CN102443088A - Uniform-size small-particle-size super-macroporous polymer microspheres and preparation method thereof - Google Patents
Uniform-size small-particle-size super-macroporous polymer microspheres and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of uniform-particle-size controllable small-particle-size super-macroporous polymer microspheres and a product thereof. The method comprises the following steps of: dispersing an oil phase containing a monomer and a high-content surfactant into a water phase; preparing first milk with a quick membrane emulsifying method; and further heating and curing to obtain super-macroporous microspheres, wherein micropores of 5-20 nanometers and ultra-large pores of over 50-100 nanometers and 100 nanometers are formed inside the super-macroporous microspheres; ultra-large pores of over 50-100 nanometers and 100 nanometers account for 10-60 percent of the internal pore volume of the microspheres; the particle sizes of the microspheres are 0.5-25 mum; the porosity is 30-80 percent; and the particle size distribution coefficient is less than 20 percent.
Description
Technical field
The present invention relates to a kind of polymer microballoon and preparation method thereof, be specifically related to controlled super large pore polymer microsphere of a kind of small particle size and uniform particle diameter and preparation method thereof.
Background technology
Along with development of biology, a large amount of biomacromolecules such as protein, polypeptide and nucleic acid etc. need separate, analysis and purifying.Column chromatography is the important means of separation and purification of biological macromolecule, and separating medium is the core of column chromatography, so the focus that develops into various countries' concern of separating medium has also obtained fast development.
Because biomacromolecule is had higher requirement to separating medium in the complicacy and the variety of aspects such as molecular structure, physico-chemical property and biological activity, hope can obtain to analyze fast and efficiently, separate.Yet; General porous medium is to utilize being separated and forming the duct between the poor solvent of cross-linked polymer; The aperture that this mechanism forms is that nano level
is because the aperture is less; The mass transfer process of moving phase in the duct mainly relies on molecular diffusion to accomplish; Cause the mass transfer velocity of biomacromolecule slow, disengaging time is long, active and yield decline.
In order to overcome the deficiency of conventional aperture medium; The researchist proposes to use the synthetic separating medium of the oversized hole with double hole channel; Its oversized hole (greater than 10 to 20 times of biomacromolecule diameter) can allow biomacromolecule to come in and go out fast; Can increase substantially the velocity of separation of protein-based biomacromolecule, aperture (diffusion hole) then can provide sufficiently high specific surface area, improves the loading capacity of medium greatly.
1991, propositions such as Regnier had perfusion chromatogram (Perfusion Chromatography) medium of double hole channel structure, and on Nature, have delivered relevant paper.Because with the perfusion chromatographic media is the applications well prospect of double hole channel oversized hole synthetic polymer medium in separation and purification of biological macromolecule of representative; Make its preparation and applied research receive domestic and international investigator's great attention, several kinds of pore methods below also having developed always:
(1) with the polymkeric substance be the suspension polymerization of pore-creating agent, this method is to replace liquid porogen commonly used with soluble polymer.Along with monomeric polymerization in the drop, produce between newly-generated cross-linked polymer and the pore-creating agent polymkeric substance and be separated, extract the pore-creating agent polymkeric substance after the finishing polymerization and can obtain bigger aperture; But its shortcoming is that the difficulty that is separated between two kinds of polymkeric substance is bigger, be difficult in to form the macropore that runs through in the synthetic medium, and the pore-creating agent polymkeric substance also is difficult to extraction totally.
(2) nano particle coacervation, commercial POROS perfusion chromatographic media prepares with this method, and has been applied in the separation and purification of protein and other, has shown that velocity of separation is fast, column capacity is high and the productive rate advantages of higher.The POROS medium has two types of holes: the through hole of
; (throughpores) and the diffusion hole of
; (diffusionpores).Moving phase when separating application in the through hole is to flow mass transfer velocity fast (shown in Fig. 1 b) to streamed; Diffusion hole then can provide sufficiently high specific surface area, has guaranteed the loading capacity of medium.Yet; The POROS medium is that employing nano-scale particle " bonding " cluster, gathering are agglomerating; And then the method that forms micron particles prepares; Therefore, control relatively difficulty of aperture, cause problems such as repeatability is relatively poor between product batches, yield is low through the irregular state of aggregation between the control nano particle.
(3) High Internal Phase Emulsion polymerization (polyHIPE, high internal phase emulsion polymer).When medium prepares a large amount of water is dispersed in the monomer (the water volume surpasses 70%) with the form of water droplet and processes w/o type High Internal Phase Emulsion (HIPE), be dispersed in outer aqueous phase to High Internal Phase Emulsion through choosing suitable stabilizers again, process emulsion.After the polymerization, just form the macropore (Fig. 2) that runs through each other in the medium.The dielectric attribute of this Magnapore by name is aperture big (1-50 μ m), density low (0.05-0.2g/cm3), porosity high (more than 70%).But just since its aperture big, though on hole wall, also prepare aperture, specific surface area still very low (2-30m2/g), and the physical strength of medium a little less than.In addition, the less stable of emulsion in polymerization process of 70% high interior water must strictly be controlled prescription and polymerization process could prepare successfully.
(4) be the method for pore-creating agent with the inorganic particle: the Sun Yan seminar of University Of Tianjin has overcome the difficult point of above-mentioned preparation method; With the inorganic particle is pore-creating agent; Prepared and both contained the 10-90nm micropore, contained the medium of 180-4000nm oversized hole again, the specific surface area of medium is 91.3m
2/ g, and discover the wide aperture that will obtain running through, the volume content of inorganic particle should be 10-40%.Though can being embedded in hydrophilic inorganic particle, this method reaches very high embedding rate in the wetting ability agarose; But the consistency between most synthesized polymer materials (like PS etc.) and the inorganic particle is poor, a large amount of inorganic particles is embedded in to reach higher embedding rate in the synthesized polymer material and remain one and be difficult to the problem that solves.
(5) multiple emulsion process (double emulsification): Gustavsson etc. are preparation oversized hole agarose medium, and researchdevelopment goes out multiple emulsion process.It is 20-100nm that Sun Yan etc. also prepare micropore in this way, and oversized hole is 300-4000nm, and specific surface area is 52.1m
2The synthetic medium of/g.Identical on this method principle with the High Internal Phase Emulsion polymerization, need two step emulsion processes, and its stir speed (S.S.) is up to 8000rpm during the preparation colostrum, if carry out scale operation, the preparation of colostrum and stability thereof etc. have certain degree of difficulty.
It is the super large pore polymer microsphere of 500-800nm that contriver of the present invention adopts tensio-active agent reverse micelle swollen method successfully to prepare the aperture, and obtains good application and result in, fast separating and purifying efficient at protein and immobilized enzyme, the SPE.
At first to file CN 1903890A and WO 2008/064525A1 preparation method of a kind of super large pore polymer microsphere and products thereof is disclosed all like the contriver; Said preparation method comprises: (1) is in the mixed solution of monomer and linking agent; Add initiator, thinner and tensio-active agent; Stir, dissolve fully until initiator; (2) stablizer is dissolved in zero(ppm) water, is mixed with the certain density aqueous solution, as water; (3) oil phase is added aqueous phase, with the speed stirring of 100～300rpm, logical nitrogen 1h, polymerization 24h under 30～100 ℃ of temperature; (4) after reaction finishes, filter,, after component cleaning, drying such as thinner, tensio-active agent, promptly get oversized hole bioseparation medium with zero(ppm) water and ethanol cleaning products several.
But the above-mentioned method for preparing the employing of oversized hole microballoon all is suspension polymerizations, and the microspherulite diameter that therefore prepares is big and homogeneity is relatively poor.For separation and purification is used, the particle diameter of medium and all once separating resulting was had material impact.Therefore; The present invention proposes a kind of size homogeneous, controlled small particle size oversized hole microballoon and preparation method thereof; The raising of microballoon dimensional homogeneity can effectively improve the resolving power of chromatography column, and the reducing of particle diameter can increase stage number and then increase separating effect, and oversized hole then provides velocity of separation faster; Can realize that separated material efficiently separates fast, guarantees good productive rate and activity.
Summary of the invention
To the deficiency of prior art, one of the object of the invention is the small particle size super large pore polymer microsphere that provides a kind of uniform particle diameter controlled.The method that said microballoon adopts quick film emulsification and suspension polymerization to combine can be prepared simplely and is suitable as performance liquid chromatography and analyzes the chromatographic stationary controlled small particle size super large pore polymer microsphere of uniform particle diameter of matrix mutually.
The controlled small particle size super large pore polymer microsphere preparation method of said uniform particle diameter is: in containing monomeric oil phase, add the tensio-active agent of high level, be distributed to water after, form colostrum after crossing film, further polymerization promptly gets product.
The oversized hole microballoon of said small particle size, size homogeneous; Its inside had both had the micropore of 5-20nm; Have the above oversized hole of 50-100nm and 100nm again, wherein the above oversized hole of 50-100nm and 100nm accounts for the 10-60% of the inner pore volume of microballoon, is preferably 20-40%.Microspherulite diameter is 0.5～25 μ m, and porosity is 30%～80%, size distribution coefficient＜20%.
Wherein 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.
One of the object of the invention also is to provide a kind of purposes of above-mentioned microballoon, and it can be used for chromatograph packing material, modifies the functional supports of back as ionite, solid-phase synthesized carrier, enzyme immobilization carrier, pharmaceutical carrier, analyzing and testing reagent, food and makeup.
One of the object of the invention also is also to provide the preparation method of the controlled small particle size super large pore polymer microsphere of a kind of uniform particle diameter; Through in oil phase, adding the tensio-active agent and the proper amount of diluting of high level, cross film earlier and prepare the controlled small particle size super large pore polymer microsphere of uniform particle diameter through suspension polymerization again.
Said preparation method preferably includes following steps:
The oil phase that (1) will contain monomer, linking agent, initiator, thinner and oil soluble surfactant mixes;
(2) preparation contains stablizer and optional water soluble surfactant active's water;
(3) the said oil phase that mixes is joined said water, continue to be stirred to solution and be creamy white, guarantee that swelling is abundant, form W/O/W type co-continuous phase emulsion this moment;
(4) film through different apertures under pressure with said emulsion;
(5) cross film according to uniform particle diameter degree one or many, emulsion is solidified behind the film excessively;
Alternatively, (6) washing is dry, makes uniform particle diameter, controlled small particle size super large pore polymer microsphere.
In the step (1), said tensio-active agent is an oil soluble surfactant, and it is different from said linking agent, initiator, thinner and stablizer.Said oil soluble surfactant is selected from non-ionics, ionogenic surfactant, amphipathic embedding end multipolymer.Said oil soluble surfactant can be sorbitan fatty acid ester, polyglycerol fatty acid ester, polyoxyethylene fatty acid ester, TX10 class, like sorbitan monooleate, paraoctyl phenol Soxylat A 25-7 etc.Said tensio-active agent is preferably sorbitan monooleate, paraoctyl phenol Soxylat A 25-7, PO-500, Arlacel 83, AOT or its mixture.
The mass content of said oil soluble surfactant in oil phase is 5%～80%, preferred 10%～70%, further preferred 25%～60%.
The monomer of the preferably any oil soluble band of the monomer vinyl that the present invention uses and their mixture; Can be vinyl, styrenic, methacrylic, acrylic acid or the like, methyl acrylic ester, esters of acrylic acid, methacryloyl amine, acrylamide monomers, and epoxies and vinyl acetate esters monomer etc.The mass content of said monomer in oil phase is 1%～90%, preferred 10%～60%, further preferred 25%～45%.
Said linking agent is the compound of any oil-soluble, band bi-vinyl or trivinyl, can be the bi-vinyl aromatics, like Vinylstyrene; Can be acrylic ester compound, like TGM 1, vinylformic acid trimethoxy propane trimethyl ester etc.The mass content of said linking agent in oil phase is 1%～90%, preferred 5%～60%, further preferred 10%～45%.
Said thinner mainly plays a part to suppress secondary nucleation in oil phase, when add-on is high, also can play the effect of perforating agent.Said thinner can be alkane, like heptane, dodecyl, n-Hexadecane, octane-iso etc.; Can be ethers, like sherwood oil etc.; Can be the benzene class, like toluene etc.Thinner also can use can be dissolved in the polymer of monomers class, such as styrene monomer.Polymkeric substance such as PS, Rohm tech inc can be dissolved in vinylbenzene, and polymkeric substance such as PS, Rohm tech inc just can be as the thinner of vinylbenzene system so.For another example to the SY-Monomer G monomer; Polymkeric substance such as poly (glycidyl methacrylate), Rohm tech inc can be dissolved in SY-Monomer G; Polymkeric substance such as poly (glycidyl methacrylate), Rohm tech inc just can be as the thinner of SY-Monomer G system so, and being dissolved in polymer of monomers is known to the researchist of this area.When not adding thinner in the oil phase, also can obtain the oversized hole microballoon, so the massfraction of thinner in oil phase be 0%～80%, preferred 0～60%, but be limited in 0%～50% scope better.
Said initiator can influence monomer polymerization speed, finally influences the productive rate of microballoon, therefore will select suitable initiator and consumption thereof.The used initiator of the present invention can be the peroxide initiator, like Lucidol; Can be azo-initiator, like Diisopropyl azodicarboxylate; It also can be their mixture.The consumption of oil-soluble polymerization initiator is 0.01%～10% of all polymerisable monomer quality, preferred 0.05%～8%, further preferred 0.1%～6%.
Step (2) aqueous phase is selected suitable stablizer of concentration and optional water soluble surfactant active, need contain a kind of stablizer at least.Said stablizer can make oil phase liquid drip and stably be dispersed in aqueous phase, and reduces or prevent the slimeball phenomenon.Said stablizer can be used water-soluble polymers, and like Z 150PH, gelatin, Mierocrystalline cellulose, Vinylpyrrolidone polymer etc., content is 0.1～10% of water quality, and preferred 0.5～8%, further preferred 0.5%～5%.
Said water soluble surfactant active can use sodium lauryl sulphate, sodium laurylsulfonate etc.The water soluble surfactant active is nonessential additive, so the person of ordinary skill in the field can select whether to add according to circumstances, its content be controlled at the water quality 10% in, in preferred 8%, further in preferred 5%.Said water soluble surfactant active be controlled at 10% grade " in ", comprise that content is 0.
In step (3), high-load said oil soluble surfactant forms a large amount of reverse micelles in oil phase, be distributed to water after; The spontaneous suction of tensio-active agent reverse micelle in the oil phase drop; Be swelled into continuous passage, form a kind of W/O/W type co-continuous phase emulsion, this moment, emulsion was creamy white.
Said emulsion under the pressure of 0KPa～5MPa, is preferably 10KPa～2MPa, and under further preferred 50KPa～1.5MPa, one or many is crossed film, and said membrane pore size is 1～30 μ m, preferred 5～25 μ m, further preferred 10～25 μ m.Cross the film number of times and once look all and confirm, be generally preferred 1～3 time 1～5 time.Form the homogeneous emulsion after crossing film, further solidify balling-up.
Polymerization is cleaned excessive tensio-active agent and thinner after accomplishing alternatively, promptly gets the super large pore polymer microsphere of small particle size.The structure of microballoon such as aperture, porosity, specific surface area etc. can be controlled through reconciliation statement surface-active agent, thinner and degree of crosslinking etc.This method does not receive the restriction of polymerization system, can select for use different monomers to prepare microballoon as required.
Processing after said polymerization is accomplished refers to remove components such as residual unconverted monomer and tensio-active agent, thinner.Said aftertreatment comprises that microballoon is used hot water and washing with alcohol respectively for several times, uses the acetone extracting then.After cleaning up, drying obtains product.
The small particle size super large pore polymer microsphere of the size homogeneous of the present invention's preparation; Microballoon inside had both had the micropore of 5-20nm, had the above oversized hole of 50-100nm and 100nm again, and wherein the above oversized hole of 50-100nm and 100nm accounts for the 10-60% of the inner pore volume of microballoon; Be preferably 20-40%; The microballoon porosity is 30%～80%, and particle diameter is controlled in 0.5～50 mu m range, size distribution coefficient＜20%.
Description of drawings
Fig. 1 is the electromicroscopic photograph of embodiment 1 oversized hole microballoon.
Fig. 2 is the electromicroscopic photograph of embodiment 1 oversized hole microballoon.
Fig. 3 is the electromicroscopic photograph of embodiment 2 oversized hole microballoons.
Fig. 4 is the size distribution figure of embodiment 3 particle diameters 13.17 μ m.
Fig. 5 is the size distribution figure of embodiment 3 oversized hole.
Fig. 6 is the electromicroscopic photograph of embodiment 4 oversized hole microballoons.
Fig. 7 is the size distribution figure of embodiment 5 oversized hole microballoons.
Fig. 8 is the electromicroscopic photograph of embodiment 5 oversized hole microballoons.
Fig. 9 is the electromicroscopic photograph of embodiment 6 oversized hole microballoons.
Figure 10 is the electromicroscopic photograph of embodiment 7 oversized hole microballoons.
Figure 11 is the electromicroscopic photograph of embodiment 8 oversized hole microballoons.
Figure 12 is the electromicroscopic photograph of embodiment 9 oversized hole microballoons.
Figure 13 is the electromicroscopic photograph of embodiment 10 oversized hole microballoons.
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 (WOR 12.5: 1 is crossed film three times for fenestra 15 μ m, mould 40Kpa)
Accurately take by weighing 6.0g vinylbenzene and the 2.0g Vinylstyrene places the 25mL beaker, add the 0.32g Lucidol, 3.2g Span80, the 0.4g n-Hexadecane stirs, and dissolves fully until initiator.Get 1.0g PVA and be dissolved in the 100mL zero(ppm) water, be made into water.Oil phase is added aqueous phase, be stirred to oyster white and guarantee abundant swelling, install quick film emulsifier unit and pressure is transferred to 40kPa cross film three times, the colostrum of crossing behind the film is put into the polymerization of 250mL there-necked flask, polymerization temperature is 75 ℃, and polymerization time is 20h.After reaction finishes, filter, with zero(ppm) water and ethanol cleaning products several, components such as thinner, tensio-active agent are cleaned, extracting after the drying, promptly gets product.Electromicroscopic photograph sees to attach Fig. 1 and 2, and particle diameter is 8.30 μ m; The size distribution coefficient is 16.3%; The oversized hole proportion is 36.2%.
Embodiment 2 (changing the fenestra mould)
Accurately take by weighing 6.0g vinylbenzene and the 2.0g Vinylstyrene places the 25mL beaker, add the 0.32g Lucidol, 3.2g Span80, the 0.4g n-Hexadecane stirs, and dissolves fully until initiator.Get 1.0g PVA and be dissolved in the 100mL zero(ppm) water, be made into water.Oil phase is added aqueous phase, stir to guarantee abundant swelling, install quick film emulsifier unit (fenestra 2.8 μ m) and pressure is transferred to 400kPa cross film three times, the colostrum of crossing behind the film is put into the polymerization of 250mL there-necked flask, polymerization temperature is 75 ℃, and polymerization time is 20h.After reaction finishes, filter, with zero(ppm) water and ethanol cleaning products several, components such as thinner, tensio-active agent are cleaned, extracting after the drying, promptly gets product.Electromicroscopic photograph is seen accompanying drawing 3, and particle diameter is 1.40 μ m; The size distribution coefficient is 7.8%; The oversized hole proportion is 10.3%.
Embodiment 3 (change WOR)
Accurately take by weighing 15.0g vinylbenzene and the 5.0g Vinylstyrene places the 50mL beaker, add the 0.8g Lucidol, 8.0g Span80, the 1.0g n-Hexadecane stirs, and dissolves fully until initiator.Get 1.0g PVA and be dissolved in the 100mL zero(ppm) water, be made into water.Oil phase is added aqueous phase, stir to guarantee abundant swelling, install quick film emulsifier unit (fenestra 19.8 μ m) and pressure is transferred to 30kPa cross film three times, the colostrum of crossing behind the film is put into the polymerization of 250mL there-necked flask, polymerization temperature is 75 ℃, and polymerization time is 20h.After reaction finishes, filter, with zero(ppm) water and ethanol cleaning products several, components such as thinner, tensio-active agent are cleaned, extracting after the drying, promptly gets product.Particle diameter is 13.17 μ m, and its size distribution figure sees Fig. 4; The size distribution coefficient is 18.7%; The oversized hole proportion is 60.4%, and its graph of pore diameter distribution is seen Fig. 5.
Embodiment 4 (changing the concentration of aqueous phase stablizer)
Accurately take by weighing 6.0g vinylbenzene and the 2.0g Vinylstyrene places the 25mL beaker, add the 0.32g Lucidol, 3.2g Span80, the 0.4g n-Hexadecane stirs, and dissolves fully until initiator.Get 2.0g PVA and be dissolved in the 100mL zero(ppm) water, be made into water.Oil phase is added aqueous phase, stir to guarantee abundant swelling, install quick film emulsifier unit (fenestra 15 μ m) and pressure is transferred to 40kPa cross film three times, the colostrum of crossing behind the film is put into the polymerization of 250mL there-necked flask, polymerization temperature is 75 ℃, and polymerization time is 20h.After reaction finishes, filter, with zero(ppm) water and ethanol cleaning products several, components such as thinner, tensio-active agent are cleaned, extracting after the drying, promptly gets product.Electromicroscopic photograph is seen accompanying drawing 6, and particle diameter is 7.36 μ m; The size distribution coefficient is 12.2%; The oversized hole proportion is 34.5%.
Embodiment 5 (change initiator)
Accurately take by weighing 6.0g vinylbenzene and the 2.0g Vinylstyrene places the 25mL beaker, add the 0.32g Diisopropyl azodicarboxylate, 3.2g Span80, the 0.4g n-Hexadecane stirs, and dissolves fully until initiator.Get 1.0g PVA and be dissolved in the 100mL zero(ppm) water, be made into water.Oil phase is added aqueous phase, stir to guarantee abundant swelling, install quick film emulsifier unit (fenestra 9.2 μ m) and pressure is transferred to 50kPa cross film three times, the colostrum of crossing behind the film is put into the polymerization of 250mL there-necked flask, polymerization temperature is 75 ℃, and polymerization time is 20h.After reaction finishes, filter, with zero(ppm) water and ethanol cleaning products several, components such as thinner, tensio-active agent are cleaned, extracting after the drying, promptly gets product.Particle diameter is 3.89 μ m, and its size distribution figure sees Fig. 7; The size distribution coefficient is 14.7%; The oversized hole proportion is 13.7%, and electromicroscopic photograph is seen Fig. 8.
Embodiment 6 (raising degree of crosslinking)
Accurately take by weighing 6.0g vinylbenzene and the 6.0g Vinylstyrene places the 25mL beaker, add the 0.32g Lucidol, 3.2g Span80, the 0.4g n-Hexadecane stirs, and dissolves fully until initiator.Get 3.0g PVA and be dissolved in the 100mL zero(ppm) water, be made into water.Oil phase is added aqueous phase, stir to guarantee abundant swelling, install quick film emulsifier unit (fenestra 9.2 μ m) and pressure is transferred to 50kPa cross film three times, the colostrum of crossing behind the film is put into the polymerization of 250mL there-necked flask, polymerization temperature is 75 ℃, and polymerization time is 20h.After reaction finishes, filter, with zero(ppm) water and ethanol cleaning products several, components such as thinner, tensio-active agent are cleaned, extracting after the drying, promptly gets product.Electromicroscopic photograph is seen accompanying drawing 9, and particle diameter is 4.41 μ m; The size distribution coefficient is 13.4%; The oversized hole proportion is 11.5%.
Embodiment 7 (polymkeric substance is made thinner)
Accurately take by weighing 6.0g vinylbenzene and the 6.0g Vinylstyrene places the 25mL beaker, add the 0.32g Lucidol, 3.2g Span80, the 0.4g PS stirs, and dissolves fully until initiator.Get 3.0g PVA and be dissolved in the 100mL zero(ppm) water, be made into water.Oil phase is added aqueous phase, stir to guarantee abundant swelling, install quick film emulsifier unit (fenestra 9.2 μ m) and pressure is transferred to 50kPa cross film three times, the colostrum of crossing behind the film is put into the polymerization of 250mL there-necked flask, polymerization temperature is 75 ℃, and polymerization time is 20h.After reaction finishes, filter, with zero(ppm) water and ethanol cleaning products several, components such as thinner, tensio-active agent are cleaned, extracting after the drying, promptly gets product.Electromicroscopic photograph is seen accompanying drawing 10, and particle diameter is 3.78 μ m; The size distribution coefficient is 16.9%; The oversized hole proportion is 10.7%.
Embodiment 8 (change monomer system)
Accurately take by weighing the 6.0g SY-Monomer G and the 2.0g Vinylstyrene places the 25mL beaker, add the 0.32g Lucidol, 3.2g Span80, the 0.4g n-Hexadecane stirs, and dissolves fully until initiator.Get 3.0g PVA and be dissolved in the 100mL zero(ppm) water, be made into water.Oil phase is added aqueous phase, stir to guarantee abundant swelling, install quick film emulsifier unit (fenestra 15 μ m) and pressure is transferred to 50kPa cross film three times, the colostrum of crossing behind the film is put into the polymerization of 250mL there-necked flask, polymerization temperature is 75 ℃, and polymerization time is 20h.After reaction finishes, filter, with zero(ppm) water and ethanol cleaning products several, components such as thinner, tensio-active agent are cleaned, extracting after the drying, promptly gets product.Electromicroscopic photograph is seen accompanying drawing 11, and particle diameter is 7.08 μ m; The size distribution coefficient is 15.4%; The oversized hole proportion is 30.3%.
Embodiment 9 (change monomer system)
Accurately take by weighing the 6.0g Rocryl 400 and the 2.0g Vinylstyrene places the 25mL beaker, add the 0.32g Lucidol, 3.2g Span80, the 0.4g n-Hexadecane stirs, and dissolves fully until initiator.Get 3.0g PVA and be dissolved in the 100mL zero(ppm) water, be made into water.Oil phase is added aqueous phase, stir to guarantee abundant swelling, install quick film emulsifier unit (fenestra 15 μ m) and pressure is transferred to 50kPa cross film three times, the colostrum of crossing behind the film is put into the polymerization of 250mL there-necked flask, polymerization temperature is 75 ℃, and polymerization time is 20h.After reaction finishes, filter, with zero(ppm) water and ethanol cleaning products several, components such as thinner, tensio-active agent are cleaned, extracting after the drying, promptly gets product.Electromicroscopic photograph is seen accompanying drawing 12, and particle diameter is 7.20 μ m; The size distribution coefficient is 16.4%; The oversized hole proportion is 35.1%.
Embodiment 10 (amplifying preparation)
Accurately take by weighing 150.0g vinylbenzene and the 50.0g Vinylstyrene places the 500mL beaker, add the 8.0g Lucidol, 80.0g Span80, the 10.0g n-Hexadecane stirs, and dissolves fully until initiator.Get 10.0g PVA and be dissolved in the 1L zero(ppm) water, be made into water.Oil phase is added aqueous phase, stir to guarantee abundant swelling, install quick film emulsifier unit (fenestra 19.8 μ m) and pressure is transferred to 40kPa cross film three times, the colostrum of crossing behind the film is put into the polymerization of 3L reaction kettle, polymerization temperature is 75 ℃, and polymerization time is 20h.After reaction finishes, filter, with zero(ppm) water and ethanol cleaning products several, components such as thinner, tensio-active agent are cleaned, extracting after the drying, promptly gets product.Particle diameter is 12.38 μ m, and the size distribution coefficient is 17.6%; The oversized hole proportion is 43.5%, and its Electronic Speculum figure sees Figure 13.
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. the preparation method of the controlled small particle size super large pore polymer microsphere of a uniform particle diameter, said preparation method preferably includes following steps:
The oil phase that (1) will contain monomer, linking agent, initiator, thinner and oil soluble surfactant mixes;
(2) preparation contains stablizer and optional water soluble surfactant active's water;
(3) the said oil phase that mixes is joined said water, continue to be stirred to solution and be creamy white, guarantee that swelling is abundant, form W/O/W type co-continuous phase emulsion this moment;
(4) film through different apertures under pressure with said emulsion;
(5) cross film according to uniform particle diameter degree one or many, emulsion is solidified behind the film excessively;
Alternatively, (6) washing is dry, makes uniform particle diameter, controlled small particle size super large pore polymer microsphere.
2. the method for claim 1 is characterized in that, said monomer is oil-soluble ethylene base monomer or its mixture; Said monomer is preferably selected from least a in vinyl, styrenic, acrylic acid or the like, methacrylic, esters of acrylic acid, methyl acrylic ester, acrylic amide, methacryloyl amine, epoxy olefines and the vinyl acetate esters monomer;
Preferably, the mass content of said monomer in oil phase is 1%～90%, preferred 10%～60%, further preferred 25%～45%.
3. according to claim 1 or claim 2 method is characterized in that, said linking agent is to be selected from least a in compound and composition thereof of oil-soluble, band bi-vinyl or trivinyl; Said linking agent is preferably selected from bi-vinyl aromatics, acrylic ester compound or its mixture, is preferably Vinylstyrene (DVB), TGM 1 (EGDMA), vinylformic acid trimethoxy propane trimethyl ester (TRIM) or its mixture;
Preferably, the mass content of said linking agent in oil phase is 1%～90%, preferred 5%～60%, further preferred 10%～45%.
4. like the described method of one of claim 1-3, it is characterized in that said initiator is selected from azo-initiator, peroxide initiator or its mixture; Be preferably selected from Lucidol, Diisopropyl azodicarboxylate or its mixture;
Preferably, the consumption of said initiator is 0.01%～10% of all polymerisable monomer quality, preferred 0.05%～8%, further preferred 0.1%～6%.
5. like the described method of one of claim 1-4, it is characterized in that said thinner is selected from alkane, alcohols, ethers, benzene class, is dissolved in polymer of monomers class or its mixture; Said thinner is preferably selected from heptane, dodecyl, n-Hexadecane, octane-iso, dodecanol, hexalin, propyl carbinol, sherwood oil, toluene, PS, gathers (methyl) propenoate or its mixture;
Preferably, the massfraction of said thinner in oil phase is 0%～80%, preferred 0～60%, further preferred 0%～50%.
6. like the described method of one of claim 1-5, it is characterized in that said oil soluble surfactant is selected from non-ionics, ionogenic surfactant, amphipathic embedding end multipolymer; Preferably from sorbitan fatty acid ester, polyglycerol fatty acid ester, polyoxyethylene fatty acid ester, TX10 class, amphiphilic block copolymer or their mixture; Said oil soluble surfactant is preferably sorbitan fatty acid ester, polyglycerol fatty acid ester, polyoxyethylene fatty acid ester, TX10 class or its mixture; Further be preferably sorbitan monooleate, paraoctyl phenol Soxylat A 25-7, PO-500, Arlacel 83, AOT or its mixture; More preferably sorbitan monooleate, paraoctyl phenol Soxylat A 25-7 or its mixture.
Preferably, the mass content of said oil soluble surfactant in oil phase is 5%～80%, preferred 10%～70%, further preferred 25%～60%.
7. like the described method of one of claim 1-6, it is characterized in that said stablizer is selected from water-soluble polymers, preferably polyethylene alcohol, gelatin, Mierocrystalline cellulose, Vinylpyrrolidone polymer or its mixture;
Preferably, said stabiliser content is 0.1～10% of a water quality, preferred 0.5～8%, further preferred 0.5%～5%.
8. like the described method of one of claim 1-7, it is characterized in that said water soluble surfactant active can use sodium lauryl sulphate, sodium laurylsulfonate; Said water soluble surfactant active be content be controlled at the water quality 10% in, in preferred 8%, further in preferred 5%;
Preferably, the said pressure of step (4) is 0KPa～5MPa, is preferably 10KPa～2MPa, further preferred 50KPa～1.5MPa;
Preferably, said membrane pore size is 1～30 μ m, preferred 5～25 μ m, further preferred 10～25 μ m;
Preferably, crossing the film number of times is 1～5 time, preferred 1～3 time.
9. the small particle size super large pore polymer microsphere that uniform particle diameter is controlled is characterized in that microballoon inside had both had the micropore of 5-20nm; Has the above oversized hole of 50-100nm and 100nm again; Wherein the above oversized hole of 50-100nm and 100nm accounts for the 10-60% of the inner pore volume of microballoon, is preferably 20-40%, and the microballoon porosity is 30%～80%; Particle diameter is controlled in 0.5～50 mu m range, size distribution coefficient＜20%; Said microballoon is preferably with the said method preparation of one of claim 1-8.
10. the purposes of the said microballoon of claim 9 is characterized in that, is used for chromatograph packing material, modifies 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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