CN107955477A - Erythrocyte shape colloidal particle and spherical colloid particles assembly and preparation method and application - Google Patents

Erythrocyte shape colloidal particle and spherical colloid particles assembly and preparation method and application Download PDF

Info

Publication number
CN107955477A
CN107955477A CN201711173551.8A CN201711173551A CN107955477A CN 107955477 A CN107955477 A CN 107955477A CN 201711173551 A CN201711173551 A CN 201711173551A CN 107955477 A CN107955477 A CN 107955477A
Authority
CN
China
Prior art keywords
particle
parts
assembly
erythrocyte
erythrocyte shape
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.)
Granted
Application number
CN201711173551.8A
Other languages
Chinese (zh)
Other versions
CN107955477B (en
Inventor
张心亚
宋刘俊
杜小林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN201711173551.8A priority Critical patent/CN107955477B/en
Publication of CN107955477A publication Critical patent/CN107955477A/en
Application granted granted Critical
Publication of CN107955477B publication Critical patent/CN107955477B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F112/06—Hydrocarbons
    • C08F112/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/04—Acids; Metal salts or ammonium salts thereof
    • C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
    • C08F271/02—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00 on to polymers of monomers containing heterocyclic nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/633—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polymers of compounds having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/004—Reflecting paints; Signal paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses erythrocyte shape colloidal particle and spherical colloid particles assembly and preparation method and application.The assembly is inlayed into the groove of erythrocyte shape particle by spheroidal particle, both closely fit together, and forms assembly；The particle diameter of the spheroidal particle is 500nm~1300nm；Erythrocyte shape particle, particle diameter are 1~5 μm, and the shape of groove is hemispherical, a diameter of 600nm~1500nm of groove；And the particle diameter of spheroidal particle is 80% the 100% of the groove diameter of erythrocyte shape particle；The present invention successfully realizes the self assembly of the high matching degree of erythrocyte shape particle and spheroidal particle, and assembling effect is significantly lifted, which applies shows excellent photonic crystal rainbow effect in photonic crystal water paint；After regulating and controlling to the dimensional structure of assembly, more gorgeous colors can also be obtained, there will be very big potential using value in water paint.

Description

Erythrocyte shape colloidal particle and spherical colloid particles assembly and preparation method thereof with Using
Technical field
The present invention relates to polymer latex particles self-assembling technique field, more particularly to aspherical polymer latex particles With the self assembly of spherical polymer latex particle, and in particular to erythrocyte shape colloidal particle and spherical colloid particles assembly and Its preparation method and application.
Background technology
High performance structures material is support aerospace, communications and transportation, photoelectric information, the great base of energy source and power and country The important substance basis in the fields such as plinth engineering construction, is one of most hotly competitive hi tech and new material field in the world at present. Polymeric colloid particle is widely used in the structure of new structural material as primitive functional particles.Traditional polymeric colloid Particle refer to diameter between nanometer between micro-meter scale, shape is spherical polyphosphazene polymer collective.Relative to isotropic Spheric granules, those are aspherical or have the anisotropic colloidal particles of asymmetry in structure and chemical composition, have only The performances such as special physics, chemistry and optics, in the simulation of unusual photonic crystal, atom or molecular model, control molecular recognition and oneself The emerging fields such as assembling have the application of uniqueness, the application range of colloidal solid have been widened significantly, to regulate and control and designing new structure Material provides new dimension.The photonic crystal such as prepared based on traditional spheric granules, its characteristic indication are photonic band Gap is very limited；And the photonic crystal prepared using aspherical colloidal particle as basic particle, the band of photonic crystal has been expanded significantly The gap limit, new approaches are provided for development of the photonic crystal in photoelectric field.In recent years, the application of photonic crystal is also increasingly Extensively, particularly in the application field of the water paint of photonic crystal, good achievement is achieved, is currently based on spheroidal particle Photonic crystal optical effect in special car coating, gradually start to be commercialized, and it is aspherical there is more excellent performance, Also among research.In view of the physical characteristic such as the Van der Waals force on nonspherical particle surface, distribution of charges, curvature, refractive index is not Spheroidal particle is same as, just generates the peculiar physical phenomenon such as characteristic such as slow light effect, negative index, it is brilliant with the photon of its preparation Body coating will expand application range significantly will, it will produces more abundant product system and application field.
At present, anisotropy aspherical particle passes through self assembly (self-assembly) with spherical polymer colloidal solid There is important application prospect to build structural material.By this method, material can be based on nanometer or micron aspect is built, Rather than the synthesis of traditional atom or molecular level, revolutionary new material can be obtained.Between aspherical colloidal particle from Assembling generally refers to colloidal particle under to extraneous response, by forming certain structure, shape or producing certain behavior To balance external influence.
The self-assembling method of nonspherical particle mainly includes field drives self assembly, electric field driven self assembly and Depletion Force certainly Assemble three kinds of methods.For externally-applied magnetic field self assembly, it is desirable to which nonspherical particle will can produce response to externally-applied magnetic field in itself, and gather Compound latex particle is not possess magnetism in itself, therefore polymer latex particles will be modified using magnetic particle, is made Magnetic field can be produced response (Sacanna S., Rossi L., Pine David J., Magnetic by obtaining polymer latex particles Click Colloidal Assembly,Journal of America Chemistry Society.2012,134(14), 6112~6115；Zerrouki D.,Baudry J.,Pine D.,Chaikin P.&Bibette J.,Chiral colloidal clusters,Nature,2008,455(1):380~382).In addition, field drives self assembly needs additional magnetic , self assembling process is relatively complicated, and poorly efficient, bad dispersibility, complex procedures, repeatable difference etc..Under normal circumstances, Whether aggregation of the aspheric particle under AC field be then powered unrelated with particle, and particle can all be polarized and produce under AC field Raw electric dipole moment, its occur under the electric field self assembly clustering phenomena (Anke K., Alfons van B., Arnout I., Synthesis of monodisperse,rodlike silica colloids with tunable aspect ratio, Journal of America Chemistry Society.2011,133(8):2346~2349).And electric field driven self assembly Additional offer electric field is provided, while self assembling process is difficult to control, so electric field driven self assembly is in aspherical latex particle Application in terms of self assembly is restricted.
(journal (the natural section of self assembly [J] Nanjing University of Cheng Zhifeng, Luo Fuhua recess colloidal particles such as Cheng Zhifeng Learn), 2014,01:The self assembly of groove-like colloidal particle and spherical PS particles 23-29) is carried out using dissipation self-assembly method；The party Method is first by the solid powder of nonspherical particle solid powder and spheroidal particle in mass ratio 1:4 are dispersed in water, and are made into The aqueous solution of 1.0wt%, takes this small amount of aqueous solution the PEO aqueous solutions that concentration is 0.5g/L to be then added dropwise, in light on glass slide Learn self assembly situation of the micro- Microscopic observation particle under the gradual Dissipative conditions of PEO.But the nonspherical particle of the preparations such as Cheng Zhifeng With multiple grooves (1~4), multiple sites of assembling are also provided for, since the influence of steric hindrance can not possibly group at the same time Fill multiple particles；Allow to assemble multiple particles, the difference for assembling site causes that there are a variety of inconsistent assembly forms； Especially the technology does not recognize the matching of the internal diameter (600nm) of the groove of preparation and the internal diameter (1100nm) of spheroidal particle Property, spheroidal particle cannot be embedded in inside grooves；The technology does not also recognize the mode of action of emptying reagent, on the glass sheet directly Connect and PEO is added dropwise, cause the uneven concentration of emptying reagent, the technology is almost without obtaining stable nonspherical particle and spherical grain The assembly of son.
The content of the invention
The present invention be directed to the deficiencies in the prior art, there is provided a kind of step is simple, and repeatability is high, groove and assembling site Single, without steric effect, matching degree is high between particle, self assembly effect good erythrocyte shape colloidal particle and sphero-colloid Particle assembly body and preparation method thereof.
Another object of the present invention is to provide the erythrocyte shape colloidal particle and spherical colloid particles assembly in light Application in sub- crystal water paint.
To reach above-mentioned purpose, the present invention provides following technical solution：
Erythrocyte shape colloidal particle and spherical colloid particles assembly, it is characterised in that inlayed by spheroidal particle into blood In the groove of red blood cell shape particle, both closely fit together, and form assembly；
The particle diameter of the spheroidal particle is 500nm~1300nm；Erythrocyte shape particle, particle diameter are 1~5 μm, groove Shape is hemispherical, a diameter of 600nm~1500nm of groove；And the groove that the particle diameter of spheroidal particle is erythrocyte shape particle The 80%-100% of diameter；
The erythrocyte shape particle is prepared by following steps：
The first step, in terms of mass fraction, by 100~200 parts of monomer, 2~10 parts of initiator, 10~50 parts of surface Activating agent, 100~500 parts of absolute ethyl alcohols and 100~500 parts of water mixing, stirring form homogeneous phase solution, lead in nitrogen removing system Oxygen, be placed in initiated polymerization in 60~80 DEG C of water-baths；
Second step, in terms of mass fraction, after 4~8h of polymerisation, then by 0~200 part of monomer, 5~50 parts of crosslinking Agent and homogeneous phase solution being slowly dropped in reaction system with 1~100 part/hour of 10~100 parts of absolute ethyl alcohol composition, hold It is continuous that 2~10h is added dropwise；After completion of dropwise addition, the reaction was continued to 20~30h；
3rd step, is centrifuged repeatedly washing by reaction product and removes unreacted monomer and surfactant, be freeze-dried, system Obtain erythrocyte shape particle；
The monomer is one kind in acrylic acid, methyl acrylate, butyl acrylate, methyl methacrylate and styrene It is or a variety of；
The initiator for potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate, azodiisobutyronitrile, azobisisoheptonitrile and One or more in benzoyl peroxide；
The surfactant is neopelex, lauryl sodium sulfate, polyvinylpyrrolidone and alkene One or more in base sodium sulfonate；
The crosslinking agent is divinylbenzene, diisocyanate, N, and N~methylene-bisacrylamide, peroxidating two are different One or more in propyl benzene.
Further to realize the object of the invention, it is preferable that the spheroidal particle is prepared via a method which：With mass fraction Meter, by 100~200 parts of monomers, 2~10 parts of initiators, 10~50 parts of surfactants, 100~500 parts of absolute ethyl alcohols and 100 ~300 parts of deionized water mixing, 100~300r/min stir to form homogeneous phase solution, lead to the oxygen in nitrogen removing system, heating To 60~80 DEG C of initiated polymerizations, 4~8h of isothermal reaction；After reaction, centrifuge washing, Ran Houleng are carried out to product repeatedly It is lyophilized dry, spheroidal particle is made；
The monomer is one kind in acrylic acid, methyl acrylate, butyl acrylate, methyl methacrylate and styrene It is or a variety of；
The initiator for potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate, azodiisobutyronitrile, azobisisoheptonitrile and One or more in benzoyl peroxide；
The surfactant is neopelex, lauryl sodium sulfate, polyvinylpyrrolidone and alkene One or more in base sodium sulfonate.
Preferably, the time of the logical nitrogen is 30~60min；The time of freeze-drying is 12~24h.
Preferably, the time of the logical nitrogen in the first step is 30~60min；The time being freeze-dried in 3rd step for 12~ 24h。。
Preferably, the solvent that the centrifuge washing is used be methanol, ethanol, acetone and deionized water in one kind or It is a variety of.
The preparation method of the erythrocyte shape colloidal particle and spherical colloid particles assembly：, will in terms of mass fraction 100~200 parts of erythrocyte shape particles, 10~50 parts of emptying reagents and and 100~500 parts of deionized waters and 100~500 parts of nothings Water-ethanol mixes, and ultrasonic disperse, obtains mixed liquor；Then by 10~50 parts of spheroidal particle dispersion liquid with 1~100 part/hour Rate of addition is slowly dropped in mixed liquor, and erythrocyte shape colloidal particle and spherical colloid particles assembly is made；
The emptying reagent is polyethylene glycol oxide (PEO) or poly(N-isopropylacrylamide) (poly-NIPAM).
Preferably, the time of the ultrasonic disperse is 20~30min.
Preferably, the drop rate of the spheroidal particle dispersion liquid is 10~100 parts/hour.
The application of the erythrocyte shape colloidal particle and spherical colloid particles assembly in photonic crystal water paint.
Chinese invention patent application CN 201610182563.6 discloses a kind of aspherical latex particle of single dispersing hat shape Preparation method, specifically disclose the synthetic method of the semicontinuous charging of dispersin polymerization a kind of to prepare monodispersed aspherical grain Son, particle prepared by this method have the characteristics that polymolecularity and single groove；If this particle is applied to assembling In system, the form just there is no space steric effect, obtained assembly is also just homogeneous, and can be by adjusting synthesis side Method, can obtain the nonspherical particle and spheroidal particle of high matching degree.
The dominant mechanism of Depletion Force self-assembly method of the present invention is erythrocyte shape grain after emptying reagent is added in dispersion liquid Son and spheroidal particle surface formed one layer emptying reagent molecule clad, be known as exclusion layer, due to particle with emptying reagent it Between steric hindrance effect, emptying reagent molecule cannot be close to particle surface.When erythrocyte shape particle and spheroidal particle are close When, exclusion layer overlaps, and the increase of reagent molecule free volume is emptied in system, causes the increase of system entropy, drives particle from group Dress.It is a discovery of the invention that rationally control emptying reagent concentration, will produce larger Depletion Force, the size of spheroidal particle needs and blood The concave size of red blood cell shape particle surface has the matching degree of 80%-100%, i.e. the diameter of spheroidal particle is that groove particle is straight During the 80-100% in footpath, good assembly matching effect can be obtained.
Compared with prior art, the present invention has following prominent effect：
1) present invention uses improved Depletion Force self-assembly method, and main cash is：Gather first with semicontinuous dispersal of feed The method of conjunction synthesized single dispersing hat shape, have single groove nonspherical particle, assembling when there is no steric hindrance imitate Should, the form of assembly is also than more uniform, only a kind of structure generation, and the size of spheroidal particle and nonspherical particle can Controlled with simple adjustment, so as to fulfill the self assembly of high matching degree between erythrocyte shape particle and spheroidal particle.
It is important that the method by controlling emptying reagent concentration and suitably stirring, makes the concentration of emptying reagent in whole body It is equally distributed in system, this like-particles obtains matched probability and increases substantially, while assembling effect is also significantly lifted.
2) preparation method step of the present invention is simple, and repeatability is high, and effect is good, can be by adjusting spheroidal particle and aspherical The quality of the size of particle diameter, erythrocyte shape particle and spheroidal particle when empties reagent quality concentration and waits simple operations success Realize erythrocyte shape particle and the accurate control of spheroidal particle self assembly.
3) procedure of the improved progress self assembly under Depletion Force effect of the invention is simple, easy to operate, to group Dress body can directly carry out practical application, and good application value is shown in terms of photonic crystal water paint.
4) with existing some nonspherical particles (such as dumbbell shaped, Xue Renzhuan, ellipsoid) being used in terms of colloidal crystal Compare, assembly produced by the present invention not only has the anisotropy on pattern and structure, but also the assembly assembled is transported In terms of photonic crystal water paint, traditional mill base or pigment can be replaced, and can make coating that there is special optical property. The Lock-and-Key assemblies are applied in photonic crystal water paint, can show gorgeous color, it is this due to Particle causes the phenomenon of the refraction and reflection to light source in physics microstructure in itself, its structure stablized, the reflection to light It is will never fade in the case that rate height and structure are not destroyed.
Brief description of the drawings
Fig. 1 is particle diameter 800nm spherical polystyrenes (PS) particle SEM pictures prepared by embodiment 1.
Fig. 2 is erythrocyte shape particle SEM pictures prepared by embodiment 1.
Fig. 3 is single Lock-and-Key assemblies electron microscopic picture made from embodiment 1.
Fig. 4 is entirety Lock-and-Key assembly electron microscopic pictures made from embodiment 1.
Fig. 5 is the picture for the iris phenomenon that photonic crystal made from embodiment 1 occurs after aqueous acrylic emulsion film forming.
Fig. 6 is the monochromatic orange-yellow photonic crystal figure of monofilm prepared by Lock-and-Key assemblies made from embodiment 1 Piece.
Fig. 7 is that the monochromatic orange-yellow photonic crystal of monofilm prepared by Lock-and-Key assemblies made from embodiment 1 is anti- Penetrate spectrogram.
Fig. 8 is erythrocyte shape particle made from embodiment 2 and the electron microscope of spherical polymethylacrylic acid particle assembly body Piece.
Fig. 9 is erythrocyte shape particle made from embodiment 3 and the electron microscopic picture of spherical polyacrylic acid particle assembly body.
Figure 10 is erythrocyte shape particle made from embodiment 4 and spherical polyacrylic acid~methyl acrylate particle assembly body Electron microscopic picture.
Embodiment
The invention will be further described with reference to the accompanying drawings and examples, it is necessary to which explanation, embodiment are not formed Restriction to the claimed scope of the invention.
Embodiment 1
A kind of spherical polystyrene (PS) particle, its preparation process are as follows：
In terms of mass fraction, by 100 parts of styrene (St), 2 parts of ammonium persulfates (APS), 10 parts of lauryl sodium sulfate (SDS), 100 parts of deionized waters are added in 250mL four-hole boiling flasks, and 300r/min stirs to form homogeneous phase solution, lead to nitrogen 30min Oxygen in removing system, is warming up to 60 DEG C of initiated polymerizations, isothermal reaction 4h.After reaction, anhydrous second is recycled Alcohol carries out centrifuge washing to remove unreacted monomer and stabilizer to product, is then freeze-dried 12h, is made spherical PS Son.
The spheroidal particle being prepared is put using the scanning electron microscope of model FE-SEM, ZEISS ULTRA 55 Big 10000 times are characterized, and Fig. 1 is the scanning electron microscopic picture for the spherical PS particles observed, it can be seen from the figure that spherical PS Particle surface is smooth, and granular size is homogeneous, has a good monodispersity, and in figure spheroidal particle a diameter of 800nm, Fig. 1 Illustrate by above-mentioned condition, the particle of the spherical PS of size required for being successfully prepared us.
A kind of erythrocyte shape particle, is prepared by following steps：
The first step, in terms of mass fraction, by 190 parts of styrene, 10 parts of acrylic acid, 2 parts of ammonium persulfates, 10 parts of polyethylene pyrroles Pyrrolidone and 100 parts of deionized waters are added in 250mL round-bottomed flasks, and 300r/min stirs to form homogeneous phase solution, lead to nitrogen Oxygen in 30min removing systems, initiated polymerization in 80 DEG C of water-baths is placed in by flask；
Second step, in terms of mass fraction, after reacting 4h, using peristaltic pump by 50 parts of styrene, 5 parts of diisocyanate and 10 The homogeneous phase solution of part absolute ethyl alcohol composition is added drop-wise in reaction system, and 2h is persistently added dropwise；After completion of dropwise addition, the reaction was continued to 20h；
3rd step, reaction product carry out centrifuge washing with second alcohol and water repeatedly and remove residual monomer, are freeze-dried 24h, system Obtain erythrocyte shape particle.
Using the scanning electron microscope of model FE-SEM, ZEISS ULTRA 55 to the erythrocyte shape that is prepared Particle amplifies 10000 times and is characterized, and Fig. 2 is the scanning electron microscopic picture for the erythrocyte shape particle observed, can be with from Fig. 2 Find out, Lock particle totality pattern is in erythrocyte shape, and particle diameter is 3 μm, has single groove, the shape of central recess is half It is spherical, the hemispheric a diameter of 800nm of groove.The non-particle morphology of erythrocyte shape is homogeneous, and has good single dispersing Property, illustrate by above-mentioned condition, be successfully prepared the aspherical erythrocyte styrene/acrylic particle for needing size.
A kind of preparation of erythrocyte shape colloidal particle and spherical colloid particles assembly
In terms of mass fraction, by 140 parts of erythrocyte shape particles of above-mentioned preparation, (particle diameter is 3 μm, central recess first Shape is hemispherical, and a diameter of 800nm of hemispherical groove), 20 parts of polyethylene glycol oxides (PEO) mix with 450 parts of deionized waters Close, ultrasonic 20min, obtains dispersed mixed liquor；Then by 10 parts of above-mentioned spherical PS particles (a diameter of 800nm) with 10 The rate of addition of part/hour is added drop-wise in above-mentioned mixed liquor, and erythrocyte shape colloidal particle and spherical colloid particles assembling is made The dispersion liquid (dispersion liquid of Lock-and-Key assemblies) of body.
Using the scanning electron microscope of model FE-SEM, ZEISS ULTRA 55 to the Lock-and- that is prepared Key assemblies amplify 30000 times and are characterized, and Fig. 3 is the single Lock-and-Key assemblies electron microscope observed, from Fig. 3 In can be clearly seen that spherical PS particles (Key particles) are tightly inlayed as key into erythrocyte shape particle (Lock Particle) groove in, both closely stably fit together, if PS particles spin off from the groove of nonspherical particle If, according to the law of thermodynamics, this process is whole system entropy is reduced process, this process is not spontaneous process, it is necessary to is provided Extra energy, thus obtain Lock-and-Key assemblies are very stable.Fig. 3 illustrates to prepare by above-mentioned condition aspherical Erythrocyte particle and spherical PS particles successfully complete self assembly.
At the same time using the scanning electron microscope of model FE-SEM, ZEISS ULTRA 55 to the Lock- that is prepared And-Key assemblies amplify 10000 times and are characterized, and Fig. 4 is the scanning electron microscopic picture of obtained assembly overall package effect, It can be seen from the figure that there is the Lock-and-Key assemblies for largely assembling and finishing in figure, pairing rate is 75% or so, this is matched somebody with somebody To effect than in contrast, assembling effect obtains significantly with the Cheng Zhi peaks assembly reported in the literature that cannot stablize Lifting.Fig. 4 illustrates the assembly prepared on this condition, and the matching degree of size is high between particle, realizes 75% matching；Illustrate non- A diameter of 3 μm of spheroidal particle, groove diameter 800nm, a diameter of 800nm of spheroidal particle, and the concentration of the emptying reagent Under the conditions of, the assembling effect of erythrocyte shape colloidal particle and spherical colloid particles entirety is good.An only assembling under the conditions of being somebody's turn to do Site, does not deposit the influence of space steric effect.
The dispersion liquid 5g of Lock-and-Key assemblies obtained above is added to the water-and acrylate lotion of 20g In, after ultrasonic disperse 10min, lightly prepared with the four sides blade applicator of model BGD 206/4 on 10*5 centimetres of asbestos board The paint film of 125 micron thickness, room temperature to paint film are completely dried, as shown in Figure 5, it can be seen that obvious paint film presents mottled Varicoloured, prismy rainbow effect, similar to the appearance of opal, this is because the Lock-and-Key assemblies in paint film Middle nonspherical particle and spherical PS particles (Key particles) are tightly inlayed as key into (Lock, erythrocyte shape particle Son) groove in, both closely stably fit together, and caused by tightly fitting together the result is that it is aspherical and Curvature difference, refractive index are different on the surface of spheroidal particle, caused by causing the reflection and refraction of different wave length light, lead The light for causing to enter observer is also to be made of the light of different wavelength, so seeing iris phenomenon, illustrates Lock- The effect that can show photonic crystal of the and-Key assemblies in aqueous emulsion paint, can apply in water paint, Used instead of conventional pigment and pigment, great change will be made to traditional pigment manufacturing.
The dispersion liquid 1g of the Lock-and-Key assemblies in Fig. 3 is equally taken, is slowly dropped to liquid-transfering gun and fills water In culture dish (a diameter of 6 centimetres of culture dish, are highly 2 centimetres), obtain one layer of Lock-and-Key's on the surface of water Film, with the volatilization of moisture in culture dish, under the action of gravity, auto-deposition obtains uniformly in culture dish bottom glass One tunic, as shown in Figure 6, it can be seen that color is homogeneous orange-yellow, this is because under the effect of gravity, Lock-and-Key Assembly is intended to Orienting ordered arrangement and light in the same place curvature and refractive index of assembly is identical, the light of reflection It is made of the light wave of same wavelength, so the color shown also can be a kind of single uniform.Using model R3~ The reflecting spectrograph of IS50~T carries out obtained orange film the test of reflectance spectrum, obtains reflectance spectrum as shown in Figure 7 Figure, for the maximum of reflectance spectrum at 609nm, the wavelength (597~622nm) of this and theoretic orange coloured light is consistent , and maximum reflectivity herein is up to 41%, and the Lock-and-Key assemblies illustrated are manufacturing gorgeous knot There is very big potential using value in terms of structure color, be fully able to replace traditional pigment and pigment, and according to Bragg reflection Law, the size by adjusting nonspherical particle and spheroidal particle can also obtain the film of other colors completely, and 41% Reflectivity explanation reflection is very high, and the brightness of color, plumpness are good as seen from the figure, and the situation that its structure stablized is not destroyed Under, it is will never fade.Big change will occurs in the manufacture and toning of following color in this, utilize stable physical arrangement color Apt to deteriorate, the aging to replace, the chemical color of migration, has very big market and application value.
Embodiment 2
A kind of spherical polymethyl acid particles, its preparation process are as follows：
In terms of mass fraction, by 200 parts of methacrylic acids (MAA), 10 parts of potassium peroxydisulfates, 50 parts of polyvinylpyrrolidones (PVP), 500 parts of absolute ethyl alcohols and 100 parts of deionized waters are added in 250mL four-hole boiling flasks, and 100r/min stirs to be formed homogeneously Solution, leads to the oxygen in nitrogen 60min removing systems, is warming up to 80 DEG C of initiated polymerizations, isothermal reaction 8h.Reaction terminates Afterwards, absolute ethyl alcohol and deionized water are recycled centrifuge washing is carried out to product to remove unreacted monomer and stabilizer, so After be freeze-dried 24h, be made spherical metering system acid particles.
Gained Key particles are smooth for spherical methacrylic acid particle surface, and monodispersity is preferable, and size is more unified, grain The a diameter of 900nm of son.
A kind of erythrocyte shape grain, is prepared by following steps：
The first step, in terms of mass fraction, by 200 parts of styrene, 10 parts of azodiisobutyronitriles, 50 parts of dodecyl benzene sulfonic acid Sodium and 500 parts of absolute ethyl alcohols and 100 parts of deionized waters are added in 250mL round-bottomed flasks, and 100r/min is stirred to be formed and mixed Liquid, leads to the oxygen in nitrogen 60min removing systems, flask is placed in initiated polymerization in 80 DEG C of water-baths；
Second step, in terms of mass fraction, after reacting 8h, using peristaltic pump by 200 parts of St, 50 parts of divinylbenzenes (DVB) It is added drop-wise to the homogeneous phase solution of 100 parts of absolute ethyl alcohol compositions in reaction system, 10h is persistently added dropwise；After completion of dropwise addition, the reaction was continued To 30h；
3rd step, reaction product carry out centrifuge washing with second alcohol and water repeatedly and remove residual monomer, are freeze-dried 12h, system Obtain erythrocyte shape particle.
Institute Lock particle totality pattern is in erythrocyte shape.Particle diameter is 2.3 μm, and the shape of groove is hemispherical, and groove is straight Footpath is 1000nm.Particle morphology is homogeneous, and has good monodispersity.
A kind of preparation of Lock-and-Key assemblies
In terms of mass fraction, by the erythrocyte shape particle of 200 parts of preparations, (particle diameter is 2.3 μm, and the shape of groove is first Hemispherical, groove diameter 1000nm), 40 parts of poly(N-isopropylacrylamide) mixed with 500 parts of deionized waters, ultrasound 30min, obtains dispersed mixed liquor；Then the spherical acrylic particles dispersion liquid (a diameter of 900nm) 50 parts prepared, It is added drop-wise to the rate of addition of 100 parts/hour in above-mentioned mixed liquor, erythrocyte shape colloidal particle and sphero-colloid can be made The dispersion liquid (dispersion liquid of Lock-and-Key assemblies) of particle assembly body.
The characterizing method of particle assembly body in this embodiment and the implementation and reality of the application in water paint It is identical to apply example 1.The same scanning electron microscope using model FE-SEM, ZEISS ULTRA 55 is to being prepared Lock-and-Key assemblies are characterized, it can be deduced that the Lock-and-Key assemblies that assembling obtains are prepared under the conditions of this and are matched somebody with somebody To rate for 50% or so and aspherical the erythrocyte particle and spheroidal particle that are prepared under the conditions of this size relatively Match somebody with somebody, as shown in figure 8, the assembly obtained on this condition, the matching degree of size is high between particle, realizes 50% matching；Explanation A diameter of 2.3 μm of nonspherical particle, groove diameter 1000nm, a diameter of 900nm of spheroidal particle, spheroidal particle it is a diameter of The 90% of aspherical erythrocyte particle groove diameter, and under the concentration conditions of the emptying reagent, erythrocyte shape colloid grains Son and the assembling effect of spherical colloid particles entirety are good, and assembling form is more unified in figure.Show there is Part-spherical particle in figure Be not assembled in groove, but 50% assembling effect than with the Cheng Zhi peaks assembly phase reported in the literature that cannot stablize Than assembling effect is greatly improved, and Fig. 8 illustrates the assembly prepared on this condition, the matching degree of size between particle Height, it is suitable to empty the concentration of reagent, only one assembling site, does not also deposit the influence of space steric effect, and assembly only exists A form of assembling, and overall assembling effect is preferable.Water-based third is prepared using the four sides blade applicator of model BGD 206/4 The paint film of olefin(e) acid dispersion, using the reflecting spectrograph of model R3~IS50~T carry out reflectance spectrum to obtained film Test, the phenomenon of the iris phenomenon of photonic crystal and homogeneous monochromatic light color film is more obvious, illustrate it is such a under the conditions of be prepared Assembly have huge application value in water paint.
Embodiment 3
A kind of spherical polyacrylic acid (AA) particle, its preparation process are as follows：、
In terms of mass fraction, by 150 parts of acrylic acid (AA), 6 parts of azodiisobutyronitriles (AIBN), 30 parts of polyvinylpyrrolidines Ketone (PVP), 300 parts of absolute ethyl alcohols and 200 parts of deionized waters are added in 250mL four-hole boiling flasks, and 200r/min stirs to be formed Phase solution, leads to the oxygen in nitrogen 45min removing systems, is warming up to 70 DEG C of initiated polymerizations, isothermal reaction 6h.Reaction terminates Afterwards, absolute ethyl alcohol and deionized water are recycled centrifuge washing is carried out to product to remove unreacted monomer and stabilizer, so After be freeze-dried 18h, be made spherical polyacrylic acid particle.
Gained Key particles are spherical PS particles, and spherical PS particle surfaces are smooth, and monodispersity is preferable, spheroidal particle it is straight Footpath is 800nm.
A kind of erythrocyte shape grain, is prepared by following steps：
The first step, in terms of mass fraction, by 130 parts of styrene, 20 parts of methacrylic acids, 6 parts of azodiisobutyronitriles, 30 parts Neopelex and 300 parts of absolute ethyl alcohols and 300 parts of deionized waters are added in 250mL round-bottomed flasks, 200r/min Stirring forms homogeneous phase solution, leads to the oxygen in nitrogen 40min removing systems, and flask is placed in 70 DEG C of water-baths and triggers polymerization anti- Should；
Second step, in terms of mass fraction, after reacting 6h, using peristaltic pump by 100 parts of styrene, 25 parts of divinylbenzenes (DVB) it is added drop-wise to the homogeneous phase solution of 55 parts of absolute ethyl alcohols and 55 parts of deionized water compositions in reaction system, 6h is persistently added dropwise；Drop After adding, the reaction was continued to 25h；
3rd step, reaction product carry out centrifuge washing with second alcohol and water repeatedly and remove residual monomer, are freeze-dried 15h, system Obtain erythrocyte shape particle.
Institute Lock particle totality pattern is in erythrocyte shape.Particle diameter is 2 μm, and the shape of groove is hemispherical, groove diameter For 850nm.Particle morphology is homogeneous, and has good monodispersity.
A kind of preparation of Lock-and-Key assemblies
In terms of mass fraction, by the erythrocyte shape particle of 150 parts of preparations, (particle diameter is 2 μm, and the shape of groove is half first Spherical, a diameter of 850nm of hemispherical of groove), 35 parts of polyethylene glycol oxide (PEO) and 200 parts of deionized waters and 300 parts it is anhydrous Ethanol mixes, and ultrasonic 25min, obtains dispersed mixed liquor；Then it is the spherical PS particles of 25 parts of preparations is (a diameter of 800nm) it is added drop-wise to the rate of addition of 30 parts/hour in above-mentioned mixed liquor, erythrocyte shape colloidal particle and spherical glue is made The dispersion liquid (dispersion liquid of Lock-and-Key assemblies) of body particle assembly body.
The characterizing method of particle assembly body in this embodiment and the implementation and reality of the application in water paint It is identical to apply example 1.The same scanning electron microscope using model FE-SEM, ZEISS ULTRA 55 is to being prepared Lock-and-Key assemblies are characterized, it can be deduced that the Lock-and-Key assemblies that assembling obtains are prepared under the conditions of this and are matched somebody with somebody To rate for 45% or so and aspherical the erythrocyte particle and spheroidal particle that are prepared under the conditions of this size relatively Match somebody with somebody, as shown in figure 9, the assembly obtained on this condition, the matching degree of size is high between particle, realizes 45% matching；Explanation A diameter of 2 μm of nonspherical particle, groove diameter 850nm, a diameter of 800nm of spheroidal particle, spheroidal particle it is a diameter of non- The 94.1% of spherical erythrocyte particle groove diameter, and under the concentration conditions of the emptying reagent, erythrocyte shape colloid grains Son and the assembling effect of spherical colloid particles entirety are good, and assembling form is more unified.Show there is Part-spherical particle not have in figure Be assembled in groove, but 45% assembling effect than compared with the Cheng Zhi peaks assembly reported in the literature that cannot stablize it Under, assembling effect is greatly improved, and it is good to empty the concentration of reagent, and only one assembling site, does not deposit steric hindrance effect yet The influence answered, assembly only exists a form of assembling, and overall assembling effect is preferable.Use model BGD 206/4 Four sides blade applicator prepare water soluble acrylic acid dispersion paint film, using model R3~IS50~T reflecting spectrograph to The phenomenon of the test of the film progress reflectance spectrum arrived, the iris phenomenon of photonic crystal and homogeneous monochromatic light color film is more obvious, says Understand it is such a under the conditions of the assembly that is prepared have huge application value in water paint.
Embodiment 4
A kind of spherical polyacrylic acid/methyl acrylate particle, its preparation process are as follows：
In terms of mass fraction, by 170 parts of acrylic acid (AA), 30 parts of methyl acrylates (MAA), 8 parts of azodiisobutyronitriles (AIBN), 10 parts of polyvinylpyrrolidones (PVP), 10 parts of absolute ethyl alcohols and 100 parts of deionized waters are added to 250mL four-hole boiling flasks In, 200r/min stirs to form homogeneous phase solution, leads to the oxygen in nitrogen 45min removing systems, is warming up to 80 DEG C and triggers polymerization anti- Should, isothermal reaction 6h.After reaction, absolute ethyl alcohol and deionized water are recycled centrifuge washing is carried out to product to remove not The monomer and stabilizer of reaction, are then freeze-dried 18h, and spheroidal particle is made.
Gained Key particles are spherical AA/MAA particles, and spherical AA/MAA particle surfaces are smooth, and monodispersity is preferable, it is most A diameter of 1000nm of big and more existing spheroidal particle or so.
A kind of erythrocyte shape grain, is prepared by following steps：
The first step, in terms of mass fraction, by 180 parts of acrylic acid (AA), 20 parts of methyl acrylates (MAA), 6 parts of persulfuric acid Potassium, 30 parts of polyvinylpyrrolidones, 150 parts of absolute ethyl alcohols and 150 parts of deionized waters are added in 250mL round-bottomed flasks, 200r/ Min stirs to form homogeneous phase solution, leads to the oxygen in nitrogen 40min removing systems, and flask is placed in 70 DEG C of water-baths and triggers polymerization Reaction；
Second step, in terms of mass fraction, after reacting 6.5h, using peristaltic pump by 100 parts of AA, 20 parts of divinylbenzenes (DVB) it is added drop-wise to the homogeneous phase solution of 50 parts of absolute ethyl alcohols and 50 parts of deionized water compositions in reaction system, 4h is persistently added dropwise；Drop After adding, the reaction was continued to 20h；
3rd step, reaction product carry out centrifuge washing with second alcohol and water repeatedly and remove residual monomer, are freeze-dried 15h, system Obtain erythrocyte shape particle.
Institute Lock particle totality pattern is in erythrocyte shape.Particle morphology is homogeneous, and monodispersity is also preferable, average aspherical A diameter of 2.5 μm of particle, groove diameter 1200nm.
A kind of preparation of Lock-and-Key assemblies
In terms of mass fraction, by the erythrocyte shape particle of 150 parts of preparations, (a diameter of 2.5 μm, groove diameter is first 1200nm), 40 parts of poly(N-isopropylacrylamide) is mixed with 200 parts of deionized waters with 200 parts of absolute ethyl alcohols, ultrasound 25min, obtains dispersed mixed liquor；Then will disposably be added by the spheroidal particle (a diameter of 1000nm) of 25 parts of preparations Into above-mentioned mixed liquor, the Lock-and-Key assemblies containing erythrocyte shape colloidal particle and spherical colloid particles are made.
The characterizing method of particle assembly body in this embodiment and the implementation and reality of the application in water paint It is identical to apply example 1.The same scanning electron microscope using model FE-SEM, ZEISS ULTRA 55 is to being prepared The amplification of Lock-and-Key assemblies is characterized, it can be deduced that the Lock-and-Key assemblings that assembling obtains are prepared under the conditions of this Body pairing rate for 35% or so and aspherical the erythrocyte particle and spheroidal particle that are prepared under the conditions of this size more Match somebody with somebody, as shown in Figure 10, the assembly obtained on this condition, the matching degree of size is high between particle, realizes 35% matching；Explanation A diameter of 2.5 μm of nonspherical particle, groove diameter 1200nm, a diameter of 1000nm of spheroidal particle, the diameter of spheroidal particle For the 83.3% of aspherical erythrocyte particle groove diameter, and under the concentration conditions of the emptying reagent, erythrocyte shape glue Body particle and the assembling effect of spherical colloid particles entirety are good, and assembling form is more unified.Use the four of model BGD 206/4 Face blade applicator prepares the paint film of water soluble acrylic acid dispersion, using the reflecting spectrograph of model R3~IS50~T to obtaining Film carry out the test of reflectance spectrum, the phenomenon of the iris phenomenon of photonic crystal and homogeneous monochromatic light color film is more obvious, illustrates The assembly being prepared under the conditions of such a has huge application value in water paint.

Claims (9)

1. erythrocyte shape colloidal particle and spherical colloid particles assembly, it is characterised in that inlayed by spheroidal particle into blood red In the groove of cellular particle, both closely fit together, and form assembly；The particle diameter of the spheroidal particle is 500nm ~1300nm；Erythrocyte shape particle, particle diameter are 1~5 μm, and the shape of groove is hemispherical, a diameter of 600nm of groove~ 1500nm；And the particle diameter of spheroidal particle is the 80%-100% of the groove diameter of erythrocyte shape particle；
The erythrocyte shape particle is prepared by following steps：
The first step, in terms of mass fraction, by 100~200 parts of monomer, 2~10 parts of initiator, 10~50 parts of surface-active Agent, 100~500 parts of absolute ethyl alcohols and 100~500 parts of water mixing, stirring form homogeneous phase solution, lead to the oxygen in nitrogen removing system Gas, is placed in initiated polymerization in 60~80 DEG C of water-baths；
Second step, in terms of mass fraction, after 4~8h of polymerisation, then by 0~200 part of monomer, 5~50 parts of crosslinking agent and Homogeneous phase solution being slowly dropped in reaction system with 1~100 part/hour of 10~100 parts of absolute ethyl alcohol composition, lasting drop Add 2~10h；After completion of dropwise addition, the reaction was continued to 20~30h；
3rd step, is centrifuged repeatedly washing by reaction product and removes unreacted monomer and surfactant, freeze-drying, is made blood Red blood cell shape particle；
The monomer be acrylic acid, methyl acrylate, butyl acrylate, methyl methacrylate and styrene in one kind or It is a variety of；
The initiator is potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate, azodiisobutyronitrile, azobisisoheptonitrile and peroxide Change the one or more in benzoyl；
The surfactant is neopelex, lauryl sodium sulfate, polyvinylpyrrolidone and alkenyl sulphur One or more in sour sodium；
The crosslinking agent is divinylbenzene, diisocyanate, N, N~methylene-bisacrylamide, cumyl peroxide In one or more.
2. erythrocyte shape colloidal particle according to claim 1 and spherical colloid particles assembly, it is characterised in that institute Spheroidal particle is stated to be prepared via a method which：In terms of mass fraction, by 100~200 parts of monomers, 2~10 parts of initiators, 10~50 Part surfactant, 100~500 parts of absolute ethyl alcohols and 100~300 parts of deionized waters mixing, 100~300r/min stir to be formed Homogeneous phase solution, leads to the oxygen in nitrogen removing system, is warming up to 60~80 DEG C of initiated polymerizations, 4~8h of isothermal reaction；Reaction After, centrifuge washing is carried out to product repeatedly, is then freeze-dried, spheroidal particle is made；
The monomer be acrylic acid, methyl acrylate, butyl acrylate, methyl methacrylate and styrene in one kind or It is a variety of；
The initiator is potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate, azodiisobutyronitrile, azobisisoheptonitrile and peroxide Change the one or more in benzoyl；
The surfactant is neopelex, lauryl sodium sulfate, polyvinylpyrrolidone and alkenyl sulphur One or more in sour sodium.
3. erythrocyte shape colloidal particle according to claim 2 and spherical colloid particles assembly, it is characterised in that institute The time for stating logical nitrogen is 30~60min；The time of freeze-drying is 12~24h.
4. erythrocyte shape colloidal particle according to claim 1 and spherical colloid particles assembly, it is characterised in that the The time of logical nitrogen in one step is 30~60min；The time being freeze-dried in 3rd step is 12~24h.
5. erythrocyte shape colloidal particle according to claim 1 and spherical colloid particles assembly, it is characterised in that institute The solvent that the centrifuge washing stated is used is the one or more in methanol, ethanol, acetone and deionized water.
6. the preparation method of any one of Claims 1 to 5 erythrocyte shape colloidal particle and spherical colloid particles assembly, It is characterized in that：In terms of mass fraction, by 100~200 parts of erythrocyte shape particles, 10~50 parts emptying reagents with and 100~ 500 parts of deionized waters and 100~500 parts of absolute ethyl alcohol mixing, ultrasonic disperse, obtains mixed liquor；Then it is spherical by 10~50 parts Particle dispersion is slowly dropped in mixed liquor with the rate of addition of 1~100 part/hour, and erythrocyte shape colloidal particle is made With spherical colloid particles assembly；
The emptying reagent is polyethylene glycol oxide or poly(N-isopropylacrylamide).
7. the preparation method of erythrocyte shape colloidal particle according to claim 6 and spherical colloid particles assembly, its It is characterized in that, the time of the ultrasonic disperse is 20~30min.
8. the preparation method of erythrocyte shape colloidal particle according to claim 6 and spherical colloid particles assembly, its It is characterized in that, the drop rate of the spheroidal particle dispersion liquid is 10~100 parts/hour.
9. any one of Claims 1 to 5 erythrocyte shape colloidal particle and spherical colloid particles assembly are in photonic crystal Application in water paint.
CN201711173551.8A 2017-11-22 2017-11-22 Erythrocyte shape colloidal particle and spherical colloid particles assembly and the preparation method and application thereof Active CN107955477B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711173551.8A CN107955477B (en) 2017-11-22 2017-11-22 Erythrocyte shape colloidal particle and spherical colloid particles assembly and the preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711173551.8A CN107955477B (en) 2017-11-22 2017-11-22 Erythrocyte shape colloidal particle and spherical colloid particles assembly and the preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN107955477A true CN107955477A (en) 2018-04-24
CN107955477B CN107955477B (en) 2019-10-18

Family

ID=61963836

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711173551.8A Active CN107955477B (en) 2017-11-22 2017-11-22 Erythrocyte shape colloidal particle and spherical colloid particles assembly and the preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN107955477B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112928013A (en) * 2019-12-05 2021-06-08 天津大学 Method for controlling particle orientation using curved surfaces and evacuation attraction potential

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101429359A (en) * 2008-12-08 2009-05-13 山西鹰鲲科技有限公司 Water-based plastic composite inner-printing ink
CN105732905A (en) * 2016-04-12 2016-07-06 华南理工大学 Raspberry-shaped organic/organic compound emulsion particles and preparation method thereof
CN105777968A (en) * 2016-03-25 2016-07-20 华南理工大学 Preparation method for monodisperse cap-shaped non-spherical emulsion particles
CN106987818A (en) * 2017-05-03 2017-07-28 吉林师范大学 A kind of cellular TiO2Ag nano-complexes and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101429359A (en) * 2008-12-08 2009-05-13 山西鹰鲲科技有限公司 Water-based plastic composite inner-printing ink
CN105777968A (en) * 2016-03-25 2016-07-20 华南理工大学 Preparation method for monodisperse cap-shaped non-spherical emulsion particles
CN105732905A (en) * 2016-04-12 2016-07-06 华南理工大学 Raspberry-shaped organic/organic compound emulsion particles and preparation method thereof
CN106987818A (en) * 2017-05-03 2017-07-28 吉林师范大学 A kind of cellular TiO2Ag nano-complexes and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
ANKE KUIJK等: "Synthesis of Monodisperse, Rodlike Silica Colloids with Tunable Aspect Ratio", 《JOURNAL OF AMERICAN CHEMICAL SOCIETY》 *
HUIFANG SHEN等: "Morphology control of anisotropic nonspherical functional polymeric particles by one-pot dispersion polymerization", 《REACTIVE AND FUNCTIONAL POLYMERS》 *
STEFANO SACANNA等: "Magnetic Click Colloidal Assembly", 《JOURNAL OF AMERICAN CHEMICAL SOCIETY》 *
程志峰等: "凹陷状胶体粒子的自组装", 《南京大学学报（自然科学）》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112928013A (en) * 2019-12-05 2021-06-08 天津大学 Method for controlling particle orientation using curved surfaces and evacuation attraction potential
CN112928013B (en) * 2019-12-05 2022-10-04 天津大学 Method for controlling particle orientation using curved surfaces and evacuation attraction potential

Also Published As

Publication number Publication date
CN107955477B (en) 2019-10-18

Similar Documents

Publication Publication Date Title
CN103409801B (en) A kind of preparation method of high intensity crosslinking polymer crystal film with photon
CN113321758B (en) Carboxyl-modified aggregation-induced emission polymer microsphere and preparation method and application thereof
CN106547040B (en) A kind of high intensity crystal film with photon and preparation method thereof
RU2591158C2 (en) Crystalline colloidal arrays with high reflecting capacity, including radiation-absorbing particles
CN109031476A (en) Have both the preparation method of stable structure and brightly painted patterning photon crystal structure chromogenic materials
CN104628923A (en) Method for preparing aggregation-induced emission type polymer fluorescent nanoparticle through mini-emulsion polymerization initiated by oil-soluble initiator
CN102492073A (en) Quantum dot-based multifunctional magnetic fluorescent microsphere and its preparation method
CN110396148A (en) A kind of magnetic polystyrene microsphere and preparation method thereof
CN107955477B (en) Erythrocyte shape colloidal particle and spherical colloid particles assembly and the preparation method and application thereof
WO2011121821A1 (en) Resin particle having convex portions on surface, method for producing same, and coating composition, coating material, and preparation for external use, each using same
CN110183703A (en) A kind of photonic crystal composite type pressure sensor and preparation method thereof and optical detecting method
CN103409802A (en) Preparation method of opal-structure polymer photonic crystal
CN104892815B (en) Surface positively charged fluorescent nanometer microsphere and its biologic applications with aggregation inducing Fluorescence Increasing property
CN108227055B (en) Preparation method and application of visible light reflecting film
JP2011164469A (en) Compact having photonic crystal structure and method of manufacturing the same
CN111072832B (en) Iridescent liquid crystal photonic crystal material and preparation method thereof
CN109957054A (en) A kind of preparation method of the monodispersity nanoscale polystyrene microsphere of size tunable
CN113289560B (en) Method for synthesizing Janus nano particles by taking Janus nano emulsion as template
JP2008165030A (en) Manufacturing method of photonic crystal membrane and photonic crystal membrane obtained thereby
CN1318539C (en) Luminous microsphere and its production method and water dispersion system
KR20180132703A (en) METAL COATED RESIN RESIN PARTICLE AND METHOD FOR MANUFACTURING THE SAME, METHOD FOR MANUFACTURING THE SAME, METHOD OF MANUFACTURING PARTICLE GROUP, AND METHOD FOR PREPARING PARTICLE ARRAY FILM
CN105777968A (en) Preparation method for monodisperse cap-shaped non-spherical emulsion particles
CN111875744A (en) Method for preparing fluorescent microspheres and corresponding fluorescent microspheres
Gao et al. Polymeric nanomaterials with aggregation-induced emission characteristics
CN101519472A (en) Composition for preparing capsule wall of hollow micro-capsule and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant