阅读说明：本技术 一种聚苯乙烯纳米棒的制备方法 (Preparation method of polystyrene nano-rod ) 是由 姜勇 龚运祺 汪洋 晋亚紧 王志飞 于 2020-06-01 设计创作，主要内容包括：本发明公开了一种聚苯乙烯纳米棒的制备方法,该制备方法包括以下步骤：(1)利用苯乙烯合成单分散的聚苯乙烯微球；(2)将上述聚苯乙烯微球加入溶胀剂及增塑剂的混合溶液中搅拌；(3)向步骤(2)所得混合溶液中加入交联剂,乳化剂和引发剂,反应后取出产物,加入蚀刻剂,继续反应,最后分离,干燥,即可得到聚苯乙烯纳米棒。与现有技术相比,本发明合成方法简单,且可在聚苯乙烯纳米棒表面掺杂功能基团,有利于其在生物医学领域的应用。(The invention discloses a preparation method of polystyrene nanorods, which comprises the following steps: (1) synthesizing monodisperse polystyrene microspheres by using styrene; (2) adding the polystyrene microspheres into a mixed solution of a swelling agent and a plasticizer, and stirring; (3) and (3) adding a cross-linking agent, an emulsifying agent and an initiator into the mixed solution obtained in the step (2), taking out a product after reaction, adding an etching agent, continuing the reaction, and finally separating and drying to obtain the polystyrene nanorod. Compared with the prior art, the synthesis method is simple, and functional groups can be doped on the surfaces of the polystyrene nanorods, thereby being beneficial to the application of the polystyrene nanorods in the field of biomedicine.)

1. The preparation method of the polystyrene nanorod is characterized by comprising the following steps of:

(1) synthesizing monodisperse polystyrene microspheres by using styrene;

(2) adding the polystyrene microspheres into a mixed solution of a swelling agent and a plasticizer, and stirring;

(3) and (3) adding a cross-linking agent, an emulsifying agent and an initiator into the mixed solution obtained in the step (2), taking out a product after reaction, adding an etching agent, continuing the reaction, and finally separating and drying to obtain the polystyrene nanorod.

2. The method for preparing polystyrene nanorods according to claim 1, wherein step (1) synthesizes monodisperse polystyrene microspheres by precipitation polymerization, emulsion polymerization, dispersion polymerization or soap-free emulsion polymerization.

3. The method for preparing polystyrene nanorods according to claim 1, wherein the method for synthesizing monodisperse polystyrene microspheres in step (1) is as follows:

and (2) adding a water-soluble free radical initiator into the styrene solution in a nitrogen environment, reacting for 6-12h at 70-80 ℃, centrifugally separating, and drying to obtain the monodisperse polystyrene microspheres.

4. The method for preparing polystyrene nanorods according to claim 3, wherein the water-soluble radical initiator is selected from one or two of potassium persulfate and ammonium persulfate, the amount of the water-soluble radical initiator is 2 wt% -3 wt% of styrene, and the reaction temperature is 70-80 ℃.

5. The preparation method of the polystyrene nanorod according to claim 1, wherein the swelling agent in the step (2) is one or more of toluene, acetone or cyclohexane, and the addition amount of the swelling agent is 3-4 times of the total addition volume of the styrene; the plasticizer is dibutyl phthalate, and the addition amount of the plasticizer is 6-7 times of the total addition volume of styrene.

6. The method for preparing polystyrene microspheres as claimed in claim 1, wherein in step (2), the polystyrene microspheres are dispersed in an aqueous solution containing a swelling agent, and then a plasticizer is added and mixed.

7. The method for preparing polystyrene nanorods according to claim 1, wherein the emulsifier in step (3) is selected from one or more of sodium dodecyl sulfate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate, and its amount is 6% -9% of the mass of styrene; the cross-linking agent is selected from a mixture of styrene and divinylbenzene, and the volume ratio of the styrene to the divinylbenzene is as follows: 1: 2-1: 1 of divinylbenzene; the initiator is selected from one of potassium persulfate or ammonium persulfate, and the using amount of the initiator is 2 to 3 weight percent of styrene; the etchant is selected from tetrahydrofuran or acetone, and the dosage of the etchant is 20-25 times of the mass of styrene.

8. The method for preparing polystyrene microspheres according to claim 1, wherein in the step (3), the mixed solution obtained in the step (2) is added into a solution containing an emulsifier and stirred uniformly, and then a cross-linking agent and an initiator are added for reaction.

9. The preparation method of polystyrene microspheres according to claim 1, wherein the initiator is added in step (3), the reaction is carried out at 70-80 ℃ for 6-8 h, and the reaction is continued for 12-24h after the etchant is added.

10. Polystyrene nanorods obtainable by the process according to any one of claims 1 to 9.

Technical Field

The invention belongs to the technical field of polystyrene nanorods, and particularly relates to a preparation method of a polystyrene nanorod.

Background

Generally, polymer particles prepared in heterogeneous polymerization systems tend to become spherical in shape, since the interfacial free energy between the particles and the medium is minimized. Unlike spherical particles, non-spherical particles generally have some other rheological, optical and mechanical properties. Non-spherical particles have been reported in the literature since the mid 1970 s and have received much attention for their use in many fields, such as colloidal crystals, microfluidics and cosmetics. To date, non-spherical particles have been prepared mainly by polymerization or mechanical methods, such as reports on the preparation of non-spherical particles with complex morphology (e.g., snowman-like and disc-like particles) by using an unbalanced polymerization between thermodynamics and kinetics. In addition, polymerization-induced self-assembly (PISA) and self-assembly of copolymers also provide a method of synthesizing non-spherical nanoparticles. Particle replication by the non-wetting template method is a powerful mechanical method for producing large size (several to tens of microns) non-spherical particles, where molten polymer is cast in a non-wetting mold and used to produce non-spherical particles, such as rod-like, cube-like and plate-like particles.

Rod-shaped particles have been used in drug delivery systems, morphology modeling and other such applications. The use of polymer particles with different geometries as model particles to stimulate certain functional cells, such as macrophages, has been reported. The resulting macrophages are more sensitive to rod-like (elliptical) particles due to their larger surface area, which is expected to improve sustained release and targeted therapy. However, styrene is a common organic material, and the reports on rod-shaped polymers are few, and the synthesis method is complicated, or the synthesis conditions are extremely harsh.

Disclosure of Invention

The purpose of the invention is as follows: in order to solve the technical problems, the invention provides a preparation method of a polystyrene nanorod, which effectively solves the problems of complicated synthesis steps, harsh synthesis conditions and the like of the polystyrene nanorod, and the surface of the polystyrene nanorod can be provided with rich functional groups, thereby being beneficial to the application of the polystyrene nanorod in the field of biomedicine.

The technical scheme is as follows: in order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of polystyrene nanorods comprises the following steps:

(1) synthesizing monodisperse polystyrene microspheres by using styrene;

(2) adding the polystyrene microspheres into a mixed solution containing a swelling agent and a plasticizer, and stirring;

(3) and (3) adding a cross-linking agent, an emulsifying agent and an initiator into the mixed solution obtained in the step (2), taking out a product after reaction, adding an etching agent, continuing the reaction, and finally separating and drying to obtain the polystyrene nanorod.

Preferably, step (1) may be carried out by precipitation polymerization, emulsion polymerization, dispersion polymerization or soap-free emulsion polymerization to synthesize monodisperse polystyrene microspheres.

As an embodiment of the present invention, the method for synthesizing monodisperse polystyrene microspheres in step (1) is as follows:

and (2) adding a water-soluble free radical initiator into a styrene solution in a nitrogen environment, reacting for 6-12h, centrifugally separating, and drying to obtain the monodisperse polystyrene microsphere.

More preferably, the water-soluble free radical initiator is selected from potassium persulfate or ammonium persulfate, the dosage of the water-soluble free radical initiator is 2% -3% of that of styrene, and the reaction temperature is 70-80 ℃.

Preferably, the swelling agent in step (2) is toluene, acetone, cyclohexane and other common solutions for swelling polystyrene microspheres, and the plasticizer is dibutyl phthalate.

In the step (2), the addition amount of the swelling agent is 3-4 times of the total addition volume of the styrene, and the addition amount of the plasticizer is 6-7 times of the total addition volume of the styrene.

In the step (2), the polystyrene microspheres are firstly dispersed in the water solution containing the swelling agent, and then the plasticizer is added for mixing.

Preferably, in the step (3), the mixed solution obtained in the step (2) is firstly added into a solution containing an emulsifier and stirred uniformly, and then a cross-linking agent and an initiator are added for reaction.

The emulsifier in the step (3) is selected from one or more of sodium dodecyl sulfate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate, and the dosage of the emulsifier is 6-9% of the mass of styrene; the cross-linking agent is selected from a mixture of styrene and divinylbenzene, and the volume ratio of the styrene to the divinylbenzene is as follows: the divinylbenzene is 1:2 to 1: 1. The initiator is selected from one of potassium persulfate or ammonium persulfate, and the using amount of the initiator is 2 to 3 weight percent of styrene; the etchant is selected from tetrahydrofuran or acetone, and the dosage of the etchant is 20-25 times of the mass of styrene.

After the initiator is added in the step (3), reacting for 6-8 h at 70-80 ℃, adding the etching agent, and continuing to react for 12-24 h;

the invention also provides the polystyrene nanorod prepared by the preparation method, wherein the polystyrene nanorod is 200-300 nm wide and 0.5-2 mu m long, the external part of the polystyrene nanorod can be added with a functional group, and the polystyrene nanorod is made of polystyrene and divinylbenzene.

The invention provides a method for preparing polystyrene nano-rods by free radical synthesis, which utilizes a swelling agent to swell monodisperse polystyrene microspheres, uses the swelled monodisperse polystyrene microspheres as a template, leads the microspheres to slowly deform under the conditions of a plasticizer and an emulsifier, adds reaction monomers such as divinyl benzene, styrene and the like and an initiator, enters the micelle to wrap the surface of the template by stirring and reacts, and leads the shape of the polystyrene nano-rods to be fixed because the divinyl benzene and the styrene react on the surface of the template. The reacted product is etched by etchant such as tetrahydrofuran and the like, and the product can be obtained by removing redundant styrene, and because functional groups can be added on the surfaces of the monodisperse microsphere in the first step and the crosslinking reaction in the second step, the nano-rods can be prevented from being aggregated or influenced by the external environment, and can be combined with antibodies to detect antigens, so that the sensitivity of immunoassay is improved.

The technical effects are as follows: compared with the prior art, the invention has the following advantages:

1) polystyrene microspheres are synthesized by different polymerization methods, and 0.05-1 mu m of monodisperse polystyrene microspheres with uniform size can be prepared respectively.

2) The synthesis method of the nano-rod is simple, the steps are few, and the reaction conditions are easy to achieve.

3) The addition of the cross-linking agent enhances the rigidity of the polystyrene nano-rod and ensures that the shape is more stable.

4) The polystyrene nanorods can carry functional groups inside and outside, so that the polystyrene nanorods are not easy to agglomerate and are little influenced by the environment, and the nanorods have functionalization and can be used for biomedical detection.

Drawings

FIG. 1 is a scanning electron microscope image of monodisperse polystyrene microspheres prepared by a dispersion polymerization method in example 1 of the present invention.

FIG. 2 is a scanning electron micrograph of the swollen polystyrene microspheres prepared in example 1 of the present invention.

FIG. 3 is a scanning electron microscope image of polystyrene nanorods obtained by tetrahydrofuran treatment in example 1 of the present invention.

FIG. 4 is a scanning electron microscope image of polystyrene nanorods obtained by acetone treatment in example 2 of the present invention.

Detailed Description

The present invention will be further illustrated with reference to the following specific examples.