CN106432641A - Carboxyl-functionalized magnetic polystyrene nanospheres and preparation method thereof - Google Patents

Carboxyl-functionalized magnetic polystyrene nanospheres and preparation method thereof Download PDF

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CN106432641A
CN106432641A CN201610817541.2A CN201610817541A CN106432641A CN 106432641 A CN106432641 A CN 106432641A CN 201610817541 A CN201610817541 A CN 201610817541A CN 106432641 A CN106432641 A CN 106432641A
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carboxyl
magnetic polystyrene
functional magnetic
styrene
polystyrene nanosphere
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陈志明
吴晓栋
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Anhui Polytechnic University
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Abstract

The invention discloses carboxyl-functionalized magnetic polystyrene nanospheres and a preparation method thereof. A carboxyl-functionalized magnetic polystyrene nanosphere is of a core-shell structure including a core and an outer layer, wherein the outer layer wraps the periphery of the core, the core is a ferroferric oxide nano particle aggregate, and the outer layer is a styrene-acrylic acid copolymer. The carboxyl-functionalized magnetic polystyrene nanospheres are uniform in particle size, the surface of the magnetic polystyrene nanosphere is rich in carboxyl, a variety of organic reactions can be further conducted, a variety of functional groups can be introduced, and thus the magnetic polystyrene nanospheres with various functions are generated; the preparation method is simple, economical, environmentally friendly and mild in condition, and has wide application prospects.

Description

A kind of carboxyl-functional magnetic polystyrene nanosphere and preparation method thereof
Technical field
The present invention relates to a kind of carboxyl-functional magnetic polystyrene nanosphere and preparation method thereof.
Background technology
Magnetic polymer particles are a kind of new functional materials, usually by inorganic magnetic substance and organic polymer material Being composited of material, has both the magnetic property of inorganic substances and the surface nature of macromolecular material simultaneously, in biological medicine, separates The fields such as engineering, environmental improvement, stealth material, catalyst are with a wide range of applications.At present, magnetic polymer particles are prepared Method is mainly monomer polymerization method and dispersion method, and monomer polymerization method is that magnetic ferroferric oxide nano-particles are distributed to reactant liquor In, then form magnetic polymer nanoparticle in ferriferrous oxide nano-particle surface aggregate monomer；Dispersion method is by magnetic four Fe 3 O nanoparticle is distributed to polymeric inner and forms magnetic polymer nanoparticle.
Magnetic polystyrene is most important at present and a kind of extensively concerned magnetic polymer nanoparticle.With regard to its preparation The existing document report of method.For example, the microemulsion polymerization method such as Jiang prepares particle diameter is 270nm～370nm magnetic Fe3O4/ PS composite Nano ball, and have studied performance (the Journal of Magnetism that magnetic polystyrene nanosphere adsorbs oils and fatss and Magnetic Materials,2015,394,14-21).It is 105nm that Gu etc. prepares particle diameter using microemulsion polymerization method Magnetic polystyrene nanoparticle (Journal of the American Chemical Society, 2006,128,15582- 15583).Tang etc. deposits Fe in styrene and methacrylic acid copolymer surface in situ3O4Or Fe2O3Nanoparticle is formed instead Formula nucleus-shell structure magnetic polystyrene nanoparticle (Journal of Colloid and Interface Science, 2005,281,432-436；Colloid and Polymer Science,2004,282,1198-1205).However, polyphenyl second Alkene it is impossible to be reacted with biomacromolecule, is limited magnetic polystyrene and applies in biological field for surface inertness polymer.Cause This, develop a kind of method preparing carboxyl-functional magnetic polystyrene nano material and have important theory and realistic meaning.
Content of the invention
It is an object of the invention to provide a kind of carboxyl-functional magnetic polystyrene nanosphere and preparation method thereof, the application Carboxyl-functional magnetic polystyrene nanometer ball surface has abundant carboxyl functional group, can occur multiple organic anti-further Should, obtain the magnetic polystyrene nanosphere with various functions；The application preparation method is simple, gentle, economic and environment-friendly.
A kind of carboxyl-functional magnetic polystyrene nanosphere, carboxyl-functional magnetic polystyrene nanosphere is including core The heart and the nucleus-shell structure of outer layer, wherein, outer layer covers are assembled for ferriferrous oxide nano-particle in the periphery of core, core Body, outer layer is Styrene-acrylic copolymer.
Carboxyl-functional magnetic polystyrene nanosphere, preferably particle diameter are the spheroidal particle of 40nm～70nm.So energy Improve the feature of carboxyl-functional magnetic polystyrene nanosphere further.
In order to improve the performance of carboxyl-functional magnetic polystyrene nanosphere further it is preferable that core is spherical, core A diameter of 35nm～65nm, the thickness of outer layer is 4nm～8nm.
The application carboxyl-functional magnetic polystyrene nanosphere is ferromagnetism hydrophobic material；Carboxyl-functional magnetic polyphenyl Ethylene nanometer ball surface has abundant carboxyl functional group.
The preparation method of above-mentioned carboxyl-functional magnetic polystyrene nanosphere, using emulsion polymerization, in magnetic four oxygen Change three-iron nanoparticle surface polymerizing styrene-acrylic acid mix monomer, the carboxyl-functional magnetic of prepared nucleus-shell structure is gathered Styrene nanosphere.
It is filled with ferromagnetic ferroso-ferric oxide inside the carboxyl-functional magnetic polystyrene nanosphere of above-mentioned gained to receive Rice corpuscles.
In order to simpler, gentle, economic and environment-friendly, guarantee the combination property of products obtained therefrom simultaneously, above-mentioned prepare carboxyl work( The method that magnetic polystyrene nanosphere can be changed, including following steps connected in order：
1) Oleic acid-ferriferrous oxide nano-particle of oleyl amine parcel, Oleic acid are prepared using solvent-thermal method or coprecipitation The ferriferrous oxide nano-particle of parcel or the ferriferrous oxide nano-particle of oleyl amine parcel；
2) by the ferriferrous oxide nano-particle of Oleic acid-oleyl amine parcel, the ferriferrous oxide nano-particle of Oleic acid parcel or The ferriferrous oxide nano-particle of oleyl amine parcel is distributed in sodium dodecyl sulfate solution, and forms magnetic under ultrasound condition Ferroso-ferric oxide emulsion；
3) styrene and acrylic monomerss are distributed in sodium dodecyl sulfate solution, and form benzene under ultrasound condition The monomer emulsion of ethylene-acrylic acid；
4) magnetic ferroferric oxide emulsion is mixed homogeneously with the monomer emulsion of Styrene And Chloroalkyl Acrylates, add and cause Agent, in nitrogen atmosphere, carries out polyreaction under condition of heating and stirring, after question response terminates, naturally cools to room temperature, and gained sinks Form sediment after Magneto separate, washing, being dried, the carboxyl-functional magnetic polystyrene nanosphere of prepared nucleus-shell structure.
Preferably, step 4) in polyreaction be under conditions of 80 ± 10 DEG C, react 12-24h；Step 4) in stir be by Each material mix homogeneously, does not require to specific speed；Step 2) in ultrasonic power be 400W；Step 3) in ultrasonic work( Rate is 200W.
In order to improve the feature of gained carboxyl-functional magnetic polystyrene nanosphere, magnetic ferroferric oxide further In emulsion, the mass-volume concentration of ferroso-ferric oxide is 6430.5mg/L～14275.8mg/L.Ferroso-ferric oxide and styrene- The mass ratio of acrylic acid mix monomer is 0.056～1.182.Styrene is 0.0256～39 with the volume ratio of acrylic monomerss. Initiator is potassium peroxydisulfate, sodium peroxydisulfate or Ammonium persulfate., and initiator with the mass ratio of Styrene And Chloroalkyl Acrylates mix monomer is 0.0082～0.102；Step 2) in sodium dodecyl sulfate solution concentration be 0.0337～0.1014mol/；Step 3) in 12 Sodium alkyl sulfate solution is 0.01～0.012mol/L.
Beneficial effect of the present invention：
1. the surface of carboxyl-functional magnetic polystyrene nanosphere has abundant carboxyl functional group, can occur further Various organic reactions, introduce several functions group, generate the magnetic polystyrene nanosphere with various functions；
2. carboxyl-functional magnetic polystyrene nanosphere has good dispersibility and uniformity；
3. carboxyl-functional magnetic polystyrene nanosphere is ferromagnetism hydrophobic material, can be scattered in multiple nonpolar molten Agent, has potential using value in fields such as biological medicine, separation engineering, environmental improvement, catalysis engineerings.
4. adopt emulsion polymerization, mix in magnetic ferroferric oxide nano-particles surface aggregate Styrene And Chloroalkyl Acrylates single Body, the method preparing carboxyl-functional magnetic polystyrene nanosphere is simple, and mild condition is economic and environment-friendly.
Brief description
Fig. 1 is the scanning electron microscope detection figure of the product prepared by embodiment 1.
Fig. 2 is the transmission electron microscope detection figure of the product prepared by embodiment 1.
Fig. 3 is the X-ray powder diffraction detection figure of the product prepared by embodiment 1.In figure 3, abscissa is the angle of diffraction 2-Theta (degree), vertical coordinate is intensity I ntensity (a.u.)；Through with standard diagram (JCPDS:77-1545) carry out Comparison, product diffraction peak, in 30.1 °, 35.5 °, 43.1 °, 53.4 °, 57.0 °, 62.6 °, 70.9 °, 74.0 °, corresponds respectively to The diffraction maximum (220) of Emission in Cubic ferroso-ferric oxide, (311), (400), (422), (511), (440), (620), (533).
Fig. 4 is the infrared spectrogram of the product prepared by embodiment 1, and in the diagram, abscissa is wave number Wavelength/ cm-1, vertical coordinate is light transmittance %Transmittance.
Fig. 5 is the hysteresis curve figure of the product of embodiment 1 preparation, and in Figure 5, abscissa is magnetic field intensity H (Oe), indulges and sits It is designated as saturation magnetization M (emu/g), figure (a) is original graph, figure (b) is partial enlarged drawing, and saturated magnetization is strong as seen from the figure Spend for 33.8emu/g, remanent magnetism is 2.7emu/g, coercivity is 34.7Oe, learns that obtained polystyrene nanospheres have ferrum Magnetic.
Fig. 6 is the water contact angle figure of the product prepared by embodiment 1, carboxyl-functional magnetic polystyrene as shown in Figure 6 The contact angle of nanosphere is 127 ± 2.0 °, is hydrophobic material.
The scanning electron microscope detection figure of the product of Fig. 7 embodiment 2 preparation.
The scanning electron microscope detection figure of the product of Fig. 8 embodiment 3 preparation.
The scanning electron microscope detection figure of the product of Fig. 9 embodiment 4 preparation.
The scanning electron microscope detection figure of the product of Figure 10 embodiment 5 preparation.
Specific embodiment
For a better understanding of the present invention, it is further elucidated with present disclosure with reference to embodiment, but the present invention Content is not limited solely to the following examples.
Embodiment 1
Step 1. weighs 1059.5mg ferric acetyl acetonade and is added in 20mL diphenyl ether, adds 2mL oleyl amine, 1mL second two Alcohol, 2mL Oleic acid, stir, and in nitrogen atmosphere, under the conditions of 200 DEG C, react 0.5h, then the 2h that flows back under the conditions of 250 DEG C Afterwards, stop heating, be cooled to room temperature, Magneto separate goes out black product, and with washing with alcohol 3 times, obtain that Oleic acid-oleyl amine wraps up four Fe 3 O nanoparticle；
36mL 12 is added in the ferriferrous oxide nano-particle of the Oleic acid that step 2. is obtained to step 1-oleyl amine parcel Sodium alkyl sulfate solution (amount of substance concentration, 0.1mol/L), after being uniformly mixed, then in ultrasonic (ultrasonic power：400W) bar Disperse 15min under part, prepare magnetic ferroferric oxide emulsion；
Step 3. sequentially adds 90mg sodium lauryl sulphate, 0.1mL styrene and 0.4mL acrylic acid in 30mL water, After being uniformly mixed, in ultrasonic (ultrasonic power：Disperse 20min under the conditions of 200W), prepare the monomer of Styrene And Chloroalkyl Acrylates Emulsion；
Magnetic ferroferric oxide emulsion that step 2 is obtained by step 4. and the Styrene And Chloroalkyl Acrylates that step 3 is obtained Monomer emulsion mix homogeneously, under nitrogen atmosphere, stirring condition add 45mg potassium peroxydisulfate initiator, under the conditions of 80 DEG C Reaction 24h, after question response terminates, naturally cools to room temperature, gained precipitation obtains carboxyl-functional after Magneto separate, washing, drying Magnetic polystyrene nanosphere.
The scanned ultramicroscope of product characterizes it was demonstrated that the diameter of the carboxyl-functional magnetic polystyrene nanosphere of gained For 40nm～70nm；Characterize it was demonstrated that the internal core of carboxyl-functional magnetic polystyrene nanosphere through transmission electron microscope It is ferriferrous oxide nano-particle aggregation, core is spherical, a diameter of 35nm～65nm of core, and outer layer is thickness is 4nm The Styrene-acrylic copolymer of～8nm, carboxyl-functional magnetic polystyrene nanosphere is nucleus-shell structure；Through X-ray Diffraction characterizes it was demonstrated that product is carboxyl-functional magnetic polystyrene nanosphere；Characterize through Fourier transformation infrared spectrometer, card Real surface crust is the copolymer of Styrene And Chloroalkyl Acrylates；Characterize it was demonstrated that carboxyl-functional magnetic polyphenyl through superconducting quantum interference device (SQUID) Ethylene nanosphere is ferromagnetism；Characterize through contact angle instrument it was demonstrated that carboxyl-functional magnetic polystyrene nanosphere is hydrophobicity material Material, its contact angle is 127 ± 2.0 °.
Embodiment 2
Step 1 and step 2 according to embodiment 1 prepare magnetic ferroferric oxide emulsion；Add successively in 30mL water Enter 90mg sodium lauryl sulphate, 3.9mL styrene and 0.1mL acrylic acid, after being uniformly mixed, in ultrasonic (ultrasonic power： Disperse 20min under the conditions of 200W), prepare Styrene And Chloroalkyl Acrylates mix monomer emulsion；The magnetic being obtained four is aoxidized three Ferrum emulsion is mixed homogeneously with Styrene And Chloroalkyl Acrylates mix monomer emulsion, adds 30mg mistake under nitrogen atmosphere, stirring condition Potassium sulfate initiator, after reaction 2h under the conditions of 80 DEG C, adds 30mg potassium peroxydisulfate initiator, and anti-again under the conditions of 80 DEG C Answer 10h, after question response terminates, naturally cool to room temperature, gained precipitation obtains carboxyl-functional magnetic after Magneto separate, washing, drying Property polystyrene nanospheres.
Embodiment 3
Step 1 and step 2 according to embodiment 1 prepare magnetic ferroferric oxide emulsion；Add successively in 30mL water Enter 90mg sodium lauryl sulphate, 0.1mL styrene and 3.9mL acrylic acid, after being uniformly mixed, in ultrasonic (ultrasonic power： Disperse 20min under the conditions of 200W), prepare Styrene And Chloroalkyl Acrylates mix monomer emulsion；The magnetic being obtained four is aoxidized three Ferrum emulsion is mixed homogeneously with Styrene And Chloroalkyl Acrylates mix monomer emulsion, adds 60mg mistake under nitrogen atmosphere, stirring condition Ammonium persulfate initiator, reacts 20h under the conditions of 80 DEG C, after question response terminates, naturally cools to room temperature, gained precipitation is divided through magnetic From, washing, be dried after carboxyl-functional magnetic polystyrene nanosphere.
Embodiment 4
Step 1 and step 2 according to embodiment 1 prepare magnetic ferroferric oxide emulsion；Add successively in 30mL water Enter 90mg sodium lauryl sulphate, 0.1mL styrene and 0.1mL acrylic acid, after being uniformly mixed, in ultrasonic (ultrasonic power： Disperse 20min under the conditions of 200W), prepare Styrene And Chloroalkyl Acrylates mix monomer emulsion；The magnetic being obtained four is aoxidized three Ferrum emulsion is mixed homogeneously with Styrene And Chloroalkyl Acrylates mix monomer emulsion, adds 20mg mistake under nitrogen atmosphere, stirring condition Potassium sulfate initiator, reacts 20h under the conditions of 80 DEG C, after question response terminates, naturally cools to room temperature, gained precipitation is divided through magnetic From, washing, be dried after carboxyl-functional magnetic polystyrene nanosphere.
Embodiment 5
Step 1. weighs 401mg FeCl2·4H2O and 542mg FeCl3·6H2O is added in 60mL distilled water, in nitrogen Under gas atmosphere, stirring condition, add 246mg NaOH and 1mL Oleic acid, after reaction 3h under the conditions of 95 DEG C, stop heating, cooling To room temperature, Magneto separate goes out black product, and with washing with alcohol 3 times, obtains the ferriferrous oxide nano-particle of Oleic acid parcel；
1050mg 12 is sequentially added in the ferriferrous oxide nano-particle of the Oleic acid parcel that step 2. is obtained to step 1 Alkyl sodium sulfate and 36mL distilled water, after being uniformly mixed, then in ultrasonic (ultrasonic power：15min is disperseed under the conditions of 400W), Prepare magnetic ferroferric oxide emulsion；
Step 3. sequentially adds 70mg sodium lauryl sulphate, 0.5mL styrene and 0.5mL acrylic acid in 20mL water, After being uniformly mixed, in ultrasonic (ultrasonic power：Disperse 20min under the conditions of 200W), prepare Styrene And Chloroalkyl Acrylates mixing single Body emulsion；
The Styrene And Chloroalkyl Acrylates that the magnetic ferroferric oxide emulsion that step 2 is obtained is obtained by step 4. with step 3 Mix monomer emulsion mix homogeneously, adds 30mg potassium peroxydisulfate initiator, in 80 DEG C of conditions under nitrogen atmosphere, stirring condition Lower reaction 16h, after question response terminates, naturally cools to room temperature, gained precipitation obtains carboxyl function after Magneto separate, washing, drying Change magnetic polystyrene nanosphere.
Embodiment 6
Step 1. weighs 530mg FeCl2·4H2O and 1080mg FeCl3·6H2O is added in 60mL distilled water, in nitrogen Under gas atmosphere, stirring condition, add 1mL ammonia (NH3Weight/mass percentage composition, 28%) and 1mL oleyl amine, react under the conditions of 95 DEG C After 3h, stop heating, be cooled to room temperature, Magneto separate goes out black product, and with washing with alcohol 3 times, obtain four oxygen that oleyl amine wraps up Change three Fe nanometer particles；
550mg 12 is sequentially added in the ferriferrous oxide nano-particle of the oleyl amine parcel that step 2. is obtained to step 1 Alkyl sodium sulfate and 36mL distilled water, after being uniformly mixed, then in ultrasonic (ultrasonic power：15min is disperseed under the conditions of 400W), Prepare magnetic ferroferric oxide emulsion；
Step 3. sequentially adds 70mg sodium lauryl sulphate, 0.2mL styrene and 0.3mL acrylic acid in 20mL water, After being uniformly mixed, in ultrasonic (ultrasonic power：Disperse 20min under the conditions of 200W), prepare Styrene And Chloroalkyl Acrylates mixing single Body emulsion；
The Styrene And Chloroalkyl Acrylates that the magnetic ferroferric oxide emulsion that step 2 is obtained is obtained by step 4. with step 3 Mix monomer emulsion mix homogeneously, adds 30mg potassium peroxydisulfate initiator, in 80 DEG C of conditions under nitrogen atmosphere, stirring condition Lower reaction 20h, after question response terminates, naturally cools to room temperature, gained precipitation obtains carboxyl function after Magneto separate, washing, drying Change magnetic polystyrene nanosphere.
Embodiment 7
Step 1. weighs 834mg FeSO4·7H2O and 811mg FeCl3·6H2O is added in 60mL distilled water, in nitrogen Under gas atmosphere, stirring condition, add 2mL ammonia (NH3Weight/mass percentage composition, 28%) and 1mL oleyl amine, anti-under the conditions of 95 DEG C After answering 3h, stop heating, be cooled to room temperature, Magneto separate goes out black product, and with washing with alcohol 3 times, obtain that oleyl amine wraps up four Fe 3 O nanoparticle；
350mg 12 is sequentially added in the ferriferrous oxide nano-particle of the oleyl amine parcel that step 2. is obtained to step 1 Alkyl sodium sulfate and 36mL distilled water, after being uniformly mixed, then in ultrasonic (ultrasonic power：15min is disperseed under the conditions of 400W), Prepare magnetic ferroferric oxide emulsion；
Step 3. sequentially adds 70mg sodium lauryl sulphate, 0.3mL styrene and 0.2mL acrylic acid in 20mL water, After being uniformly mixed, in ultrasonic (ultrasonic power：Disperse 20min under the conditions of 200W), prepare Styrene And Chloroalkyl Acrylates mixing single Body emulsion；
The Styrene And Chloroalkyl Acrylates that the magnetic ferroferric oxide emulsion that step 2 is obtained is obtained by step 4. with step 3 Mix monomer emulsion mix homogeneously, adds 20mg potassium peroxydisulfate initiator, in 80 DEG C of conditions under nitrogen atmosphere, stirring condition Lower reaction 20h, after question response terminates, naturally cools to room temperature, gained precipitation obtains carboxyl function after Magneto separate, washing, drying Change magnetic polystyrene nanosphere.
Embodiment 8
Step 1. weighs 1059.5mg ferric acetyl acetonade and is added in 20mL diphenyl ether, adds 2mL oleyl amine, 2mL Oleic acid, Stir, in nitrogen atmosphere, under the conditions of 200 DEG C, react 0.5h, then after backflow 2h under the conditions of 250 DEG C, stop adding Heat, is cooled to room temperature, and Magneto separate goes out black product, and with washing with alcohol 3 times, obtains the ferroso-ferric oxide of Oleic acid-oleyl amine parcel Nanoparticle；
Sequentially add in the ferriferrous oxide nano-particle of the Oleic acid that step 2. is obtained to step 1-oleyl amine parcel 1040mg sodium lauryl sulphate and 36mL distilled water, after being uniformly mixed, then in ultrasonic (ultrasonic power：Under the conditions of 400W) Dispersion 15min, prepares magnetic ferroferric oxide emulsion；
Step 3. sequentially adds 72mg sodium lauryl sulphate, 0.3mL styrene and 0.2mL acrylic acid in 20mL water, After being uniformly mixed, in ultrasonic (ultrasonic power：Disperse 20min under the conditions of 200W), prepare Styrene And Chloroalkyl Acrylates mixing single Body emulsion；
Magnetic ferroferric oxide emulsion that step 2 is obtained by step 4. and the Styrene And Chloroalkyl Acrylates that step 3 is obtained Mix monomer emulsion mix homogeneously, adds 30mg sodium peroxydisulfate initiator, in 80 DEG C of conditions under nitrogen atmosphere, stirring condition Lower reaction 24h, after question response terminates, naturally cools to room temperature, gained precipitation obtains carboxyl function after Magneto separate, washing, drying Change magnetic polystyrene nanosphere.
Embodiment 9
The concrete preparation process of carboxyl-functional magnetic polystyrene nanosphere fixed fat enzyme：
Lyophilizing fat enzyme powder from Pancreas Sus domestica gland is configured to 1mg/mL's using pH=7.4 phosphate buffer by step 1. Lipase solution, saves backup as in 4 DEG C of refrigerators；
Step 2. weighs the carboxyl-functional magnetic polystyrene nanosphere that 100mg embodiment 1 is obtained, and sequentially adds
191.7mg EDC HCl (1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride, C8H17N3· HCl), 115.1mg NHS (N-hydroxy-succinamide) and 20mL MES (2- (N- morpholine) ethyl sulfonic acid) buffer solution (0.1M, pH=6.0), ultrasonic disperse 2min, and react 2h under the conditions of 30 DEG C, products obtained therefrom is through Magneto separate, washing, you can Magnetic polystyrene nanosphere to activation.
The magnetic polystyrene nanosphere of the activation that step 2 is obtained by step 3., adds the above-mentioned lipase solution of 40mL In, react 1.5h under the conditions of 30 DEG C, products obtained therefrom is through Magneto separate, washing, you can obtain magnetic polystyrene nanosphere and fix Digestive Enzyme.
The mensure of the catalysis activity of carboxyl-functional magnetic polystyrene nanosphere fixed fat enzyme：
Step 1. weighs 50mg Radix Acaciae senegalis, and (Shanghai Suo Laibao biotechnology has to add 200mg Triton X-100 Limit company) and 45mL pH=7.4 phosphate buffer, mix homogeneously formed cocktail buffer；
Step 2. weighs 15mg paranitrophenol cetylate (p-NPP), adds 5mL isopropanol, adds after being completely dissolved Above-mentioned cocktail buffer, mix homogeneously prepares p-NPP substrate, saves backup as in 4 DEG C of refrigerators；
Step 3. takes 4mL p-NPP substrate solution, adds above-mentioned magnetic immobilized Digestive Enzyme (or Digestive Enzyme after preheating 5min Solution), measure magnetic immobilized Digestive Enzyme (or Digestive Enzyme) hydrolysis reaction under the conditions of 45 DEG C；Calculate magnetic with difference assay Fe3O4The supported quantity of/P (St-AA) nanosphere；Magnetic immobilized Digestive Enzyme (or free-fat enzyme) is respectively placed in 50 DEG C of preservations Same time, then the catalysis activity of magnetic immobilized Digestive Enzyme is measured with p-NPP method, the heat of research magnetic immobilized Digestive Enzyme is steady Qualitative.
Step 4. adds 0.2mL organic acid and 0.2mL alcohol in 5mL normal hexane, adds 30mg magnetic immobilized fat Enzyme, reacts 30min under the conditions of 45 DEG C, and Magneto separate goes out magnetic immobilized Digestive Enzyme, detects the yield of fat with GC-MS；Machine acid is Glacial acetic acid, propanoic acid, butanoic acid, benzoic acid or adipic acid, alcohol is ethanol, n-butyl alcohol, propanol, hexanol, ethylene glycol or glycerol, has Machine acid and alcohol is specifically chosen any has no effect on final result.
Detection Digestive Enzyme is in magnetic Fe3O4Supported quantity on/P (St-AA) nanosphere is 176.7mg/g；Magnetic immobilized fat Fat enzymatic activity is 0.94 times of free-fat enzymatic activity；After placing 10h under the conditions of 50 DEG C, magnetic immobilized fat The activity of enzyme remains to keep 80.5%, is 2.45 times of resolvase；In normal hexane, magnetic immobilized Digestive Enzyme remains to keep relatively High catalysis activity, the yield of Catalytic Synthesis of n-Butyl Acetate is up to 78%.

Claims (10)

1. a kind of carboxyl-functional magnetic polystyrene nanosphere is it is characterised in that carboxyl-functional magnetic polystyrene nanometer Ball is the nucleus-shell structure including core and outer layer, and wherein, outer layer covers are received for ferroso-ferric oxide in the periphery of core, core Rice corpuscles aggregation, outer layer is Styrene-acrylic copolymer.
2. carboxyl-functional magnetic polystyrene nanosphere as claimed in claim 1 it is characterised in that for particle diameter be 40nm～ The spheroidal particle of 70nm.
3. carboxyl-functional magnetic polystyrene nanosphere as claimed in claim 1 or 2 it is characterised in that core be spherical, A diameter of 35nm～65nm of core, the thickness of outer layer is 4nm～8nm.
4. carboxyl-functional magnetic polystyrene nanosphere as claimed in claim 1 or 2 is it is characterised in that carboxyl-functional Magnetic polystyrene nanosphere is ferromagnetism hydrophobic material；Carboxyl-functional magnetic polystyrene nanometer ball surface has carboxyl official Can group.
5. the preparation method of the carboxyl-functional magnetic polystyrene nanosphere described in claim 1-4 any one, its feature It is, using emulsion polymerization, in magnetic ferroferric oxide nano-particles surface aggregate Styrene And Chloroalkyl Acrylates mix monomer, make Obtain the carboxyl-functional magnetic polystyrene nanosphere of nucleus-shell structure.
6. the preparation method of carboxyl-functional magnetic polystyrene nanosphere as claimed in claim 5 is it is characterised in that include Following steps connected in order：
1) ferriferrous oxide nano-particle, the Oleic acid parcel of Oleic acid-oleyl amine parcel is prepared using solvent-thermal method or coprecipitation Ferriferrous oxide nano-particle or oleyl amine parcel ferriferrous oxide nano-particle；
2) by the ferriferrous oxide nano-particle of Oleic acid-oleyl amine parcel, the ferriferrous oxide nano-particle of Oleic acid parcel or oleyl amine The ferriferrous oxide nano-particle of parcel is distributed in sodium dodecyl sulfate solution, and forms magnetic four oxygen under ultrasound condition Change three-iron emulsion；
3) styrene and acrylic monomerss are distributed in sodium dodecyl sulfate solution, and form benzene second under ultrasound condition Alkene-acrylic acid monomer emulsion；
4) magnetic ferroferric oxide emulsion is mixed homogeneously with the monomer emulsion of Styrene And Chloroalkyl Acrylates, add initiator, In nitrogen atmosphere, under condition of heating and stirring, carry out polyreaction, after question response terminates, naturally cool to room temperature, gained precipitates warp Magneto separate, washing, be dried after, the carboxyl-functional magnetic polystyrene nanosphere of prepared nucleus-shell structure.
7. the preparation method of carboxyl-functional magnetic polystyrene nanosphere as claimed in claim 6 is it is characterised in that magnetic In ferroso-ferric oxide emulsion, the mass-volume concentration of ferroso-ferric oxide is 6430.5mg/L～14275.8mg/L.
8. carboxyl-functional magnetic polystyrene nanosphere as claimed in claims 6 or 7 preparation method it is characterised in that Ferroso-ferric oxide is 0.056～1.182 with the mass ratio of Styrene And Chloroalkyl Acrylates mix monomer；Styrene and acrylic monomerss Volume ratio is 0.0256～39.
9. carboxyl-functional magnetic polystyrene nanosphere as claimed in claims 6 or 7 preparation method it is characterised in that Initiator is potassium peroxydisulfate, sodium peroxydisulfate or Ammonium persulfate., and initiator with the mass ratio of Styrene And Chloroalkyl Acrylates mix monomer is 0.0082～0.102；Step 2) in sodium dodecyl sulfate solution concentration be 0.0337～0.1014mol/；Step 3) in 12 Sodium alkyl sulfate solution is 0.01～0.012mol/L.
10. carboxyl-functional magnetic polystyrene nanosphere as claimed in claims 6 or 7 preparation method it is characterised in that Step 4) in polyreaction be under conditions of 80 ± 10 DEG C, react 12-24h.
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Publication number Priority date Publication date Assignee Title
CN110216020A (en) * 2019-04-23 2019-09-10 中南大学 A kind of charged magnetic hydrophobic material and preparation method thereof and the application in fine-particle minerals separation
CN111701544A (en) * 2020-05-22 2020-09-25 湖北新纵科病毒疾病工程技术有限公司 Preparation method of magnetic polystyrene microspheres

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Title
刘春丽: "《Fe3O4/磁性高分子微球的制备与表征》", 《吉林大学硕士学位论文》 *
刘春丽等: "《Fe3O4/聚苯乙烯磁性微球的合成与表征》", 《高分子材料科学与工程》 *
赵吉利等: "《表面含羧基磁性高分子复合微球的制备》", 《高分子材料科学与工程》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110216020A (en) * 2019-04-23 2019-09-10 中南大学 A kind of charged magnetic hydrophobic material and preparation method thereof and the application in fine-particle minerals separation
CN110216020B (en) * 2019-04-23 2020-11-03 中南大学 Charged magnetic hydrophobic material and preparation method and application thereof
CN111701544A (en) * 2020-05-22 2020-09-25 湖北新纵科病毒疾病工程技术有限公司 Preparation method of magnetic polystyrene microspheres

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