CN103435731B - A kind of preparation method of porous polymer microsphere - Google Patents
A kind of preparation method of porous polymer microsphere Download PDFInfo
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Abstract
The invention provides a kind of preparation method of porous polymer microsphere, it comprises the steps: to obtain oil phase by after oil-soluble monomer, linking agent, emulsifying agent mixing; Oil phase is mixed with water, obtained double emulsion; By double emulsion initiated polymerization, namely obtain porous polymer microsphere.Double emulsion stability in the preparation method of porous polymer microsphere provided by the invention is high, does not need interpolation ionogen and stablizer to increase the stability of double emulsion; Be polymerized the porous polymer microsphere productive rate obtained high, regular shape, the connectivity in hole is good; The size monodisperse of microballoon is good, and size regulation range is wide, and the aftertreatment of the final product obtained is simple and easy.
Description
Technical field
The present invention relates to porous microsphere Material Field, particularly a kind of preparation method of porous polymer microsphere.
Background technology
High Internal Phase Emulsion (HighInternalPhaseEmulsion, HIPE) refer to the emulsion of volume fraction more than 74% of interior phase (disperse phase), it can prepare the through porous material with multi-stage porous (comprising macropore, mesoporous and micropore) structure of hole as template.This material has good application prospect, such as, owing to having high specific surface area, can as support of the catalyst or itself as catalyzer; Possess aperture controllability, may be used for separating and filtering field; In addition, porous material has good prospect at biological fields such as histocyte cultivation, drug release.
High Internal Phase Emulsion can be divided into water-in-oil (W/O) type and oil-in-water (O/W) type.According to the difference of monomer character, applicable emulsion kind is also different, wherein oil-in-water-type (O/W) High Internal Phase Emulsion refer to be disperse phase with organic solvent, the High Internal Phase Emulsion that is external phase with the solution of containing water-soluble monomer; Water-in-oil (W/O) type High Internal Phase Emulsion is then take the aqueous solution as disperse phase, to contain the High Internal Phase Emulsion that the oil phase of hydrophobic monomer is external phase.
With the common method preparing porous material as compared with reversed phase method, phase separation method, solvent pore method etc., High Internal Phase Emulsion template has the size of aperture and channel diameter and the advantage that can accurately control that distributes, its general first initiated polymerization containing the external phase of monomer, then can obtain the polymer materials with vesicular structure after removing disperse phase and emulsifying agent.Owing to being external phase polymerization, the shape of the high internal phase polymeric porous material (polyHIPEs) obtained after polymerization is consistent with the shape of reactor, such as, test tube will obtain columniform bulk material as reactor, and bulk material is unfavorable for the removing of the impurity such as unconverted monomer in system, emulsifying agent, ionogen, also comparatively inconvenience in actual applications.
U.S. Patent application the 5th, 583, No. 162 reports, High Internal Phase Emulsion is transferred in difform mould, obtain the millimetre-sized porous ball of the shapes such as spherical, oval, cylinder, but this method die design and manufacturing cost too high, particle size is minimum also can only control to several millimeter;
with (React.Funct.Polym.2005 such as Krajnc, 65,37) first prepare the anti-phase High Internal Phase Emulsion of chloride cinnamic water-in-oil (W/O), be then distributed to by High Internal Phase Emulsion in the PVP aqueous solution, settling flux polymerization obtains polyHIPEs porous polymer microballon.But the shortcoming of this method is High Internal Phase Emulsion is a kind of full-bodied emulsion, disperseed more difficult, namely allow to disperse also to be difficult to the spherical of formation rule, and contain ionogen by containing interior aqueous phase, inside and outside aqueous phase forms the double emulsion instability that osmotic pressure causes being formed; The anti-phase High Internal Phase Emulsion prepared is distributed in the PVA aqueous solution by micro-fluidic technologies by Gokmen etc. (Macromolecules2009,42,9289), obtains porous polymer particles (ball and rod) by ultraviolet initiated polymerization.But the micro-fluidic technologies adopted can only under lab realize at present, is difficult to be applied in actual industrial production.
Therefore, how to prepare that a kind of cost is low, preparation is simple and become problem demanding prompt solution in this area for spherical porous polymer.
Summary of the invention
In view of this, the invention provides a kind of cost low, preparation is simple, the preparation method of the much higher pore polymer microsphere of productive rate.
For achieving the above object, the invention provides a kind of preparation method of porous polymer microsphere, it comprises the steps:
(1) oil phase is obtained by after oil-soluble monomer, linking agent, emulsifying agent mixing;
(2) under the condition stirred, the oil phase obtained in step (1) is mixed with water, obtained double emulsion;
(3) by double emulsion initiated polymerization obtained in step (2), namely porous polymer microsphere is obtained.
Preferably, the mass ratio of described step (1) oil-soluble monomer, linking agent, emulsifying agent is (3 ~ 8): (1 ~ 4): (1 ~ 3).
Preferably, the general formula of described oil-soluble monomer is CH
2=CR
1r
2, wherein R
1for hydrogen or methyl, R
2for aryl, ester group or COOR
3, R
3for alkyl or haloalkyl.
Preferably, the general formula of described linking agent is R
4(CR
5=CH
2)
n, wherein R
4for aryl, alkyl, containing ether or containing ester group, R
5for hydrogen or methyl, n is the integer of 2 ~ 4.
Preferably, the structural formula of described emulsifying agent is
wherein X is NH
4 +, Na
+, K
+or amine salt, R is saturated or undersaturated aliphatic group or aryl, and a is the integer of 6 ~ 14, b be 1 or 2, c be the integer of 3 ~ 14.
Preferably, also add pore-creating agent in the oil phase in described step (1), the mass ratio of described pore-creating agent and oil phase is (0 ~ 5): 5.
Preferably, described step (1) also comprises the pH value of oil phase is adjusted to 6 ~ 9.
Preferably, in described step (2), the mass ratio of oil phase and water is 1:(12 ~ 25).
Preferably, the polyreaction in described step (3) is caused by gamma Rays.
Preferably, described in step (3), polyreaction is caused by radical initiator.
The preparation method of porous polymer microsphere provided by the invention has following characteristics: double emulsion stability prepared by the present invention is high, does not need interpolation ionogen and stablizer to increase the stability of double emulsion; Be polymerized the porous polymer microsphere productive rate obtained high, regular shape, the connectivity in hole is good; The size monodisperse of microballoon is good, and size regulation range is wide, and the aftertreatment of the final product obtained is simple and easy.
Accompanying drawing explanation
Fig. 1 is the mechanism schematic diagram that different hydrophilic lipophilic emulsifier and different water oil ratio form emulsion types;
The photo of the opticmicroscope of Fig. 2 emulsion that to be S1 formed at different watr-proportions, wherein a is aqueous phase massfraction 60wt% (scale length is 100 μm), b is aqueous phase massfraction 76wt% (scale length is 100 μm), c is aqueous phase massfraction 92wt% (scale length is 100 μm), and d is aqueous phase massfraction 92wt% (scale length is 50 μm);
The specific conductivity of Fig. 3 emulsion that to be S1 formed at different watr-proportions is with the variation diagram of aqueous phase massfraction;
Fig. 4 is the electron scanning micrograph of S1;
Fig. 5 is the electron scanning micrograph of S2;
Fig. 6 is the electron scanning micrograph of S3;
Fig. 7 is the change curve of aqueous phase massfraction with pH value of emulsion phase transition point;
The optical microscopy map of double emulsion when Fig. 8 is different pH value, wherein a is pH=6, b be pH=7, c be pH=8, d is pH=9, and scale length is all 200 μm;
Fig. 9 is the electron scanning micrograph of S8;
Figure 10 is the optical microscope photograph of the double emulsion obtained under different rotating speeds, wherein a is 300r/min (scale length is 200 μm), b is 600r/min (scale length is 200 μm), c is 800r/min (scale length is 100 μm), and d is 1000r/min (scale length is 100 μm);
Figure 11 is the electron scanning micrograph of S12;
Figure 12 is the electron scanning micrograph of S13.
Embodiment
For enabling above-mentioned purpose, the feature and advantage of invention more become apparent, below the specific embodiment of the present invention is described in detail.
Set forth a lot of detail in the following description so that fully understand the present invention, but the present invention can also adopt other to be different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar popularization when intension of the present invention, therefore the present invention is by the restriction of following public specific embodiment.
As shown in Figure 1, the preparation method of the porous polymer microsphere that the present invention proposes make use of " phase in version " (phaseinversion) phenomenon of emulsion, transition process as indicated by the arrows, when the interior disperse water phase volume fraction of water-in-oil (W/O) reversed-phase emulsion is increased to a certain degree, the type of emulsion can change, and is namely transformed into the double emulsion of water-in-oil-in-water (W/O/W) from the reversed-phase emulsion of water-in-oil (W/O).If containing polymerisable monomer in oil phase, just can porous polymer microsphere be obtained by initiated polymerization.
The invention provides a kind of preparation method of porous polymer microsphere, comprise the steps:
The first step: obtain oil phase by after oil-soluble monomer, linking agent, emulsifying agent mixing.Those skilled in the art easily know, the ratio of oil-soluble monomer, linking agent and emulsifying agent can be selected according to practical situation, preferably, the mass ratio of oil-soluble monomer, linking agent, emulsifying agent is (3 ~ 8): (1 ~ 4): (1 ~ 3), more preferably, the mass ratio of oil-soluble monomer, linking agent, emulsifying agent is (9 ~ 13): (4 ~ 6): (3 ~ 5).
The general formula of described oil-soluble monomer is preferably CH
2=CR
1r
2, wherein R
1for hydrogen or methyl, R
2for aryl, ester group or COOR
3, R
3for alkyl or haloalkyl, it is more preferably at least one in vinylbenzene, 4-vinyl toluene, 4-ethyl styrene, chloro-styrene, 1-chloro-4-methyl-benzene, butyl acrylate, butyl methacrylate and 2-ethylhexyl acrylate etc.
Described linking agent not only can accelerate polymerization velocity, can also improve the physical strength of porous polymer microsphere, and can introduce functional groups, and its general formula is preferably R
4(CR
5=CH
2)
n, wherein R
4for aryl, alkyl, containing ether or containing ester group, R
5for hydrogen or methyl, n is the integer of 2 ~ 4; It is more preferably at least one in ethylene glycol dimethacrylate, pungent pentanediol acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate and divinylbenzene.
Described emulsifying agent is ionogenic surfactant, and its character can be regulated by pH value and electrolyte concentration, and can stablize positive phase emulsion and can stablize reversed-phase emulsion again, can also stablize High Internal Phase Emulsion, its preferred structural formula is
wherein X is NH
4 +, Na
+, K
+or amine salt, R is saturated or undersaturated aliphatic group or aryl, and a is the integer of 6 ~ 14, b be 1 or 2, c be the integer of 3 ~ 14.Mentioned emulsifier is Y type emulsifying agent, and its constructional feature is the side chain with one or two ester group on longer chain fatty acid, and wherein the carbon chain lengths of longer chain fatty acid is 12 ~ 24; The general structure of preferred emulsifying agent is
wherein X is NH
4 +or Na
+or K
+or amine salt, R is saturated or unsaturated aliphatic hydrocarbyl moiety or aryl, such as CH
3or CH=CH
2or C
6h
5or CH
2cH
2cH
3or CH
2cH
2cH
2cH
2cH
3; Again preferably, described emulsifying agent is 12-acryloxy-9-octadecenoic acid (AOA, 12-acryloxy-9-octadecenoicacid), and its structural formula is as follows:
AOA has activity double key, can participate in the polymerization of monomer and linking agent, does not thus need, except de-emulsifier, to enormously simplify the aftertreatment of product; Emulsifying agent end, with carboxyl, can regulate its amphipathic property (HLB) by adjust ph and electrolyte concentration, so it both can stablize positive phase emulsion also can stablize reversed-phase emulsion; In addition, this emulsifying agent has special y-type structure can be increased sterically hindered in interface, and Ionized end group can improve interface film strength greatly due to stronger electrostatic repulsion.
In order to increase specific surface area and the connectivity of material, also can add pore-creating agent in oil phase, those skilled in the art can select the add-on of pore-creating agent according to the actual requirements, and preferably, the mass ratio of pore-creating agent and oil phase is (0 ~ 5): 5; More preferably, the mass ratio of pore-creating agent and oil phase is (1 ~ 4): 5.In the present invention, pore-creating agent is preferably non-polar organic solvent, and more preferably, pore-creating agent is at least one in toluene, chlorobenzene, chloroform, tetracol phenixin etc.
In the present invention, in order to adjust the time of phase in version, and the size of double emulsion, it mixes with water by the pH value of the oil phase obtained in the adjustable the first step again.Change pH value, phase in version can be caused to shift to an earlier date or postpone, detect whether phase in version occurs by the change of specific conductivity in monitoring mixture.PH is larger, and the aqueous phase massfraction needed for specific conductivity sudden change is less, phase in version occurs more early; PH is less, and the aqueous phase massfraction needed for specific conductivity sudden change is larger, phase in version occurs more late.PH value is larger, and the size that double emulsion drips is less; When pH is weak base scope, be conducive to forming stable double emulsion.Those skilled in the art can select different pH value according to the actual requirements, preferably, the pH value of described oil phase are adjusted to 6 ~ 9; More preferably, the pH value of described oil phase is adjusted to 7.5 ~ 8.5.In addition, pH alkali used is regulated also can to select flexibly according to the actual requirements, as organic basess etc. such as ammoniacal liquor, the NaOH aqueous solution, triethylamines.
Second step: under the condition stirred, the oil phase obtained in the first step is mixed with water, obtained double emulsion.Those skilled in the art easily know, oil phase can be selected water to add in oil phase or by oil phase to be added to the water with mixing of water, and wherein water adds in oil phase obtained double emulsion when there is phase in version, is added by oil phase in aqueous phase and also can obtain double emulsion.Described phase in version refers to the process that emulsion types is transformed to water-in-oil-in-water (W/O/W) double emulsion by oil-in-water (W/O) High Internal Phase Emulsion, can be judged by the sudden change of observation specific conductivity or opticmicroscope morphology change.In W/O High Internal Phase Emulsion before there is not phase in version, because oil phase is as external phase, so specific conductivity is very low; After there is phase in version, aqueous phase is external phase, and specific conductivity has uprushing of the order of magnitude.In addition, High Internal Phase Emulsion and double emulsion have obvious pattern to distinguish, and High Internal Phase Emulsion has the closely packed structure of dispersant liquid drop, and the large drop that double emulsion then comprises many small dropletss by a lot of inside is formed, these two kinds of structures are all micron orders, can be observed by opticmicroscope.
In the present invention, stir and be conducive to accelerating the formation of double emulsion, and make double emulsion drop evenly, preferably, rotating speed is 200r/min to 1000r/min; More preferably, rotating speed is 300r/min to 500r/min.
In second step, the mass ratio of oil phase and water can be selected according to the actual requirements, and when water is added oil phase, water can add at twice, after generation phase in version obtains double emulsion, preferably can continue to stir emulsion for some time, double emulsion size is reduced and homogenizing.After double emulsion homogenizing, the viscosity of system is still very large, and high viscosity is unfavorable for polymerization, can continue to add water makes system viscosity reduce, continue under agitation to add water, the mass ratio of oil phase and water is preferably 1:(12 ~ 25), be more preferably 1:(15 ~ 20).When being added to the water by oil phase, can select disposablely to add or dropwise add, oil phase is same with the mass ratio of water is preferably 1:(12 ~ 25), be more preferably 1:(15 ~ 20).
3rd step: by the double emulsion initiated polymerization obtained in second step, namely obtain porous polymer microsphere.In this step, can use any known method initiated polymerization in this area, cause preferably by gamma Rays, more preferably select co-60 radiation source, its absorbed dose rate is 10 ~ 160Gymin
-1, absorption dose is 30 ~ 100KGy, and irradiation temperature is room temperature.
In the present invention, the initiation of polyreaction also causes by radical initiator, and described radical initiator is preferably peroxide, azo or redox type initiators, as benzoyl peroxide (BPO), Diisopropyl azodicarboxylate (AIBN) etc.When selecting oleosoluble radical initiators, radical initiator can be added in oil phase in a first step, preferably, the mass ratio of radical initiator and oil phase is (0.5 ~ 3.5): 100; When selecting water-soluble free radical initiator, radical initiator can be added to the water, preferably, the mass ratio of radical initiator and oil phase is (0.5 ~ 3.5): 100; When selecting redox type free base initiator, can add in oil phase by its oil-soluble initiator, water soluble starter is added to the water, preferably, oxidisability and reductive free radical initiator mol ratio are 1:1, and the mass ratio of its total mass and oil phase is (0.5 ~ 3.5): 100.In a specific embodiment, by radical initiator initiated polymerization, preferred oil soluble initiator.
The particle diameter of the porous polymer microsphere prepared by method of the present invention can reach 30 μm ~ 6mm, and specific surface area can reach 13.6 ~ 325.8m
2/ g, the porous polymer microsphere particle diameter wherein prepared by gamma Rays initiated polymerization can at 30 μm ~ 300 μm, the particle diameter of the porous polymer microsphere prepared by radical initiator initiated polymerization can at 60 μm ~ 6mm, all good by the size monodisperse of the microballoon prepared by gamma Rays and radical initiator initiated polymerization.
Use vinylbenzene (98%), toluene (analytical pure), ammoniacal liquor (25%), ethanol that Chemical Reagent Co., Ltd., Sinopharm Group produces in an embodiment, use the Vinylstyrene (80%) of Aldrich-Sigmal, use the Ethylene glycol dimethacrylate (95%) of Fluka, use 12-acryloxy-9-octadecenoic acid (AOA) that University of Science and Technology Creative Company produces;
The D2010W type constant speed mechanical stirrer adopting Shanghai Si Le Instrument Ltd. to produce in an embodiment stirs; The specific conductivity of DDS-307 type electric conductivity instrument to double emulsion adopting Shanghai Lei Ci company to produce detects, the DM1000 type opticmicroscope of Leica company is adopted to observe emulsion droplet, utilize the JEOLJSM-6700 type scanning electronic microscope of Hitachi company to detect the pattern of porous polymer microsphere and size, adopt the specific surface area of ASAP2020 type nitrogen adsorption analyser to porous microsphere of Micromeritics company to measure.
Embodiment 1
(1) by 2.25g vinylbenzene, 0.75g Ethylene glycol dimethacrylate and 0.75g12-acryloxy-9-octadecenoic acid, join in 100ml beaker, get a certain amount of ammoniacal liquor with syringe and regulate pH to 8, obtain flaxen thickness opaque liq after mixing, be oil phase;
(2) under the condition of 300r/min stirring, 60.0g distilled water is added drop-wise in oil phase, obtained double emulsion;
(3) transferred to by double emulsion in 100ml wide-necked bottle, after the oxygen in logical nitrogen 30 minutes removing systems, the radiation-initiated polymerization of cobalt source sent into by sealed vessel, and dose rate remains on 30.2Gymin
-1, take out product after 48 hours, use distilled water wash 2 times after sieving, then use washing with alcohol, just obtain porous polymer microsphere S1 after drying, its productive rate can reach 70%.
As shown in Figures 2 and 3, only reversed-phase emulsion can be produced (see Fig. 2 a) after just having started to drip distilled water; When aqueous phase massfraction is less than 90.5%, the specific conductivity of emulsion is less than 5 μ S/cm, and the emulsion formed when aqueous phase massfraction is greater than 74% is the anti-phase High Internal Phase Emulsion (see Fig. 2 b) of thickness; When aqueous phase massfraction is greater than 90.5%, specific conductivity is uprushed to being greater than 30 μ S/cm, can observe the formation (see Fig. 2 c and 2d) of double emulsion.
As shown in Figure 4, surface and the inside of S1 have through open-celled structure, and microballoon mean sizes is 60 μm, and specific surface area is 18.6m
2/ g.
Embodiment 2
Repeat embodiment 1, have following difference: " Ethylene glycol dimethacrylate " replaced with " Vinylstyrene ".
Finally obtain porous polymer microsphere S2, its productive rate can reach 70%.
As shown in Figure 5, surface and the inner hole of S2 are closed, and the mean sizes of microballoon is 52 μm, and specific surface area is 13.6m
2/ g.
Embodiment 3
Repeat embodiment 1, have following difference: also add 3.0g toluene in step (1) as pore-creating agent.
Finally obtain porous polymer microsphere S3, its productive rate can reach 65%.
As shown in Figure 6, the surface of S3 has a lot of nano level aperture, and the mean sizes of microballoon is 41 μm, and specific surface area is 325.8m
2/ g.
Embodiment 4
Repeat embodiment 1, have following difference: by ammoniacal liquor adjust ph to 6.
Finally obtain porous polymer microsphere S4.
As shown in Figure 8 a, the mean sizes of the double emulsion drop of formation is 397 μm.
Embodiment 5
Repeat embodiment 1, have following difference: by ammoniacal liquor adjust ph to 7.
Finally obtain porous polymer microsphere S5.
As shown in Figure 8 b, the mean sizes of the double emulsion drop of formation is 115 μm.
Embodiment 6
Repeat embodiment 1, have following difference: by ammoniacal liquor adjust ph to 8.
Finally obtain porous polymer microsphere S6.
As shown in Figure 8 c, the mean sizes of the double emulsion drop of formation is 52 μm.
Embodiment 7
Repeat embodiment 1, have following difference: by ammoniacal liquor adjust ph to 9.
Finally obtain porous polymer microsphere S7.
As shown in figure 8d, the mean sizes of the double emulsion drop of formation is 30 μm.
As shown in Figure 7, pH is larger, and the aqueous phase massfraction needed for specific conductivity sudden change is less, phase in version occurs more early; PH is less, and the aqueous phase massfraction needed for specific conductivity sudden change is larger, phase in version occurs more late.
As shown in Figure 8, double emulsion drop size increases with pH and reduces, when pH is respectively 6,7,8,9, the mean sizes of the double emulsion drop of formation is respectively 397 μm, 115 μm, 52 μm, 30 μm, and the mean sizes of being polymerized the polymer microballoon obtained thus also can diminish.
Embodiment 8
(1) by 2.25g vinylbenzene, 0.75g Ethylene glycol dimethacrylate and 0.75g12-acryloxy-9-octadecenoic acid, join in 100ml beaker, get a certain amount of ammoniacal liquor with syringe and regulate pH to 8, obtain flaxen opaque mixing liquid after mixing, be oil phase;
(2) under the condition of 300r/min stirring, oil phase is added drop-wise in 60.0g distilled water, obtained double emulsion;
(3) transfer in the wide-necked bottle of 100ml by double emulsion, after the oxygen in logical nitrogen 30 minutes removing systems, the radiation-initiated polymerization of cobalt source sent into by sealed vessel, and dose rate remains on 30.2Gymin
-1, take out product after 48 hours, use distilled water wash 2 times after sieving, then use washing with alcohol, just obtain porous polymer microsphere S8 after drying, its productive rate can reach 75%.
As shown in Figure 9, S8 surface and inside have through open-celled structure, and microsphere average grain diameter is 169 μm, and specific surface area is 20.2m
2/ g.
As shown in Figure 10 a, the mean sizes of the double emulsion drop of formation is 198 μm.
Embodiment 9
Repeat embodiment 8, have following difference: rate-determining steps (2) medium speed is 600r/min.
Finally obtain porous polymer microsphere S9.
As shown in fig. lob, the mean sizes of the double emulsion drop of formation is 98 μm.
Embodiment 10
Repeat embodiment 8, have following difference: rate-determining steps (2) medium speed is 800r/min.
Finally obtain porous polymer microsphere S10.
As shown in figure l oc, the mean sizes of the double emulsion drop of formation is 78 μm.
Embodiment 11
Repeat embodiment 8, have following difference: rate-determining steps (2) medium speed is 1000r/min.
Finally obtain porous polymer microsphere S11.
As shown in fig. 10d, the mean sizes of the double emulsion drop of formation is 55 μm.
As shown in Figure 10, change stir speed (S.S.), the size of double emulsion drop can change thereupon, when rotating speed is respectively 300r/min, 600r/min, 800r/min, 1000r/min, the mean sizes of the double emulsion drop formed is respectively 198 μm, 98 μm, 78 μm, 55 μm, and the mean sizes of being polymerized the polymer microballoon obtained thus also can diminish.
Embodiment 12
(1) by 2.25g vinylbenzene, 0.75g Ethylene glycol dimethacrylate, 0.75g12-acryloxy-9-octadecenoic acid and 0.13g Diisopropyl azodicarboxylate (AIBN), join in 100ml beaker, get a certain amount of ammoniacal liquor with syringe and regulate pH to 8, obtain flaxen thickness opaque liq after mixing, be oil phase;
(2) be added drop-wise in oil phase by 60.0g distilled water under the condition of 300r/min stirring, obtained double emulsion;
(3) transfer in the there-necked flask of 125ml by double emulsion, under the protection of nitrogen, in 70 DEG C of water-baths, 200rpm reacts 24h under stirring; after taking-up product sieves; with distilled water wash 2 times, then use washing with alcohol, after drying, just obtain porous polymer microsphere S12.
As shown in figure 11, the microtexture of S12 has vesicular structure, and microballoon mean sizes is 456 μm, and specific surface area is 15.8m
2/ g.
Embodiment 13
Repeat embodiment 12, have following difference: oil phase is added drop-wise in 60.0g distilled water in (2) by step.
Finally obtain porous polymer microsphere S13.
As shown in figure 12, the microtexture of S13 has vesicular structure, and microballoon mean sizes is 2.97mm, and specific surface area is 14.6m
2/ g.
Although the present invention is described in conjunction with above embodiment, but the present invention is not defined to above-described embodiment, and only by the restriction of claims, those of ordinary skill in the art can easily modify to it and change, but do not leave essential idea of the present invention and scope.
Claims (8)
1. a preparation method for porous polymer microsphere, is characterized in that, comprises the steps:
(1) obtain oil phase by after oil-soluble monomer, linking agent, emulsifying agent mixing, described emulsifying agent is 12-acryloxy-9-octadecenoic acid;
(2) under the condition stirred, the oil phase obtained mixed with water in step (1), obtained double emulsion, the mass ratio of wherein said oil phase and described water is 1:(12 ~ 25);
(3) by double emulsion initiated polymerization obtained in step (2), namely porous polymer microsphere is obtained.
2. the preparation method of porous polymer microsphere according to claim 1, it is characterized in that, the mass ratio of described step (1) oil-soluble monomer, linking agent, emulsifying agent is (3 ~ 8): (1 ~ 4): (1 ~ 3).
3. the preparation method of porous polymer microsphere according to claim 1, is characterized in that, the general formula of described oil-soluble monomer is CH
2=CR
1r
2, wherein R
1for hydrogen or methyl, R
2for aryl, ester group or COOR
3, R
3for alkyl or haloalkyl.
4. the preparation method of porous polymer microsphere according to claim 1, is characterized in that, the general formula of described linking agent is R
4(CR
5=CH
2)
n, wherein R
4for aryl, alkyl, containing ether or containing ester group, R
5for hydrogen or methyl, n is the integer of 2 ~ 4.
5. the preparation method of porous polymer microsphere according to claim 1, is characterized in that, also adds pore-creating agent in the oil phase in described step (1), and the mass ratio of described pore-creating agent and oil phase is (0 ~ 5): 5.
6. the preparation method of porous polymer microsphere according to claim 1, is characterized in that, described step (1) also comprises the pH value of oil phase is adjusted to 6 ~ 9.
7. the preparation method of porous polymer microsphere according to claim 1, is characterized in that, the polyreaction in described step (3) is caused by gamma Rays.
8. the preparation method of porous polymer microsphere according to claim 1, is characterized in that, described in step (3), polyreaction is caused by radical initiator.
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| CN106916260B (en) * | 2017-03-29 | 2019-04-16 | 中山大学惠州研究院 | A kind of preparation method of hud typed porous high water absorption microballoon |
| CN108794798A (en) * | 2018-05-18 | 2018-11-13 | 金学芳 | A kind of preparation method of porous oil-absorbing resin |
| CN109021282B (en) * | 2018-06-26 | 2021-05-14 | 中国工程物理研究院激光聚变研究中心 | Preparation method of monodisperse three-dimensional ordered porous material and material prepared by same |
| CN110833802A (en) * | 2018-08-15 | 2020-02-25 | 漯河医学高等专科学校 | Method for preparing magnetic starch microspheres by gamma-ray irradiation |
| CN110237727B (en) * | 2019-06-19 | 2021-04-23 | 中国科学技术大学 | Preparation method of super-hydrophobic separation membrane |
| CN112876796B (en) * | 2021-03-12 | 2022-01-07 | 四川大学 | Monodisperse polymer porous microsphere and preparation method thereof |
| CN114369278B (en) * | 2022-01-24 | 2023-01-31 | 西南石油大学 | Method for preparing super-hydrophobic porous material based on double-emulsion template |
| CN114538949B (en) * | 2022-02-24 | 2023-04-11 | 洛阳理工学院 | Preparation method of SiOC microspheres with multi-scale pore structure |
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Non-Patent Citations (1)
| Title |
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| "Synthesis and characterization of porous glycidylmethacrylate- divinylbenzene monoliths using the high internal phase emulsion approach";Andrea Barbetta et al.;《Reactive & Functional Polymers》;20090606;第69卷(第9期);724-736 * |
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