CN111978441B - Hollow polystyrene nano-particles and preparation method and application thereof - Google Patents
Hollow polystyrene nano-particles and preparation method and application thereof Download PDFInfo
- Publication number
- CN111978441B CN111978441B CN202010787247.8A CN202010787247A CN111978441B CN 111978441 B CN111978441 B CN 111978441B CN 202010787247 A CN202010787247 A CN 202010787247A CN 111978441 B CN111978441 B CN 111978441B
- Authority
- CN
- China
- Prior art keywords
- reaction
- initiator
- solution
- particles
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
Abstract
The invention discloses a preparation method of hollow polystyrene nano-particles, which comprises the steps of dispersing styrene in a solvent under the stirring condition, and adding small molecular alcohol to form uniform and transparent mixed solution; adding a composite initiator into the mixed solution to form initial reaction liquid, and carrying out soap-free emulsion polymerization on the initial reaction liquid; taking reaction liquid with different reaction time in the reaction process, diluting the reaction liquid by using small molecular alcohol aqueous solution containing a composite initiator with the same concentration as the initial reaction liquid, continuously stirring the reaction liquid to finish the reaction, and separating and purifying the reaction liquid to obtain the target product. The product prepared by the invention can be widely used in the aspects of medicines, gene delivery vectors, vaccine adjuvants, cancer diagnosis and treatment and the like. Compared with the prior art, the method for preparing the concave polystyrene nano-particles with uniform particle size by using the one-pot method is simple, the product can be prepared in batches, a stabilizer is not needed in the reaction process, and the synthesis process is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of soap-free emulsion polymerization, and relates to a hollow polystyrene nanoparticle and a preparation method and application thereof.
Background
Emulsion polymerization is a reaction in which monomers are dispersed in water to form an emulsion by means of an emulsifier and mechanical stirring, and then an initiator is added to initiate polymerization of the monomers, and is an important preparation method for synthesizing high molecular materials. The advantages are that: (1) the polymerization speed is high, and the molecular weight of the product is high; (2) water is used as a dispersant medium, which is beneficial to heat transfer and temperature control; (3) after the reaction reaches high conversion rate, the viscosity of the emulsion system is still very low, the dispersion system is stable, and the continuous operation is easy to control and realize. However, conventional emulsion polymerization also has problems, such as: the addition of emulsifiers increases the post-processing difficulty and reduces the water resistance, solvent resistance and mechanical properties of the polymer product. Matsumoto and Ochi (literature) synthesized polystyrene, polymethyl methacrylate and polyvinyl acetate emulsions with uniform-sized latex particles in 1960 in the complete absence of emulsifiers, after which the preparation of polymer microspheres by soap-free emulsion polymerization was rapidly developed. The emulsion synthesized by the soap-free emulsion polymerization method has single dispersed particle size and clean surface, and does not need the post-treatment of removing the emulsifier. The product is widely applied to the fields of clinical medicine, cytology, material science, chromatographic separation and the like.
In recent years, the uniform polymer microspheres have attracted much attention due to the characteristics of controllable form, adjustable molecular weight, easy introduction of different functional groups on the surface, and the like. In the polymer microspheres, the preparation and application of polystyrene particles are the most extensive, and templates or construction units are provided for the construction of ordered low-dimensional nanostructures.
Early researches on polystyrene particles mostly lie in that the polystyrene particles are prepared into spheres with single dispersity, spherical appearance and smooth and regular surfaces so as to be used as standard spheres or templates; in recent years, it has become popular to produce particles with irregular morphology, particularly Janus particles. Gennes first borrowed Janus in the nobel prize thesaurus 1991 and indicated particles having 2 different properties simultaneously. The traditional method for preparing Janus particles is a Pickering emulsion template method, the experimental operation of the method is complex, and the prepared particles are not pure enough. The anisotropy of Janus particles leads to wide application, and related preparation methods are increasingly researched in recent years. At present, the preparation of the hollow polystyrene particles with the micron-scale depressions is realized, and the preparation of the hollow polystyrene particles with the nanometer-scale depressions is still a great challenge.
Disclosure of Invention
In order to widen the application range of polystyrene particles and overcome the defects in the prior art, the invention provides a preparation method of hollow polystyrene nano particles, which takes styrene as a monomer and is prepared by soap-free emulsion polymerization initiated by a composite initiator (a dual initiator) in the presence of a solvent and micromolecule alcohol. During preparation, styrene is dispersed in water under the condition of stirring, and then micromolecular alcohol is added to form uniform and transparent mixed liquid; adding a composite initiator solution into the mixed solution, and uniformly mixing to form an initial reaction solution; under the condition of stirring in a constant-temperature water bath, taking a certain volume of reaction liquid for dilution in the reaction process and continuing to react. The target product can be obtained by centrifugal separation (alcohol washing and water washing). The target product obtained by the invention is the hollow polystyrene nanoparticle with good uniformity, excellent storage stability and good optical performance.
The invention can prepare the hollow polystyrene nano-particles by a one-step method under the dilution condition by utilizing the traditional soap-free emulsion method, and the product is pure and has no surfactant, thereby greatly widening the application field.
The invention provides a preparation method of hollow polystyrene nanoparticles, which specifically comprises the following steps:
step (1): adding styrene, a solvent and micromolecular alcohol into a container, stirring until the mixed solution is clear and transparent, and then carrying out ultrasonic homogenization to form the mixed solution.
Step (2): and (2) adding a composite initiator into the mixed solution obtained in the step (1) to form an initial reaction solution, and then carrying out soap-free emulsion polymerization.
And (3): and (3) taking the reaction liquid of the step (2) with different reaction time, and taking a small molecular alcohol aqueous solution containing the composite initiator as a diluent for dilution and finishing the reaction.
And (4): and (4) carrying out centrifugation, water washing and redispersion on the product obtained by the reaction in the step (3) to obtain the hollow polystyrene nano-particles.
In the step (1), the solvent is one or two of deionized water, secondary distilled water, high purity water and the like so as to reduce the influence of foreign impurities; preferably, it is double distilled water.
In step (1), the container can be a three-neck flask or other standard flask or conical flask.
In the step (1), the small molecule alcohol is preferably added dropwise into the container.
In the step (1), the small molecule alcohol refers to C1-C8 alcohol, and includes but is not limited to one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like; preferably, methanol, ethanol, isopropanol, tert-butanol. The function of the catalyst is to reduce the surface tension of the solvent, so that the styrene can be conveniently dispersed in the solvent.
In the step (1), the stirring temperature is 20-25 ℃; preferably, it is 25 ℃.
In the step (1), the stirring time is 10-15 min; preferably, it is 15 min.
In the step (1), the rotating speed of stirring is 50-100 rmp; preferably 100 rmp.
In the step (1), the temperature of the ultrasonic wave is 20-25 ℃; preferably, it is 25 ℃.
In the step (1), the ultrasonic treatment time is 10-15 min; preferably, it is 15 min.
In the step (1), the volume ratio of the solvent to the styrene is (80-90): (7-8);
preferably, it is 80: 7.
In the step (1), the volume ratio of the small molecular alcohol to the styrene is (120- & ltSUB & gt 140-): (7-8); preferably, 120: 7.
in the step (2), the composite initiator is a combination of an initiator and a reducing agent.
Wherein the initiator is one or more of potassium persulfate (KPS), Azobisisobutyronitrile (AIBN), dibenzoyl peroxide (BPO) and the like; preferably, it is potassium persulfate (KPS).
Wherein the reducing agent is sodium bisulfite (NaHSO)3) Sodium sulfite (NaSO)3) One or more of the following; preferably, sodium bisulfite (NaHSO)3)。
Wherein the mass ratio of the initiator to the reducing agent is (1-2): (0.7-1.4); preferably, is (1-2): (0.7-1.3); further preferably, is 2: 1.3.
in the step (2), preferably, the composite initiator, the small molecular alcohol and the solvent are prepared into a solution, and then the solution is added into the mixed solution in the step (1). Specifically, the steps for preparing the composite initiator are as follows: preparing a mixed solution (A) by using an initiator, micromolecular alcohol and a solvent, preparing a mixed solution (B) by using a reducing agent, micromolecular alcohol and a solvent, and finally mixing the two mixed solutions. Preferably, the initiator, ethanol and water are prepared into a mixed solution (A), then the reducing agent, ethanol and water are prepared into a mixed solution (B), and finally the two mixed solutions are mixed.
In the step (2), the mass ratio of the composite initiator to the styrene is (0.01-0.02): (0.5-1); preferably, it is 0.02: 1.
in the step (2), the mass ratio of the reducing agent to the styrene is (0.01-0.013): (0.5-1); preferably, it is 0.013: 1.
in the step (2), the temperature of the soap-free emulsion polymerization reaction is 20-30 ℃; preferably, it is 25 ℃.
In the step (2), the soap-free emulsion polymerization reaction is preferably a constant-temperature soap-free emulsion polymerization reaction.
In the step (2), the stirring speed of the soap-free emulsion polymerization reaction is 150-350 rmp; preferably 250 rmp.
In the step (3), the reaction solution with different reaction time is the reaction solution which reacts for 20min-400 min; preferably, it is 80min, 250 min.
In the step (3), the dilution multiple is 5-30 times; preferably, 5 to 20 times; more preferably, it is 10 times, 20 times.
In the step (3), the small molecular alcohol aqueous solution containing the composite initiator is the small molecular alcohol aqueous solution containing the composite initiator, the concentration of which is the same as that of the initial reaction solution.
Wherein the volume ratio of the small molecular alcohol to the water is (0-40): (100-60); preferably, it is 0: 100 or 20: 80.
in the step (3), the sample after dilution operation continuously reacts for 4-7 days at the temperature of 25 ℃ under stirring; preferably, it is 4 days.
In the step (4), the treatment processes of centrifugation, water washing and redispersion are carried out for 1-3 times; preferably 3 times.
Wherein the parameter conditions of the centrifugation are as follows: rotating at 10000-; preferably, the rotation speed is 12000 r, and the centrifugation is carried out for 10 min.
Wherein the step of washing with water is ultrasonic dispersion after washing with secondary distilled water.
In the step (4), the particle size of the hollow polystyrene nanoparticle is 180-250 nm; preferably 200 nm.
Further, the method also comprises a step of purifying styrene before the step (1), and the specific steps are as follows: washing styrene with the solution, then washing with the solvent, and carrying out reduced pressure distillation to obtain purified styrene.
Wherein the solution is one of sodium hydroxide solution, alkaline alumina and the like; preferably, it is a sodium hydroxide solution.
Wherein the concentration of the used solution is 5-10 wt%; preferably, it is 10 wt%.
The purpose of washing the styrene by the solution is to remove the polymerization inhibitor in the styrene, and the standard for judging whether the polymerization inhibitor is completely removed is that the separated solution is clear and transparent.
Wherein the number of times of washing with the solution is 1-3 times; preferably 3 times.
Wherein the solvent is one or more of redistilled water, high-purity water and the like; preferably, it is double distilled water.
Wherein the purpose of the solvent is to wash the styrene to neutrality.
Wherein the number of times of solvent washing is 2-4 times; preferably 4 times.
Wherein the temperature of the reduced pressure distillation is 18-25 ℃; preferably, it is 25 ℃.
Wherein the time of the reduced pressure distillation is 20-50 min; preferably, it is 40 min.
Wherein, in the reduced pressure distillation process, the distillate at about 20 ℃ is the purified styrene.
Wherein, after the step of purifying the styrene, the styrene is placed in a closed container for drying and low-temperature storage.
The invention also provides the hollow polystyrene nanoparticle prepared by the method.
Wherein the particle size of the hollow polystyrene nanoparticle is 180-250 nm; preferably 200 nm.
The invention also needs to carry out the dilution reaction of the step (3) in order to change the reaction environment of the reaction liquid of the step (1) and the step (2) and dissolve unreacted styrene and short chain oligomer in the particles due to the change of the conditions, thereby obtaining the target product, namely the hollow polystyrene nanoparticles.
When the hollow polystyrene particles are prepared by adopting the traditional template method, the removal of the hollow template is a very complicated process and can generate adverse influence on the generated hollow structure, but the preparation method only carries out simple dilution operation on the basis of the conventional soap-free emulsion polymerization method, greatly shortens the reaction steps, is simple and easy to operate, can prepare products in batches, does not need to add other reagents and heating operation in the reaction process, and has environment-friendly synthesis process.
The invention also provides application of the hollow polystyrene nano-particles in preparation of drugs and gene delivery vectors.
The invention also provides application of the hollow polystyrene nano-particles in preparation of products for diagnosing and treating cancers.
In a specific embodiment, the preparation method of the hollow polystyrene nanoparticle with controllable opening, disclosed by the invention, specifically comprises the following steps:
step (a): washing styrene with a solution, then washing with a solvent, and carrying out reduced pressure distillation to obtain purified styrene;
step (b): adding the purified styrene obtained in the step (a) and a solvent which is the same as the solvent obtained in the step (a) into a container, then dropwise adding small molecular alcohol, stirring until the mixed solution is clear and transparent, and then performing ultrasonic homogenization to form an initial mixed solution;
step (c): the composite initiators of potassium persulfate (KPS) and sodium bisulfite (NaHSO)3) And (c) adding the mixed solution in the step (b) to form an initial reaction solution, and carrying out soap-free emulsion reaction on the initial reaction solution.
Step (d): taking the reaction liquid in the step (c) for a certain reaction time, and diluting the reaction liquid by using a small molecular alcohol aqueous solution containing the composite initiator with the same concentration as that in the initial reaction liquid.
A step (e): and (d) centrifuging, washing and redispersing the product obtained by the reaction in the step (d) to prepare the hollow polystyrene nano-particles with adjustable openings.
Wherein, in the step (a), the solution is one or two of sodium hydroxide solution or alkaline alumina.
Wherein, in step (d), for the sample with higher dilution ratio, a coagulating agent, such as ammonium chloride, can be added to coagulate the styrene. The deposition time is generally 1-2 days; preferably, it is 1 day.
The term "dilution" as used herein means that in the polymerization process of the styrene soap-free emulsion, the reaction solution of different reaction times is added to the aqueous solution of the small molecular alcohol of the diinitiator with the same concentration as the initial reaction solution to perform the dilution reaction step.
In step (c) of the present invention, the preferred steps for preparing the composite initiator are: preparing a mixed solution (A) by using an initiator, micromolecular alcohol and a solvent, preparing a mixed solution (B) by using a reducing agent, micromolecular alcohol and a solvent, and finally mixing the two mixed solutions. Preferably, the initiator, ethanol and water are prepared into a mixed solution (A), then the reducing agent, ethanol and water are prepared into a mixed solution (B), and finally the two mixed solutions are mixed.
In the invention, the solution refers to one or two of sodium hydroxide solution or alkaline alumina.
In the invention, the solvent refers to one or two of secondary distilled water and high-purity water.
In the invention, the raw mixed liquid is a clear and transparent mixed liquid formed by mixing styrene subjected to reduced pressure distillation, a solvent and small molecular alcohol.
The invention has the beneficial effects that: compared with the prior art, the preparation method of the hollow polystyrene nano-particles with the adjustable and controllable openings has the following advantages:
(1) the prepared hollow polystyrene nano-particles have controllable opening size and good uniformity, and the particle opening size can be controlled according to simple dilution times, sampling time, the content of small molecular alcohol in a diluent and the types of added small molecular alcohol;
(2) by applying knowledge in colloid aspect and adopting a soap-free emulsion polymerization method to prepare a dispersion system of the hollow polystyrene nano-particles, the storage stability is good;
(3) the one-step reaction is adopted, and the preparation process is simple;
(4) the micromolecular alcohol has low toxicity and little environmental pollution;
(5) the process does not need to use a stabilizer and does not need to additionally remove the stabilizer in the product;
(6) the raw materials and the products are nontoxic and harmless and are relatively environment-friendly;
(6) the product can be prepared in batch;
(7) the prepared hollow polystyrene nano-particles can be widely applied to the fields of clinical medicine, cytology, material science, chromatographic separation and the like.
Drawings
FIG. 1 is an electron micrograph of the hollow polystyrene nanoparticles prepared in example 1.
FIG. 2 is an electron micrograph of the hollow polystyrene nanoparticles prepared in example 2.
FIG. 3 is an electron micrograph of the hollow polystyrene nanoparticles prepared in example 3.
FIG. 4 is an electron micrograph of the hollow polystyrene nanoparticles prepared in example 4.
FIG. 5 is an electron micrograph of the hollow polystyrene nanoparticles prepared in example 5.
FIG. 6 is an electron micrograph of the hollow polystyrene nanoparticles prepared in example 6.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The specific examples are implemented on the premise of the technical solution of the present invention, and include detailed implementation and specific operation procedures, but the scope of the present invention is not limited to the following examples.
The earlier stage of the embodiment is a preparation stage of a mixed solution of styrene, water and small molecular alcohol, and the method comprises the following steps:
3.5mL of purified styrene monomer and 40mL of pure water are measured and added into a 250mL conical flask, under the operation of stirring (the stirring speed is proper and is about 300rmp) and introducing argon, about 60mL of ethanol solution (the ethanol specification is selected as Hu type, the analytical purity is high, the content is more than or equal to 99.7 percent) is added until the mixed solution becomes uniform, clear and transparent, and then the conical flask is placed into an ultrasonic instrument (the ultrasonic power is set to be 99 percent, and the ultrasonic time is set to be 15 min). Preparing solution from 0.0566g of potassium persulfate KPS (potassium persulfate is Kaghai type, analytically pure, content is not less than 99.5%) and 30ml of ethanol-water mixed solution, and preparing solution from 0.0400g of sodium bisulfite NaHSO3(sodium bisulfite is selected in Shanghai type, analytically pure, content is not less than 58.5%) and 5ml of mixed solution of ethanol and water are prepared into solution, and the solution is stirred and reacted in a water bath kettle at 25 ℃ (the rotating speed is generally 250 rmp). Wherein the volume ratio of the ethanol and water mixed solution isEthanol: water 3: 2.
The reactants are diluted according to the following method of examples 1-6, and the specific operation steps are as follows:
example 1
In this embodiment, a sample is taken when the reaction process is carried out for 80min, and the mixed solution is diluted to about 10 times, the method includes the following steps:
1ml of the reaction solution was measured in a 150ml Erlenmeyer flask, and 0.0037g K was added to about 6ml of water2S2O8Preparing a solution of about 3ml of water and 0.0025g of reducing agent NaHSO3Preparing a solution, quickly adding the two solutions into the conical flask, and placing the conical flask in a constant-temperature water bath at 25 ℃ to stir and react for 4 days at the rotating speed of 250 rmp. And centrifuging, washing and redispersing the product to obtain the target product, namely the hollow polystyrene nano-particles. The product was dissolved in ethanol and characterized by TEM. The hollow polystyrene nanoparticles with recesses prepared in this example are shown in fig. 1, and each particle is bowl-shaped as viewed from fig. 1 as a whole.
Example 2
In this embodiment, a sample is taken when the reaction process is carried out for 80min, and the mixed solution is diluted to about 20 times, the method includes the following steps:
1ml of the reaction solution was measured in a 150ml Erlenmeyer flask, and 0.0077g K was added to about 12.5ml of water2S2O8Preparing a solution by mixing about 6.5ml of water with 0.0055g of reducing agent NaHSO3Preparing a solution, quickly adding the two solutions into the conical flask, and placing the conical flask in a constant-temperature water bath at 25 ℃ to stir and react for 4 days at the rotating speed of 250 rmp. And centrifuging, washing and redispersing the product to obtain the target product, namely the hollow polystyrene nano-particles. The product was dissolved in ethanol and characterized by TEM. The hollow polystyrene nanoparticles with concave cavities prepared in this example are shown in fig. 2, and it can be seen from fig. 2 that most of the particles are hemispherical.
Example 3
In this embodiment, a sample is taken when the reaction process is performed for 250min, and the mixed solution is diluted to about 10 times, the method includes the following steps:
1ml of the reaction solution was measured in a 150ml Erlenmeyer flask, and 0.0037g K was added to about 6ml of water2S2O8Preparing a solution of about 3ml of water and 0.0025g of reducing agent NaHSO3Preparing a solution, quickly adding the two solutions into the conical flask, and placing the conical flask in a constant-temperature water bath at 25 ℃ to stir and react for 4 days at the rotating speed of 250 rmp. And centrifuging, washing and redispersing the product to obtain the target product, namely the hollow polystyrene nano-particles. The product was dissolved in ethanol and characterized by TEM. The hollow polystyrene nanoparticles with concave cavities prepared in this example are shown in fig. 3, and it can be seen from fig. 3 that the openings of each particle are obviously smaller than the particle morphology in examples 1 and 2.
Example 4
In this embodiment, a sample is taken when the reaction process is performed for 250min, and the mixture is diluted to about 20 times, the method includes the following steps:
1ml of the reaction solution was measured in a 150ml Erlenmeyer flask, and 0.0077g K was added to about 12.5ml of water2S2O8Preparing a solution by mixing about 6.5ml of water with 0.0055g of NaHSO3Preparing a solution, quickly adding the two solutions into the conical flask, and placing the conical flask in a constant-temperature water bath at 25 ℃ to stir and react for 4 days at the rotating speed of 250 rmp. And centrifuging, washing and redispersing the product to obtain the target product, namely the hollow polystyrene nano-particles. The product was dissolved in ethanol and characterized by TEM. The hollow polystyrene nanoparticles with hollow pits prepared in this example are shown in fig. 4, and it can be seen from fig. 4 that the opening size of each particle is significantly smaller than that of the particles in examples 1, 2 and 3.
Example 5
The method for preparing the small molecular alcohol comprises the following steps of:
1ml of the reaction solution was measured in a 150ml Erlenmeyer flask, and 0.0037g K was added to about 6ml of water2S2O8Preparing a solution of about 3ml of water and 0.0025g of reducing agent NaHSO3Preparing a solution, quickly adding the two solutions into the conical flask, and placing the conical flask in a constant-temperature water bath at 25 ℃ to stir and react for 4 days at the rotating speed of 250 rmp. Centrifuging, washing and redispersing the product to obtain the target product hollow polystyrene nano-particles. The product was dissolved in tert-butanol and characterized by TEM. As shown in fig. 5, when viewed from fig. 5, the opening size of each hollow polystyrene nanoparticle prepared in this example is significantly smaller than that of the particles in examples 1, 2 and 3, and a plurality of openings may appear in some cases.
Example 6
In this embodiment, a sample is taken when the reaction process is performed for 250min, and the mixed solution is diluted to about 10 times, the method includes the following steps:
measuring 1ml of reaction solution into a 150ml conical flask, wherein the volume ratio of ethanol to water in the diluent is 20: 80, i.e. about 4.8ml of water and 1.2ml of ethanol solution 0.0037g K2S2O8Preparing a solution, adding 0.0025g of reducing agent NaHSO into 2.4ml of water and 0.6ml of ethanol solution3Preparing a solution, quickly adding the two solutions into the conical flask, and placing the conical flask in a constant-temperature water bath at 25 ℃ to stir and react for 4 days at the rotating speed of 250 rmp. And centrifuging, washing and redispersing the product to obtain the target product, namely the hollow polystyrene nano-particles. The product was dissolved in ethanol and characterized by TEM. The hollow polystyrene nanoparticles with recesses prepared in this example are shown in fig. 6, and it can be seen from fig. 6 that the size of the opening and the degree of recess of each particle are reduced relative to the morphology of the particles in example 3.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected.
Claims (7)
1. A preparation method of hollow polystyrene nanoparticles, which is characterized by comprising the following steps:
(1): adding styrene, a solvent and micromolecular alcohol into a container, stirring until a mixed solution is clear and transparent, and then carrying out ultrasonic homogenization to form a mixed solution; wherein the solvent is one of deionized water, secondary distilled water and high-purity water;
(2): adding a composite initiator into the mixed solution obtained in the step (1) to form an initial reaction solution, and then carrying out soap-free emulsion polymerization;
the composite initiator is the combination of an initiator and a reducing agent; wherein the initiator is one or more of potassium persulfate KPS, azodiisobutyronitrile AIBN and dibenzoyl peroxide BPO; the reducing agent is sodium bisulfite NaHSO3Sodium sulfite NaSO3One or two of them;
(3): taking the reaction liquid of the step (2) with different reaction time, and taking a small molecular alcohol aqueous solution containing the composite initiator as a diluent to dilute and finish the reaction;
the composite initiator is the combination of an initiator and a reducing agent; wherein the initiator is one or more of potassium persulfate KPS, azodiisobutyronitrile AIBN and dibenzoyl peroxide BPO; the reducing agent is sodium bisulfite NaHSO3Sodium sulfite NaSO3One or two of them;
(4): and (4) carrying out centrifugation, water washing and redispersion on the product obtained by the reaction in the step (3) to obtain the hollow polystyrene nano-particles.
2. The method according to claim 1, wherein in the step (1), the volume ratio of the solvent to the styrene is (80-90): (7-8); and/or the temperature of the ultrasonic wave is 20-25 ℃; and/or the ultrasonic time is 10-15 min; and/or the stirring temperature is 20-25 ℃; and/or the stirring time is 10-15 min; and/or the rotation speed of the stirring is 50-100 rmp.
3. The method according to claim 1, wherein in the step (1), the small molecule alcohol is C1-C8 alcohol, and comprises one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol; and/or the volume ratio of the small molecular alcohol to the styrene is (120- & ltSUB & gt 140-): (7-8).
4. The method according to claim 1, wherein in the step (2), the mass ratio of the initiator to the reducing agent is (1-2): (0.7-1.4).
5. The method according to claim 1, wherein in the step (2), the mass ratio of the composite initiator to the styrene is (0.01-0.02): (0.5-1); and/or the temperature of the soap-free emulsion polymerization reaction is 20-30 ℃; and/or the stirring speed of the soap-free emulsion polymerization reaction is 150-350 rmp.
6. The method according to claim 1, wherein in the step (3), the reaction solution with different reaction time is the reaction solution after 20-400 min; and/or, the dilution factor is 5-30;
and/or the volume ratio of the small molecular alcohol to the water in the small molecular alcohol aqueous solution is (0-40): (100-60).
7. The method as claimed in claim 1, wherein in step (4), the particle size of the hollow polystyrene nanoparticles is 180-250 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010787247.8A CN111978441B (en) | 2020-08-07 | 2020-08-07 | Hollow polystyrene nano-particles and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010787247.8A CN111978441B (en) | 2020-08-07 | 2020-08-07 | Hollow polystyrene nano-particles and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111978441A CN111978441A (en) | 2020-11-24 |
| CN111978441B true CN111978441B (en) | 2021-09-10 |
Family
ID=73446216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010787247.8A Active CN111978441B (en) | 2020-08-07 | 2020-08-07 | Hollow polystyrene nano-particles and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111978441B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006257139A (en) * | 2005-03-15 | 2006-09-28 | Osaka Prefecture | Core-shell type polymer particulate and method for producing the same |
| CN101250244A (en) * | 2008-04-03 | 2008-08-27 | 武汉昂泰科技有限公司 | Polymer hollow microsphere and preparation method thereof |
| CN103372409A (en) * | 2012-04-16 | 2013-10-30 | 三光株式会社 | Hollow polymer particle and manufacturing method thereof |
| CN103432971A (en) * | 2013-09-11 | 2013-12-11 | 天津知顺科技有限公司 | Preparation method of dissymmetric hollow microspheres based on polymer template particles |
| CN104844751A (en) * | 2015-05-17 | 2015-08-19 | 北京化工大学 | Micron-sized cross-linked polymer hollow microspheres and preparation method for same |
| CN107312116A (en) * | 2017-05-23 | 2017-11-03 | 程志峰 | A kind of preparation method of macromolecule Janus microsphere particles |
| CN109180844A (en) * | 2018-07-02 | 2019-01-11 | 华东师范大学 | A kind of shaggy polystyrene microsphere and its preparation method and application |
-
2020
- 2020-08-07 CN CN202010787247.8A patent/CN111978441B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006257139A (en) * | 2005-03-15 | 2006-09-28 | Osaka Prefecture | Core-shell type polymer particulate and method for producing the same |
| CN101250244A (en) * | 2008-04-03 | 2008-08-27 | 武汉昂泰科技有限公司 | Polymer hollow microsphere and preparation method thereof |
| CN103372409A (en) * | 2012-04-16 | 2013-10-30 | 三光株式会社 | Hollow polymer particle and manufacturing method thereof |
| CN103432971A (en) * | 2013-09-11 | 2013-12-11 | 天津知顺科技有限公司 | Preparation method of dissymmetric hollow microspheres based on polymer template particles |
| CN104844751A (en) * | 2015-05-17 | 2015-08-19 | 北京化工大学 | Micron-sized cross-linked polymer hollow microspheres and preparation method for same |
| CN107312116A (en) * | 2017-05-23 | 2017-11-03 | 程志峰 | A kind of preparation method of macromolecule Janus microsphere particles |
| CN109180844A (en) * | 2018-07-02 | 2019-01-11 | 华东师范大学 | A kind of shaggy polystyrene microsphere and its preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| Mechanism of Emulsion Polymerization of Styrene in Soap-Free Systems;A.R.GOODALL et al.;《JOURNAL OF POLYMER SCIENCE：Polymer Chemistry Edition》;19771231;第15卷;第2193-2218页 * |
| Shape engineering of polystyrene particles from spherical to raspberry-like to hollow flower-like via one-step non-surfactant self-templating polymerization of styrene in ethanol-water mixtures;Xuechen Xiang et al.;《RSC Advances》;20200320;第10卷;第11535-11542页 * |
| Study of the Anomalous Particles Formed during the Surfactant-Free Emulsion Polymerization of Styrene;R.A.COX et al.;《JOURNAL OF POLYMER SCIENCE：Polymer Chemistry Edition》;19771231;第2311-2319页 * |
| 交联聚苯乙烯粒子的中空结构及其分析;顾军等;《南京大学学报(自然科学)》;20070930;第43卷(第5期);第489-493页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111978441A (en) | 2020-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4130523A (en) | High solids latexes | |
| WO2008009997A1 (en) | Polymerisation process | |
| Eldin et al. | Poly (acrylonitrile-co-methyl methacrylate) nanoparticles: I. Preparation and characterization | |
| CN104194003B (en) | The preparation method of black monodisperse polymer micro-sphere | |
| CN109985584B (en) | Preparation method of adjustable and controllable strawberry-shaped silicon dioxide-organic hybrid composite microspheres | |
| CN109180844B (en) | Polystyrene microsphere with rough surface as well as preparation method and application thereof | |
| CN111978441B (en) | Hollow polystyrene nano-particles and preparation method and application thereof | |
| Yu et al. | A facile approach preparing PMMA nanospheres through in-situ surfactant miniemulsion photopolymerization under green LED irradiation | |
| Zou et al. | Model filled polymers. VIII. Synthesis of crosslinked polymeric beads by seed polymerization | |
| JPH06233691A (en) | Production of xerogel of bacterial cellulose and derivative produced thereby | |
| WO2007049867A1 (en) | Method and apparatus for production of polyvinyl alcohol with high degree of polymerization | |
| CN113150204A (en) | Method for preparing soap-free acrylic polymer material by microchannel continuous flow active polymerization | |
| JP4009752B2 (en) | Self-activated polymer particles having a narrow particle size distribution and method for producing the same | |
| Yang et al. | Polyacrylate/SiO 2 nanocomposites prepared by combining non-aqueous sol–gel process and miniemulsion polymerization | |
| CN115677898A (en) | Monodisperse hollow polystyrene-divinylbenzene composite microsphere, preparation method thereof and application thereof in enzyme-linked immunosorbent assay | |
| JP2002542318A (en) | Method for producing monodisperse polymer particles | |
| CN113980486B (en) | Preparation method of soap-free chemical crosslinking type copolymer nanoparticle coated organic pigment hybrid latex | |
| Chen et al. | Controlling morphology and particle size of hollow poly (styrene-divinylbenzene) microspheres fabricated by template-based method | |
| CN114773515A (en) | Preparation method of submicron carboxyl functionalized polystyrene microspheres | |
| CN108794672B (en) | Monodisperse polystyrene microsphere and preparation method and application thereof | |
| CN110028611B (en) | Monodisperse shell-core polystyrene microsphere and preparation method thereof | |
| McCracken et al. | The preparation of uniform polystyrene latices by true emulsion polymerization | |
| YUAN et al. | Synthesis and characterization of polystyrene/nanosilica organic-inorganic hybrid | |
| CN107082837B (en) | A kind of preparation method of partial size and the controllable monodisperse polystyrene microsphere of surface charge | |
| CN113480697B (en) | Monodisperse CO 2 And NH 3 Anisotropic nanoparticle and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |