阅读说明：本技术 一种磁性高分子微球的制备方法 (A kind of preparation method of magnetic macromolecular microsphere ) 是由 阳承利 于 2019-09-06 设计创作，主要内容包括：本发明公开了一种磁性高分子微球的制备方法,所述制备方法包括以下步骤：将聚合物种子加入含有稳定剂和引发剂的水溶液中,搅拌均匀,形成均匀分散的种子悬浮液；将油酸铁和单体均匀混合,形成油酸铁单体溶液；将所述油酸铁单体溶液通过喷嘴形成均一液滴进入所述种子悬浮液中,种子吸收液滴生长并一步聚合,得油酸铁高分子微球；升温,使所述油酸铁分解,得磁性高分子微球。本发明制备的磁性高分子微球不仅可以控制微球的磁性能,还可以进一步提升微球的粒径均一性。而且,提高了磁性高分子微球的产率、效率以及稳定性,适于大规模生产。(The invention discloses a kind of preparation methods of magnetic macromolecular microsphere, and the preparation method comprises the following steps: polymer seeds being added in the aqueous solution containing stabilizer and initiator, stirs evenly, forms evenly dispersed seed suspension liquid；Iron oleate and monomer are uniformly mixed, iron oleate monomer solution is formed；The iron oleate monomer solution is formed uniform drop by nozzle to enter in the seed suspension liquid, neutron absorption droplet growth and one-step polymerization obtain iron oleate polymer microsphere；Heating decomposes the iron oleate, obtains magnetic macromolecular microsphere.Magnetic macromolecular microsphere prepared by the present invention not only can control the magnetic property of microballoon, can also further promote the uniform particle diameter of microballoon.Moreover, improving the yield of magnetic macromolecular microsphere, efficiency and stability, it is suitable for large-scale production.)

1. a kind of preparation method of magnetic macromolecular microsphere, which is characterized in that the preparation method includes:

Polymer seeds are added in the aqueous solution containing stabilizer and initiator, stirs evenly, forms evenly dispersed seed Suspension；

Iron oleate and monomer are uniformly mixed, iron oleate monomer solution is formed；

The iron oleate monomer solution is formed uniform drop by nozzle to enter in the seed suspension liquid, neutron absorption drop Simultaneously one-step polymerization is grown, iron oleate polymer microsphere is obtained；

Heating decomposes the iron oleate, obtains magnetic macromolecular microsphere.

2. preparation method according to claim 1, which is characterized in that the polymer seeds are as follows: by emulsion polymerization, divide Dissipate the polystyrene seed or styrene-divinylbenzene seed of polymerization or suspension polymerization preparation.

3. preparation method according to claim 1, which is characterized in that the stabilizer is surfactant.

4. preparation method according to claim 3, which is characterized in that the surfactant is polyvinyl alcohol, polyethylene At least one of pyrrolidones, hydroxymethyl cellulose, oleic acid, oleyl alcohol, hydroxypropyl cellulose or octadecyl alcolol.

5. preparation method according to claim 1, which is characterized in that the initiator is benzoyl peroxide, peroxidating At least one of lauroyl, peroxidating t-butyl formate.

6. preparation method according to claim 1, which is characterized in that the monomer is styrene, divinylbenzene, 2,4- bis- Chlorostyrene, acrylic acid, metering system amino acid methyl esters, ethyl acrylate, vinylacetate, in glycidyl methacrylate At least one.

7. preparation method according to claim 1, which is characterized in that the average grain diameter of the magnetic macromolecular microsphere is 100nm~1000 μm.

8. preparation method according to claim 1, which is characterized in that by the iron oleate monomer solution by nozzle with liquid Drop mode is dispersed into the seed suspension liquid

The seed suspension liquid is put into the first container；

The iron oleate monomer solution is put into second container, the nozzle is mounted on the second container；

Preset pressure is applied to the second container, under the preset pressure, the iron oleate monomer solution is through the nozzle It is dispersed into the seed suspension liquid with drop form.

9. preparation method according to claim 8, which is characterized in that the preset pressure is 0.1~10MPa.

Technical field

The present invention relates to polymeric material field, in particular to a kind of preparation method of magnetic macromolecular microsphere.

Background technique

In recent years, magnetic macromolecular microsphere nucleic acid extraction, cell separation, immobilised enzymes, immune detection, targeted drug, The equal fields that isolate and purify of protein and enzyme are widely used.But it is controllable how to synthesize uniform particle diameter, magnetic property Magnetic macromolecular microsphere is the hot and difficult issue of presently relevant area research.

Summary of the invention

In order to solve the above technical problems, the present invention provides a kind of preparation methods of magnetic macromolecular microsphere.

In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:

The embodiment of the invention provides a kind of preparation method of magnetic macromolecular microsphere, the preparation method includes:

Polymer seeds are added in the aqueous solution containing stabilizer and initiator, stirs evenly, is formed evenly dispersed Seed suspension liquid；

Iron oleate and monomer are uniformly mixed, iron oleate monomer solution is formed；

The iron oleate monomer solution is formed uniform drop by nozzle to enter in the seed suspension liquid, neutron absorption Droplet growth and one-step polymerization, obtain iron oleate polymer microballoon；

Heating decomposes the iron oleate, obtains magnetic macromolecular microsphere.

Further, the polymer seeds are as follows: by the poly- of emulsion polymerization, dispersion copolymerization method or suspension polymerization preparation Styrene seed or styrene-divinylbenzene seed.

Further, the stabilizer is surfactant.

Further, the surfactant is polyvinyl alcohol, polyvinylpyrrolidone, hydroxymethyl cellulose, oleic acid, oil At least one of alcohol, hydroxypropyl cellulose or octadecyl alcolol.

Further, the initiator be benzoyl peroxide, lauroyl peroxide, in peroxidating t-butyl formate extremely Few one kind.

Further, the monomer is styrene, divinylbenzene, 2,4- dichlorostyrene, acrylic acid, metering system amino acid At least one of methyl esters, ethyl acrylate, vinylacetate, glycidyl methacrylate.

Further, the average grain diameter of the magnetic polymer microsphere is 100nm~1000 μm.

Further, the iron oleate monomer solution is dispersed into the seed suspension liquid by nozzle with drop form Include:

The seed suspension liquid is put into the first container；

The iron oleate monomer solution is put into second container, the nozzle is mounted on the second container；；

Preset pressure is applied to the second container, under the preset pressure, described in the iron oleate monomer solution warp Nozzle is dispersed into the seed suspension liquid with drop form.

Further, the preset pressure is 0.1~10MPa.

The embodiment of the invention provides a kind of preparation method of magnetic macromolecular microsphere, using eruption mode by iron oleate list Liquid solution forms uniform drop, and is dispersed in seed suspension liquid, and seed rapidly absorbs iron oleate monomer droplet and grows, It polymerize and obtains the iron oleate polymer microsphere of uniform particle diameter, after heat resolve, obtains magnetic macromolecular microsphere.Because of oil of the invention Sour iron monomer solution size droplet diameter is uniform, it is easier to be fully absorbed by polymer seeds, the entire system of iron oleate polymer microsphere Standby process is completed in 2 hours, and the time greatly shortens.In addition, uniform iron oleate monomer solution drop is easier by polymer Seed fully absorbs, is magnetic strong, and little particle impurity is free of in the magnetic macromolecular microsphere of preparation.Therefore, magnetic prepared by the present invention Property polymer microsphere not only can control the magnetic property of microballoon, can also further promote the uniform particle diameter of microballoon.Moreover, mentioning The high yield of magnetic macromolecular microsphere, efficiency and stability, are suitable for large-scale production.

Detailed description of the invention

Fig. 1 is the electron microscope of magnetic macromolecular microsphere in the embodiment of the present invention one；

Fig. 2 is the grading curve of magnetic macromolecular microsphere in the embodiment of the present invention one.

Specific embodiment

In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention Attached drawing, the technical solution of the embodiment of the present invention is clearly and completely described.Obviously, described embodiment is this hair Bright a part of the embodiment, rather than whole embodiments.Based on described the embodiment of the present invention, those skilled in the art institute The every other embodiment obtained, belongs to the scope of the present invention.

The embodiment of the invention provides a kind of preparation method of magnetic macromolecular microsphere, preparation method includes:

Polymer seeds are added in the aqueous solution containing stabilizer and initiator, stirs evenly, is formed evenly dispersed Seed suspension liquid；

Iron oleate and monomer are uniformly mixed, iron oleate monomer solution is formed；

The iron oleate monomer solution is formed uniform drop by nozzle to enter in the seed suspension liquid, neutron absorption Droplet growth and one-step polymerization, obtain iron oleate polymer microballoon；

Heating decomposes the iron oleate, obtains magnetic macromolecular microsphere.

Iron oleate can current existing system, the preparation method of specific iron oleate is well known to those skilled in the art.Preferably, Following methods preparation can be used in iron oleate: by Dissolvable Fe³⁺Salt and enuatrol are added in the mixed liquor of alcoholic solution and n-hexane, add Thermal agitation obtains iron oleate after filtering, vacuum drying.Alcoholic solution is the aqueous solution of methanol, ethyl alcohol or isopropanol etc..Dissolvable Fe³⁺ Salt includes but is not limited to iron chloride, ferric sulfate etc..

The preparation method of the embodiment of the present invention is constantly grown using seed, by adjusting the size and use of polymer seeds The purpose to size tunable can be realized in the conditions such as amount, iron oleate and monomer dosage.Specifically, oleic acid in iron oleate monomer solution Iron and monomer grow polymer seeds, after reaching default microspherulite diameter, stop that iron oleate monomer solution is added, in polymerization temperature Reaction obtains iron oleate macromolecule under (preferably 70~100 DEG C, such as: 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 100 DEG C etc.) Microballoon, heating (temperature after heating is preferably 250~300 DEG C, such as: 250 DEG C, 260 DEG C, 290 DEG C, 300 DEG C etc.) continue instead It answers, obtains magnetic macromolecular microsphere.

Iron oleate monomer solution is added with uniform drops into seed suspension liquid using nozzle, is guaranteeing stronger magnetic Under the premise of property performance, polymer seeds are improved to the adsorption efficiency of monomer and iron oleate, reduce the generation of little particle impurity, Reaction condition is easier to control, and not only preparation process is simple, further improves size tunable and uniform particle diameter, product Quality stability is more preferable.It is suitable for mass production.

Further, iron oleate monomer solution is dispersed into seed suspension liquid packet by nozzle with uniform drop form It includes:

Seed suspension liquid is put into the first container；

Iron oleate monomer solution is put into second container, nozzle is mounted on second container；

Preset pressure is applied to second container, under preset pressure, iron oleate monomer solution is through nozzle with uniform drop side Formula is dispersed into seed suspension liquid.

Preferably, preset pressure is 0.1~10MPa.The pressure for improving second container advantageously forms drop, accelerates oleic acid The jet velocity of iron monomer solution improves reaction speed.

Preferably, the aperture of nozzle can be 50nm~5000 μm, it is further preferred that the aperture of nozzle be 10 μm~ 200μm。

Unrestrictedly, polymer seeds are as follows: the polyphenyl second prepared by emulsion polymerization, dispersion copolymerization method or suspension polymerization Alkene seed or styrene-divinylbenzene seed.

In some embodiments of the invention, stabilizer is surfactant.It is further preferred that surfactant is poly- At least one in vinyl alcohol, polyvinylpyrrolidone, hydroxymethyl cellulose, oleic acid, oleyl alcohol, hydroxypropyl cellulose or octadecyl alcolol Kind.

According to some embodiments of the present invention, initiator is benzoyl peroxide, lauroyl peroxide, peroxidating formic acid uncle At least one of butyl ester.

Further, monomer is styrene, divinylbenzene, 2,4- dichlorostyrene, acrylic acid, metering system amino acid first At least one of ester, ethyl acrylate, vinylacetate, glycidyl methacrylate.

In some embodiments of the invention, the average grain diameter of magnetic macromolecular microsphere is 100nm~1000 μm.The present invention The preparation method further expansion particle size range of magnetic macromolecular microsphere.

Preparation method of the invention is described further combined with specific embodiments below, it is to be understood that the present invention It is not limited to following embodiment: