CN108568278A - A kind of novel instant aerogel microball and preparation method thereof - Google Patents

A kind of novel instant aerogel microball and preparation method thereof Download PDF

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Publication number
CN108568278A
CN108568278A CN201710143602.6A CN201710143602A CN108568278A CN 108568278 A CN108568278 A CN 108568278A CN 201710143602 A CN201710143602 A CN 201710143602A CN 108568278 A CN108568278 A CN 108568278A
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China
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aeroge
instant
coating
microballoon
admixture
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CN201710143602.6A
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Chinese (zh)
Inventor
周咏梅
其他发明人请求不公开姓名
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Guangzhou Core Biotechnology Co Ltd
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Guangzhou Core Biotechnology Co Ltd
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Priority to CN201710143602.6A priority Critical patent/CN108568278A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02Making microcapsules or microballoons

Abstract

The present invention relates to one kind using aerogel microball as core, the instant aerogel microball of surface cladding or doping functional material or functional group.The aerogel microball includes at least one functional material or functional group and at least one aeroge.Also disclose the purposes of the method and the aerogel microball that manufacture the instant aerogel microball.The method disclosed by the invention for manufacturing the instant aerogel microball; be first by aerogel particle or prepare aeroge precursor substance homogenized with superhigh pressure water jet device or magnetic grinding or a combination of both homogenize; it admixes again or coats lid light-sensitive material/photo-curing material, functional material or function monomer substance or their compositions, finally acted on three spectral line photocurings and obtain instant aerogel microball material.

Description

A kind of novel instant aerogel microball and preparation method thereof
Technical field
The present invention relates to the invention belongs to biomedicine, analytical chemistry, nanometer material science, synthesising chemical technology, green woods Material, neoformation technology, macromolecular polymerization reaction technology, Solid-phase organic synthesis, macromolecule material surface modification, polymers function are micro- Ball, instant aerogel microball, aerogel particle, multifunctional material, the aeroge instant of field of polymer microsphere materials are micro- Ball, and preparation method thereof and the aeroge instant microballoon purposes.More particularly it relates to coat/admix work( The aeroge instant microballoon of energy material.
Background technology
Aerogel particle can have extra-low density, high voidage and small-bore.Their weight can it is extremely low and they Usually formed by with the particle in gas instead gel.Nanoscale aeroge has high specific area, low thermal conductivity and low ratio Weight characteristic, can be used for the dispersion of particulate matter in the solution, enhances its suspension stability, while can enhance the absorption of particle surface Property.
Aerogel particle has been used to need the occasion of low-density packing material, is such as measured for deep-sea flow velocity, anti-submarine warfare It strives, sandwich composite heat-insulated material, seabed/marine equipment of aerospace industry and auto industry, petroleum pipeline, boiler, household electrical appliance Equal fields.
Chinese patent CN101346420 describes a kind of composite material based on aeroge, which includes at least A kind of polymer and at least one aeroge.The aeroge at least substantially prevents from gathering with coating/admixture substance is coated with It closes in object intrusion aerogel pores.Also disclose the purposes of the method and the composite material that manufacture the composite material.
Chinese patent CN102746440A describe it is a kind of the present invention relates to it is a kind of be applied to enhancing than turbid reagent polyphenyl The preparation process of ethylene microballoon.The polystyrene microsphere of the preparation process production of the invention, cost are offshore company's microballoon price 1%, anti-freezing collection effect is that more than ten times of offshore company's microballoon and the cross-linking efficiency of antibody improve 50%, and disclosure satisfy that The requirement of multiple projects, a ball are multi-purpose.But it is easy after being stored for a long time with microballoon prepared by this method or after activated protein crosslinking poly- Collection precipitation, the latex of preparation once freeze, and melting again can cause latex demulsification and active material denaturation.
Chinese patent CN101679657 discloses a kind of aerogel particle of average grain diameter less than 1 micron, contains the gas Product, the method for the manufacture aerogel particle and the purposes of the aerogel particle of gel particle.It also discloses simultaneously The method for manufacturing the particle, wherein aerogel particle is homogenized or wet-milling.The aerogel particle can be with It is surface-treated during attrition process to prevent from agglomerating or assemble.The aerogel particle can be used for various products and answer With.But this aerogel particle is not suitable for external diagnosis reagent, medicine, food and cosmetic field, usually as heat-insulated material Material uses.
Chinese patent CN102516437B discloses a kind of preparation method of polystyrene functional microsphere, and this method first will Styrene, contraposition substituted styrene derivative, crosslinking agent and the initiator mixing of metering, obtain suspension polymerisation oil phase, then hang Floating polymerization obtains polystyrene multi-component copolymer microballoon, and multi-component copolymer microballoon is finally implemented complete alkylation or is acylated work( It can react, obtain the polystyrene functional microsphere that built-in function group is evenly distributed.The present invention is implementing functionalizing reaction When can realize the complete substitution of polystyrene component, therefore the distribution of microballoon built-in function group is visibly homogeneous, group content Also it can realize and accurately control, be very beneficial for the solid phase carrier as Solid-phase organic synthesis and combinatorial chemistry, for polypeptide, more The Solid-phase organic synthesis of the substances such as sugar, nucleic acid, natural products, organic molecule.
China applies for a patent CN102731701A and discloses that a kind of to prepare monodisperse polymer function micro- using photochemical method The method of ball.Under the regulation and control of reversible addition-fracture chain tra nsfer (RAFT) reagent, uniform particle diameter is synthesized using photochemical method The polymers function microballoon of nanoscale, micron order sizes.First by simple function group carbon carbon double bond monomer, polyfunctional group carbon carbon Mixed solvent is added in double bond crosslinking agent, monomer containing functional group, dispersant, stabilizer, RAFT reagents, photoinitiator pore-foaming agent etc. In, ultrasonic emulsification is made the dispersion liquid of stable homogeneous, and dispersion liquid moves into reaction bulb, and stirring vacuumizes rear nitrogen charging to constant pressure, It uses ultra violet lamp to stop within 8 hours or so reaction at room temperature, single point of uniform particle diameter is obtained after reaction solution centrifugal sedimentation, washing, drying Dissipate polymers function microballoon.The preparation process production efficiency is high, energy conservation and environmental protection.Can prepare as needed grain size from 5 nanometers to The mono-dispersion microballoon of 1000 microns of thousands of kinds of specifications.It is widely used in coating, adhesive, biological medicine and electronic information correlation neck Domain.
China applies for a patent CN102989401A and discloses a kind of reflux precipitation polymerization preparation side of polymer gel microsphere Method.The present invention improves distillation sedimentation and prepares monodisperse hydrophilicity functional microsphere, and distilation steps therein are changed to reflux step Suddenly, magnetic agitation is added;Monomer can additionally be added dropwise during the reaction and increase microspherulite diameter.Present invention preserves distillations to precipitate Technology take it is short, without adding emulsifier or stabilizer, the advantages that reaction is mildly easy to control, and simplify device, reduce The colloid unstable phenomenon in precipitation process is distilled, the controllability and operability of reaction are improved.The polymer gel of preparation is micro- Spherolite diameter is uniform in size, and grain size and yield can be by changing the conditional regulatories such as reaction time, monomer concentration, content of crosslinking agent, tool There is good application prospect.
China apply for a patent CN102492073A disclose a kind of multi-functional microballoon of the magnetic fluorescence based on quantum dot and its Preparation method belongs to multifunctional material field.The present invention is by hydrophobic magnetic nano particle, hydrophobic monomer, oil-soluble quantum Point and oil-soluble initiator are sufficiently mixed, and form evenly dispersed oil phase fluid;Using jet flow suspension polymerization by oil phase fluid Broken dispersion forms uniform oil droplet, and O/W type suspension is formed in water phase, and it is multi-functional that constant temperature aggregates into magnetic fluorescence Microballoon.Uniform particle diameter, the microballoon size of the multi-functional microballoon of magnetic fluorescence prepared by the present invention are controllable, magnetic content is high, fluorescence efficiency High, chemical property is stablized, and is had potential application in food safety detection and biomedical sector.
It is fully incorporated herein by reference above with the patent and publication mentioned by text of the statement and constitutes the application A part.
A feature of the present invention is to provide one kind using aeroge nano particle as kernel, and surface layer coats/admix work( Energy material/functional group, it is therefore an objective to by the low-density and high adsorption of aeroge, play enhancing suspension stability and dispersion Effect.
It is another feature that providing the aeroge with low-gravity, high absorption capacity, superpower suspension stability Instant microballoon.
The present invention is coating/is admixing functional material/functional group another feature is that providing on aeroge surface, and passes through After activation process, bioactive substance connection can be directly carried out, and there is low-temperature resistance characteristic and higher suspension stability.Also can simultaneously Stablize the conformation of bioactive substance.
Another feature of the invention that providing a kind of grinding of magnetic, high-pressure jet technology and three spectral line high energy photocurings The method that technology was combined prepare functional microsphere, the method use magnetic grinding, three spectral line photocuring of high-pressure jet and two steps for the first time Series connection method has the characteristics that simple, quick, flexible, efficient, uniform, time saving and highly sensitive in combination with microflow control technique progress Degree, high-throughput detection and analysis, and new optical analysis detection technique can be carried out by this method and established;The three spectral line light Solidification processing method is three spectral line photocuring processing method of high-energy, and high energy light is including but not limited to high energy UV, high energy Infrared light, high energy visible light, X-ray, gamma-rays, microwave and combination thereof etc.;Three spectral lines photocuring processing such as Fig. 4 therein Shown, G01 lasers or transmitter are located at conveying device tangential direction, more excellent with transfer device plane in 45 ± 45 degree of arrangements Choosing is 45 ± 43 degree, most preferred 45 ± 0.05 degree;G02 lasers or transmitter are located at conveying device vertically to direction, with Transfer device plane is more preferably 90 ± 3.0 degree in 90 degree of arrangements, most preferred 90 ± 0.05 degree;G03 lasers or transmitting Device is located at conveying device forward direction, is more preferably 45 ± 43 degree, most preferably with transfer device plane in 45 ± 45 degree of arrangements 45 ± 0.05 degree, three lasers or transmitter can carry out being based on x, y, z axis by artificial mechanism or the driving of automatic motor It moves in direction;Laser power therein is more preferably 0.001w~1000w, preferably in 0.0001w~5000w 0.01w~500w.
Others features and advantages of the invention will carry out part and illustrate in the following description, and partly clear from the description It is clear or can be to understand by the practice of the present invention.Objectives and other advantages of the present invention can pass through the description and appended claims In the element that particularly points out and combination and realize and obtain.
Invention content
In order to realize the above feature and further advantage, and the mesh of the invention according to embodiment herein and wide in range description , the present invention relates to a kind of microballoon is prepared comprising at least one functional material/functional group and at least one aeroge.One In a or multiple embodiments, coating/admixture of the functional material/functional group preferably as aeroge nano particle.One As the aeroge with adsorptivity at least partly, if not fully, at least one functional material be surface-treated with Functional material/the functional group on substantially capable absorption or connection surface layer.Preferably, coating/admixture on aeroge Only on aerogel particle outer surface or a small amount of blending wherein, to be conducive to the absorption or connection of bioactive substance. In one or more embodiments, coating/admixture can prevent aeroge from collapsing, fragmentation and other materials immerse airsetting Adsorptivity/connectivity of glue.By providing this coating/admixture, the characteristic of aeroge is maintained, so that gas Gel can play itself intrinsic performance, such as low-density, low heat conductivity and high-ratio surface.Conducive to coating/admixture It suspends and stablizes.
Aeroge used in the present invention can be hydrophilic aerogel, can also be hydrophobic hydrophilic aerogel, be book hair Bright another feature.
The invention further relates to a kind of aeroges comprising at least one functional material/functional group and at least one processing Functional material.The aeroge of general tool adsorptivity or active group at least partly, if not progress surface fully, is needed changes Property processing.The aeroge of processing has adsorptivity or can connect activity.In one or more embodiments, when the gas that will be handled Gel introducing is when leading at least one functional material/functional group, as kernel aeroge due to, such as aeroge it is hydrophobic/ Hydrophilic nmature and substantially wherein not by the incorporation of functional material/functional group.
The invention further relates to one kind including a kind of at least one functional material/functional group and at least one pretreated gas Gel.The aeroge of general tool adsorptivity or the active group in surface at least partly, if not all, needs to be located in advance Reason.The aeroge of processing keeps high adsorption or connectivity.In one or more embodiments, when aeroge will be pre-processed As kernel, when cladding/blending at least one functional material/functional group, functional material/functional group is due in aeroge The hydrophobic/hydrophilic property in portion and substantially do not enter pretreatment aeroge inside.Pretreated aeroge can improve cladding/blending Functional material/functional group and its combination enhance suspension stability and absorption property.
In at least one embodiment, the present invention relates to comprising at least one functional material as cladding/admixture/ Functional group and at least one pretreated aeroge.The pretreated aeroge can be used for many fields.For example, latex microsphere The aeroge instant microballoon of cladding/blending can be used for preparing latex enhancing immune turbidimetry reagent, and the micro-spheres that shine/ The aeroge instant microballoon of blending can be used for preparing liquid crystal display, Mobile phone screen, electrochemiluminescent immunoassay diagnostic reagent, fluidic cell Instrument analytical reagent, digital pcr reagent, internal cell imaging, histocyte analysis etc..Aeroge can be pretreated aeroge And/or the aeroge of cladding or blending functional material/functional group.Functional material/functional group of cladding/blending can be aqueous With cladding/blending on aeroge surface layer in solvent or organic solvent.Functional material/functional group of cladding/blending can be aqueous Or it dissolves or disperses in non-aqueous solvent.
In another embodiment, wherein at least a part of the present invention relates to the aeroge with absorption/connectivity energy The aeroge at least partly coats/admixes above-mentioned functional material/functional group.
In one or more embodiments, the invention further relates to a kind of the complete of manufacture instant aerogel microball of the present invention New method includes that one or more claddings/admix into functional material/functional group, Yi Jitong are formed on the surface of aeroge Cross magnetic grinding, the method for preparing feature capability microballoon that high injection technology is combined with three spectral line high energy photocuring technologies, the party Method can carry out highly sensitive, high-throughput detection and analysis in combination with microflow control technique, and new light can be carried out by this method Analytical technology is learned to establish and analysis and detection device manufacture.
Moreover, it relates to which a kind of method of manufacture functional microsphere, includes that the surface of nano particle is a kind of or more The functional microsphere system of progress that functional material/functional group is ground with magnetic, high injection technology is connected with three spectral line high energy photocuring technologies It is standby.
The present invention further relates to the purposes of instant aerogel microball of the present invention, include, but are not limited to diagnostic reagent manufacture, Histocytology imaging analysis, functional paint, function cosmetics, functional food, fertilizers, liquid crystal product, paper etc., and on The purposes stated.
Specific embodiment
The present invention includes, but are not limited to the following embodiment of label.
1. a kind of instant aerogel microball, including at least one as shell material or functional material/function of cladding/blending Group and at least one tool nanoporous aerogel particle, wherein functional material/functional group of shell material or cladding/blending are substantially not Into inside the aeroge.
2. the instant aerogel microball of embodiment 1, including at least one as shell material or the function material of cladding/blending Material/functional group and at least one tool nanoporous aerogel particle, wherein at least a part of aeroge at least partly functional material/work( Energy group is to basically prevent inside functional material/functional group intrusion aeroge.
3. the instant aerogel microball of any one of embodiment 1-2, aeroge therein is pretreated aeroge.
4. the instant aerogel microball of any one of embodiment 1-3, wherein instant aerogel microball are latex gas Gel micro-ball or luminous microballoon aeroge.
5. the instant aerogel microball of any one of embodiment 1-4, wherein at least one functional material is poly- γ paddy Propylhomoserin.
6. the instant aerogel microball of any one of embodiment 1-5, wherein at least one functional material is photosensitive material Material.
7. the instant aerogel microball of any one of embodiment 1-6, wherein at least one functional material is hexahydro neighbour Phthalic acid bisglycidyl ester is poly-(Methyl vinyl ether/maleic acid)Copolymer is poly-(Methyl vinyl ether/maleic acid Acid anhydride)Copolymer is poly-(Methyl vinyl ether/maleic acid)Half-ester copolymerization object is poly-(Methyl vinyl ether/maleic anhydride)Half ester is total Polymers or bis- ((3,4- epoxycyclohexyls) methyl) adipate esters or photosensitive resin or photocuring adhesive or light curing agent or light Initiator or their mixture.
8. the instant aerogel microball of any one of embodiment 2-7, wherein aeroge have adsorption and can Connectivity has adsorptivity or connectivity, and is easily dispersed without being destroyed.
9. the instant aerogel microball of any one of embodiment 2-8, wherein aeroge, which have, prevents functional material/work( Energy group enters the ability inside aeroge completely or partially.
10. the instant aerogel microball of any one of embodiment 2-9, cladding/admixture wherein on aeroge It is functional material/functional group.
11. the instant aerogel microball of any one of embodiment 2-10, wherein cladding/blend include at least one Book hydrophobic/hydrophilic character material.
12. the instant aerogel microball of any one of embodiment 2-11, wherein cladding/blend are modified comprising surface Agent.
13. the instant aerogel microball of any one of embodiment 2-12, wherein cladding/blend are organic/inorganics Functional material/functional group.
14. the instant aerogel microball of any one of embodiment 2-13, wherein cladding/blend is by aeroge The functional material for coating/mixing/functional group composition.
15. the instant aerogel microball of any one of embodiment 2-14, wherein cladding/blend is to biological active matter Matter or reactive dye have adsorptivity or connectivity.
16. the instant aerogel microball of any one of embodiment 1-15, wherein functional material/functional group are that have Machine/inorganic functional material/functional group and cladding/admixture are functional material/functional groups of hydrophilic/hydrophobic.
17. the instant aerogel microball of any one of embodiment 2-16, wherein functional material/functional group are parents Water/hydrophobic function material/functional group and cladding/admixture include surface modifier, including but not limited to crosslinking agent, absorption Agent, surfactant etc..
18. the instant aerogel microball of any one of embodiment 1-17, functional material/functional group therein will not Completely in incorporation aeroge.
19. a kind of method for the instant aerogel microball preparing any one of embodiment 1-18 or 27-44, including will Aeroge enters homogeneous in high-pressure jet homogenizer after tentatively being ground in magnetic grinding machine at least one functional material/functional group Afterwards, make functional material/functional group cladding/blending in aeroge through three spectral line high energy light solidifications into light curring unit Surface, to form instant aerogel microball.
20. a kind of method for the instant aerogel microball preparing any one of embodiment 1-19 or 27-45, including By being penetrated into high pressure after tentatively grinding pretreated aeroge in magnetic grinding machine at least one functional material/functional group In stream homogenizer after homogeneous, make functional material/functional group packet through three spectral line high energy light solidifications into light curring unit It covers/admixes in aeroge surface, to form instant aerogel microball.
21. a kind of method for the instant aerogel microball preparing any one of embodiment 1-20 or 27-46, including will Aeroge is with molten containing hydrophilic/hydrophobic comprising dissolving or dispersion or the first reactant for being emulsified in aqueous solvent/organic solvent Liquid coats and includes that nonpolarity/polarity of the second reactant is molten then to addition in the aeroge coated with hydrophilic/hydrophobic solution Agent, and then remove and nonpolar solvent/polar solvent is spent by photocuring to obtain the reaction production of the first and second reactants Object is to form the aeroge of cladding/blending functional material/functional group, to form instant aerogel microball.
22. instant aeroge latex microsphere includes the airsetting of the cladding latex microsphere/microballoon that shines with embodiment 4 Glue microballoon.
23. a kind of microballoon includes the instant aerogel microball of any one of embodiment 1-22 or 27-48.
24. instant aeroge latex/shine microballoon, including the cladding of any one of embodiment 1-23 or 27-49/mix With the luminous microballoon of instant aeroge/latex of the latex/microballoon that shines.
25. the aeroge of a kind of functional material/functional group cladding/blending, including the gas with adsorptivity/connectivity Gel, wherein aeroge are at least partially by least one functional material/functional group cladding/blending on aeroge surface layer with basic On prevent functional material/functional group from entering inside aeroge.
26. the aeroge of the functional material of embodiment 25/functional group cladding/blending, functional material/function therein Group has adsorptivity/connectivity and wherein functional material/functional group is on the surface of aeroge, to enter gas Inside gel.
27. the aeroge of the functional material of any one of embodiment 25-26/functional group cladding/blending, wherein work( Energy material/functional group itself has the internal capacity prevented into aeroge.
28. the aeroge of the functional material of any one of embodiment 25-27/functional group cladding/blending, wherein gas Cladding/admixture on gel is functional material/functional group.
29. the aeroge of the functional material of any one of embodiment 25-28/functional group cladding/blending, wherein airsetting Cladding/admixture on glue includes functional material/functional group of at least one hydrophobic/hydrophilic.
30. the aeroge of the functional material of any one of embodiment 25-29/functional group cladding/blending, wherein airsetting Cladding/admixture on glue includes surface modifier.
31. the aeroge of the functional material of any one of embodiment 25-30/functional group cladding/blending, wherein gas Cladding/admixture on gel is organic/inorganic functional material, as carboxylated latex, amino latex, carboxyl fluorescent microsphere, algae are blue Albumen, carboxyl quantum dot fluorescence microballoon etc..
32. the aeroge of the functional material of any one of embodiment 25-31/functional group cladding/blending, wherein wrapping Cover/admixture is made of surface functional material/functional group on aeroge.
33. the aeroge of the functional material of any one of embodiment 25-32/functional group cladding/blending, wherein wrapping Cover/admixture have adsorptivity/connectivity.
34. the aeroge of the functional material of any one of embodiment 25-33/functional group cladding/blending, wherein wrapping Cover/admixture is organic/inorganic functional material/functional group and cladding/admixture is hydrophilic/hydrophobic functional material/function base Group.
35. the aeroge of the functional material of any one of embodiment 25-34/functional group cladding/blending, wherein wrapping Cover/admixture is hydrophilic/hydrophobic functional material and cladding/admixture includes surface modifier.
36. the aeroge of the functional material of any one of embodiment 25-35/functional group cladding/blending, wherein wrapping Covering object/admixture will not enter inside aeroge.
37. the aeroge of the functional material of any one of embodiment 25-36/functional group cladding/blending, including depositing It is the surface modifier of coating/between admixture and aeroge.
38. the aeroge of the functional material of any one of embodiment 25-37/functional group cladding/blending, including extremely Few difunctional/biradical coating/admixture.
39. the aeroge of the functional material of embodiment 38/functional group cladding/blending, wherein covering object/admixture One function/group is mainly combined with aeroge, and wherein at least one coating/the second function of admixture/group provides one kind Or multiple functions property, in order to combine active material.
40. a kind of instant aerogel microball, including at least one be used as functional material/functional group and at least one Aeroge with adsorptivity/connectivity, wherein functional material/functional group do not enter inside aeroge substantially.
41. a kind of instant aerogel microball, including at least one as functional material/functional group and at least one tool There are the aeroge of adsorptivity/connectivity, wherein active function material/functional group not to enter inside aeroge substantially.
42. a kind of instant aerogel microball, including at least one as the inorganic/organic of functional material/functional group Material and at least one aeroge with adsorptivity/connectivity, wherein inorganic/organic material does not enter aeroge substantially It is internal.
43. a kind of instant aerogel microball, including at least one ceramics and/or glass and at least one as matrix Aeroge with adsorptivity/connectivity, wherein ceramics and/or glass do not enter the hole of aeroge substantially.
44. the instant aerogel microball of embodiment 43, including it is at least one as functional material/functional group and/ Active function material/activity functional groups and at least one aeroge with adsorptivity/connectivity, it is wherein at least a part of Aeroge is coated at least partially by coating/admixture basically prevents functional material/functional group and/active function material Material/activity functional groups enter inside aeroge.
45. the instant aerogel microball of any one of embodiment 43-44, wherein at least a part of aeroge is at least A kind of processing of surface modifier to be formed keeps that aeroge is substantially made to have adsorptivity/connectivity.
46. the instant aerogel microball of any one of embodiment 43-45, wherein instant aerogel microball are to use Type aeroge latex microsphere/instant aeroge shines microballoon.
47. the instant aerogel microball of any one of embodiment 44-46, wherein aeroge have adsorptivity/can connect Connecing property and wherein coating/admixture are on the surface of aeroge, to which closing function material/functional group enters aeroge It is internal.
48. the instant aerogel microball of any one of embodiment 44-47, wherein aeroge have adsorptivity/can connect Connecing property and coating/admixture prevent at least one functional material/functional group and/active function material/activity functional groups Into inside aeroge.
49. the instant aerogel microball of any one of embodiment 44-48, coating/blending wherein on aeroge Object is functional material/functional group or functional material/functional group of activation.
50. the instant aerogel microball of any one of embodiment 44-49, wherein coating/admixture include at least A kind of hydrophobic/hydrophilic functional material/functional group.
51. the instant aerogel microball of any one of embodiment 44-50, wherein coating/admixture include surface Modifying agent, such as crosslinking agent/coupling agent, adsorbent, adhesive, surfactant.
52. the instant aerogel microball of any one of embodiment 44-51, wherein coating/admixture are organic/nothings Machine material such as carboxylated latex, amino latex, difunctional or multi-functional PEG, difunctional or Multifunctional tree branch compound.
53. the instant aerogel microball of any one of embodiment 45-53, wherein coating/admixture is by aeroge On functional material/functional group composition.
54. the instant aerogel microball of any one of embodiment 44-53, wherein coating/admixture cladding/blending On aeroge surface, there is adsorptivity/connectivity.
55. the instant aerogel microball of any one of embodiment 44-54, wherein coating/admixture are hydrophilic/thin Coating/admixture of water.
56. the instant aerogel microball of any one of embodiment 44-55, wherein coating/admixture include surface Modifying agent.
57. the instant aerogel microball of any one of embodiment 44-56, wherein coating/admixture will not enter Inside aeroge.
58. a kind of method for the instant aerogel microball preparing any one of embodiment 43-57, including will pre-process After the aeroge crossed first tentatively is ground in magnetic grinding machine at least one coating/admixture, high-pressure jet homogenizer is entered back into In homogenize, then be coated with three spectral line high energy photocurings the aeroge to form cladding and then by the aeroge of cladding at least A kind of functional material/functional group and/active function material/activity functional groups are combined and are subsequently cured functional material/work( Energy group and/active function material/activity functional groups are to form instant aerogel microball.
59. a kind of method for the instant aerogel microball preparing any one of embodiment 43-57, including by function material Material/functional group is coated on aeroge and is acted on by three spectral line photocurings to form coating/admixture on aeroge To coat/admix aeroge, and then by the aeroge of cladding and at least one functional material/functional group and/activity work( Energy material/activity functional groups are combined to form instant aerogel microball.
60. a kind of method for the instant aerogel microball preparing any one of embodiment 43-57, including by aeroge With coated comprising dissolving or dispersion or the solution containing hydrophilic/hydrophobic of the first reactant being emulsified in hydrophilic/hydrophobic solvent and with Nonpolar solvent/polar solvent comprising the second reactant is added to afterwards in the aeroge coated with hydrophilic/hydrophobic solution, and Then nonpolar solvent/polar solvent is removed to obtain the reaction product of the first and second reactants with shape with three spectral line photocurings At the aeroge of cladding, and then by the aeroge of cladding and at least one functional material/functional group and/or the function of activation Material/functional group is combined to form instant aerogel microball.
61. instant aerogel microball includes instant aeroge latex microsphere/instant gas with embodiment 46 Gel shines microballoon.
62. the instant aerogel microball of any one of a kind of instant aerogel microball, including embodiment 43-57.
63. the instant gas of the activation of any one of the instant aerogel microball, including embodiment 43-57 of activation Gel micro-ball.
64. a kind of aeroge of cladding includes the aeroge with adsorptivity/connectivity, wherein aeroge at least portion It point is coated with substantially functional material/functional group at least one coating/admixture and is entered inside aeroge.
65. the aeroge of the cladding of embodiment 64, wherein coating/admixture have adsorptivity/connectivity and its Middle coating/admixture is on the surface of aeroge, to which closing function material/functional group enters inside aeroge.
66. the aeroge of the cladding of any one of embodiment 64-65, wherein coating ,/admixture has adsorptivity/can Connectivity and coating/admixture prevent functional material/functional group from entering the inside of aeroge.
67. the aeroge of the cladding of any one of embodiment 64-66, coating/admixture wherein on aeroge are Functional material/functional group.
68. the aeroge of the cladding of any one of embodiment 64-67, wherein coating/admixture include at least one Hydrophilic/hydrophobic functional material/functional group.
69. the aeroge of the cladding of any one of embodiment 64-68, wherein coating/admixture are modified comprising surface Agent.
70. the aeroge of the cladding of any one of embodiment 64-69, wherein coating/admixture are organic/inorganic materials Expect such as carboxylated latex, phycocyanin, carboxyl fluorescent microsphere, carboxyl rare-earth fluorescent microballoon, carboxyl quantum dot fluorescence microballoon.
71. the aeroge of the cladding of any one of embodiment 64-70, wherein coating/admixture is by aeroge Surface cover/admixture composition.
72. the aeroge of the cladding of any one of embodiment 64-71, wherein coating ,/admixture has adsorptivity/can Connectivity.
73. the aeroge of the cladding of any one of embodiment 64-72, wherein coating/admixture are organic/inorganic work( It can material/functional group.
74. the aeroge of the cladding of any one of embodiment 64-73, wherein coating/admixture are hydrophilic/hydrophobic work( Energy material/functional group and coating/admixture include surface modifier.
75. the aeroge of the cladding of any one of embodiment 64-74, wherein coating/admixture will not enter airsetting Inside glue.
76. the aeroge of the cladding of any one of embodiment 64-75, including the cladding with adsorptivity/connectivity Object/admixture.
77. the aeroge of the cladding of any one of embodiment 64-76, including the coating of at least two functional groups/ Admixture.
78. the aeroge of the cladding of embodiment 77, wherein first functional group of coating/admixture is substantially main For adsorbing/connecting aerogel particles, and wherein at least one coating/the second functional group of admixture is to the aeroge of cladding One or more functional performances are provided, in order to adsorb/connect active material, such as antibody, enzyme, antibiotic, bacteriostatic agent.
It should be noted that in any type instant aerogel microball for being related to embodiment 1-78, method, product or cladding Aeroge surface, aeroge can be organically-modified functionalization aeroge, contain the functional groups such as hydroxyl/amino/carboxyl.
It should be understood that aforementioned general description and it is described in detail below be merely exemplary with it is illustrative and have no intention to provide The claimed invention is explained further.
Fig. 1, which is the present invention, to be had by the knot of the embodiment of the aerogel microball of functional material/functional group cladding/blending Structure schematic diagram, including using aeroge as kernel, surface layer coats/admixes functional material/functional group of hydrophilic/hydrophobic.
Fig. 2 is schematic diagram, provides the exclusive magnetic grinding of the present invention, high-pressure jet and three spectral line photocuring series connection methods Simple flow explanation.
Fig. 3 is flow chart, provides the required modified aerogels preparation flow figure of the present invention.
Fig. 4 is schematic diagram, provides the present invention curing reaction schematic diagram for using three spectral line process for photocuring.
Fig. 5 schematically depicts aeroge nanoparticle surface richness hydroxyl structure.
Fig. 6 is schematic diagram, shows that modified aeroge surface is wrapped by/admixes vinyl methylether and is linearly copolymerized with maleic anhydride Object bifunctional material.
The present invention relates to the aeroge of processing and/or the aeroges of cladding.The aeroge of processing and/or the aeroge of cladding It can be used for numerous areas, including be used to form the instant aerogel microball at least one functional material/functional group.This Invention further relates to the instant aerogel microball for including aeroge.The invention further relates to manufacturing, these instant aeroges are micro- The purposes of the method for ball and these instant aerogel microballs.It is more particularly related to which a kind of including at least one The instant aerogel microball of functional material/functional group and at least one aeroge.Usually, in instant aerogel microball Functional material/functional group exist as framework material.It substitutes, or is combined with functional material/functional group, the skeleton material Material also may include at least one inorganic/organic material, for example, gellan gum, hyaluronic acid, Polyurethane-epoxy resin, reed fragrant plant glue, Pu Lu Blue polysaccharide or their derivative or their mixture.They disperse or are crosslinking in aeroge using aeroge as kernel.Gas Gel can be uniform or non-homogeneous, or randomly exists.In the present invention, aeroge is a kind of aeroge of three spectral lines spectral manipulation.Separately Outer or optional commercially available commodity aeroge is modified it processing.Inorganic agent can be, for example, at least one surface is modified Agent, light-sensitive material.In addition, aeroge is after processing, there is connectivity/adsorptivity.Aeroge surface modifier and coating/ Blending agent is discussed in detail in following specific examples.
For functional material/functional group, instant aerogel microball may include one or more functional materials/function base Group, such as two kinds, three kinds, four kinds or more different types of functional material/functional groups.Generally, functional material/functional group by The composition of one or more type monomers/compounds.Functional material/functional group can be low molecular weight functional material/function Group or high molecular weight functional material/functional group.Functional material/functional group can be crosslinking functional material/functional group. Functional material/functional group can be latex beads or luminous microballoon or other microballoons.Functional material/functional group can be nothing Machine functional material/functional group or organic functional material/functional group.To the type of functional material/functional group there is no limit, As long as functional material/functional group of instant aerogel microball can be formed.More than one functional material/functional group.Work( Energy material/functional group can form cladding/blend.If there is more than one functional material/functional groups, Yi Zhonggong Energy material/functional group can form cladding/blend and one or more other functional material/functional groups can be used as non-packet Cover/blend and exist or more than one functional materials/functional group forms cladding/blend.In some embodiments, appoint Functional material/functional group of which kind of class can be used for the present invention.Generally, forming functional material/functional group of skeleton can account for i.e. With the more amount of type aerogel microball.For example, in one or more embodiments, functional material/functional group can be formed i.e. With about 0.00001% to about 98.00% weight of type aerogel microball, more preferably from about 0.0005% to about 97.00%, or about 0.005% to about 91.00%, in terms of instant aerogel microball weight.
Functional material/functional group can be hydrophilic/hydrophobic functional material/functional group or organic/inorganic base function material Material/functional group.Functional material/the function of being used in the method for manufacturing instant aeroge latex of the present invention/luminous microballoon Group can be any functional material/functional group for being efficiently used for the instant aeroge latex/Microsphere manufacture that shines.For The type of functional material/functional group of the aeroge latex/Microsphere manufacture that shines may include but be not limited to junction cold glue, hyalomitome Acid, pulullan polysaccharide, reed fragrant plant glue, Polyurethane-epoxy resin or their derivative or their mixture are as skeleton and novel light Quick material, aeroge or precursor effect prepare aeroge use material and novel dissolvent, essential oil, novel fixative, buffer, Degradable high polymer material, water retention agent, fungicide, new food preservative, novel dissolvent, novel fixative, protein and work Property polypeptide, thickener, adhesive, emulsifier, nutrition fortifier, minerals, inorganic salts, acidity-basicity regulator, polyphenoils etc. Raw material, these high molecular materials and functional material including but not limited to various compound essential oils, pulullan polysaccharide, glycine betaine and its spread out Biology, laureth -4, benzyl alcohol, vanillyl butyl ether, diphenhydramine, silica, hydroxyapatite, aluminium oxide, litsea citrate oil, Orange oil, Cineole, lemon oil, Artemisia oil, compound essential oil, titanium dioxide, PEG-8 octanoic acids/azelatin, salai carry Take object, p-phenylacetophenone, biological carbohydrate gum -3, PEG- octanoic acids/nonyl pipe glyceride, Radix Asteris extract, Radix Saposhnikoviae extract, radix bardanae Extract, glycol divinyl ether, 4- hydroxy butyl vinyl ethers, acrylic ether, glycerin polyether -26, tetra- methoxies of 1,1,3,3- Base propane, 3,4- 7-oxa-bicyclo[4.1.0s carboxylate methyl ester, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters, tetrahydrochysene neighbour's benzene Dioctyl phthalate bisglycidyl ester, gathers hexahydrophthalic acid bisglycidyl ester(Methyl vinyl ether/maleic acid)Half-ester copolymerization Object gathers(Methyl vinyl ether/maleic anhydride)Half-ester copolymerization object, Natrulon H-10, Echinacea extract, kuh-seng root extract, water Solve Isin glue collagen, ammonium mercaptoacetate, pyrrolidone sodium carboxylate, N, N- n,N-diethyl meta-toluamides, 3-(N- normal-butyl-N- second Acyl)Alanine ethyl ester, N-Acetyl-D-glucosamine, Kaempferol, thatch non-alcohol, mangostin, magnolol, olive oil PEG-6 are poly- - 6 ester of glycerine, elastin laminin, bis- ((3,4- epoxycyclohexyls) methyl) adipate esters, polyglycerine, hyaluronic acid and its spread out Biology, gathers at oligomerization hyaluronic acid, chitosan and its derivative(Methyl vinyl ether/maleic acid)Copolymer, trehalose, seaweed Oligosaccharide, benzophenone, methoxy ethylene and maleic anhydride copolymer free acid, methoxy ethylene and maleic anhydride linearly altogether The calcium of polymers, methoxy ethylene and copolymer-maleic anhydride/sodium mixture, siloxanes original washing powder, povidone iodine, povidone be white, second Vinyl pyrrolidone and acetate ethylene copolymer, crosslinked polyvinylpyrrolidone, starch and its derivative, dextrin, cellulose and Its derivative, gelatin and its derivative, protein and its derivative, amino acid and its derivative, lacticin, he is mould Element, penicillin, gentamicin, neomycin, streptomysin, hydroxypropyl acrylate, epoxy(Methyl)Acrylate, BIOLOGICAL CALCIUM, silk peptide, Silk-fibroin, silk gum, carnosine, casein and its derivative, dihydroxymethyl glycolylurea, calcium lactate, calcium phosphate, gluconic acid- ca, seaweed Hydrochlorate, zinc gluconate, hippophae rhamnoides, Seabuckthorm Seed Oil, deep sea fish oil, saualane, unsaturated fatty acid, aliphatic acid, glycerine Three esters and its derivative, cholesterol and its derivative, vitamin C and its derivative, ursin and its derivative, perfluoropolyether are low Polymers, 1,3 butyleneglycol diacrylate, edetate, dodecyl amine oxide, phytic acid, pantothenic acid, tranexamic acid, fertility Phenol, hypophosphites, malt polysaccharide, maltose, iso-bornyl acrylate, zein, albumin, benzoyl peroxide, Peroxidating carbon, urea peroxide, chlorine dioxide, sulfur dioxide, niacinamide, Eleutheroside B+E, sodium sulfite, sodium hydrogensulfite, 1, 6- hexanediyl esters, tartaric acid, malic acid, citric acid, neopelex, sarcosyl, sea Algae carbohydrates and their derivative, chitin, chitosan, tetradecyl trimethyl ammonium chloride, decyl trimethyl ammonium chloride, agar, peace It is the fragrant ether of breath, caseinate, Arabic gum, carragheen, guar gum and its derivative, acetone, cyclodextrin and its derivative, sweet Oxalic acid, 4- ethyl -4- soybean-based ethyl-sulfates morpholine, PEG-6 caprylic/caprics glyceride, PEG-50 sher butters, stearyl alcohol heptan Acid esters, octyldodecyl, soybean lecithin and its derivative, phosphatide and its derivative, tripotassium phosphate, tertiary sodium phosphate, phosphoric acid hydrogen Disodium, sodium dihydrogen phosphate, sodium pyrophosphate, sodium tripolyphosphate, metaphosphate, pepsin, chymotrypsin, pancreatin, amylase, wood Melon protease, renin, pectase, food bacterium, paraffin, lac, silicone emulsion, Tween-20, Qula be logical -100, Tween-80, Brij-35, Bu Lijie -98, Qula lead to -405, other nonionic surfactants, triphenylphosphine oxide, tributylphosphine, sun Ion exchange resin, resin anion (R.A.), chelating resin, hybrid resin, sapn, potassium ferrocyanide, the potassium ferricyanide, xanthans, essential oil, food With oil, olive oil, polyvinyl alcohol, polyacrylamide, acrylic acid and methacrylate polymer, polyethylene glycol and its derivative, It is polyethylene glycol oxide, poly, polylactic acid, water soluble polyurethane resin, polyethers and its derivative, polyvinylpyrrolidone, sweet Oxalates, ethyl alcohol, glycerine, sugarcane carbohydrates and their derivative, 16 octadecyl polyethers(12)Phosphate, ethanol amine thioglycolate salt, Thioacetic acid ammonium derivative, DL-cysteine hydrochloride, INCROQUAT TMC-80, Polyquaternium-10, polyquaternary amine Salt -6, nutmeg alcohol ether PPG-3, octadecyltrimethylammonium chloride, extra large ermine oil, laurylsarcosine polyethers based quaternary ammonium salt, hydroxyl pyrrole Ketone, cocounut oil acyl methyl taurine sodium, linseed oil amido propyl pg dimonium chloride, gathers phenylethylene ethylene/propenoic acid ester copolymer Dimethyl siloxane, four oleic acid polyoxyethylene sorbitols, polyethylene glycol-8, methyl glucose alcohol polyethers -10, erythrite, polyglycereol - 2, sponge gourd root extract, shea butter, sub- right amido propyl PG-Dimonium Chloride Phosphate, glucose fat acid phosphoric acid Ester salt, poly dimethyl silicon propylene glycol, propylene glycol block polyether, fatty alcohol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, aliphatic acid Polyoxyethylene ester, castor oil polyoxyethylene ether, aliphatic amine polyoxyethylene ether, defoaming king FAG470, environment-friendly type penetrating agent JFC, first Base allyl polyethenoxy ether HPEG(Also known as modified polyether-TPEG), calcium carbonate, magnesium carbonate, silicon carbide, carbon black, n-hexane, just Heptane, petroleum ether, sodium sulfate of polyethenoxy ether of fatty alcohol, sodium xylene sulfonate, tartaric acid, Glycolic acid, panthenol, azelaic acid, black stone Mud, volcanic mud, allantoin, blue copper peptide, Argireline, cocounut oil diglycollic amide, C12-14 alkyl glycosides, aloe gel freeze Dry powder, barbaloin, hydrogenated castor are by polyoxyethylene ether, SUNSOFT 700P-2, nitrilo sodium tripolyphosphate, glutamic acid-N, N- diethyl Sour four sodium, hexylene glycol, ethylene glycol, butylated hydroxy anisole, propylgallate, dibutyl hydroxy toluene, hydroxycitric acid, hydroxyl Base tyrosol, Glucosinolates, hydroxyapatite, hydroxycitric acid, 5-ALA hydrochloride, macamide, fourth butyrolactone, second Base maltol, fruit carbohydrates and their derivative, octamethylcy-clotetrasiloxane, polyglyceryl fatty acid ester, tert-butylhydroquinone, tartaric acid Hydrogen potassium, sodium bicarbonate, alum, sodium nitrite, white oil, sulfhydryl oxidase sodium, sulfhydryl oxidase zinc, stearic acid, ammonium hydroxide, three ethyl alcohol Amine, diethanol amine, tetramethylammonium hydroxide, isomery hexadecane hydrocarbon, taurine, benzoic acid, oleic acid, leukotrienes, linoleic acid, sorb Acid, mannitol, calcium chloride, xylitol, potassium permanganate, ethyl caprilate, peppermint oil, camphor, attar of rose, lavender oil, sweet tea apricot oil, Aloe, pelargonium oil, wheat-germ oil, thyme linaloe oil, vetiver oil, orange oil, sage oil, Java Cananga Oil, You Jiali oil, silk Pitch, camphorated oil, basil, bergamot oil, black pepper oil, oleum menthae piperitae, grape seed oil, CAB-35, OP-10, ginger oil, folium eucalypti Oil, lemon oil, menthol, jasmine oil, tea oil, Blumea oil, amine oxide and its derivative, adenosine and its derivative, linoleic acid, Ethyl orthosilicate, bodhi tree extract, corn flower extract, Flos Tagetis Erectae extract, 12/tetradecyl alchohol of benzoic acid ester, library Kui fruit Oil, water-soluble silicone wax, double amido silicon oils, the rough gentian anti-irritant factor, full five acid, furans ether, petroleum ether 60-90, benzoic acid 12/ Tetradecyl alchohol ester, propylene glycol methyl ether acetate, furans glycol, Hericium erinaceus extract, erinacine, calcium sulfate, fine silica powder, Isopropanol, 4- hydroxyls -3-(3- methyl-2-butene oxygroups)-5-(3- methyl-2-butene bases)Benzoic acid, hexadecyl pyrrole Pyridine, papper oil, ammonium dihydrogen phosphate, 2,4,7,9- tetramethyl -5- decine -4,7- glycol, trimethyl amine oxide, 3,6- dimethyl - 1- heptyne -3- alcohol, azone, 3,6- dimethyl -4- octynes -3,6- glycol, phloroglucin, azide, foreign glycosides elecampane oil, lotus lotus Bar oil, Angelica oil, sulfate, nitrite, lotus heart alkali, neoabietic acid, new Schisandra chinensis acid, the algae peptide that quivers, quiver algae amide, polypropylene Sour sodium, acrylic acid and various of monomer copolymer, a-cyanoacrylate glue, acetyl chitosamine, polyglutamic acid sodium, gamma-amino fourth Acid, caffeic acid and its derivative, Chlorphenesin, ferulic acid and its derivatives, acrylic-ethylene alcohol copolymer, polyvinyl alcohol are handed over It is linked polymer, hexamethyldisiloxane, silicon rubber or methyl vinyl phenyl silicon rubber, Thiamphenicol, ascorbic acid glucoside, big Beans lecithin, cephalin, α-cyanoacrylatealkyl, Symwhite-337, benzoic acid, 4 amino-antipyrines, periodic acid Potassium, hydroxycarbamide, alum, aluminum sulfate, Citric Acid Mono, phosphotungstic acid, lithium carbonate, reddish black, orange, brilliant green, is consolidated sodium iodide Green, n- dodecyl mereaptan, propylene glycol methyl ether acetate, dimethyl carbonate, Porous deproteinized bone solvent naphtha D80, N- ethyl-N- (3- sulphurs third Base) -3- methylanilines sodium salt, hematoxylin, ethoxy urea, two polypropylene glycols, reed fragrant plant glue, hydrolecithin, H60A coupling agents, Dimethyl silscone, linoleamide base propyl PG-dimonium chlorinated phosphate esters, cocamidopropyl propyl amide/pg dimonium chloride Phosphatide, biological carbohydrate gum -3, hydrolysis Scleroglucan, Scleroglucan, xanthan gum, aluminum magnesium silicate imidazolidinyl urea, trihydroxy methyl amino Methane, 1- thioglycerols, disodium EDTA, imidazolidinyl urea, iodine propilolic alcohol butyl mephenesin Carbamate, pyrrolidones carboxylic It is sour sodium, polyethylene glycol 400, double(Methylol)Imidazolidinyl urea, formaldehyde, glutaraldehyde, carbodiimide and its derivative, 4- ethoxys Piperazine ethanesulfonic acid, proline and derivative, dithiothreitol (DTT), bovine serum albumin(BSA), vitamin C-β-glucose, azide, Beta glucan and derivative, proganoside, Pfansteihl, polylactic acid and its derivative, poly-D-lysine, poly asparatate, Poly paddy amino acid, soluble freeze-drying silk-fibroin, hematopoietin, lysozyme, digitalis glucoside, 2- methacryloxypropyls Ethylphosphocholine, choline chloride, phosphatidylserine, chenodeoxycholic acid, hyodesoxycholic acid, injection soybean lecithin, sweet wormwood Element, Artemisia oil, alkene phosphatidyl choline, glycerolphosphocholine, serinephosphatide, trimethylene carbonate(TMC), olive oil, Golden flower small cups oil, avocado oil, aloe, print plus fruit oil, linseed oil, cade oil, patchouli oil, wintergreen, crocodile plough oil, benzene sea are drawn Bright, spearmint oil, Asiatic sweet leaf sesame oil, SUNMIX NMF(Serine, glycine, alanine, aspartic acid, valine, arginine, Ten kinds of isoleucine, leucine, glutamic acid, proline ispols), it is polymethyl methacrylate, polyurethane -34, poly- Urethane -35, C12-13 alkyl lactate esters, tridecyl salicylate, PEG-10 Polydimethylsiloxane, five poly dimethyl silicon of ring Oxygen alkane, ceramide, isomery dodecane, isononyl isononanoate, 1,3 butylene glycol, Argireline sterling freeze-dried powder, rilanit special, Copaiba balsam, niacinamide(Vitamin B3), nano-titanium dioxide, nm-class boron nitride, silica, the rough gentian anti-irritant factor, Metadelphene, 1,2- hexylene glycols, green wood oil fat, ethohexadiol, 1,2- pentanediols, Sensiva SC50,1,2- alkanols, glycerin polyether -26, PEG- 20 glycerine, three iso-stearate, PEG-8 caprylic/caprics, fatty alcohol polyoxyethylene ether(3)Sulfosuccinic acid monoesters disodium, cocounut oil Amidopropyl amine oxide, dodecanamide propyl amine oxide, caprylhydroxamic acid, Octopirox, five-leaved pine seed oil, solubility Collagen, deacetylated chitosan list succinamide, phytic acid, reed fragrant plant oil, natto gum, dimerization Asia oleyl alcohol dimerized linoleic acid Ester, octyl heteroside, dipotassium glycyrrhizinate, Calcium Dobesilate, etamsylate, antiseptic polypeptide, cecropins, alexin, skin are antibacterial Peptide, histatins, Magainin, ammonium glycyrrhizinate, mannosan, hydrogenation(Soybean)Lecithin/cholesterine, zinc phenolsulfonate, the moon Osmanthus acyl glycine potassium, sodium lauroyl glutamate, undecenoic acid glyceride, octyl dodecanol myristinate, Bu Luoboer, chloromethane Base isothiazolinone, pungent methyl polysiloxane, PEG-10 amino silicones, acetylation glutamine, cellulose gum, oligopeptides- 1, oligopeptides -11, oligopeptides -2, oligopeptides -3, folic acid, 7- dehydrocholesterols Phenoxyethanol, the iodo- 2-propynyl-N- n-butylaminos of 3- Formic acid esters, creatine, HA Plus Sodium Hyaluronates, purslane extract, flavones, slips extract, solketal, centella Total glycosides, Gotu Kola P.E, Horsetail P.E, foreign ivy extract, septfoil extract, fucose and its derivative, Trimethylglycine, PB-1007 sintering resin, PVB sintering resin, transdermal small peptide, epidermal growth factor, biological fiber silk, Enoxolone, licoflavone, sesame alcohol ester, cetanol(Thylhexoic acid))Ester, acetylcholine, tranexamic acid, hexamidine(Ethoxy Sulfonic acid)Salt, piroctone olamine salt, dimethyl methyl epoxide benzodihydropyran alcohol, dimethyl methyl oxygroup benzodihydropyran Palmitate(0.05~0.5%), Trenaxmine, enzyme, antigen, antibody, biotin, Avidin, phytohemagglutin phytolectin, phycocyanin, It is cyanine dye, rare-earth fluorescent particle, quantum dot fluorescent particles, fluorescence metal nano particles, graphene quantum dot nano particle, dilute Soil blending upper conversion fluorescent nano particle, Multifunction fluorescent nano particle, color nano particle, various coupling agent/crosslinking agents, (methyl) hydroxy-ethyl acrylate, N, Phenhenzamine (methyl) acrylate, trimethylolpropane trimethacrylate, ethoxy Base trimethylolpropane trimethacrylate, glycerol tri-acrylate, pentaerythritol tetraacrylate, five propylene of dipentaerythritol Acid esters, (methyl) hydroxypropyl acrylate, ethoxyquin ethoxy (methyl) acrylate, six condensed ethandiol ester of (methyl) acrylic acid, (methyl) lauryl acrylate, (methyl) octadecyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylate Ester, (methyl) isobornyl acrylate, (methyl) acrylic acid dicyclopentadienyl ester, (methyl) allyl acrylate, (methyl) Acrylic acid tetrahydrofurfural ester, (methyl) glycidyl acrylate, (methyl) acrylic acid 2- phenoxy ethyls, 2- hydroxyls -4 ' - (2- hydroxy ethoxies) -2- methyl phenyl ketones, bis- (pentafluorophenyl group) titaniums cyclopentadienyl, fluorinated diphenyl titanium cyclopentadienyl, hydroxycyclohexyl phenyl ketone, Trimethylbenzoy-dipheny phosphine oxide, trimethylbenzoyl phenyl phosphinic acid ethyl ester, 2- dimethylamino -2- benzyls -1- [4- (4- morpholinyls) phenyl] -1- butanone, 2- hydroxy-2-methyls -1- [4- (2- hydroxyl-oxethyls) phenyl] -1- acetone, 2- first Base -2- (4- morpholinyls) -1- [4- (methyl mercapto) phenyl] -1- acetone, benzoin dimethylether, benzophenone, 2,4,6- trimethyls Benzoyl-diphenyl phosphine oxide, 2- phenyl benzyl -2- dimethyl amines -1-(4- morpholine benzyl phenyl)Bis- (the 2,4,6- of butanone, phenyl Trimethylbenzoyl) phosphine oxide, 1- hydroxy-cyclohexyl-phenyls ketone, 2- hydroxy-methyl phenyl-propane -1- ketone etc. and its with The composition of upper substance.
In addition, as a kind of selection, one or more crosslinking agents or photoinitiator may be present in instant aerogel microball In formula.According to the property of functional material/functional group, functional material/functional group may include causing functional material/function base The crosslinking agent or initiator of group's material reaction.If energy material/functional group includes the crosslinking agent or initiator for reaction, excellent The weight ratio of choosing, initiator and energy material/functional group is 1~100: 2~100.Initiator and energy material/functional group Ratio can according to can material/functional group type and the required degree of cross linking or blending degree and change.For example, incrementss Initiator can carry out reactive solidification under three spectral line light actions.It can be opposite with energy material/functional group by initiator Amount is reduced to weight ratio down to 1~50: 5~50, but may need longer action time.
Any aeroge can be used for the present invention.Aeroge can be any form, such as film, film, monolithic, fracture or cracking Monolithic, particle, covering, pad, cotton-wool, and/or its other fiber reinforcement form, it is currently preferred be aeroge nanometer Grain or its precursor substance.For example, silicon rubber, sodium metasilicate, Ludox, organo-silicon compound, can be particle forms, can also be Elastomer or gel form.Aeroge can be nano particle, agglomerate, particulate, cluster and larger shape, depend on specific Final use.Aeroge can be hydrophobic aerogel or can be hydrophilic aerogel or can be mixture.In at least one reality Apply in scheme, for the present invention preferred aeroge be based on be suitable for sol-gel technique (C.J.Brinker, G.W.Scerer, Sol-Gel Science, 1990, the 2nd and 3 chapters) metal oxide, such as Si or Al compounds, or based on suitable For the organic substance of sol-gel technique, such as melamine-formaldehyde condensation product (United States Patent (USP) No.5,086,085) or isophthalic Diphenol-formaldehyde condensation products (United States Patent (USP) No.4,873,218).They are alternatively the mixture based on above-mentioned material.Gas Gel can also be that the organically-modified silica for being described in U.S. Patent bulletin No.2005/0192366 or 2005/0192367 (ormosil) aeroge is fully incorporated herein by reference.Preferably, it can be used comprising silicon (Si) and/or other elements such as Ti, W, Zr etc. or the aeroge of its compound and, it is highly preferred that using SiO2.Aeroge can have any particle size so that The particle of Nano grade can be obtained after they can be ground by magnetic, high-pressure jet homogenizes.Aeroge can have various particle rulers Very little distribution.Aeroge can be the form of comminuted powder.
In one or more embodiments, any commercially available hydrophobic or hydrophilic aerogel can be used for the present invention.Specifically Include, but are not limited to the aerogel powder available commercially from the one nanometer of company in day.Specific commercially available type includes, but are not limited to Aeroge and its precursor substance.The present invention, and in particular for one of preferred technique of the present invention the advantage is that aeroge It is to homogenize to act on photocuring by level-one/secondary grinder, high-pressure jet to obtain, this is different from the preparation of traditional aeroge, It is uniform with particle, prepare efficient, quick, time saving feature.Pretreated aeroge can be different-grain diameter, lightweight sum Flexible or other characteristics, and the characteristic is essentially present in final product.
Aerogel particle for the present invention can have hydrophobic/hydrophilic surface groups.In order to avoid aeroge because in hole Condensate moisture and any collapsing for then generating, it is preferred that skeleton sexual function material is added, as gellan gum, hyaluronic acid, Polyurethane-epoxy resin, reed fragrant plant glue, pulullan polysaccharide or their derivative or their mixture, and made by light curing agent Grain conformation is more stable;Wherein light curing agent draws including but not limited to various light-sensitive materials, photosensitive resin, photocuring adhesive, light Send out agent etc..
Known patent CN200680048778.3 describes trimethyl-and dimethylsilyl groups can be particularly advantageous Ground is used for the permanent hydrophobisation of aeroge.These groups can as described in WO 94/25149 (being fully incorporated herein by reference) and Be introduced into or by aeroge and, for example, the trialkylsilane derivative of activation, such as two silicon nitrogen of chlorine trialkylsilane or six alkyl Gas phase reaction (referring to R.Iler, The Chemistry ofSilica, Wiley&Sons, 1979) between alkane and be introduced into. They are partly introduced by this patent as reference.
Aeroge can have any particle size that can make them as kernel, such as from about 1nm to 20mm or 25nm to 1mm/ Or 10 microns to 5mm.Aeroge can have various particle size distributions, and relatively choosing is 20nm~3000nm, preferably 50nm ~350nm.Aeroge can be the form of comminuted powder or particle or slurry.
Aeroge can be any desired amount there is the specific density to realize overall instant aerogel microball and/or lead Heating rate.For example, the amount of aeroge can be based on overall instant aerogel microball volume about 0.00001% to about 98.00%, and more preferably about 0.0001% to about 97.00% or about 0.001% to about 91.00%.
As previously mentioned, the aeroge for instant aerogel microball of the present invention is the aeroge of modification.For The aeroge that the photocuring of the present invention is pretreated has adsorptivity/connectivity.Surface layer is the packet of active functional group Object/admixture is covered, they can be the structure of shell, layer or other similar types, they are located on the surface of aeroge to be used for Connect other types of functional material/functional group.Coating/admixture can be such as connected chemically in any manner, absorption, Etc. being connected on the surface of aeroge.More specifically, which can be organic or inorganic coating/blending Object.For example, coating/admixture can be functional material/functional group and include one or more functional material/functional groups Or it is made of one or more functional material/functional groups.Coating/admixture can be reactant or polymerizable or initiation Polymerisation.Coating/admixture can be coating/admixture based on surface modified function.Coating/admixture its Its example include, but are not limited to photosensitive resin, light-sensitive material, photosensitive adhesive,.Alternatively, coating/admixture can be had Machine or inorganic functional material/functional group.In at least one embodiment, coating/admixture is as wet coating/blending Object and apply the uniform cladding to realize aeroge and then dry wet coating/admixture or layer and be not easy to remove to be formed It is hard or solidification coating/admixture.In one or more embodiments, coating/blending nitride layer on aeroge is preferred It is poly-(Methyl vinyl ether/maleic acid)Copolymer gathers(Methyl vinyl ether/maleic acid)Half-ester copolymerization object gathers(Ethylene methacrylic Base ether/maleic anhydride)It is half-ester copolymerization object, 2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones or photoinitiator, photosensitive viscous The copolymer free acid of jelly, methoxy ethylene and maleic anhydride, methoxy ethylene and maleic anhydride linear copolymer, vinyl The calcium of methyl ether and copolymer-maleic anhydride/sodium mixture etc. has adsorptivity/connectivity functional material/functional group.Airsetting Coating/admixture on glue can be it is uniform, it is substantially uniformly or non-uniform.Again it is preferred to no matter uniformly or uneven Even, which preferably has connectivity/adsorptivity.It is preferred that coating/admixture on aeroge has layer Thickness about 5nm to about 5mm, such as from about 20nm to about 10 μm or about 50nm to about 5 μm.Following sections describes each on aeroge The formation of kind coating/admixture and coating/admixture, it is noted that these examples are enumerated to the present invention.
The example of coating/admixture includes, but are not limited to hydrophilic/hydrophobic functional material/functional group, such as vinyl Pyrrolidones and acetate ethylene copolymer, copolymerization povidone, crosslinked polyvinylpyrrolidone, starch and its derivative, dextrin, fibre Dimension element and its derivative, gelatin and its derivative, protein and its derivative, amino acid and its derivative, acrylic-ethylene alcohol Copolymer, polyvinyl alcohol crosslinked polymer, plant extracts, polyethers, polyethylene glycol and its derivative, cyclodextrin and its derivative Object, pulullan polysaccharide, malt carbohydrates and their derivative, glucan and its derivative etc..As described above, the aerogel particle of the present invention Can be hydrophobic and/or have hydrophobic surface group, but after pretreatment have hydrophily.Surface modifier therein can Selected from for example, ion (anion and cation) surfactant, amphoteric surfactant, nonionic surfactant, high score Sub- surfactant and high-molecular compound.
Coating/admixture on aeroge can be two or more coating/admixtures or coating object.For example, such as There are two or more coating/admixtures, coating/admixtures to be same or different to each other for fruit.For example, water base coating/ Admixture can be applied on aeroge and organic group or oil base coating/admixture are then administered to the airsetting coated before To form the aeroge of double coating/admixtures or multilayer coating structure on glue.The aeroge of multilayer coating structure is beneficial, because each Coating/admixture can be used for required purpose.
As described above, at least one embodiment of the present invention, aeroge can use at least one pre-treatment treatment with Form the aeroge with adsorptivity/connectivity.Pretreating agent is including but not limited to above-mentioned surface modifier agent macromolecule Compound or light-sensitive compound monomer.It is that the surface of aeroge or embedding is present in by absorption, the hydrogen bond etc. of aeroge itself Enter and forms skeleton structure into aeroge.In the present invention, pretreating agent and/or coating/admixture and instant aeroge Another component of microballoon can be polymerizable and/or reactive or adsorb.
As described above, at least one embodiment of the present invention, aeroge can be pretreated to form functionalization first Aeroge and then cladding/blending are to form cladding/blending, aeroge with connectivity/adsorptivity.For example, poly- γ The carboxyl or amino of glutamic acid, the hydroxyl of polysaccharide material, half ester compound carboxyl etc. all there is cross linkable or characterization of adsorption. One or more embodiments of the present invention are related to pretreated aeroge of photocuring itself and the gas of cladding/blending itself Gel.
The another way of cladding/blending aeroge is with the very thin nano particle for being significantly less than aerogel particle size Coat aeroge.The nano particle then substantially coats/admixes the surface of aeroge.Then, nano particle cladding/blending Aeroge then can photocuring/coupled action and be wrapped by/admix on pretreated aeroge surface.In other words, this behaviour Make the cross-linking reaction of approximate common hydroxyl latex and protein.Therefore, in one or more embodiments, pretreated gas Gel has the skeleton structure of hydrophilic/hydrophobic, is easy to generate link by external functional material/functional group, and with preferable Flexibility.Nano particle can be latex beads, shine microballoon, fluorescent microsphere, as carboxylated latex, amino latex, carboxyl are glimmering Light microballoon etc..Generally, be coated on nanoparticle on aeroge have particle size about 20nm to about 10 μm or 50nm to 5 μm or 1 micron to 5.0mm.Aeroge can be pretreated to put forward adhesiveness/connectivity of the nanoparticle on the surface of aeroge.Packet The nanoparticle overlayed on aeroge can have the fusing point less than aeroge.
It is to use particular kind of magnetic grinding machine or height that coating/admixture, which is administered to the another way on aerogel particle, Jet flow homogenizer or a combination of both is acted in conjunction with three spectral line photocurings, realizes cladding/blending.
Various components, i.e. aerogel particle and coating/admixture can be added into magnetic grinding machine.Available parameter adjusts The homogeneous size of particle.Coating/admixture can feed together with aerogel particle.
For forming instant aerogel microball of the present invention, usual manner can be used.For example, those skilled in the art are That knows forms any of instant aerogel microball at least one functional material/functional group and a kind of crosslinking agent/curing agent Mode can be used for the present invention.As more specific example, one or more functional material/functions of forming instant aerogel microball Group when in uncured or non cross-linked state (e.g., latex particle monomer) can with it is to be covered/blending aeroge together with by It introduces and mixes or stir or cure so that cladding/blending is on aeroge surface.Instant aerogel microball is also injected into mould It is molded in tool.Substantially, it can be used in the present invention for functional material/functional group processing or molding any means.Use Type aerogel microball may include other conventional constituents or the ingredient being typically found in instant aerogel microball.For example, i.e. It may include conventional sterilization agent, such as azido compound with type aerogel microball, antibacterial peptide, etc..Instant aerogel microball of the present invention (or constituting one or more independent components of instant aerogel microball) may include other ingredients, such as antigen, antibody, protectiveness Colloid, photosensitive solvent, photosensitive adhesive, stabilizer, and/or nano functional microballoon.These various conventional ingredients can be according to ability Convention amount known to field technique personnel uses.When forming instant aerogel microball, the aeroge of cladding/blending can be by function Cladding/the blending completely or partially of material/functional group, can be in the form of liquid suspension or solid granular form exists, and can Different particle sizes is controlled according to final use demand.
The component for forming instant aerogel microball can be by high-molecular compound, light-sensitive material, solvent or other function materials Material/functional group is homogenised processing, through photocuring act on or shape, be used in combination cladding/blending in aeroge surface layer.Ability Domain those of ordinary skill should be understood that the exact details of operational elements will be based on purposes, and e.g., the operation of aeroge latex microsphere is special Property, as speed, temperature and time and select and obtain.
Instant aerogel microball (e.g., the luminous microballoon of aeroge) of the present invention can have so that instant aerogel microball can Any particle size needed for various analysis projects.In addition, precuring or rear cured instant aerogel microball can structures Any grain size is caused, and coats/admix different types of functional material/functional group, such as albumin A, albumen L, antigen, antibody.
The present invention instant aerogel microball can be used as function carrier, for medicine, external diagnosis reagent, health products, The fields such as food, biological pesticide, bioactive materials, electronics, papermaking, printing.
In addition, instant aerogel microball of the present invention can be used for the covering of aerogel-congtg.Covering may include aeroge, Fiber and other ingredients.The details for being such as described in the covering of the aerogel-congtg of U.S. patent applications No.11/013,306 is available In aeroge of the present invention.It is fully introduced into this application herein as reference.
Aeroge, such as the instant aerogel microball of the present invention, as the functional microsphere in polystyrene latex application The purposes of substitute, can be widely used for latex enhancing immune turbidimetric analysis, lateral chromatography immunoassay, flow cyctometry analysis, Analyzing biochips and bio-sensing analysis.
In addition, as optional components, one or more high-molecular compound blendings are made in instant aerogel microball For skeleton, and can be added when the instant aerogel microball is uncured instant aerogel microball mixture.
Be suitable for the invention suitable macromolecule compound object including but not limited to cyclodextrin, polyamino acid, reed fragrant plant Glue, dendrimer, gellan gum, guar gum, pulullan polysaccharide, silk gum, silk peptide, carnosine, xanthans, seaweed glycan, sweet dew Glycan, sorbitan etc..
The present invention is furtherd elucidate by the following embodiment for enumerating the present invention.
Embodiment
Embodiment 1:
Instant aerogel microball lotion is by by 170 nano-size silica aerogel particles (600g), poly-(Methyl second Alkene ether/maleic acid)Half-ester copolymerization object (5.0g), absolute ethyl alcohol(150 milliliters), it is added in 6.7 liters of isomery dodecanes, in magnetic It is fully ground in grinding machine spare;Separately weigh containing poly- γ glutamic acid(3.0g), low acyl degree gellan gum(0.05g), hyaluronic acid elasticity Body(1.0g), trimethyl amine oxide(1.5g), absolute ethyl alcohol(150 milliliters), ammonium hydroxide(9.0 milliliter), purified water (2.9 rising)It is slowly added dropwise and is added in above-mentioned spare aerosil suspension after high-speed homogenization machine stirring and dissolving, then It rapidly joins in high-pressure jet homogenizer, use is specified(Flow:6L/h, operating pressure:800bar, stroke of machine number:110 beats/min Clock, highest product temperature:80℃)Parameter carry out homogenize process after, then use three spectral line high energy light curing process, recycle twice Obtain pretreated instant aerogel microball suspension.This instant aerogel microball is used directly for activated protein mark Note, such as biological enzyme label, antibody label, antigen sensibilization can be used to make particle enhancing immunoturbidimetry reagent and promotion tradition are anti- The sensitivity of antigen-antibody reaction.Three spectral lines photocuring processing therein is as shown in figure 4, the G01 lasers selected are that 255nm is ultraviolet Laser, power 3W are located at conveying device tangential direction, are more preferably 45 with transfer device plane in 45 ± 5 degree of arrangements ± 3 degree, most preferred 45 ± 0.05 degree;G02 lasers are 550nm semiconductor lasers, and power 10W is located at conveying device It is more preferably vertically 90 ± 1.0 degree with transfer device plane in 90 degree of arrangements to direction, most preferred 90 ± 0.05 degree; G03 lasers are 1024nm carbon dioxide lasers, power 50W is located at conveying device forward direction, flat with transfer device Face in 45 ± 5 degree arrangement, be more preferably 45 ± 3 degree, most preferred 45 ± 0.05 degree, three lasers can by manually or Automatic motor driving moved based on x, y, z axis direction.
Embodiment 2:
Instant aerogel microball lotion is by by 110 nano-size silica aerogel particles (300g), poly-(Methyl second Alkene ether/maleic acid)Half-ester copolymerization object (3.0g), absolute ethyl alcohol(300 milliliters), be added to 7.7 liters of isomery dodecanes, it is bis- ((3, 4- epoxycyclohexyls) methyl) 33 in adipate ester and isobornyl methacrylate:1:1 mixed liquor is protected from light item in magnetic grinding machine It is fully ground under part spare;Separately weigh containing poly- γ glutamic acid(2.0g), low acyl degree gellan gum(0.10g), acetylation hyaluronic acid Sodium(0.5g), PVP K90 ((4.5g)), 2,4,7,9- tetramethyl -5- decine -4,7- glycol(1.0g), ammonium hydroxide (4.5 milliliter), purified water(2.0 rising)It is slowly added dropwise after high-speed homogenization machine stirring and dissolving and above-mentioned spare silica airsetting is added In glue suspension, it is then quickly added into high-pressure jet homogenizer, use is specified(Flow:6L/h, operating pressure:800bar, machine Number of stroke:110 beats/min, highest product temperature:80℃)Parameter carry out homogenize process after, then with three spectral line high energy lights consolidate Change is handled, and cycle obtains pretreated instant aerogel microball suspension twice.This instant aerogel microball can be direct It is marked for activated protein, such as biological enzyme label, antibody label, antigen sensibilization, can be used to do particle enhancing immunoturbidimetry examination Agent and the sensitivity for promoting traditional antigen-antibody reaction.Three spectral lines photocuring processing therein is as shown in figure 4, the G01 selected swashs Light device is 255nm ultraviolet lasers, and power 5W is located at conveying device tangential direction, is in 45 ± 5 degree of cloth with transfer device plane It sets, is more preferably 45 ± 3 degree, most preferred 45 ± 0.05 degree;G02 lasers are 550nm semiconductor lasers, and power is 50W, it is more preferably 90 ± 1.0 degree with transfer device plane in 90 degree of arrangements to direction to be located at conveying device vertically, optimal 90 ± 0.05 degree of choosing;G03 lasers are 1024nm carbon dioxide lasers, power 50W, to side before conveying device To, it is more preferably 45 ± 3 degree with transfer device plane in 45 ± 5 degree of arrangements, most preferred 45 ± 0.05 degree, three laser Device can be driven by manual or automatic motor and moved based on x, y, z axis direction.
Embodiment 3:
Instant aerogel microball lotion is by by 250 nano-size silica aerogel particles (450g), poly-(Methyl second Alkene ether/maleic acid)Half-ester copolymerization object (3.0g), absolute ethyl alcohol(300 milliliters), it is added to 6.7 liters of 2- hydroxyls -4 '-(2- hydroxyls Ethyoxyl) -2- methyl phenyl ketones, fluorinated diphenyl titanium cyclopentadienyl and isobornyl methacrylate 1:1:60 mixed liquors, in magnetic grinding machine In be protected from light under the conditions of be fully ground it is spare;Separately weigh containing poly- γ glutamic acid(1.0g), high acyl degree gellan gum(0.02g), hyalomitome Sour sodium oligosaccharides(0.5g), polyvinylpyrrolidone K60 ((3.0g)), 2,4,7,9- tetramethyl -5- decine -4,7- glycol (1.5g), ammonium hydroxide(5.5 milliliter), purified water(2.9 rising)It is above-mentioned spare that addition is slowly added dropwise after high-speed homogenization machine stirring and dissolving In aerosil suspension, it is then quickly added into high-pressure jet homogenizer, use is specified(Flow:6L/h, work pressure Power:800bar, stroke of machine number:110 beats/min, highest product temperature:80℃)Parameter carry out homogenize process after, then use Three spectral line high energy light curing process, cycle obtain pretreated instant aerogel microball suspension twice.The airsetting of this instant Glue microballoon is used directly for activated protein label, such as biological enzyme label, antibody label, antigen sensibilization, can be used to do particle Enhance immunoturbidimetry reagent and promotes the sensitivity of traditional antigen-antibody reaction.Three spectral lines photocuring processing therein is such as Fig. 4 institutes Show, the G01 lasers of selection are 255nm ultraviolet lasers, and power 3W is located at conveying device tangential direction, with transfer device Plane is more preferably 45 ± 3 degree in 45 ± 5 degree of arrangements, most preferred 45 ± 0.05 degree;G02 lasers are 550nm semiconductors Laser, power 50W, it is more preferably 90 with transfer device plane in 90 degree of arrangements to direction to be located at conveying device vertically ± 1.0 degree, most preferred 90 ± 0.05 degree;G03 lasers are 1024nm carbon dioxide lasers, power 80W is located at defeated Device forward direction is sent, is more preferably 45 ± 3 degree with transfer device plane in 45 ± 5 degree of arrangements, most preferred 45 ± 0.05 Degree, three lasers can be driven by manual or automatic motor and moved based on x, y, z axis direction.
Embodiment 4:
Instant aeroge latex microsphere lotion by by 165 nano-size silica aerogel particles (550g), 2,4,7, 9- tetramethyl -5- decine -4,7- glycol(1.5g), 10% 172 nanometer carboxylic polystyrene latexs (300 milliliters), poly-(Methyl Vinyl ether/maleic anhydride)Half-ester copolymerization object (3.0g), absolute ethyl alcohol(300 milliliters), it is added to 5.7 liters of hexahydro neighbour benzene two Formic acid bisglycidyl ester, 2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones, fluorinated diphenyl titanium cyclopentadienyl and metering system Sour isobornyl thiocyanoacetate 1:1:1:In 33 mixed liquors, it is fully ground under the conditions of being protected from light in magnetic grinding machine spare;Separately weigh containing poly- γ paddy ammonia Acid(3.0g), high acyl degree gellan gum(0.05g), Sodium Hyaluronate oligosaccharides(0.5g), PVP K30 ((3.0g))、 Ammonium hydroxide(6.5 milliliter), purified water(3.9 rising)It is slowly added dropwise after high-speed homogenization machine stirring and dissolving and above-mentioned spare silica is added In aeroge suspension, it is then quickly added into high-pressure jet homogenizer, use is specified(Flow:6L/h, operating pressure:800bar, Stroke of machine number:110 beats/min, highest product temperature:80℃)Parameter carry out homogenize process after, then with three spectral line high energy Photocuring processing, cycle obtain pretreated instant aerogel microball suspension twice.This instant aerogel microball can be with It is directly used in activated protein label, such as biological enzyme label, antibody label, antigen sensibilization, can be used to do the immune ratio of particle enhancing Turbid reagent and the sensitivity for promoting traditional antigen-antibody reaction.Three spectral lines photocuring therein processing is as shown in figure 4, select G01 lasers are 355nm ultraviolet lasers, and power 3W is located at conveying device tangential direction, with transfer device plane in 45 ± 5 degree of arrangements, are more preferably 45 ± 3 degree, most preferred 45 ± 0.05 degree;G02 lasers are 570nm semiconductor lasers, work( Rate is 25W, and it is more preferably 90 ± 1.0 degree with transfer device plane in 90 degree of arrangements to direction to be located at conveying device vertically, Most preferred 90 ± 0.05 degree;G03 lasers are 1024nm carbon dioxide lasers, power 30W, before being located at conveying device To direction, is arranged in 45 ± 5 degree with transfer device plane, be more preferably 45 ± 3 degree, most preferred 45 ± 0.05 degree, three Laser can be driven by manual or automatic motor and moved based on x, y, z axis direction.
Embodiment 5:
Instant aeroge shines microballoon lotion by by 295 nano-size silica aerogel particles (550g), 2,4,7, 9- tetramethyl -5- decine -4,7- glycol(1.5g), 5% 200 nanometers of up-conversion luminescence microballoons (600 milliliters), poly-(Ethylene methacrylic Base ether/maleic anhydride)Half-ester copolymerization object (1.0g), absolute ethyl alcohol(300 milliliters), it is added to 6.7 liters of hexahydrophthalic acid Bisglycidyl ester, 2- hydroxyls -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones, fluorinated diphenyl titanium cyclopentadienyl and methacrylic acid are different Norbornene ester 1:1:1:In 50 mixed liquors, it is fully ground under the conditions of being protected from light in magnetic grinding machine spare;Separately weigh containing poly- γ glutamic acid (2.0g), high acyl degree gellan gum(0.03g), special affinity Sodium Hyaluronate(0.5g), tetradecyltrimethylammonium glycine betaine ((2.0g)), ammonium hydroxide(7.5 milliliter), purified water(2.9 rising)It is above-mentioned spare that addition is slowly added dropwise after high-speed homogenization machine stirring and dissolving Aerosil suspension in, be then quickly added into high-pressure jet homogenizer, use is specified(Flow:6L/h, work pressure Power:800bar, stroke of machine number:110 beats/min, highest product temperature:80℃)Parameter carry out homogenize process after, then use Three spectral line high energy light curing process, cycle obtain pretreated instant aerogel microball suspension twice.The airsetting of this instant Glue microballoon is used directly for activated protein label, such as biological enzyme label, antibody label, antigen sensibilization, can be used to do particle The luminous lateral chromatography immunoassay of enhancing, the immunoluminescence trace of latex intensified and linear immunoassay and promotion tradition antigen The sensitivity of antibody response.Three spectral lines photocuring processing therein is as shown in figure 4, the G01 lasers selected are 355nm ultraviolet sharp Light device, power 5W are located at conveying device tangential direction, are arranged in 45 ± 5 degree with transfer device plane, more preferably for 45 ± 3 degree, most preferred 45 ± 0.05 degree;G02 lasers are 570nm semiconductor lasers, and power 50W hangs down positioned at conveying device It is more preferably directly 90 ± 1.0 degree with transfer device plane in 90 degree of arrangements to direction, most preferred 90 ± 0.05 degree;G03 Laser is 1024nm carbon dioxide lasers, power 100W is located at conveying device forward direction, with transfer device plane It is arranged in 45 ± 5 degree, is more preferably 45 ± 3 degree, most preferred 45 ± 0.05 degree, three lasers can be by manually or certainly Dynamic motor driving moved based on x, y, z axis direction.
Embodiment 6:
Instant aeroge fluorescent microsphere lotion by by 172 nano-size silica aerogel particles (550g), 2,4,7, 9- tetramethyl -5- decine -4,7- glycol(1.0g), 2% 110 nanometer carboxylic semiconductor point quantum dot microspheres (600 milliliters), poly- (Methyl vinyl ether/maleic anhydride)Half-ester copolymerization object (3.0g), absolute ethyl alcohol(600 milliliters), it is added to 5.7 liters of 2- hydroxyls Base -4 '-(2- hydroxy ethoxies) -2- methyl phenyl ketones, fluorinated diphenyl titanium cyclopentadienyl and bis- ((3,4- epoxycyclohexyls) methyl) oneself two Acid esters 1:1:1:In 40 mixed liquors, it is fully ground under the conditions of being protected from light in magnetic grinding machine spare;Separately weigh containing poly- γ glutamic acid (3.0g), high acyl degree gellan gum(0.06g), high molecular weight sodium hyaluronate(2.0g), tetradecyltrimethylammonium amine oxide ((3.0g)), ammonium hydroxide(7.5 milliliter), purified water(3.9 rising)It is above-mentioned spare that addition is slowly added dropwise after high-speed homogenization machine stirring and dissolving Aerosil suspension in, be then quickly added into high-pressure jet homogenizer, use is specified(Flow:6L/h, work pressure Power:800bar, stroke of machine number:110 beats/min, highest product temperature:80℃)Parameter carry out homogenize process after, then use Three spectral line high energy light curing process, cycle obtain pretreated instant aerogel microball suspension twice.The airsetting of this instant Glue microballoon is used directly for activated protein label, such as biological enzyme label, antibody label, antigen sensibilization, can be used to do particle The fluorescence lateral chromatography immunoassay of enhancing, the immunofluorescence trace of latex intensified and linear immunoassay, flow cyctometry are glimmering Light analysis, immunohistochemical analysis and the sensitivity for promoting traditional antigen-antibody reaction.Three spectral lines photocuring processing such as Fig. 4 therein Shown, the G01 lasers of selection are 365nm ultraviolet lasers, and power 3W is located at conveying device tangential direction, is filled with transhipment Horizontalization face is more preferably 45 ± 3 degree in 45 ± 5 degree of arrangements, most preferred 45 ± 0.05 degree;G02 lasers are that 488nm is partly led Body laser, power 10W are located at conveying device vertically to direction, are arranged in 90 degree with transfer device plane, more preferably for 90 ± 1.0 degree, most preferred 90 ± 0.05 degree;G03 lasers are 1024nm carbon dioxide lasers, power 50W is located at Conveying device forward direction is more preferably 45 ± 3 degree with transfer device plane in 45 ± 5 degree of arrangements, most preferred 45 ± 0.05 degree, three lasers can be driven by manual or automatic motor and moved based on x, y, z axis direction.
Embodiment 7:
Instant aeroge β2-microglobulin antibody sensitized microballoon passes through the silica gas for preparing embodiment 2 and embodiment 4 Gel particle (each 25ml), β2-microglobulin rabbit-anti human antibody (100ml), are added to the 0.2M boron of pH8.30 ± 0.05 850ml It injects in magnetic grinding machine and homogenizes 15 minutes after being mixed in phthalate buffer for 300 revs/min;It is then quickly added into high-pressure jet homogeneous In machine, use is specified(Flow:6L/h, operating pressure:800bar, stroke of machine number:110 beats/min, highest product temperature:48 ℃)Parameter carry out homogenize process after, then use three spectral line high energy light curing process, cycle twice i.e. obtain it is pretreated i.e. use Type aeroge β2-microglobulin antibody sensitized microsphere suspensions.This instant aerogel microball is used directly for 2 microballoon eggs of human body β White analysis, such as latex enhancing immune analysis.Three spectral lines photocuring processing therein is as shown in figure 4, the G01 lasers selected are 255nm ultraviolet lasers, power 3W are located at conveying device tangential direction, are arranged in 45 ± 5 degree with transfer device plane, compared with Preferably 45 ± 3 degree, most preferred 45 ± 0.05 degree;G02 lasers are 570nm semiconductor lasers, power 10W, position In conveying device vertically to direction, is arranged in 90 degree with transfer device plane, be more preferably 90 ± 1.0 degree, most preferred 90 ± 0.05 degree;G03 lasers are 1024nm carbon dioxide lasers, power 10W is located at conveying device forward direction, with Transfer device plane is more preferably 45 ± 3 degree in 45 ± 5 degree of arrangements, most preferred 45 ± 0.05 degree, three lasers By the driving of manual or automatic motor move based on x, y, z axis direction.Compared with conventional method, this law sensitization microballoon is faster Prompt, simple, efficient, uniform, product reproducibility is more preferable.
Wherein high molecular weight sodium hyaluronate, molecular weight are more than 2,000,000 kDa.
The full content of the reference paper of all references is specifically introduced into present disclosure by applicant.In addition, if Amount, concentration or other values or parameter are provided as range, preferred scope or upper limit preferred value and enumerating for lower preferable values, It should be understood as specifically disclosing and be formed by by any upper limit or preferred value and any lower limit or any pair of of preferred value All ranges, not scope tube whether be separately disclosed.If enumerating numberical range herein, unless otherwise indicated, range meaning Taste all integers and score including its endpoint and in the range.When the scope of the invention is not only restricted to define a certain range Cited particular value.
Consider from the practice of this specification disclosed herein and the present invention, the other embodiments of the present invention are for this field skill Art personnel are obvious.This specification and embodiment are seen merely as being example, and the actual scope of the present invention and spirit are by appended Claims and its equivalent are determined.
The present invention relates to the invention belongs to biomedicine, analytical chemistry, nanometer material science, synthesising chemical technology, green woods Material, neoformation technology, macromolecular polymerization reaction technology, Solid-phase organic synthesis, macromolecule material surface modification, polymers function are micro- Ball, instant aerogel microball, aerogel particle, multifunctional material, the aeroge instant of field of polymer microsphere materials are micro- Ball, and preparation method thereof and the aeroge instant microballoon purposes.More particularly it relates to coat/admix work( The aeroge instant microballoon of energy material.It is a kind of completely new new green environment protection material, can be widely used for medical diagnosis on disease, examines Analysis, building decoration, haze improvement, water purification, sewage disposal, soil improvement, space flight, medicine, food, chemical industry, cosmetics, electronics Information, medical instrument, agriculture livestock products, building decoration, petroleum and petrochemical industry, papermaking, printing, ink, anti-fog haze cosmetics and skin care The fields such as articles for use, anti-fog haze infant article, anti-aging.

Claims (40)

1. a kind of aeroge instant microballoon, including at least one functional material/functional group as coating/admixture and At least one aeroge or aerogel precursor substance, wherein at least part of the functional material/functional group is at least partly With cladding/blending in aeroge surface layer.
2. the aeroge instant microballoon of claim 1, wherein at least one function base of at least part of the aeroge Group/material processing with formed can coat/admix characteristic.
3. the aeroge instant microballoon of claim 1, wherein the aeroge instant microballoon is instant complex microsphere material Material.
4. the aeroge instant microballoon of claim 1, wherein functional material/work(of at least one coating/admixture Energy group is Polyurethane-epoxy resin and its derivative.
5. the aeroge instant microballoon of claim 1, wherein functional material/work(of at least one coating/admixture Energy group is hyaluronic acid and its derivative.
6. the aeroge instant microballoon of claim 1, wherein functional material/work(of at least one coating/admixture Energy group is latex microsphere or luminous microballoon or both.
7. the aeroge instant microballoon of claim 1, wherein functional material/work(of at least one coating/admixture Energy group is photosensitive resin or light-sensitive material or photoinitiator or their compositions.
8. the aeroge instant microballoon of claim 1, wherein functional material/work(of at least one coating/admixture Energy group is hexahydrophthalic acid bisglycidyl ester or gathers(Methyl vinyl ether/maleic acid)Copolymer is poly-(Methyl second Alkene ether/maleic anhydride)Copolymer is poly-(Methyl vinyl ether/maleic acid)Half-ester copolymerization object is poly-(Methyl vinyl ether/horse Carry out acid anhydrides)Half-ester copolymerization object or bis- ((3,4- epoxycyclohexyls) methyl) adipate esters or photosensitive resin or photocuring adhesive or Light curing agent or photoinitiator or their mixture.
9. the aeroge instant microballoon of claim 1, wherein at least one silica aerogel powder or titanium dioxide Aerogel particles or titania aerogel or graphene aerogel or carbon aerogels or metal aerogel or it is other it is inorganic, have Machine aeroge or aerogel precursor substance.
10. the aeroge instant microballoon of claim 1, wherein the aeroge has bore volume and is easy to by above-mentioned work( It can material/functional group cladding/blending.
11. the aeroge instant microballoon of claim 1 the, wherein coating/admixture on the aeroge is that have The functional material of function/functional group coating.
12. the aeroge instant microballoon of claim 1, wherein the coating/admixture includes at least one oleophylic/hydrophilic Functional material/functional group.
13. the aeroge instant microballoon of claim 1, wherein the coating/admixture also includes surface modifier, including But it is not limited to surfactant, wetting agent or combination thereof.
14. the aeroge instant microballoon of claim 1 the, wherein coating/admixture is latex beads or luminous microballoon Or functional material or functional group.
15. the aeroge instant microballoon of claim 1 the, wherein coating/admixture is by the surface on the aeroge Coating forms.
16. the aeroge instant microballoon of claim 1, wherein the coating/admixture cladding or blending are in aeroge table Face.
17. the aeroge instant microballoon of claim 1, wherein functional material/functional group of the coating/admixture is Functional material/functional group of organic or inorganic and the coating/admixture are that hydrophilic functional material/functional group applies Layer.
18. the aeroge instant microballoon of claim 1, wherein functional material/functional group of the coating/admixture is Functional material/functional group of hydrophily coating/admixture and include surface modifier.
19. the aeroge instant microballoon of claim 1 the, wherein coating/admixture is not easily accessible aeroge internal holes Chamber.
20. a kind of method for the aeroge instant microballoon preparing claim 1, including the aeroge is wrapped at least one Object/admixture in high pressure jet machine or magnetic grinding machine coat/is covered to mix to form the aeroge for coating/mixing and then will The aeroge for coating // mixing is combined with functional material/functional group of at least one uncured coating/admixture And then use functional material/functional group of coating/admixture described in three spectral line high energy photocurings to form the airsetting Glue instant microballoon.
21. a kind of method for the aeroge instant microballoon preparing claim 1, including by coating/admixing nano particle On to the aeroge and use aeroge described in three spectral line high energy photocurings with formed the nano particle/nanoparticle with Coating is formed on the aeroge to coat/admix the aeroge, and then by the aerogel microball of the cladding/blending and extremely A kind of few functional material/functional group of uncured coating/admixture is combined and is subsequently cured the coating/admixture Functional material/functional group to form the aeroge instant microballoon.
22. a kind of method for the aeroge instant microballoon preparing claim 1, including by the aeroge with comprising dissolving or Disperse or be emulsified in contain organic solution/purified water cladding/blending containing the first reactant in novel organic solvent/purified water, Purified water/organic molten is added to the aeroge of the cladding containing organic solution/blending after three spectral line high energy photocurings Liquid, and then homogenized with high pressure jet machine or magnetic grinding machine again to obtain the reaction product of the first and second reactants to be formed The aerogel microball of cladding/blending, and then by the aerogel microball of the cladding/blending and at least one uncured cladding The functional material/functional group is combined and then uses coating described in three spectral line high energy photocurings again/of object/admixture is mixed Functional material/functional group with object is to form the aeroge instant microballoon.
23. latex microsphere/shine microballoon, include the aeroge of the cladding/blending latex microsphere/microballoon that shines with claim 1 Instant microballoon.
24. the aerogel microball of cladding/blending of claim 1, wherein the aerogel microball preparation method of cladding/blending are one The method for preparing functional microsphere that the grinding of kind magnetic, high-pressure jet technology are combined with three spectral line high energy photocuring technologies, the method are first It is secondary using magnetic grinding, three spectral line photocuring series connection method of high-pressure jet and two steps, with simple, quick, flexible, efficient, uniform, Time saving feature, and highly sensitive, high-throughput detection and analysis are carried out in combination with microflow control technique, and can be carried out by this method New optical analysis technique is established and analytical equipment manufactures and designs.
25. a kind of instant aerogel microball includes the aeroge instant microballoon of claim 1.
26. the instant aerogel microball of activation, includes the aeroge instant microballoon of the activation of claim 1.
27. a kind of aeroge for coating/mixing, including using aeroge as kernel, wherein the aeroge is at least partially by least A kind of coating/blend coats/mixes, on the surface of the aeroge, to be conducive to latex beads/luminous microballoon Suspension.
28. the aerogel microball of cladding/blending of claim 24 the, wherein coating/admixture on the aeroge Functional material/the functional group for being.
29. the aerogel microball of cladding/blending of claim 24 the, wherein coating/admixture includes at least one parent Oily/hydrophilic functional material/functional group.
30. the aerogel microball of cladding/blending of claim 24, wherein the coating includes profit surface modifier.
31. the aerogel microball of cladding/blending of claim 24 the, wherein coating/admixture is functional material or work( It can group.
32. the aerogel microball of cladding/blending of claim 24 the, wherein coating/admixture is by the aeroge Surface cladding/blending layer composition.
33. the aerogel microball of cladding/blending of claim 24, wherein the surface cover/blending nitride layer photocuring in Aeroge surface.
34. the aerogel microball of cladding/blending of claim 24, wherein the coating/blending nitride layer is organic/inorganic packet Cover functional material/functional group of object/admixture and the coating/blending nitride layer be oleophylic/hydrophilic functional material/function Group.
35. the aerogel microball of cladding/blending of claim 24, wherein the coating is functional material/work(of oleophylic/hydrophilic Energy group and the coating/blending nitride layer include surface modifier.
36. the aerogel microball of cladding/blending of claim 24, including three spectral line photocurings act at least twice.
37. the aerogel microball of cladding/blending of claim 35, wherein the functional material/functional group material include but It is not limited to organic/inorganic materials, bioactive materials or metal, is used to prepare functional microsphere.
38. the aerogel microball of cladding/blending of claim 35, including two or more is the material that is same or different to each other Other functional materials/functional group material.
39. the aerogel microball of cladding/blending of claim 37, wherein the method for preparing microballoon, includes by nano particle Surface is a kind of or multifunctional material/functional group is ground with magnetic, high injection technology is connected with three spectral line high energy photocuring technologies Carry out functional microsphere preparation.
40. the aeroge described in claim 39 adulterates/coat multi-functional instant composite material and preparation method thereof, feature exists In:The three spectral line photocuring processing methods are three spectral line photocuring processing methods of high-energy, and high energy light includes but unlimited In high energy UV, high-energy throughput light, high energy visible light, X-ray, gamma-rays, microwave and combination thereof etc.;Three spectrum therein Linear light solidification processing is in transfer device plane as shown in figure 4, G01 lasers or transmitter are located at conveying device tangential direction 45 ± 45 degree of arrangements, are more preferably 45 ± 43 degree, most preferred 45 ± 0.05 degree;G02 lasers or transmitter are located at conveying Device is more preferably vertically 90 ± 3.0 degree with transfer device plane in 90 degree of arrangements to direction, most preferred 90 ± 0.05 Degree;G03 lasers or transmitter are located at conveying device forward direction, with transfer device plane in 45 ± 45 degree of arrangements, more preferably It it is 45 ± 43 degree, most preferred 45 ± 0.05 degree, three lasers or transmitter can pass through artificial mechanism or automatic motor Driving moved based on x, y, z axis direction;Laser power therein is more preferably 0.001w in 0.0001w~5000w ~1000w, preferably 0.01w~500w.
CN201710143602.6A 2017-03-13 2017-03-13 A kind of novel instant aerogel microball and preparation method thereof Pending CN108568278A (en)

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