CN107955477B - Erythrocyte shape colloidal particle and spherical colloid particles assembly and the preparation method and application thereof - Google Patents
Erythrocyte shape colloidal particle and spherical colloid particles assembly and the preparation method and application thereof Download PDFInfo
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- 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
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- 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
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- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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- 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
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- C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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Abstract
The invention discloses erythrocyte shape colloidal particles and spherical colloid particles assembly and the preparation method and application thereof.The assembly is inlayed by spheroidal particle into the groove of erythrocyte shape particle, and the two closely fits together, and forms assembly；The partial size of the spheroidal particle is 500nm~1300nm；Erythrocyte shape particle, partial size are 1~5 μm, and the shape of groove is hemispherical, and the diameter of groove is 600nm~1500nm；And the partial size of spheroidal particle is the 80%-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 promoted, 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
Technical field
The present invention relates to polymer latex particles self-assembling technique fields, 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
Preparation method and application.
Background technique
High performance structures material is support aerospace, communications and transportation, photoelectric information, the great base of energy source and power and country
The important material base in the fields such as plinth engineering construction is most hotly competitive one of hi tech and new material field in the world at present.
Polymeric colloid particle is widely used in the building 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 unique application, have widened the application range of colloidal solid, significantly to regulate and control and designing new structure
Material provides new dimension.The photonic crystal such as prepared based on traditional spheric granules, characteristic indication are photonic band
Gap is very limited；And the band of photonic crystal is expanded for the photonic crystal of basic particle preparation with aspherical colloidal particle significantly
The gap limit, the development for photonic crystal in photoelectric field provide new approaches.In recent years, the application of photonic crystal is also increasingly
Extensively, especially in the application field of the water paint of photonic crystal, good achievement is achieved, currently based on spheroidal particle
Photonic crystal optical effect in special car coating, gradually start to be commercialized, and it is aspherical have superior performance,
Also among research.Not in view of physical characteristics such as the Van der Waals force on nonspherical particle surface, distribution of charges, curvature, refractive index
It is same as spheroidal particle, just produces the characteristics such as peculiar physical phenomenon 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 generates product system and application field more abundant.
Currently, anisotropy aspherical particle and spherical polymer colloidal solid pass through self assembly (self-assembly)
It is with important application prospects to construct structural material.By this method, material can be constructed based on nanometer or micron level,
Rather than the synthesis of traditional atom or molecular level, it can get revolutionary new material.Between aspherical colloidal particle from
Assembling generally refers to colloidal particle under to extraneous response, by forming certain structure, shape or generating certain behavior
To balance external influence.
The self-assembling method of nonspherical particle mainly include field drives self assembly, electric field driven self assembly and Depletion Force from
Assemble three kinds of methods.For externally-applied magnetic field self assembly, it is desirable that nonspherical particle itself wants that response can be generated to externally-applied magnetic field, and gathers
Closing object latex particle itself is not have magnetism, therefore magnetic particle will be used to modify polymer latex particles, is made
Response (Sacanna S., Rossi L., Pine David J., Magnetic can be generated to magnetic field 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 inefficient, bad dispersibility, complex procedures, repeatable difference etc..Under normal circumstances,
It is unrelated whether aggregation of the aspheric particle under AC field is then charged with particle, and particle can all be polarized under AC field and be produced
Raw electric dipole moment, will appear 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 needed, 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, self assembly [J] Nanjing University of Cheng Zhifeng, Luo Fuhua recess colloidal particle such as Cheng Zhifeng
Learn), 2014,01:23-29) using the self assembly of dissipation self-assembly method progress groove-like colloidal particle and spherical shape PS particle；The party
The solid powder of nonspherical particle solid powder and spheroidal particle 1:4 in mass ratio is dispersed in water by method first, is made into
The aqueous solution of 1.0wt% takes this small amount of aqueous solution on glass slide, the PEO aqueous solution that concentration is 0.5g/L is then added dropwise, in light
Learn self assembly situation of the microscopically observation particle at PEO gradually Dissipative condition.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 is it is not possible that while group
Fill multiple particles；Allow to assemble multiple particles, the difference for assembling site causes that there are a variety of inconsistent assembly forms；
The especially technology matching of not recognizing 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
It connects 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.
Summary of the invention
The present invention be directed to the deficiencies in the prior art, provide that 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.
In order to achieve the above objectives, the invention provides the following technical scheme:
Erythrocyte shape colloidal particle and spherical colloid particles assembly, which is characterized in that inlayed by spheroidal particle into blood
In the groove of red blood cell shape particle, the two is closely fitted together, and forms assembly；
The partial size of the spheroidal particle is 500nm~1300nm；Erythrocyte shape particle, partial size are 1~5 μm, groove
Shape is hemispherical, and the diameter of groove is 600nm~1500nm；And the partial size of spheroidal particle is the groove of 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 dehydrated 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 polymerization reaction, then by 0~200 part of monomer, 5~50 parts of crosslinking
Homogeneous phase solution being slowly dropped in reaction system with 1~100 part/hour of agent and 10~100 parts of dehydrated alcohol composition, holds
It is continuous that 2~10h is added dropwise；After completion of dropwise addition, the reaction was continued to 20~30h；
Reaction product is centrifuged repeatedly washing and removes unreacted monomer and surfactant, is freeze-dried by third step, system
Obtain erythrocyte shape particle；
The monomer is one of acrylic acid, methyl acrylate, butyl acrylate, methyl methacrylate and styrene
Or it is a variety of；
The initiator be potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate, azodiisobutyronitrile, azobisisoheptonitrile and
One or more of benzoyl peroxide；
The surfactant is neopelex, lauryl sodium sulfate, polyvinylpyrrolidone and alkene
One or more of base sodium sulfonate；
The crosslinking agent is divinylbenzene, diisocyanate, N, and N~methylene-bisacrylamide, peroxidating two are different
One or more of propyl benzene.
To further 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 dehydrated 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 is carried out to product repeatedly, it is then cold
Dry, obtained spheroidal particle is lyophilized；
The monomer is one of acrylic acid, methyl acrylate, butyl acrylate, methyl methacrylate and styrene
Or it is a variety of；
The initiator be potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate, azodiisobutyronitrile, azobisisoheptonitrile and
One or more of benzoyl peroxide；
The surfactant is neopelex, lauryl sodium sulfate, polyvinylpyrrolidone and alkene
One or more of base sodium sulfonate.
Preferably, the time of the logical nitrogen is 30~60min；The time of freeze-drying is 12~for 24 hours.
Preferably, the time of the logical nitrogen in the first step is 30~60min；The time being freeze-dried in third step be 12~
24h。。
Preferably, the solvent that the centrifuge washing is used be one of methanol, ethyl alcohol, acetone and deionized water 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 with and 100~500 parts of deionized waters and 100~500 parts of nothings
Water-ethanol mixing, ultrasonic disperse obtain 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 monodisperse hat shape
Preparation method, specifically disclose a kind of synthetic method of semicontinuous charging of dispersin polymerization to prepare monodispersed aspherical grain
The particle of son, this method preparation has the characteristics that polymolecularity and single groove；If this particle is applied to assembling
In system, it is also just uniform that space steric effect, the form of obtained assembly is just not present, and can pass through and adjust synthesis side
Method, the nonspherical particle and spheroidal particle of available 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 form the clad of one layer of emptying reagent molecule, referred to as exclusion layer, due to particle and 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 reagent molecule free volume is emptied in system and is increased, system entropy is caused to increase, drives particle from group
Dress.It is a discovery of the invention that rationally control emptying reagent concentration, will generate biggish Depletion Force, the size of spheroidal particle needs and blood
The size of red blood cell shape particle surface recess has the matching degree of 80%-100%, i.e. the diameter of spheroidal particle is that groove particle is straight
When the 80-100% of diameter, 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, main to cash are as follows: poly- first with semicontinuous dispersal of feed
The method of conjunction has synthesized monodisperse hat shape, nonspherical particle with single groove, and in assembling, there is no steric hindrances to imitate
It answers, the form of assembly is also than more uniform, and only a kind of structural body generates, and the size of spheroidal particle and nonspherical particle can
It is controlled with simple adjustment, to realize the self assembly of high matching degree between erythrocyte shape particle and spheroidal particle.
It is important that the method by control emptying reagent concentration and suitably stirring, makes the concentration for emptying reagent in entire body
Be in system it is equally distributed, this like-particles obtains matched probability and increases substantially, while assembling effect is also significantly promoted.
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 partial size, erythrocyte shape particle and spheroidal particle when empties reagent quality concentration and waits simple operations success
Realize the accurate control of erythrocyte shape particle and spheroidal particle self assembly.
3) the improved method process that self assembly is carried out 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 the existing some nonspherical particles (such as dumbbell shaped, Xue Renzhuan, ellipsoid) being used in terms of colloidal crystal
It compares, assembly produced by the present invention not only has the anisotropy on pattern and structure, but also assembled assembly is transported
In terms of photonic crystal water paint, traditional mill base or pigment can replace, and can make coating that there is special optical property.
The Lock-and-Key assembly is applied in photonic crystal water paint, can show gorgeous color, it is this due to
Particle itself is the phenomenon that causing the refraction and reflection to light source in physics microstructure, stable structure, the reflection to light
It is will never fade in the case that rate is high and structure is not destroyed.
Detailed description of the invention
Fig. 1 is partial size 800nm spherical polystyrene (PS) particle SEM picture prepared by embodiment 1.
Fig. 2 is erythrocyte shape particle SEM picture prepared by embodiment 1.
Fig. 3 is single Lock-and-Key assembly electron microscopic picture made from embodiment 1.
Fig. 4 is entirety Lock-and-Key assembly electron microscopic picture 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 of the preparation of Lock-and-Key assembly made from embodiment 1
Piece.
Fig. 7 is that the monochromatic orange-yellow photonic crystal of monofilm of the preparation of Lock-and-Key assembly made from embodiment 1 is anti-
Penetrate spectrogram.
Fig. 8 is the electron microscope of erythrocyte shape particle made from embodiment 2 and spherical polymethylacrylic acid particle assembly body
Piece.
Fig. 9 is the electron microscopic picture of erythrocyte shape particle made from embodiment 3 and 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.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and examples, it should be noted that embodiment is not constituted
Restriction to the claimed scope of the invention.
Embodiment 1
A kind of spherical polystyrene (PS) particle, 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 flask, 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 product to remove unreacted monomer and stabilizer, is then freeze-dried 12h, and spherical shape PS is made
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 particle observed, it can be seen from the figure that spherical shape PS
Particle surface is smooth, and granular size is uniform, has good monodispersity, and the diameter of spheroidal particle is 800nm, Fig. 1 in figure
Illustrate the particle that the spherical PS of our required sizes is successfully prepared by above-mentioned condition.
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 flask, and 300r/min stirs to form homogeneous phase solution, lead to nitrogen
Flask is placed in initiated polymerization in 80 DEG C of water-baths by the oxygen in 30min removing system；
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 dehydrated 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；
Third step, reaction product carry out centrifuge washing with second alcohol and water repeatedly and remove residual monomer, and freeze-drying for 24 hours, is made
Obtain erythrocyte shape particle.
Using the scanning electron microscope of model FE-SEM, ZEISS ULTRA 55 to the erythrocyte shape being 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 partial size is 3 μm, has single groove, and the shape of center groove is half
Spherical shape, the hemispheric diameter of groove are 800nm.The non-particle morphology of erythrocyte shape is uniform, and has good monodisperse
Property, it illustrates to be successfully prepared the aspherical erythrocyte styrene/acrylic particle for needing size by above-mentioned condition.
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, (partial size is 3 μm, center groove first
Shape is hemispherical, and the diameter of hemispherical groove is 800nm), 20 parts of polyethylene glycol oxides (PEO) and 450 parts of deionized waters are mixed
It closes, ultrasonic 20min obtains evenly dispersed mixed liquor；Then by 10 parts of above-mentioned spherical shape PS particles (diameter 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 assembly) of body.
Using the scanning electron microscope of model FE-SEM, ZEISS ULTRA 55 to the Lock-and- being prepared
Key assembly amplifies 30000 times and is characterized, and Fig. 3 is the single Lock-and-Key assembly electron microscope observed, from Fig. 3
In can be clearly seen that spherical PS particle (Key particle) is tightly inlayed as key into erythrocyte shape particle (Lock
Particle) groove in, the two closely steadily fits together, if PS particle is detached from the groove of nonspherical particle
If, according to the law of thermodynamics, this process is that whole system entropy is made to reduce process, this process is not spontaneous process, it is necessary to be provided
Additional energy, thus obtain Lock-and-Key assembly is very stable.Fig. 3 illustrates to prepare by above-mentioned condition aspherical
Erythrocyte particle and spherical PS particle successfully complete self assembly.
Simultaneously using the scanning electron microscope of model FE-SEM, ZEISS ULTRA 55 to the Lock- being prepared
And-Key assembly amplifies 10000 times and is characterized, and Fig. 4 is the scanning electron microscopic picture of assembly overall package effect obtained,
The Lock-and-Key assembly finished is largely assembled it can be seen from the figure that existing in figure, pairing rate is 75% or so, this is matched
To effect compared in contrast, assembling effect obtains significantly with the peak Cheng Zhi assembly that cannot be stable reported in the literature
It is promoted.Fig. 4 illustrates the assembly prepared with this condition, and the matching degree of size is high between particle, realizes 75% matching；Illustrate non-
The diameter of spheroidal particle is 3 μm, groove diameter 800nm, and spheroidal particle diameter is 800nm 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.Only one is assembled under this condition
The influence of space steric effect is not deposited in site.
The dispersion liquid 5g of Lock-and-Key assembly obtained above is added to the water-and acrylate lotion of 20g
In, after ultrasonic disperse 10min, lightly prepared on 10*5 centimetres of asbestos board with the four sides blade applicator of model BGD 206/4
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 apparent paint film presents mottled
Varicoloured, prismy rainbow effect, similar to the appearance of opal, this is because the Lock-and-Key assembly in paint film
Middle nonspherical particle is tightly inlayed as key with spherical shape PS particle (Key particle) into (Lock, erythrocyte shape particle
Son) groove in, the two closely steadily fits 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
It causes to enter the light of observer to be 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 assembly in aqueous emulsion paint, can apply in water paint,
It is used instead of conventional pigment and pigment, great change will be made to traditional pigment manufacturing.
The dispersion liquid 1g for equally taking the Lock-and-Key assembly in Fig. 3, is slowly dropped to liquid-transfering gun and fills water
In culture dish (diameter of culture dish is 6 centimetres, is 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, gravity under the action of, auto-deposition obtains uniformly in culture dish bottom glass
One tunic, as shown in Figure 6, it can be seen that color is uniform 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 the test of reflectance spectrum to obtained orange film, obtains reflectance spectrum as shown in Figure 7
Figure, for the maximum value of reflectance spectrum present in 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 assembly illustrated is 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, by adjusting the size of the nonspherical particle and spheroidal particle also film of other available colors completely, and 41%
Reflectivity illustrates the case where reflection is very high, and the brightness of color, plumpness are good as seen from the figure, and its stable structure 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 structure color
Apt to deteriorate, the aging to replace, the chemical color of migration have very big market and application value.
Embodiment 2
A kind of spherical shape polymethyl acid particles, 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 dehydrated alcohols and 100 parts of deionized waters are added in 250mL four-hole boiling flask, and 100r/min stirs to be formed homogeneously
Solution leads to the oxygen in nitrogen 60min removing system, is warming up to 80 DEG C of initiated polymerizations, isothermal reaction 8h.Reaction terminates
Afterwards, dehydrated alcohol and deionized water are recycled, centrifuge washing is carried out to remove unreacted monomer and stabilizer, so to product
After be freeze-dried for 24 hours, spherical shape metering system acid particles are made.
Gained Key particle is that spherical methacrylic acid particle surface is smooth, and monodispersity is preferable, and size is more unified, grain
Sub- diameter is 900nm.
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 dehydrated alcohols and 100 parts of deionized waters are added in 250mL round-bottomed flask, and 100r/min is stirred to be formed and be mixed
Liquid leads to the oxygen in nitrogen 60min removing system, 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 in reaction system with the homogeneous phase solution of 100 parts of dehydrated alcohols composition, 10h is persistently added dropwise；After completion of dropwise addition, the reaction was continued
To 30h；
Third 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.Partial size is 2.3 μm, and the shape of groove is hemispherical, and groove is straight
Diameter is 1000nm.Particle morphology is uniform, and has good monodispersity.
A kind of preparation of Lock-and-Key assembly
In terms of mass fraction, (partial size is 2.3 μm to the erythrocyte shape particle for first preparing 200 parts, and the shape of groove is
Hemispherical, groove diameter 1000nm), 40 parts of poly(N-isopropylacrylamide) mixed with 500 parts of deionized waters, ultrasound
30min obtains evenly dispersed mixed liquor；Then the spherical acrylic particles dispersion liquid (diameter 900nm) 50 parts prepared,
It is added drop-wise in above-mentioned mixed liquor with the rate of addition of 100 parts/hour, erythrocyte shape colloidal particle and sphero-colloid can be made
The dispersion liquid (dispersion liquid of Lock-and-Key assembly) of particle assembly body.
The characterizing method of particle assembly body in this embodiment and the implementation method 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 assembly is characterized, it can be deduced that is prepared the Lock-and-Key assembly that assembling obtains under this condition and is matched
Be 50% or so to rate and the size of aspherical erythrocyte particle and spheroidal particle for preparing under this condition relatively
Match, as shown in figure 8, the assembly obtained with this condition, the matching degree of size is high between particle, realizes 50% matching；Explanation
The diameter of nonspherical particle is 2.3 μm, groove diameter 1000nm, and spheroidal particle diameter is 900nm, and the diameter of spheroidal particle is
The 90% of aspherical erythrocyte particle groove diameter and the concentration conditions of the emptying reagent under, 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 compared with the peak Cheng Zhi assembly phase that cannot be stable reported in the literature
Than assembling effect is greatly improved, and Fig. 8 illustrates the assembly prepared with this condition, the matching degree of size between particle
Height, the concentration for emptying reagent is suitable, only one assembling site does not deposit the influence of space steric effect, assembly only exists yet
A form of assembling, and whole assembling effect is preferable.Aqueous third is prepared using the four sides blade applicator of model BGD 206/4
The paint film of olefin(e) acid dispersion carries out reflectance spectrum to obtained film using model R3~IS50~T reflecting spectrograph
Test, the phenomenon that iris phenomenon of photonic crystal and uniform monochromatic light color film, are more obvious, illustrate it is such under the conditions of be prepared
Assembly have huge application value in water paint.
Embodiment 3
A kind of spherical shape polyacrylic acid (AA) particle, 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 dehydrated alcohols and 200 parts of deionized waters are added in 250mL four-hole boiling flask, and 200r/min stirs to be formed
Phase solution leads to the oxygen in nitrogen 45min removing system, is warming up to 70 DEG C of initiated polymerizations, isothermal reaction 6h.Reaction terminates
Afterwards, dehydrated alcohol and deionized water are recycled, centrifuge washing is carried out to remove unreacted monomer and stabilizer, so to product
After be freeze-dried 18h, spherical shape polyacrylic acid particle is made.
Gained Key particle be spherical shape PS particle, spherical PS particle surface is smooth, and monodispersity is preferable, spheroidal particle it is straight
Diameter 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 dehydrated alcohols and 300 parts of deionized waters are added in 250mL round-bottomed flask, 200r/min
Stirring forms homogeneous phase solution, leads to the oxygen in nitrogen 40min removing system, and flask is placed in 70 DEG C of water-baths and causes polymerization instead
It answers；
Second step, in terms of mass fraction, after reacting 6h, using peristaltic pump by 100 parts of styrene, 25 parts of divinylbenzenes
(DVB) and 55 parts of dehydrated alcohols and 55 parts of deionized waters composition homogeneous phase solution be added drop-wise in reaction system, 6h is persistently added dropwise；Drop
After adding, the reaction was continued to 25h；
Third 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.Partial size is 2 μm, and the shape of groove is hemispherical, groove diameter
For 850nm.Particle morphology is uniform, and has good monodispersity.
A kind of preparation of Lock-and-Key assembly
In terms of mass fraction, (partial size is 2 μm to the erythrocyte shape particle for first preparing 150 parts, and the shape of groove is half
Spherical shape, the hemispherical diameter of groove is 850nm), 35 parts of polyethylene glycol oxide (PEO) and 200 parts of deionized waters and 300 parts are anhydrous
Ethyl alcohol mixing, ultrasonic 25min obtain evenly dispersed mixed liquor；Then (diameter is the spherical PS particle 25 parts prepared
It 800nm) is added drop-wise in above-mentioned mixed liquor with the rate of addition of 30 parts/hour, erythrocyte shape colloidal particle and spherical glue is made
The dispersion liquid (dispersion liquid of Lock-and-Key assembly) of body particle assembly body.
The characterizing method of particle assembly body in this embodiment and the implementation method 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 assembly is characterized, it can be deduced that is prepared the Lock-and-Key assembly that assembling obtains under this condition and is matched
Be 45% or so to rate and the size of aspherical erythrocyte particle and spheroidal particle for preparing under this condition relatively
Match, as shown in figure 9, the assembly obtained with this condition, the matching degree of size is high between particle, realizes 45% matching；Explanation
The diameter of nonspherical particle is 2 μm, groove diameter 850nm, and spheroidal particle diameter is 800nm, and the diameter of spheroidal particle is non-
The 94.1% of spherical erythrocyte particle groove diameter and the concentration conditions of the emptying reagent under, 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 compared with compared with the peak Cheng Zhi assembly that cannot be stable reported in the literature it
Under, assembling effect is greatly improved, and the concentration for emptying reagent is good, and steric hindrance effect is not deposited in only one assembling site yet
The influence answered, assembly only exists a form of assembling, and whole 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 that test of the film progress reflectance spectrum arrived, the iris phenomenon of photonic crystal and uniform monochromatic light color film, is more obvious, says
Be illustrated it is such under the conditions of the assembly that is prepared have huge application value in water paint.
Embodiment 4
A kind of spherical shape polyacrylic acid/methyl acrylate particle, 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 dehydrated alcohols and 100 parts of deionized waters are added to 250mL four-hole boiling flask
In, 200r/min stirs to form homogeneous phase solution, leads to the oxygen in nitrogen 45min removing system, and it is anti-to be warming up to 80 DEG C of initiation polymerizations
It answers, isothermal reaction 6h.After reaction, dehydrated alcohol and deionized water are recycled, centrifuge washing is carried out to remove not to product
The monomer and stabilizer of reaction, are then freeze-dried 18h, and spheroidal particle is made.
Gained Key particle is spherical shape AA/MAA particle, and spherical AA/MAA particle surface is smooth, and monodispersity is preferable, most
The diameter of big and more existing spheroidal particle is 1000nm 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 dehydrated alcohols and 150 parts of deionized waters are added in 250mL round-bottomed flask, 200r/
Min stirs to form homogeneous phase solution, leads to the oxygen in nitrogen 40min removing system, and flask is placed in 70 DEG C of water-baths and causes 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) and 50 parts of dehydrated alcohols and 50 parts of deionized waters composition homogeneous phase solution be added drop-wise in reaction system, 4h is persistently added dropwise；Drop
After adding, the reaction was continued to 20h；
Third 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 uniform, and monodispersity is also preferable, average aspherical
The diameter of particle is 2.5 μm, groove diameter 1200nm.
A kind of preparation of Lock-and-Key assembly
In terms of mass fraction, (diameter is 2.5 μm to the erythrocyte shape particle for first preparing 150 parts, and groove diameter is
1200nm), 40 parts of poly(N-isopropylacrylamide) is mixed with 200 parts of deionized waters with 200 parts of dehydrated alcohols, ultrasound
25min obtains evenly dispersed mixed liquor；Then the spheroidal particle (diameter 1000nm) prepared by 25 parts is added at one time
Into above-mentioned mixed liquor, the Lock-and-Key assembly containing erythrocyte shape colloidal particle and spherical colloid particles is made.
The characterizing method of particle assembly body in this embodiment and the implementation method 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 assembly is characterized, it can be deduced for preparing the Lock-and-Key assembling that assembling obtains under this condition
Body pairing rate be 35% or so and the size of aspherical erythrocyte particle and spheroidal particle for preparing under this condition more
Match, as shown in Figure 10, the assembly obtained with this condition, the matching degree of size is high between particle, realizes 35% matching；Explanation
The diameter of nonspherical particle is 2.5 μm, groove diameter 1200nm, and spheroidal particle diameter is 1000nm, the diameter of spheroidal particle
For under the 83.3% of aspherical erythrocyte particle groove diameter and 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 model R3~IS50~T reflecting spectrograph to obtaining
Film carry out the test of reflectance spectrum, the phenomenon that iris phenomenon of photonic crystal and uniform monochromatic light color film, is more obvious, illustrates
The assembly being prepared under the conditions of such has huge application value in water paint.
Claims (7)
1. erythrocyte shape colloidal particle and spherical colloid particles assembly, which is characterized in that inlayed by spheroidal particle into blood red
In the groove of cellular particle, the two is closely fitted together, and forms assembly；The partial size of the spheroidal particle is 500nm
~1300nm；Erythrocyte shape particle, partial size are 1 ~ 5 μm, and the shape of groove is hemispherical, the diameter of groove be 600nm ~
1500nm；And the partial size 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 surfactant,
100 ~ 500 parts of dehydrated alcohols and 100 ~ 500 parts of water mixing, stirring form homogeneous phase solution, lead to the oxygen in nitrogen removing system, set
The initiated polymerization in 60 ~ 80 DEG C of water-baths；
Second step, in terms of mass fraction, after 4 ~ 8h of polymerization reaction, then by 0 ~ 200 part of monomer, 5 ~ 50 parts of crosslinking agent and 10 ~
100 parts dehydrated alcohol composition homogeneous phase solution being slowly dropped in reaction system with 1 ~ 100 part/hour, persistently be added dropwise 2 ~
10h；After completion of dropwise addition, the reaction was continued to 20 ~ 30h；
Reaction product is centrifuged repeatedly washing and removes unreacted monomer and surfactant by third step, and blood is made in freeze-drying
Red blood cell shape particle；
The monomer be one of acrylic acid, methyl acrylate, butyl acrylate, methyl methacrylate and styrene or
It is a variety of；
The initiator is potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate, azodiisobutyronitrile, azobisisoheptonitrile and peroxide
Change one or more of benzoyl；
The surfactant is neopelex, lauryl sodium sulfate, polyvinylpyrrolidone and alkenyl sulphur
One or more of sour sodium；
The crosslinking agent is divinylbenzene, diisocyanate, N, in N ~ methylene-bisacrylamide, cumyl peroxide
One or more；
In terms of mass fraction, by 100 ~ 200 parts of erythrocyte shape particles, 10 ~ 50 parts of emptying reagents and and 100 ~ 500 parts of deionizations
Water and 100 ~ 500 parts of dehydrated alcohol mixing, ultrasonic disperse obtain mixed liquor；Then by 10 ~ 50 parts of spheroidal particle dispersion liquid with 10
The rate of addition of ~ 100 parts/hour is slowly dropped in mixed liquor, and erythrocyte shape colloidal particle and spherical colloid particles are made
Assembly；The time of the ultrasonic disperse is 20 ~ 30min；
The emptying reagent is polyethylene glycol oxide or poly(N-isopropylacrylamide).
2. erythrocyte shape colloidal particle according to claim 1 and spherical colloid particles assembly, which is characterized in that institute
It states spheroidal particle 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 parts
Surfactant, 100 ~ 500 parts of dehydrated alcohols and 100 ~ 300 parts of deionized water mixing, 100 ~ 300r/min stir to be formed homogeneously
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 terminates
Afterwards, centrifuge washing is carried out to product repeatedly, be then freeze-dried, spheroidal particle is made；
The monomer be one of acrylic acid, methyl acrylate, butyl acrylate, methyl methacrylate and styrene or
It is a variety of；
The initiator is potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate, azodiisobutyronitrile, azobisisoheptonitrile and peroxide
Change one or more of benzoyl；
The surfactant is neopelex, lauryl sodium sulfate, polyvinylpyrrolidone and alkenyl sulphur
One or more of sour sodium.
3. erythrocyte shape colloidal particle according to claim 2 and spherical colloid particles assembly, which is characterized in that institute
The time for stating logical nitrogen is 30 ~ 60min；The time of freeze-drying is 12 ~ for 24 hours.
4. erythrocyte shape colloidal particle according to claim 1 and spherical colloid particles assembly, which is characterized in that the
The time of logical nitrogen in one step is 30 ~ 60min；The time being freeze-dried in third step be 12 ~ for 24 hours.
5. erythrocyte shape colloidal particle according to claim 1 and spherical colloid particles assembly, which is characterized in that institute
The solvent that the centrifuge washing stated is used is one or more of methanol, ethyl alcohol, acetone and deionized water.
6. the preparation method of any one of claim 1 ~ 5 the erythrocyte shape colloidal particle and spherical colloid particles assembly,
It is characterized by: in terms of mass fraction, by 100 ~ 200 parts of erythrocyte shape particles, 10 ~ 50 parts of emptying reagents and and 100 ~ 500
Part deionized water and 100 ~ 500 parts of dehydrated alcohols mixing, ultrasonic disperse obtain mixed liquor；Then by 10 ~ 50 parts of spheroidal particle point
Dispersion liquid is slowly dropped in mixed liquor with the rate of addition of 10 ~ 100 parts/hour, and erythrocyte shape colloidal particle and spherical shape is made
Colloidal particle assembly；The time of the ultrasonic disperse is 20 ~ 30min；
The emptying reagent is polyethylene glycol oxide or poly(N-isopropylacrylamide).
7. any one of the claim 1 ~ 5 erythrocyte shape colloidal particle and spherical colloid particles assembly are in photonic crystal water
Application in property coating.
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Citations (4)
| 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 |
-
2017
- 2017-11-22 CN CN201711173551.8A patent/CN107955477B/en active Active
Patent Citations (4)
| 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)
| Title |
|---|
| Magnetic Click Colloidal Assembly;Stefano Sacanna等;《Journal of American Chemical Society》;20120327;全文 * |
| Morphology control of anisotropic nonspherical functional polymeric particles by one-pot dispersion polymerization;Huifang Shen等;《Reactive and Functional Polymers》;20170116;全文 * |
| Synthesis of Monodisperse, Rodlike Silica Colloids with Tunable Aspect Ratio;Anke Kuijk等;《Journal of American Chemical Society》;20110121;全文 * |
| 凹陷状胶体粒子的自组装;程志峰等;《南京大学学报（自然科学）》;20140131;全文 * |
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