CN103545077B - The Fe that oxazine ring is modified 3o 4siO 2magnetic Nano microsphere and preparation method thereof and application - Google Patents

The Fe that oxazine ring is modified 3o 4siO 2magnetic Nano microsphere and preparation method thereof and application Download PDF

Info

Publication number
CN103545077B
CN103545077B CN201310547397.1A CN201310547397A CN103545077B CN 103545077 B CN103545077 B CN 103545077B CN 201310547397 A CN201310547397 A CN 201310547397A CN 103545077 B CN103545077 B CN 103545077B
Authority
CN
China
Prior art keywords
sio
nano microsphere
magnetic nano
oxazine ring
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201310547397.1A
Other languages
Chinese (zh)
Other versions
CN103545077A (en
Inventor
张腾
贝逸翎
鲁在君
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong University
Original Assignee
Shandong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong University filed Critical Shandong University
Priority to CN201310547397.1A priority Critical patent/CN103545077B/en
Publication of CN103545077A publication Critical patent/CN103545077A/en
Application granted granted Critical
Publication of CN103545077B publication Critical patent/CN103545077B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The present invention relates to the Fe that oxazine ring is modified 3o 4siO 2magnetic Nano microsphere and preparation method thereof and application.Hydro thermal method is adopted to prepare the Fe of uniform particle sizes, good dispersion 3o 4magnetic Nano microsphere; Again by sol-gal process at Fe 3o 4the Surface coating SiO of one deck densification 2, prepared Fe 3o 4siO 2magnetic Nano microsphere; Again by sol-gal process at Fe 3o 4siO 2the silane coupler of Surface coating one deck Han oxazine ring of magnetic Nano microsphere, thus the Fe preparing the modification of oxazine ring 3o 4siO 2magnetic Nano microsphere.This magnetic Nano microsphere has great application prospect preparing in magnetic high-molecular composite material, and has potential using value in stealth material, magnetic storage material.

Description

The Fe that oxazine ring is modified 3o 4siO 2magnetic Nano microsphere and preparation method thereof and application
Technical field
This invention She is Ji the Fe of oxazine ring modification 3o 4siO 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 liposome be made, 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, having the chemical group of specific function (as-OH ,-NH 2,-SH ,-COOH ,-CHO etc.) be grafted to magnetic Nano microsphere surface, and the magnetic Nano microsphere formed.It not only has the magnetic of magnetic Nano microsphere but also has the functional of surperficial specified chemical group.Therefore, this functional magnetic Nano microsphere obtains application to a certain degree at numerous areas such as separation engineering, bioengineering, biomedicine and cytology, shows application prospect widely.
In recent years, the research of functional magnetic Nano microsphere is a more popular problem, receives the common concern of Chinese scholars, wherein functionalization Fe 3o 4siO 2the research of magnetic Nano microsphere is one of them importance.But due to Fe 3o 4oxidative resistance is poor in atmosphere, so at Fe 3o 4the SiO of the coated one deck densification of microsphere surface 2the oxidative resistance that effectively can strengthen microballoon.Farzaneh etc. have prepared the coated Fe of gamma-aminopropyl-triethoxy-silane 3o 4siO 2magnetic Nano microsphere, then utilizes the coordinating of the amino of microsphere surface, then with Cu (en) 2the reactions such as I, prepare the magnetic Nano microsphere with high catalytic performance, effectively can promote oxidative coupling reaction (F.Farzaneh, the Z.Shafie of alkynyl compounds, E.Rashtizadeh, ReacKinetMechCat (2013) 110:119-129.).Zhang etc. have prepared the Fe that mercapto is modified 3o 4siO 2magnetic Nano microsphere, to Au(III) there is good adsorption effect (Y.Zhang, Q.Xu, S.Zhang, SeparationandPurificationTechnology (2013) 116:391-397.).Zhang etc. have prepared poly-(1,2-diaminobenzene) coated Fe 3o 4siO 2magnetic Nano microsphere, its magnetic intensity reaches 60 ~ 70emu/g, utilize its absorption property, heavy metal ion (F.Zhang, J.Lan, the Z.Zhao such as the As (III) in the aqueous solution, Cu (II), Cr (III) can be removed efficiently and effectively, Y.Yang, R.Tan, W.Song, JournalofColloidandInterfaceScience (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; First synthesize the magnetic microsphere of tri-iron tetroxide, then add excessive concentrated ammonia liquor and tetraethoxy-silicane, to make tetraethoxy-silicane in the polymerization of magnetic microsphere surface hydrolysis, obtain Fe 3o 4/ SiO 2magnetic material, the dichloromethane solution finally adding excessive 2-(4-chlorine sulfonyl-phenyl)-ethyl trimethoxy silane obtains the magnetic microsphere of finishing benzene sulfonic acid by Silanization reaction; Obtained magnetic microsphere particle diameter evenly, surface area is comparatively large, size is controlled, adopt simple externally-applied magnetic field effect can realize the quick separating of solid phase and liquid phase in the solution, alkaline compound can be adsorbed from complex matrices by the hydrophobic effect of sulfonic strong electrostatic interaction and phenyl ring.
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 2the high magnetic loading conducting polymer microballoon of the outer composition of protective layer, polypyrrole (Polypyrrole) absorption; This adsorbent reacts acquisition Fe by soluble iron hydrochlorate by solvothermal 3o 4magnetic ball bunch, then obtain Fe by tetraethyl orthosilicate basic hydrolysis process 3o 4-SiO 2nuclear shell ball cluster, obtains Fe finally 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, have better absorption and recyclability, and preparation process is simple, material is cheap, non-environmental-pollution to the dichromate ion in sewage.
Disclosed in above-mentioned document, magnetic Nano microsphere is used for ionic adsorption, catalytic reaction etc.But, at present easily and monomer reaction and can be used for prepares the magnetic Nano microsphere of magnetic high-molecular nano composite material and preparation has 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 4siO 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 4siO 2magnetic Nano microsphere, this magnetic Nano microsphere comprises Fe 3o 4nano microsphere, thickness are the SiO of 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, preferably, the Fe of Suo Shu oxazine ring modification 3o 4siO 2magnetic Nano microsphere is solid microsphere, and microsphere diameter is 150 ~ 400nm.
The Fe that oxazine ring of the present invention is modified 3o 4siO 2magnetic Nano microsphere, by Fe 3o 4the uniform coated one deck SiO of Nano microsphere outer surface 2, then the silane coupler of Han oxazine ring is coated to uniformly is coated with SiO 2fe 3o 4nano microsphere outer surface obtains; SiO 2clad ratio be the clad ratio of 3.2% ~ 10.5% ， oxazine ring be 2.5% ~ 11.2%.
The Fe that Gen modifies according to ， oxazine ring of the present invention 3o 4siO 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, stirring at room temperature, solid is dissolved completely, obtains mixed solution; Joined by mixed solution in the embedded stainless steel high temperature reactor of polytetrafluoroethylene, at 100 ~ 240 DEG C, react 8h, use ethanol washing after product cools naturally, be 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 4siO 2the preparation of magnetic Nano microsphere:
Take Fe prepared by step (1) 3o 4magnetic Nano microsphere, after spending deionized water, joins in ethanol water, ultrasonic disperse 30min, instillation tetraethoxysilane and ammoniacal liquor, stirring reaction 48h at 30 ~ 80 DEG C; Product is separated through external magnetic field, and ethanol washs, and vacuumize, obtains Fe 3o 4siO 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 DEG C of stirring reaction 8h, decompression distillation removing dioxane, 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 4siO 2magnetic Nano microsphere (Fe 3o 4siO 2bZS) preparation:
Take Fe prepared by step (2) 3o 4siO 2magnetic Nano microsphere and step (3) prepare the silane coupler of Han oxazine ring, join in organic solvent, ultrasonic disperse 80min, stirring reaction 48h at 30 ~ 120 DEG C, product is separated through external magnetic field, and ethanol washs, vacuumize, the Fe that get oxazine ring is modified 3o 4siO 2magnetic Nano microsphere; Described Fe 3o 4siO 2magnetic Nano microsphere is Yu the mass ratio of silane coupler of Han oxazine ring is (0.1 ~ 0.5): 0.5, described Fe 3o 4siO 2the mass volume ratio of magnetic Nano microsphere and organic solvent is 0.5:(50 ~ 100) g/ml.
According to the present invention, preferably, the reaction temperature described in step (1) is 170 ~ 220 DEG C; Described FeCl 36H 2the mass ratio of O and sodium acetate is 6.75:(12.00 ~ 20.00).
According to the present invention, preferably, 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, preferably, the reaction temperature described in step (3) is 75 ~ 95 DEG C, and the stir speed (S.S.) of described stirring reaction is 2000 ~ 2600r/min.
According to the present invention, preferably, the organic solvent described in step (4) is the one in dioxane, toluene, methyl alcohol, isopropyl alcohol, ethyl acetate, carrene or chloroform; Described reaction temperature is 60 ~ 110 DEG C, 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 4siO 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 occurred in recent years, and its oxazine ring functional group both can easily synthesize, and can carry out ring-opening polymerization easily again under heat or catalyst action.The present invention, by sol-gal process, modifies Fe Ba the silane coupler of Han oxazine ring 3o 4siO 2magnetic Nano microsphere surface, thus the Fe preparing a kind of novel oxazine ring modification 3o 4siO 2magnetic Nano microsphere.The Fe that Zhe Zhong oxazine ring is modified 3o 4siO 2magnetic Nano microsphere have very large potentiality preparing in magnetic high-molecular composite material.Fe 3o 4siO 2magnetic Nano microsphere finishing oxazine ring heat or catalyst action under can there is ring-opening reaction, thus can with the material generation cross-linking reaction of other Ju You oxazine rings.Therefore, can the Fe of Zhe Zhong oxazine ring modified 3o 4siO 2magnetic Nano microsphere is distributed in benzoxazine monomer uniformly, then hot setting, prepares the Polybenzoxazine compound resin that thermal endurance, mechanicalness and anti-flammability are good; The magnetic Nano microsphere simultaneously adulterated, makes the compound resin of synthesis be provided with magnetic, thus prepares magnetic high-molecular composite material; This magnetic high-molecular composite material has potential using value in 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 4siO 2magnetic Nano microsphere uniform particle sizes, surface area are comparatively large, size is controlled.
2, the present invention prepares the Fe that oxazine ring is modified 3o 4siO 2magnetic Nano microsphere has the enough large magnetization, simultaneously surface the is coated again silane coupler of more Han oxazine ring, and application is good.
3, the present invention proposes the Fe that oxazine ring is modified 3o 4siO 2the preparation process of magnetic Nano microsphere is simple, material is cheap, non-environmental-pollution.
Accompanying drawing explanation
Fig. 1 is Fe prepared by the embodiment of the present invention 1 3o 4the transmission electron microscope photo of magnetic Nano microsphere.
Fig. 2 is Fe prepared by the embodiment of the present invention 1 3o 4siO 2the transmission electron microscope photo of magnetic Nano microsphere.
Fig. 3 is the Fe that the embodiment of the present invention 1 prepares the modification of oxazine ring 3o 4siO 2the transmission electron microscope photo of magnetic Nano microsphere.
Fig. 4 is the Fe that the embodiment of the present invention 1 prepares the modification of oxazine ring 3o 4siO 2magnetic Nano microsphere, Fe 3o 4siO 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 prepares the modification of oxazine ring 3o 4siO 2magnetic Nano microsphere, Fe 3o 4siO 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 thereto.
Raw materials usedly in embodiment be convenient source, commercial products.
Embodiment 1
(1) Fe 3o 4the preparation of magnetic Nano microsphere:
Take 6.75gFeCl 36H 2o, 11.00g sodium acetate is dissolved in 240ml ethylene glycol, and stirring at room temperature makes solid dissolve completely, obtains mixed solution; Joined by mixed solution in the embedded stainless steel high temperature reactor of 250ml polytetrafluoroethylene, at 200 DEG C, react 8h, use ethanol washing after product cooling for several times, external magnetic field is separated, and vacuumize, obtains Fe 3o 4magnetic Nano microsphere;
(2) Fe 3o 4siO 2the preparation of magnetic Nano microsphere:
Take preparation Fe in 0.50g step (1) 3o 4magnetic Nano microsphere, after deionized water washs three times, joins second alcohol and water with in the ethanol water of 8:1 volume proportion, ultrasonic disperse 30min, instillation 0.20ml tetraethoxysilane and 8ml28wt% ammoniacal liquor, vigorous mechanical agitation reaction 48h at 80 DEG C; Product is separated through external magnetic field, and for several times, vacuumize, obtains Fe in ethanol washing 3o 4siO 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 DEG C of mechanic whirl-nett reaction 8h; Decompression distillation, removing dioxane, obtains the silane coupler of Han oxazine ring;
(the Fe that 4) oxazine rings are modified 3o 4siO 2magnetic Nano microsphere (Fe 3o 4siO 2bZS) preparation:
Take the Fe of preparation in 0.25g step (2) 3o 4siO 2magnetic Nano microsphere, 0.50g step (3) prepares the silane coupler of Han oxazine ring, joins in 50ml isopropyl alcohol, ultrasonic disperse 80min, vigorous mechanical agitation 48h at 120 DEG C; Product is separated through external magnetic field, ethanol washing several, vacuumize, the Fe that get oxazine ring is modified 3o 4siO 2magnetic Nano microsphere.
The present embodiment prepares the Fe that oxazine ring is modified 3o 4siO 2the microsphere diameter of magnetic Nano microsphere is that microsphere diameter is about 200 ~ 300nm, SiO 2clad ratio be the clad ratio of 6.5% ， oxazine ring be 8.5%.
As can be seen from Fig. 1 ~ Fig. 3, Fe 3o 4siO 2the surface ratio Fe of magnetic Nano microsphere 3o 4the material of surface how coated one deck 5 ~ 10nm light color of magnetic Nano microsphere, shows Fe 3o 4siO has successfully been wrapped up in surface 2layer; The Fe that oxazine ring is modified 3o 4siO 2magnetic Nano microsphere surface ratio Fe 3o 4siO 2the material that how coated magnetic Nano microsphere surface one deck 10 ~ 30nm be more light, and boundary is obvious, shows Fe 3o 4siO 2the silane coupling agent layer of the coated Han oxazine ring of the surperficial success of magnetic Nano microsphere.
As seen from Figure 4, Fe 3o 4siO 2the infrared spectrum of magnetic Nano microsphere and Fe 3o 4the infrared spectrum of magnetic Nano microsphere is compared, and significantly increases 1083.95cm -1the Si-O key stretching vibration absworption peak at place, shows Fe 3o 4siO has successfully been wrapped up in surface 2layer.Fe 3o 4siO 2the infrared spectrum of magnetic Nano microsphere is Yu the Fe that modifies of oxazine ring 3o 4siO 2the infrared spectrum of magnetic Nano microsphere is compared, and significantly increases 2855cm -1and 2925cm -1place -cH 2-key stretching vibration absworption peak, shows Fe 3o 4siO 2the silane coupling agent layer of the coated Han oxazine ring of the surperficial success of magnetic Nano microsphere.
As seen from Figure 5, Fe 3o 4magnetic Nano microsphere, Fe 3o 4siO 2magnetic Nano microsphere is with the Fe of oxazine ring modification 3o 4siO 2the magnetization under the same magnetic field intensity of magnetic Nano microsphere reduces successively, shows Fe 3o 4magnetic Nano microsphere, Fe 3o 4siO 2magnetic Nano microsphere is with the Fe of oxazine ring modification 3o 4siO 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 6.75gFeCl 36H 2o, 18.00g sodium acetate is dissolved in 240ml ethylene glycol, and stirring at room temperature makes solid dissolve completely, obtains mixed solution; Mixed solution gradation added in the embedded stainless steel high temperature reactor of 50ml polytetrafluoroethylene, at 200 DEG C, react 8h, use ethanol washing after product cooling for several times, external magnetic field is separated, and vacuumize, obtains Fe 3o 4magnetic Nano microsphere;
(2) Fe 3o 4siO 2the preparation of magnetic Nano microsphere:
Take preparation Fe in 0.50g step (1) 3o 4magnetic Nano microsphere, after deionized water washs three times, join second alcohol and water with in the ethanol water of 4:1 proportioning, ultrasonic disperse 30min, instillation 0.20ml tetraethoxysilane and 1ml28wt% ammoniacal liquor, vigorous mechanical agitation reaction 48h at 80 DEG C, product is separated through external magnetic field, for several times, vacuumize, obtains Fe in ethanol washing 3o 4siO 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 DEG C of mechanic whirl-nett reaction 8h; Decompression distillation, removing dioxane, obtains the silane coupler of Han oxazine ring;
(magnetic Nano microsphere (the Fe that 4) oxazine rings are modified 3o 4siO 2bZS) preparation:
Take the Fe of preparation in 0.25g step (2) 3o 4siO 2magnetic Nano microsphere, 0.50g step (3) prepares the silane coupler of Han oxazine ring, joins in 50ml toluene, ultrasonic disperse 80min, vigorous mechanical agitation 48h at 70 DEG C; Product is separated through external magnetic field, ethanol washing several, vacuumize, the Fe that get oxazine ring is modified 3o 4siO 2magnetic Nano microsphere.
The present embodiment prepares the Fe that oxazine ring is modified 3o 4siO 2the microsphere diameter of magnetic Nano microsphere is that microsphere diameter is about 180 ~ 250nm, SiO 2clad ratio be 4.4% ， oxazine ring clad ratio be 3.5%.
Embodiment 3
As described in Example 1, unlike:
Step takes 6.75gFeCl in (1) 36H 2o, 10.00g sodium acetate is dissolved in 180ml ethylene glycol, and stirring at room temperature makes solid dissolve completely, obtains mixed solution;
0.20ml tetraethoxysilane and 1ml15wt% ammoniacal liquor is instilled after ultrasonic disperse in step (2);
Step takes 22.14g gamma-aminopropyl-triethoxy-silane in (3), 5.00g phenol, 3.00g paraformaldehyde; Join in 80ml dioxane;
The Fe of preparation in 0.10g step (2) is taken in step (4) 3o 4siO 2magnetic Nano microsphere, 0.50g step (3) prepares the silane coupler of Han oxazine ring, joins in 50ml toluene.
The present embodiment prepares the Fe that oxazine ring is modified 3o 4siO 2the microsphere diameter of magnetic Nano microsphere is that microsphere diameter is about 190 ~ 270nm, SiO 2clad ratio be the clad ratio of 7.5% ， oxazine ring be 10.2%.
Embodiment 4
(1) Fe 3o 4the preparation of magnetic Nano microsphere:
Take 6.75gFeCl 36H 2o, 12.00g sodium acetate is dissolved in 240ml ethylene glycol, and stirring at room temperature makes solid dissolve completely, obtains mixed solution; Mixed solution gradation added in the embedded stainless steel high temperature reactor of 50ml polytetrafluoroethylene, at 180 DEG C, react 8h, use ethanol washing after product cooling for several times, external magnetic field is separated, and vacuumize, obtains Fe 3o 4magnetic Nano microsphere;
(2) Fe 3o 4siO 2the preparation of magnetic Nano microsphere:
Take preparation Fe in 0.50g step (1) 3o 4magnetic Nano microsphere, after deionized water washs three times, join second alcohol and water with in the ethanol water of 8:1 proportioning, ultrasonic disperse 30min, instillation 0.20ml tetraethoxysilane and 8ml28wt% ammoniacal liquor, vigorous mechanical agitation 48h at 60 DEG C, product is separated through external magnetic field, for several times, vacuumize, obtains Fe in ethanol washing 3o 4siO 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 DEG C of mechanical agitation 8h; Decompression distillation, removing dioxane, obtains the silane coupler of Han oxazine ring;
(magnetic Nano microsphere (the Fe that 4) oxazine rings are modified 3o 4siO 2bZS) preparation:
Take the Fe of preparation in 0.25g step (2) 3o 4siO 2magnetic Nano microsphere, 0.50g step (3) prepares the silane coupler of Han oxazine ring, joins in the toluene of 50ml, ultrasonic disperse 80min, vigorous mechanical agitation 48h at 120 DEG C; Product is separated through external magnetic field, ethanol washing several, vacuumize, the Fe that get oxazine ring is modified 3o 4siO 2magnetic Nano microsphere.
The present embodiment prepares the Fe that oxazine ring is modified 3o 4siO 2the microsphere diameter of magnetic Nano microsphere is that microsphere diameter is about 200 ~ 260nm, SiO 2clad ratio be 8.6% ， oxazine ring clad ratio be 6.4%.
Embodiment 5
As described in Example 4, unlike:
Step takes 6.75gFeCl in (1) 36H 2o, 25.00g sodium acetate is dissolved in 270ml ethylene glycol, and stirring at room temperature makes solid dissolve completely, obtains mixed solution;
1ml tetraethoxysilane and 8ml15wt% ammoniacal liquor is instilled after ultrasonic disperse in step (2);
Step takes 22.14g gamma-aminopropyl-triethoxy-silane in (3), 15.00g phenol, 9.00g paraformaldehyde; Join in 80ml dioxane;
The Fe of preparation in 0.50g step (2) is taken in step (4) 3o 4siO 2magnetic Nano microsphere, 0.50g step (3) prepares the silane coupler of Han oxazine ring, joins in 100ml methyl alcohol.
The present embodiment prepares the Fe that oxazine ring is modified 3o 4siO 2the microsphere diameter of magnetic Nano microsphere is that microsphere diameter is about 220 ~ 280nm, SiO 2clad ratio be the clad ratio of 3.8% ， oxazine ring be 3.5%.
Embodiment 6
(1) Fe 3o 4the preparation of magnetic Nano microsphere:
Take 6.75gFeCl 36H 2o, 12.00g sodium acetate is dissolved in 240ml ethylene glycol, and stirring at room temperature makes solid dissolve completely, obtains mixed solution; Mixed solution gradation added in the embedded stainless steel high temperature reactor of 50ml polytetrafluoroethylene, at 200 DEG C, react 8h, use ethanol washing after product cooling for several times, external magnetic field is separated, and vacuumize, obtains Fe 3o 4magnetic Nano microsphere;
(2) Fe 3o 4siO 2the preparation of magnetic Nano microsphere:
Take preparation Fe in 0.50g step (1) 3o 4magnetic Nano microsphere, after deionized water washs three times, join second alcohol and water with in the ethanol water of 6:1 proportioning, ultrasonic disperse 30min, instillation 0.20ml tetraethoxysilane and 6ml28wt% ammoniacal liquor, vigorous mechanical agitation 48h at 80 DEG C, product is separated through external magnetic field, for several times, vacuumize, obtains Fe in ethanol washing 3o 4siO 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 DEG C of mechanical agitation 8h; Decompression distillation, removing dioxane, obtains the silane coupler of Han oxazine ring;
(magnetic Nano microsphere (the Fe that 4) oxazine rings are modified 3o 4siO 2bZS) preparation:
Take the Fe of preparation in 0.25g step (2) 3o 4siO 2magnetic Nano microsphere, 0.50g step (3) prepares the silane coupler of Han oxazine ring, joins in 50ml dioxane, ultrasonic disperse 80min, vigorous mechanical agitation 48h at 40 DEG C; Product is separated through external magnetic field, ethanol washing several, vacuumize, the Fe that get oxazine ring is modified 3o 4siO 2magnetic Nano microsphere.
The present embodiment prepares the Fe that oxazine ring is modified 3o 4siO 2the microsphere diameter of magnetic Nano microsphere is that microsphere diameter is about 240 ~ 310nm, SiO 2clad ratio be 4.9% ， oxazine ring clad ratio be 5.8%.
Embodiment 7
As described in Example 6, unlike:
Reaction temperature described in step (1) is 170 DEG C;
0.5ml tetraethoxysilane and 5ml20wt% ammoniacal liquor is instilled after ultrasonic disperse in step (2);
Reaction temperature described in step (3) is 75 DEG C;
Reaction temperature described in step (4) is 60 DEG C.
The present embodiment prepares the Fe that oxazine ring is modified 3o 4siO 2the microsphere diameter of magnetic Nano microsphere is that microsphere diameter is about 260 ~ 350nm, SiO 2clad ratio be the clad ratio of 5.2% ， oxazine ring be 6.1%.
Embodiment 8
(1) Fe 3o 4the preparation of magnetic Nano microsphere:
Take 6.75gFeCl 36H 2o, 10.00g sodium acetate is dissolved in 240ml ethylene glycol, and stirring at room temperature makes solid dissolve completely, obtains mixed solution; Mixed solution gradation added in the embedded stainless steel high temperature reactor of 50ml polytetrafluoroethylene, at 180 DEG C, react 8h, use ethanol washing after product cooling for several times, external magnetic field is separated, and vacuumize, obtains Fe 3o 4magnetic Nano microsphere;
(2) Fe 3o 4siO 2the preparation of magnetic Nano microsphere:
Take preparation Fe in 0.50g step (1) 3o 4nano particle, after deionized water washs three times, join second alcohol and water with in the ethanol water of 8:1 proportioning, ultrasonic disperse 30min, instillation 0.20ml tetraethoxysilane and 2ml28wt% ammoniacal liquor, vigorous mechanical agitation 48h at 80 DEG C, product is separated through external magnetic field, for several times, vacuumize, obtains Fe in ethanol washing 3o 4siO 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 DEG C of mechanical agitation 8h; Decompression distillation, removing dioxane, obtains the silane coupler of Han oxazine ring;
(magnetic Nano microsphere (the Fe that 4) oxazine rings are modified 3o 4siO 2bZS) preparation:
Take the Fe of preparation in 0.25g step (2) 3o 4siO 2magnetic Nano microsphere, 0.50g step (3) prepares the silane coupler of Han oxazine ring, joins in 50ml chloroform, ultrasonic disperse 80min, vigorous mechanical agitation 48h at 70 DEG C; Product is separated through external magnetic field, ethanol washing several, vacuumize, the Fe that get oxazine ring is modified 3o 4siO 2magnetic Nano microsphere.
The present embodiment prepares the Fe that oxazine ring is modified 3o 4siO 2the microsphere diameter of magnetic Nano microsphere is that microsphere diameter is about 280 ~ 370nm, SiO 2clad ratio be 9.1% ， oxazine ring clad ratio be 7.4%.
Embodiment 9
As described in Example 8, unlike:
In step (1), the addition of sodium acetate is 20g, and described reaction temperature is 220 DEG C;
0.8ml tetraethoxysilane and 8ml25wt% ammoniacal liquor is instilled after ultrasonic disperse in step (2);
Reaction temperature described in step (3) is 95 DEG C;
Reaction temperature described in step (4) is 90 DEG C.
The present embodiment prepares the Fe that oxazine ring is modified 3o 4siO 2the microsphere diameter of magnetic Nano microsphere is that microsphere diameter is about 290 ~ 390nm, SiO 2clad ratio be the clad ratio of 8.3% ， oxazine ring be 6.7%.
Application examples
The Fe that oxazine ring is modified prepared by embodiment 1 3o 4siO 2magnetic Nano microsphere, join two (3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl-) in different oxide monomer, 80 DEG C of heated mechanical mixer 4h, magnetic Nano microsphere is made to evenly spread in monomer, then mixture is poured in the mould customized, put into air dry oven, respectively heat 2h 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C and 200 DEG C successively, obtaining filemot film, is namely Polybenzoxazine magnetic coupling resin.The Fe that Suo Shu oxazine ring is modified 3o 4siO 2magnetic Nano microsphere is 4:100 with the mass ratio of two (3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl-) isopropyl alkane.
At the Fe that the preparation process Zhong ， oxazine ring of Polybenzoxazine magnetic coupling resin is modified 3o 4siO 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 4siO 2magnetic Nano microsphere, with after the performance of its uniqueness and high polymer compound, makes the mechanical property of the Polybenzoxazine magnetic coupling resin of preparation, heat resistance and anti-wear performance be greatly improved, and has stronger magnetic.

Claims (10)

1. the Fe of oxazine ring modification 3o 4siO 2magnetic Nano microsphere, is characterized in that this magnetic Nano microsphere comprises Fe 3o 4nano microsphere, thickness are the SiO of 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. according to the Fe that claim 1 Suo Shu oxazine ring is modified 3o 4siO 2magnetic Nano microsphere, is characterized in that the Fe that Suo Shu oxazine ring is modified 3o 4siO 2magnetic Nano microsphere is solid microsphere, and microsphere diameter is 150 ~ 400nm.
3. the Fe that the oxazine ring that a claim 1 or 2 is stated is modified 3o 4siO 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, stirring at room temperature, solid is dissolved completely, obtains mixed solution; Joined by mixed solution in the embedded stainless steel high temperature reactor of polytetrafluoroethylene, at 100 ~ 240 DEG C, react 8h, use ethanol washing after product cools naturally, be 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 4siO 2the preparation of magnetic Nano microsphere:
Take Fe prepared by step (1) 3o 4magnetic Nano microsphere, after spending deionized water, joins in ethanol water, ultrasonic disperse 30min, instillation tetraethoxysilane and ammoniacal liquor, stirring reaction 48h at 30 ~ 80 DEG C; Product is separated through external magnetic field, and ethanol washs, and vacuumize, obtains Fe 3o 4siO 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 DEG C of stirring reaction 8h, decompression distillation removing dioxane, 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 4siO 2magnetic Nano microsphere (Fe 3o 4siO 2bZS) preparation:
Take Fe prepared by step (2) 3o 4siO 2magnetic Nano microsphere and step (3) prepare the silane coupler of Han oxazine ring, join in organic solvent, ultrasonic disperse 80min, stirring reaction 48h at 30 ~ 120 DEG C, product is separated through external magnetic field, and ethanol washs, vacuumize, the Fe that get oxazine ring is modified 3o 4siO 2magnetic Nano microsphere; Described Fe 3o 4siO 2magnetic Nano microsphere is Yu the mass ratio of silane coupler of Han oxazine ring is (0.1 ~ 0.5): 0.5, described Fe 3o 4siO 2the mass volume ratio of magnetic Nano microsphere and organic solvent is 0.5:(50 ~ 100) g/ml.
4. according to the Fe that claim 3 Suo Shu oxazine ring is modified 3o 4siO 2the preparation method of magnetic Nano microsphere, is characterized in that the reaction temperature described in step (1) is 170 ~ 220 DEG C.
5. according to the Fe that claim 3 Suo Shu oxazine ring is modified 3o 4siO 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. according to the Fe that claim 3 Suo Shu oxazine ring is modified 3o 4siO 2the preparation method of magnetic Nano microsphere, is characterized in that the volume ratio of second alcohol and water in the ethanol water described in step (2) is for (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. according to the Fe that claim 3 Suo Shu oxazine ring is modified 3o 4siO 2the preparation method of magnetic Nano microsphere, is characterized in that the reaction temperature described in step (3) is 75 ~ 95 DEG C, and the stir speed (S.S.) of described stirring reaction is 2000 ~ 2600r/min.
8. according to the Fe that claim 3 Suo Shu oxazine ring is modified 3o 4siO 2the preparation method of magnetic Nano microsphere, is characterized in that the organic solvent described in step (4) is the one in dioxane, toluene, methyl alcohol, isopropyl alcohol, ethyl acetate, carrene or chloroform.
9. according to the Fe that claim 3 Suo Shu oxazine ring is modified 3o 4siO 2the preparation method of magnetic Nano microsphere, is characterized in that the reaction temperature described in step (4) is 60 ~ 110 DEG C, and the stir speed (S.S.) of described stirring reaction is 2000 ~ 2600r/min.
10. the Fe of claim 1 or 2 Shu oxazine ring modifications 3o 4siO 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)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310547397.1A CN103545077B (en) 2013-11-07 2013-11-07 The Fe that oxazine ring is modified 3o 4siO 2magnetic Nano microsphere and preparation method thereof and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310547397.1A CN103545077B (en) 2013-11-07 2013-11-07 The Fe that oxazine ring is modified 3o 4siO 2magnetic Nano microsphere and preparation method thereof and application

Publications (2)

Publication Number Publication Date
CN103545077A CN103545077A (en) 2014-01-29
CN103545077B true CN103545077B (en) 2015-12-30

Family

ID=49968452

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310547397.1A Expired - Fee Related CN103545077B (en) 2013-11-07 2013-11-07 The Fe that oxazine ring is modified 3o 4siO 2magnetic Nano microsphere and preparation method thereof and application

Country Status (1)

Country Link
CN (1) CN103545077B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105097161B (en) * 2015-08-11 2018-09-18 甘肃省科学院传感技术研究所 Coated with silica ferriferrous oxide nano cluster and preparation method thereof as magnetic marker material
CN105632575B (en) * 2016-01-29 2017-07-21 北京师范大学 Magnetic material with Adsorption of Radioactive nucleic function and preparation method based on hydroxyl modification
CN108620100B (en) * 2017-03-23 2020-12-18 中国科学院城市环境研究所 Efficient magnetic near-infrared light composite catalyst and preparation method thereof
CN108452772A (en) * 2018-02-24 2018-08-28 鲁东大学 A kind of preparation method of Schiff base functionalized magnetic metal ion adsorbent
CN110508222B (en) * 2019-08-02 2022-03-18 复旦大学 Monodisperse core-shell microsphere with mesoporous silica shell and preparation method thereof
CN110396221B (en) * 2019-08-15 2020-12-22 蚌埠壹石通聚合物复合材料有限公司 Preparation method of PTFE (polytetrafluoroethylene) coated silica filler
CN110619985B (en) * 2019-09-18 2021-11-09 横店集团东磁股份有限公司 Scale-shaped Fe-Si-Al composite structure magnetic powder and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4505902B2 (en) * 1999-11-12 2010-07-21 Ｔｄｋ株式会社 Rare earth bonded magnet
CN103028351A (en) * 2012-12-04 2013-04-10 天津大学 Benzene sulfonic acid modified magnetic microsphere and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4505902B2 (en) * 1999-11-12 2010-07-21 Ｔｄｋ株式会社 Rare earth bonded magnet
CN103028351A (en) * 2012-12-04 2013-04-10 天津大学 Benzene sulfonic acid modified magnetic microsphere and preparation method and application thereof

Also Published As

Publication number Publication date
CN103545077A (en) 2014-01-29

Similar Documents

Publication Publication Date Title
CN103545077B (en) The Fe that oxazine ring is modified 3o 4siO 2magnetic Nano microsphere and preparation method thereof and application
WO2016026464A1 (en) Organic/inorganic hybrid janus particle and preparation method and modification method, and modified janus particle and use thereof
CN103041758B (en) Magnetic hollow multihole carbon ball with core-shell structure and preparation method of magnetic hollow multihole carbon ball
CN102716716B (en) Preparation method of activated carbon and alumina composite material
CN103159891B (en) Magnetic amino-modified superhighly-crosslinked resin and preparation method thereof
CN103657545A (en) Magnetic polymer/carbon-based microsphere material with core-shell structure and preparation method thereof
CN102229711B (en) Preparation and application of silicane functionalized high-water-solubility silicon dioxide nano particles
CN102964542A (en) RAFT (Reversible addition-fragmentation chain transfer) polymerization preparation method of magnetic mesoporous molecular imprinted hybrid silicon spheres
CN102786817A (en) Silica-supported organic alkane phase change material, and preparation method and application thereof
CN102728329B (en) Porous silica gel used as liquid chromatography stationary phase material and preparation method thereof
CN110508249B (en) Amidoxime modified silicon dioxide nano microsphere composite material and preparation method thereof
CN101774577A (en) Phenolic resin activated carbon microballon and rapid preparation method thereof
CN101665250A (en) Polymerizing-pyrolytic method for preparing mesocarbon microbead in asphaltic base
CN103342991A (en) Composite nanocapsule phase-change material and preparation method thereof
CN104941542B (en) Simple method for preparing phenolic resin microspheres without adoption of dispersing agent
CN106823471B (en) Core-shell mesoporous silica microsphere material with adjustable surface roughness and preparation method thereof
CN102114413A (en) Macroporous spherical polyacrylonitrile chelatesorbent and microwave radiating preparation process thereof
CN108187641A (en) A kind of preparation method and applications of sodium alginate/polyvinyl alcohol@polyacrylamide nucleocapsid gel balls
CN101891936B (en) Preparation method of composite material based on epoxy resin and phosphazene nanotubes
CN105879910A (en) Poly(styrene-methacrylic acid)/nano-silver composite microsphere and preparation method thereof
CN108905501A (en) A kind of fluent material and preparation method thereof with porous structure
CN104485191A (en) Magnetic hollow nanometer ball and preparation method thereof
CN107245136B (en) A kind of ordered mesoporous polymer material and its preparation method and application
CN110215896A (en) A kind of lithium absorption resin of porous silicon ball support and preparation method thereof
CN110862498A (en) Preparation method of asymmetric aminated silicon dioxide/phenolic resin composite particles

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20151230

Termination date: 20171107