CN110117380A - The preparation method and its usage of pH responsiveness magnetic polystyrene base porous microsphere - Google Patents
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Abstract
The present invention provides a kind of preparation methods of pH responsiveness magnetic polystyrene base porous microsphere, 1) specific method is the following steps are included: prepare ferroferric oxide nano granules by coprecipitation；2) magnetic ferroferric oxide nanometer particle is dispersed in polystyrene solution, using nanometer hydroxyapatite as nucleating agent, polystyrene magnetic porous microspheres is prepared by Thermal inactive method；3) magnetic porous microspheres are activated to obtain polystyrene magnetic porous microspheres free radical by benzophenone；4) acrylic acid and maleic anhydride are grafted on activated polystyrene magnetic porous microspheres by ultraviolet radioactive polymerization.The present invention utilizes the bigger serface and high porosity of polystyrene porous microballoon, make the quick diffusion of porous microsphere hydrone in swelling and contraction, the pH speed of response for substantially increasing carboxyl on acrylic acid and maleic anhydride improves the pH responsiveness of porous microsphere.
Description
Technical field
The present invention relates to a kind of method for preparing environment-responsive porous microsphere more particularly to a kind of pH responsiveness magnetism are poly-
The preparation method and its usage of styryl porous microsphere.
Background technique
The characteristics such as polyalcohol stephanoporate microballoons are easy to large-scale production with it, repeatability is high, physicochemical properties are stablized,
Applied to organizational project, separation engineering, cell engineering, pharmaceutical carrier and biotechnology etc..How to be modified to microballoon makes it
Functionalization becomes the emphasis of researcher research.
There is polystyrene microsphere controllable particle size, large specific surface area, physicochemical properties stabilization and surface to be easy to
Many advantages, such as modified, it is widely used in the fields such as biotechnology, catalyst carrier, biomedicine and adsorbent, is current
Using most polymer microballoon materials.It is molten mainly to pass through suspension polymerization, seed for the preparation method of polystyrene microsphere at present
Swollen method, precipitation polymers and micro- engineering emulsifying technology etc..The polystyrene microsphere of above method preparation is solid construction, hole
Rate is low, and specific surface area is small, limits the application of polystyrene microsphere.In order to improve the application range of polystyrene microsphere, scientific research
Polystyrene microsphere is often made into cellular by personnel, to improve its porosity and specific surface area.Such as Liu et al. people (Liu S Q,
Cai M L, Deng R H, et al., Korea-Australia Rheology Journal, 2014,26,63) with three chloromethanes
Alkane is solvent, and hexadecane is poor solvent, and polystyrene shakes dispersion in water phase, and the induction of volatilization chloroform is poly- under room temperature
Styrene is mutually separated with hexadecane generation, obtains polystyrene porous microballoon.By controlling the rate of volatilization of solvent, obtain not
With the microballoon of porous form.Although simple process, rate of volatilization of the chloroform in water phase is very slow under room temperature, consumption
Duration, production efficiency is low, can not industrialized production.
Summary of the invention:
In order to solve the above technical problems, the purpose of the present invention is to propose to a kind of pH responsiveness magnetic polystyrene Quito holes
The preparation method and its usage of microballoon
The present invention is achieved by the following technical solutions:
A kind of preparation method of pH responsiveness magnetic polystyrene base porous microsphere comprising following steps:
Iron dichloride tetrahydrate and ferric chloride hexahydrate are dissolved in distilled water, ammonium hydroxide is added, after reaction, filtered,
Washing and drying, obtain ferroferric oxide nano granules；
N,N-Dimethylformamide and Isosorbide-5-Nitrae-dioxane in the mixed solvent is added in polystyrene, is added after dissolution
Nanometer hydroxyapatite and the ferroferric oxide nano granules, mixing form quenching liquid；
By the quenching liquid quench at a certain temperature after a certain period of time, using water remove n,N-Dimethylformamide and
Isosorbide-5-Nitrae-dioxane mixed solvent, it is freeze-dried to obtain polystyrene/Fe 3 O 4 magnetic composite porous microspheres；
The polystyrene/Fe 3 O 4 magnetic composite porous microspheres are impregnated into 5min in benzophenone/acetone soln
After being activated, it is added in grafted monomers mixed liquor, is uniformly dispersed, obtains polymerization liquid；
By the polymerization liquid under the protection of nitrogen, radiation grafting copolymerization is carried out with ultraviolet source, obtains polyphenyl second
Alkene is grafted poly- (acrylic acid-co- maleic anhydride) magnetic polymer porous microsphere, i.e., the described pH responsiveness magnetic polystyrene base
Porous microsphere；
The grafted monomers mixed liquor the preparation method comprises the following steps:
By acrylic acid, maleic anhydride, N, N- methylene-bisacrylamide and potassium peroxydisulfate are dissolved in distilled water.
Preferably, the concentration of the ammonium hydroxide is 1mol/L, the Iron dichloride tetrahydrate and ferric chloride hexahydrate
Molar ratio be 1:2.
Preferably, in the quenching liquid, polystyrene, n,N-Dimethylformamide, Isosorbide-5-Nitrae-dioxane, four
The weight ratio of Fe 3 O nano particle and nanometer hydroxyapatite is (1~1.5): (4~6): (2~4): (0.02~
0.06) (0.002~0.004).
Preferably, the temperature of the quenching is -50~-10 DEG C, 2~4h of cool time.
Preferably, in the benzophenone/acetone soln, the mass fraction of benzophenone is 5%.
Preferably, in the polymerization liquid, polystyrene/Fe 3 O 4 magnetic composite porous microspheres, third
Olefin(e) acid, maleic anhydride, N,N methylene bis acrylamide and potassium peroxydisulfate weight ratio be (1.5~3): (3~7): (2~
5): (0.1~0.2): (0.1~0.2).
Preferably, in the radiation grafting copolymerization, the power of ultraviolet source is 500W, irradiation distance 50cm,
Reaction time is 30min.
A kind of pH responsiveness magnetic polystyrene base porous microsphere obtained by aforementioned preparation process.
A kind of purposes of pH responsiveness magnetic polystyrene base porous microsphere as the aforementioned in target therapeutic agent.
Mechanism of the invention is:
Prepare ferroferric oxide nano granules by coprecipitation, after magnetic ferroferric oxide nanometer particle is dispersed in it is poly-
In styrene solution, using nanometer hydroxyapatite as nucleating agent, it is magnetic porous that polystyrene is prepared by Thermal inactive method
Microballoon.Magnetic porous microspheres are activated to obtain free radical by benzophenone, finally by ultraviolet radioactive polymerization by acrylic acid and
Maleic anhydride is grafted on polystyrene magnetic porous microspheres.Bigger serface and high hole using polystyrene porous microballoon
Gap rate makes the quick diffusion of porous microsphere hydrone in swelling and contraction, substantially increases carboxylic on acrylic acid and maleic anhydride
The pH speed of response of base improves the pH responsiveness of porous microsphere.Utilize the magnetic steering of ferroferric oxide magnetic nano-particles
Property realizes the purpose of the targeted therapy of porous microsphere.
Compared with prior art, the present invention have it is following the utility model has the advantages that
It 1, is that solution crystallization occurs for polystyrene by Thermal inactive method using nanometer hydroxyapatite as nucleating agent,
Form spherocrystal, i.e. porous microsphere structure.Simple process, yield are high, are very suitable for industrialized production；
2, by maleic anhydride and acrylic acid-grafted on polystyrene magnetic porous microspheres, compare table greatly using porous microsphere
Area and high porosity substantially increase the pH responsiveness of the carboxyl on acrylic acid and maleic anhydride, that is, improve porous microsphere
PH responsiveness.
3, the purpose of targeted therapy is realized using the magnetic conductance tropism of ferroferric oxide magnetic nano-particles.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
The scanning electron microscope (SEM) photograph for the pH responsiveness magnetic polymer porous microsphere that in Fig. 1 present invention prepared by embodiment 1；
Embodiment 1 prepares pH responsiveness magnetic polymer porous microsphere swelling ratio with pH change curve in Fig. 2 present invention.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the common skill of this field
For art personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to this
The protection scope of invention.
Embodiment 1
Step 1: by 0.1987g FeCl2·4H2O and 0.5404g FeCl3·6H2O is added in 50mL distilled water, room temperature
Magnetic agitation dissolution, it is rear that 1mol/L ammonium hydroxide 10mL, normal-temperature reaction 3h is added, after reaction, filters, washs, is dry, obtaining
Fe3O4Nano particle.
Step 2: 6gN, dinethylformamide and 4g1,4- dioxane solvent is added in 1.2g polystyrene (PS)
In, magnetic agitation dissolution, by 0.03g Fe after dissolution completely3O4Nano particle and 0.002g nanometer hydroxyapatite are added above-mentioned
In solution, high speed magnetic stirring forms quenching mixed liquor.Quenching mixed liquor is quenched into the 2h time in -30 DEG C of low temperature refrigerators,
After quenching, 500mL mixture of ice and water is added into system, removes n,N-Dimethylformamide and Isosorbide-5-Nitrae-dioxane, often
6h changes primary distilled water, changes 4 times, finally freeze-drying obtains PS/Fe3O4Magnetic coupling porous microsphere.
Step 3: by PS/Fe3O4Magnetic coupling porous microsphere is immersed in 5g benzophenone and 95g acetone soln, activation
It takes out, is dried in vacuo after 5min, obtain activation PS/Fe3O4Magnetic coupling porous microsphere, it is spare.
Step 4: by 4g acrylic acid and 2g maleic anhydride, 0.1gN, N '-methylene-bisacrylamide and 0.1g potassium peroxydisulfate
It is dissolved in 200mL distilled water, 1.5g is activated into PS/Fe3O4Magnetic coupling porous microsphere is immersed in above-mentioned mixed liquor, in system
Logical N2Protection.It opens ultraviolet source (500 W high-pressure sodium lamp), radiation length 50cm, radioreaction 30min.After reaction,
Products therefrom is washed with distilled water, is dried in vacuo, it is magnetic poly- to obtain polystyrene graft poly- (acrylic acid-co- maleic anhydride)
Close object porous microsphere.
The diameter of poly- (acrylic acid-co- maleic anhydride) the magnetic polymer porous microsphere of polystyrene graft be 20.15 ±
4.15 μm, as shown in Figure 1.Porosity and specific surface area are respectively 90.1% and 17.1m2/g.Poly- (the propylene of polystyrene graft
Acid-co- maleic anhydride) swelling ratio of magnetic polymer porous microsphere when reaching swelling equilibrium be 24.1g/g.Fig. 2 is polyphenyl second
Alkene is grafted the relation curve of poly- (acrylic acid-co- maleic anhydride) between magnetic polymer porous microsphere swelling ratio and pH value.From
It is found that poly- (acrylic acid-co- maleic anhydride) the magnetic polymer porous microsphere of polystyrene graft is unexpected at pH=4.2 in figure
Increase, until it is 26.1g/g that pH=7.8, which reaches maximum value,.It is gradually reduced afterwards as pH increases.Poly- (the propylene of polystyrene graft
Acid-co- maleic anhydride) the apparent saturation magnetization of magnetic polymer porous microsphere be 0.071emu/g.
Embodiment 2
Step 1: by 0.1987g FeCl2·4H2O and 0.5404g FeCl3·6H2O is added in 50mL distilled water, room temperature
Magnetic agitation dissolution, it is rear that 1mol/L ammonium hydroxide 10mL, normal-temperature reaction 3h is added, after reaction, filters, washs, is dry, obtaining
Fe3O4Nano particle.
Step 2: 8gN, in dinethylformamide and 2g1,4- dioxane solvent, magnetic agitation is added in 1.5g PS
Dissolution, by 0.04g Fe after dissolution completely3O4Nano particle and 0.004g nanometer hydroxyapatite are added in above-mentioned solution, high speed
Magnetic agitation forms quenching mixed liquor.Quenching mixed liquor is quenched into 2.5h in -20 DEG C of low temperature refrigerators, after quenching, to
500mL mixture of ice and water is added in system, removes n,N-Dimethylformamide and Isosorbide-5-Nitrae-dioxane, every 6h changes single flash
Water changes 4 times, and finally freeze-drying obtains PS/Fe3O4Magnetic coupling porous microsphere.
Step 3: by PS/Fe3O4Magnetic coupling porous microsphere is immersed in 5g benzophenone and 95g acetone soln, activation
It takes out, is dried in vacuo after 5min, obtain activation PS/Fe3O4Magnetic coupling porous microsphere, it is spare.
Step 4: by 5g acrylic acid and 3g maleic anhydride, 0.15gN, N '-methylene-bisacrylamide and 0.13g persulfuric acid
Potassium is dissolved in 200mL distilled water, and 2g is activated PS/Fe3O4Magnetic coupling porous microsphere is immersed in above-mentioned mixed liquor, in system
Logical N2Protection.It opens ultraviolet source (500 W high-pressure sodium lamp), radiation length 50cm, radioreaction 30min.After reaction,
Products therefrom is washed with distilled water, is dried in vacuo, it is magnetic poly- to obtain polystyrene graft poly- (acrylic acid-co- maleic anhydride)
Close object porous microsphere.
The diameter of poly- (acrylic acid-co- maleic anhydride) the magnetic polymer porous microsphere of polystyrene graft be 18.24 ±
4.26 μm, porosity and specific surface area are respectively 92.1% and 17.1m2/g.Poly- (the Malaysia acrylic acid-co- of polystyrene graft
Acid anhydrides) swelling ratio of magnetic polymer porous microsphere when reaching swelling equilibrium be 20.4g/g.Poly- (the propylene of polystyrene graft
Acid-co- maleic anhydride) the apparent saturation magnetization of magnetic polymer porous microsphere be 0.076emu/g.
Embodiment 3
Step 1: by 0.1987g FeCl2·4H2O and 0.5404g FeCl3·6H2O is added in 50mL distilled water, room temperature
Magnetic agitation dissolution, it is rear that 1mol/L ammonium hydroxide 10mL, normal-temperature reaction 3h is added, after reaction, filters, washs, is dry, obtaining
Fe3O4Nano particle.
Step 2: 7gN is added in 1g PS, in dinethylformamide and 3g1,4- dioxane solvent, magnetic agitation is molten
Solution, by 0.03g Fe after dissolution completely3O4Nano particle and 0.003g nanometer hydroxyapatite are added in above-mentioned solution, high speed magnetic
Power stirring forms quenching mixed liquor.Quenching mixed liquor is quenched into 3h in -40 DEG C of low temperature refrigerators, after quenching, to system
Middle addition 500mL mixture of ice and water, removes n,N-Dimethylformamide and Isosorbide-5-Nitrae-dioxane, every 6h change primary distilled water, change
4 times, finally freeze-drying obtains PS/Fe3O4Magnetic coupling porous microsphere.
Step 3: by PS/Fe3O4Magnetic coupling porous microsphere is immersed in 5g benzophenone and 95g acetone soln, activation
It takes out, is dried in vacuo after 5min, obtain activation PS/Fe3O4Magnetic coupling porous microsphere, it is spare.
Step 4: by 7g acrylic acid and 4g maleic anhydride, 0.2gN, N '-methylene-bisacrylamide and 0.18g persulfuric acid
Potassium is dissolved in 200mL distilled water, and 2.5g is activated PS/Fe3O4Magnetic coupling porous microsphere is immersed in above-mentioned mixed liquor, system
In lead to N2Protection.It opens ultraviolet source (500 W high-pressure sodium lamp), radiation length 50cm, radioreaction 30min.Reaction terminates
Afterwards, products therefrom is washed with distilled water, is dried in vacuo, obtain poly- (acrylic acid-co- maleic anhydride) magnetic of polystyrene graft
Property polyalcohol stephanoporate microballoons.
The diameter of poly- (acrylic acid-co- maleic anhydride) the magnetic polymer porous microsphere of polystyrene graft be 20.90 ±
5.45 μm, porosity and specific surface area are respectively 94.3% and 18.9m2/g.Poly- (the Malaysia acrylic acid-co- of polystyrene graft
Acid anhydrides) swelling ratio of magnetic polymer porous microsphere when reaching swelling equilibrium be 22.9g/g.Poly- (the propylene of polystyrene graft
Acid-co- maleic anhydride) the apparent saturation magnetization of magnetic polymer porous microsphere be 0.068emu/g.
Comparative example 1
Difference from Example 1 is: polystyrene dosage is 0.3g, subsequent step and 1 phase of embodiment in step 2)
Together.It finally is unable to get micro-sphere structure, can only obtain fibrous structure.It is relatively low to be primarily due to polymer concentration, polystyrene without
Crystalline therefore is unable to get porous microsphere structure at spherocrystal to method in the solution.
Comparative example 2
Difference from Example 1 is: the additive amount of Added Nucleating Agents hydroxyapatite is 0 in step 2), subsequent step
It is same as Example 1, it is finally unable to get micro-sphere structure, can only obtain rough surface film.Since without nucleating agent, polystyrene
In the solution can not nucleation and crystallization, therefore be unable to get porous microsphere structure.
Comparative example 3
Difference from Example 1 is: N,N-dimethylformamide and 1,4- dioxane solvent adds in step 2)
Dosage is respectively 10g and 0g, finally obtains nanofibrous structures.
Comparative example 4
Difference from Example 1 is: the amount of acrylic acid and maleic anhydride is respectively 1g and 0.5g in step 4), is obtained
To poly- (acrylic acid-co- maleic anhydride) the magnetic polymer porous microsphere of polystyrene graft, the diameter of microballoon is 19.90 ±
4.85 μm, porosity and specific surface area are respectively 93.3% and 17.2m2/g.Poly- (the Malaysia acrylic acid-co- of polystyrene graft
Acid anhydrides) swelling ratio of magnetic polymer porous microsphere when reaching swelling equilibrium be 10.7g/g.Poly- (the propylene of polystyrene graft
Acid-co- maleic anhydride) the apparent saturation magnetization of magnetic polymer porous microsphere be 0.067emu/g.It is compared to embodiment
1, saturation swelling ratio when microballoon balances is reduced to 10.7g/g from 24.1g/g, is primarily due to the acrylic acid of porous microsphere grafting
It is reduced with maleic anhydride content, microballoon saturation swelling ratio is caused to reduce.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (9)
1. a kind of preparation method of pH responsiveness magnetic polystyrene base porous microsphere, which comprises the steps of:
Iron dichloride tetrahydrate and ferric chloride hexahydrate are dissolved in distilled water, ammonium hydroxide is added, after reaction, filtered, washed
And drying, obtain ferroferric oxide nano granules；
N,N-Dimethylformamide and Isosorbide-5-Nitrae-dioxane in the mixed solvent is added in polystyrene, nanometer hydroxyl is added after dissolution
Base apatite and the ferroferric oxide nano granules, mixing form quenching liquid；
The quenching liquid is quenched after a certain period of time at a certain temperature, removes n,N-Dimethylformamide and Isosorbide-5-Nitrae-two using water
The mixed solvent of six ring of oxygen, it is freeze-dried to obtain polystyrene/Fe 3 O 4 magnetic composite porous microspheres；
The polystyrene/Fe 3 O 4 magnetic composite porous microspheres are impregnated to 5min progress in benzophenone/acetone soln
After activation, it is added in grafted monomers mixed liquor, is uniformly dispersed, obtains polymerization liquid；
By the polymerization liquid under the protection of nitrogen, radiation grafting copolymerization is carried out with ultraviolet source, polystyrene is obtained and connects
Poly- (acrylic acid-co- maleic anhydride) the magnetic polymer porous microsphere of branch, i.e., described pH responsiveness magnetic polystyrene Quito hole are micro-
Ball；
The grafted monomers mixed liquor the preparation method comprises the following steps:
By acrylic acid, maleic anhydride, N, N- methylene-bisacrylamide and potassium peroxydisulfate are dissolved in distilled water.
2. the preparation method of pH responsiveness magnetic polystyrene base porous microsphere as described in claim 1, which is characterized in that institute
The concentration of ammonium hydroxide is stated as 1mol/L, the molar ratio of the Iron dichloride tetrahydrate and ferric chloride hexahydrate is 1:2.
3. the preparation method of pH responsiveness magnetic polystyrene base porous microsphere as described in claim 1, which is characterized in that institute
It states in quenching liquid, polystyrene, n,N-Dimethylformamide, Isosorbide-5-Nitrae-dioxane, ferroferric oxide nano granules and nanometer hydroxyl
The weight ratio of base apatite is (1~1.5): (4~6): (2~4): (0.02~0.06) (0.002~0.004).
4. the preparation method of pH responsiveness magnetic polystyrene base porous microsphere as described in claim 1, which is characterized in that institute
The temperature for stating quenching is -50~-10 DEG C, 2~4h of cool time.
5. the preparation method of pH responsiveness magnetic polystyrene base porous microsphere as described in claim 1, which is characterized in that institute
In the benzophenone/acetone soln stated, the mass fraction of benzophenone is 5%.
6. the preparation method of pH responsiveness magnetic polystyrene base porous microsphere as described in claim 1, which is characterized in that institute
It states in polymerization liquid, polystyrene/Fe 3 O 4 magnetic composite porous microspheres, acrylic acid, maleic anhydride, N, N- methylene
The weight ratio of bisacrylamide and potassium peroxydisulfate is (1.5~3): (3~7): (2~5): (0.1~0.2): (0.1~0.2).
7. the preparation method of pH responsiveness magnetic polystyrene base porous microsphere as described in claim 1, which is characterized in that institute
It states in radiation grafting copolymerization, the power of ultraviolet source is 500W, irradiation distance 50cm, reaction time 30min.
8. a kind of pH responsiveness magnetic polystyrene Quito that the preparation method as described in any one of claim 1~7 obtains
Hole microballoon.
9. a kind of use of pH responsiveness magnetic polystyrene base porous microsphere as claimed in claim 8 in target therapeutic agent
On the way.
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| CN110523397A (en) * | 2019-09-10 | 2019-12-03 | 晋江瑞碧科技有限公司 | A kind of SiO2/ chitosan-based lead ion trace hollow microsphere preparation method |
| CN113262308A (en) * | 2021-04-07 | 2021-08-17 | 桂林医学院 | Folic acid receptor mediated paclitaxel and hydroxycamptothecine superparamagnetic iron oxide nanoparticle and preparation method and application thereof |
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| CN113571282B (en) * | 2021-07-23 | 2024-07-05 | 重庆邮电大学 | Preparation method and product of hexagonal polymer magnetic mesoporous nanomaterial |
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