CN103545077A - Oxazine ring modified Fe3O4@SiO2 magnetic nano microsphere and preparation method and application thereof - Google Patents

Oxazine ring modified Fe3O4@SiO2 magnetic nano microsphere and preparation method and application thereof Download PDF

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CN103545077A
CN103545077A CN201310547397.1A CN201310547397A CN103545077A CN 103545077 A CN103545077 A CN 103545077A CN 201310547397 A CN201310547397 A CN 201310547397A CN 103545077 A CN103545077 A CN 103545077A
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nano microsphere
magnetic nano
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preparation
oxazine ring
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CN103545077B (en
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张腾
贝逸翎
鲁在君
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Shandong University
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Shandong University
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Abstract

The invention relates to an oxazine ring modified Fe3O4@SiO2 magnetic nano microsphere and a preparation method and application thereof. The preparation method comprises the steps of preparing a Fe3O4 magnetic nano microsphere which is uniform in particle size and good in dispersity through a hydrothermal method; coating a layer of dense SiO2 on the surface of Fe3O4 through a sol-gel method to prepare a Fe3O4@SiO2 magnetic nano microsphere; coating a layer of silane coupling agents containing oxazine rings on the Fe3O4@SiO2 magnetic nano microsphere through the sol-gel method to prepare the oxazine ring modified Fe3O4@SiO2 magnetic nano microsphere. The magnetic nano microsphere has wide application prospects in preparing polymer based composite and has potential application value in stealth materials and magnetic storage materials.

Description

The Fe that oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere and preparation method thereof and application
Technical field
This invention She is Ji the Fe that oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere and preparation method thereof and application, belong to new material technology field.
Background technology
Magnetic Nano microsphere is a kind of novel nano-functional material, because its particle diameter is little, suspension stability is good, specific area is large, surface activity is high, high adsorption capacity, both can make liposome, also can be coated by macromolecular material, carry out chemical modification, as the carrier of other functional materials.Functional magnetic Nano microsphere refers to by certain chemical method, have specific function chemical group (as-OH ,-NH 2,-SH ,-COOH ,-CHO etc.) be grafted to magnetic Nano microsphere surface, and the magnetic Nano microsphere forming.It not only has the magnetic of magnetic Nano microsphere but also have the functional of surperficial specific chemical group.Therefore, this functional magnetic Nano microsphere has obtained application to a certain degree at numerous areas such as separation engineering, bioengineering, biomedicine and cytology, has demonstrated application prospect widely.
In recent years, the research of functional magnetic Nano microsphere is a more popular problem, has been subject to the common concern of Chinese scholars, wherein functionalization Fe 3o 4@SiO 2the research of magnetic Nano microsphere is one of them importance.But due to Fe 3o 4in air, oxidative resistance is poor, so at Fe 3o 4the SiO of the coated one deck densification of microsphere surface 2the oxidative resistance that can effectively strengthen microballoon.Farzaneh etc. have prepared the coated Fe of gamma-aminopropyl-triethoxy-silane 3o 4@SiO 2magnetic Nano microsphere, then utilizes the amino coordination of microsphere surface, then with Cu (en) 2the reactions such as I, prepare the magnetic Nano microsphere with high catalytic performance, can effectively promote oxidative coupling reaction (F.Farzaneh, the Z.Shafie of alkynyl compounds, E.Rashtizadeh, Reac Kinet Mech Cat (2013) 110:119-129.).Zhang etc. have prepared the Fe that mercapto is modified 3o 4@SiO 2magnetic Nano microsphere, to Au(III) there is a good adsorption effect (Y.Zhang, Q.Xu, S.Zhang, Separation and Purification Technology (2013) 116:391-397.).Zhang etc. have prepared poly-(1,2-diaminobenzene) coated Fe 3o 4@SiO 2magnetic Nano microsphere, its magnetic intensity reaches 60～70emu/g, utilize its absorption property, can remove efficiently and effectively heavy metal ion (F.Zhang, J.Lan, the Z.Zhao such as As (III), Cu (II) in the aqueous solution, Cr (III), Y.Yang, R.Tan, W.Song, Journal of Colloid and Interface Science (2012) 387:205 – 212.).
Chinese patent literature CN103028351A(application number: 201210514810.X) disclose benzene sulfonic acid modified magnetic microballoon and its preparation method and application; The magnetic microsphere of first synthetic tri-iron tetroxide, then adds excessive concentrated ammonia liquor and tetraethoxy-silicane, so that tetraethoxy-silicane is in the polymerization of magnetic microsphere surface hydrolysis, obtains Fe 3o 4/ SiO 2magnetic material, finally adds the dichloromethane solution of excessive 2-(4-chlorine sulfonyl-phenyl)-ethyl trimethoxy silane by Silanization reaction, to obtain the magnetic microsphere of finishing benzene sulfonic acid; The magnetic microsphere particle diameter making evenly, surface area is large, size is controlled, in solution, adopt simple externally-applied magnetic field effect can realize the quick separated of solid phase and liquid phase, the hydrophobic effect by sulfonic strong electrostatic interaction and phenyl ring can adsorb alkaline compound from complex matrices.
Chinese patent literature CN101708463A(application number: 200910153946.0) disclose a kind of high-magnetic heavy-metal ion adsorbent carrying conductive high molecules and preparation method thereof; This adsorbent is from the inside to the outside by Fe 3o 4polycrystalline ball bunch, amorphous SiO 2protective layer, the outer high magnetic loading conducting polymer microballoon forming of polypyrrole (Polypyrrole) absorption; This adsorbent is to be reacted and obtained Fe by solvothermal by soluble iron hydrochlorate 3o 4magnetic ball bunch, then make Fe by tetraethyl orthosilicate basic hydrolysis process 3o 4-SiO 2nuclear shell ball cluster, finally obtains Fe by pyrrole monomer Raolical polymerizable 3o 4-SiO 2-Polypyrrole functional particulate; This adsorbent for heavy metal has stable in properties, fast, the reproducible feature of adsorption rate, the dichromate ion in sewage is had to better absorption and recyclability, and preparation process is simple, material is cheap, non-environmental-pollution.
The disclosed magnetic Nano microsphere of above-mentioned document is used for ionic adsorption, catalytic reaction etc.But, at present easily and monomer reaction and can be used for magnetic Nano microsphere and the preparation thereof of preparing magnetic high-molecular nano composite material have no report.
Summary of the invention
For the deficiencies in the prior art, the Fe that this invention Ti Gong oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere and preparation method thereof and application.
Technical scheme of the present invention is as follows:
The Fe that oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere, this magnetic Nano microsphere comprises Fe 3o 4the SiO that Nano microsphere, thickness are 5～10nm 2layer and thickness are 10～30nm oxazine ring decorative layer, described SiO 2layer is coated on Fe uniformly 3o 4the outer surface of Nano microsphere, Suo Shu oxazine ring decorative layer is coated on SiO uniformly 2the outer surface of layer.
According to the present invention, preferred, the Fe that Suo Shu oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere is solid microsphere, and microsphere diameter is 150～400nm.
The Fe that oxazine ring of the present invention is modified 3o 4@SiO 2magnetic Nano microsphere, by Fe 3o 4nano microsphere outer surface is coated one deck SiO uniformly 2, then the silane coupler of Han oxazine ring is coated to uniformly and is coated with SiO 2fe 3o 4nano microsphere outer surface makes; SiO 2clad ratio be that the clad ratio of 3.2%～10.5% ， oxazine ring is 2.5%～11.2%.
The Fe that Gen modifies according to ， oxazine ring of the present invention 3o 4@SiO 2the preparation method of magnetic Nano microsphere, step is as follows:
(1) Fe 3o 4the preparation of magnetic Nano microsphere:
Take FeCl 36H 2o and sodium acetate are dissolved in ethylene glycol, and stirring at room is dissolved solid completely, obtains mixed solution; Mixed solution is joined in the embedded stainless steel high temperature reactor of polytetrafluoroethylene, at 100～240 ℃, react 8h, the naturally cooling rear use ethanol washing of product, separated with external magnetic field, vacuumize, obtains Fe 3o 4magnetic Nano microsphere; Described FeCl 36H 2the mass ratio of O and sodium acetate is 6.75:(10.00～25.00), described FeCl 36H 2the mass volume ratio of O and ethylene glycol is 6.75:(180～270) g/ml;
(2) Fe 3o 4@SiO 2the preparation of magnetic Nano microsphere:
Take Fe prepared by step (1) 3o 4magnetic Nano microsphere, with after deionized water washing, joins in ethanol water, and ultrasonic dispersion 30min, splashes into tetraethoxysilane and ammoniacal liquor, stirring reaction 48h at 30～80 ℃; Product is separated through external magnetic field, ethanol washing, and vacuumize, obtains Fe 3o 4@SiO 2magnetic Nano microsphere; Described Fe 3o 4the mass volume ratio of magnetic Nano microsphere and tetraethoxysilane is 0.50:(0.2～1.0) g/ml, described Fe 3o 4the mass volume ratio of magnetic Nano microsphere and ammoniacal liquor is 0.50:(1～8) g/ml; The concentration of described ammoniacal liquor is 15～28wt%;
(preparation of the silane coupler (BZS) of 3) Han oxazine rings:
Take gamma-aminopropyl-triethoxy-silane, phenol and paraformaldehyde, join in dioxane, 60～98 ℃ of stirring reaction 8h, dioxane is removed in decompression distillation, obtains the silane coupler of Han oxazine ring; The mass ratio of described gamma-aminopropyl-triethoxy-silane, phenol and paraformaldehyde is 22.14:(5～15): (3～9); Described gamma-aminopropyl-triethoxy-silane and the mass volume ratio of dioxane are (22.14:80) g/ml;
(the Fe that 4) oxazine rings are modified 3o 4@SiO 2magnetic Nano microsphere (Fe 3o 4@SiO 2@BZS) preparation:
Take Fe prepared by step (2) 3o 4@SiO 2magnetic Nano microsphere and step (3) are prepared the silane coupler of Han oxazine ring, join in organic solvent, ultrasonic dispersion 80min, stirring reaction 48h at 30～120 ℃, product is separated through external magnetic field, ethanol washing, vacuumize, the Fe that get oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere; Described Fe 3o 4@SiO 2magnetic Nano microsphere is Yu the mass ratio of the silane coupler of Han oxazine ring is (0.1～0.5): 0.5, and described Fe 3o 4@SiO 2the mass volume ratio of magnetic Nano microsphere and organic solvent is 0.5:(50～100) g/ml.
According to the present invention, preferred, the reaction temperature described in step (1) is 170～220 ℃; Described FeCl 36H 2the mass ratio of O and sodium acetate is 6.75:(12.00～20.00).
According to the present invention, preferred, in the ethanol water described in step (2), the volume ratio of second alcohol and water is (4～8): 1; Described Fe 3o 4the mass volume ratio of magnetic Nano microsphere and ammoniacal liquor is 0.50:(2～6) g/ml.
According to the present invention, preferred, the reaction temperature described in step (3) is 75～95 ℃, and the stir speed (S.S.) of described stirring reaction is 2000～2600r/min.
According to the present invention, preferred, the organic solvent described in step (4) is a kind of in dioxane, toluene, methyl alcohol, isopropyl alcohol, ethyl acetate, carrene or chloroform; Described reaction temperature is 60～110 ℃, and the stir speed (S.S.) of described stirring reaction is 2000～2600r/min.
The Fe that oxazine ring of the present invention is modified 3o 4@SiO 2magnetic Nano microsphere is applied to the preparation of magnetic coupling resin, is especially applied to the preparation of Polybenzoxazine magnetic coupling resin.
Benzoxazine colophony is the class heat resistance resin occurring in recent years, and its oxazine ring functional group both can easily synthesize, and can under heat or catalyst action, carry out easily ring-opening polymerization again.The present invention, by sol-gal process, modifies Fe Ba the silane coupler of Han oxazine ring 3o 4@SiO 2magnetic Nano microsphere surface, thus prepare the Fe that a kind of novel oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere.The Fe that Zhe Zhong oxazine ring is modified 3o 4@SiO 2on magnetic Nano microsphere, there are very large potentiality preparing aspect magnetic high-molecular composite material.Fe 3o 4@SiO 2under heat or catalyst action, can there is ring-opening reaction in magnetic Nano microsphere finishing oxazine ring, thus can with the material generation cross-linking reaction of other Ju You oxazine rings.Therefore, can be the Fe of Zhe Zhong oxazine ring modified 3o 4@SiO 2magnetic Nano microsphere is distributed in benzoxazine monomer uniformly, and then hot setting, prepares the good Polybenzoxazine compound resin of thermal endurance, mechanicalness and anti-flammability; The magnetic Nano microsphere of doping, makes synthetic compound resin have magnetic, thereby prepares magnetic high-molecular composite material simultaneously; This magnetic high-molecular composite material has potential using value aspect stealth material and magnetic storage material.
The present invention has following beneficial effect:
1, the present invention prepares the Fe that oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere particle diameter evenly, surface area is large, size is controlled.
2, the present invention prepares the Fe that oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere has enough large magnetization, and surface has been coated again the silane coupler of more Han oxazine ring simultaneously, and application is good.
3, the present invention proposes the Fe that oxazine ring is modified 3o 4@SiO 2the preparation process of magnetic Nano microsphere is simple, material is cheap, non-environmental-pollution.
Accompanying drawing explanation
Fig. 1 is the Fe of the embodiment of the present invention 1 preparation 3o 4the transmission electron microscope photo of magnetic Nano microsphere.
Fig. 2 is the Fe of the embodiment of the present invention 1 preparation 3o 4@SiO 2the transmission electron microscope photo of magnetic Nano microsphere.
Fig. 3 is the Fe that the embodiment of the present invention 1 preparation oxazine ring is modified 3o 4@SiO 2the transmission electron microscope photo of magnetic Nano microsphere.
Fig. 4 is the Fe that the embodiment of the present invention 1 preparation oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere, Fe 3o 4@SiO 2magnetic Nano microsphere, Fe 3o 4the infared spectrum of magnetic Nano microsphere.
Fig. 5 is the Fe that the embodiment of the present invention 1 preparation oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere, Fe 3o 4@SiO 2magnetic Nano microsphere, Fe 3o 4the magnetic hysteresis loop of magnetic Nano microsphere.
Embodiment
Below by specific embodiment, also the present invention will be further described by reference to the accompanying drawings, but be not limited to this.
Raw materials used conventional raw material, the commercial product of being in embodiment.
Embodiment 1
(1) Fe 3o 4the preparation of magnetic Nano microsphere:
Take 6.75g FeCl 36H 2o, 11.00g sodium acetate is dissolved in 240ml ethylene glycol, and stirring at room is dissolved solid completely, obtains mixed solution; Mixed solution is joined in the embedded stainless steel high temperature reactor of 250ml polytetrafluoroethylene, at 200 ℃, react 8h, for several times, external magnetic field is separated for the cooling rear use ethanol washing of product, and vacuumize, obtains Fe 3o 4magnetic Nano microsphere;
(2) Fe 3o 4@SiO 2the preparation of magnetic Nano microsphere:
Take preparation Fe in 0.50g step (1) 3o 4magnetic Nano microsphere, after deionized water washing three times, joins in the ethanol water of second alcohol and water with 8:1 volume proportion, and ultrasonic dispersions 30min, splashes into 0.20ml tetraethoxysilane and 8ml28wt% ammoniacal liquor, and violent mechanical agitation is reacted 48h at 80 ℃; Product is separated through external magnetic field, and for several times, vacuumize, obtains Fe in ethanol washing 3o 4@SiO 2magnetic Nano microsphere;
(preparation of the silane coupler (BZS) of 3) Han oxazine rings:
Take 22.14g gamma-aminopropyl-triethoxy-silane, 9.41g phenol, 6.00g paraformaldehyde; Join in 80ml dioxane 90 ℃ of mechanical agitation reaction 8h; Decompression distillation, removes dioxane, obtains the silane coupler of Han oxazine ring;
(the Fe that 4) oxazine rings are modified 3o 4@SiO 2magnetic Nano microsphere (Fe 3o 4@SiO 2@BZS) preparation:
Take the Fe of preparation in 0.25g step (2) 3o 4@SiO 2magnetic Nano microsphere, 0.50g step (3) is prepared the silane coupler of Han oxazine ring, joins in 50ml isopropyl alcohol, ultrasonic dispersion 80min, violent mechanical agitation 48h at 120 ℃; Product is separated through external magnetic field, ethanol washing several, vacuumize, the Fe that get oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere.
The present embodiment is prepared the Fe that oxazine ring is modified 3o 4@SiO 2the microsphere diameter of magnetic Nano microsphere is that microsphere diameter is about 200～300nm, SiO 2clad ratio be that the clad ratio of 6.5% ， oxazine ring is 8.5%.
By Fig. 1～Fig. 3, can be found out Fe 3o 4@SiO 2the surface ratio Fe of magnetic Nano microsphere 3o 4the surface of magnetic Nano microsphere has been coated the material of one deck 5～10nm light color more, shows Fe 3o 4siO has successfully been wrapped up on surface 2layer; The Fe that oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere surface ratio Fe 3o 4@SiO 2magnetic Nano microsphere surface has been coated the more light material of one deck 10～30nm more, and boundary is obvious, shows Fe 3o 4@SiO 2magnetic Nano microsphere surface has successfully been coated the silane coupling agent layer of Han oxazine ring.
As seen from Figure 4, Fe 3o 4@SiO 2the infrared spectrum of magnetic Nano microsphere and Fe 3o 4the infrared spectrum of magnetic Nano microsphere is compared, and has obviously increased 1083.95cm -1the Si-O key stretching vibration absworption peak at place, shows Fe 3o 4siO has successfully been wrapped up on surface 2layer.Fe 3o 4@SiO 2the infrared spectrum of magnetic Nano microsphere is Yu the Fe that oxazine ring is modified 3o 4@SiO 2the infrared spectrum of magnetic Nano microsphere is compared, and has obviously increased 2855cm -1and 2925cm -1place -cH 2-key stretching vibration absworption peak, shows Fe 3o 4@SiO 2magnetic Nano microsphere surface has successfully been coated the silane coupling agent layer of Han oxazine ring.
As seen from Figure 5, Fe 3o 4magnetic Nano microsphere, Fe 3o 4@SiO 2magnetic Nano microsphere is with the Fe that oxazine ring is modified 3o 4@SiO 2the magnetization under the same magnetic field intensity of magnetic Nano microsphere reduces successively, shows Fe 3o 4magnetic Nano microsphere, Fe 3o 4@SiO 2magnetic Nano microsphere is with the Fe that oxazine ring is modified 3o 4@SiO 2the thickness of the surface coating layer of magnetic Nano microsphere increases successively.
Embodiment 2
(1) Fe 3o 4the preparation of magnetic Nano microsphere:
Take 6.75g FeCl 36H 2o, 18.00g sodium acetate is dissolved in 240ml ethylene glycol, and stirring at room is dissolved solid completely, obtains mixed solution; Mixed solution gradation is added in the embedded stainless steel high temperature reactor of 50ml polytetrafluoroethylene, at 200 ℃, react 8h, for several times, external magnetic field is separated for the cooling rear use ethanol washing of product, and vacuumize, obtains Fe 3o 4magnetic Nano microsphere;
(2) Fe 3o 4@SiO 2the preparation of magnetic Nano microsphere:
Take preparation Fe in 0.50g step (1) 3o 4magnetic Nano microsphere, after deionized water washing three times, join in the ethanol water of second alcohol and water with 4:1 proportioning, ultrasonic dispersion 30min, splashes into 0.20ml tetraethoxysilane and 1ml28wt% ammoniacal liquor, violent mechanical agitation reaction 48h at 80 ℃, product is separated through external magnetic field, for several times, vacuumize, obtains Fe in ethanol washing 3o 4@SiO 2magnetic Nano microsphere;
(preparation of the silane coupler (BZS) of 3) Han oxazine rings:
Take 22.14g gamma-aminopropyl-triethoxy-silane, 9.41g phenol, 6.00g paraformaldehyde; Join in 80ml dioxane 90 ℃ of mechanical agitation reaction 8h; Decompression distillation, removes dioxane, obtains the silane coupler of Han oxazine ring;
(magnetic Nano microsphere (the Fe that 4) oxazine rings are modified 3o 4@SiO 2@BZS) preparation:
Take the Fe of preparation in 0.25g step (2) 3o 4@SiO 2magnetic Nano microsphere, 0.50g step (3) is prepared the silane coupler of Han oxazine ring, joins in 50ml toluene, ultrasonic dispersion 80min, violent mechanical agitation 48h at 70 ℃; Product is separated through external magnetic field, ethanol washing several, vacuumize, the Fe that get oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere.
The present embodiment is prepared the Fe that oxazine ring is modified 3o 4@SiO 2the microsphere diameter of magnetic Nano microsphere is that microsphere diameter is about 180～250nm, SiO 2clad ratio be that 4.4% ， oxazine ring clad ratio is 3.5%.
Embodiment 3
As described in Example 1, different:
Step takes 6.75g FeCl in (1) 36H 2o, 10.00g sodium acetate is dissolved in 180ml ethylene glycol, and stirring at room is dissolved solid completely, obtains mixed solution;
In step (2), after ultrasonic dispersion, splash into 0.20ml tetraethoxysilane and 1ml15wt% ammoniacal liquor;
Step takes 22.14g gamma-aminopropyl-triethoxy-silane in (3), 5.00g phenol, 3.00g paraformaldehyde; Join in 80ml dioxane;
In step (4), take the Fe of preparation in 0.10g step (2) 3o 4@SiO 2magnetic Nano microsphere, 0.50g step (3) is prepared the silane coupler of Han oxazine ring, joins in 50ml toluene.
The present embodiment is prepared the Fe that oxazine ring is modified 3o 4@SiO 2the microsphere diameter of magnetic Nano microsphere is that microsphere diameter is about 190～270nm, SiO 2clad ratio be that the clad ratio of 7.5% ， oxazine ring is 10.2%.
Embodiment 4
(1) Fe 3o 4the preparation of magnetic Nano microsphere:
Take 6.75g FeCl 36H 2o, 12.00g sodium acetate is dissolved in 240ml ethylene glycol, and stirring at room is dissolved solid completely, obtains mixed solution; Mixed solution gradation is added in the embedded stainless steel high temperature reactor of 50ml polytetrafluoroethylene, at 180 ℃, react 8h, for several times, external magnetic field is separated for the cooling rear use ethanol washing of product, and vacuumize, obtains Fe 3o 4magnetic Nano microsphere;
(2) Fe 3o 4@SiO 2the preparation of magnetic Nano microsphere:
Take preparation Fe in 0.50g step (1) 3o 4magnetic Nano microsphere, after deionized water washing three times, join in the ethanol water of second alcohol and water with 8:1 proportioning, ultrasonic dispersion 30min, splashes into 0.20ml tetraethoxysilane and 8ml28wt% ammoniacal liquor, violent mechanical agitation 48h at 60 ℃, product is separated through external magnetic field, for several times, vacuumize, obtains Fe in ethanol washing 3o 4@SiO 2magnetic Nano microsphere;
(preparation of the silane coupler (BZS) of 3) Han oxazine rings:
Take 22.14g gamma-aminopropyl-triethoxy-silane, 9.41g phenol, 6.00g paraformaldehyde; Join in 80ml dioxane 90 ℃ of mechanical agitation 8h; Decompression distillation, removes dioxane, obtains the silane coupler of Han oxazine ring;
(magnetic Nano microsphere (the Fe that 4) oxazine rings are modified 3o 4@SiO 2@BZS) preparation:
Take the Fe of preparation in 0.25g step (2) 3o 4@SiO 2magnetic Nano microsphere, 0.50g step (3) is prepared the silane coupler of Han oxazine ring, joins in the toluene of 50ml, ultrasonic dispersion 80min, violent mechanical agitation 48h at 120 ℃; Product is separated through external magnetic field, ethanol washing several, vacuumize, the Fe that get oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere.
The present embodiment is prepared the Fe that oxazine ring is modified 3o 4@SiO 2the microsphere diameter of magnetic Nano microsphere is that microsphere diameter is about 200～260nm, SiO 2clad ratio be that 8.6% ， oxazine ring clad ratio is 6.4%.
Embodiment 5
As described in Example 4, different:
Step takes 6.75g FeCl in (1) 36H 2o, 25.00g sodium acetate is dissolved in 270ml ethylene glycol, and stirring at room is dissolved solid completely, obtains mixed solution;
In step (2), after ultrasonic dispersion, splash into 1ml tetraethoxysilane and 8ml15wt% ammoniacal liquor;
Step takes 22.14g gamma-aminopropyl-triethoxy-silane in (3), 15.00g phenol, 9.00g paraformaldehyde; Join in 80ml dioxane;
In step (4), take the Fe of preparation in 0.50g step (2) 3o 4@SiO 2magnetic Nano microsphere, 0.50g step (3) is prepared the silane coupler of Han oxazine ring, joins in 100ml methyl alcohol.
The present embodiment is prepared the Fe that oxazine ring is modified 3o 4@SiO 2the microsphere diameter of magnetic Nano microsphere is that microsphere diameter is about 220～280nm, SiO 2clad ratio be that the clad ratio of 3.8% ， oxazine ring is 3.5%.
Embodiment 6
(1) Fe 3o 4the preparation of magnetic Nano microsphere:
Take 6.75g FeCl 36H 2o, 12.00g sodium acetate is dissolved in 240ml ethylene glycol, and stirring at room is dissolved solid completely, obtains mixed solution; Mixed solution gradation is added in the embedded stainless steel high temperature reactor of 50ml polytetrafluoroethylene, at 200 ℃, react 8h, for several times, external magnetic field is separated for the cooling rear use ethanol washing of product, and vacuumize, obtains Fe 3o 4magnetic Nano microsphere;
(2) Fe 3o 4@SiO 2the preparation of magnetic Nano microsphere:
Take preparation Fe in 0.50g step (1) 3o 4magnetic Nano microsphere, after deionized water washing three times, join in the ethanol water of second alcohol and water with 6:1 proportioning, ultrasonic dispersion 30min, splashes into 0.20ml tetraethoxysilane and 6ml28wt% ammoniacal liquor, violent mechanical agitation 48h at 80 ℃, product is separated through external magnetic field, for several times, vacuumize, obtains Fe in ethanol washing 3o 4@SiO 2magnetic Nano microsphere;
(preparation of the silane coupler (BZS) of 3) Han oxazine rings:
Take 22.14g gamma-aminopropyl-triethoxy-silane, 9.41g phenol, 6.00g paraformaldehyde; Join in 80ml dioxane 90 ℃ of mechanical agitation 8h; Decompression distillation, removes dioxane, obtains the silane coupler of Han oxazine ring;
(magnetic Nano microsphere (the Fe that 4) oxazine rings are modified 3o 4@SiO 2@BZS) preparation:
Take the Fe of preparation in 0.25g step (2) 3o 4@SiO 2magnetic Nano microsphere, 0.50g step (3) is prepared the silane coupler of Han oxazine ring, joins in 50ml dioxane, ultrasonic dispersion 80min, violent mechanical agitation 48h at 40 ℃; Product is separated through external magnetic field, ethanol washing several, vacuumize, the Fe that get oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere.
The present embodiment is prepared the Fe that oxazine ring is modified 3o 4@SiO 2the microsphere diameter of magnetic Nano microsphere is that microsphere diameter is about 240～310nm, SiO 2clad ratio be that 4.9% ， oxazine ring clad ratio is 5.8%.
Embodiment 7
As described in Example 6, different:
Reaction temperature described in step (1) is 170 ℃;
In step (2), after ultrasonic dispersion, splash into 0.5ml tetraethoxysilane and 5ml20wt% ammoniacal liquor;
Reaction temperature described in step (3) is 75 ℃;
Reaction temperature described in step (4) is 60 ℃.
The present embodiment is prepared the Fe that oxazine ring is modified 3o 4@SiO 2the microsphere diameter of magnetic Nano microsphere is that microsphere diameter is about 260～350nm, SiO 2clad ratio be that the clad ratio of 5.2% ， oxazine ring is 6.1%.
Embodiment 8
(1) Fe 3o 4the preparation of magnetic Nano microsphere:
Take 6.75g FeCl 36H 2o, 10.00g sodium acetate is dissolved in 240ml ethylene glycol, and stirring at room is dissolved solid completely, obtains mixed solution; Mixed solution gradation is added in the embedded stainless steel high temperature reactor of 50ml polytetrafluoroethylene, at 180 ℃, react 8h, for several times, external magnetic field is separated for the cooling rear use ethanol washing of product, and vacuumize, obtains Fe 3o 4magnetic Nano microsphere;
(2) Fe 3o 4@SiO 2the preparation of magnetic Nano microsphere:
Take preparation Fe in 0.50g step (1) 3o 4nano particle, after deionized water washing three times, join in the ethanol water of second alcohol and water with 8:1 proportioning, ultrasonic dispersion 30min, splashes into 0.20ml tetraethoxysilane and 2ml28wt% ammoniacal liquor, violent mechanical agitation 48h at 80 ℃, product is separated through external magnetic field, for several times, vacuumize, obtains Fe in ethanol washing 3o 4@SiO 2magnetic Nano microsphere;
(preparation of the silane coupler (BZS) of 3) Han oxazine rings:
Take 22.14g gamma-aminopropyl-triethoxy-silane, 9.41g phenol, 6.00g paraformaldehyde; Join in 80ml dioxane 90 ℃ of mechanical agitation 8h; Decompression distillation, removes dioxane, obtains the silane coupler of Han oxazine ring;
(magnetic Nano microsphere (the Fe that 4) oxazine rings are modified 3o 4@SiO 2@BZS) preparation:
Take the Fe of preparation in 0.25g step (2) 3o 4@SiO 2magnetic Nano microsphere, 0.50g step (3) is prepared the silane coupler of Han oxazine ring, joins in 50ml chloroform, ultrasonic dispersion 80min, violent mechanical agitation 48h at 70 ℃; Product is separated through external magnetic field, ethanol washing several, vacuumize, the Fe that get oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere.
The present embodiment is prepared the Fe that oxazine ring is modified 3o 4@SiO 2the microsphere diameter of magnetic Nano microsphere is that microsphere diameter is about 280～370nm, SiO 2clad ratio be that 9.1% ， oxazine ring clad ratio is 7.4%.
Embodiment 9
As described in Example 8, different:
In step (1), the addition of sodium acetate is 20g, and described reaction temperature is 220 ℃;
In step (2), after ultrasonic dispersion, splash into 0.8ml tetraethoxysilane and 8ml25wt% ammoniacal liquor;
Reaction temperature described in step (3) is 95 ℃;
Reaction temperature described in step (4) is 90 ℃.
The present embodiment is prepared the Fe that oxazine ring is modified 3o 4@SiO 2the microsphere diameter of magnetic Nano microsphere is that microsphere diameter is about 290～390nm, SiO 2clad ratio be that the clad ratio of 8.3% ， oxazine ring is 6.7%.
Application examples
The Fe that embodiment 1 preparation oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere, join two (3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl-), in isopropyl alkane monomer, 80 ℃ of heated mechanical stir 4h, magnetic Nano microsphere is evenly spread in monomer, then mixture is poured in the mould having customized, put into air dry oven, at 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃ and 200 ℃, respectively heat 2h successively, obtaining filemot film, is Polybenzoxazine magnetic coupling resin.The Fe that Suo Shu oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere is 4:100 with the mass ratio of two (3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl-) isopropyl alkane.
The Fe that ， oxazine ring is modified Zhong the preparation process of Polybenzoxazine magnetic coupling resin 3o 4@SiO 2magnetic Nano microsphere is in the Polybenzoxazine magnetic coupling resin of preparation, dispersed, and Nano microsphere agglomeration does not occur.The Fe that oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere with its unique performance and high polymer compound after, mechanical property, heat resistance and the anti-wear performance of Polybenzoxazine magnetic coupling resin of preparation is greatly improved, and there is stronger magnetic.

Claims (10)

1. the Fe that oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere, is characterized in that this magnetic Nano microsphere comprises Fe 3o 4the SiO that Nano microsphere, thickness are 5～10nm 2layer and thickness are 10～30nm oxazine ring decorative layer, described SiO 2layer is coated on Fe uniformly 3o 4the outer surface of Nano microsphere, Suo Shu oxazine ring decorative layer is coated on SiO uniformly 2the outer surface of layer.
2. the Fe modifying according to claim 1 Suo Shu oxazine ring 3o 4@SiO 2magnetic Nano microsphere, is characterized in that the Fe that Suo Shu oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere is solid microsphere, and microsphere diameter is 150～400nm.
3. the Fe that the oxazine rings that a claim 1 or 2 is stated are modified 3o 4@SiO 2the preparation method of magnetic Nano microsphere, step is as follows:
(1) Fe 3o 4the preparation of magnetic Nano microsphere:
Take FeCl 36H 2o and sodium acetate are dissolved in ethylene glycol, and stirring at room is dissolved solid completely, obtains mixed solution; Mixed solution is joined in the embedded stainless steel high temperature reactor of polytetrafluoroethylene, at 100～240 ℃, react 8h, the naturally cooling rear use ethanol washing of product, separated with external magnetic field, vacuumize, obtains Fe 3o 4magnetic Nano microsphere; Described FeCl 36H 2the mass ratio of O and sodium acetate is 6.75:(10.00～25.00), described FeCl 36H 2the mass volume ratio of O and ethylene glycol is 6.75:(180～270) g/ml;
(2) Fe 3o 4@SiO 2the preparation of magnetic Nano microsphere:
Take Fe prepared by step (1) 3o 4magnetic Nano microsphere, with after deionized water washing, joins in ethanol water, and ultrasonic dispersion 30min, splashes into tetraethoxysilane and ammoniacal liquor, stirring reaction 48h at 30～80 ℃; Product is separated through external magnetic field, ethanol washing, and vacuumize, obtains Fe 3o 4@SiO 2magnetic Nano microsphere; Described Fe 3o 4the mass volume ratio of magnetic Nano microsphere and tetraethoxysilane is 0.50:(0.2～1.0) g/ml, described Fe 3o 4the mass volume ratio of magnetic Nano microsphere and ammoniacal liquor is 0.50:(1～8) g/ml; The concentration of described ammoniacal liquor is 15～28wt%;
(preparation of the silane coupler (BZS) of 3) Han oxazine rings:
Take gamma-aminopropyl-triethoxy-silane, phenol and paraformaldehyde, join in dioxane, 60～98 ℃ of stirring reaction 8h, dioxane is removed in decompression distillation, obtains the silane coupler of Han oxazine ring; The mass ratio of described gamma-aminopropyl-triethoxy-silane, phenol and paraformaldehyde is 22.14:(5～15): (3～9); Described gamma-aminopropyl-triethoxy-silane and the mass volume ratio of dioxane are (22.14:80) g/ml;
(the Fe that 4) oxazine rings are modified 3o 4@SiO 2magnetic Nano microsphere (Fe 3o 4@SiO 2@BZS) preparation:
Take Fe prepared by step (2) 3o 4@SiO 2magnetic Nano microsphere and step (3) are prepared the silane coupler of Han oxazine ring, join in organic solvent, ultrasonic dispersion 80min, stirring reaction 48h at 30～120 ℃, product is separated through external magnetic field, ethanol washing, vacuumize, the Fe that get oxazine ring is modified 3o 4@SiO 2magnetic Nano microsphere; Described Fe 3o 4@SiO 2magnetic Nano microsphere is Yu the mass ratio of the silane coupler of Han oxazine ring is (0.1～0.5): 0.5, and described Fe 3o 4@SiO 2the mass volume ratio of magnetic Nano microsphere and organic solvent is 0.5:(50～100) g/ml.
4. the Fe modifying according to claim 3 Suo Shu oxazine ring 3o 4@SiO 2the preparation method of magnetic Nano microsphere, is characterized in that the reaction temperature described in step (1) is 170～220 ℃.
5. the Fe modifying according to claim 3 Suo Shu oxazine ring 3o 4@SiO 2the preparation method of magnetic Nano microsphere, is characterized in that the FeCl described in step (1) 36H 2the mass ratio of O and sodium acetate is 6.75:(12.00～20.00).
6. the Fe modifying according to claim 3 Suo Shu oxazine ring 3o 4@SiO 2the preparation method of magnetic Nano microsphere, the volume ratio that it is characterized in that second alcohol and water in the ethanol water described in step (2) is (4～8): 1; Described Fe 3o 4the mass volume ratio of magnetic Nano microsphere and ammoniacal liquor is 0.50:(2～6) g/ml.
7. the Fe modifying according to claim 3 Suo Shu oxazine ring 3o 4@SiO 2the preparation method of magnetic Nano microsphere, is characterized in that the reaction temperature described in step (3) is 75～95 ℃, and the stir speed (S.S.) of described stirring reaction is 2000～2600r/min.
8. the Fe modifying according to claim 3 Suo Shu oxazine ring 3o 4@SiO 2the preparation method of magnetic Nano microsphere, is characterized in that the organic solvent described in step (4) is a kind of in dioxane, toluene, methyl alcohol, isopropyl alcohol, ethyl acetate, carrene or chloroform.
9. the Fe modifying according to claim 3 Suo Shu oxazine ring 3o 4@SiO 2the preparation method of magnetic Nano microsphere, is characterized in that the reaction temperature described in step (4) is 60～110 ℃, and the stir speed (S.S.) of described stirring reaction is 2000～2600r/min.
10. the Fe that claim 1 or 2 Shu oxazine rings are modified 3o 4@SiO 2magnetic Nano microsphere is applied to the preparation of Polybenzoxazine magnetic coupling resin.
CN201310547397.1A 2013-11-07 2013-11-07 The Fe that oxazine ring is modified 3o 4siO 2magnetic Nano microsphere and preparation method thereof and application Expired - Fee Related CN103545077B (en)

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