃ of assemblings obtain, only have CH
2Group, this explanation is when comparatively high temps is assembled, emulsion particle shell part with hard styrene core, soft polymethylmethacrylate and polyacrylic acid group, turn under usefulness and the certain temperature situation at water solvent, segment carries out microphase-separated again, has realized that hydrophilic radical is to the inner transfer of emulsion particle, hydrophobic hydrocarbon chain partly departs to the emulsion particle shell, make finally emulsion particle generation phase reversion to become hydrophobicity that this is its wetting property key of decision by former wetting ability.
Embodiment 3: the water-proof coating that is applied to ultraviolet or visible region
By embodiment 1 method just concentration be that 15wt% adopts single dispersed latex grain of the terpolymer poly-(vinylbenzene-methyl methacrylate-vinylformic acid) that the described method of aforementioned patent applications prepares (particle diameter is that particle diameter is from 100～300nm, has tangible nucleocapsid structure, its stratum nucleare is hard polystyrene, shell is that soft and whippy polymethylmethacrylate and polyacrylic acid are formed, thick 20～25 nanometers of the shell of monodisperse polymer emulsion particle) emulsion, evenly cover on the stainless steel plate base material of cleaning, the base material of filming is put in certain temperature (70 ℃ or more than), after treating that wherein dispersion liquid moisture evaporation is done, just form the orderly three-D photon crystal film of periodic arrangement, this film can be as the water-proof coating of ultraviolet or visibility region.The water resistance of preparation-obtained crystal film with photon sees that Fig. 6 (has listed particle diameter and has been respectively 100nm among the figure, 150nm, 170nm, 230nm, the emulsion particle of 298nm is 50 ℃ in the assembling temperature, and (Fig. 6 a), the water droplet of the film that obtains of 90 ℃ (Fig. 6 b) assembling drops on the film its contact angle over time), as seen from the figure, the assembling temperature is that 50 ℃ film is coated back 5 minutes water droplets near sprawling fully at water droplet, but the assembling temperature is 90 ℃ a film water dripped upward back 5 minutes, and its film still keeps hydrophobic state.
Embodiment 4: be used as waterproof paint or waterproof and prevent ultraviolet material in Clear paint
To be 230 nanometers with particle diameter, concentration is poly-(vinylbenzene-methyl methacrylate-vinylformic acid) the emulsion particle emulsion of the monodisperse ternary multipolymer of 12wt%, adopting embodiment 1 method is that 80 ℃ of green colloid photonic crystal films that prepare are peeled off (consumption is 10wt%) from glass baseplate in the assembling temperature, be crushed to the micron order size, mix use mutually with acrylic varnish (60wt%) and a certain amount of ethanol (30wt%), obtain having the green coating of controllable immersing.
With concentration is poly-(vinylbenzene-methyl methacrylate-vinylformic acid) polyalcohol emulsion particle emulsion of monodisperse ternary multipolymer of 9wt%, by embodiment 1 method is the photon crystal membrane of polymer colloid with controlled infiltration for preparing under 70 ℃ of conditions in temperature, when the particle diameter of monodisperse polymer emulsion particle is respectively 100nm, 115nm, 120nm, 125nm, 130nm, 150nm or 160nm, the photon band gap position of corresponding preparation-obtained photon crystal membrane of polymer colloid is respectively 253nm, 281nm, 300nm, 319nm, 327nm, 345nm, 380nm.Resulting coating can be directly used in pre-antiultraviolet, and according to base materials employed difference, used coating can be used in automobile adhesive film, on the facilities such as cover plate.
Embodiment 5: be applied to color make-up or pre-antiultraviolet lipstick
TiO
2(10wt%), poly-(vinylbenzene-methyl methacrylate-vinylformic acid) colloidal photon crystal of red terpolymer (8.0wt% replaces the pigment part), gama wax (5.0wt%), ceresin (4.0wt%), carnauba wax (2.0wt%), Viscotrol C (30.0wt%), Unimac 5680 two glyceryl ester (28.50wt%), polyoxyethylene (25) polyoxypropylene (202) tetradecane ether (1.5wt%), deionized water (8.0wt%), glycerine (2.0wt%), propylene glycol (1.0wt%).
Method for making: with TiO
2And particle diameter is 284nm, concentration is poly-(vinylbenzene-methyl methacrylate-vinylformic acid) the polyalcohol emulsion particle emulsion of the monodisperse ternary multipolymer of 8wt%, adopting embodiment 1 method is that 85 ℃ of red colloidal photon crystals that prepare on silicon chip (being crushed to the micron size) add in the Viscotrol C in temperature, uses roller process; With deionized water, glycerine, propylene glycol forms water 80 ℃ of homogeneous dissolvings; After other composition Hybrid Heating fusion, aforementioned roller process part and aqueous portion are added, use homogeneous stirrer homogeneous to disperse, subsequently, making it flow into mould postcooling becomes thin round strip, can obtain the color make-up lipstick, when the particle diameter of monodisperse polymer emulsion particle is 100nm, 115nm, 120nm, 125nm, 130nm, when 150nm or 160nm, what the employing method for preparing obtained is pre-antiultraviolet lipstick.
Embodiment 6: be used for color printer
With particle diameter is that poly-(vinylbenzene-methyl methacrylate-vinylformic acid) the polyalcohol emulsion particle emulsion of monodispersity terpolymer, glycol ether, propylene glycol, the deionized water of 170 nanometers fully mixes, and the print cartridge that injects color printer is stand-by.Wherein, the weight percent of glycol ether and propylene glycol is 1: 1, and the concentration of monodisperse polymer emulsion particle emulsion is 8wt% in the system, and the concentration of glycol ether and propylene glycol mixture is 1wt%, and surplus is a deionized water.
Claims (10)
1. photon crystal membrane of polymer colloid with controllable immersing, it is characterized in that: this film is to be piled up with face-centered cubic by the monodisperse polymer emulsion particle with hard core-soft core structure to form, and the monodisperse polymer emulsion particle can be 30～90 ℃ of temperature generation phase reversions in various degree; Thick 20～the 50nm of the shell of monodisperse polymer emulsion particle, monodisperse polymer latex particle size scope is 100～300nm, polydispersity index is less than or equal to 0.005; Described film has dense structure.
2. photon crystal membrane of polymer colloid according to claim 1 is characterized in that: the photon band gap of described photon crystal membrane of polymer colloid is distributed in ultraviolet and the full visibility region of 200～800nm; Along with the descending variation of latex particle size, the peak generation blue shift of the reflection spectrum of resulting photon crystal membrane of polymer colloid.
3. photon crystal membrane of polymer colloid according to claim 1 and 2 is characterized in that: described photon crystal membrane of polymer colloid can be realized the infiltrating adjustment of light epitaxial, and water contact angle is by being lower than 15 ° to 145 °.
4. photon crystal membrane of polymer colloid according to claim 1 is characterized in that, described monodisperse polymer emulsion particle prepares by following method:
With the monomer 1 that wetting ability increases successively, monomer 2, monomer 3 blending dispersion are in the aqueous solution that contains pH buffer reagent and emulsifying agent; Be to mix under the rotating speed of 300～800rpm resulting emulsion polymerization systems at rotating speed, and be heated to 65～85 ℃, the initiator that adds initiator total amount 1/2 makes reaction begin to carry out, react the initiator that adds initiator total amount 1/4 after 2～4.5 hours again, remaining initiator is continuing reaction adding after 2～4.5 hours, the 0.2wt%～1wt% of the suitable total monomer weight of the total consumption of described initiator; Obtain single dispersion index after reaction finishes and be less than or equal to 0.005, particle size range is the monodisperse polymer emulsion particle with hard core-soft core structure of 100～300nm;
11～17wt% that described monomeric total consumption is the emulsion polymerization systems gross weight; The consumption of monomer 1 is 88～94wt% of total monomer weight in the emulsion polymerization systems, and monomer 2 is 3～6wt%, and monomer 3 is 3～6wt%; The concentration of pH buffer reagent in emulsion polymerization systems is 0.02～0.99wt%, and the concentration of emulsifying agent in emulsion polymerization systems is 0～0.067wt%;
Described monomer 1 is selected from vinylbenzene, vinyl toluene or their mixture;
Described monomer 2 is selected from esters of acrylic acid, vinyl acetate or their mixture;
Described monomer 3 is selected from vinylformic acid, methacrylic acid, acrylamide, propylene cyanogen or their any mixture.
5. photon crystal membrane of polymer colloid according to claim 4 is characterized in that: described esters of acrylic acid is selected from methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, isobutyl acrylate or their any mixture.
6. photon crystal membrane of polymer colloid according to claim 4 is characterized in that: described initiator is that the form with the aqueous solution is incorporated in the polymerization system, and its strength of solution is 2～5wt%; Initiator is selected from alkali metal sulfates, ammonium persulphate or their mixture.
7. photon crystal membrane of polymer colloid according to claim 4 is characterized in that: described emulsifying agent is selected from one or more the mixture in sodium laurylsulfonate, sodium lauryl sulphate, the Sodium dodecylbenzene sulfonate.
8. photon crystal membrane of polymer colloid according to claim 4 is characterized in that: described pH buffer reagent is selected from one or more the mixture in bicarbonate of ammonia, sodium bicarbonate, the sodium hydrogen phosphate.
9. the preparation method according to each described photon crystal membrane of polymer colloid of claim 1～8 is characterized in that, described method may further comprise the steps:
(1) under the normal temperature monodisperse polymer emulsion particle is dispersed in the water, then resulting monodisperse polymer emulsion particle emulsion is evenly covered on the flat substrates, wherein the concentration of monodisperse polymer emulsion particle emulsion is 5～30wt%;
(2) temperature of the monodisperse polymer emulsion particle solvent evaporates that obtains of set-up procedure (1), temperature is 30～90 ℃, make the aqueous solvent volatilization, the monodisperse polymer emulsion particle is piled up with face-centered cubic on base material, behind dried coating film, film is peeled off from base material, obtained having the colloid photonic crystal film of photon band gap in ultraviolet and full visibility region.
10. the purposes according to each described photon crystal membrane of polymer colloid of claim 1～8 is characterized in that: described water-proof coating material, waterproof printing material or water resistant cosmetic coloured coating with photon crystal membrane of polymer colloid of controllable immersing as UV resistant.
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| CN102031566A (en) * | 2010-09-20 | 2011-04-27 | 哈尔滨工业大学 | All-organic one-dimensional photonic crystal based on surface plasma effect and preparation method thereof |
| CN102732942A (en) * | 2011-03-31 | 2012-10-17 | 中国科学院化学研究所 | Preparation method of self-supporting crack-free photonic crystal |
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| JP4190239B2 (en) * | 2002-09-13 | 2008-12-03 | 財団法人川村理化学研究所 | Colloidal crystal and method for producing the same |
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| CN102031566A (en) * | 2010-09-20 | 2011-04-27 | 哈尔滨工业大学 | All-organic one-dimensional photonic crystal based on surface plasma effect and preparation method thereof |
| CN102732942A (en) * | 2011-03-31 | 2012-10-17 | 中国科学院化学研究所 | Preparation method of self-supporting crack-free photonic crystal |
| CN102732942B (en) * | 2011-03-31 | 2015-08-19 | 中国科学院化学研究所 | The preparation method of self-supporting crack-free optical crystal |
| WO2015021920A1 (en) * | 2013-08-13 | 2015-02-19 | 厦门大学 | Preparation method for high-strength cross-linked polymer photonic crystal film |
| CN104437283A (en) * | 2014-11-05 | 2015-03-25 | 河北师范大学 | Super colloidal crystal assembly body particles with controllable morphology and sizes, and preparation method of super colloidal crystal assembly body particles |
| CN104437283B (en) * | 2014-11-05 | 2016-09-07 | 河北师范大学 | Colloidal crystal super assembly particle that a kind of pattern is controlled with size and preparation method thereof |
| CN106908898A (en) * | 2015-12-23 | 2017-06-30 | 中国科学院化学研究所 | A kind of preparation method of photonic crystal and the photonic crystal prepared by the method |
| CN106908898B (en) * | 2015-12-23 | 2019-06-21 | 中国科学院化学研究所 | A kind of preparation method of photonic crystal and the photonic crystal prepared by this method |
| WO2018165973A1 (en) * | 2017-03-17 | 2018-09-20 | The Procter & Gamble Company | Article with aesthetic substrate |
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