CN103354144A - Magnetic composite microsphere as well as preparation method and application thereof - Google Patents
Magnetic composite microsphere as well as preparation method and application thereof Download PDFInfo
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- CN103354144A CN103354144A CN2013102575831A CN201310257583A CN103354144A CN 103354144 A CN103354144 A CN 103354144A CN 2013102575831 A CN2013102575831 A CN 2013102575831A CN 201310257583 A CN201310257583 A CN 201310257583A CN 103354144 A CN103354144 A CN 103354144A
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Abstract
The invention discloses a magnetic composite microsphere as well as a preparation method and an application thereof. The magnetic composite microsphere has an autologous active epoxy group with the content ranging from 0.1 mmol/g to 2.0 mmol/g, the diameter of the magnetic composite microsphere ranges from 50 nm to 150 nm, the magnetic composite microsphere is regularized, Fe3O4 nano particles are packaged in a network structure of a polymer, the content of Fe3O4 in the microsphere accounts for 20%-70%, and the specific saturation magnetization ranges from 20 emu/g to 60 emu/g. Simultaneously, the preparation method of the magnetic composite microsphere is provided, the method is mild in condition, convenient to operate and simple in device; and the prepared magnetic composite microsphere can covalently bind biomolecules through the autologous active epoxy group, can rapidly settle under the action of a magnetic field, and has high separation efficiency, low cost, simple process and industrialized application value.
Description
Technical field
The invention belongs to the composite high-molecular technical field of function materials, relate to a kind of magnetic composite microsphere Preparation Method And The Use.
Background technology
Magnetic macromolecular microsphere is by inorganic Fe
3O
4Be composited etc. magnetic material and organic polymer, the diversity of its function and easily control property have caused people's common concern.This class functional material has the character of macromolecular material, by the selection of polymerization single polymerization monomer, easily realizes its functional adjustment, such as hydrophily and hydrophobicity and bio-compatibility etc.; And the reactive functional group that the surface exists, can the binding bioactive molecule, thereby have a wide range of applications at aspects such as immobilised enzymes, cell separation and targeted drugs.
The method for preparing at present polymer magnetic micro-sphere mainly contains the macromolecule investment, monomer polymerization method and in-situ method, wherein monomer polymerization method is under the condition of magnetic particle and organic monomer existence, adopt different polymerization methods (suspension polymerisation, dispersin polymerization and emulsion polymerisation etc.), polymerization prepares high molecule magnetic microsphere under the initator effect.Compare with investment, the large small scale of monomer polymerization method synthesizing magnetic polymer microballoon is easy to control, and spherical regular.Utilize in-situ method to prepare high molecule magnetic microsphere, the magnetic responsiveness of microballoon a little less than, and complex technical process, practicality is lower.United States Patent (USP) 4339337 discloses the method that a kind of suspension polymerisation prepares magnetic polymer microsphere, is the magnetic Fe with the oleophylic processing
3O
4The oil phase that particulate and lipophile vinyl monomer and oiliness initator form is dispersed in the aqueous phase that contains surfactant, forms oil-in-water suspensions, and add thermal-initiated polymerization and form magnetic polymer microsphere, but the microballoon Fe that obtains
3O
4Content low (0.8-2.7%), a little less than the magnetic, homogenieity is poor.
The domestic microsuspension polymerization method (CN1566169A) close with the present invention is to coat Fe with the oleic-acid surfactant
3O
4Be scattered in behind the particulate and form magnetic fluid in the styrene; magnetic fluid mixes with divinylbenzene and oiliness initator benzoyl peroxide; be added drop-wise to the aqueous solution aqueous phase that contains lauryl sodium sulfate and hexadecanol emulsifying agent; elder generation's initiated polymerization is after a period of time; drip again functional monomer and the water soluble starter potassium persulfate solutions such as methacrylic acid; again carry out polymerization reaction (after polymerization), form complex microsphere.Analyze above-mentioned preparation process and experiment as can be known, this invention comes with some shortcomings: (1) takes the secondary initiated polymerization, and preparation procedure is many, and process is long.(2) prepared magnetic microsphere specific surface is very little, lacks special functional groups, be unfavorable for biomedical, particularly in the application in the fields such as immobilised enzymes and cell separation.Patent CN1105741C provides net formula sieve plate vibration suspension polymerization device, comprises in this device outside reactor, oil phase storage tank and the water storage tank in the polymerization reaction conventional equipment, and also be equipped with scattered tower, equipment is complicated.
Summary of the invention
The object of the invention is to overcome the defective that exists in the prior art, a kind of epoxide group magnetic composite microsphere Preparation Method And The Use that contains is provided, its concrete technical scheme is:
A kind of magnetic composite microsphere, self has active epoxy group magnetic composite microsphere, and described epoxy group content is in the 0.1-2.0mmol/g scope, and the magnetic composite microsphere diameter is at 50-150nm, and the magnetic composite microsphere sphere is regular, Fe
3O
4Nano particle is wrapped in the network configuration of polymer, Fe
3O
4Content in microballoon is 20-70%, and specific saturation magnetization is in the 20-60emu/g scope.
A kind of preparation method of magnetic composite microsphere may further comprise the steps:
The glycidyl methacrylate of 0.4-2g and the crosslinking agent of 0.8-8.0g and the ferriferrous oxide nano magnetic of 0.1-1.0g initator and 0.5-5g are dispersed in the 100ml-500ml polar solvent, ultrasonic it is mixed after, be transferred to still is housed, condenser pipe and connecing in the reaction unit of liquid bottle, slowly be heated to the solution boiling and keep constant temperature, solution becomes gradually muddy and begins to steam solvent, the control polymerization time stops reaction at 1~4h, the gained magnetic composite microsphere in magnetic field with separated from solvent, use oxolane, acetone, absolute ether is respectively washed 3 times, at room temperature the vacuum drying chamber inner drying.
Further preferred, described crosslinking agent is divinylbenzene or Ethylene glycol dimethacrylate, or two kinds of crosslinking agents mix the mixed cross-linker of acquisition mutually.
Further preferred, the mass ratio that described two kinds of crosslinking agents mix mutually is 1: 1-1: 4.
Further preferred, described polar organic solvent is acetonitrile, formamide or ethanol.
Further preferred, described initator is azodiisobutyronitrile or dibenzoyl peroxide.
Magnetic composite microsphere of the present invention is in the separation of biomolecule and the application in the immobilization.
Compared with prior art, beneficial effect of the present invention is: the present invention with glycidyl methacrylate, crosslinking agent directly and Fe
3O
4Nano particle one coexists and is scattered in the polar solvent acetonitrile Fe in the ultrasonic wave
3O
4Nano particle does not need the lipophile pretreatment procedure, and monomer generation cross-linked polymeric is with Fe under initator causes
3O
4Particle is embedded in the polymer network.At Fe
3O
4Nano particle exists lower, by supersonic oscillations, with Fe
3O
4Nano particle, monomer and crosslinking agent are dispersed in polar solvent, have formed magnetic fluid, and magnetic fluid rapid polymerization under the initator effect under fluidized state has obtained ferromagnetism and contained active epoxy base magnetic composite microsphere.The method mild condition, easy to operate, equipment is simple, the magnetic composite microsphere of preparation can covalently bonding to biomolecules by the active epoxy group of self, rapid subsidence under magnetic fields, and separative efficiency is high, cost is low, and technique is simple and direct, thereby has industrial applications value.
Description of drawings
Fig. 1 is the electron scanning micrograph of magnetic composite microsphere of the present invention;
Fig. 2 is the infrared spectrogram of magnetic composite microsphere of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments technical scheme of the present invention is described in more detail.
That adopts the present invention's preparation contains active epoxy base magnetic composite microsphere, is to utilize the glycidyl methacrylate monomer that contains epoxide group, with Fe
3O
4Nano particle and crosslinking agent form uniform magnetic fluid in polar solvent, under the initator effect cross-linked polymeric occurs, Fe
3O
4Nano particle is embedded in the polymer network, obtains magnetic composite microsphere.This magnetic composite microsphere can at room temperature by the epoxide group open loop covalent bond enzyme molecule of self, as in conjunction with Pseudomonas Lipases (Pseudomonas cepacia Lipase, PSL), obtain the magnetic immobilized enzyme of high vigor.The hydrolysis vigor employing olive oil emulsification conventional method mensuration of immobilized lipase PSL (enzyme application manual [M]. Shanghai: science tech publishing house, 1989:204).The unit enzyme activity is defined as: under 37 ℃, it is 1 unit of activity U (U=μ mol/min) that the per minute Hydrolysis of Olive Oil produces the required enzyme amount of 1 μ mol aliphatic acid.
The catalyzing hydrolysis vigor (A) of immobilised enzymes is calculated as follows:
In the formula, C
NaOH: the molar concentration of NaOH (mol/L)
V: the volume (mL) of the NaOH solution that working sample consumes
V
0: the volume (mL) of the NaOH solution that blank assay consumes
M: carrier dry weight (g) t: reaction time (min)
Embodiment 1
The glycidyl methacrylate of 1.0g and the crosslinking agent divinylbenzene of 3.0g and the ferriferrous oxide nano magnetic of 0.8g initator dibenzoyl peroxide and 2.5g are dispersed in the 200ml acetonitrile solvent, ultrasonic wave disperses, be transferred to after mixing and still, condenser pipe are housed and connect in the reaction unit of liquid bottle, slowly be heated to the solution boiling and keep constant temperature, solution becomes gradually muddy and begins to steam solvent, and the control polymerization time stops reaction at 2h.The gained magnetic composite microsphere in magnetic field with separated from solvent, respectively wash 3 times with oxolane, acetone, absolute ether, at room temperature the vacuum drying chamber inner drying.The magnetic composite microsphere specific saturation magnetization of preparation is 46.8emu/g, and the surface activity epoxy group content is 0.82mmol/g, and the hydrolysis vigor (A) of its By Immobilized Pseudomonas Sp lipase is 812U/g.
Embodiment 2
The glycidyl methacrylate of 1.0g and the crosslinking agent Ethylene glycol dimethacrylate of 3.0g and the ferriferrous oxide nano magnetic of 0.8g initator azodiisobutyronitrile and 2.0g are dispersed in the 200ml acetonitrile solvent, ultrasonic wave disperses, be transferred to after mixing and still, condenser pipe are housed and connect in the reaction unit of liquid bottle, slowly be heated to the solution boiling and keep constant temperature, solution becomes gradually muddy and begins to steam solvent, and the control polymerization time stops reaction at 4h.The gained magnetic composite microsphere in magnetic field with separated from solvent, respectively wash 3 times with oxolane, acetone, absolute ether, at room temperature the vacuum drying chamber inner drying.The magnetic composite microsphere specific saturation magnetization of preparation is 38.8emu/g, and the surface activity epoxy group content is 0.67mmol/g, and the hydrolysis vigor (A) of its By Immobilized Pseudomonas Sp lipase is 1015U/g.
Embodiment 3
With the 2.0g glycidyl methacrylate, be dispersed in the 300ml acetonitrile solvent with the crosslinking agent divinylbenzene of 2.0g and the ferriferrous oxide nano magnetic of 1.2g initator dibenzoyl peroxide and 2.5g, ultrasonic wave disperses, be transferred to after mixing and still, condenser pipe are housed and connect in the reaction unit of liquid bottle, slowly be heated to the solution boiling and keep constant temperature, solution becomes gradually muddy and begins to steam solvent, and the control polymerization time stops reaction at 2h.The gained magnetic composite microsphere in magnetic field with separated from solvent, respectively wash 3 times with oxolane, acetone, absolute ether, at room temperature the vacuum drying chamber inner drying.The magnetic composite microsphere specific saturation magnetization of preparation is 42.6emu/g, and the surface activity epoxy group content is 0.97mmol/g, and the hydrolysis vigor (A) of its By Immobilized Pseudomonas Sp lipase is 792U/g.
Embodiment 4
With the 2.0g glycidyl methacrylate, be dispersed in the 300ml acetonitrile solvent with the ferriferrous oxide nano magnetic of 2.0g crosslinking agent Ethylene glycol dimethacrylate and 1.2g initator dibenzoyl peroxide and 2.0g, ultrasonic wave disperses, be transferred to after mixing and still, condenser pipe are housed and connect in the reaction unit of liquid bottle, slowly be heated to the solution boiling and keep constant temperature, solution becomes gradually muddy and begins to steam solvent, and the control polymerization time stops reaction at 4h.The gained magnetic composite microsphere in magnetic field with separated from solvent, respectively wash 3 times with oxolane, acetone, absolute ether, at room temperature the vacuum drying chamber inner drying.The magnetic composite microsphere specific saturation magnetization of preparation is 30.8emu/g, and the surface activity epoxy group content is 0.84mmol/g, and the hydrolysis vigor (A) of its By Immobilized Pseudomonas Sp lipase is 1024U/g.
Embodiment 5
With the 1.0g glycidyl methacrylate, be dispersed in the 200ml acetonitrile solvent with the crosslinking agent divinylbenzene of 3.0g and the ferriferrous oxide nano magnetic of 1.2g initator dibenzoyl peroxide and 2.5g, ultrasonic wave disperses, be transferred to after mixing and still, condenser pipe are housed and connect in the reaction unit of liquid bottle, slowly be heated to the solution boiling and keep constant temperature, solution becomes gradually muddy and begins to steam solvent, and the control polymerization time stops reaction at 2h.The gained magnetic composite microsphere in magnetic field with separated from solvent, respectively wash 3 times with oxolane, acetone, absolute ether, at room temperature the vacuum drying chamber inner drying.The magnetic composite microsphere specific saturation magnetization of preparation is 38.6emu/g, and the surface activity epoxy group content is 0.63mmol/g, and the hydrolysis vigor (A) of its By Immobilized Pseudomonas Sp lipase is 772U/g.
Embodiment 6
The glycidyl methacrylate of 1.0g and the crosslinking agent divinylbenzene of 3.0g and the ferriferrous oxide nano magnetic of 0.8g initator dibenzoyl peroxide and 2.0g are dispersed in the 200ml formamide solvent, ultrasonic wave disperses, be transferred to after mixing and still, condenser pipe are housed and connect in the reaction unit of liquid bottle, slowly be heated to the solution boiling and keep constant temperature, solution becomes gradually muddy and begins to steam solvent, and the control polymerization time stops reaction at 2h.The gained magnetic composite microsphere in magnetic field with separated from solvent, respectively wash 3 times with oxolane, acetone, absolute ether, at room temperature the vacuum drying chamber inner drying.The magnetic composite microsphere specific saturation magnetization of preparation is 29.8emu/g, and the surface activity epoxy group content is 0.46mmol/g, and the hydrolysis vigor (A) of its By Immobilized Pseudomonas Sp lipase is 843U/g.
As shown in Figure 1, the magnetic composite microsphere of preparation is regular spherical, does not have adhesion between the microballoon, and its diameter is in the 50-150nm scope.Be positioned at 906cm among Fig. 2
-1, 849cm
-1And 806cm
-1Infrared absorption peak be the characteristic absorption peak of epoxide group, illustrate the preparation magnetic composite microsphere contain a large amount of epoxide groups.
The above; only be the better embodiment of the present invention; protection scope of the present invention is not limited to this; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses, the simple change of the technical scheme that can obtain apparently or equivalence are replaced and are all fallen within the scope of protection of the present invention.
Claims (7)
1. a magnetic composite microsphere is characterized in that, self has active epoxy group magnetic composite microsphere, and described epoxy group content is in the 0.1-2.0mmol/g scope, and the magnetic composite microsphere diameter is at 50-150nm, and the magnetic composite microsphere sphere is regular, Fe
3O
4Nano particle is wrapped in the network configuration of polymer, Fe
3O
4Content in microballoon is 20-70%, and specific saturation magnetization is in the 20-60emu/g scope.
2. the preparation method of the described magnetic composite microsphere of claim 1 is characterized in that, may further comprise the steps:
The glycidyl methacrylate of 0.4-2g and the crosslinking agent of 0.8-8.0g and the ferriferrous oxide nano magnetic of 0.1-1.0g initator and 0.5-5g are dispersed in the 100ml-500ml polar solvent, ultrasonic it is mixed after, be transferred to still is housed, condenser pipe and connecing in the reaction unit of liquid bottle, slowly be heated to the solution boiling and keep constant temperature, solution becomes gradually muddy and begins to steam solvent, the control polymerization time stops reaction at 1~4h, the gained magnetic composite microsphere in magnetic field with separated from solvent, use oxolane, acetone, absolute ether is respectively washed 3 times, at room temperature the vacuum drying chamber inner drying.
3. the preparation method of described magnetic composite microsphere according to claim 2 is characterized in that, described crosslinking agent is divinylbenzene or Ethylene glycol dimethacrylate, or two kinds of crosslinking agents mix the mixed cross-linker of acquisition mutually.
4. the preparation method of described magnetic composite microsphere according to claim 3 is characterized in that, described two kinds of crosslinking agents mutually mixed mass ratio are 1: 1-1: 4.
5. the preparation method of described magnetic composite microsphere according to claim 2 is characterized in that, described polar organic solvent is acetonitrile, formamide or ethanol.
6. the preparation method of described magnetic composite microsphere according to claim 2 is characterized in that, described initator is azodiisobutyronitrile or dibenzoyl peroxide.
7. the described magnetic composite microsphere of claim 1 is in the separation of biomolecule and the application in the immobilization.
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CN103602041A (en) * | 2013-11-15 | 2014-02-26 | 哈尔滨工业大学 | Method for preparing microstructural ordered porous composite material for improving wear-resisting property of edge of pore of porous composite material |
CN106861570A (en) * | 2017-03-03 | 2017-06-20 | 江苏大学 | A kind of magnetic composite microsphere and its preparation method and application |
CN108855001A (en) * | 2018-06-27 | 2018-11-23 | 浙江大学 | A kind of Magnetic solid phases extraction polyphenol adsorbent and preparation method thereof that tannic acid guidance copolymerization coats |
TWI767966B (en) * | 2016-12-19 | 2022-06-21 | 美商3M新設資產公司 | Thermoplastic polymer composite containing soft, ferromagnetic particulate material and methods of making thereof |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103602041A (en) * | 2013-11-15 | 2014-02-26 | 哈尔滨工业大学 | Method for preparing microstructural ordered porous composite material for improving wear-resisting property of edge of pore of porous composite material |
CN103602041B (en) * | 2013-11-15 | 2016-01-20 | 哈尔滨工业大学 | A kind of preparation method improving the microstructure containing hole composite material bore edges abrasion resistance properties and contain hole composite material in order |
TWI767966B (en) * | 2016-12-19 | 2022-06-21 | 美商3M新設資產公司 | Thermoplastic polymer composite containing soft, ferromagnetic particulate material and methods of making thereof |
CN106861570A (en) * | 2017-03-03 | 2017-06-20 | 江苏大学 | A kind of magnetic composite microsphere and its preparation method and application |
CN106861570B (en) * | 2017-03-03 | 2020-06-26 | 江苏大学 | Magnetic composite microsphere and preparation method and application thereof |
CN108855001A (en) * | 2018-06-27 | 2018-11-23 | 浙江大学 | A kind of Magnetic solid phases extraction polyphenol adsorbent and preparation method thereof that tannic acid guidance copolymerization coats |
CN108855001B (en) * | 2018-06-27 | 2020-05-22 | 浙江大学 | Tannin-guided copolymerization-coated magnetic solid-phase extraction polyphenol adsorbent and preparation method thereof |
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