CN103435731A - Preparation method of porous polymer microspheres - Google Patents
Preparation method of porous polymer microspheres Download PDFInfo
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- CN103435731A CN103435731A CN2013103863501A CN201310386350A CN103435731A CN 103435731 A CN103435731 A CN 103435731A CN 2013103863501 A CN2013103863501 A CN 2013103863501A CN 201310386350 A CN201310386350 A CN 201310386350A CN 103435731 A CN103435731 A CN 103435731A
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Abstract
The invention provides a preparation method of porous polymer microspheres. The preparation method comprises the following steps: mixing an oil soluble monomer, a cross-linking agent and an emulsifying agent to obtain an oil phase; mixing the oil phase with water to obtain double emulsion; and performing polymerization reaction on the double emulsion to obtain the porous polymer microspheres. According to the preparation method of the porous polymer microspheres, the double emulsion is high in stability, so that an electrolyte and a stabilizer are not needed for improving the stability of the double emulsion; the polymerized porous polymer microspheres are high in yield and have regular shape and high pore connectivity; the microspheres are high in size monodispersity and wide in size adjustment range; and the finally obtained product is simple to process.
Description
Technical field
The present invention relates to the porous microsphere Material Field, particularly a kind of preparation method of porous polymer microsphere.
Background technology
High Internal Phase Emulsion (High Internal Phase Emulsion, HIPE) volume fraction that refers to interior phase (disperse phase) is in the emulsion more than 74%, and it can prepare as template the porous material with multi-stage porous (comprising macropore, mesoporous and micropore) structure that hole connects.This material has good application prospect, for example, owing to having high specific surface area, can be used as support of the catalyst or own as catalyzer; Possess the aperture controllability, can be for separating of filtration art; 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, and wherein oil-in-water-type (O/W) High Internal Phase Emulsion refers to and take the High Internal Phase Emulsion that organic solvent is external phase as disperse phase, the solution of containing water-soluble monomer of take; Water-in-oil (W/O) type High Internal Phase Emulsion is to take the High Internal Phase Emulsion that the aqueous solution is external phase as disperse phase, the oil phase of take containing hydrophobic monomer.
With the common method for preparing porous material, as reversed phase method, phase separation method, solvent pore method etc., compare, the High Internal Phase Emulsion template has advantages of the size of aperture and channel diameter and distributes and can accurately control, its general first initiated polymerization is containing the external phase of monomer, then removes after disperse phase and emulsifying agent the polymer materials that can obtain having vesicular structure.Owing to being the external phase polymerization, the shape of the high internal phase polymeric porous material (polyHIPEs) obtained after polymerization and the shape of reactor are consistent, for example, test tube will obtain columniform bulk material as reactor, and bulk material is unfavorable for 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, obtained the millimetre-sized porous ball of the shape such as spherical, oval, cylinder, but this method die design and manufacturing cost are too high, the particle size minimum also can only control to several millimeters;
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), then High Internal Phase Emulsion is distributed in the PVP aqueous solution, then suspension polymerization obtains polyHIPEs porous polymer microballon.But the shortcoming of this method is High Internal Phase Emulsion, it is a kind of full-bodied emulsion, its dispersion is more difficult, allow to disperse also to be difficult to the spherical of formation rule, and contain ionogen by containing interior water, inside and outside water forms osmotic pressure and causes the double emulsion of formation unstable; Gokmen etc. (Macromolecules2009,42,9289) are distributed to the anti-phase High Internal Phase Emulsion prepared in the PVA aqueous solution by micro-fluidic technologies, by the ultraviolet initiated polymerization, obtain porous polymer particles (ball and rod).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-soluble monomer, linking agent, emulsifying agent are obtained to oil phase after mixing;
(2) under the condition stirred, the oil phase obtained in step (1) is mixed with water, make double emulsion;
(3) by the double emulsion initiated polymerization made in step (2), obtain porous polymer microsphere.
Preferably, in described step (1), the mass ratio of 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, R wherein
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, R wherein
4for aryl, alkyl, containing ether or containing ester group, R
5for hydrogen or methyl, the integer that n is 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, the integer that a is 6～14, and b is 1 or 2, the c integer that is 3～14.
Preferably, in the oil phase in described step (1), also add pore-creating agent, 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) causes by gamma Rays.
Preferably, described in step (3), polyreaction causes 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 to add the stability that ionogen and stablizer increase double emulsion; The porous polymer microsphere productive rate that polymerization obtains is high, regular shape, and the connectivity in hole is good; The size monodispersity of microballoon is good, and the size regulation range is wide, and the aftertreatment of the final product obtained is simple and easy.
The accompanying drawing explanation
Fig. 1 is the mechanism schematic diagram that different hydrophilic lipophilic emulsifier and different water oil ratio form the emulsion type;
Fig. 2 is the photo of S1 at the opticmicroscope of the emulsion of different watr-proportion formation, wherein a is water massfraction 60wt% (scale length is 100 μ m), b is water massfraction 76wt% (scale length is 100 μ m), c is water massfraction 92wt% (scale length is 100 μ m), and d is water massfraction 92wt% (scale length is 50 μ m);
The specific conductivity of Fig. 3 emulsion that to be S1 form at different watr-proportions is with the variation diagram of water massfraction;
The electron scanning micrograph that Fig. 4 is S1;
The electron scanning micrograph that Fig. 5 is S2;
The electron scanning micrograph that Fig. 6 is S3;
The water massfraction that Fig. 7 is the emulsion phase transition point is with the change curve of pH value;
The optical microscopy map of double emulsion when Fig. 8 is different pH value, wherein a is pH=6, and b is pH=7, and c is pH=8, and d is pH=9, scale length is all 200 μ m;
The electron scanning micrograph that Fig. 9 is S8;
The optical microscope photograph that Figure 10 is the double emulsion that obtains under different rotating speeds, wherein a is 300r/min (scale length is 200 μ m), b is 600r/min (scale length is 200 μ m), c is 800r/min (scale length is 100 μ m), and d is 1000r/min (scale length is 100 μ m);
The electron scanning micrograph that Figure 11 is S12;
The electron scanning micrograph that Figure 12 is S13.
Embodiment
For above-mentioned purpose, the feature and advantage that make invention can become apparent more, below the specific embodiment of the present invention is described in detail.
A lot of details have been set forth 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 and implement, those skilled in the art can be in the situation that do similar popularization without prejudice to intension of the present invention, so the present invention is not subject to 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 has utilized emulsion " to change mutually " (phase inversion) phenomenon, transition process is as indicated as arrow, 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 from the reversed-phase emulsion of water-in-oil (W/O), is transformed into the double emulsion of water-in-oil-in-water (W/O/W).If contain polymerisable monomer in oil phase, by initiated polymerization, just can obtain porous polymer microsphere.
The invention provides a kind of preparation method of porous polymer microsphere, comprise the steps:
The first step: oil-soluble monomer, linking agent, emulsifying agent are obtained to oil phase after 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, R wherein
1for hydrogen or methyl, R
2for aryl, ester group or COOR
3, R
3for alkyl or haloalkyl, be 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 be accelerated 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, R wherein
4for aryl, alkyl, containing ether or containing ester group, R
5for hydrogen or methyl, the integer that n is 2～4; Be more preferably at least one in ethylene glycol dimethacrylate, hot 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, can stablize positive phase emulsion and can stablize reversed-phase emulsion again, can also stablize High Internal Phase Emulsion, and its preferred structural formula is
wherein X is NH
4 +, Na
+, K
+or amine salt, R is saturated or undersaturated aliphatic group or aryl, the integer that a is 6～14, and b is 1 or 2, the c integer that is 3～14.Mentioned emulsifier is Y type emulsifying agent, its constructional feature be on longer chain fatty acid with the side chain of one or two ester group, 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, for example 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-octadecenoic acid), and its structural formula is as follows:
AOA has activity double key, can participate in the polymerization of monomer and linking agent, thereby does not need, except de-emulsifier, greatly to have simplified the aftertreatment of product; The emulsifying agent end, with carboxyl, can be regulated its amphipathic property (HLB) by regulating pH value 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 in interface sterically hinderedly, and Ionized end group is because stronger electrostatic repulsion can improve the interface film strength greatly.
For specific surface area and the connectivity that increases material, also can in oil phase, add pore-creating agent, 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 changed mutually, and the size of double emulsion, can regulate the pH value of the oil phase obtained in the first step and again it be mixed with water.Change change pH values, can cause changing mutually in advance or postpone, can detect and whether occur to change mutually by the variation of specific conductivity in the monitoring mixture.PH is larger, and the water massfraction that specific conductivity is suddenlyd change required is less, occurs to change mutually; PH is less, and the water massfraction that specific conductivity is suddenlyd change required is larger, occurs to change mutually more late.The pH value is larger, and the size that double emulsion drips is less; When pH is the weak base scope, be conducive to form stable double emulsion.Those skilled in the art can select different pH values 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, regulate pH alkali used and also can select flexibly according to the actual requirements, as organic basess such as ammoniacal liquor, the NaOH aqueous solution, triethylamines etc.
Second step: under the condition stirred, the oil phase obtained in the first step is mixed with water, make double emulsion.Those skilled in the art easily know, oil phase can be selected water is added in oil phase or by oil phase and is added to the water with mixing of water, and wherein water adds in oil phase while occurring to change mutually and makes double emulsion, and oil phase is added in water and also can obtain double emulsion.The described process that refers to that the emulsion type is transformed to water-in-oil-in-water (W/O/W) double emulsion by oil-in-water (W/O) High Internal Phase Emulsion that changes mutually, can judge by observing specific conductivity sudden change or opticmicroscope morphology change.Transformation mutually before not occurring, because oil phase is as external phase, so specific conductivity is very low in the W/O High Internal Phase Emulsion; After occurring to change mutually, water 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 difference, and High Internal Phase Emulsion has the closely packed structure of dispersant liquid drop, and the large drop that double emulsion comprises many small dropletss by a lot of inside forms, these two kinds of structures are all micron orders, can observe by opticmicroscope.
In the present invention, stir and be conducive to accelerate the formation of double emulsion, and make the drop of double emulsion more even, 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 to oil phase, water can add at twice, after occurring to change mutually and obtaining double emulsion, preferably can continue to stir emulsion for some time, and the double emulsion size is reduced and homogenizing.After the double emulsion homogenizing, the viscosity of system is still very large, and high viscosity is unfavorable for polymerization, can continue to add water reduces system viscosity, continue under agitation to add water, the mass ratio of oil phase and water is preferably 1:(12～25), 1:(15～20 more preferably).When oil phase is added to the water, can select disposablely to add or dropwise add, the mass ratio of oil phase and water is preferably 1:(12～25 equally), 1:(15～20 more preferably).
The 3rd step: the double emulsion initiated polymerization by making in second step obtains porous polymer microsphere.In this step, can use any known method initiated polymerization in this area, preferably by gamma Rays, cause, more preferably select the co-60 radiation source, its absorbed dose rate is 10～160Gymin
-1, absorption dose is 30～100KGy, irradiation temperature is room temperature.
In the present invention, the initiation of polyreaction also can cause by radical initiator, and described radical initiator is preferably peroxide, azo or redox class initiator, as benzoyl peroxide (BPO), Diisopropyl azodicarboxylate (AIBN) etc.When selecting the oil soluble radical initiator, radical initiator can be added in the first step in oil phase, preferably, the mass ratio of radical initiator and oil phase is (0.5～3.5): 100; While being elected to water-soluble 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, its oil-soluble initiator can be added in oil phase, 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 the 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 μ m～6mm, and specific surface area can reach 13.6～325.8m
2/ g, the porous polymer microsphere particle diameter wherein prepared by the gamma Rays initiated polymerization can be at 30 μ m～300 μ m, the particle diameter of the porous polymer microsphere prepared by the radical initiator initiated polymerization can be at 60 μ m～6mm, all good by the size monodispersity of gamma Rays and the prepared microballoon of radical initiator initiated polymerization.
The vinylbenzene (98%), toluene (analytical pure), ammoniacal liquor (25%), the ethanol that use in an embodiment Chemical Reagent Co., Ltd., Sinopharm Group to produce, use the Vinylstyrene (80%) of Aldrich-Sigmal, use the Ethylene glycol dimethacrylate (95%) of Fluka, the 12-acryloxy that uses University of Science and Technology Creative Company to produce-9-octadecenoic acid (AOA);
The D2010W type constant speed mechanical stirrer that adopts in an embodiment Shanghai Si Le Instrument Ltd. to produce is stirred; The DDS-307 type electric conductivity instrument that adopts Shanghai Lei Ci company to produce is detected the specific conductivity of double emulsion, adopt the DM1000 type opticmicroscope of Leica company to be observed emulsion droplet, the JEOL JSM-6700 type scanning electronic microscope of utilizing Hitachi company is detected pattern and the size of porous polymer microsphere, adopts the ASAP2020 type nitrogen adsorption analyser of Micromeritics company to be measured the specific surface area of porous microsphere.
Embodiment 1
(1) by 2.25g vinylbenzene, 0.75g Ethylene glycol dimethacrylate and 0.75g12-acryloxy-9-octadecenoic acid, join in the 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 stirred at 300r/min, 60.0g distilled water being added drop-wise to oil phase, make double emulsion;
(3) double emulsion is transferred in the 100ml wide-necked bottle, after the oxygen that logical nitrogen is removed in system in 30 minutes, sealed vessel is sent into the radiation-initiated polymerization of cobalt source, and dose rate remains on 30.2Gymin
-1, take out product after 48 hours, sieve rear with distilled water wash 2 times, 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, just started to drip after distilled water and only can produce reversed-phase emulsion (referring to Fig. 2 a); When the water massfraction is less than 90.5%, the specific conductivity of emulsion is less than 5 μ S/cm, the anti-phase High Internal Phase Emulsion (referring to Fig. 2 b) that the emulsion formed when the water massfraction is greater than 74% is thickness; When the water massfraction is greater than 90.5%, specific conductivity is uprushed to being greater than 30 μ S/cm, can observe the formation (referring to Fig. 2 c and 2d) of double emulsion.
As shown in Figure 4, the surface of S1 and the inner open-celled structure with perforation, the microballoon mean sizes is 60 μ m, specific surface area is 18.6m
2/ g.
Embodiment 2
Repeat embodiment 1, following difference is arranged: " Ethylene glycol dimethacrylate " replaced with to " Vinylstyrene ".
Finally obtain porous polymer microsphere S2, its productive rate can reach 70%.
As shown in Figure 5, the surface of S2 and inner hole are sealed, and the mean sizes of microballoon is 52 μ m, and specific surface area is 13.6m
2/ g.
Embodiment 3
Repeat embodiment 1, following difference is arranged: in step (1), also added 3.0g toluene 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 apertures, and the mean sizes of microballoon is 41 μ m, and specific surface area is 325.8m
2/ g.
Embodiment 4
Repeat embodiment 1, following difference is arranged: with ammoniacal liquor, regulate pH value 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 μ m.
Embodiment 5
Repeat embodiment 1, following difference is arranged: with ammoniacal liquor, regulate pH value 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 μ m.
Embodiment 6
Repeat embodiment 1, following difference is arranged: with ammoniacal liquor, regulate pH value 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 μ m.
Embodiment 7
Repeat embodiment 1, following difference is arranged: with ammoniacal liquor, regulate pH value to 9.
Finally obtain porous polymer microsphere S7.
As shown in Fig. 8 d, the mean sizes of the double emulsion drop of formation is 30 μ m.
As shown in Figure 7, pH is larger, and the water massfraction that specific conductivity is suddenlyd change required is less, occurs to change mutually; PH is less, and the water massfraction that specific conductivity is suddenlyd change required is larger, occurs to change mutually more late.
As shown in Figure 8, the double emulsion drop size increases and reduces with pH, pH is respectively 6,7,8,9 o'clock, and the mean sizes of the double emulsion drop of formation is respectively 397 μ m, 115 μ m, 52 μ m, 30 μ m, and the mean sizes of the polymer microballoon that polymerization obtains 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 the 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 stirred at 300r/min, oil phase being added drop-wise to 60.0g distilled water, make double emulsion;
(3) double emulsion is transferred in the wide-necked bottle of 100ml, after the oxygen that logical nitrogen is removed in system in 30 minutes, sealed vessel is sent into the radiation-initiated polymerization of cobalt source, and dose rate remains on 30.2Gymin
-1, take out product after 48 hours, sieve rear with distilled water wash 2 times, 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 the inner open-celled structure with perforation, microsphere average grain diameter is 169 μ m, 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 μ m.
Embodiment 9
Repeat embodiment 8, following difference is arranged: controlling step (2) medium speed is 600r/min.
Finally obtain porous polymer microsphere S9.
As shown in Figure 10 b, the mean sizes of the double emulsion drop of formation is 98 μ m.
Embodiment 10
Repeat embodiment 8, following difference is arranged: controlling step (2) medium speed is 800r/min.
Finally obtain porous polymer microsphere S10.
As shown in Figure 10 c, the mean sizes of the double emulsion drop of formation is 78 μ m.
Embodiment 11
Repeat embodiment 8, following difference is arranged: controlling step (2) medium speed is 1000r/min.
Finally obtain porous polymer microsphere S11.
As shown in Figure 10 d, the mean sizes of the double emulsion drop of formation is 55 μ m.
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 μ m, 98 μ m, 78 μ m, 55 μ m, and the mean sizes of the polymer microballoon that polymerization obtains 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 the 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 stirred at 300r/min, by being added drop-wise to oil phase in 60.0g distilled water, make double emulsion;
(3) double emulsion is transferred in the there-necked flask of 125ml, under the protection of nitrogen, in 70 ℃ of water-baths, 200rpm reacts 24h under stirring; after the taking-up product sieves; with distilled water wash 2 times, then use washing with alcohol, just obtain porous polymer microsphere S12 after drying.
As shown in figure 11, the microtexture of S12 has vesicular structure, and the microballoon mean sizes is 456 μ m, and specific surface area is 15.8m
2/ g.
Embodiment 13
Repeat embodiment 12, following difference is arranged: step is added drop-wise to oil phase in 60.0g distilled water in (2).
Finally obtain porous polymer microsphere S13.
As shown in figure 12, the microtexture of S13 has vesicular structure, and the 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 being subject to the restriction of claims, those of ordinary skills can easily modify to it and change, but do not leave essence design of the present invention and scope.
Claims (10)
1. the preparation method of a porous polymer microsphere, is characterized in that, comprises the steps:
(1) oil-soluble monomer, linking agent, emulsifying agent are obtained to oil phase after mixing;
(2) under the condition stirred, the oil phase obtained in step (1) is mixed with water, make double emulsion;
(3) by the double emulsion initiated polymerization made in step (2), obtain porous polymer microsphere.
2. the preparation method of porous polymer microsphere according to claim 1, is characterized in that, in described step (1), the mass ratio of 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, R wherein
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, R wherein
4for aryl, alkyl, containing ether or containing ester group, R
5for hydrogen or methyl, the integer that n is 2～4.
5. the preparation method of porous polymer microsphere according to claim 1, is characterized in that, 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, the integer that a is 6～14, and b is 1 or 2, the c integer that is 3～14.
6. the preparation method of porous polymer microsphere according to claim 1, is characterized in that, in the oil phase in described step (1), also adds pore-creating agent, and the mass ratio of described pore-creating agent and oil phase is (0～5): 5.
7. 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.
8. the preparation method of porous polymer microsphere according to claim 1, is characterized in that, in described step (2), the mass ratio of oil phase and water is 1:(12～25).
9. the preparation method of porous polymer microsphere according to claim 1, is characterized in that, the polyreaction in described step (3) causes by gamma Rays.
10. the preparation method of porous polymer microsphere according to claim 1, is characterized in that, described in step (3), polyreaction causes by radical initiator.
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Cited By (9)
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| CN103897099A (en) * | 2014-03-27 | 2014-07-02 | 中科院广州化学有限公司南雄材料生产基地 | Filter-pressed light pervious material and preparation method thereof |
| CN106916260A (en) * | 2017-03-29 | 2017-07-04 | 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 |
| CN109021282A (en) * | 2018-06-26 | 2018-12-18 | 中国工程物理研究院激光聚变研究中心 | The preparation method of monodisperse three dimensional ordered porous material and its material obtained |
| CN110237727A (en) * | 2019-06-19 | 2019-09-17 | 中国科学技术大学 | A kind of preparation method of super-hydrophobic seperation film |
| 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 |
| CN112876796A (en) * | 2021-03-12 | 2021-06-01 | 四川大学 | Monodisperse polymer porous microsphere and preparation method thereof |
| CN114369278A (en) * | 2022-01-24 | 2022-04-19 | 西南石油大学 | Method for preparing super-hydrophobic porous material based on double-emulsion template |
| CN114538949A (en) * | 2022-02-24 | 2022-05-27 | 洛阳理工学院 | Preparation method of SiOC microspheres with multi-scale pore structure |
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2013
- 2013-08-30 CN CN201310386350.1A patent/CN103435731B/en not_active Expired - Fee Related
Non-Patent Citations (1)
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| ANDREA BARBETTA ET AL.: ""Synthesis and characterization of porous glycidylmethacrylate- divinylbenzene monoliths using the high internal phase emulsion approach"", 《REACTIVE & FUNCTIONAL POLYMERS》, vol. 69, no. 9, 6 June 2009 (2009-06-06), pages 724 - 736, XP026375345 * |
Cited By (15)
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| CN103897099B (en) * | 2014-03-27 | 2016-08-10 | 中科院广州化学有限公司南雄材料生产基地 | A kind of filter pressing lightweight seepy material and preparation method thereof |
| CN103897099A (en) * | 2014-03-27 | 2014-07-02 | 中科院广州化学有限公司南雄材料生产基地 | Filter-pressed light pervious material and preparation method thereof |
| 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 |
| CN106916260A (en) * | 2017-03-29 | 2017-07-04 | 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 |
| CN109021282A (en) * | 2018-06-26 | 2018-12-18 | 中国工程物理研究院激光聚变研究中心 | The preparation method of monodisperse three dimensional ordered porous material and its material obtained |
| 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 |
| CN110237727A (en) * | 2019-06-19 | 2019-09-17 | 中国科学技术大学 | A kind of preparation method of super-hydrophobic seperation film |
| CN110237727B (en) * | 2019-06-19 | 2021-04-23 | 中国科学技术大学 | Preparation method of super-hydrophobic separation membrane |
| CN112876796A (en) * | 2021-03-12 | 2021-06-01 | 四川大学 | Monodisperse polymer porous microsphere and preparation method thereof |
| CN112876796B (en) * | 2021-03-12 | 2022-01-07 | 四川大学 | Monodisperse polymer porous microsphere and preparation method thereof |
| CN114369278A (en) * | 2022-01-24 | 2022-04-19 | 西南石油大学 | Method for preparing super-hydrophobic porous material based on double-emulsion template |
| 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 |
| CN114538949A (en) * | 2022-02-24 | 2022-05-27 | 洛阳理工学院 | Preparation method of SiOC microspheres with multi-scale pore structure |
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