CN101457007A - Multi-shoot polymer composite microsphere and preparation method thereof - Google Patents
Multi-shoot polymer composite microsphere and preparation method thereof Download PDFInfo
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- CN101457007A CN101457007A CNA2009100760672A CN200910076067A CN101457007A CN 101457007 A CN101457007 A CN 101457007A CN A2009100760672 A CNA2009100760672 A CN A2009100760672A CN 200910076067 A CN200910076067 A CN 200910076067A CN 101457007 A CN101457007 A CN 101457007A
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Abstract
The invention provides a poly-4-vinyl pridinium chloride/polystyrene multi-head composite microsphere and a preparation method thereof, which belongs to the technical field of novel polymer microsphere material, particularly relating to a multi-head composite microsphere with a controllable structure. A poly-4-vinyl pridinium chloride microsphere synthesized by a non-soap emulsion polymerization is adopted as a seed, the poly-4-vinyl pridinium chloride/polystyrene multi-head composite microsphere is prepared by utilizing a seed swelling and polymerization, which goes like the following: first, a styrene monomer and a crosslinking agent are added into ethanol solution with a poly-4-vinyl pridinium chloride seed microsphere in, after being swelled for a certain time, the monomer and the crosslinking agent enter the poly-4-vinyl pridinium chloride seed microsphere, and an initiator is added in to initiate polymerization. The styrene monomer and the crosslinking agent polymerized and then gradually form a phase separation area on the surface of the poly-4-vinyl pridinium chloride seed microsphere, and the poly-4-vinyl pridinium chloride/polystyrene multi-head composite microsphere is obtained. The structure of the multi-head microsphere can be controlled by regulating reaction parameters.
Description
Technical field
The invention belongs to novel high polymer micro-sphere material technical field, particularly a kind of multi-shoot polymer composite microsphere and preparation method thereof.
Background technology
Polymer microballoon has that specific surface area is big, adsorptivity is strong, and performance such as surface reaction ability, as functional high molecule material, have a wide range of applications at standard metering, biological chemistry, immune medical science, analytical chemistry, chemical industry, information, microelectronic and some high-technology field.
Advantages such as polystyrene microsphere is with its stable in properties, and synthesis technique is simple and with low cost have been subjected to paying close attention to the most widely.At present, the synthetic method of polystyrene microsphere is ripe relatively, just reported the synthetic method of several other polystyrene microspheres of submicron level respectively as " preparation method of polyphenylethylene microball with grain diameter continuous controllable single dispersing " (publication number CN 1793187A) and " the particle diameter controllable preparation method of monodisperse polystyrene microsphere " (publication number CN 101293936A), it can realize effectively control to the particle diameter of microballoon, has promoted the development of polystyrene synthetic technology greatly.But polystyrene microsphere is typical non-polar material, because molecular structure polar functionalities not, its surface tension is lower, be difficult to be soaked into, cause its adsorptive power that significant limitation is arranged, make its application be subjected to considerable restraint some predetermined substance by some polar liquid.
In recent years, poly-4-vinylpyridine is subjected to extensive concern, and this polymkeric substance has the pyridine functional group, has very active chemical property, is the stronger material of a kind of polarity, in fields such as chemical, medical and health boundless application prospect is arranged all.But poly-4-vinylpyridine is on the high side, and too active chemical property has produced considerable influence to aspects such as polymerization and stability, therefore uses and has been subjected to certain limitation.
Therefore, people wish to obtain a kind of NEW TYPE OF COMPOSITE polymer materials that has two kinds of material advantages simultaneously concurrently.But, in reality synthetic, often can only obtain the polystyrene/poly-4-vinylpyridine composite polymer microballoon of nucleocapsid structure because the polarity difference has caused polymer microballoon balling-up mechanism different.As just having reported poly-4-vinylpyridine among " cross-linking polyvinyl pyridine microspheres of phase chromatography-use and preparation method thereof " (publication number CN 1257891A) is shell, polystyrene is the compound microballoon of nuclear, the poly-4-vinylpyridine of this microsphere surface makes microsphere surface have active chemical property, comparing pure poly-4-vinylpyridine microballoon has all had bigger improvement on cost and stability, be a kind of good composite microsphere material.But regrettably, the surface of this microballoon by poly-4-vinylpyridine parcel, makes its surface can only show the physical and chemical performance of poly-4-vinylpyridine fully, and the advantage of polystyrene non-polar material then can not effectively be taken into account.Along with the deep development of research and application, often wish to obtain the composite microsphere material that the surface has polarity and apolar regions concurrently.
Summary of the invention
The objective of the invention is to: with the surperficial polymer composite microsphere of seed swelling polymerization preparation with polystyrene and poly-4-vinylpyridine areal distribution, and can provide serial poly-4-vinylpyridine/polystyrene bull type complex microsphere by the quantity and the size of conditioned reaction parameter regulation and control areal distribution.
Another object of the present invention is to:, provide a kind of preparation to have the method for the poly-4-vinylpyridine/polystyrene bull type complex microsphere in poly-4-vinylpyridine of polarity and nonpolar polystyrene zone concurrently with the polymer composite microsphere that seed swelling polymerization preparation surface has polystyrene and poly-4-vinylpyridine areal distribution.
The present invention is made of bull type complex microsphere poly-4-vinylpyridine/polystyrene constructional feature forms the microballoon supporter for poly-4-vinylpyridine, and polystyrene forms semisphere nanometer phase-separating section on its surface.Along with the increase of polystyrene quality, the polystyrene phase-separating section increases with volume in the quantity of gathering the 4-vinylpyridine microsphere surface and increases.
Preparation method of the present invention is achieved by the following technical solution:
The present invention adopts the poly-4-vinylpyridine microballoon of emulsifier-free emulsion polymerization method preparation as seed, utilize the poly-4-vinylpyridine of seed swelling polymerization preparation/polystyrene bull type complex microsphere, at first styrene monomer and linking agent are joined in the ethanolic soln of poly-4-vinylpyridine seed microballoon, stirring through certain hour, monomer and linking agent swelling enter in the poly-4-vinylpyridine seed microballoon, add the ethanolic soln initiated polymerization of initiator then.By radical polymerization, swelling in the seed microballoon monomer and linking agent generation polymerization and gradually phase-splitting obtain a series of poly-4-vinylpyridine/polystyrene bull type complex microsphere at poly-4-vinylpyridine seed microsphere surface formation microcell.
Concrete preparation process is:
1) preparation of the high crosslinked poly-4-vinylpyridine seed microballoon in surface:
Adopt the poly-4-vinylpyridine microballoon of emulsifier-free emulsion polymerization method preparation.The 4-vinylpyridine monomer is joined in the deionized water, and monomer mass concentration is 3%～8%, is warmed up to 50～90 ℃ under nitrogen protection, adds the initiator initiated polymerization.Polymerization adds the linking agent of monomer weight 5%～15% after 10～120 minutes, continue polymerization 1～12 hour.Reaction is carried out emulsion after finishing centrifugal, and uses deionized water and absolute ethanol washing successively, obtains yellow-white and slightly transparent poly-4-vinylpyridine microballoon powder after the drying.
2) preparation of poly-4-vinylpyridine/polystyrene bull type complex microsphere:
Adopt the poly-4-vinylpyridine of seed swelling polymerization preparation/polystyrene bull type complex microsphere.Take by weighing the poly-4-vinylpyridine microballoon of above-mentioned preparation, and it is distributed in the ethanol, be made into emulsion and logical nitrogen protection, microspheres quality concentration is 1%～5%.Add styrene monomer and linking agent, monomer mass concentration is 0.5%～15%, and linking agent accounts for 3%～10% of monomer weight, and swelling is 8～24 hours under mechanical stirring.Be warming up to 50～90 ℃ then, add the ethanolic soln of initiator, reacted 4～24 hours.The reaction back that finishes is carried out centrifugally to emulsion, and use deionized water and absolute ethanol washing successively, obtains poly-4-vinylpyridine/polystyrene bull type complex microsphere powder after the drying.
Described initiator is a kind of in Diisopropyl azodicarboxylate (AIBN), Potassium Persulphate (KPS), ammonium persulphate (APS), 2,2 ' azo (2-amidine propane) dihydrochloride (V-50), the dibenzoyl peroxide (BPO).
Described linking agent is divinylbenzene (DVB), N, a kind of in N '-methylene-bisacrylamide (MBA), the ethylene glycol dimethacrylate (EGDMA).
Advantage of the present invention is: adopt the seed swelling polymerization to prepare poly-4-vinylpyridine/polystyrene bull type complex microsphere, the preparation method is simple, and the productive rate height is raw materials used cheap, has the low toxicity characteristic mostly, is very suitable for producing in enormous quantities; The bull type complex microsphere surface of preparation has hydrophilic poly-4-vinylpyridine zone and oleophylic polystyrene zone, and effectively the control area distributes and size, thus the amphipathic characteristic of control microsphere surface, and this complex microsphere is with a wide range of applications.
Description of drawings
Fig. 1. embodiment 1 synthetic gathers the SEM photo of 4-vinylpyridine/polystyrene bull type complex microsphere
Fig. 2. embodiment 2 synthetic gather the SEM photo of 4-vinylpyridine/polystyrene bull type complex microsphere
Embodiment
Embodiment 1
A certain amount of 4-vinylpyridine monomer is joined in the deionized water, and monomer mass concentration is 5%, is warmed up to 65 ℃ and insulation under nitrogen protection, adds the aqueous solution initiated polymerization that is made into by the Potassium Persulphate that accounts for monomer mass 3%.Polyase 13 adds the linking agent divinylbenzene of monomer weight 10% after 0 minute, further polymerization is 90 minutes.The product that obtains behind the stopped reaction cleans with deionized water and ethanol, obtain after the drying evenly and monodispersity better, macroscopic view is yellow-white and slightly transparent poly-4-vinylpyridine microballoon powder.
Take by weighing a certain amount of poly-4-vinylpyridine seed microballoon for preparing; be distributed in the ethanol; be made into mass concentration and be 1.7% mixed solution; and add styrene monomer (mass concentration 1%) and account for the linking agent divinylbenzene of monomer mass 5%; under nitrogen protection; mechanical stirring swelling 18 hours is warming up to 65 ℃ and insulation then.The Diisopropyl azodicarboxylate that will account for monomer mass 3% this moment is dissolved in a certain amount of ethanol, prepares to such an extent that mass concentration is 0.6% initiator solution, joins it in reaction solution and reacts 5 hours.The product that obtains behind the stopped reaction obtains the complex microsphere of poly-4-vinylpyridine/polystyrene bull type with deionized water and washing with alcohol.Fig. 1 is the stereoscan photograph of this complex microsphere.
Embodiment 2
A certain amount of 4-vinylpyridine monomer is joined in the deionized water, and monomer mass concentration is 3%, is warmed up to 70 ℃ and insulation under nitrogen protection, adds the aqueous solution (mass concentration 2%) initiated polymerization that is made into by the Potassium Persulphate that accounts for monomer mass 3%.Polyase 13 adds the linking agent divinylbenzene of monomer weight 10% after 0 minute, further polymerization 10h.The product that obtains behind the stopped reaction cleans with deionized water and ethanol, obtain after the drying evenly and monodispersity better, macroscopic view is yellow-white and slightly transparent poly-4-vinylpyridine microballoon powder.
Take by weighing a certain amount of polyvinyl pyridine seed microballoon for preparing; be distributed in the ethanol; be made into mass concentration and be 2% mixed solution; and add styrene monomer (mass concentration 2%) and account for the linking agent divinylbenzene of monomer mass 5%; under nitrogen protection; mechanical stirring swelling 18 hours is warming up to 70 ℃ then.The Diisopropyl azodicarboxylate that will account for monomer mass 3% this moment is dissolved in a certain amount of ethanol, prepares to such an extent that mass concentration is 0.8% initiator solution, joins it in reaction solution and reacts 12 hours.The product that obtains behind the stopped reaction obtains the complex microsphere of poly-4-vinylpyridine/polystyrene bull type with deionized water and washing with alcohol.Fig. 2 is the stereoscan photograph of this complex microsphere.
Embodiment 3
A certain amount of 4-vinylpyridine monomer is joined in the deionized water, and monomer mass concentration is 7%, is warmed up to 70 ℃ under nitrogen protection, adds the aqueous solution (mass concentration 2%) initiated polymerization that is made into by the ammonium persulphate that accounts for monomer mass 3%.Polymerization adds the linking agent ethylene glycol dimethacrylate of monomer weight 12% after 20 minutes, further polymerization 12h.The product that obtains behind the stopped reaction cleans with deionized water and ethanol, obtain after the drying evenly and monodispersity better, macroscopic view is yellow-white and slightly transparent poly-4-vinylpyridine microballoon powder.
Take by weighing a certain amount of polyvinyl pyridine seed microballoon that obtains; be distributed in the ethanol; be made into mass concentration and be 5% mixed solution; and add styrene monomer (mass concentration 10%) and account for the linking agent ethylene glycol dimethacrylate of monomer mass 5%; under nitrogen protection; mechanical stirring swelling 18 hours is warming up to 85 ℃ then.2,2 ' azo (2-amidine propane) dihydrochloride that will account for monomer mass 3% this moment is dissolved in a certain amount of ethanol, joins it in reaction solution and reacts 8 hours.The product that obtains behind the stopped reaction obtains the complex microsphere of poly-4-vinylpyridine/polystyrene bull type with deionized water and washing with alcohol.
Embodiment 4
A certain amount of 4-vinylpyridine monomer is joined in the deionized water, and monomer mass concentration is 7%, is warmed up to 70 ℃ under nitrogen protection, adds the aqueous solution (mass concentration 2%) initiated polymerization that is made into by the ammonium persulphate that accounts for monomer mass 3%.Polymerization adds the linking agent N of monomer weight 12% after 20 minutes, N '-methylene-bisacrylamide, further polymerization 6h.The product that obtains behind the stopped reaction cleans with deionized water and ethanol, obtain after the drying evenly and monodispersity better, macroscopic view is yellow-white and slightly transparent poly-4-vinylpyridine microballoon powder.
Take by weighing a certain amount of polyvinyl pyridine seed microballoon that obtains; be distributed in the ethanol; be made into mass concentration and be 1% mixed solution; and add styrene monomer (mass concentration 2%) and account for the linking agent N of monomer mass 5%; N '-methylene-bisacrylamide; under nitrogen protection, mechanical stirring swelling 18 hours is warming up to 65 ℃ then.The Diisopropyl azodicarboxylate that will account for monomer mass 3% this moment is dissolved in the small amount of ethanol, joins it in reaction solution and reacts 12 hours.The product that obtains behind the stopped reaction obtains the complex microsphere of poly-4-vinylpyridine/polystyrene bull type with deionized water and washing with alcohol.
Claims (4)
1, a kind of multi-shoot polymer composite microsphere is characterized in that, forms bull type complex microsphere by poly-4-vinylpyridine/polystyrene, and constructional feature forms the microballoon supporter for poly-4-vinylpyridine, and polystyrene forms semisphere nanometer phase-separating section on its surface.
2, a kind of preparation method of multi-shoot polymer composite microsphere is characterized in that, preparation process of the present invention is:
1) adopts the poly-4-vinylpyridine microballoon of emulsifier-free emulsion polymerization method preparation, the 4-vinylpyridine monomer is joined in the deionized water, monomer mass concentration is 3%～8%, be warmed up to 50～90 ℃ under nitrogen protection, add the initiator initiated polymerization, polymerization adds the linking agent of monomer weight 5%～15% after 10～120 minutes, continue polymerization 1～12 hour, reaction is carried out emulsion after finishing centrifugal, and uses deionized water and absolute ethanol washing successively, obtains poly-4-vinylpyridine microballoon powder after the drying;
2) adopt the poly-4-vinylpyridine of seed swelling polymerization preparation/polystyrene bull type complex microsphere, take by weighing the poly-4-vinylpyridine microballoon of above-mentioned preparation, and it is distributed in the ethanol, be made into emulsion and logical nitrogen protection, microspheres quality concentration is 1%～5%.Add styrene monomer and linking agent, monomer mass concentration is 0.5%～15%, linking agent accounts for 3%～10% of monomer weight, swelling is 8～24 hours under mechanical stirring, is warming up to 50～90 ℃ then, adds the ethanolic soln of initiator, reacted 4～24 hours, the reaction back that finishes is carried out centrifugally to emulsion, and use deionized water and absolute ethanol washing successively, obtains poly-4-vinylpyridine/polystyrene bull type complex microsphere powder after the drying.
3, preparation method as claimed in claim 1 is characterized in that, described initiator is a kind of in Diisopropyl azodicarboxylate, Potassium Persulphate, ammonium persulphate 2,2 ' azo dihydrochloride, the dibenzoyl peroxide.
4, preparation method as claimed in claim 1 is characterized in that, described linking agent is divinylbenzene, N, a kind of in N '-methylene-bisacrylamide, the ethylene glycol dimethacrylate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532406A (en) * | 2012-03-05 | 2012-07-04 | 厦门大学 | Morphological control method for functionalized microsphere |
| CN102585421A (en) * | 2012-03-01 | 2012-07-18 | 北京科技大学 | Preparation method for PH responsiveness non-spherical polymer microparticle with charges of different polarities |
| CN102603962A (en) * | 2012-03-05 | 2012-07-25 | 厦门大学 | Preparation method of surface functionalized porous irregularly-shaped microspheres |
| CN102675545A (en) * | 2012-05-08 | 2012-09-19 | 中国科学院化学研究所 | Monodisperse micro colloidal particles with raised spots on surface and preparation method for colloidal particles |
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2009
- 2009-01-06 CN CN2009100760672A patent/CN101457007B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585421A (en) * | 2012-03-01 | 2012-07-18 | 北京科技大学 | Preparation method for PH responsiveness non-spherical polymer microparticle with charges of different polarities |
| CN102585421B (en) * | 2012-03-01 | 2014-05-28 | 北京科技大学 | Preparation method for PH responsiveness non-spherical polymer microparticle with charges of different polarities |
| CN102532406A (en) * | 2012-03-05 | 2012-07-04 | 厦门大学 | Morphological control method for functionalized microsphere |
| CN102603962A (en) * | 2012-03-05 | 2012-07-25 | 厦门大学 | Preparation method of surface functionalized porous irregularly-shaped microspheres |
| CN102532406B (en) * | 2012-03-05 | 2014-02-05 | 厦门大学 | Morphological control method for functionalized microsphere |
| CN102603962B (en) * | 2012-03-05 | 2014-02-05 | 厦门大学 | Preparation method of surface functionalized porous irregularly-shaped microspheres |
| CN102675545A (en) * | 2012-05-08 | 2012-09-19 | 中国科学院化学研究所 | Monodisperse micro colloidal particles with raised spots on surface and preparation method for colloidal particles |
| CN102675545B (en) * | 2012-05-08 | 2014-10-01 | 中国科学院化学研究所 | Monodisperse micro colloidal particles with raised spots on surface and preparation method for colloidal particles |
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