CN106292117B - A kind of electrophoresis particle and preparation method thereof, microcapsules and electronic ink screen - Google Patents
A kind of electrophoresis particle and preparation method thereof, microcapsules and electronic ink screen Download PDFInfo
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- CN106292117B CN106292117B CN201610569912.XA CN201610569912A CN106292117B CN 106292117 B CN106292117 B CN 106292117B CN 201610569912 A CN201610569912 A CN 201610569912A CN 106292117 B CN106292117 B CN 106292117B
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- 238000001962 electrophoresis Methods 0.000 title claims abstract description 92
- 239000002245 particle Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000003094 microcapsule Substances 0.000 title claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 61
- 239000004793 Polystyrene Substances 0.000 claims abstract description 51
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 38
- 230000004048 modification Effects 0.000 claims abstract description 36
- 238000012986 modification Methods 0.000 claims abstract description 36
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920002223 polystyrene Polymers 0.000 claims abstract description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- 239000004005 microsphere Substances 0.000 claims description 53
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 50
- 238000010526 radical polymerization reaction Methods 0.000 claims description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 15
- 150000002148 esters Chemical class 0.000 claims description 15
- -1 Ether metacrylic acid ester Chemical class 0.000 claims description 11
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 10
- 229920002125 Sokalan® Polymers 0.000 claims description 10
- 239000004584 polyacrylic acid Substances 0.000 claims description 10
- 238000005886 esterification reaction Methods 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- NAPFTKQHGOVNPC-UHFFFAOYSA-N 2-methoxyethanol;2-methylprop-2-enoic acid Chemical compound COCCO.CC(=C)C(O)=O NAPFTKQHGOVNPC-UHFFFAOYSA-N 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical group [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 claims description 3
- 239000012989 trithiocarbonate Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 2
- 125000006202 diisopropylaminoethyl group Chemical group [H]C([H])([H])C([H])(N(C([H])([H])C([H])([H])*)C([H])(C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000000758 substrate Substances 0.000 description 8
- 239000002775 capsule Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- BIKWAIVFONQVDV-UHFFFAOYSA-N COCCO.COC(=O)C=C Chemical compound COCCO.COC(=O)C=C BIKWAIVFONQVDV-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 230000033444 hydroxylation Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 230000011218 segmentation Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- DUDCYUDPBRJVLG-UHFFFAOYSA-N ethoxyethane methyl 2-methylprop-2-enoate Chemical compound CCOCC.COC(=O)C(C)=C DUDCYUDPBRJVLG-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/165—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on translational movement of particles in a fluid under the influence of an applied field
- G02F1/166—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on translational movement of particles in a fluid under the influence of an applied field characterised by the electro-optical or magneto-optical effect
- G02F1/167—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on translational movement of particles in a fluid under the influence of an applied field characterised by the electro-optical or magneto-optical effect by electrophoresis
-
- 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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- 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
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/165—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on translational movement of particles in a fluid under the influence of an applied field
- G02F1/1675—Constructional details
- G02F2001/1678—Constructional details characterised by the composition or particle type
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Nonlinear Science (AREA)
- Electrochemistry (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a kind of electrophoresis particle and preparation method thereof, microcapsules and electronic ink screens.Electrophoresis particle according to the present invention is the nanoparticle of nucleocapsid structure, wherein core TiO2Or ZnO；Shell is high molecular polymer of the modification on core, and high molecular polymer includes hydrophobic section and hydrophilic section.The preparation method of electrophoresis particle according to the present invention, comprising steps of modification chain-transferring agent；Modify polystyrene；Modify poly- oligomeric ethylene glycol methyl ether methacrylate；Modify polyelectrolyte.Microcapsules according to the present invention include electrophoresis particle of the invention.Electronic ink screen according to the present invention includes microcapsules of the invention.
Description
Technical field
The present invention relates to electric ink fields, and in particular to a kind of electrophoresis particle and preparation method thereof, microcapsules and electronics
Ink screen.
Background technique
The traditional preparation methods of electrophoresis particle are that coupling agent is added in alcohol water and carries out the pre- modification in surface to pigment molecule,
It is ground after centrifugal drying, adds polymer material and package processing is carried out to pigment molecule, i.e., by physical blending to it
It is prepared.
Traditional preparation methods exist as following drawbacks: (1) easily reuniting in drying process；(2) it can be generated in process of lapping
Dust；(3) pigment molecule needs successively to be surface modified, dry and grind, and technique is cumbersome；(4) it is limited, is gathered by modification efficiency
It closes object covering amount and is usually no more than 8%, therefore, dispersibility, stability and the ability for carrying charge of conventional electrophoretic particle have very
Big limitation.
Summary of the invention
The present invention provides a kind of electrophoresis particle and preparation method thereof, microcapsules and electronic ink screens, solve existing skill
Electrophoresis particle bad dispersibility present in art, problem easy to reunite, movement is insensitive and poor load-carrying ability.
According to an aspect of the present invention, a kind of electrophoresis particle is provided, the electrophoresis particle is the nanoparticle of nucleocapsid structure
Son, wherein
The core is TiO2Or ZnO；
The shell is high molecular polymer of the modification on the core, and the high molecular polymer includes hydrophobic section and hydrophilic
Section.
Optionally, electrophoresis particle according to the present invention, the hydrophobic section are made of polystyrene.
Optionally, electrophoresis particle according to the present invention, the hydrophilic section is by poly- oligomeric ethylene glycol methyl ether methacrylate
It is formed with polyelectrolyte.
Optionally, electrophoresis particle according to the present invention, the polyelectrolyte are polymethylacrylic acid diisopropylaminoethyl ethyl ester
Or polyacrylic acid.
Optionally, electrophoresis particle according to the present invention, the electrophoresis particle include: such as Formulas I, Formula II, formula III and formula IV institute
The nanoparticle of the nucleocapsid structure shown,
Wherein, P is selected from 40~60 integer；M is selected from 15~25 integer；N is selected from 15~25 integer.
According to another aspect of the present invention, a kind of preparation method of electrophoresis particle according to the present invention, including step are provided
It is rapid:
Modify chain-transferring agent: in TiO2Chain-transferring agent is modified in microballoon or ZnO microsphere；
Modify polystyrene: in the TiO for having modified chain-transferring agent2Polystyrene is modified in microballoon or ZnO microsphere；
Modify poly- oligomeric ethylene glycol methyl ether methacrylate: in the TiO for having modified polystyrene2Microballoon or ZnO microsphere
On, modify poly- oligomeric ethylene glycol methyl ether methacrylate；
Modify polyelectrolyte: in the TiO for having modified oligomeric ethylene glycol methyl ether methacrylate2Or it is modified in ZnO microsphere
Polyelectrolyte.
Optionally, preparation method according to the present invention, in the modification chain-transferring agent step,
The chain-transferring agent is trithiocarbonate or dithiocarbonates；
The TiO2Hydroxyl is contained on microballoon or ZnO microsphere surface；
The TiO of 1 equivalent2Esterification occurs for the chain-transferring agent of microballoon or ZnO microsphere and 5~10 equivalents, described
TiO2Or the chain-transferring agent is modified on the microballoon of ZnO.
Optionally, preparation method according to the present invention, in the modification polystyrene step,
1 equivalent has modified the TiO of chain-transferring agent2Microballoon or ZnO microsphere carry out activity certainly with the styrene of 40~60 equivalents
It is polymerize by base, in the TiO for having modified chain-transferring agent2Polystyrene has been modified in microballoon or ZnO microsphere.
Optionally, preparation method according to the present invention, in the poly- oligomeric ethylene glycol methyl ether methacrylate step of the modification
In rapid,
1 equivalent has modified the TiO of polystyrene2Microballoon or ZnO microsphere, the oligomeric ethylene glycol methyl ether first with 15~25 equivalents
Base acrylate carries out active free radical polymerization, in the TiO for having modified polystyrene2Or poly- oligomerization is modified on the microballoon of ZnO
Ethylene glycol monomethyl ether methacrylate.
Optionally, preparation method according to the present invention, in the modification polyelectrolyte step,
1 equivalent has modified the TiO of poly- oligomeric ethylene glycol methyl ether methacrylate2Or ZnO, the electrolysis with 15~25 equivalents
Matter monomer carries out active free radical polymerization, in the TiO for having modified poly- oligomeric ethylene glycol methyl ether methacrylate2Or it is repaired on ZnO
Polyelectrolyte is adornd.
Optionally, preparation method according to the present invention, the polyelectrolyte are polymethylacrylic acid diisopropylaminoethyl ethyl ester
Or polyacrylic acid.
According to another aspect of the present invention, a kind of microcapsules are provided, the microcapsules include electrophoresis particle of the invention.
According to another aspect of the present invention, a kind of electronic ink screen is provided, the electronic ink screen includes of the invention
Microcapsules.
Beneficial effects of the present invention are as follows:
Electrophoresis particle according to the present invention, the high molecular polymer density as electrophoresis particle shell structure is lower, reduces
The density of electrophoresis particle can make electrophoresis particle movement sensitiveer；High molecular polymer as electrophoresis particle shell structure has
Hydrophobic section and hydrophilic section make electrophoresis particle produce the property of surfactant-like, have good suspended dispersed.
The available movement sensitive of preparation method according to the present invention, with good suspended dispersed and not easy to reunite
Electrophoresis particle.
Electrophoresis particle in microcapsules according to the present invention has a good dispersibility, movement sensitive, and not easy to reunite
Property can make microcapsules of the invention for electronic ink screen.
Electronic ink screen according to the present invention, have it is good, clearly indicate effect.
Detailed description of the invention
Fig. 1 is the electronic ink screen according to one embodiment of the present invention；
Appended drawing reference:
First substrate 110, transparent electrode 120, capsule layer 130, positive charge electrophoresis particle 131, negative electrical charge electrophoresis particle
132, divide electrode 140 and the second substrate 150.
Specific embodiment
Specific embodiment is only the description of the invention, without constituting the limitation to the content of present invention, below in conjunction with
Invention is further explained and description for specific embodiment.
According to an aspect of the present invention, a kind of electrophoresis particle is provided, electrophoresis particle is the nanoparticle of nucleocapsid structure,
Wherein,
Core is TiO2Or ZnO；
Shell is high molecular polymer of the modification on core, and high molecular polymer includes hydrophobic section and hydrophilic section.
Electrophoresis particle according to the present invention, the high molecular polymer density as electrophoresis particle shell structure is lower, therefore drops
The low density of electrophoresis particle keeps electrophoresis particle movement sensitiveer；High molecular polymer as electrophoresis particle shell structure has
Hydrophobic section and hydrophilic section make electrophoresis particle produce the property of surfactant-like, and electrophoresis particle is made to have good suspension
Dispersibility.
A kind of embodiment of electrophoresis particle according to the present invention, hydrophobic section are made of polystyrene.
The density of electrophoresis particle according to the present invention, polystyrene is relatively small, and hydrophobic section is made of polystyrene can be with
The density of electrophoresis particle is reduced, so as to improve the autokinesis of electrophoresis particle.
A kind of embodiment of electrophoresis particle according to the present invention, hydrophilic section is by poly- oligomeric ethylene glycol methyl ether methacrylic acid
Ester and polyelectrolyte composition.
Electrophoresis particle according to the present invention, poly- oligomeric ethylene glycol methyl ether methacrylate contain the structure of ethylene glycol, because
This performance with lubricant can reduce the surface energy of electrophoresis particle, solve the problems, such as that electrophoresis particle is easy to reunite；Another party
The poly- oligomeric ethylene glycol methyl ether methacrylate in face can play stabilization to the dispersion of electrophoresis particle by steric effect.
Electrophoresis particle according to the present invention, polyelectrolyte are polymethylacrylic acid diisopropylaminoethyl ethyl ester or polyacrylic acid.
The amido of electrophoresis particle according to the present invention, polymethylacrylic acid diisopropylaminoethyl ethyl ester can adsorb H+Make electrophoresis
Particle is positively charged；Carboxyl in polyacrylic acid can ionize out H+, keep electrophoresis ion negatively charged, to form positive charge electrophoresis grain
Son and negative electrical charge electrophoresis particle.
A kind of embodiment of electrophoresis particle according to the present invention, electrophoresis particle include: such as Formulas I, Formula II, formula III and formula
The nanoparticle of nucleocapsid structure shown in IV,
Wherein, P is selected from 40~60 integer；M is selected from 15~25 integer；N is selected from 15~25 integer.
Electrophoresis particle according to the present invention, nanoparticle shown in Formulas I, Formula II, formula III and formula IV, the small movement spirit of density
It is quick, with good stable suspended dispersed, not easy to reunite.
In addition, within the above range by p, m and n limitation, p, m and n value are in upper range hereinafter, can control electrophoresis particle
It is unlikely to excessive, it is made to be easy to happen precipitating, influences its electrophoresis sensitivity；When p, m and n value be also unlikely to more than lower range
Keep the content of high molecular polymer very few, influences the stability and electrically charged amount of electrophoresis particle.
According to another aspect of the present invention, a kind of preparation method of electrophoresis particle according to the present invention, including step are provided
It is rapid:
Modify chain-transferring agent: in TiO2Chain-transferring agent is modified in microballoon or ZnO microsphere；
Modify polystyrene: in the TiO for having modified chain-transferring agent2Polystyrene is modified in microballoon or ZnO microsphere；
Modify poly- oligomeric ethylene glycol methyl ether methacrylate: in the TiO for having modified polystyrene2Microballoon or ZnO microsphere
On, modify poly- oligomeric ethylene glycol methyl ether methacrylate；
Modify polyelectrolyte: in the TiO for having modified poly- oligomeric ethylene glycol methyl ether methacrylate2Microballoon or ZnO microsphere
Upper modification polyelectrolyte.
Preparation method according to the present invention can be prepared the small movement sensitive of density, have good suspended dispersed and
Electrophoresis particle not easy to reunite.Wherein, TiO2Microballoon or the partial size of ZnO microsphere are typically distributed across 1~100um.
A kind of embodiment of preparation method according to the present invention, in modification chain-transferring agent step,
Chain-transferring agent is trithiocarbonate or dithiocarbonates；
TiO2Hydroxyl is contained on microballoon or ZnO microsphere surface；
1 equivalent TiO2Esterification occurs for the chain-transferring agent of microballoon or ZnO microsphere and 5~10 equivalents, in TiO2Microballoon or
Chain-transferring agent has been modified in ZnO microsphere.
Preparation method according to the present invention can be in TiO2Or chain transfer is modified on the core of ZnO, so as to carry out
The reaction of other high molecular polymers in grafting or block
In modification chain-transferring agent step, solvent, 1 equivalent TiO are with toluene2The chain of microballoon or ZnO microsphere and 5~10 equivalents
Transfer agent reacts, and makees base catalyst with the 4-dimethylaminopyridine (DMAP) of 5~50 equivalents, is azeotroped off in reaction system
Water, add dehydrated alcohol, room temperature reaction 24~48 hours, filtering three times, can be in TiO2It is repaired in microballoon or ZnO microsphere
Chain-transferring agent is adornd.
A kind of embodiment of method produced according to the present invention, in modification polystyrene step,
1 equivalent has modified the TiO of chain-transferring agent2Microballoon or ZnO microsphere carry out activity certainly with the styrene of 40~60 equivalents
It is polymerize by base, in the TiO for having modified chain-transferring agent2Upper polystyrene is modified on microballoon or ZnO microsphere.
Preparation method according to the present invention can modify the polystyrene of 40~60 degree of polymerization, control the benzene second of polymerization
The amount of alkene prevents electrophoresis particle excessive, and electrophoresis particle is made to be easy to precipitate in the solution.
In modification polystyrene step, solvent is done using dimethylformamide (DMF), 1 equivalent has modified chain tra nsfer
The TiO of agent2Microballoon or ZnO microsphere and the styrene of 40~60 equivalents react, different using the azo two of 0.1~0.2 equivalent
Butyronitrile (AIBN) is used as radical initiator, and pump drainage three times, sufficiently pumps the oxygen in system in liquid nitrogen-vacuum-dissolution system
Gas, then system is reacted 8~14 hours at 60~80 DEG C, is settled in ether three times, 20~30 hours dry, is modifying chain
The TiO of transfer agent2Microballoon or ZnO microsphere modify upper polystyrene.
A kind of embodiment of preparation method according to the present invention, in modification oligomeric ethylene glycol methyl ether methacrylate step
In rapid,
1 equivalent has modified the TiO of polystyrene2Microballoon or ZnO microsphere, the oligomeric ethylene glycol methyl ether first with 15~25 equivalents
Base acrylate carries out active free radical polymerization, in the TiO for having modified polystyrene2Gather widow on microballoon or ZnO microsphere in modification
Methoxypolyethylene glycol methacrylate.
Preparation method according to the present invention can modify the oligomeric ethylene glycol methyl ether metering system of 15~25 degree of polymerization
Acid esters, the amount of control polymerization oligomeric ethylene glycol methyl ether methacrylate, makes it be unlikely to keep particle excessive, poor dispersion,
Also it is unlikely to keep the amount of modification very little, does not have corresponding effect.
Preparation method according to the present invention, in modifying poly- oligomeric ethylene glycol methyl ether methacrylate (OEGMA) step,
Solvent is made with DMF, 1 equivalent has modified the TiO of polystyrene2The OEGMA of microballoon or ZnO microsphere and 15~25 equivalents occurs anti-
It answers, radical initiator is used as using the azodiisobutyronitrile (AIBN) of 0.1~0.2 equivalent, in liquid nitrogen-vacuum-dissolution system
Middle pump drainage three times, sufficiently pumps the oxygen in system, and then system is reacted 8~14 hours at 60~80 DEG C, settles in ether
Three times, 20~30 hours dry, in the TiO for having modified polystyrene2Microballoon or ZnO microsphere modify upper POEGMA.
A kind of embodiment of method produced according to the present invention is modifying polyelectrolyte step,
1 equivalent has modified the TiO of poly- oligomeric ethylene glycol methyl ether methacrylate2On microballoon or ZnO microsphere, activity is carried out
Radical polymerization closes the polyelectrolyte of 15~25 equivalents.
Preparation method according to the present invention can modify the polyelectrolyte of 15~25 degree of polymerization.
A kind of embodiment of method produced according to the present invention, polyelectrolyte are polymethylacrylic acid diisopropylaminoethyl ethyl ester
Or polyacrylic acid.
Preparation method according to the present invention, when polyelectrolyte is polymethylacrylic acid diisopropylaminoethyl ethyl ester, amido
H can be adsorbed+, keep electrophoresis particle positively charged；When polyelectrolyte is polyacrylic acid, carboxyl can ionize out H+, make electrophoresis ion
It is negatively charged.
Preparation method according to the present invention, using DMF as solvent, 1 equivalent has modified the TiO of POEGMA2Microballoon or ZnO are micro-
The methacrylic acid diisopropylaminoethyl ethyl ester (DPA) or acrylic acid (AA) of ball and 15~25 equivalents react, using 0.1~
The azodiisobutyronitrile (AIBN) of 0.2 equivalent is used as radical initiator, and pump drainage three times, fills in liquid nitrogen-vacuum-dissolution system
Divide the oxygen pumped in system, then system is reacted 8~14 hours at 60~80 DEG C, is settled in ether three times, dry 20~
30 hours, in the TiO for having modified POEGMA2Microballoon or ZnO microsphere modify upper POEGMA.
According to another aspect of the present invention, a kind of microcapsules are provided, microcapsules include electrophoresis particle of the invention.
Electrophoresis particle in microcapsules according to the present invention includes good dispersibility, movement sensitive, and appearance not easy to reunite
Easily make positive charge electrophoresis particle and negative electrical charge electrophoresis particle
According to another aspect of the present invention, a kind of electronic ink screen is provided, electronic ink screen includes micro- glue of the invention
Capsule.
Electronic ink screen according to the present invention, have it is good, clearly indicate effect.
It can be seen that electrophoresis particle according to the present invention and preparation method thereof, microcapsules and electronic ink screen optional factor
More, claim can be combined into different embodiments according to the present invention, therefore embodiment cannot function as to limit of the invention
System, but of the invention is further described.Below in conjunction with electrophoresis particle preparation method embodiment to the present invention carry out into
The description of one step.
Embodiment 1
The preparation method of electrophoresis particle according to the present invention, comprising steps of modification chain-transferring agent: chain-transferring agent is three thio
Carbonic ester；TiO2Microsphere surface contains hydroxyl, 1 equivalent TiO2Esterification occurs for the chain-transferring agent of microballoon and 5 equivalents, in modification
Chain-transferring agent；Modify polystyrene: 1 equivalent has modified the TiO of chain-transferring agent2Microballoon carries out activity with the styrene of 40 equivalents
Free radical polymerization, in the TiO for having modified chain-transferring agent2Upper polystyrene is modified on microballoon；Modify oligomeric ethylene glycol methyl ether methyl
Acrylate: 1 equivalent has modified the TiO of polystyrene2Or the microballoon of ZnO, the oligomeric ethylene glycol methyl ether methyl-prop with 15 equivalents
Olefin(e) acid ester carries out active free radical polymerization, in the TiO for having modified polystyrene2Or upper poly- oligomerization second two is modified on the microballoon of ZnO
Alcohol methyl ether methacrylate；Modify polyelectrolyte: 1 equivalent has modified the TiO of poly- oligomeric ethylene glycol methyl ether methacrylate2
On microballoon, the polyelectrolyte of 15 equivalents on active free radical polymerization is carried out, polyelectrolyte is polymethylacrylic acid diisopropylaminoethyl
Ethyl ester.
Embodiment 2
The preparation method of electrophoresis particle according to the present invention, comprising steps of modification chain-transferring agent: chain-transferring agent is two thio
Carbonic ester；TiO2Microsphere surface contains hydroxyl, 1 equivalent TiO2Esterification occurs for the chain-transferring agent of microballoon and 10 equivalents, in modification
Chain-transferring agent；Modify polystyrene: 1 equivalent has modified the TiO of chain-transferring agent2Microballoon carries out activity with the styrene of 60 equivalents
Free radical polymerization, in the TiO for having modified chain-transferring agent2Microballoon on modify upper polystyrene；Modify oligomeric ethylene glycol methyl ether first
Base acrylate: 1 equivalent has modified the TiO of polystyrene2Microballoon, the oligomeric ethylene glycol methyl ether methacrylic acid with 125 equivalents
Ester carries out active free radical polymerization, in the TiO for having modified polystyrene2Microballoon on modify upper poly- oligomeric ethylene glycol methyl ether methyl
Acrylate；Modify polyelectrolyte: 1 equivalent has modified the TiO of poly- oligomeric ethylene glycol methyl ether methacrylate2On microballoon, into
The polyelectrolyte of 25 equivalents on row active free radical polymerization, polyelectrolyte are polyacrylic acid.
Embodiment 3
The preparation method of electrophoresis particle according to the present invention, comprising steps of modification chain-transferring agent: chain-transferring agent is three thio
Carbonic ester；The microsphere surface of ZnO contains hydroxyl, and esterification, modification occur for the microballoon of 1 equivalent ZnO and the chain-transferring agent of 8 equivalents
Chain transfer；Modify polystyrene: 1 equivalent has modified the ZnO microsphere of chain-transferring agent, carries out activity with the styrene of 50 equivalents
Upper polystyrene is modified in free radical polymerization in the ZnO microsphere for modified chain-transferring agent；Modify oligomeric ethylene glycol methyl ether methyl-prop
Olefin(e) acid ester: 1 equivalent has modified the ZnO microsphere of polystyrene, carries out with the oligomeric ethylene glycol methyl ether methacrylate of 20 equivalents
Active free radical polymerization modifies upper poly- oligomeric ethylene glycol methyl ether methacrylic acid on the microballoon for the ZnO for having modified polystyrene
Ester；Modify polyelectrolyte: 1 equivalent has been modified in the ZnO microsphere of poly- oligomeric ethylene glycol methyl ether methacrylate, carries out activity certainly
It polymerize the polyelectrolyte of upper 20 equivalent by base, polyelectrolyte is polymethylacrylic acid diisopropylaminoethyl ethyl ester.
Embodiment 4
The preparation method of electrophoresis particle according to the present invention, comprising steps of modification chain-transferring agent: chain-transferring agent is two thio
Carbonic ester；The microsphere surface of ZnO contains hydroxyl, and esterification, modification occur for the microballoon of 1 equivalent ZnO and the chain-transferring agent of 9 equivalents
Chain transfer；Modify polystyrene: 1 equivalent has modified the microballoon of the ZnO of chain-transferring agent, lives with the styrene of 55 equivalents
Upper polystyrene is modified in the polymerization of free love base on the microballoon for the ZnO for having modified chain-transferring agent；Modify oligomeric ethylene glycol methyl ether first
Base acrylate: 1 equivalent has modified the ZnO microsphere of polystyrene, the oligomeric ethylene glycol methyl ether methacrylate with 23 equivalents
Active free radical polymerization is carried out, upper poly- oligomeric ethylene glycol methyl ether metering system is modified in the ZnO microsphere for modified polystyrene
Acid esters；Modify polyelectrolyte: 1 equivalent has been modified in the ZnO microsphere of poly- oligomeric ethylene glycol methyl ether methacrylate, carries out activity
Radical polymerization closes the polyelectrolyte of 18 equivalents, and polyelectrolyte is polyacrylic acid.
Embodiment 5
The preparation method of electrophoresis particle according to the present invention, comprising steps of modification chain-transferring agent: chain-transferring agent is three thio
Carbonic ester；TiO2Microsphere surface contains hydroxyl, 1 equivalent TiO2Esterification occurs for the chain-transferring agent of microballoon and 7 equivalents, in modification
Chain-transferring agent；Modify polystyrene: 1 equivalent has modified the TiO of chain-transferring agent2Microballoon carries out activity with the styrene of 45 equivalents
Free radical polymerization, in the TiO for having modified chain-transferring agent2Microballoon on modify upper polystyrene；Modify poly- oligomeric ethylene glycol methyl ether
Methacrylate: 1 equivalent has modified the TiO of polystyrene2Microballoon, the oligomeric ethylene glycol methyl ether methacrylic acid with 21 equivalents
Ester carries out active free radical polymerization, in the TiO for having modified polystyrene2Upper poly- oligomeric ethylene glycol methyl ether methyl-prop is modified on microballoon
Olefin(e) acid ester；Modify polyelectrolyte: 1 equivalent has modified the TiO of poly- oligomeric ethylene glycol methyl ether methacrylate2On microballoon, carry out
The polyelectrolyte of 17 equivalents on active free radical polymerization, polyelectrolyte are polyacrylic acid.
It can be seen that according to embodiments of the present invention 1~5 has been prepared positive charge electrophoresis particle and negative electrical charge electrophoresis grain
Son, the electrophoresis particle being prepared include good and stable dispersibility, movement sensitive, and not easy to reunite are easy to make positive electricity
Lotus electrophoresis particle and negative electrical charge electrophoresis particle.
By the positive charge electrophoresis particle and negative electrical charge electrophoresis particle of the embodiment of the present invention 1~5, it is prepared into microcapsules and is used for electricity
Sub- ink screen, the electronic ink screen includes: first substrate 110, transparent electrode 120, capsule layer 130, positive charge as shown in Figure 1:
Electrophoresis particle 131, negative electrical charge electrophoresis particle 132, segmentation electrode 140 and the second substrate 150；Wherein capsule layer 130 is located at first
It include positive charge electrophoresis particle 131 according to the present invention in capsule layer 130 and negative between substrate 110 and the second substrate 150
Charge electrophoresis particle 132；Transparent electrode 120 is provided with towards capsule is laminated in first substrate；In the second substrate towards capsule
Layer is provided with segmentation electrode on one side.
Electronic ink screen according to the present invention have it is good, clearly indicate effect.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (9)
1. a kind of electrophoresis particle, which is characterized in that the electrophoresis particle is the nanoparticle of nucleocapsid structure, wherein
The core is TiO2Or ZnO；
The shell is high molecular polymer of the modification on the core, and the high molecular polymer includes hydrophobic section and hydrophilic section；
The electrophoresis particle includes: the nanoparticle of the nucleocapsid structure as shown in Formulas I, Formula II, formula III and formula IV,
Wherein, P is selected from 40~60 integer；M is selected from 15~25 integer；N is selected from 15~25 integer.
2. a kind of preparation method of electrophoresis particle as described in claim 1, which is characterized in that comprising steps of
Modify chain-transferring agent: in TiO2Chain-transferring agent is modified in microballoon or ZnO microsphere；
Modify polystyrene: in the TiO for having modified chain-transferring agent2Polystyrene is modified in microballoon or ZnO microsphere；
Modify poly- oligomeric ethylene glycol methyl ether methacrylate: in the TiO for having modified polystyrene2On microballoon or ZnO microsphere, repair
Adorn poly- oligomeric ethylene glycol methyl ether methacrylate；
Modify polyelectrolyte: in the TiO for having modified poly- oligomeric ethylene glycol methyl ether methacrylate2It is modified in microballoon or ZnO microsphere
Polyelectrolyte.
3. preparation method according to claim 2, which is characterized in that in the modification chain-transferring agent step,
The chain-transferring agent is trithiocarbonate or dithiocarbonates；
The TiO2The microsphere surface of microballoon or ZnO contain hydroxyl；
The TiO of 1 equivalent2Esterification occurs for the chain-transferring agent of microballoon or ZnO microsphere and 5~10 equivalents, in the TiO2It is micro-
The chain-transferring agent is modified on the microballoon of ball or ZnO.
4. preparation method according to claim 3, which is characterized in that in the modification polystyrene step,
1 equivalent has modified the TiO of chain-transferring agent2Microballoon or ZnO microsphere carry out living radical with the styrene of 40~60 equivalents
Polymerization, in the TiO for having modified chain-transferring agent2Polystyrene has been modified in microballoon or ZnO microsphere.
5. the preparation method according to claim 4, which is characterized in that in the poly- oligomeric ethylene glycol methyl ether methyl-prop of modification
In olefin(e) acid ester step,
1 equivalent has modified the TiO of polystyrene2Or ZnO microsphere, the oligomeric ethylene glycol methyl ether methacrylic acid with 15~25 equivalents
Ester carries out active free radical polymerization, in the TiO for having modified polystyrene2Poly- oligomeric ethylene glycol first is modified on microballoon or ZnO microsphere
Ether metacrylic acid ester.
6. preparation method according to claim 5, which is characterized in that in the modification polyelectrolyte step,
1 equivalent has modified the TiO of poly- oligomeric ethylene glycol methyl ether methacrylate2Microballoon or ZnO microsphere, with 15~25 equivalents
Electrolyte monomer carries out active free radical polymerization, in the TiO for having modified poly- oligomeric ethylene glycol methyl ether methacrylate2Microballoon or
Polyelectrolyte is modified in ZnO microsphere.
7. preparation method according to claim 6, which is characterized in that the polyelectrolyte is polymethylacrylic acid diisopropyl
Amino ethyl ester or polyacrylic acid.
8. a kind of microcapsules, which is characterized in that the microcapsules include electrophoresis particle described in claim 1.
9. a kind of electronic ink screen, which is characterized in that the electronic ink screen includes microcapsules according to any one of claims 8.
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| CN111704701B (en) * | 2020-07-15 | 2021-11-16 | 北京理工大学 | Unsaturated carboxylic acid/styrene monomer/methoxy polyethylene glycol carboxylate copolymer, preparation method, aqueous suspending agent and application |
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| CN1891735A (en) * | 2006-05-26 | 2007-01-10 | 上海大学 | Self-assembled water dispersible polyisocyanate composition, and its synthesizing method |
| CN100432817C (en) * | 2005-04-19 | 2008-11-12 | 精工爱普生株式会社 | Method for producing electrophoretic particles, electrophoretic dispersion solution, micro-capsule, electrophoresis display device and electronic machine |
| JP2010105365A (en) * | 2008-10-31 | 2010-05-13 | Fuji Xerox Co Ltd | Ink receptive particle, ink recording material, recording method, recording device and cartridge for storing ink receptive particle |
| CN103217847A (en) * | 2012-01-18 | 2013-07-24 | 广州奥翼电子科技有限公司 | Electrophoresis display particle comprising metal component and preparation method as well as functions thereof |
| EP2923695A1 (en) * | 2014-03-25 | 2015-09-30 | DendroPharm GmbH | Hyperbranched polyglycerol sulfates with hydrophobic cores |
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| JP2004233630A (en) * | 2003-01-30 | 2004-08-19 | Canon Inc | Electrophoresis particle and method for manufacturing the same, and electrophoresis display element using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100432817C (en) * | 2005-04-19 | 2008-11-12 | 精工爱普生株式会社 | Method for producing electrophoretic particles, electrophoretic dispersion solution, micro-capsule, electrophoresis display device and electronic machine |
| CN1891735A (en) * | 2006-05-26 | 2007-01-10 | 上海大学 | Self-assembled water dispersible polyisocyanate composition, and its synthesizing method |
| JP2010105365A (en) * | 2008-10-31 | 2010-05-13 | Fuji Xerox Co Ltd | Ink receptive particle, ink recording material, recording method, recording device and cartridge for storing ink receptive particle |
| CN103217847A (en) * | 2012-01-18 | 2013-07-24 | 广州奥翼电子科技有限公司 | Electrophoresis display particle comprising metal component and preparation method as well as functions thereof |
| EP2923695A1 (en) * | 2014-03-25 | 2015-09-30 | DendroPharm GmbH | Hyperbranched polyglycerol sulfates with hydrophobic cores |
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