CN101608048A - A kind of dumbbell-shaped amphiphilic polymer composite microspheres and preparation method thereof - Google Patents
A kind of dumbbell-shaped amphiphilic polymer composite microspheres and preparation method thereof Download PDFInfo
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Abstract
The invention provides the poly-4-vinylpyridine of a kind of dumb-bell shape/polystyrene dumb-bell shape complex microsphere and preparation method thereof, belong to polymer architecture micro-sphere material preparing technical field, the amphipathic dumb-bell shape polymer composite microsphere of particularly a kind of profit.The present invention is a seed with the poly-4-vinylpyridine microballoon of the suitable degree of crosslinking of emulsifier-free emulsion polymerization method synthetic, utilize the seeding polymerization method to prepare the poly-4-vinylpyridine of dumb-bell shape/polystyrene complex microsphere, to gather the 4-vinylpyridine seed earlier is dispersed in a certain amount of dehydrated alcohol, then with styrene monomer, initiator and linking agent join in the poly-4-vinylpyridine seed emulsion, swelling through certain hour, the intensification polymerization, newly-generated polystyrene occur incompatible with poly-4-vinylpyridine is separated, the poly-4-vinylpyridine degree of crosslinking of control seed and the second polystyrene degree of crosslinking mutually, polystyrene is separated fully, obtains the poly-4-vinylpyridine of dumb-bell shape/polystyrene complex microsphere.
Description
Technical field
The invention belongs to polymer architecture micro-sphere material preparing technical field, particularly a kind of poly 4 vinyl pyridine/polystyrene (P4VP/PS) dumb-bell shape polymer composite microsphere and preparation method thereof.
Background technology
Polymer microballoon be meant diameter at nano level to micron order, be shaped as the polymer materials or the polymer composites of sphere or other solids, its pattern can be diversified, comprises solid, hollow, porous, dumb-bell shape, cepaeform etc.Monodisperse polymer micro-sphere has good sphericity, size is little, specific surface area is big, adsorptivity is strong, the surface reaction ability strong, be easy to characteristics such as separation and purification.In recent years, polymer microballoon has a wide range of applications in standard metering, biological chemistry, immune medical science, analytical chemistry, chemical industry, information, microelectronic and some hi-tech industries as a kind of new functional macromolecule material of excellent property.
Characteristics such as polystyrene (PS) microballoon has stable in properties, synthesis technique is simple and with low cost have been subjected to extensive concern.The technology of preparing of PS microballoon is fairly perfect, to micron-sized single technology of preparing of PS microballoon of disperseing report is arranged all again from nano level to submicron order.Eur.Pat.0003905 (1979), U.S.Pat.4530956 (1985) and Chinese patent publication number CN1132213A etc. have reported the method based on the monodisperse cross-linked PS microballoon of seed swelling polymerization prepared sizes, have realized the effective control to microspherulite diameter substantially.But the PS microballoon of one-component is nonpolar stronger, causes its surface tension lower, makes its application in a lot of fields all be restricted.
Poly-4-vinylpyridine (P4VP) microballoon is the stronger material of a kind of polarity, owing to wherein contain the active pyridine functional of chemical property group, more and more about the research report of this material in the last few years, and obtained widespread use in fields such as chemical industry and medical and health.But, because the too active chemical property of pyridine functional groups, cause the less stable of P4VP microballoon, and its raw-material price is also than higher, these all make the P4VP microballoon be subjected to certain limitation in application.
Has certain limitation when using in some field, so the notion of polymer composite microsphere has been carried in view of the polymer microballoon of one-component.Polymer composite microsphere is meant the microballoon that is formed by two or more mixed with polymers.Polymer composite microsphere has the performance that general polymerization thing microballoon is not had, and it can utilize two kinds of polymkeric substance strong point separately, realizes the complementation of two kinds of performances, as the mixing of mixing, wetting ability and the hydrophobic material of rigidity and flexible materials etc.Also can use its property,, utilize surface functional group again at fixing active substance as there is not the microballoon nuclear of function group with the polymer overmold that has a functional group.Except that microballoon was formed, microballoon composition profiles and pattern had significant effects to its application, must utilize certain method to control the form of complex microsphere.
In actual applications, people often wish that polymer composite microsphere had both had doping region, have nonpolar district again, and wherein the P4VP/PS complex microsphere is exactly a kind of comparatively ideal parent-hydrophobic polymer complex microsphere.But, owing to the polarity difference of these two kinds of polymkeric substance, caused the mechanism of nucleation difference of polymer microballoon, so the easier P4VP/PS that obtains nucleocapsid structure in general synthesizing.As just having reported in the patent " cross-linking polyvinyl pyridine microspheres of phase chromatography-use and preparation method thereof " (publication number CN 1257891A) that PS is nuclear, P4VP is the synthetic method of the polymer composite microsphere of shell.The complex microsphere of this nucleocapsid structure has surface tissue and the surface chemical property identical with single component P4VP, and the stability of microballoon improves greatly than single component P4VP microballoon, has reduced cost simultaneously, is a kind of good composite microsphere material.But because the surface of this microballoon is wrapped up by P4VP fully, the feasible oleophilic properties that is in the PS phase at ball position can not show, and causes microballoon to show stronger wetting ability.In recent years, the research of relevant profit amphiphilic polymer composite microspheres report increases gradually, and we have reported P4VP/PS bull type complex microsphere and preparation method thereof (a kind of multi-shoot polymer composite microsphere and preparation method thereof, publication number CN101457007).The polymer composite microsphere of this structure is a kind of parent-hydrophobic type complex microsphere, and PS distributes at P4VP microsphere surface multiple spot, makes microsphere surface both have hydrophilic P4VP district, and hydrophobic PS district is arranged again, has widened the Application Areas of complex microsphere greatly.In order further to widen the application of polymer microballoon, also need the amphipathic micro-sphere structure of polymkeric substance is continued to explore, prepare the novel texture amphiphilic polymer composite microspheres.
Summary of the invention
The objective of the invention is to: prepare a kind of " solid surfactant ", promptly microsphere surface has water-wet side and hydrophobic side.Utilize the seeding polymerization method to prepare a spherical crown and be polarity PS district, another spherical crown is the PS/P4VP dumb-bell shape complex microsphere in nonpolar P4VP district, and can provide poly-4-vinylpyridine/polystyrene dumb-bell shape complex microsphere by regulating the size of two-phase controlling of quality phase region.
Another object of the present invention is to:, provide a kind of method for preparing amphipathic poly-4-vinylpyridine/polystyrene dumb-bell shape complex microsphere with the get everything ready dumb-bell shape polymer composite microsphere of polystyrene and the complete phase-splitting of poly-4-vinylpyridine of seeding polymerization legal system.
The dumb-bell shape complex microsphere is made up of water-wet side and hydrophobic end, and wherein water-wet side is made up of the poly-4-vinylpyridine spherical crown of wetting ability, and the hydrophobic end is made up of lipophilicity polystyrene spherical crown, and two ends closely link to each other and form " dumb-bell shape " structure, and concrete structure as shown in drawings.
Dumb-bell shape complex microsphere of the present invention is achieved through the following technical solutions:
The present invention adopts the emulsifier-free emulsion polymerization method to prepare crosslinked poly-4-vinylpyridine microballoon as seed, utilizes the seeding polymerization legal system to be equipped with P4VP/PS dumb-bell shape complex microsphere.Complex microsphere influence factor in preparation process is very many, different preparation conditions will cause the different structure microballoon, and for P4VP/PS dumbbell shape complex microsphere, wherein most important influence factor is the P4VP seed degree of crosslinking and the second phase degree of crosslinking, have only when the two degree of crosslinking all is in certain suitable scope, could make is separated obtains the microballoon of dumbbell-shaped structure fully.
Concrete preparation process is:
1) preparation of crosslinked P4VP seed microballoon:
Crosslinked P4VP seed microballoon is by the preparation of emulsifier-free emulsion polymerization method, and adopting divinylbenzene (DVB) or ethylene glycol dimethacrylate (EGDMA) is linking agent, and its quality accounts for 0.5%～5% of 4-vinylpyridine (4VP) monomer mass.
2) preparation of dumb-bell shape P4VP/PS complex microsphere:
Dumb-bell shape P4VP/PS complex microsphere is prepared by the seeding polymerization method.The above-mentioned P4VP seed microballoon for preparing is distributed in the ethanol, forms emulsion, microspheres quality concentration is 1%～8%, joins in the four-hole boiling flask the logical N2 air in the reactor of draining.Initiator dibenzoyl peroxide (BPO) and Diisopropyl azodicarboxylate (AIBN), styrene monomer, DVB or EGDMA, toluene are joined in the emulsion of P4VP simultaneously, the styrene monomer mass concentration is 1%～15%, DVB or EGDMA account for 0.1%～3% of vinylbenzene (St) monomer mass, BPO accounts for 0.1%～4% of styrene monomer quality, AIBN accounts for 0.4%～6% of styrene monomer quality, swelling under mechanical stirring, carry out centrifugation, washing, lyophilize after the reacting by heating, obtain the dumb-bell shape P4VP/PS complex microsphere powder of white.
Described swelling time is 10～30 hours, and reacting by heating was reacted 8～24 hours for being warming up to 50～90 ℃.
Advantage of the present invention is: (1) adopts the seeding polymerization method to prepare dumb-bell shape P4VP/PS complex microsphere, and the preparation method is simple, and productive rate is higher, and good reproducibility is suitable for producing in enormous quantities, and used cost of material is cheap in the preparation process; (2) the dumb-bell shape complex microsphere for preparing had not only had hydrophilic P4VP end but also had had lipophilic PS end, and it is amphipathic promptly to have a profit, is a kind of novel " solid surfactant ", and this dumb-bell shape complex microsphere all is with a wide range of applications in a lot of fields.
Description of drawings
Fig. 1 is the SEM photo of example 1 synthetic dumb-bell shape P4VP/PS complex microsphere
Fig. 2 is the SEM photo of example 2 synthetic dumb-bell shape P4VP/PS complex microspheres
Embodiment
Example 1
The four-hole boiling flask that reaction vessel uses 1000ml band tetrafluoroethylene to stir, logical water of condensation is used N
2The oil bath heating is used in protection.
1) preparation of crosslinked P4VP seed microballoon
4-vinylpyridine (4VP) monomer is joined in the deionized water, and monomer mass concentration is 5%, at N
2Be warmed up to 65 ℃ under the protection, add initiator potassium persulfate (KPS) solution initiated polymerization, KPS accounts for 2% of 4VP monomer mass.Polymerization adds the EGDMA of 4VP monomer mass 3% after 50 minutes, continue polymerization 5 hours.Reaction is carried out centrifugation with emulsion after finishing, and uses dehydrated alcohol and deionized water wash successively three times, carries out lyophilize then, obtains the P4VP microballoon powder of white.
2) preparation of dumb-bell shape P4VP/PS complex microsphere
The above-mentioned P4VP seed microballoon for preparing is distributed in the ethanol, forms emulsion, microspheres quality concentration is 5%, joins in the four-hole boiling flask, logical N
2Drain air in the reactor.Initiator B PO and AIBN, St monomer, DVB and toluene are joined in the emulsion of P4VP, St monomer mass concentration is 5%, DVB accounts for 3% of St monomer mass, BPO accounts for 1% of St monomer mass, AIBN accounts for 2% of St monomer mass, swelling is 20 hours under mechanical stirring, is warming up to 65 ℃ then, reacts 10 hours.Centrifugation is carried out to emulsion in the reaction back that finishes, and uses dehydrated alcohol and deionized water wash successively three times, carries out lyophilize afterwards, obtains the dumb-bell shape P4VP/PS complex microsphere powder of white.
Example 2
1) preparation of crosslinked P4VP seed microballoon
4-vinylpyridine (4VP) monomer is joined in the deionized water, and monomer mass concentration is 8%, at N
2Be warmed up to 70 ℃ under the protection, add initiator potassium persulfate (KPS) solution initiated polymerization, KPS accounts for 3% of 4VP monomer mass.Polymerase 17 adds the DVB of 4VP monomer mass 1% after 0 minute, continue polymerization 10 hours.Reaction is carried out centrifugation with emulsion after finishing, and uses dehydrated alcohol and deionized water wash successively three times, carries out lyophilize then, obtains the P4VP microballoon powder of white.
2) preparation of dumb-bell shape P4VP/PS complex microsphere
The above-mentioned P4VP seed microballoon for preparing is distributed in the ethanol, forms emulsion, microspheres quality concentration is 3%, joins in the four-hole boiling flask, logical N
2Drain air in the reactor.Initiator B PO and AIBN, St monomer, EGDMA and toluene are joined in the emulsion of P4VP, St monomer mass concentration is 3%, and EGDMA accounts for 3% of St monomer mass, and BPO accounts for 2% of St monomer mass, AIBN accounts for 1% of St monomer mass, and swelling is 25 hours under mechanical stirring.Be warming up to 70 ℃ then, reacted 15 hours.Centrifugation is carried out to emulsion in the reaction back that finishes, and uses dehydrated alcohol and deionized water wash successively three times, carries out lyophilize afterwards, obtains the dumb-bell shape P4VP/PS complex microsphere powder of white.
Example 3
1) preparation of crosslinked P4VP seed microballoon
4-vinylpyridine (4VP) monomer is joined in the deionized water, and monomer mass concentration is 4%, at N
2Be warmed up to 50 ℃ under the protection, add initiator potassium persulfate (KPS) solution initiated polymerization, KPS accounts for 0.5% of 4VP monomer mass.Polymerization adds the EGDMA of 4VP monomer mass 5% after 150 minutes, continue polymerization 12 hours.Reaction is carried out centrifugation with emulsion after finishing, and uses dehydrated alcohol and deionized water wash successively three times, carries out lyophilize then, obtains the P4VP microballoon powder of white.
2) preparation of dumb-bell shape P4VP/PS complex microsphere
The above-mentioned P4VP seed microballoon for preparing is distributed in the ethanol, forms emulsion, microspheres quality concentration is 1%, joins in the four-hole boiling flask, logical N
2Drain air in the reactor.Initiator B PO and AIBN, St monomer, DVB and toluene are joined in the emulsion of P4VP, St monomer mass concentration is 1%, and DVB accounts for 0.1% of St monomer mass, and BPO accounts for 0.1% of St monomer mass, AIBN accounts for 6% of St monomer mass, and swelling is 30 hours under mechanical stirring.Be warming up to 90 ℃ then, reacted 8 hours.Centrifugation is carried out to emulsion in the reaction back that finishes, and uses dehydrated alcohol and deionized water wash successively three times, carries out lyophilize afterwards, obtains the dumb-bell shape P4VP/PS complex microsphere powder of white.
Example 4
1) preparation of crosslinked P4VP seed microballoon
4-vinylpyridine (4VP) monomer is joined in the deionized water, and monomer mass concentration is 10%, at N
2Be warmed up to 80 ℃ under the protection, add initiator potassium persulfate (KPS) solution initiated polymerization, KPS accounts for 5% of 4VP monomer mass.Polyase 13 adds the DVB of 4VP monomer mass 0.5% after 0 minute, continue polymerization 1 hour.After reaction finishes emulsion is carried out centrifugation, and wash respectively three times with dehydrated alcohol and deionized water successively, carry out lyophilize then, obtain the P4VP microballoon powder of white.
2) preparation of dumb-bell shape P4VP/PS complex microsphere
The above-mentioned P4VP seed microballoon for preparing is distributed in the ethanol, forms emulsion, microspheres quality concentration is 8%, joins in the four-hole boiling flask, logical N
2Drain air in the reactor.Initiator B PO and AIBN, St monomer, EGDMA and toluene are joined in the emulsion of P4VP, St monomer mass concentration is 15%, and EGDMA accounts for 0.5% of St monomer mass, and BPO accounts for 4% of St monomer mass, AIBN accounts for 0.4% of St monomer mass, and swelling is 10 hours under mechanical stirring.Be warming up to 50 ℃ then, reacted 24 hours.After reaction finishes emulsion is carried out centrifugation, and wash respectively three times with dehydrated alcohol and deionized water successively, carry out lyophilize afterwards, obtain the dumb-bell shape P4VP/PS complex microsphere powder of white.
Claims (3)
1, a kind of dumbbell-shaped amphiphilic polymer composite microspheres, it is characterized in that complex microsphere is made up of water-wet side and hydrophobic end, wherein water-wet side is made up of the poly-4-vinylpyridine P4VP spherical crown of wetting ability, and the hydrophobic end is made up of lipophilicity polystyrene PS spherical crown, and two ends closely link to each other and form dumb-bell shape.
2, the preparation method of dumbbell-shaped amphiphilic polymer composite microspheres, adopt the emulsifier-free emulsion polymerization method to prepare crosslinked P4VP microballoon as seed, utilize the seeding polymerization legal system to be equipped with P4VP/PS dumb-bell shape complex microsphere, it is characterized in that, it is linking agent that P4VP seed microballoon adopts divinylbenzene DVB or ethylene glycol dimethacrylate EGDMA, and its quality accounts for 0.5%～5% of 4-vinylpyridine monomer mass; Crosslinked P4VP seed microballoon is distributed in the emulsion that forms behind the ethanol, microspheres quality concentration is 1%～8%, with initiator B PO and AIBN, vinylbenzene St monomer, divinylbenzene or ethylene glycol dimethacrylate, toluene joins in the emulsion of P4VP simultaneously, St monomer mass concentration is 1%～15%, divinylbenzene or ethylene glycol dimethacrylate account for 0.1%～3% of St monomer mass, BPO accounts for 0.1%～4% of St monomer mass, AIBN accounts for 0.4%～6% of St monomer mass, swelling under mechanical stirring, carry out centrifugation after the reacting by heating, washing, lyophilize obtains white dumb-bell shape P4VP/PS complex microsphere powder.
3, preparation method as claimed in claim 2 is characterized in that, described swelling time is 10～30 hours, and reacting by heating was reacted 8～24 hours for being warming up to 50～90 ℃.
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Cited By (2)
| 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 |
| CN103242733A (en) * | 2012-10-29 | 2013-08-14 | 苏州大学 | Simple method for preparing photoresponsive super-hydrophobic surface |
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Cited By (4)
| 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 |
| CN103242733A (en) * | 2012-10-29 | 2013-08-14 | 苏州大学 | Simple method for preparing photoresponsive super-hydrophobic surface |
| CN103242733B (en) * | 2012-10-29 | 2015-08-05 | 苏州大学 | Simple method for preparing photoresponsive super-hydrophobic surface |
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Application publication date: 20091223 |