CN114456326A - Carboxylated polystyrene nano-microsphere and preparation method and application thereof - Google Patents
Carboxylated polystyrene nano-microsphere and preparation method and application thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
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Abstract
The invention belongs to the technical field of high polymer material preparation, and particularly discloses a carboxylated polystyrene nano microsphere as well as a preparation method and application thereof. The method comprises the steps of dispersing a mixed solution of styrene, a carboxyl monomer and an initiator into an ethanol aqueous solution containing a stabilizer, and reacting at 60-80 ℃ for 6-12 hours to obtain the carboxylated polystyrene nanospheres. And removing unreacted monomers and other small molecular substances by centrifuging and washing with ethanol and water for multiple times to obtain the carboxylated polystyrene nano microsphere solution with uniform particle size. The surface of the carboxylated polystyrene nano microsphere prepared by the invention carries carboxyl, has excellent properties of good surface reaction capability, large specific surface area and the like, has high reaction activity on biological molecules (such as protein), and can be applied to the biomedical fields of cell marking, protein marking and the like.
Description
Technical Field
The invention relates to the technical field of preparation of high polymer materials, in particular to carboxylated polystyrene nano microspheres and a preparation method and application thereof.
Background
The monodisperse and functionalized polymer microsphere is widely applied to various fields of biomedicine due to the excellent physical and chemical properties, and the polystyrene microsphere is most widely applied due to the advantages of excellent mechanical property, good adsorbability, strong surface reaction capability and the like. The prior methods for preparing polystyrene microspheres include emulsion polymerization, dispersion polymerization, suspension polymerization, seed polymerization and the like. The advantages of dispersion polymerization are simple operation, wide selection range of monomer and solvent; the disadvantage is that it is difficult to introduce a crosslinking agent into the polymerization reaction to prepare highly crosslinked microspheres, because the highly crosslinked core does not easily absorb the monomer and the crosslinking agent, so that the polymerization is mainly carried out on the surface of the core, thereby easily causing crosslinking between the microspheres and non-uniformity of particle size. Therefore, the preparation of monodisperse polystyrene microspheres with uniform particle size by dispersion polymerization still has technical difficulties.
The carboxylated polystyrene microsphere is a polystyrene microsphere with carboxyl introduced by modifying the polystyrene microsphere. There are also a number of methods suitable for the preparation of carboxylated microspheres, two of the currently mainly used strategies: one is to mix the monomer with carboxyl and styrene monomer and then to polymerize, i.e. to adopt the method of copolymerization modification. The other method is a graft modification method, namely, polystyrene is synthesized by using styrene through methods such as dispersion polymerization and the like, and then the obtained polystyrene and a monomer with carboxyl are polymerized by adopting a dispersion polymerization method, so that the carboxylated microsphere is prepared. Compared with other microspheres with different functional groups carried on the surfaces, the carboxyl group of the carboxylated microsphere has the advantages of good stability and wide application prospect, and can react with biological macromolecules.
Therefore, how to provide a carboxylated polystyrene nano microsphere and a preparation method and application thereof, so that the prepared polystyrene nano microsphere is subjected to carboxyl modification, and the particle size of the modified microsphere is uniform and is in a monodisperse state is a difficult problem to be solved in the field.
Disclosure of Invention
In view of the above, the present invention provides a carboxylated polystyrene nanoparticle, and a preparation method and an application thereof, which avoid the problem of non-uniform particle size during the preparation of the polystyrene nanoparticle, and simplify the carboxyl modification process.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of carboxylated polystyrene nano-microspheres comprises the following steps:
1) mixing styrene, a carboxyl monomer and an initiator to obtain a mixed solution A;
2) mixing a stabilizer with an ethanol solution to obtain a mixed solution B;
3) and mixing the mixed solution A and the mixed solution B, and reacting to obtain the carboxylated polystyrene nano-microspheres.
Preferably, the carboxyl monomer is one or more of maleic anhydride, acrylic acid, methacrylic acid and methyl methacrylate.
Preferably, the initiator is one or more of azobisisobutyronitrile, dibenzoyl peroxide and acetyl peroxide.
Preferably, the stabilizer is one or more of polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol.
Preferably, the ethanol solution is an ethanol water solution, wherein the mass ratio of ethanol to water is 7: 3-9: 1.
Preferably, the reaction in the step 3) is carried out under the stirring condition of 300-600 rpm, the reaction temperature is 60-80 ℃, and the reaction time is 6-10 h.
Preferably, the mass ratio of the styrene to the carboxyl monomer to the mass ratio of the initiator to the stabilizer to the ethanol solution is 10-45: 1.5-8: 0.3-1.2: 1-30: 100.
the invention also aims to provide the carboxylated polystyrene nano-microsphere prepared by the preparation method of the carboxylated polystyrene nano-microsphere.
Preferably, the particle size of the carboxylated polystyrene nano-microsphere is 500-1200 nm.
The invention further aims to provide application of the carboxylated polystyrene nano microspheres in cell labeling and protein labeling.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
the surface of the carboxylated polystyrene nano microsphere prepared by the invention carries carboxyl, has excellent properties of good surface reaction capability, large specific surface area and the like, provides reaction sites for other various reaction substances, such as olefin catalysts, and prepares immune microspheres as clinical diagnosis reagents and the like, especially biomolecules (such as protein), has very high reaction activity, and can be applied to the biomedical fields of cell labeling, protein labeling and the like.
The preparation method disclosed by the invention is simple and is easy to realize large-scale preparation of the carboxylated polystyrene nano-microspheres.
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 a scanning electron microscope image of the apparent morphology of carboxylated polystyrene nanospheres prepared in example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of the apparent morphology of carboxylated polystyrene nanospheres prepared in example 2 of the present invention.
FIG. 3 is a scanning electron microscope image of the apparent morphology of carboxylated polystyrene nanospheres prepared in example 3 of the present invention.
FIG. 4 is a scanning electron microscope image of the apparent morphology of carboxylated polystyrene nanospheres prepared in example 4 of the present invention.
FIG. 5 is a scanning electron microscope image of the apparent morphology of carboxylated polystyrene nanospheres prepared in example 5 of the present invention.
FIG. 6 is an infrared curve diagram of carboxylated polystyrene nano-microspheres and polystyrene nano-microspheres prepared in examples 1-5 of the present invention.
Detailed Description
The invention provides a preparation method of carboxylated polystyrene nano microspheres, which comprises the following steps:
1) mixing styrene, a carboxyl monomer and an initiator to obtain a mixed solution A;
2) mixing a stabilizer with an ethanol solution to obtain a mixed solution B;
3) and mixing the mixed solution A and the mixed solution B, and reacting to obtain the carboxylated polystyrene nano-microspheres.
In the invention, the method also comprises a styrene refining step, and the concrete operations are as follows: washing with alkali liquor to remove polymerization inhibitor in the styrene, and washing with water to remove residual alkali liquor in the styrene to complete the refining step; the alkali liquor is preferably a sodium hydroxide solution with the mass fraction of 5-10%, and is further preferably a sodium hydroxide solution with the mass fraction of 5%.
In the invention, the carboxyl monomer is one or more of maleic anhydride, acrylic acid, methacrylic acid and methyl methacrylate, and acrylic acid is preferred.
In the invention, the initiator is one or more of azobisisobutyronitrile, dibenzoyl peroxide and acetyl peroxide, and preferably azobisisobutyronitrile.
In the invention, the stabilizer is one or more of polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol, and is preferably polyvinylpyrrolidone.
In the invention, the ethanol solution is an ethanol water solution, wherein the mass ratio of ethanol to water is 7: 3-9: 1; preferably 8: 2-9: 1; further preferably 8.5: 1.5.
In the invention, the reaction in the step 3) is carried out under the stirring condition of 300-600 rpm, preferably 300-400 rpm, and more preferably 300 rpm; the reaction temperature is 60-80 ℃, preferably 65-75 ℃, and further preferably 60 ℃; the reaction time is 6-10 h, preferably 7-9 h, and more preferably 8 h.
In the invention, the mass ratio of the styrene to the carboxyl monomer to the mass ratio of the initiator to the stabilizer to the ethanol solution is 10-45: 1.5-8: 0.3-1.2: 1-30: 100, preferably 26 to 28: 3-4: 0.6-0.8: 10-20: 100, more preferably 27: 3.5: 0.7: 15: 100.
in the invention, after the carboxylated polystyrene nano-microsphere is prepared in the step 3), the method further comprises a post-treatment process, and the method comprises the following specific steps:
respectively carrying out centrifugal water washing and centrifugal alcohol washing on the obtained carboxylated polystyrene nano microspheres for multiple times, removing unreacted monomers such as styrene, acrylic acid and the like and impurity micromolecule substances, and preparing a carboxylated polystyrene nano microsphere solution with uniform particle size; preferably, the operation sequence is not limited by centrifugal water washing and centrifugal alcohol washing, and the washing times are independent, preferably 2-4 times, and further preferably 3 times; the centrifugal rotation speed is preferably 7000-10000 rpm, and more preferably 8000 rpm.
The invention also provides the carboxylated polystyrene nano-microsphere prepared by the preparation method of the carboxylated polystyrene nano-microsphere.
In the invention, the particle size of the carboxylated polystyrene nano-microsphere is 500-1200 nm, preferably 700-1000 nm, and further preferably 800 nm; the carboxylated polystyrene nano-microspheres prepared by the invention have uniform particle size.
The invention also provides application of the carboxylated polystyrene nano-microsphere in cell labeling and protein labeling.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
Example 1
And adding a NaOH solution with the mass fraction of 5% into the styrene, washing to remove the polymerization inhibitor, and then washing the residual NaOH with deionized water to make the solution neutral, thereby finishing the refining of the styrene.
1) Mixing 25g of refined styrene, 2.5g of maleic anhydride and 0.8g of azobisisobutyronitrile, and stirring until the mixture is completely dissolved to obtain a mixed solution A;
2) adding 5g of polyvinylpyrrolidone into an ethanol solution (85g of ethanol and 15g of water), and stirring until the polyvinylpyrrolidone is completely dissolved to obtain a mixed solution B;
3) adding the mixed solution B into an oil bath kettle, adding the mixed solution A at 65 ℃, and reacting for 8 hours (keeping stirring at a speed of 300rpm in the reaction process) to obtain a reaction solution containing the carboxylated polystyrene nano-microspheres.
4) Adding the reaction solution into a centrifugal tube, washing for 3 times at 8000rpm by using ethanol and deionized water respectively to obtain white carboxylated polystyrene nano-microsphere precipitate, and dissolving the white precipitate in ethanol or water to obtain a monodisperse carboxylated polystyrene nano-microsphere solution with uniform particle size.
The scanning electron microscope image of the apparent morphology of the carboxylated polystyrene nanospheres prepared in this example is shown in fig. 1, and it can be seen from fig. 1 that the carboxylated polystyrene nanospheres prepared in this example are in a single dispersion state and have uniform particle size.
Example 2
1) 27g of purified styrene (the purification process is the same as in example 1), 3g of acrylic acid and 0.7g of azobisisobutyronitrile were mixed and stirred until completely dissolved to obtain a mixed solution A;
2) adding 10g of polyvinylpyrrolidone into an ethanol solution (90g of ethanol and 10g of water), and stirring until the polyvinylpyrrolidone is completely dissolved to obtain a mixed solution B;
3) adding the mixed solution B into an oil bath kettle, adding the mixed solution A at 65 ℃, and reacting for 6h (keeping the stirring speed of 400rpm in the reaction process) to obtain a reaction solution containing the carboxylated polystyrene nano-microspheres.
4) Adding the reaction solution into a centrifugal tube, washing for 4 times at 8000rpm by using ethanol and deionized water respectively to obtain white carboxylated polystyrene nano-microsphere precipitate, and dissolving the white precipitate in ethanol or water to obtain a monodisperse carboxylated polystyrene nano-microsphere solution with uniform particle size.
An apparent morphology scanning electron microscope image of the carboxylated polystyrene nanospheres prepared in this example is shown in fig. 2, and it can be seen from fig. 2 that the carboxylated polystyrene nanospheres prepared in this example are in a single dispersion state and have uniform particle size.
Example 3
1) 10g of purified styrene (the purification process is the same as in example 1), 1.5g of acrylic acid and 0.3g of dibenzoyl peroxide are mixed and stirred until completely dissolved to obtain a mixed solution A;
2) adding 1g of polyethylene glycol into an ethanol solution (85g of ethanol and 15g of water), and stirring until the polyethylene glycol is completely dissolved to obtain a mixed solution B;
3) adding the mixed solution B into an oil bath kettle, adding the mixed solution A at 60 ℃, and reacting for 10h (keeping the stirring speed of 300rpm in the reaction process) to obtain a reaction solution containing the carboxylated polystyrene nano-microspheres.
4) Adding the reaction solution into a centrifugal tube, washing with ethanol and deionized water at 7000rpm for 3 times respectively to obtain white precipitate of the carboxylated polystyrene nano-microsphere, and dissolving the white precipitate in ethanol or water to obtain a monodisperse carboxylated polystyrene nano-microsphere solution with uniform particle size.
An apparent morphology scanning electron microscope image of the carboxylated polystyrene nanospheres prepared in this example is shown in fig. 3, and it can be seen from fig. 3 that the carboxylated polystyrene nanospheres prepared in this example are in a single dispersion state and have uniform particle size.
Example 4
1) 30g of purified styrene (the purification process is the same as in example 1), 4.5g of acrylic acid and 0.6g of azobisisobutyronitrile were mixed and stirred until completely dissolved to obtain a mixed solution a;
2) adding 20g of polyvinyl alcohol into an ethanol solution (70g of ethanol and 30g of water), and stirring until the polyvinyl alcohol is completely dissolved to obtain a mixed solution B;
3) adding the mixed solution B into an oil bath kettle, adding the mixed solution A at 65 ℃, and reacting for 8 hours (keeping the stirring speed of 600rpm in the reaction process) to obtain a reaction solution containing the carboxylated polystyrene nano-microspheres.
4) Adding the reaction solution into a centrifugal tube, washing for 2 times by using ethanol and deionized water at 8000rpm respectively to obtain white precipitates of the carboxylated polystyrene nano microspheres, and dissolving the white precipitates in the ethanol or water to obtain a monodisperse carboxylated polystyrene nano microsphere solution with uniform particle size.
An apparent morphology scanning electron microscope image of the carboxylated polystyrene nanospheres prepared in this example is shown in fig. 4, and it can be seen from fig. 4 that the carboxylated polystyrene nanospheres prepared in this example are in a single dispersion state and have uniform particle size.
Example 5
1) 45g of purified styrene (the purification process is the same as in example 1), 8g of acrylic acid and 1.2g of acetyl peroxide were mixed and stirred until completely dissolved to obtain a mixed solution A;
2) adding 30g of polyvinylpyrrolidone into an ethanol solution (85g of ethanol and 15g of water), and stirring until the polyvinylpyrrolidone is completely dissolved to obtain a mixed solution B;
3) adding the mixed solution B into an oil bath kettle, adding the mixed solution A at 80 ℃, and reacting for 6h (keeping the stirring speed of 300rpm in the reaction process) to obtain a reaction solution containing the carboxylated polystyrene nano-microspheres.
4) Adding the reaction solution into a centrifugal tube, washing for 3 times at 8000rpm by using ethanol and deionized water respectively to obtain white carboxylated polystyrene nano-microsphere precipitate, and dissolving the white precipitate in ethanol or water to obtain a monodisperse carboxylated polystyrene nano-microsphere solution with uniform particle size.
An apparent morphology scanning electron microscope image of the carboxylated polystyrene nanospheres prepared in this example is shown in fig. 5, and it can be seen from fig. 5 that the carboxylated polystyrene nanospheres prepared in this example are in a single dispersion state and have uniform particle size.
The infrared curve of the carboxylated polystyrene nanospheres prepared in examples 1-5 is shown in FIG. 6. FIG. 6 shows that except the characteristic peak of polystyrene nanosphere (PSt) (the preparation method of polystyrene nanosphere is different from that of example 1 only in that no carboxyl monomer is added), examples 1-5 are 1707cm-1And infrared characteristic peaks of carboxyl (-COOH) are also present, which shows that the carboxylated polystyrene nano microspheres are successfully prepared.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of carboxylated polystyrene nano microspheres is characterized by comprising the following steps:
1) mixing styrene, a carboxyl monomer and an initiator to obtain a mixed solution A;
2) mixing a stabilizer with an ethanol solution to obtain a mixed solution B;
3) and mixing the mixed solution A and the mixed solution B, and reacting to obtain the carboxylated polystyrene nano-microspheres.
2. The method for preparing carboxylated polystyrene nano-microspheres according to claim 1, wherein the carboxyl monomer is one or more of maleic anhydride, acrylic acid, methacrylic acid and methyl methacrylate.
3. The method for preparing carboxylated polystyrene nano-microspheres according to claim 2, wherein the initiator is one or more of azobisisobutyronitrile, dibenzoyl peroxide and acetyl peroxide.
4. The method for preparing carboxylated polystyrene nano-microspheres according to claim 3, wherein the stabilizer is one or more of polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol.
5. The preparation method of the carboxylated polystyrene nanosphere according to claim 4, wherein the ethanol solution is an ethanol aqueous solution, and the mass ratio of ethanol to water is 7: 3-9: 1.
6. The preparation method of carboxylated polystyrene nanospheres according to any of claims 1 to 5, wherein the reaction in step 3) is carried out under stirring conditions of 300 to 600rpm, the reaction temperature is 60 to 80 ℃, and the reaction time is 6 to 10 hours.
7. The preparation method of carboxylated polystyrene nano-microspheres according to claim 6, wherein the mass ratio of styrene to carboxyl monomer to the mass ratio of the initiator to the stabilizer to the ethanol solution is 10-45: 1.5-8: 0.3-1.2: 1-30: 100.
8. the carboxylated polystyrene nanosphere prepared by the preparation method of the carboxylated polystyrene nanosphere according to any one of claims 1 to 7.
9. The carboxylated polystyrene nanosphere according to claim 8, wherein the particle size of said carboxylated polystyrene nanosphere is 500-1200 nm.
10. Use of the carboxylated polystyrene nanospheres of claim 8 or 9 in cell labeling and protein labeling.
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