CN109423300A - The preparation method of monodisperse polymer particle - Google Patents
The preparation method of monodisperse polymer particle Download PDFInfo
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- CN109423300A CN109423300A CN201710740022.5A CN201710740022A CN109423300A CN 109423300 A CN109423300 A CN 109423300A CN 201710740022 A CN201710740022 A CN 201710740022A CN 109423300 A CN109423300 A CN 109423300A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 91
- 239000002245 particle Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 179
- 150000001875 compounds Chemical class 0.000 claims abstract description 95
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 25
- 239000006210 lotion Substances 0.000 claims description 19
- 239000000839 emulsion Substances 0.000 claims description 18
- 239000003995 emulsifying agent Substances 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000004988 Nematic liquid crystal Substances 0.000 claims description 5
- 238000006392 deoxygenation reaction Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 239000012456 homogeneous solution Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000011807 nanoball Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 45
- 238000001514 detection method Methods 0.000 abstract description 12
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- 238000006555 catalytic reaction Methods 0.000 abstract description 3
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- UWCWUCKPEYNDNV-LBPRGKRZSA-N 2,6-dimethyl-n-[[(2s)-pyrrolidin-2-yl]methyl]aniline Chemical compound CC1=CC=CC(C)=C1NC[C@H]1NCCC1 UWCWUCKPEYNDNV-LBPRGKRZSA-N 0.000 description 2
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- 230000003197 catalytic effect Effects 0.000 description 2
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000003098 cholesteric effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- GZQKNULLWNGMCW-PWQABINMSA-N lipid A (E. coli) Chemical compound O1[C@H](CO)[C@@H](OP(O)(O)=O)[C@H](OC(=O)C[C@@H](CCCCCCCCCCC)OC(=O)CCCCCCCCCCCCC)[C@@H](NC(=O)C[C@@H](CCCCCCCCCCC)OC(=O)CCCCCCCCCCC)[C@@H]1OC[C@@H]1[C@@H](O)[C@H](OC(=O)C[C@H](O)CCCCCCCCCCC)[C@@H](NC(=O)C[C@H](O)CCCCCCCCCCC)[C@@H](OP(O)(O)=O)O1 GZQKNULLWNGMCW-PWQABINMSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N phenyl propionaldehyde Natural products CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3833—Polymers with mesogenic groups in the side chain
- C09K19/3842—Polyvinyl derivatives
- C09K19/3852—Poly(meth)acrylate derivatives
-
- 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
- C08F122/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/10—Esters
- C08F122/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
-
- 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
- C08F122/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/10—Esters
- C08F122/12—Esters of phenols or saturated alcohols
- C08F122/20—Esters containing oxygen in addition to the carboxy oxygen
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3833—Polymers with mesogenic groups in the side chain
- C09K19/3842—Polyvinyl derivatives
- C09K19/3852—Poly(meth)acrylate derivatives
- C09K19/3857—Poly(meth)acrylate derivatives containing at least one asymmetric carbon atom
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- 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
- C08F216/00—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1458—Monomers containing nitrogen
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- 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
- C08F220/00—Copolymers 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
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- 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
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
- C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
- C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
- C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
- C09K2019/122—Ph-Ph
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/542—Macromolecular compounds
- C09K2019/546—Macromolecular compounds creating a polymeric network
Abstract
The invention discloses a kind of preparation methods of monodisperse polymer particle, the described method includes: monodispersed liquid crystal droplet is initially formed, wherein the monodisperse liquid crystal droplet includes at least one reactive liquid crystalline compound, at least one non-reactive liquid crystal compound and at least one polymerization initiator;Secondly at least one reactive liquid crystalline compound in the polymerization monodispersed liquid crystal droplet, forms intermediate particle;Then at least one non-reactive liquid crystal compound is removed from the intermediate particle, forms polymer particles;It is finally separating, washs and disperses or dry the polymer particles.The method for the matrix polymerization that preparation method of the invention is assisted using liquid crystal prepares the monodisperse polymer particle of size, shape and structure-controllable, easy to operate, saves cost, can be mass-produced;The monodisperse polymer particle of preparation can be widely applied to the fields such as bio-chemistry separation and catalysis, biological detection, drug delivery.
Description
Technical field
The present invention relates to a kind of preparation methods of monodisperse polymer particle, in particular to a kind of to have controlled dimensions, shape
The preparation method of shape and the monodisperse polymer particle of structure.
Background technique
Polymer particles are due to being widely used in biochemistry with controllable size, shape and huge specific surface area structure
The fields such as separation, catalytic reaction, biological detection and drug release.Its industrial application in biochemical separation processes mainly includes
Catalytic reactor and chromatographic reactor.Conventional chromatographic column filler is the particle accumulated at random in this kind of reactor, these with
The particle of machine accumulation has the advantages that be easy preparation and production cost is relatively low, still, the random hole geometric form for filling particle
Shape and distribution are complicated, and are difficult to control.When filler microballoon uniform for particle size, the performance of reactor is improved,
But specific surface area is not still high.Meanwhile microballoon isolates and purifies packing material as a kind of widely used tradition, can not still have
Effect improves the pressure drop in chromatographic column.In recent years, many theoretical works have confirmed that orderly filling Microellipsoid can obtain preferably
Flow pattern and the resistance in flow field and separation process can be optimized.The filler of these spheroid shapes can effectively improve color
It composes separating property and increases its heat-transfer capability, reduce pressure drop.Therefore, spheroid shape particle has in modern biochemical separation processes
Huge potentiality and market.In addition, ellipsoidal particle shows high-specific surface area, high fluidity is easy to the properties such as reversible dispersion, can
To be widely used in catalytic field.In addition to this, the particle of these spheroid shapes possesses unique shape, there is extensive rheology
Using.
On the other hand, today of severe industry, atmosphere and environmental pollution, pernicious gas, biochemistry are faced in the whole world
The detection of substance has particularly important social effect, and wherein biological detection is almost related to all industries, especially medical treatment, ring
The industries such as guarantor, food, prospect are extremely wide.The conventional method of Bacteria Detection in biological detection is to cultivate sample, divide
From purifying, be configured to the bacterial solution of certain turbidity, then various different biochemical reactions are carried out, finally integrated obtained biochemical anti-
It should identification of the result realization to bacterium.This method influence factor is more, trivial operations, requires height, detection cycle long instrument and equipment
And it is high to technical staff's professional skill requirement, or even qualification result is unable to get because of the particular/special requirement of individual bacteria growth.Mesh
Preceding liquid crystal material becomes the sensibility of the external force such as electricity, heat, light, machinery, magnetic the technical foundation of liquid crystal base microballoon Bacteria Detection.
Liquid crystal base microballoon Bacteria Detection has many advantages, such as that response is rapid, reaction is intuitive and easy to carry, and then substantially shortens Bacteria Identification
Identification bacterium can be realized without separating-purifying in period, and can high-throughput detection bacterium.However it is existing in the domestic market, towards
Public liquid crystal base microballoon Bacteria Detection technology not yet occurs.
The method for preparing polymer particles in the world at present is included in the intracavitary in-situ polymerization in miniflow hole, based on two-photon polymerized
Photoetching, template spherical particle assembling and in the above drawing process of microballoon glass transition temperature.Although these methods have
Reapective features, but it is usually directed to the use (for example, system of exposure/print system or application mechanical stress) of special equipment, it needs
It wants very long program, or complicated interfacial assembly, these factors that it is made still to be only limitted to laboratory scope, can not be applied to extensive
Production and preparation.In addition to this, these methods can not all accurately control the internal structure and shape of polymer particles.
Accordingly, it is desirable to provide it is a kind of can be mass-produced accurately control size, shape and internal structure monodisperse it is poly-
The method for closing object particle.
Summary of the invention
To meet the demand, it is micro- that the present invention proposes that a kind of matrix polymerization assisted by liquid crystal prepares monodisperse polymer
The method of grain, which comprises
I monodispersed liquid crystal droplet) is formed, wherein the monodisperse liquid crystal droplet includes at least one reactive liquid crystalline
Close object, at least one non-reactive liquid crystal compound and at least one polymerization initiator;
II at least one reactive liquid crystalline compound) polymerizeing in the monodisperse liquid crystal droplet, forms intermediate micro-
Grain;
III the non-reactive liquid crystal compound) is removed from the intermediate particle, forms polymer particles;
IV) separation, washing and dispersion or the dry polymer particles.
In a preferred embodiment of the invention, described to be polymerized to photopolymerization.
In embodiments of the invention, at least one reactive liquid crystalline accounts for the ratio of the liquid crystal compound gross mass
Example is between 0.05 to 0.50.
In some embodiments of the present invention, the non-reactive liquid crystalline compound of at least one is nematic liquid crystal, institute
Stating polymer particles is polymer ellipsoid, and draw ratio (long axis length/minor axis length) changes between 1.0 to 3.0.In this hair
In bright some embodiments, at least one non-reactive liquid crystal is cholesteric liquid crystal.
In some embodiments of the present invention, the step of formation monodispersed liquid crystal droplet includes: to be formed uniformly
Liquid crystal compound, the liquid crystal compound is formed into liquid crystal droplet by film emulsifier unit and is dispersed in continuous phase, is formed with institute
State the lotion that liquid crystal droplet is dispersed phase.
In some embodiments of the present invention, the step of formation monodispersed liquid crystal droplet includes: to be formed uniformly
Liquid crystal compound;The liquid crystal compound is pre-dispersed in continuous phase, dispersion emulsion is formed;The dispersion emulsion is passed through
Film emulsifier unit is formed using the liquid crystal droplet as the lotion of dispersed phase.
In embodiments of the invention, the continuous phase is water and any system miscible with water.Of the invention one
In a little preferred embodiments, the continuous phase is the mixture of glycerol and water.In some preferred embodiments of the invention
In, the continuous phase is water.In some preferred embodiments of the invention, the continuous phase is the mixed of glycerol, water and PVP
Close object.
In embodiments of the invention, after the step of forming uniform liquid crystal compound, can also include will be described
Liquid crystal compound carries out deoxygenation operation.
In embodiments of the invention, the size of the monodispersed liquid crystal droplet can be from 0.1 micron to 100 micron
Range.
In some embodiments of the present invention, the step of liquid crystal compound being dispersed in continuous phase further includes being added
Liquid crystal droplet conformational change agent.In present invention further optimization embodiment, the liquid crystal droplet conformational change agent is ten
Sodium dialkyl sulfate.
In some embodiments of the present invention, the polymer particles are porous polymer microballoon, the polymer
The particle size of microballoon is 0.1 micron to 100 microns.
In some embodiments of the present invention, the step of formation uniform liquid crystal compound includes: described in mixing
At least one reactive liquid crystalline compound, at least one non-reactive liquid crystal compound and at least one polymerization cause
Dosage form resulting mixture;The mixture is heated into liquid condition;It is uniformly mixed;It is slowly cooled to room temperature.
In some embodiments of the present invention, the step of formation uniform liquid crystal compound includes: described in mixing
At least one reactive liquid crystalline compound, at least one non-reactive liquid crystal compound and at least one polymerization cause
Dosage form resulting mixture;Organic solvent is added into the mixture;Dissolution forms homogeneous solution;It is uniformly mixed;Slowly vapor away
The organic solvent.
In some embodiments of the present invention, the step of formation monodispersed liquid crystal droplet further includes being added to be total to
Poly- functional monomer.
It in some embodiments of the present invention, further include that function is added in the step of formation monodispersed liquid crystal droplet
It can property nanosphere.
The present invention utilizes the method preparation size of the matrix polymerization of liquid crystal auxiliary, the monodisperse polymer of shape and structure-controllable
Object particle, preparation method are simple to operation, it can be achieved that large-scale production.Prepared monodisperse polymer particle not only has simultaneously
There is the anisotropy of structure and shape, while the optically anisotropic characteristic of liquid crystal can be kept, biochemistry can be widely applied to
The fields such as separation, biological detection, drug delivery and biochemical catalysis.
Detailed description of the invention
The present invention may be better understood by referring to illustrating for embodiment of the present invention, in the accompanying drawings:
Fig. 1 is that the process for the method that the matrix polymerization assisted by liquid crystal prepares monodisperse polymer particle schematically illustrates
Figure.
Fig. 2 is the schematic diagram for preparing the film emulsifying technology of monodispersed liquid crystal droplet.
Fig. 3 is the schematic diagram of another film emulsifying technology for preparing monodispersed liquid crystal droplet.
Fig. 4 is the microscope schematic diagram of the liquid crystal droplet prepared according to embodiments of the present invention.
Fig. 5 is the microscope schematic diagram of the monodisperse polymer ellipsoid of the big L/D ratio prepared according to embodiments of the present invention.
Fig. 6 is the microscope schematic diagram of the monodisperse polymer ellipsoid of the small draw ratio prepared according to embodiments of the present invention.
Fig. 7 is the microscope schematic diagram of the large-sized monodisperse polymer ellipsoid prepared according to embodiments of the present invention.
Fig. 8, which is that (a) of the monodisperse polymer ellipsoid with patch structure prepared according to embodiments of the present invention is micro-, to be shown
It is intended to show the SEM schematic diagram of its external structure with (b).
Fig. 9 is (a) microscope signal of the monodisperse polymer ellipsoid with hydroxyl prepared according to embodiments of the present invention
Figure and (b) infrared spectrogram.
Figure 10 is the structure of the monodisperse polymer micro-sphere with internal aperture structure prepared according to embodiments of the present invention
Schematic diagram.
Figure 11 is the microscope schematic diagram of the large-sized monodisperse polymer micro-sphere prepared according to embodiments of the present invention.
It is monodisperse polymer prepared by non-reactive liquid crystal that Figure 12, which is according to an embodiment of the present invention as cholesteric liquid crystal,
The structural schematic diagram of object particle.
Specific embodiment
In the following description, it in order to reach purpose of explanation to have a comprehensive understanding to the present invention, illustrates
A large amount of detail, it will be evident, however, that those skilled in the art, it can also be real without these details
The existing present invention.In other examples, well known construction and device is shown in box chart.In this respect, that is lifted is illustrative
Example embodiment only for explanation, the present invention is not caused to limit.Therefore, protection scope of the present invention is not by above-mentioned
Specific embodiment is limited, and is only subject to the range of appended claims.
Abbreviated list used herein:
5CB:4- cyano -4 '-pentylbiphenyl
RM257:2- methyl-1,4- phenylene-bis- [4- (3- acryloxy propoxyl group) benzoic ether]
HCM062:
HCM126:
DMPAP:2- bi-methoxy -2- Phenyl ethyl ketone
SPG film: Shirasu Porous Glass SPG membrane
PVP: polyvinylpyrrolidone
PVA: polyvinyl alcohol
PEG: polyethylene glycol
SDS: lauryl sodium sulfate
HEMA: hydroxyethyl methacrylate
CB15:
With reference first to Fig. 1, there is shown with preparations provided by the invention to prepare monodisperse by the matrix polymerization that liquid crystal assists
The method flow of polymer particles.It is non-anti-that it is mixed in a certain proportion at least one reactive liquid crystalline compound, at least one first
Answering property liquid-crystal compounds and at least one polymerization initiator, form monodispersed liquid crystal droplet.Then it polymerize the monodisperse liquid
At least one reactive liquid crystalline in brilliant droplet, formation includes that the centre for the non-reactive liquid crystal not polymerizeing is micro-
Grain.Then the non-reactive liquid crystal not polymerizeing is removed from the intermediate particle, is further formed size, shape and structure
Controllable polymer particles.It is finally separating, washs and dispersion/drying polymer particles.
The ratio that reactive liquid crystalline compound accounts for liquid crystal compound gross mass can be 0.05 to 0.50.Reactive liquid crystalline chemical combination
Object has polymerizable chemical group, can react in the presence of polymerization initiator and form polymer, such as esters of acrylic acid liquid crystal
(RM257), methyl acrylic ester liquid crystal (HCM062), allylic liquid crystal (HCM126) etc..
Polymerization methods can be photopolymerization, thermal polymerization or radiation polymerization.
Non-reactive liquid crystal compound does not have polymerizable chemical group, will not further polymerize, to be not involved in poly-
Close reaction.Non-reactive liquid crystal compound can be nematic liquid crystal, cholesteric liquid crystal, smectic liquid crystal and other liquid crystal materials,
According to the difference of its type, the final shape of the polymer particles of synthesis can control.
Meanwhile by the way that the agent of liquid crystal droplet conformational change is added in continuous phase, the changeable liquid crystal molecule as template exists
Arrangement mode in liquid crystal droplet, to influence the structure and shape of final polymer particles.Liquid crystal droplet conformational change agent can
For surfactant, such as SDS or lipid, such as synthetic phospholipid, lipid A.Can also by monodispersed liquid crystal droplet introduce can
HEMA is such as added to form the polymer particles with corresponding function in the functional monomer of copolymerization, can introduce hydroxyl most
In polymer particles made of end.By introducing nanosphere in monodispersed liquid crystal droplet, can be formed with patch structure
Monodisperse polymer particle.In addition, by the ratio of control reactive liquid crystalline compound and non-reactive liquid crystal compound, it can
The further shape and structure of the synthesized monodisperse polymer particle of control.
It is nematic liquid crystal and the liquid crystal mixing that liquid crystal droplet conformational change agent is not added for non-reactive liquid crystal compound
Object, final product are polymer ellipsoid, and draw ratio (length/short axle length of long axis) is by reactive liquid crystalline compound
Account for what the mass percent of liquid crystal compound total amount was determined, it can be between 1.0 to 3.0.
In order to form monodispersed liquid crystal droplet, it is necessary to be initially formed comprising reactive liquid crystalline compound, non-reactive liquid crystal
The uniform liquid crystal mixture of compound and polymerization initiator, is then dispersed in continuous phase that form monodispersed liquid crystal micro-
Drop.Continuous phase can be water, can also be any system miscible with water, such as the mixture, PVP aqueous solution, PVA water of glycerol and water
Solution, PEG aqueous solution, PVP and glycerol and water mixture.After forming liquid crystal compound, deoxygenation can be carried out to whole system
Operation increases the yield of polymerizate, and can further exclude oxygen to polymer to increase the free radical generated in polymerization
The influence of particle preparation process.
In order to form uniform liquid crystal compound, first hybrid reaction liquid-crystal compounds, non-reactive liquid crystal compound and
Polymerization initiator heats mixture into isotropic liquid, is uniformly mixed it, this liquid is then slowly cooled to room
Temperature.For some photosensitive polymerization initiators, causing polymerization reaction when to avoid Slow cooling in advance, can be used to be protected from light and arrange
It applies.In alternative embodiments, can first hybrid reaction liquid-crystalize and close object, non-reactive liquid crystal compound and polymerization initiator,
A small amount of dissolvable liquid crystal compound and volatile organic solvent are added, such as toluene, acetone, methylene chloride, tetrahydrofuran, chlorine
Imitate, be sufficiently mixed until liquid crystal compound be completely dissolved to form uniform solution, then slowly vapor away organic solvent.For
Some photosensitive polymerization initiators, causing polymerization reaction in advance, can be used and be protected from light when to avoid slow volatile organic solvent
Measure.
In order to ensure the monodisperse polymer particle size of preparation is controllable together, liquid crystal compound is dispersed in continuous phase
Being formed by liquid crystal droplet must size uniformity and controllable.In embodiments of the invention, it is emulsified using one kind based on film
Dispersion technology realize the preparation of monodisperse liquid crystal droplet, its principle is as shown in Figure 2, by the liquid crystal compound as dispersed phase
A kind of inoranic membrane with micropore is passed through slowly, liquid crystal compound forms liquid crystal droplet dispersion after being extruded from inorganic membrane micropore
Into continuous phase, to be formed a kind of using liquid crystal droplet as the dispersion of dispersed phase.Since inoranic membrane has specification uniform
Micron order aperture, to make the liquid crystal droplet for entering continuous phase by inoranic membrane that also there is the uniform partial size ruler of same size
It is very little, further to prepare monodispersed polymer particles.By choosing the inoranic membrane of different micropore size sizes, institute's shape can control
At liquid crystal droplet size, to control the particle size size of polymer particles.In following embodiments, I
Select it is a kind of using have micropore SPG film film emulsifier unit, and select have suitable micropore size size, by liquid crystal
Mixture is by SPG film, to form tool by the monodispersed liquid crystal droplet of target size.The size of the liquid crystal droplet of formation can be
Range from 0.1 micron to 100 micron, so that the particle size of final polymer particles obtained can be from 0.1 micron to 100
The range of micron.In alternative embodiments, first liquid crystal compound can be pre-dispersed in continuous phase, it is larger forms size
Dispersion emulsion, then by pre-emulsified dispersion emulsion by film emulsifier unit, to form the monodispersed liquid crystal of target size
Droplet, as shown in Figure 3.
In the present invention unless otherwise specified, the ratio is mass ratio.
Embodiment 1: monodispersed liquid crystal droplet is prepared
890 milligrams of non-reactive liquid crystal compound 5CB, 100 milligrams of reactive liquid crystalline compound are mixed first
This mixture is heated to mixed liquid crystal clearing point or more until becoming equal by RM257 and 10 milligram of photoinitiator DMPAP
One solution, sufficiently vibration are uniformly mixed it, are then slowly cooled to room temperature this solution, form liquid crystal compound.Due to
Photoinitiator DMPAP is light sensitive, and solution must be placed at the place of being protected from light and carry out Slow cooling.In alternative embodiments, may be used
First mix 890 milligrams of non-reactive liquid crystal compound 5CB, 100 milligrams of reactive liquid crystalline compound R M257 and 10 millis
Gram photoinitiator DMPAP, a small amount of toluene or acetone are added, until mixture is completely dissolved to form uniform solution, sufficiently
Vibration mixed solution make its be uniformly mixed, then slowly vapor away organic solvent until solution become cloudy, show no solvent residue,
To form uniform liquid crystal compound.Since photoinitiator DMPAP is light sensitive, when slow volatile organic solvent, which must be placed on, is kept away
At light.
100 milligrams of above-mentioned uniform liquid crystal compound is taken, the film that membrane micropore aperture is 20 microns is slow transitted through and emulsified
Device is 10 micro- to form average-size into the continuous phase of the mixture (volume ratio of glycerol and water is 9:1) of glycerol and water
The monodispersed liquid crystal droplet of rice, as shown in Figure 4.
Embodiment 2: the monodisperse polymer ellipsoid of big L/D ratio is prepared
With the step of preparing liquid crystal compound, prepared in embodiment 1 liquid crystal compound (wherein 10%RM257,1%
DMPAP).100 milligrams of liquid crystal compound are taken, is added into that (volume ratio of glycerol and water is to the mixture of 2 milliliters of glycerol and water
In 9:1).Then to 200 microlitres of PVP solution of 1% mass concentration are added in system.It by the pre- cream of this solution, is sufficiently mixed, is formed
Dispersion emulsion.Then the film emulsifier unit for being 20 microns by membrane micropore aperture by above-mentioned dispersion emulsion, formation contain monodisperse
The lotion of liquid crystal droplet.Later, the lotion containing monodisperse liquid crystal droplet is placed under UV light source and carries out solidification polymerization, radiated
Intensity is 2.5mW/cm2, polymerization time is 30 minutes.It needs to be stirred continuously system in polymerization process.After polymerization, it will react molten
It is to be sufficiently mixed in its 10 times ethanol solution that liquid, which is dispersed to volume, is then centrifuged (8000rpm, 10 minutes), removal upper layer is clear
Liquid.After being centrifugated in triplicate, ethanol solution is removed, the polymer ellipsoid of non-reactive liquid crystal 5CB has been removed, by it
It is dispersed in water.It, can also dry polymer ellipsoid according to the needs that the later period is applied.The length of the long axis of polymer ellipsoid is by liquid
What the size of brilliant droplet determined, and its draw ratio (length/short axle length of long axis) is to account for mixed liquid crystal by reactive liquid crystalline
What the mass percent of total amount was determined.In the present embodiment, as shown in figure 5, prepared polymer ellipsoid long axis is averaged
Length is 19 microns, average aspect ratio 2.36.
Embodiment 3: the monodisperse polymer ellipsoid of small draw ratio is prepared
With the step of preparing liquid crystal compound, prepared in embodiment 1 liquid crystal compound (wherein 45%RM257,1%
DMPAP).Take 100 milligrams of liquid crystal compound, be added into 2 milliliters of glycerol and water mixture (volume ratio of glycerol and water be 9:
1) in, then to 200 microlitres of PVP solution that addition mass concentration in system is 1%.By the pre- cream of this solution, it is thoroughly mixed to form
Dispersion emulsion.Then the film emulsifier unit for being 20 microns by membrane micropore aperture by above-mentioned dispersion emulsion, formation contain monodisperse
The lotion of liquid crystal droplet.Later, the lotion containing monodisperse liquid crystal droplet is placed under UV light source and carries out solidification polymerization, radiated
Intensity is 2.5mW/cm2, polymerization time is 30 minutes.It needs to be stirred continuously system in polymerization process.After polymerization, it will react molten
It is to be sufficiently mixed in its 10 times ethanol solution that liquid, which is dispersed to volume, is then centrifuged (8000rpm, 10 minutes), removal upper layer is clear
Liquid.After being centrifugated in triplicate, ethanol solution is removed, the polymer ellipsoid of non-reactive liquid crystal 5CB has been removed, by it
It is dispersed in water.It, can also dry polymer ellipsoid according to the needs that the later period is applied.As shown in fig. 6, reactive liquid in this embodiment
The mass percent that brilliant RM257 accounts for liquid crystal compound total amount is 45%, and prepared polymer ellipsoid average aspect ratio is reduced to
1.20。
Embodiment 4: large-sized monodisperse polymer ellipsoid is prepared
With the step of preparing liquid crystal compound, prepared in embodiment 1 liquid crystal compound (wherein 10%RM257,1%
DMPAP).By the mixture (body of glycerol and water for 20 milliliters of PVP solution additions, 130 milliliters of glycerol and water that mass concentration is 1%
Product is than being 9:1) in, form continuous phase solution.10 grams of liquid crystal compound then are taken, it is 15 microns that it is passed through to membrane micropore aperture
Film emulsifier unit forms the lotion containing monodisperse liquid crystal droplet into continuous phase solution.Later, monodisperse liquid will be contained
The lotion of brilliant droplet, which is placed under UV light source, carries out solidification polymerization, radiation intensity 2.5mW/cm2, polymerization time is 30 minutes.
It needs to be stirred continuously system in polymerization process.After polymerization, by reaction solution be dispersed to volume be its 10 times ethanol solution in,
It is sufficiently mixed, is then centrifuged (8000rpm, 10 minutes), remove supernatant liquor.After being centrifugated in triplicate, removal ethyl alcohol is molten
Liquid has been removed the polymer ellipsoid of non-reactive liquid crystal 5CB, has been dispersed in water.According to the later period apply needs,
It can dry polymer ellipsoid.As shown in fig. 7, the film emulsifier unit due to using big membrane micropore aperture, prepared polymer are ellipse
The average length of ball long axis increases to 65 microns, and average aspect ratio is still 2.36.
Embodiment 5: the monodisperse polymer ellipsoid with patch structure is prepared
With the step of preparing liquid crystal compound, prepared in embodiment 1 liquid crystal compound (wherein 10%RM257,1%
DMPAP).Take 50 milligrams of liquid crystal compound, be added into 2 milliliters of glycerol and water mixture (volume ratio of glycerol and water be 9:
1) in.Then to 100 microlitres of PVP solution that addition mass concentration in system is 1%.It is subsequently added into the first that mass concentration is 10%
Silica nanosphere (diameter is 300 nanometers) solution of base esters of acrylic acid modified.By the pre- cream of mixed solution, it is sufficiently mixed
Form dispersion emulsion.Then the film emulsifier unit for being 20 microns by membrane micropore aperture by above-mentioned dispersion emulsion is formed containing single
The lotion of dispersed LCD droplet.Later, the lotion containing monodisperse liquid crystal droplet is placed under UV light source and carries out solidification polymerization,
Radiation intensity is 2.5mW/cm2, polymerization time is 30 minutes.It needs to be stirred continuously system in polymerization process.It, will be anti-after polymerization
Answering solution to be dispersed to volume is to be sufficiently mixed in its 10 times ethanol solution, then (8000rpm, 10 minutes) is centrifuged, in removal
Layer clear liquid.After being centrifugated in triplicate, ethanol solution is removed, the polymer ellipsoid of non-reactive liquid crystal 5CB has been removed,
It is dispersed in water.It, can also dry polymer ellipsoid according to the needs that the later period is applied.As shown in figure 8, the polymer of preparation is ellipse
The surface of ball has apparent patch structure.
Embodiment 6: preparation has hydroxy functionalized monodisperse polymer ellipsoid
With the step of preparing liquid crystal compound, prepared in embodiment 1 liquid crystal compound (wherein 10%RM257,1%
DMPAP).100 milligrams of liquid crystal compound are taken, is added into that (volume ratio of glycerol and water is to the mixture of 2 milliliters of glycerol and water
In continuous phase 9:1).Then to 200 microlitres of PVP solution that addition mass concentration in system is 1%.10 are added into solution again
Milligram HEMA.By the pre- cream of this solution, it is thoroughly mixed to form dispersion emulsion.Then it is by membrane micropore aperture by above-mentioned dispersion emulsion
5 microns of film emulsifier unit forms the lotion containing monodisperse liquid crystal droplet.Later, by the cream containing monodisperse liquid crystal droplet
Liquid, which is placed under UV light source, carries out solidification polymerization, radiation intensity 2.5mW/cm2, polymerization time is 30 minutes.In polymerization process
System need to be stirred continuously.After polymerization, it is to be sufficiently mixed in its 10 times ethanol solution that reaction solution, which is dispersed to volume,
Then centrifugation (8000rpm, 10 minutes) removes supernatant liquor.After being centrifugated in triplicate, ethanol solution is removed, is obtained
The polymer ellipsoid for removing non-reactive liquid crystal 5CB, is dispersed in water.According to the needs that the later period is applied, can also dry poly-
Close object ellipsoid.The hydroxyl that there is unsaturated bond and be attached thereto due to HEMA, it is possible to it is copolymerized with reactive liquid crystalline RM257,
And hydroxyl is introduced into the polymer particles being finally made.As shown in figure 9, the hydroxy functionalized polymer particles of preparation have
The shape of ellipsoid, and its infrared spectroscopy shows the function peak (dotted portion) of hydroxyl in corresponding position, and function peak is with adding
The amount of the HEMA added increases (a.0 milligram, b.10 milligram, c.50 milligram, d.100 milligram) and becomes readily apparent from.
Embodiment 7: the monodisperse polymer micro-sphere with internal aperture structure is prepared
With the step of preparing liquid crystal compound, prepared in embodiment 1 liquid crystal compound (wherein 10%RM257,1%
DMPAP).50 milligrams of liquid crystal compound are taken, is added into 2 milliliters of water.Then to the SDS that addition molar concentration is 1M in system
150 microlitres of solution.By the pre- cream of this solution, it is thoroughly mixed to form dispersion emulsion.Then above-mentioned dispersion emulsion is passed through into membrane micropore hole
The film emulsifier unit that diameter is 5 microns forms the lotion containing monodisperse liquid crystal droplet.Later, monodisperse liquid crystal droplet will be contained
Lotion be placed under UV light source and carry out solidification polymerization, radiation intensity 2.5mW/cm2, polymerization time is 30 minutes.It polymerize
Cheng Zhongxu is stirred continuously system.After polymerization, it is sufficiently to mix in its 10 times ethanol solution that reaction solution, which is dispersed to volume,
It closes, is then centrifuged (8000rpm, 10 minutes), remove supernatant liquor.After being centrifugated in triplicate, ethanol solution is removed, is obtained
The polymer microballoon for having removed non-reactive liquid crystal 5CB, is dispersed in water.According to the needs that the later period is applied, can also dry
Polymer microballoon.As shown in Figure 10, due to introducing liquid crystal droplet conformational change agent SDS, liquid crystal molecule is in liquid crystal droplet
Arrangement mode is changed, so that final polymer particles be made no longer to be spheroid-like, but still keeps removing non-reacted liquid
Microballoon appearance before crystalline substance, but there is porous internal structure.The average particle diameter size of polymer microballoon is 4 microns.
Embodiment 8: preparation has large-sized monodisperse polymer micro-sphere
With the step of preparing liquid crystal compound, prepared in embodiment 1 liquid crystal compound (wherein 10%RM257,1%
DMPAP).By in 15 milliliters of SDS solution additions, 200 milliliters of continuous phase water of 1M, solution is formed.7.5 grams of liquid crystal compound are taken, it will
Its film emulsifier unit for being 15 microns by membrane micropore aperture is formed micro- containing monodisperse liquid crystal into the continuous phase containing SDS
The lotion of drop.Later, the lotion containing monodisperse liquid crystal droplet is placed under UV light source and carries out solidification polymerization, radiation intensity is
2.5mW/cm2, polymerization time is 30 minutes.It needs to be stirred continuously system in polymerization process.After polymerization, reaction solution is dispersed
It is to be sufficiently mixed in its 10 times ethanol solution to volume, is then centrifuged (8000rpm, 10 minutes), removes supernatant liquor.Weight
After multiple centrifuge separation three times, ethanol solution is removed, the polymer microballoon of non-reactive liquid crystal 5CB has been removed, has been dispersed
In ethanol.It, can also dry polymer microballoon according to the needs that the later period is applied.As shown in figure 11, there is porous internal structure
Polymer microballoon average particle diameter size increase to 35 microns.
Embodiment 9: the monodisperse polymer particle with chiral doping is prepared
890 milligrams of non-reactive liquid crystal compound 5CB, 100 milligrams of reactive liquid crystalline compound are mixed first
It is clear to be heated to mixed liquid crystal by RM257,10 milligrams of photoinitiator DMPAP and 50 milligrams of chiral agent CB15 for this mixture
More than bright spot until becoming uniform solution, abundant vibrating liquid mixture is uniformly mixed it, is then placed on this solution
The place of being protected from light is slowly cooled to room temperature, and forms liquid crystal compound.Wherein chiral agent CB15 and nematic liquid crystal 5CB forms cholesteric phase liquid
It is brilliant.100 milligrams of liquid crystal compound are taken, is added into 2 milliliters of water.Then to the SDS that addition molar concentration is 1M in system
150 microlitres of solution.By the pre- cream of liquid crystal compound, dispersion emulsion is formed.It then is 20 micro- by membrane micropore aperture by dispersion emulsion
The film emulsifier unit of rice forms the lotion containing monodisperse liquid crystal droplet.Later, the lotion containing monodisperse liquid crystal droplet is put
It is placed under UV light source and carries out solidification polymerization, radiation intensity 2.5mW/cm2, polymerization time is 30 minutes.It is needed not in polymerization process
Disconnected stirring system.After polymerization, it is to be sufficiently mixed, then in its 10 times ethanol solution that reaction solution, which is dispersed to volume,
It is centrifuged (8000rpm, 10 minutes), removes supernatant liquor.After being centrifugated in triplicate, ethanol solution is removed, has been removed
The polymer particles of non-reactive liquid crystal 5CB, are dispersed in water.It, can also dry polymer according to the needs that the later period is applied
Particle.As shown in figure 12, the polymer particles of preparation have and use polymer prepared by nematic phase non-reactive liquid crystal ellipse
The different structure of ball.
Although having been described above with the several exemplary implementation schemes of datail description, disclosed embodiment is only
Exemplary and those skilled in the art will readily appreciate that and not restrictive, a lot of other in an exemplary embodiment
It is possible for modifying, changing and/or replacing, and the novel teachings and advantage of the disclosure are deviateed without essence.Therefore, all these
Modification, change and/or replacement are intended to be included in the scope of the present disclosure as defined by the appended claims.
Claims (10)
1. a kind of method for preparing monodisperse polymer particle, which comprises
(I) monodispersed liquid crystal droplet is formed, wherein the monodispersed liquid crystal droplet includes at least one reactive liquid crystalline
Close object, at least one non-reactive liquid crystal compound and at least one polymerization initiator;
(II) at least one reactive liquid crystalline compound polymerizeing in the monodispersed liquid crystal droplet, forms intermediate micro-
Grain;
(III) at least one non-reactive liquid crystal compound is removed from the intermediate particle, forms polymer particles;
(IV) separation, washing and dispersion or the dry polymer particles.
2. the step of the method as described in claim 1, the formation monodispersed liquid crystal droplet, includes:
1) uniform liquid crystal compound is formed;
2) liquid crystal compound is formed into liquid crystal droplet by film emulsifier unit and is dispersed in continuous phase, formed micro- with the liquid crystal
Drop is the lotion of dispersed phase;Or
1) uniform liquid crystal compound is formed;
2) liquid crystal compound is pre-dispersed in continuous phase, forms dispersion emulsion;
3) dispersion emulsion is formed by film emulsifier unit using the liquid crystal droplet as the lotion of dispersed phase.
3. method according to claim 2, wherein after the step of forming uniform liquid crystal compound, the method also includes
The liquid crystal compound is subjected to deoxygenation operation.
4. the step of method according to claim 2, the formation uniform liquid crystal compound, includes:
A) mix at least one reactive liquid crystalline compound, at least one non-reactive liquid crystal compound and it is described extremely
A kind of few polymerization initiator forms mixture;
B) mixture is heated into liquid condition;
C) it is uniformly mixed;
D) it is slowly cooled to room temperature;Or
A) mix at least one reactive liquid crystalline compound, at least one non-reactive liquid crystal compound and it is described extremely
A kind of few polymerization initiator forms mixture;
B) organic solvent is added in Xiang Suoshu mixture and forms homogeneous solution;
C) it is uniformly mixed;
D) organic solvent is slowly vapored away.
5. such as method of any of claims 1-2, wherein the step of liquid crystal compound is dispersed in continuous phase
It further include continuously being added to liquid crystal droplet conformational change agent to described.
6. such as method of any of claims 1-2, wherein the step of formation monodispersed liquid crystal droplet also wraps
It includes and copolymerizable functional monomer or functional nano ball is added.
7. such as method of any of claims 1-2, wherein the size of the monodisperse liquid crystal droplet is from 0.1 micron
To 100 microns.
8. the method as described in claim 1, wherein at least one non-reactive liquid crystal is nematic liquid crystal.
9. method according to claim 8, wherein the polymer particles are polymer ellipsoid, the length of the polymer ellipsoid
Diameter ratio is 1.0 to 3.0.
10. method as claimed in claim 5, wherein the polymer particles are porous polymer microballoon, the polymer
The particle size of microballoon is 0.1 micron to 100 microns.
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---|---|---|---|---|
IT201900023820A1 (en) * | 2019-12-12 | 2021-06-12 | Advanced Customized Solutions S R L | MESOMORPHIC COMPOSITION FOR ELECTRO-OPTICAL LIQUID CRYSTAL MODULATORS AND MODULATOR INCLUDING THE SAME |
CN112433404B (en) * | 2020-11-22 | 2021-08-27 | 北京科技大学 | Method for preparing wide wave reflection cholesteric liquid crystal film by photo-thermal response technology |
CN114773893B (en) * | 2022-04-25 | 2023-03-21 | 安徽省建筑科学研究设计院 | Preparation method of infrared reflection emulsion with surface-modified colloidal particles |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07278544A (en) * | 1994-04-05 | 1995-10-24 | Hitachi Chem Co Ltd | Production of purified liquid crystal, liquid crystal cell and display device for liquid crystal |
JPH1095979A (en) * | 1996-09-26 | 1998-04-14 | Toshiba Corp | Liquid crystal microcapsule and its production |
CN1625592A (en) * | 2002-02-01 | 2005-06-08 | 巴斯福股份公司 | Aqueous mini-emulsions which are stable in storage and based on cholesteric mixtures |
CN101080672A (en) * | 2004-12-14 | 2007-11-28 | 荷兰聚合物研究所 | Porous holographic film |
CN101225308A (en) * | 2007-09-17 | 2008-07-23 | 北京科技大学 | Method for preparing polymer dispersion liquid crystal material by ultraviolet-heating step-polymerization process |
CN102099400A (en) * | 2008-05-21 | 2011-06-15 | 东丽株式会社 | Method for producing polymer fine particle |
CN106749871A (en) * | 2016-12-19 | 2017-05-31 | 江南大学 | A kind of preparation method of printing in textiles liquid crystal microcapsule |
CN106832201A (en) * | 2016-12-30 | 2017-06-13 | 济南大学 | A kind of method for preparing monodisperse polymer microsphere in micro level at room temperature |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI447211B (en) * | 2010-12-30 | 2014-08-01 | Au Optronics Corp | Chiral compound with isosorbide moiety and chiral composition and blue phase liquid christal composition thereof |
KR101971300B1 (en) * | 2011-05-09 | 2019-04-22 | 메르크 파텐트 게엠베하 | Reactive mesogen based polymer particles |
US10441936B2 (en) * | 2014-09-02 | 2019-10-15 | Jnc Corporation | Liquid crystal capsule and method for producing the same |
CN104307445B (en) * | 2014-09-30 | 2016-03-30 | 永发印务(东莞)有限公司 | A kind of manufacture method of many shells liquid crystal microcapsule of cross polymerization |
-
2017
- 2017-08-23 CN CN201710740022.5A patent/CN109423300B/en active Active
-
2018
- 2018-08-13 WO PCT/CN2018/100203 patent/WO2019037613A1/en active Application Filing
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07278544A (en) * | 1994-04-05 | 1995-10-24 | Hitachi Chem Co Ltd | Production of purified liquid crystal, liquid crystal cell and display device for liquid crystal |
JPH1095979A (en) * | 1996-09-26 | 1998-04-14 | Toshiba Corp | Liquid crystal microcapsule and its production |
CN1625592A (en) * | 2002-02-01 | 2005-06-08 | 巴斯福股份公司 | Aqueous mini-emulsions which are stable in storage and based on cholesteric mixtures |
CN101080672A (en) * | 2004-12-14 | 2007-11-28 | 荷兰聚合物研究所 | Porous holographic film |
CN101225308A (en) * | 2007-09-17 | 2008-07-23 | 北京科技大学 | Method for preparing polymer dispersion liquid crystal material by ultraviolet-heating step-polymerization process |
CN102099400A (en) * | 2008-05-21 | 2011-06-15 | 东丽株式会社 | Method for producing polymer fine particle |
CN106749871A (en) * | 2016-12-19 | 2017-05-31 | 江南大学 | A kind of preparation method of printing in textiles liquid crystal microcapsule |
CN106832201A (en) * | 2016-12-30 | 2017-06-13 | 济南大学 | A kind of method for preparing monodisperse polymer microsphere in micro level at room temperature |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112439465A (en) * | 2019-08-28 | 2021-03-05 | 南京理工大学 | Micro-fluidic-based spherical particle preparation system and method |
WO2023236487A1 (en) * | 2022-06-07 | 2023-12-14 | 江苏集萃智能液晶科技有限公司 | Polymeric microparticle having pore channels of two sizes and preparation method therefor |
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