CN102675545A - Monodisperse micro colloidal particles with raised spots on surface and preparation method for colloidal particles - Google Patents
Monodisperse micro colloidal particles with raised spots on surface and preparation method for colloidal particles Download PDFInfo
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Abstract
The invention relates to monodisperse micro colloidal particles with raised spots on surfaces. The surface spots of the colloidal particles are nano-scale, the distribution density and the size of the spots can be controlled, and the colloidal particles have core-shell structures, wherein the core is a non-crosslinked polymer, and the shell is a crosslinked polymer. The invention also provides a preparation method for the colloidal particles. The preparation method is simple and efficient, and can be used for large-scale production.
Description
Invention field
The present invention relates to the mono dispersed micrograde colloidal particle that a kind of surface has the projection spot, particularly the preparation method of this colloidal particle and nano surface level spot distribution density and spot size is adjustable.
Background of invention
All the time, people tend to through regulating that the colloidal particle surface chemistry is formed but not surface topography obtains different physicochemical property.Wherein most important reason is still not have at present a kind of simple and colloidal particle that effective means comes large batch of preparation surface topography accurately to regulate.And in some field, field such as release in the organizational project, body for example, adaptable chemical substance is very few, and this has greatly limited the progress of association area.Than surface chemical modification, obtain different physicochemical property through adjusting colloidal particle surface topography and have more advantage.For example, can improve the hydrophilicity and hydrophobicity of these particles significantly through the roughness that increases the colloidal particle surface.In addition; The people's such as professor Stellacci of MIT work recently shows that the periodicity ripples shape structure on nano Au particle surface can reduce absorption of proteins effectively, and this correlative study for control medicine carrying particle residence time in the animal blood circulation opens up a new way.
At present, the method for adjusting material surface pattern commonly used mainly contains chemical deposition, physisorphtion and plasma etching method etc.But lower productive rate and trivial step have greatly limited the practical application of these methods.In addition, the surface tissue that makes through these methods is often stablized inadequately.Therefore, there is a kind of demand for preparing the adjustable and constitutionally stable single dispersoid particle of surface topography through simple method in enormous quantities.
Seeding polymerization generally is used to prepare the large size composite gel particle of smooth surface or complex topography.Under action of evocating, second monomer forms shell (monomer that forms seed is called first monomer) in the seed-coat polymerization.Because the consumption of emulsifying agent is less than its micelle-forming concentration, so thereby can avoid the generation of secondary particle to obtain monodispersed colloidal particle in the polymerization system.In addition, the height that the concentration of seed can be suitable in the polymerization system (being not less than 5%).
The inventor finds through experiment, these characteristics of seeding polymerization meet above-mentioned about in the adjustable colloidal particle preparation of roughness about implementing facility, high yield and monodispersed requirement.The requirement of the stability of surface tissue then can be satisfied through in second monomer, adding linking agent.In addition, the introducing of linking agent can produce disturbance to the forming process of shell, thereby changes the surface topography of shell significantly.In conjunction with the Related Mechanism of emulsifier-free emulsion polymerization, it is not only convenient, efficient but also structure is enough stable to be with above-mentioned improved seeding polymerization method that means prepare the adjustable colloidal particle of surface topography, can fully satisfy the needs of related basic research and practical application.
Summary of the invention
The object of the present invention is to provide a kind of surface to have mono dispersed micrograde colloidal particle of projection spot and preparation method thereof.The distribution density of colloidal particle protrusion of surface spot of the present invention, size and chemical constitution are adjustable, Stability Analysis of Structures, and the preparation method is simply efficient.
In order to realize the present invention, the present invention provides following technical proposals:
There is the mono dispersed micrograde colloidal particle of projection spot on a kind of surface, and this colloidal particle pimple is a nano level, and this colloidal particle is a nucleocapsid structure.
According to the present invention, wherein said stratum nucleare is noncrosslinking polymkeric substance, and said shell is crosslinked polymkeric substance.
According to the present invention, said stratum nucleare material is selected from noncrosslinking monodisperse polymer particle, like polyacrylic particle and polystyrene type particle, and preferred polystyrene type particle.Monodisperse polymer particle in the said stratum nucleare makes monomer on seed grain, to grow as seed grain.According to the present invention, preferred seed grain is spherical.
According to the present invention, said shell material is selected from cross-linked polymer, optimization polypropylene tert-butyl acrylate, polymethylmethacrylate, Vinalac 5920, polyene propyl trimethoxy silicane etc., more preferably the ROHM tert-butyl ester.ROHM tert-butyl ester hydrolyzable under acidic conditions is a ROHM, conveniently realizes the counter-rotating of above-mentioned colloidal particle surface properties, widens the range of application of such colloidal particle.
According to the present invention, the distribution density of said nano level spot and size can be regulated.Preferably, the distribution density of said crosslinked shell pimple and size can be regulated through reaction times, monomer and dosage of crosslinking agent and emulsifier concentration, and more preferably said adjusting parameter is an emulsifier concentration.Said mono dispersed micrograde colloidal particle surface topography is adjustable.
According to the present invention, the chemical composition of said kernel, shell and pimple can be regulated, and preferably adopts styrenic or acrylic polymer.
According to the present invention, said surface contains in the initial reactant of crosslinked shell of nano level spot and also comprises monomer, linking agent, initiator, emulsifying agent and water.
According to the present invention, said monomer consumption is the 15%-85wt% of seed grain, preferred 15%-65wt%, more preferably 32.5%-60wt%; Dosage of crosslinking agent is monomeric 10%-50wt%; Preferred 12-35wt%.Emulsifier concentration 0.05-2.5g/L, preferred 0.125-2.0g/L, more preferably 0.25-1g/L, also more preferably 0.375-0.5g/L.Initiator amount is monomeric 0.5-2wt%, preferred 0.8-1wt%.
According to the present invention, the consumption of seed grain can be not less than 5wt% with respect to water in the said initiator polymerization system, more preferably no higher than 10wt%.
According to the present invention, said linking agent be preferably can be in monomer and seed grain the dissolved linking agent, be preferably the oil soluble linking agent, like Vinylstyrene.The introducing of linking agent can produce disturbance to the forming process of shell, thereby changes the surface topography of shell significantly.Thereby linking agent joined help obtaining the stable colloidal particle of surface tissue in the monomer.
According to the present invention, said emulsifying agent is the water-soluble ionic-type emulsifying agent, is selected from X 2073, sodium laurylsulfonate, sodium lauryl sulphate, hexadecyl brometo de amonio etc., preferred sodium laurylsulfonate.Preferred sodium laurylsulfonate.Because the consumption of emulsifying agent is less than its micelle-forming concentration, so thereby can avoid the generation of secondary particle to obtain monodispersed colloidal particle in the polymerization system.
According to the present invention; Said initiator is preferably water soluble starter; Be selected from Potassium Persulphate, ammonium persulphate and water-soluble azo class initiator; Narrow hydrochloride, azo two isobutyl imidazole hydrochlorides, azo dicyano valeric acid, azo di-isopropyl tetrahydroglyoxaline etc. like the azo diisobutyl, preferred Potassium Persulphate.
According to the present invention, said shell and spot surface also have functional functional group.This functional functional group can carry out further modification.
The inventor finds through experiment, these characteristics of seeding polymerization meet above-mentioned about in the adjustable colloidal particle preparation of roughness about implementing facility, high yield and monodispersed requirement.
The present invention also provides a kind of aforesaid surface to have the preparation method of the mono dispersed micrograde colloidal particle of projection spot; It is characterized in that said mono dispersed micrograde colloidal particle forms through seeding polymerization under action of evocating in dispersion medium (preferably water).
Preparation in accordance with the present invention, the pimple of said mono dispersed micrograde colloidal particle are nano level, and this colloidal particle is a nucleocapsid structure.Wherein said stratum nucleare is noncrosslinking polymkeric substance, and said shell is crosslinked polymkeric substance.
Preparation in accordance with the present invention, said initial reactant further comprises linking agent, initiator and emulsifying agent, wherein said linking agent is preferably the oil soluble linking agent, like Vinylstyrene; Said initiator is preferably water soluble starter and said emulsifying agent is preferably the water-soluble ionic-type emulsifying agent.
Preparation in accordance with the present invention, said monomer consumption are the 15%-85wt% of seed grain, preferred 15%-65wt%, more preferably 32.5%-60wt%; Said linking agent is the 10%-50wt% of monomer consumption, preferred 12-35wt%.Emulsifier concentration 0.05-2.5g/L, preferred 0.125-2.0g/L, more preferably 0.25-1g/L, also more preferably 0.375-0.5g/L.Initiator is the 0.5%-2wt% of monomer consumption, preferred 0.8-1wt%.
Preparation in accordance with the present invention, said monomer is selected from oil-soluble monomer, like tert-butyl acrylate, TEB 3K, n-BMA, allyltrimethoxysilanis etc. are preferably the ROHM tert-butyl ester.
Preparation in accordance with the present invention, said water soluble starter are selected from Potassium Persulphate, ammonium persulphate and water-soluble azo class initiator, narrow hydrochloride like the azo diisobutyl; Azo two isobutyl imidazole hydrochlorides; Azo dicyano valeric acid, azo di-isopropyl tetrahydroglyoxaline etc., preferred Potassium Persulphate.
Preparation in accordance with the present invention, said water-soluble ionic-type emulsifying agent is selected from X 2073, sodium laurylsulfonate, sodium lauryl sulphate, hexadecyl brometo de amonio etc.Preferred sodium laurylsulfonate.
According to the present invention, said preparation method further comprises the steps:
(1) will single disperse the non-crosslinked seed grain, water soluble starter in water with emulsifier mix, add the monomer mixture that contains linking agent afterwards, form stable emulsion;
(2) emulsion stable in the step (1) was stirred under certain temperature polymerization 1-24 hour, obtain the mono dispersed micrograde composite gel particle that the surface contains the nano level spot.
Preparation in accordance with the present invention is a benchmark with the consumption of said non-crosslinked seed, and oil-soluble monomer is 15%-85wt%, preferred 10%-65wt%.
Preparation in accordance with the present invention, said non-crosslinked seed is selected from noncrosslinking monodisperse polymer particle, like polyacrylic particle and polystyrene type particle, preferred polystyrene type particle.Monodisperse polymer particle in the said stratum nucleare makes monomer on seed grain, to grow as seed grain.
Preparation in accordance with the present invention, said temperature are 50-95 ℃, preferred 65-75 ℃.
Preparation in accordance with the present invention, said polymerization time is preferably 1-24 hour, more preferably 4-12 hour.
In the present invention, linking agent and water soluble starter are the keys that forms the nano level spot.Thereby the introducing of linking agent on the one hand can form cross-linked network at the non-crosslinked seed-coat stops the oligopolymer that is adsorbed in seed-coat to become the vegetative point of above-mentioned spot to the seed internal divergence, on the other hand with can prevent that these spots from being dissolved by monomer in process of growth.Thereby water soluble starter then guarantees the monomer that diffuses into water and is initiated the formation oligopolymer at water that these oligopolymers further are adsorbed on the vegetative point that seed-coat becomes spot.The adding of emulsifying agent helps forming stable emulsion on the one hand, can also stop noncrosslinking seed particles to be dissolved by monomer on the other hand.The concentration of emulsifying agent is most important, and when emulsifier concentration when too high (being higher than micelle-forming concentration), monomer tends to polymerization in the micella that is formed by the emulsifying agent molecule, thereby forms secondary particle, the monodispersity of the final composite particles of remarkably influenced.
The colloidal particle that the surface of the present invention's preparation contains the nano level spot has the following advantages:
1. this colloidal particle desired raw material is simple, cheap and easy to get, and the preparation method is simple, can be mass-produced.
2. the distribution density and the size convenient regulation and control of the nano level spot on this colloidal particle surface, regulated variable is various.
3. this colloidal particle narrow size distribution, surface tissue is stable.
4. this colloidal particle surface chemical property can be realized counter-rotating through hydrolysis treatment, obtains surface reaction functional group, helps further modification, and range of application is wider.
Description of drawings
Shell contains the photo of different distributions density and size nano level spot list dispersoid particle among the embodiment 1 that Fig. 1 obtains for sem, and the surface that promptly obtains during different emulsifiers concentration has the SEM photo of the mono dispersed micrograde colloidal particle of projection spot.
Shell contains the photo of different distributions density and size nano level spot list dispersoid particle among the embodiment 2 that Fig. 2 obtains for sem, and the surface that promptly obtains during the monomer consumption has the SEM photo of the mono dispersed micrograde colloidal particle of projection spot.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done further detailed description.
Protection scope of the present invention is not limited only to above embodiment.According to content disclosed by the invention, those skilled in the art will recognize that under the situation that does not break away from given technical characterictic of technical scheme of the present invention and scope variation and modification that the above embodiment is made all belong to protection scope of the present invention.
Embodiment 1
Raw material adopts the spherical seed (the about 800nm of particle diameter, polydispersity coefficient 1.04) of noncrosslinking monodisperse polystyrene, tert-butyl acrylate monomer, linking agent Vinylstyrene, initiator potassium persulfate, emulsifying agent sodium laurylsulfonate and water.Wherein, polystyrene seed consumption 0.4g, tert-butyl acrylate consumption are the 60wt% of seed; The Vinylstyrene add-on is the monomeric 12wt% of tert-butyl acrylate; The Potassium Persulphate add-on is monomeric 1wt%, and emulsifier concentration is respectively 0.125g/L, 0.250g/L; 0.375g/L and 0.50g/L, all the other are water 20g.Earlier polystyrene seed, initiator, emulsifying agent and water are mixed according to above-mentioned formula rate, then add the mixture of tert-butyl acrylate monomer and Vinylstyrene, under the effect of magnetic agitation, form stable emulsion.The emulsion that this is stable stirs polymerization 12 hours in 70 ℃ of lower magnetic forces, promptly forms the nano level spot list dispersoid particle that a kind of shell contains different distributions density and size.
The colloidal particle of above-mentioned preparation is used field emission scanning electron microscope (JSM-6700) the observation particle morphology of Japanese JEOL company.
Can know in conjunction with accompanying drawing 1 disclosed content; Along with the increase of emulsifier concentration (0.125,0.25,0.375 and 0.50g/l); The size of the nano level spot on colloidal particle surface reduces gradually; Distribution density reduces after then increasing (emulsifier concentration reaches extreme value during for 0.375g/L, and the area on colloidal particle surface about 12% is covered by spot) earlier.Meanwhile, the size of colloidal particle and monodispersity remain unchanged basically.
Embodiment 2
Raw material adopts the spherical seed (the about 800nm of particle diameter, polydispersity coefficient 1.04) of noncrosslinking monodisperse polystyrene, tert-butyl acrylate monomer, linking agent Vinylstyrene, initiator potassium persulfate, emulsifying agent sodium laurylsulfonate and water.Wherein, Polystyrene seed consumption 0.4g; The consumption of tert-butyl acrylate is the 32.5wt% and the 65wt% of seed grain consumption, and the add-on of Vinylstyrene is the monomeric 12wt% of tert-butyl acrylate, and the add-on of Potassium Persulphate is the monomeric 1wt% of tert-butyl acrylate; Emulsifier concentration is 0.250g/L, and all the other are water 20g.Earlier polystyrene seed, initiator, emulsifying agent and water are mixed according to above-mentioned formula rate, then add the mixture of tert-butyl acrylate monomer and Vinylstyrene, under the effect of magnetic agitation, form stable emulsion.The emulsion that this is stable stirs polymerization 12 hours in 70 ℃ of lower magnetic forces, promptly forms the nano level spot list dispersoid particle that a kind of shell contains different distributions density and size.
The colloidal particle of above-mentioned preparation is used field emission scanning electron microscope (JSM-6700) the observation particle morphology of Japanese JEOL company.
Can know to have only when monomer concentration reaches certain value (32.5wt%) in conjunction with accompanying drawing 2 disclosed contents, colloidal particle surface could generate tangible nano level spot, and along with increase (65wt%) of monomer consumption, the spot size increase that colloidal particle is surperficial.The size of colloidal particle also increases simultaneously.
Embodiment 3
Raw material adopts the spherical seed (the about 800nm of particle diameter, polydispersity coefficient 1.04) of noncrosslinking monodisperse polystyrene, methacrylate monomer, linking agent Vinylstyrene, initiator azo two isobutyl imidazole hydrochlorides, emulsifier sodium lauryl sulfate and water.Wherein, Polystyrene seed consumption 0.4g; The consumption of tert-butyl acrylate is the 60wt% of seed grain consumption, and the add-on of Vinylstyrene is the monomeric 12wt% of tert-butyl acrylate, and the add-on of azo two isobutyl imidazole hydrochlorides is the monomeric 1.5wt% of tert-butyl acrylate; Emulsifier concentration is 0.375g/L, and all the other are water 20g.Earlier polystyrene seed, initiator, emulsifying agent and water are mixed according to above-mentioned formula rate, then add the mixture of methacrylate monomer and Vinylstyrene, under the effect of magnetic agitation, form stable emulsion.The emulsion that this is stable stirs polymerization 15 minutes in 70 ℃ of lower magnetic forces, 3 hours and 12 hours, promptly forms the nano level spot list dispersoid particle that a kind of shell contains different distributions density and size.
The colloidal particle of above-mentioned preparation is used field emission scanning electron microscope (JSM-6700) the observation particle morphology of Japanese JEOL company.
Along with the prolongation in reaction times, the nano level spot size and the distribution density on colloidal particle surface increase simultaneously, and in the entire reaction course, the size and the monodispersity of colloidal particle remain unchanged basically.
Embodiment 4
Raw material adopts spherical seed (the about 800nm of particle diameter of noncrosslinking monodisperse polystyrene; Polydispersity coefficient 1.04), n-BMA monomer, linking agent Vinylstyrene, initiator azo diisobutyl are narrowed hydrochloride, emulsifying agent X 2073 and water.Wherein, polystyrene seed consumption 0.4g, tert-butyl acrylate consumption are the 60wt% of seed; The Vinylstyrene add-on is the monomeric 12wt% of tert-butyl acrylate; The add-on that the azo diisobutyl is narrowed hydrochloride is monomeric 2wt%, and emulsifier concentration is respectively 0.8g/L, and all the other are water 20g.Earlier polystyrene seed, initiator, emulsifying agent and water are mixed according to above-mentioned formula rate, then add the mixture of n-BMA monomer and Vinylstyrene, under the effect of magnetic agitation, form stable emulsion.The emulsion that this is stable stirs polymerization 15 minutes in 70 ℃ of lower magnetic forces, 3 hours and 12 hours, promptly forms the nano level spot list dispersoid particle that a kind of shell contains different distributions density and size.
The colloidal particle of above-mentioned preparation is used field emission scanning electron microscope (JSM-6700) the observation particle morphology of Japanese JEOL company.
Along with the prolongation in reaction times, the nano level spot size and the distribution density on colloidal particle surface increase simultaneously, and in the entire reaction course, the size and the monodispersity of colloidal particle remain unchanged basically.
Claims (10)
1. a surface has the mono dispersed micrograde colloidal particle of nano level projection spot, it is characterized in that this colloidal particle pimple is a nano level, and said colloidal particle is a nucleocapsid structure.
2. according to the colloidal particle of claim 1, it is characterized in that said stratum nucleare is noncrosslinking polymkeric substance, said shell is crosslinked polymkeric substance.Preferably, said stratum nucleare material is selected from noncrosslinking monodisperse polymer particle, like polyacrylic particle and polystyrene type particle, and preferred polystyrene type particle.Monodisperse polymer particle in the said stratum nucleare makes monomer on seed grain, to grow as seed grain.Said shell material is selected from cross-linked polymer, optimization polypropylene tert-butyl acrylate, polymethylmethacrylate, Vinalac 5920, polyene propyl trimethoxy silicane etc., more preferably the ROHM tert-butyl ester.
3. according to the colloidal particle of claim 1 or 2, it is characterized in that the distribution density of said nano level spot and size can be regulated.Preferably, the distribution density of said crosslinked shell pimple and size can be regulated through reaction times, monomer and dosage of crosslinking agent and emulsifier concentration, and more preferably said adjusting parameter is an emulsifier concentration.
4. according to each described colloidal particle of claim 1-3, it is characterized in that said surface contains in the initial reactant of crosslinked shell of nano level spot and also comprises monomer, linking agent, initiator, emulsifying agent and water.
5. according to each described colloidal particle of claim 1-4, it is characterized in that said monomer consumption is the 15%-85wt% of seed grain, preferred 15%-65wt%, more preferably 32.5%-60wt%; Dosage of crosslinking agent is monomeric 10%-50wt%; Preferred 12-35wt%.Emulsifier concentration 0.05-2.5g/L, preferred 0.125-2.0g/L, more preferably 0.25-1g/L, also more preferably 0.375-0.5g/L.Initiator amount is monomeric 0.5-2wt%, preferred 0.8-1wt%.
6. each described surface of claim 1-5 has the preparation method of the mono dispersed micrograde colloidal particle of projection spot; It is characterized in that said mono dispersed micrograde colloidal particle forms through seeding polymerization under action of evocating in dispersion medium (preferably water).
7. according to the preparation method of claim 6, it is characterized in that the pimple of said mono dispersed micrograde colloidal particle is a nano level, this colloidal particle is a nucleocapsid structure.Wherein said stratum nucleare is noncrosslinking polymkeric substance, and said shell is crosslinked polymkeric substance.
8. according to the preparation method of claim 6 or 7, it is characterized in that said initial reactant further comprises linking agent, initiator and emulsifying agent.Wherein said linking agent is preferably the oil soluble linking agent; Said initiator is preferably water soluble starter and said emulsifying agent is preferably the water-soluble ionic-type emulsifying agent.
9. according to each described preparation method of claim 6-8, it is characterized in that said preparation method further comprises the steps:
(1) will single disperse the non-crosslinked seed grain, water soluble starter in water with emulsifier mix, add the monomer mixture that contains linking agent afterwards, form stable emulsion;
(2) emulsion stable in the step (1) was stirred under certain temperature polymerization 1-24 hour, obtain the mono dispersed micrograde composite gel particle that the surface contains the nano level spot.
10. according to each described preparation method of claim 6-9, it is characterized in that,, be benchmark with the consumption of said non-crosslinked seed, oil-soluble monomer is 15%-85wt%, preferred 10%-65wt%.
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| CN104497573B (en) * | 2014-12-02 | 2017-01-11 | 中国科学院化学研究所 | Silicone rubber composition |
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| CN101092470A (en) * | 2006-06-22 | 2007-12-26 | 广东鸿昌化工有限公司 | Method for preparing microemulsion with high solid content of crosslinked polystyrene and acrylic (ester) |
| CN101402053A (en) * | 2008-11-21 | 2009-04-08 | 北京科技大学 | Process for producing sea urchin shaped polyaniline microsphere supported catalyst |
| CN101457007A (en) * | 2009-01-06 | 2009-06-17 | 北京科技大学 | Multi-shoot polymer composite microsphere and preparation method thereof |
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| CN101092470A (en) * | 2006-06-22 | 2007-12-26 | 广东鸿昌化工有限公司 | Method for preparing microemulsion with high solid content of crosslinked polystyrene and acrylic (ester) |
| CN101402053A (en) * | 2008-11-21 | 2009-04-08 | 北京科技大学 | Process for producing sea urchin shaped polyaniline microsphere supported catalyst |
| CN101457007A (en) * | 2009-01-06 | 2009-06-17 | 北京科技大学 | Multi-shoot polymer composite microsphere and preparation method thereof |
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| CN104497573B (en) * | 2014-12-02 | 2017-01-11 | 中国科学院化学研究所 | Silicone rubber composition |
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