阅读说明：本技术 一种聚合物纳米球及其制备方法与应用 (Polymer nanosphere and preparation method and application thereof ) 是由 曲剑波 古红亮 蔺洋洋 彭文舒 朱冰琪 孙勇军 张晓云 于 2019-11-28 设计创作，主要内容包括：本发明公开了一种聚合物纳米球及其制备方法与应用,属于高分子材料技术领域。所述制备方法包括下列步骤：将水溶性引发剂、12-冠醚-4和去离子水混合得到水相,将水相和油相混合,搅拌；通惰性气体的条件下除氧后密封,密封后保温；离心,将得到的沉淀依次经水洗、离心、醇洗、离心、真空干燥,得聚合物纳米球。本发明制备的聚合物纳米球的粒径在20-100nm之间,可以实现对纳米球尺寸的精确调控。该粒径范围的纳米球在粒度标准物质、药物载体、生物成像、生物传感器、生物催化、光子晶体、矿物浮选、气体分离以及作为多孔材料软模板等领域具有很大的应用前景。(The invention discloses a polymer nanosphere and a preparation method and application thereof, belonging to the technical field of high molecular materials. The preparation method comprises the following steps: mixing a water-soluble initiator, 12-crown ether-4 and deionized water to obtain a water phase, mixing the water phase and an oil phase, and stirring; deoxidizing under the condition of introducing inert gas, sealing, and preserving heat after sealing; centrifuging, and sequentially washing the obtained precipitate with water, centrifuging, washing with alcohol, centrifuging, and vacuum drying to obtain the polymer nanosphere. The particle size of the polymer nanosphere prepared by the invention is between 20-100nm, and the precise regulation and control of the nanosphere size can be realized. The nanospheres with the particle size range have great application prospects in the fields of particle size standard substances, drug carriers, biological imaging, biosensors, biocatalysis, photonic crystals, mineral flotation, gas separation, porous material soft templates and the like.)

1. A preparation method of polymer nanospheres is characterized by comprising the following steps:

(1) mixing a water-soluble initiator, 12-crown ether-4 and deionized water to obtain a water phase, mixing the water phase and an oil phase, and stirring to obtain a feed liquid A; wherein the oil phase is any one or a mixture of several of vinyl monomers, conjugated diene monomers and acrylate monomers;

(2) deoxidizing the feed liquid A for 10-30 min at a stirring speed of 100-500 rpm under the condition of introducing inert gas, sealing, and then preserving heat for 2-24 h at 50-90 ℃ to obtain feed liquid B;

(3) and centrifuging the feed liquid B, and sequentially washing, centrifuging, washing with alcohol, centrifuging and vacuum-drying the obtained precipitate to obtain the polymer nanospheres.

2. The method for preparing the polymer nanosphere according to claim 1, wherein the molar concentration of 12-crown-4 in the water phase in step (1) is 1-50mM, and the mass ratio of the water-soluble initiator to the oil phase is (1-20): 200.

3. the method for preparing polymer nanospheres according to claim 2, wherein the volume ratio of the water phase to the oil phase in step (1) is (5-100): 1.

4. a method of making polymer nanospheres as claimed in claim 1 wherein: the vinyl monomer is styrene, chloromethyl styrene, vinyl pyridine, vinyl pyrrolidone, divinyl benzene, vinyl acetate, acrylonitrile or vinyl chloride.

5. A method of making polymer nanospheres as claimed in claim 1 wherein: the conjugated diene monomer is butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene or chloroprene.

6. A method of making polymer nanospheres as claimed in claim 1 wherein: the acrylate monomer is methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, N-dimethylaminoethyl methacrylate, N-dimethylaminoethyl acrylate, N-diethylamine ethyl methacrylate or N, N-diethylamine ethyl acrylate.

7. A method for preparing polymer nanospheres as claimed in claim 1 wherein step (3) is specifically operated by: and centrifuging the feed liquid B for 15-30 min by 15000-20000 Xg, centrifuging the obtained precipitate for 15-30 min by 15000-20000 Xg after primary water washing, centrifuging for 15-30 min by 15000-20000 Xg after secondary alcohol washing, and drying for 24h in vacuum at 50 ℃ to obtain the polymer nanospheres.

8. The method of any of claims 1-7, wherein the polymer nanospheres comprise: the water-soluble initiator is a decomposition initiator or an oxidation-reduction initiator.

9. The method of claim 8, wherein the nanospheres are prepared by: the decomposition initiator is one or a mixture of more of potassium persulfate, sodium persulfate, ammonium persulfate and azodiisobutylamine hydrochloride; the oxidation-reduction initiator is a persulfate-mercaptan system or a persulfate-bisulfite system.

10. Use of the polymer nanospheres prepared by the method of claim 8 in particle size standards, drug carriers, bio-imaging, biosensors, biocatalysis, photonic crystals, mineral flotation, gas separation, and as soft templates for porous materials.

Technical Field

The invention relates to the technical field of high molecular materials, in particular to a polymer nanosphere and a preparation method and application thereof.

Background

The preparation and research of nano materials always belong to one of international leading research subjects. The polymer nanospheres are important members of a nano material family, and have great application potential in the fields of particle size standard substances, drug carriers, biological imaging, biosensors, biocatalysis, photonic crystals, mineral flotation, gas separation, porous material soft templates and the like. The preparation method of the polymer nanosphere comprises two channels of monomer polymerization and high-molecular prepolymer redispersion. Monomer polymerization generally includes emulsion (conventional emulsion, soap-free emulsion) polymerization, miniemulsion polymerization, microemulsion polymerization, precipitation polymerization, interfacial polymerization, and the like; the dispersion method of the high molecular prepolymer includes emulsion-solvent evaporation, emulsion-solvent diffusion, salting out, dialysis, supercritical fluid technology and the like. The corresponding method is usually selected according to the requirements of the application field, the polymerization system and the size, wherein the monomer polymerization method has the advantages of wide range of selectable monomers, high specific surface area, easy derivation and modification and the like, and is always dominant in the preparation of the polymer nanospheres. At present, the conventional emulsion polymerization is easy to scale up and is the polymerization technology mainly adopted for producing the polymer latex in industry at present.

However, the preparation of nanoparticles by conventional emulsion, microemulsion and miniemulsion polymerization requires the addition of large amounts of surfactants, wherein microemulsion polymerization also requires the addition of cosurfactants, which can cause a series of problems: for example, the emulsifier is environmentally friendly due to post-treatment, the emulsifier is expensive and the product cost is high, and the residue of the emulsifier on the surface of the nanoparticles can have adverse effects on the electrical properties, optical properties, film-forming properties, water resistance and other surface properties of the product. The soap-free emulsion polymerization effectively solves the problems because no surfactant is added, and the prepared nano particles are widely concerned because of 'surface purity', particularly in the field of biological medicines. Furthermore, as nanoparticles, size and size distribution control of polymer nanospheres is critical, as these two parameters determine key properties of nanoparticles such as size effect, specific surface area, bulk density, and system viscosity. The sizes of the nano particles prepared by soap-free emulsion polymerization and miniemulsion polymerization are generally more than 100 nm. Meanwhile, the precise regulation and control of the size of the nanoparticles by the above polymerization technology still needs to be further improved.

Therefore, it is an urgent need to solve the problems of the art to provide a polymer nanosphere and a preparation method and application thereof, and to prepare a monodisperse polymer nanosphere with a "clean surface" and a particle size of less than 100nm by using a soap-free emulsion technology.

Disclosure of Invention

In view of this, the invention provides a polymer nanosphere and a preparation method and application thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of polymer nanospheres comprises the following steps:

(1) mixing a water-soluble initiator, 12-crown ether-4 and deionized water to obtain a water phase, mixing the water phase and an oil phase, and stirring to obtain a feed liquid A; wherein the oil phase is any one or a mixture of several of vinyl monomers, conjugated diene monomers and acrylate monomers;

(2) deoxidizing the feed liquid A for 10-30 min at a stirring speed of 100-500 rpm under the condition of introducing inert gas, sealing, and then preserving heat for 2-24 h at 50-90 ℃ to obtain feed liquid B;

(3) and (3) centrifuging the feed liquid B, and sequentially washing, centrifuging, washing with alcohol, centrifuging and drying in vacuum to obtain the polymer nanospheres.

Wherein, the feed liquid A can be placed in a glass reaction kettle with a mechanical stirring and condensing device; the specific components of the water-soluble initiator, the vinyl monomer, the conjugated diene monomer and the acrylate monomer are reagent-grade reagents, and the purity of a single reagent is more than or equal to 98%.

Preferably: in the step (1), the molar concentration of the 12-crown ether-4 in the water phase is 1-50mM, and the mass ratio of the water-soluble initiator to the oil phase is (1-20): 200.

preferably: in the step (1), the volume ratio of the water phase to the oil phase is (5-100): 1.

preferably: the vinyl monomer is styrene, chloromethyl styrene, vinyl pyridine, vinyl pyrrolidone, divinyl benzene, vinyl acetate, acrylonitrile or vinyl chloride.

Preferably: the conjugated diene monomer is butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene or chloroprene.

Preferably: the acrylate monomer is methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, N-dimethylaminoethyl methacrylate, N-dimethylaminoethyl acrylate, N-diethylamine ethyl methacrylate or N, N-diethylamine ethyl acrylate.

Preferably: the operation of the step (3) is as follows: and centrifuging the feed liquid B for 15-30 Min at 15000-20000 Xg, centrifuging the obtained precipitate for 15-30 Min at 15000-20000 Xg after primary water washing, centrifuging for 15-30 Min at 15000-20000 Xg after secondary alcohol washing, and drying for 24h at 50 ℃ in vacuum to obtain the polymer nanospheres.

Preferably: the water-soluble initiator is a decomposition initiator or an oxidation-reduction initiator.

Preferably: the decomposition initiator is one or a mixture of more of potassium persulfate, sodium persulfate, ammonium persulfate and azodiisobutylamine hydrochloride; the oxidation-reduction initiator is a persulfate-mercaptan system or a persulfate-bisulfite system.

The invention also provides application of the polymer nanosphere prepared by the method in granularity standard substances, drug carriers, biological imaging, biosensors, biocatalysis, photonic crystals, mineral flotation, gas separation and serving as a porous material soft template.

According to the technical scheme, compared with the prior art, the invention discloses and provides the polymer nanosphere and the preparation method and application thereof, and the technical effect is that the polymer nanosphere with pure surface and granularity less than 100nm is prepared by adopting a soap-free emulsion method. Specifically, a 12 crown ether-4-assisted soap-free emulsion polymerization method is adopted, monodisperse narrow-distribution polymer nanospheres with the particle size range of 20-100nm are prepared simply and conveniently, and the precise regulation and control on the nanosphere size can be realized.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.

FIG. 1 is an IR spectrum of polystyrene nanospheres prepared in example 1 of the present invention and comparative example, wherein line a is the nanosphere prepared in example 1; line b is the nanosphere prepared in the comparative example.

FIG. 2 is a transmission electron microscope image of polystyrene nanospheres in example 1 of the present invention and comparative example;

wherein, a in the figure is a nanosphere prepared in example 1; panel b is a nanosphere prepared in comparative example.

FIG. 3 is a transmission electron microscope image of the polymer nanospheres obtained in example 3 of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The embodiment of the invention discloses a polymer nanosphere and a preparation method and application thereof.