CN102417552A - Polymer nanomicrosphere product with uniform and controllable size and preparation method thereof - Google Patents
Polymer nanomicrosphere product with uniform and controllable size and preparation method thereof Download PDFInfo
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- CN102417552A CN102417552A CN2011102830249A CN201110283024A CN102417552A CN 102417552 A CN102417552 A CN 102417552A CN 2011102830249 A CN2011102830249 A CN 2011102830249A CN 201110283024 A CN201110283024 A CN 201110283024A CN 102417552 A CN102417552 A CN 102417552A
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Abstract
The invention relates to a polymer nanomicrosphere product with uniform and controllable size and a preparation method thereof. The preparation method comprises the following steps: preparing polymerizable olefine monomers, an initiator, assistants and the like into an oil phase, and preparing water, a stabilizer, an emulsifier and the like into a water phase; and mixing the oil phase and water phase into an O/W pre-emulsion, quickly passing the pre-emulsion through a uniform-pore-size microporous membrane under pressure to form a uniform-particle-size O/W emulsion, and polymerizing and curing emulsion droplets in the emulsion into the uniform-particle-size polymer nanomicrospheres. The average particle size of the microspheres can be controlled within the range of tens of nanometers to 50 micrometers, and the particle size distribution coefficient C.V. is smaller than 20%. The method has the advantages of simple steps, favorable batch repetitiveness, uniform and controllable particle size, no need of subsequent screening and the like, is easy to control, can easily implement large-scale production, and therefore, has the characteristics of fewer emissions and low preparation cost.
Description
Technical field
The present invention relates to a kind of polymer nano microspheres product and preparation method thereof; Be particularly related to controlled polymer nano microspheres product of a kind of size homogeneous and preparation method thereof, be specifically related to a kind of uniform particle diameter, the polymer nano microspheres product below 50 microns and preparation method thereof.
Background technology
Polymer microballoon has excellent mechanical intensity, excellent chemical stability and acid and alkali-resistance thereof, is easy to the advantage of modification, is one type of extraordinary multifunctional product.In recent years, the polymer nano microballoon has all obtained widely using in various fields such as biological medicine, environment, catalyzer, functional materialss, like medicine sustained and controlled release carrier, bioseparation microballoon medium, clinical detection with microballoon reagent etc.The application requiring microspherulite diameter homogeneous of these high additive values, controlled, and preparation good reproducibility, otherwise can have a strong impact on effect.And existing microsphere preparation technology is difficult to produce the microballoon of size homogeneous, and particle diameter is uncontrollable, batch poor repeatability; Not only influence quality product, and need loaded down with trivial details aftertreatment and extra separating device, wasted big content of starting materials, cause valuable product.Only several kinds of homogeneous microsphere preparation technologies also are difficult to realize the structure control of microballoon at present.Therefore, particle diameter and the structure of being badly in need of the exploitation excellent performance are all controlled, the homogeneous polymer nano microspheres product and the technology of preparing thereof of batch good reproducibility.
Methods combination chemical polymerizations such as high-pressure homogenization, ultrasonic emulsification are the common technologies of preparation polymer nano microballoon at present, but this type of technological microspheres prepared particle diameter heterogeneity, uncontrollable, batch repeatability is relatively poor, and quality product does not reach the requirement of high added value.And the preparation method of existing homogeneous polymer microballoon mainly contains several kinds of dispersion copolymerization method, emulsion polymerization, seed swelling methods etc.
Dispersion copolymerization method is that preparation has monomer, dispersion agent and initiator in dispersion system, is homogeneous system; After polymerization began, the polymkeric substance that monomer generates was insoluble to dispersion system, from dispersion system, was precipitated out gradually along with the continuous increase of polymericular weight and formed stable microballoon.Typical dispersion copolymerization method is shown in CN101559344A; It discloses the method that a kind of dispersion polymerization prepares the ST/BA copolymerization microsphere, and its composition of raw materials comprises dispersion medium, dispersion agent, monomer, initiator, and monomer is made up of vinylbenzene and Bing Xisuandingzhi; Dispersion medium and dispersion agent joined in logical nitrogen and the there-necked flask with prolong be heated to 70 ℃; The back adds monomer and initiator for reaction 12h, and obtained microspherulite diameter is about 1 micron, and solid content is more than 10%.But the micro-sphere structure of this method preparation is more single, is difficult to prepare porous or is surrounded by the polymorphic microballoon of functional materials.
Letex polymerization and soap-free polymerization method are a kind of domestic methods that is used to prepare the submicron order polymer microballoon.CN 101543758A discloses a kind of method of using polymerizable VIOLOGEN tensio-active agent to carry out emulsion polymerization prepared nuclear-shell nano-antibacterial polymer microballoon; Use and not only to have the surface active function group, but also have polymerizable double bond functional group, also have a VIOLOGEN dication polymerisable surfactant of antibacterial group simultaneously; In the reaction medium of water or water and organic solvent, carry out the stable emulsion polymerization as comonomer, reinforced or reinforced nanometer, the core-shell polymer microsphere for preparing the antibiotic group of surperficial covalency keyed jointing of segmentation through a step.This technology also is difficult to the control of step realization micro-sphere structure.
The seed swelling method is a kind of method for preparing the homogeneous microballoon of foundation such as Ugelstad, at first utilizes method such as letex polymerization to prepare the small particle size microballoon of homogeneous, is prepared into the polymer microballoon of required particle diameter again through a step or multistep swelling process.CN 101058614A discloses the method that a kind of polarity seed swelling legal system is equipped with micron-level magnetic polymer micro-sphere; May further comprise the steps: (1) utilizes the high molecular polymerization method to synthesize 0.05～8MM, and CV is less than 10% the non-alkyl ester of monodispersed polyvinylpyridine, polyalkyl methacrylate, polyalkyl acrylate, polymethyl acrylic acid, the homopolymer or the multipolymer polarity seed of the non-alkyl ester of ROHM for the number size-grade distribution; (2) carboxylic acid esters monomer, radical initiator, linking agent and the pore-forming material mixing back with the two keys of polar band is added to the aqueous phase that is dissolved with dispersion stabilizer, soluble salt, stopper as organism, is prepared into the emulsion droplet that diameter is no more than 0.3mm in 30 minutes through ultrasound-enhanced dispersion; (3) seed of step (1) and the emulsion droplet of step (2) are mixed stirring 12～24 hours under room temperature; Organism absorbs in the seed through water dispersion medium mutually; Be heated to 70 ℃ of polymerizations 24 hours, successively water/washing with acetone/dispersion is 4 times, dry again carboxylate polymer microballoon; (4) the carboxylate polymer microballoon of step (3) is hydrolyzed under alkaline condition and obtains the polymer microballoon with carboxyl; (5) polymer microballoon in the step (4) is joined Fe
2+/ Fe
3+In the hybrid ionic aqueous solution, at room temperature stirred 30 minutes～12 hours, wash unnecessary Fe then off
2+/ Fe
3+Ion adds strong aqua, and reacted 24 hours adjustment pH to 10～14, and centrifuge washing promptly obtains the porous micron-level magnetic polymer micro-sphere then.The preparation process of this method is loaded down with trivial details, waste time and energy cause product cost high, cost an arm and a leg, be difficult to large-scale application.
To the deficiency and the controlled difficult key issue of polymer microballoon preparation of size homogeneous of traditional preparation process method, contriver of the present invention has been developed direct film emulsification-suspension polymerization technique and has been prepared the homogeneous polymer microballoon.
(microporous membrane emulsification and suspension polymerization combined techniques prepare homogeneous PST-DVB porous microsphere to Qin Lu etc.; Qin Lu etc.; The process engineering journal; 2007 the 3rd phases) method that a kind of microporous membrane emulsification and suspension polymerization combined techniques prepare homogeneous PST-DVB porous microsphere is disclosed; It uses large-scale film emulsifier unit under certain pressure, the micropore of disperse phase through the film surface to be pressed in the round-robin external phase, disperses because the micropore on film surface is homogeneous, and the O/W type emulsion that in suitable membrane pressure scope, obtains is monodispersity.Prepared O/W type emulsion immigration is had in the four-hole reactor drum of prolong, stirring rod, nitrogen conduit; Behind the logical nitrogen replacement oxygen, at 80 ℃ of following polyreaction 24h, after the finishing polymerization; Obtain the microballoon medium with the B suction filtration; Behind deionized water and ethanol repetitive scrubbing microballoon, put into the vacuum drying oven inner drying, make PST-DVB porous microsphere product.
The king wait quietly (polydivinylbenezene microballoon preparation and in small molecules and polypeptide reversed phase chromatography separation, using, the king waits quietly, the process engineering journal; 2009 the 4th phases) disclose a kind of polydivinylbenezene method for preparing microsphere, it uses the film emulsifier unit under certain pressure, the oil phase for preparing to be gone into aqueous phase through the homogeneous mould, forms the size homogenous emulsion; After oil phase has been pressed, emulsion is moved in the four-hole reaction flask of belt stirrer, prolong, nitrogen access tube, be warming up to 75 ℃ behind the logical nitrogen replacement oxygen 1h; Polymerization 24h; After the finishing polymerization, obtain microballoon, microballoon is washed respectively 3 times with hot water and ethanol with the B suction filtration; Dry with acetone extracting 24h final vacuum, make the PDVB microballoon.Said microballoon is the porous sphere structure, and particle diameter is about 25 μ m, and mean pore size is 14nm, and specific surface area reaches 520m2/g.
The pacing items that directly film emulsification-suspension polymerization technique obtains the homogeneous emulsion droplet is that the surperficial IT of disperse phase and microporous membrane wants enough big; When the microporous membrane that adopts the small-bore prepares when receiving the homogeneous controllable polymer micro-ball of microstage; Emulsion preparation speed is very slow, and adopts this technology to be difficult to the polymer microballoon of preparation particle diameter below 1 μ m.
Because directly the film emulsifying technology exists above-mentioned defective when preparation small particle size microballoon; Therefore; We are necessary to research and develop the novel technology of preparing of receiving the microstage microballoon; Prepare the polymer nano microballoon that uniform particle diameter is controlled, morphological structure is controlled, with the range of application of further expansion polymer nano microballoon.
Summary of the invention
To the deficiency of prior art, one of the object of the invention is to provide a kind of preparation method of polymer nano microspheres product.The preparation method of polymer nano microspheres product according to the invention has solved traditional polymer and has received microspherulite diameter heterogeneity, uncontrollable preparation difficult point; The median size of the polymer nano microspheres product of preparation is in tens nanometer to 50 micrometer ranges; Median size is preferably between 50 nanometers-50 micron; For example 100 nanometers-40 micron, or 500 nanometers-30 micron, its size distribution coefficient＜20%.
Said size distribution coefficient is calculated as follows,
C.V.＝{[∑(d
i-d)
2/N]
1/2/d}×100％
In the formula, C.V. representative diameter distribution coefficient; d
iRepresent each to receive diameter of micro ball; The number average median size of microballoon is received in d representative, d=∑ d
i/ N; N be used to calculate particle diameter receive microballoon quantity, and N>=200.
The median size of polymer nano microballoon is preferably between 50 nanometers-50 micron among the present invention, for example 100 nanometers-40 micron, or 500 nanometers-30 micron.
The present invention can prepare the polymer nano microballoon with various polymerisable vinyl monomers, for example monomer and two kinds and the above monomeric mixture of vinylbenzene (ST), ethyl styrene (EST), Vinylstyrene (DVB), Rocryl 400 (HEMA), TEB 3K (MMA), SY-Monomer G (GMA), trimethylolpropane trimethacrylate (TMPTMA), TGM 1 (EDGMA), the reaction of dimethylaminoethyl methacrylate polymerizables such as (DMAEMA).
Can also realize the control of polymer nano microballoon morphological structure among the present invention according to difference adjuvant used in the oil phase prescription, the structure optimization of the polymer nano microballoon of preparation is forms such as solid, simple eye, concavo-convex, porous, hollow.
As preferably, the method for preparing the polymer nano microspheres product of the present invention, it comprises following concrete steps:
(1) provide dissolved auxiliary agent the aqueous solution as water, said auxiliary agent is preferably stablizer and/or emulsifying agent etc.;
(2) provide contain oil-soluble initiator, polymerization single polymerization monomer and other auxiliarys oily solution as oil phase;
(3) water is mixed with oil phase obtain O/W type pre-emulsion;
(4) said pre-emulsion is obtained O/W type emulsion through the microporous membrane of aperture homogeneous fast under constant compression force;
(5) O/W type homogeneous emulsion is prepared into the polymer nano microballoon of homogeneous behind polymerizing curable;
Alternatively, (6) will obtain receive microballoon through filtration, washing or/and drying treatment obtains the polymer nano microspheres product.
Among the preparation method of the present invention, emulsifying agent in the step (1) and stablizer are preferably Z 150PH (PVA), gelatin (Gelatin), Mierocrystalline cellulose (Cellulose), hydroxy alkyl cellulose, Vinylpyrrolidone polymer (PVP), SODIUM SULPHATE ANHYDROUS 99PCT (Na
2SO
4), sodium lauryl sulphate (SDS), sodium laurylsulfonate (SLS) etc. or its mixture, its weight percent concentration at aqueous phase is 0.02-5%, preferred 0.03-4%, for example 0.1-4%.
Among the preparation method of the present invention; Initiator in the step (2) is preferably Lucidol (BPO), dilauroyl peroxide (LPO), peroxy dicarbonate ethylhexyl (EHP), Diisopropyl azodicarboxylate (AIBN), ABVN (ADVN) etc.; Its weight percent concentration in oil phase is 0.1-10%; Preferred 0.2-8%, for example 0.5-6% or 1-5%.
Said other auxiliarys mean the auxiliary agent that is different from step (1); Be preferably the mixture of hydrophobic C4-C22 alkanes, C4-C22 alkane chain alcohols, aromatics, saturated aromatics, linear styrene oligomer and several kinds of compounds thereof etc.; Its weight percent concentration in oil phase is 0-70%; Preferred 0.05-60%, for example 1-50%.Said weight percent concentration is 0 to mean and do not add/do not exist other auxiliarys.
Among the preparation method of the present invention, the oil phase in the step (3) and the volume ratio of water are preferably 1: 1-1: 25, for example 1: 1-1: 20, more for example 1: 1-1: 15.
Among the preparation method of the present invention, pre-emulsion passes through microporous membrane described in the step (4) under the constant compression force effect.This working pressure is relevant with used membrane pore size and profit phase ratio, is preferably 0.005-3.0MPa, more preferably 0.01-2.5MPa.Said substantially invariable pressure is meant that the fluctuation of pressure is no more than 10%, is preferably and is no more than 5%.
Fast through microporous membrane, said " fast " produces under elevated pressures the preferred said pre-emulsion of the present invention under the constant compression force effect, and it is shorter to mean the time of passing through.Compared to prior art, one of emphasis of the present invention is to make pre-emulsion under the constant compression force effect, to pass through microporous membrane fast.The person of ordinary skill in the field all knows; Pre-emulsion is relevant with the mean pore size of mould and film through the speed of microporous membrane; Therefore the person of ordinary skill in the field can be known the concrete speed of said " fast " from processing condition of the present invention; Because should " fast " implication be clearly, the present invention no longer describes with regard to its numerical range.
In the step (4), can select one or many to press the process of microporous membrane according to the homogeneous degree of emulsion, until obtaining homogenous emulsion.The number of times that said pre-emulsion is crossed film can be repeatedly, promptly at least once obtains said O/W type emulsion through same microporous membrane, is preferably 2-7 time, and is more preferably 3-5 time, each through under identical pressure condition, carrying out.
Microporous membrane is preferably high-molecular porous film, porous silica film, ceramic porous membrane described in the step (4).High-molecular porous film can be Zylox pervaporation membrane (film that is especially prepared by YSR 3286), poly tetrafluoroethylene, tetrafluoroethylene filled silicon rubber film, high-molecular polythene film, macromolecule polypropylene film, high molecular polyether sulfone film etc.Ceramic porous membrane can be the film of materials such as barium titanate, strontium titanate, calcium zirconate, magnesium zirconate, silit, norbide.The shape of microporous membrane is preferably plate shaped, and is tubular; Wherein tubular shape of cross section is preferably circle, square, rectangle, ellipse, round shape.
The mean pore size scope of said microporous membrane is preferably 0.05-100 μ m, more preferably 0.1-50 μ m, for example 0.2-40 μ m.Wherein mean pore size is the volume averaging aperture, defines as follows:
d
v＝[(∑n
i?d
i 3)/∑n
i]
1/3
In the formula, d
vBe volume averaging aperture, d
iBe the diameter of each micropore, n
iFor the aperture is d
iThe number of micropore.
The pore size distribution of said microporous membrane is most important to the influence of the size distribution of polymer nano microballoon, and membrane pore size distributes narrow more, and the size distribution of the prepared polymer nano microballoon that obtains is got over homogeneous.Therefore, the pore size distribution span Span value of said microporous membrane is below 0.7.The definition of pore size distribution span Span value is as shown in the formula said:
Span＝(d
90-d
10)/d
50
In the formula, d
90, d
10And d
50The aperture of representing to have in all apertures 90%, 10%, 50% hole respectively is less than the represented aperture size of this value.Pore size distribution span (Span value) is more little, and pore size distribution is narrow more, and promptly homogeneous is got in the aperture.
Among the preparation method of the present invention; The curing of emulsion can select heated polymerizable or uv irradiation method to carry out according to the kind of initiator in the step (5); The Heating temperature of curing reaction is 30-150 ℃, and preferred Heating temperature is 50-120 ℃, further preferred 50-90 ℃.The curing reaction time is preferably 8-30 hour; If adopt the UV-irradiation reaction, then the reaction times is preferably 1-20 hour.
Among the preparation method of the present invention, the polymer nano microballoon that obtains described in the step (6) has the median size between about tens nanometers to 50 micron, the median size between preferred tens nanometers to 30 micron and less than about 20% size distribution coefficient.Therefore, method of the present invention is particularly suitable for preparing the above-mentioned polymer nano microballoon of the present invention.Yet, should be understood that method of the present invention also can be used to prepare the polymer nano microballoon with other particle diameter and size distribution.
The morphological structure of the polymer nano microballoon that obtains described in the step (6) can be realized regulation and control according to the difference of kind adjuvant used in the step (2) and consumption, and structure optimization is different forms such as solid, porous, hollow, simple eye, depression.
Washing described in the step (6) for washing, alcohol washes, acetone extracting or its combination, preferably wash in order, alcohol is washed and the acetone extracting.Said drying is preferably dried or freeze-drying.
As preferably, the method for preparing the polymer nano microspheres product of the present invention, as shown in Figure 1, the step of the preparation of polymer nano microballoon is following:
1) preparation of O/W type pre-emulsion
A certain amount of emulsifying agent, stablizer and other auxiliary agents joined be mixed with the homogeneous aqueous solution in a certain amount of deionized water as water; One or more chemical monomers, a certain amount of initiator and other auxiliary agents are mixed with the homogeneous oil solution as oil phase.Water and oil phase are mixed the back rapidly prepare O/W type pre-emulsion through homogenizing emulsifying, stirring or method such as ultrasonic.
2) homogeneous is received preparation of microemulsion
Under the constant certain pressure, pre-emulsion obtained the O/W type emulsion of uniform particle diameter rapidly through the aperture of microporous membrane, this emulsion process is repeatedly capable of circulation, reaches requirement of experiment until the dimensional homogeneity of emulsion, and generally circulating can reach requirement 2-7 time.
3) preparation of homogeneous polymer nano microballoon
According to the mode of excitation of initiator, the homogeneous O/W type emulsion employing polymerization of preparation or the curing mode of illumination are cured, and carry out aftertreatments such as filtration washing, extracting, finally obtain the polymer nano microballoon of uniform particle diameter.
One of the object of the invention also is to provide this a kind of microballoon of receiving, and the said microballoon of receiving is prepared by preparation method of the present invention.Other microballoons compared to prior art; The microballoon of receiving of the present invention, the median size of polymer nano microspheres product that means preparation at nano level in micron order, in preferred tens nanometer to 50 micrometer ranges of the present invention; Median size is preferably between 50 nanometers-50 micron; For example 100 nanometers-40 micron, or 500 nanometers-30 micron, its size distribution coefficient＜20%.Said tens nanometers mean double figures, 20,25,30,46,50 nanometers etc. for example, or bigger.Can know that by the characteristic of receiving microballoon according to the invention preparation method of the present invention gives its new features that are different from prior art.
The preparation method of polymer nano microballoon provided by the invention has advantages such as the size homogeneous is controlled, the micro-sphere structure form is controlled, preparation speed is fast, output big, batch good reproducibility.The prepared homogeneous polymer nano microballoon of the present invention has that physical strength height, physical and chemical performance are stable, acid and alkali-resistance, be easy to characteristics such as modification.
Therefore one of the object of the invention also is to provide a kind of purposes of polymer nano microballoon; It can be used for chromatograph packing material, modify the many fields such as functional supports of back as ionite, solid-phase synthesized carrier, enzyme immobilization carrier, pharmaceutical carrier, analyzing and testing reagent, food and makeup, has wide practical use.
The present invention has adopted quick film emulsifying technology to prepare the polymer nano microballoon that particle diameter is tens nanometers to tens micron.Adopt the homogeneous dispersiveness of polymer nano microballoon of this novel film emulsion process preparation fine; But also can realize the prepared control of receiving microsphere average grain diameter through selecting different membrane pore size and working pressure, the size distribution coefficient of microballoon received can be controlled in 20%.
Polymer nano microspheres product uniform particle diameter prepared according to the methods of the invention; This technology has solved the traditional preparation process method and has been difficult to prepare the key issue that controlled, the conventional film emulsion process of uniform particle diameter is difficult to prepare small particle size polymer nano microballoon, under the prerequisite that guarantees uniform particle diameter, can prepare the polymer nano microballoon of small particle size fast.The preparation technology of this technology of preparing is easy, and operation is easy to amplify and large-scale production, and the generating rate of emulsion is fast, batch good reproducibility.
Description of drawings
Fig. 1 is the preparation process synoptic diagram of polymer nano microballoon.
Fig. 2 is the stereoscan photograph of PS (PST) solid microsphere of embodiment 1 preparation.
Fig. 3 is the stereoscan photograph of PS (PST) porous microsphere of embodiment 2 preparations.
Fig. 4 is the stereoscan photograph of polydivinylbenezene (PDVB) the depression microballoon of embodiment 3 preparations.
Fig. 5 is the size distribution figure (laser particle analyzer test) of the polymer microballoon of preparation among the embodiment 1,2,3.
Fig. 6 is the stereoscan photograph of the solid nanometer ball of PS (PST) of embodiment 5 preparations.
Fig. 7 is the light microscopic photo of vinylbenzene (ST) the homogeneous emulsion of embodiment 8 preparations.
Fig. 8 is the median size and the graph of a relation between the microporous membrane aperture (experimental result of embodiment 2,4,5,6,7,8) of PST microballoon that adopts the microporous membrane preparation in different apertures.
Fig. 9 is the stereoscan photograph of the simple eye microballoon of PS of embodiment 9 preparations.
Figure 10 is the laser co-focusing photo of the PS hollow microsphere of embodiment 10 preparations.
Figure 11 is the stereoscan photograph of PS-TEB 3K (P (ST-MMA)) micropore microballoon of embodiment 11 preparations.
Figure 12 is the stereoscan photograph of PS-Rocryl 400 (P (ST-HEMA)) parents surface microballoon of preparation among the embodiment 12.
Embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment only is used for helping to understand the present invention, should not be regarded as concrete restriction of the present invention.
Embodiment 1 (2.8 microns in the aperture of microporous membrane, structure are solid, and monomer is ST)
It is for use that the aperture is that 2.8 microns microporous membrane places deionized water for ultrasonic to handle it to be installed supporting membrane emulsifier after 30 minutes.Accurately measure the 150ml deionized water, take by weighing 1.8gPVA, 0.0003g SDS and 0.0045g Na
2SO
4Be dissolved in the deionized water Deng auxiliary agent that to form water subsequent use.0.5g BPO is dissolved among the 20g ST fully forms oil phase.The oil phase for preparing is joined aqueous phase, under 300rpm, stirred 10 minutes, form pre-emulsion with mechanical stirring.Then; The gained pre-emulsion is poured into rapidly in the membrane emulsifier storage tank, under the nitrogen pressure of 0.95MPa, made it pass through the microporous membrane of aperture homogeneous fast; Obtain the O/W type emulsion of particle diameter ratio than homogeneous; The gained emulsion is passed through microporous membrane once more as pre-emulsion under the nitrogen pressure of 0.95MPa, emulsification is 4 times repeatedly, finally obtains the O/W type emulsion of uniform particle diameter; Emulsification finishes, emulsion is transferred in three mouthfuls of reaction flasks, and 70 ℃ of following polyreactions 16 hours, the PST solid microsphere powder that reaction solution is obtained preparing after filtration, washing, extracting, drying.The stereoscan photograph of microballoon is as shown in Figure 2, and thus obtained microsphere is solid construction, and median size is 2.2 microns, productive rate 95%, and size distribution C.V. value is 13.8%.
Embodiment 2 (2.8 microns in the aperture of microporous membrane, structure are micropore, and monomer is ST)
Microporous membrane, the aqueous phase solution 150ml of employing and embodiment 1 same apertures add 10g normal heptane (HP) again and form oil phase in identical oil phase.The oil phase for preparing is joined aqueous phase, under 300rpm, stirred 10 minutes, form pre-emulsion with mechanical stirring.Then; The gained pre-emulsion is poured into rapidly in the film emulsifier unit storage tank, under the nitrogen pressure of 1.05MPa, made it pass through the microporous membrane of aperture homogeneous fast; Obtain the O/W type emulsion of particle diameter ratio than homogeneous; The gained emulsion is passed through microporous membrane once more as pre-emulsion under the nitrogen pressure of 1.05MPa, emulsification is 5 times repeatedly, finally obtains the O/W type emulsion of uniform particle diameter; Emulsification finishes, emulsion is transferred in three mouthfuls of reaction flasks, and 80 ℃ of following polyreactions 20 hours, the PST micropore microballoon that reaction solution is obtained preparing after filtration, washing, extracting, drying.The stereoscan photograph of microballoon is as shown in Figure 3, and thus obtained microsphere is microvoid structure, and median size is 2.3 microns, productive rate 90%, and size distribution C.V. value is 14.6%.
Embodiment 3 (2.8 microns in the aperture of microporous membrane, structure is depression, monomer is DVB)
Adopt microporous membrane with embodiment 1 same apertures.Accurately measure the 200ml deionized water, take by weighing 1.2gPVA, 0.008g SDS and be dissolved in that to form water in the deionized water subsequent use.1.1g BPO is dissolved in formation oil phase in 28g DVB, the 11g n-Hexadecane (HD) fully.The oil phase for preparing is joined aqueous phase, under 500rpm, stirred 10 minutes, form pre-emulsion with mechanical stirring.Then; The gained pre-emulsion is poured into rapidly in the film emulsifier unit storage tank, under the nitrogen pressure of 1.1MPa, made it pass through microporous membrane fast; Obtain the O/W type emulsion of particle diameter ratio than homogeneous; The gained emulsion is passed through microporous membrane once more as pre-emulsion under the nitrogen pressure of 1.1MPa, emulsification is 3 times repeatedly, finally obtains the O/W type emulsion of uniform particle diameter; Emulsification finishes, and emulsion is transferred in three mouthfuls of reaction flasks, 90 ℃ of following polyreactions 14 hours, with the PDVB depression microballoon of reaction solution through filtering, obtaining preparing after the washing.The stereoscan photograph of microballoon is as shown in Figure 4, and thus obtained microsphere is sunk structure, and median size is 2.0 microns, productive rate 89%, and size distribution C.V. value is 15.4%.
Fig. 5 is the microspherulite diameter distribution plan of embodiment 1,2,3.The microspherulite diameter difference that is drawn three kinds of different structures that utilize the identical micro pores membrane prepare by these data is little, has realized the control of micro-sphere structure, has good batch of repeatability simultaneously.
Embodiment 4 (0.8 micron in the aperture of microporous membrane, structure are solid, and monomer is ST)
The selection aperture is 0.8 micron a microporous membrane, and used oil phase is identical with embodiment 1 with water.The oil phase for preparing is joined aqueous phase, under 800rpm, stirred 10 minutes, form pre-emulsion with mechanical stirring.Then; The gained pre-emulsion is poured into rapidly in the film emulsifier unit storage tank, under the nitrogen pressure of 2.1MPa, made it pass through the microporous membrane of aperture homogeneous fast; Obtain the O/W type emulsion of particle diameter ratio than homogeneous; The gained emulsion is passed through microporous membrane once more as pre-emulsion under the nitrogen pressure of 2.1MPa, emulsification is 5 times repeatedly, finally obtains the O/W type emulsion of uniform particle diameter; Emulsification finishes, emulsion is transferred in three mouthfuls of reaction flasks, and 75 ℃ of following polyreactions 20 hours, the solid nanometer ball of PST that reaction solution is obtained preparing after filtration, washing, extracting, drying.The thus obtained microsphere median size is 500 nanometers, productive rate 86%, and size distribution C.V. value is 15.9%.
Embodiment 5 (1.4 microns in the aperture of microporous membrane, structure are solid, and monomer is ST)
The selection aperture is 1.4 microns a microporous membrane, and used oil phase is identical with embodiment 1 with water.Emulsion preparation technology is also identical with embodiment 1, but employed emulsification pressure is 1.6MPa; Emulsification finishes, emulsion is transferred in three mouthfuls of reaction flasks, and 70 ℃ of following polyreactions 16 hours, the solid nanometer ball of PST that reaction solution is obtained preparing after filtration, washing, extracting, drying.The stereoscan photograph of product is as shown in Figure 6, and the thus obtained microsphere median size is 900 nanometers, productive rate 85%, and size distribution C.V. value is 17.9%.
Embodiment 6 (5.4 microns in the aperture of microporous membrane, structure are solid, and monomer is ST)
The selection aperture is 5.4 microns a microporous membrane, and used oil phase is identical with embodiment 1 with water.Emulsion preparation technology is also identical with embodiment 1, but employed emulsification pressure is 0.45MPa; Emulsification finishes, emulsion is transferred in three mouthfuls of reaction flasks, and 70 ℃ of following polyreactions 16 hours, the PST solid microsphere that reaction solution is obtained preparing after filtration, washing, extracting, drying.The thus obtained microsphere median size is 4.1 microns, productive rate 92%, and size distribution C.V. value is 13.9%.
Embodiment 7 (9.0 microns in the aperture of microporous membrane, structure are solid, and monomer is ST)
The selection aperture is 9.0 microns a microporous membrane, and used oil phase is identical with embodiment 1 with water.Emulsion preparation technology is also identical with embodiment 1, but employed emulsification pressure is 0.20MPa; Emulsification finishes, emulsion is transferred in three mouthfuls of reaction flasks, and 70 ℃ of following polyreactions 16 hours, the PST solid microsphere that reaction solution is obtained preparing after filtration, washing, extracting, drying.The thus obtained microsphere median size is 6.9 microns, productive rate 85%, and size distribution C.V. value is 17.3%.
Embodiment 8 (40 microns in the aperture of microporous membrane, structure are porous, and monomer is ST)
The selection aperture is 40 microns a microporous membrane, and used oil phase is identical with embodiment 2 with water, and emulsion preparation technology is also identical with embodiment 2, but employed emulsification pressure is 0.01MPa, and the homogeneous emulsion light microscopic photo of preparation is as shown in Figure 7.Emulsification finishes, emulsion is transferred in three mouthfuls of reaction flasks, and 80 ℃ of following polyreactions 20 hours, the PST micropore microballoon that reaction solution is obtained preparing after filtration, washing, extracting, drying.The thus obtained microsphere median size is 32 microns, productive rate 87%, and size distribution C.V. value is 15.6%.
Fig. 8 is shown as the variation relation between the membrane pore size of median size and used microporous membrane of microballoon, and along with the increase of membrane pore size, the microspheres prepared particle diameter also increases thereupon, thereby can utilize the size of membrane pore size to realize the control of microspherulite diameter.
Embodiment 9 (8.2 microns in the aperture of microporous membrane, structure are simple eye, and monomer is ST)
It is for use after 8.2 microns the microporous membrane supersound process selecting the aperture.Accurately measure the 200ml deionized water, take by weighing 2.0gPVP, 0.075g SLS, 0.01gNa
2SO
4Be dissolved in and form water in the deionized water.0.2gADVN is dissolved among 20g ST, 2.0g n-Hexadecane (HD), the 0.5g DMAEMA fully forms oil phase.The oil phase for preparing is joined aqueous phase, under 600rpm, stirred 10 minutes, form pre-emulsion with mechanical stirring.Then; The gained pre-emulsion is poured into rapidly in the film emulsifier unit storage tank, under the nitrogen pressure of 0.25MPa, made it pass through microporous membrane fast; Obtain the O/W type emulsion of particle diameter ratio than homogeneous; The gained emulsion is passed through microporous membrane once more as pre-emulsion under the nitrogen pressure of 0.25MPa, emulsification is 4 times repeatedly, finally obtains the O/W type emulsion of uniform particle diameter; Emulsification finishes, and emulsion is transferred in three mouthfuls of reaction flasks, 85 ℃ of following polyreactions 10 hours, with the PST simple eye microballoon of reaction solution through filtering, obtaining preparing after the washing.As shown in Figure 9, the median size of thus obtained microsphere is 5.5 microns, productive rate 84%, and size distribution C.V. value is 16.4%.
Embodiment 10 (5.2 microns in the aperture of microporous membrane, structure are hollow, and monomer is ST and DVB copolymerization)
It is for use after 5.2 microns the microporous membrane supersound process selecting the aperture.Accurately measure the 150ml deionized water, take by weighing 1.5gPVA, 0.11gSDS, 0.035g Na
2SO
4Be dissolved in and form water in the deionized water.0.4gBPO is dissolved in formation oil phase in 10g ST, 10gDVB, the 15g n-Hexadecane (HD) fully.The oil phase for preparing is joined aqueous phase, under 400rpm, stirred 10 minutes, form pre-emulsion with mechanical stirring.Then; The gained pre-emulsion is poured into rapidly in the film emulsifier unit storage tank, under the nitrogen pressure of 0.55MPa, made it pass through microporous membrane fast; Obtain the O/W type emulsion of particle diameter ratio than homogeneous; The gained emulsion is passed through microporous membrane once more as pre-emulsion under the nitrogen pressure of 0.55MPa, emulsification is 5 times repeatedly, finally obtains the O/W type emulsion of uniform particle diameter; Emulsification finishes, and emulsion is transferred in three mouthfuls of reaction flasks, 70 ℃ of following polyreactions 20 hours, with P (ST-DVB) hollow microsphere of reaction solution through filtering, obtaining preparing after the washing.The fluorescence co-focusing photo of microballoon is shown in figure 10, and the median size of thus obtained microsphere is 3.5 microns, productive rate 88%, and size distribution C.V. value is 17.1%.
Embodiment 11 (9.0 microns in the aperture of microporous membrane, structure are porous, and monomer is ST and MMA copolymerization)
It is for use after 9.0 microns the microporous membrane supersound process selecting the aperture.Accurately measure the 200ml deionized water, take by weighing 4.5gPVA and be dissolved in the deionized water that to form water subsequent use.0.75g AIBN is dissolved in 20gST, 5g MMA, 18g HP, the 2g whiteruss fully forms oil phase.The oil phase for preparing is joined aqueous phase, under 200rpm, stirred 10 minutes, form pre-emulsion with mechanical stirring.Then; The gained pre-emulsion is poured into rapidly in the film emulsifier unit storage tank, under the nitrogen pressure of 0.18MPa, made it pass through the microporous membrane of aperture homogeneous fast; Obtain the O/W type emulsion of particle diameter ratio than homogeneous; The gained emulsion is passed through microporous membrane once more as pre-emulsion under the nitrogen pressure of 0.18MPa, emulsification is 3 times repeatedly, finally obtains the O/W type emulsion of uniform particle diameter; Emulsification finishes, emulsion is transferred in three mouthfuls of reaction flasks, and 85 ℃ of following polyreactions 20 hours, P (ST-MMA) the micropore microballoon that reaction solution is obtained preparing after filtration, washing, extracting, drying.The stereoscan photograph of microballoon is shown in figure 11, and the thus obtained microsphere median size is 7.2 microns, productive rate 86%, and size distribution C.V. value is 14.8%.
Embodiment 12 (30 microns in the aperture of microporous membrane, structure are surperficial parents, and monomer is ST and HEMA copolymerization)
It is for use after 30 microns the microporous membrane supersound process selecting the aperture, and water is identical with embodiment 3.0.45g BPO is dissolved in 15g ST, 3g HEMA, 10g toluene, the linear PS of 5g fully forms oil phase.The oil phase for preparing is joined aqueous phase, under 600rpm, stirred 10 minutes, form pre-emulsion with mechanical stirring.Then; The gained pre-emulsion is poured into rapidly in the film emulsifier unit storage tank, under the nitrogen pressure of 0.05MPa, made it pass through the microporous membrane of aperture homogeneous fast; Obtain the O/W type emulsion of particle diameter ratio than homogeneous; The gained emulsion is passed through microporous membrane once more as pre-emulsion under the nitrogen pressure of 0.05MPa, emulsification is 4 times repeatedly, finally obtains the O/W type emulsion of uniform particle diameter; Emulsification finishes, emulsion is transferred in three mouthfuls of reaction flasks, and 80 ℃ of following polyreactions 18 hours, P (ST-HEMA) the micropore microballoon that reaction solution is obtained preparing after filtration, washing, extracting.The stereoscan photograph of microballoon is shown in figure 12, and the thus obtained microsphere median size is 24 microns, productive rate 83%, and size distribution C.V. value is 16.2%.。
Through reading the present invention, those skilled in the art may expect many changes of the present invention and other embodiment, and instruct its benefit of prevision according to the present invention.Therefore, should be appreciated that above embodiment and embodiment do not limit the present invention, and its change carried out and other embodiment are also included within the scope of accompanying claims.Though this paper uses particular term, they with using with descriptive sense as the one of which, are not the scope of the present invention that defines in the claim in order to limit only.
Claims (10)
1. method for preparing the polymer nano microspheres product, it comprises following concrete steps:
(1) with the aqueous solution that dissolved auxiliary agent as water, said auxiliary agent is preferably stablizer and/or emulsifying agent;
(2) with the oily solution that contains oil-soluble initiator, polymerization single polymerization monomer and other auxiliary agents as oil phase;
(3) water is mixed with oil phase obtain O/W type pre-emulsion;
(4) said pre-emulsion is obtained O/W type emulsion through microporous membrane fast under constant compression force;
(5) O/W type emulsion is prepared into the polymer nano microballoon of homogeneous behind polymerizing curable;
Alternatively, (6) will obtain receive microballoon through filtration, washing or/and drying treatment obtains the polymer nano microspheres product.
2. the method for claim 1; It is characterized in that emulsifying agent in the step (1) and stablizer are preferably Z 150PH (PVA), gelatin (Gelatin), Mierocrystalline cellulose (Cellulose), hydroxy alkyl cellulose, Vinylpyrrolidone polymer (PVP), SODIUM SULPHATE ANHYDROUS 99PCT (Na
2SO
4), sodium lauryl sulphate (SDS), sodium laurylsulfonate (SLS) or its mixture, its weight percent concentration at aqueous phase is 0.02-5%, preferred 0.03-4%, for example 0.1-4%.
3. according to claim 1 or claim 2 method; It is characterized in that; Said monomer in the step (2) is the monomer of vinylbenzene (ST), ethyl styrene (EST), Vinylstyrene (DVB), Rocryl 400 (HEMA), TEB 3K (MMA), SY-Monomer G (GMA), trimethylolpropane trimethacrylate (TMPTMA), TGM 1 (EDGMA), the reaction of dimethylaminoethyl methacrylate (DMAEMA) polymerizable, or two kinds and above monomeric mixture;
Preferably; Said initiator in the step (2) is preferably Lucidol (BPO), dilauroyl peroxide (LPO), peroxy dicarbonate ethylhexyl (EHP), Diisopropyl azodicarboxylate (AIBN), ABVN (ADVN) or its mixture; Its weight percent concentration in oil phase is 0.1-10%; Preferred 0.2-8%, for example 0.5-6%;
Preferably; Said other auxiliary agents in the step (2) are hydrophobic C4-C22 alkanes, C4-C22 alkane chain alcohols, aromatics, saturated aromatics, linear styrene oligomer and composition thereof; Its weight percent concentration in oil phase is 0-70%; Preferred 0.05-60%, for example 1-50%.
4. like the described method of one of claim 1-3, it is characterized in that the oil phase in the step (3) and the volume ratio of water are 1: 1-1: 25, for example 1: 1-1: 20, for example 1: 1-1: 15.
5. like the described method of one of claim 1-4, it is characterized in that, constant compression force 0.005-3.0MPa described in the step (4), 0.01-2.5MPa more preferably, the fluctuation of said constant compression force is no more than 10%, is preferably and is no more than 5%;
Preferably, in the step (4), said pre-emulsion passes through microporous membrane fast under the constant compression force effect;
Preferably, in the step (4), select the fast ram compression of one or many to cross microporous membrane according to the homogeneous degree of emulsion, until obtaining homogenous emulsion; Saidly repeatedly be preferably 2-7 time, more preferably 3-5 time, under identical pressure condition, carry out at every turn;
Preferably, in the step (4), said microporous membrane is preferably high-molecular porous film, porous silica film, ceramic porous membrane; High-molecular porous film is the Zylox pervaporation membrane, by film, poly tetrafluoroethylene, tetrafluoroethylene filled silicon rubber film, high-molecular polythene film, macromolecule polypropylene film or the high molecular polyether sulfone film of YSR 3286 preparation; Ceramic porous membrane is barium titanate, strontium titanate, calcium zirconate, magnesium zirconate, silit or carbonization boron film; Being shaped as of microporous membrane is plate shaped or tubular, and wherein tubular shape of cross section is circle, square, rectangle, ellipse or round shape;
Preferably, the mean pore size scope of said microporous membrane is 0.05-100 μ m, more preferably 0.1-50 μ m, for example 0.2-40 μ m;
Preferably, the pore size distribution span Span value of said microporous membrane is below 0.7.
6. like the described method of one of claim 1-5, it is characterized in that the curing of emulsion is heated polymerizable or uv irradiation method in the step (5); The Heating temperature of said curing reaction is 30-150 ℃, and preferred Heating temperature is 50-120 ℃, further preferred 50-90 ℃; The curing reaction time is 8-30 hour; If adopt the UV-irradiation reaction, then the reaction times is 1-20 hour.
7. like the described method of one of claim 1-6, it is characterized in that, the said polymer nano microballoon that obtains in the step (6) have between tens nanometers to 50 micron median size and less than 20% size distribution coefficient; Said median size preferably between 50 nanometers-50 micron, for example 100 nanometers-40 micron, or 500 nanometers-30 micron;
Preferably, the morphological structure of the said polymer nano microballoon that obtains in the step (6) is realized regulation and control according to the difference of kind adjuvant used in the step (2) and consumption, and structure is solid, porous, hollow, simple eye or depression form;
Preferably, washing described in the step (6) for washing, alcohol washes, acetone extracting or its combination, preferably wash in order, alcohol is washed and the acetone extracting; Said drying is preferably dried or freeze-drying.
8. method for preparing the polymer nano microspheres product, the step of the preparation of said polymer nano microballoon is following:
1) preparation of O/W type pre-emulsion
A certain amount of emulsifying agent, stablizer and other auxiliary agents joined be mixed with the homogeneous aqueous solution in a certain amount of deionized water as water; One or more chemical monomers, a certain amount of initiator and other auxiliary agents are mixed with the homogeneous oil solution as oil phase; Water and oil phase are mixed the back rapidly prepare O/W type pre-emulsion through homogenizing emulsifying, stirring or ultrasonic method;
2) homogeneous is received preparation of microemulsion
Under the constant certain pressure, said pre-emulsion obtained the O/W type emulsion of uniform particle diameter rapidly through the aperture of microporous membrane, this emulsion process is repeatedly capable of circulation, until the size homogeneous of emulsion, preferred cycle 3-7 time;
3) preparation of homogeneous polymer nano microballoon
Adopt the curing mode of polymerization or illumination to be cured the homogeneous O/W type emulsion of preparation, and filter, washing, extracting and drying treatment, finally obtain the polymer nano microballoon of uniform particle diameter.
9. the polymer nano microballoon for preparing of the said method of one of claim 1-8; It is characterized in that said polymer nano microspherulite diameter is in tens nanometer to 50 micrometer ranges; Median size is preferably between 50 nanometers-50 micron; For example 100 nanometers-40 micron, or 500 nanometers-30 micron, its size distribution coefficient＜20%.
10. the purposes of the said polymer nano microballoon of claim 9; It is characterized in that, be used for chromatograph packing material, modify the functional supports of back as ionite, solid-phase synthesized carrier, enzyme immobilization carrier, pharmaceutical carrier, analyzing and testing reagent, food and makeup.
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