A kind of preparation method of porous polymer microspheres

A porous polymer and microsphere technology, applied in the field of preparation of porous polymer microspheres, can solve the problems that the particle size can only be controlled to a few millimeters, the cost of mold design and manufacturing is high, and it is difficult to form a regular spherical shape. Wide range of size adjustment, increased stability, and good penetration of holes

Inactive Publication Date: 2015-12-02
UNIV OF SCI & TECH OF CHINA
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  • Summary
  • Abstract
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  • Claims
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Problems solved by technology

Due to the continuous phase polymerization, the shape of the high internal phase polymer porous material (polyHIPEs) obtained after polymerization is consistent with the shape of the reactor. For example, a test tube as a reactor will obtain a cylindrical block material, which is not conducive to The removal of impurities such as unpolymerized monomers, emulsifiers, and electrolytes in the system is also inconvenient in practical applications
[0005] U.S. Patent Application No. 5,583,162 reported that the high internal phase emulsion was transferred to molds of different shapes, and millimeter-scale porous balls in shapes such as spheres, ellipses, and cylinders were obtained, but the mold design and manufacturing costs of this method were too high. The smallest size can only be controlled to a few millimeters; (React.Funct.Polym.2005,65,37) and Krajnc et al. (React.Funct.Polym.2005,65,37) first prepared the water-in-oil (W / O) reverse phase high internal phase emulsion containing chlorostyrene, and then dispersed the high internal phase emulsion into the PVP aqueous solution , resuspension polymerization to obtain polyHIPEs porous polymer microbeads
But the disadvantage of this method is that the high internal phase emulsion is a high viscosity emulsion, it is difficult to disperse it, even if it can be dispersed, it is difficult to form a regular spherical shape, and the internal water phase contains electrolytes, and the internal and external water phases form osmotic pressure. The double emulsion that causes formation is unstable; Gokmen et al. (Macromolecules2009,42,9289) disperses the prepared inverse high internal phase emulsion into PVA aqueous solution by microfluidic technology, and obtains porous polymer particles (spheres and rods) by UV-induced polymerization. )
However, the microfluidic technology used can only be realized in the laboratory at present, and it is difficult to apply it to actual industrial production.

Method used

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  • A kind of preparation method of porous polymer microspheres
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  • A kind of preparation method of porous polymer microspheres

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preparation example Construction

[0037] The invention provides a kind of preparation method of porous polymer microsphere, comprises the steps:

[0038] Step 1: Mix the oil-soluble monomer, cross-linking agent and emulsifier to obtain the oil phase. Those skilled in the art know easily that the ratio of oil-soluble monomer, cross-linking agent and emulsifier can be selected according to actual conditions. Preferably, the mass ratio of oil-soluble monomer, cross-linking agent and emulsifier is (3~8): (1~4):(1~3), more preferably, the mass ratio of oil-soluble monomer, crosslinking agent and emulsifier is (9~13):(4~6):(3~5).

[0039] The general formula of the oil-soluble monomer is preferably CH 2 =CR 1 R 2 , where R 1 is hydrogen or methyl, R 2 Is aryl, ester or COOR 3 , R 3 is alkyl or haloalkyl, more preferably styrene, 4-methylstyrene, 4-ethylstyrene, chlorostyrene, chloromethylstyrene, butyl acrylate, butyl methacrylate and 2- At least one of ethylhexyl acrylate and the like.

[0040]The crosslin...

Embodiment 1

[0055] (1) Add 2.25g of styrene, 0.75g of ethylene glycol dimethacrylate and 0.75g of 12-acryloyloxy-9-octadecenoic acid into a 100ml beaker, and use a syringe to take a certain amount of ammonia water to adjust pH to 8, after mixing evenly, a light yellow viscous opaque liquid is obtained, which is the oil phase;

[0056] (2) Add 60.0g of distilled water dropwise to the oil phase under stirring at 300r / min to prepare a double emulsion;

[0057] (3) Transfer the double emulsion to a 100ml wide-mouth bottle, and after 30 minutes of nitrogen gas to remove the oxygen in the system, the sealed container is sent into the cobalt source radiation to initiate polymerization, and the dose rate is kept at 30.2Gy·min -1 , After 48 hours, the product was taken out, sieved, washed twice with distilled water, and then washed with ethanol. After drying, the porous polymer microsphere S1 was obtained, and the yield could reach 70%.

[0058] Such as figure 2 with image 3 As shown, only an...

Embodiment 2

[0061] Repeat Example 1 with the following difference: replace "ethylene glycol dimethacrylate" with "divinylbenzene".

[0062] Finally, porous polymer microspheres S2 were obtained with a yield of up to 70%.

[0063] Such as Figure 5 As shown, the surface and internal pores of S2 are closed, the average size of the microspheres is 52 μm, and the specific surface area is 13.6 m 2 / g.

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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 [0001] The invention relates to the field of porous microsphere materials, in particular to a preparation method of porous polymer microspheres. Background technique [0002] High Internal Phase Emulsion (High Internal Phase Emulsion, HIPE) refers to the internal phase (disperse phase) of the volume fraction of more than 74% of the emulsion, which can be used as a template to prepare holes through the hierarchical pores (including macropores, mesopores and micropores) Structured porous material. This material has good application prospects. For example, due to its high specific surface area, it can be used as a catalyst carrier or as a catalyst itself; it has adjustable pore size and can be used in the field of separation and filtration; in addition, porous materials can be used in tissue cell culture, drug release, etc. and other biological fields have good prospects. [0003] High internal phase emulsions can be divided into water-in-oil (W / O) type and oi...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F212/08C08F222/14C08F212/36C08F2/46C08F2/00C08J9/28
Inventor 刘华蓉李梓超
Owner UNIV OF SCI & TECH OF CHINA
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