CN110117380B - preparation method and application of pH-responsive magnetic polystyrene porous microspheres - Google Patents
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Abstract
The invention provides a preparation method of pH responsive magnetic polystyrene-based porous microspheres, which comprises the following steps: 1) preparing ferroferric oxide nano particles by a coprecipitation method; 2) dispersing magnetic ferroferric oxide nano particles in a polystyrene solution, and preparing polystyrene magnetic porous microspheres by a thermally induced phase separation method by taking nano hydroxyapatite as a nucleating agent; 3) activating the magnetic porous microspheres by benzophenone to obtain polystyrene magnetic porous microsphere free radicals; 4) acrylic acid and maleic anhydride are grafted to the activated polystyrene magnetic porous microspheres by an ultraviolet radiation polymerization method. The invention utilizes the large specific surface area and high porosity of the polystyrene porous microsphere to ensure that water molecules are rapidly diffused when the porous microsphere is swelled and shrunk, thereby greatly improving the pH response rate of carboxyl on acrylic acid and maleic anhydride, namely improving the pH responsiveness of the porous microsphere.
Description
Technical Field
The invention relates to a method for preparing environment-responsive porous microspheres, in particular to a method for preparing pH-responsive magnetic polystyrene-based porous microspheres and application thereof.
Background
The polymer porous microspheres have been applied to tissue engineering, separation engineering, cell engineering, drug carriers, biotechnology and the like due to the characteristics of easy large-scale production, high repeatability, stable physicochemical properties and the like. How to modify the microspheres to functionalize the microspheres becomes the key point of research of researchers.
The polystyrene microsphere has the advantages of controllable particle size, large specific surface area, stable physical and chemical properties, easy surface modification and the like, is widely applied to the fields of biotechnology, catalyst carriers, biomedicine, adsorbents and the like, and is a polymer microsphere material which is most applied at present. The preparation method of the polystyrene microsphere mainly comprises a suspension polymerization method, a seed swelling method, a polymer precipitation, a micro-engineering emulsification technology and the like. The polystyrene microsphere prepared by the method has a solid structure, low porosity and small specific surface area, and the application of the polystyrene microsphere is limited. In order to increase the application range of polystyrene microspheres, researchers often make the polystyrene microspheres porous to increase the porosity and specific surface area thereof. For example, Liu et al (Liu S Q, Cai M L, Deng R H, et al, Korea-Australia Rheology Journal,2014,26,63) use chloroform as a solvent and hexadecane as a poor solvent, polystyrene is dispersed in an aqueous phase by shaking, and the chloroform is volatilized at normal temperature to induce phase separation of polystyrene and hexadecane, thereby obtaining the polystyrene porous microspheres. By controlling the volatilization rate of the solvent, microspheres with different porous forms are obtained. Although the process is simple, the volatilization rate of the trichloromethane in the water phase at normal temperature is very slow, the time consumption is long, the production efficiency is low, and the industrial production cannot be realized.
The invention content is as follows:
in order to solve the technical problems, the invention aims to provide a preparation method of a pH-responsive magnetic polystyrene-based porous microsphere and application thereof
The invention is realized by the following technical scheme:
a preparation method of pH-responsive magnetic polystyrene-based porous microspheres comprises the following steps:
dissolving ferrous chloride tetrahydrate and ferric chloride hexahydrate in distilled water, adding ammonia water, reacting, and performing suction filtration, washing and drying to obtain ferroferric oxide nanoparticles;
adding polystyrene into a mixed solvent of N, N-dimethylformamide and 1, 4-dioxane, dissolving, adding nano hydroxyapatite and the ferroferric oxide nano particles, and uniformly mixing to form a quenching liquid;
quenching the quenching liquid at a certain temperature for a certain time, removing a mixed solvent of N, N-dimethylformamide and 1, 4-dioxane by using water, and freeze-drying to obtain the polystyrene/ferroferric oxide magnetic composite porous microspheres;
soaking the polystyrene/ferroferric oxide magnetic composite porous microspheres in a benzophenone/acetone solution for 5min for activation, adding the activated polystyrene/ferroferric oxide magnetic composite porous microspheres into a grafting monomer mixed solution, and uniformly dispersing to obtain a polymerization reaction solution;
carrying out irradiation graft polymerization on the polymerization reaction liquid by using an ultraviolet light source under the protection of nitrogen to obtain polystyrene grafted poly (acrylic acid-co-maleic anhydride) magnetic polymer porous microspheres, namely the pH-responsive magnetic polystyrene-based porous microspheres;
the preparation method of the grafting monomer mixed solution comprises the following steps:
dissolving acrylic acid, maleic anhydride, N-methylene bisacrylamide and potassium persulfate in distilled water.
Preferably, the concentration of the ammonia water is 1mol/L, and the molar ratio of the ferrous chloride tetrahydrate to the ferric chloride hexahydrate is 1: 2.
Preferably, in the quenching liquid, the weight ratio of polystyrene, N-dimethylformamide, 1, 4-dioxane, ferroferric oxide nanoparticles to nano-hydroxyapatite is (1-1.5): (4-6): (2-4): (0.02-0.06) (0.002-0.004).
Preferably, the quenching temperature is-50 to-10 ℃, and the quenching time is 2 to 4 hours.
Preferably, the benzophenone/acetone solution contains benzophenone in a mass fraction of 5%.
Preferably, in the polymerization reaction liquid, the weight ratio of polystyrene/ferroferric oxide magnetic composite porous microspheres, acrylic acid, maleic anhydride, N-methylene bisacrylamide and potassium persulfate is (1.5-3): (3-7): (2-5): (0.1-0.2): (0.1-0.2).
Preferably, in the radiation graft polymerization, the power of an ultraviolet light source is 500W, the radiation distance is 50cm, and the reaction time is 30 min.
The pH-responsive magnetic polystyrene-based porous microsphere is prepared by the preparation method.
The application of the pH-responsive magnetic polystyrene-based porous microspheres in targeted therapeutic drugs.
The mechanism of the invention is as follows:
preparing ferroferric oxide nano particles by a coprecipitation method, dispersing the magnetic ferroferric oxide nano particles in a polystyrene solution, taking nano-hydroxyapatite as a nucleating agent, and preparing the polystyrene magnetic porous microspheres by a thermally induced phase separation method. Activating the magnetic porous microspheres with benzophenone to obtain free radicals, and finally grafting acrylic acid and maleic anhydride onto the polystyrene magnetic porous microspheres by an ultraviolet radiation polymerization method. The large specific surface area and the high porosity of the polystyrene porous microsphere are utilized, so that water molecules are rapidly diffused when the porous microsphere is swelled and shrunk, the pH response rate of carboxyl on acrylic acid and maleic anhydride is greatly improved, and the pH responsiveness of the porous microsphere is improved. The magnetic conductivity of the ferroferric oxide magnetic nanoparticles is utilized to realize the target treatment of the porous microspheres.
Compared with the prior art, the invention has the following beneficial effects:
1. nano hydroxyapatite is taken as a nucleating agent, and polystyrene is subjected to solution crystallization by a thermally induced phase separation method to form spherulites, namely a porous microsphere structure. The process is simple, the yield is high, and the method is very suitable for industrial production;
2. maleic anhydride and acrylic acid are grafted to the polystyrene magnetic porous microspheres, and the pH responsiveness of carboxyl on the acrylic acid and the maleic anhydride is greatly improved by utilizing the large specific surface area and the high porosity of the porous microspheres, namely the pH responsiveness of the porous microspheres is improved.
3. The aim of targeted therapy is achieved by utilizing the magnetic guidance of the ferroferric oxide magnetic nanoparticles.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a scanning electron microscope image of pH responsive magnetic polymer porous microspheres prepared in example 1 of the present invention;
FIG. 2 is a graph showing the swelling ratio of the pH-responsive magnetic polymer porous microspheres according to the pH variation prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
Step 1: 0.1987g of FeCl2·4H2O and 0.5404g FeCl3·6H2Adding O into 50mL of distilled water, magnetically stirring at normal temperature to dissolve, adding 10mL of 1mol/L ammonia water, reacting at normal temperature for 3h, after the reaction is finished, performing suction filtration, washing and drying to obtain Fe3O4And (3) nanoparticles.
Step 2: adding 1.2g of Polystyrene (PS) into 6g of N, N-dimethylformamide and 4g of 1, 4-dioxane solvent, magnetically stirring for dissolving, and adding 0.03g of Fe after complete dissolution3O4Adding the nano-particles and 0.002g of nano-hydroxyapatite into the solution, and magnetically stirring at a high speed to form a quenching mixed solution. Quenching the quenching mixed solution in a low-temperature refrigerator at-30 ℃ for 2hAfter quenching, adding 500mL of ice-water mixture into the system, removing N, N-dimethylformamide and 1, 4-dioxane, changing distilled water once every 6h for 4 times, and finally freeze-drying to obtain PS/Fe3O4Magnetic composite porous microspheres.
And step 3: mixing PS/Fe3O4Soaking the magnetic composite porous microspheres in 5g of benzophenone and 95g of acetone solution, activating for 5min, taking out, and vacuum drying to obtain activated PS/Fe3O4Magnetic composite porous microspheres for later use.
And 4, step 4: 4g of acrylic acid and 2g of maleic anhydride, 0.1g of N, N' -methylenebisacrylamide and 0.1g of potassium persulfate were dissolved in 200mL of distilled water, and 1.5g of activated PS/Fe3O4Soaking the magnetic composite porous microspheres in the mixed solution, and introducing N into the system2And (4) protecting. And starting an ultraviolet light source (a 500W high-pressure mercury lamp), radiating for 30min at a radiation distance of 50 cm. And after the reaction is finished, washing the obtained product with distilled water, and drying in vacuum to obtain the polystyrene grafted poly (acrylic acid-co-maleic anhydride) magnetic polymer porous microspheres.
The diameter of the polystyrene grafted poly (acrylic acid-co-maleic anhydride) magnetic polymer porous microsphere is 20.15 +/-4.15 mu m, as shown in figure 1. The porosity and the specific surface area were 90.1% and 17.1m, respectively2(ii) in terms of/g. The swelling ratio of the polystyrene grafted poly (acrylic acid-co-maleic anhydride) magnetic polymer porous microspheres when the swelling balance is achieved is 24.1 g/g. FIG. 2 is a graph showing the relationship between the swelling ratio of porous polystyrene-grafted poly (acrylic acid-co-maleic anhydride) magnetic polymer microspheres and pH. As can be seen from the figure, the porous microspheres of polystyrene grafted poly (acrylic acid-co-maleic anhydride) magnetic polymer suddenly increased at pH 4.2 to pH 7.8 to reach a maximum of 26.1 g/g. And then gradually decreases as the pH increases. The apparent saturation magnetization of the polystyrene grafted poly (acrylic acid-co-maleic anhydride) magnetic polymer porous microsphere is 0.071 emu/g.
Example 2
Step 1: 0.1987g of FeCl2·4H2O and 0.5404g FeCl3·6H2Adding O into 50mL of distilled water, magnetically stirring at normal temperature to dissolve, and adding10mL of 1mol/L ammonia water, reacting at normal temperature for 3h, after the reaction is finished, performing suction filtration, washing and drying to obtain Fe3O4And (3) nanoparticles.
Step 2: adding 1.5g PS into 8g N, N-dimethylformamide and 2g1, 4-dioxane solvent, magnetically stirring for dissolving, and dissolving 0.04g Fe3O4Adding the nano-particles and 0.004g of nano-hydroxyapatite into the solution, and magnetically stirring at a high speed to form a quenching mixed solution. Quenching the quenching mixed solution in a low-temperature refrigerator at the temperature of-20 ℃ for 2.5h, adding 500mL of ice-water mixture into the system after quenching is finished, removing N, N-dimethylformamide and 1, 4-dioxane, changing distilled water once every 6h for 4 times, and finally freeze-drying to obtain PS/Fe3O4Magnetic composite porous microspheres.
And step 3: mixing PS/Fe3O4Soaking the magnetic composite porous microspheres in 5g of benzophenone and 95g of acetone solution, activating for 5min, taking out, and vacuum drying to obtain activated PS/Fe3O4Magnetic composite porous microspheres for later use.
And 4, step 4: 5g of acrylic acid and 3g of maleic anhydride, 0.15g of N, N' -methylenebisacrylamide and 0.13g of potassium persulfate were dissolved in 200mL of distilled water, and 2g of activated PS/Fe3O4Soaking the magnetic composite porous microspheres in the mixed solution, and introducing N into the system2And (4) protecting. And starting an ultraviolet light source (a 500W high-pressure mercury lamp), radiating for 30min at a radiation distance of 50 cm. And after the reaction is finished, washing the obtained product with distilled water, and drying in vacuum to obtain the polystyrene grafted poly (acrylic acid-co-maleic anhydride) magnetic polymer porous microspheres.
The diameter of the polystyrene grafted poly (acrylic acid-co-maleic anhydride) magnetic polymer porous microsphere is 18.24 +/-4.26 mu m, and the porosity and the specific surface area are respectively 92.1 percent and 17.1m2(ii) in terms of/g. The swelling ratio of the polystyrene grafted poly (acrylic acid-co-maleic anhydride) magnetic polymer porous microspheres when the swelling balance is achieved is 20.4 g/g. The apparent saturation magnetization of the polystyrene grafted poly (acrylic acid-co-maleic anhydride) magnetic polymer porous microsphere is 0.076 emu/g.
Example 3
Step 1: 0 is added.1987g FeCl2·4H2O and 0.5404g FeCl3·6H2Adding O into 50mL of distilled water, magnetically stirring at normal temperature to dissolve, adding 10mL of 1mol/L ammonia water, reacting at normal temperature for 3h, after the reaction is finished, performing suction filtration, washing and drying to obtain Fe3O4And (3) nanoparticles.
Step 2: adding 1g of PS into 7g of N, N-dimethylformamide and 3g of 1, 4-dioxane solvent, magnetically stirring to dissolve, and adding 0.03g of Fe after complete dissolution3O4And adding the nano particles and 0.003g of nano hydroxyapatite into the solution, and magnetically stirring at a high speed to form a quenching mixed solution. Quenching the quenching mixed solution in a low-temperature refrigerator at the temperature of minus 40 ℃ for 3h, adding 500mL of ice-water mixture into the system after quenching is finished, removing N, N-dimethylformamide and 1, 4-dioxane, changing distilled water every 6h for 4 times, and finally freeze-drying to obtain PS/Fe3O4Magnetic composite porous microspheres.
And step 3: mixing PS/Fe3O4Soaking the magnetic composite porous microspheres in 5g of benzophenone and 95g of acetone solution, activating for 5min, taking out, and vacuum drying to obtain activated PS/Fe3O4Magnetic composite porous microspheres for later use.
And 4, step 4: 7g of acrylic acid and 4g of maleic anhydride, 0.2g of N, N' -methylenebisacrylamide and 0.18g of potassium persulfate were dissolved in 200mL of distilled water, and 2.5g of activated PS/Fe3O4Soaking the magnetic composite porous microspheres in the mixed solution, and introducing N into the system2And (4) protecting. And (3) starting an ultraviolet light source (a 500W high-pressure mercury lamp), radiating for 50cm, and performing radiation reaction for 30 min. And after the reaction is finished, washing the obtained product with distilled water, and drying in vacuum to obtain the polystyrene grafted poly (acrylic acid-co-maleic anhydride) magnetic polymer porous microspheres.
The diameter of the polystyrene grafted poly (acrylic acid-co-maleic anhydride) magnetic polymer porous microsphere is 20.90 +/-5.45 mu m, and the porosity and the specific surface area are respectively 94.3 percent and 18.9m2(ii) in terms of/g. The swelling ratio of the polystyrene grafted poly (acrylic acid-co-maleic anhydride) magnetic polymer porous microspheres when the swelling balance is reached is 22.9 g/g. Porous micro-porous polystyrene grafted poly (acrylic acid-co-maleic anhydride) magnetic polymerThe saturation magnetization of the spherical surface is 0.068 emu/g.
Comparative example 1
The difference from the embodiment 1 is that: the amount of polystyrene used in step 2) was 0.3g, and the subsequent steps were the same as in example 1. Finally, the microsphere structure cannot be obtained, and only a fibrous structure can be obtained. Mainly because the concentration of the polymer is low, the polystyrene can not be crystallized in the solution to form spherulites, and therefore, a porous microsphere structure can not be obtained.
Comparative example 2
The difference from the embodiment 1 is that: the addition amount of the nucleating agent hydroxyapatite added in the step 2) is 0, the subsequent steps are the same as those in the example 1, and finally, the microsphere structure cannot be obtained, but only a rough surface film can be obtained. Because of no nucleating agent, the polystyrene cannot be nucleated and crystallized in the solution, and therefore, a porous microsphere structure cannot be obtained.
Comparative example 3
The difference from the embodiment 1 is that: in the step 2), the addition amounts of the N, N-dimethylformamide and the 1, 4-dioxane solvent are respectively 10g and 0g, and finally the nanofiber structure is obtained.
Comparative example 4
The difference from the embodiment 1 is that: the amounts of acrylic acid and maleic anhydride in the step 4) are respectively 1g and 0.5g to obtain the porous microsphere of the polystyrene grafted poly (acrylic acid-co-maleic anhydride) magnetic polymer, the diameter of the microsphere is 19.90 +/-4.85 mu m, and the porosity and the specific surface area are respectively 93.3 percent and 17.2m2(ii) in terms of/g. The swelling ratio of the polystyrene grafted poly (acrylic acid-co-maleic anhydride) magnetic polymer porous microspheres when the swelling balance is achieved is 10.7 g/g. The apparent saturation magnetization of the polystyrene grafted poly (acrylic acid-co-maleic anhydride) magnetic polymer porous microsphere is 0.067 emu/g. Compared with example 1, the saturation swelling ratio of the microspheres at equilibrium is reduced from 24.1g/g to 10.7g/g, mainly because the content of acrylic acid and maleic anhydride grafted on the porous microspheres is reduced, so that the saturation swelling ratio of the microspheres is reduced.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (8)
1. A preparation method of pH-responsive magnetic polystyrene-based porous microspheres is characterized by comprising the following steps:
dissolving ferrous chloride tetrahydrate and ferric chloride hexahydrate in distilled water, adding ammonia water, reacting, and performing suction filtration, washing and drying to obtain ferroferric oxide nanoparticles;
adding polystyrene intoN,NDissolving dimethylformamide and 1, 4-dioxane in a mixed solvent, adding nano hydroxyapatite and the ferroferric oxide nano particles, and uniformly mixing to form a quenching liquid;
quenching the quenching liquid at a certain temperature for a certain time, and removing by using waterN,NA mixed solvent of dimethylformamide and 1, 4-dioxane is frozen and dried to obtain the polystyrene/ferroferric oxide magnetic composite porous microspheres;
soaking the polystyrene/ferroferric oxide magnetic composite porous microspheres in a benzophenone/acetone solution for 5min for activation, adding the activated polystyrene/ferroferric oxide magnetic composite porous microspheres into a grafting monomer mixed solution, and uniformly dispersing to obtain a polymerization reaction solution;
carrying out irradiation graft polymerization on the polymerization reaction liquid by using an ultraviolet light source under the protection of nitrogen to obtain polystyrene grafted poly (acrylic acid-co-maleic anhydride) magnetic polymer porous microspheres, namely the pH-responsive magnetic polystyrene porous microspheres;
the preparation method of the grafting monomer mixed solution comprises the following steps:
acrylic acid, maleic anhydride,N,Ndissolving methylene bisacrylamide and potassium persulfate in distilled water;
the quenching temperature is-50 to-10 ℃, and the quenching time is 2 to 4 hours.
2. The method for preparing pH-responsive magnetic polystyrene-based porous microspheres according to claim 1, wherein the concentration of ammonia water is 1mol/L, and the molar ratio of ferrous chloride tetrahydrate to ferric chloride hexahydrate is 1: 2.
3. The method for preparing pH-responsive magnetic polystyrene-based porous microspheres according to claim 1, wherein polystyrene, or polystyrene-based porous microspheres are added to the quenching liquid,N,NThe weight ratio of the dimethylformamide to the 1, 4-dioxane to the ferroferric oxide nanoparticles to the nano-hydroxyapatite is (1-1.5): (4-6): (2-4): (0.02-0.06) (0.002-0.004).
4. The method for preparing pH-responsive magnetic polystyrene-based porous microspheres according to claim 1, wherein the mass fraction of benzophenone in the benzophenone/acetone solution is 5%.
5. The method for preparing the pH-responsive magnetic polystyrene-based porous microspheres according to claim 1, wherein in the polymerization reaction solution, polystyrene/ferroferric oxide magnetic composite porous microspheres, acrylic acid, maleic anhydride, and the like,N,NThe weight ratio of the methylene bisacrylamide to the potassium persulfate is (1.5-3): (3-7): (2-5): (0.1-0.2): (0.1-0.2).
6. The method for preparing pH-responsive magnetic polystyrene-based porous microspheres according to claim 1, wherein in the irradiation graft polymerization, the power of an ultraviolet light source is 500W, the irradiation distance is 50cm, and the reaction time is 30 min.
7. A pH-responsive magnetic polystyrene-based porous microsphere obtained by the preparation method of any one of claims 1 to 6.
8. Use of the pH-responsive magnetic polystyrene-based porous microspheres of claim 7 in targeted therapeutic drugs.
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| CN110508260B (en) * | 2019-09-03 | 2022-02-15 | 晋江瑞碧科技有限公司 | Preparation method of lead ion imprinted composite hollow microspheres |
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