CN107446546A - A kind of novel magnetic encapsulant and preparation method thereof - Google Patents
A kind of novel magnetic encapsulant and preparation method thereof Download PDFInfo
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- CN107446546A CN107446546A CN201710778089.8A CN201710778089A CN107446546A CN 107446546 A CN107446546 A CN 107446546A CN 201710778089 A CN201710778089 A CN 201710778089A CN 107446546 A CN107446546 A CN 107446546A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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- H—ELECTRICITY
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- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/44—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids
- H01F1/445—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids the magnetic component being a compound, e.g. Fe3O4
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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Abstract
The invention discloses a kind of novel magnetic encapsulant, the magnetic seal material is made up of nucleocapsid scion grafting group particulate；The core is ferromagnetic nanoparticle, and the particle diameter of the ferromagnetic nanoparticle is 5 ~ 100nm；The shell is the inert metal oxides layer or resin bed for being coated on core surface；And hydroxyl, carboxyl, amino or the sulfydryl on the shell being capable of chemical scion grafting groups；The thickness of the shell is 1 ~ 100nm；The scion grafting group is carbon fluorine chain of the scion grafting on inert metal oxides layer or resin bed, and coverage of the carbon fluorine chain on shell surface is 5 ~ 95%.The invention provides a kind of novel magnetic encapsulant as the magnetic particle in magnetic fluid so that the problem of magnetic particle directly stable and uniform can be dispersed in carrier fluid, and magnetic particle is not in sedimentation and reunited so that the magnetic seal effect of magnetic fluid is more preferable.
Description
Technical field
The invention belongs to magnetic seal material, and in particular to a kind of novel magnetic encapsulant and preparation method thereof.
Background technology
Magnetic seal is a kind of new Sealing Technology, the magnetic seal part prepared using the technology, is not only able to resistance to
High/low temperature, without abrasion, there is splendid functional reliability, even in final vacuum 10-6Slip is also extremely low under Pa.Because its property
Excellent it can be widely used in the multiple fields such as chemical industry, machinery, the energy.Magnetic fluid in magnetic seal part is to influence sealing
The good and bad key factor of effect.
Magnetic fluid is made up of magnetic particle, carrier fluid and dispersant；Because seal member needs to meet in high temperature and high pressure
Actual demand, it is necessary to carrier fluid has that viscosity is low and saturated vapor forces down, and is thermostabilization with higher boiling point and chemistry
Property, make to be dispersed in the magnetic particle in carrier fluid and do not condense, do not precipitate.Fluorine ether oil is because chemically and thermally stablizing high and not vaporizing, viscosity
Magnetic particle is suspended and not precipitated by low, density high energy, is preferable magnetic fluid carrier fluid.But due to the carbon fluorine in fluorine ether oil
Chain has the characteristics of hydrophobic, oleophobic " double to hate ", and therefore, conventional surfactant is difficult that magnetic particle is distributed in fluorine ether.Though
So carbon fluorine surface-active can help magnetic particle being dispersed in fluorine ether oil, but because magnetic material and carbon fluorine surface-active now
The stability of interaction magnetic fluid in high temperature environments between agent becomes extreme difference, ultimately result in magnetic particle occur to reunite and
The phenomenon of sedimentation, cause magnetic seal part can not meet the requirement of sealing.
The content of the invention
For above-mentioned the deficiencies in the prior art, the technical problems to be solved by the invention are：It is close to provide a kind of novel magnetic
Closure material, solves in present magnetic fluid that conventional surfactant is difficult to magnetic particle being distributed in carrier fluid, and magnetic is micro-
Grain by surfactant-dispersed into carrier fluid after, the stability of magnetic fluid becomes extreme difference, and reuniting and sinking also occur in magnetic particle
The technical problems such as the phenomenon of drop.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：
A kind of novel magnetic encapsulant, the magnetic seal material are made up of core-shell structure copolymer-scion grafting group particulate；The core
For ferromagnetic nanoparticle, the particle diameter of the ferromagnetic nanoparticle is 5~100nm；The shell is be coated on core surface lazy
Property metal oxide layer or resin bed；And hydroxyl, carboxyl, amino or the sulfydryl on the shell being capable of chemical scion grafting groups；
The thickness of the shell is 1~100nm；The scion grafting group is carbon fluorine of the scion grafting on inert metal oxides layer or resin bed
Chain, coverage of the carbon fluorine chain on shell surface are 5~95%.
The preparation method of novel magnetic encapsulant described in claim 1-6 any one, is comprised the following steps that：
1) preparation of ferromagnetic nanoparticle；Pass through coprecipitation, solvent-thermal method, emulsion synthetic method and sol-gal process
Synthesis obtains Fe3O4、γ-Fe2O3Magnetic metal oxide nanoparticle；Or synthesized by the precipitation method, solvent-thermal method, emulsion
Method and sol-gal process synthesize to obtain the metal oxide nanoparticles or cobalt-neodymium of iron, cobalt, nickel, platinum-iron, the alloy of palladium-iron
After oxides nanoparticles, then by obtained iron, cobalt, nickel metal oxide nanoparticles or cobalt-neodymium, platinum-iron, palladium-iron
Alloyed oxide nanoparticle carries out electrochemistry, hydrogen, carbon monoxide or chemical reduction method and obtains iron, cobalt, the metal of nickel and receive
Rice particulate is cobalt-neodymium, platinum-iron, the magnetic alloy nano particles such as palladium-iron；
2) modification of ferromagnetic nanoparticle and cladding；The ferromagnetic nanoparticle obtained in step 1) progress chemistry is changed
Property so that ferromagnetic nanoparticle can be dispersed in water or organic solvent, then again to being dispersed in water or organic molten
Tetraethyl orthosilicate or positive quanmethyl silicate or tetraisopropyl titanate or the fourth of metatitanic acid four are added in ferromagnetic nanoparticle in agent
One kind of ester or aluminium isopropoxide, and carry out stirring reaction realization and coat inert metal oxides on ferromagnetic nanoparticle surface
Layer；On ferromagnetic nanoparticle coat inert metal oxides layer course of reaction in add vinyltrimethoxy silane,
Aminopropyl front three silicyl oxide, 3- mercaptopropyl trimethoxysilanes, VTES, the ethoxyquin silane of aminopropyl three
Or the one or more in 3- mercaptopropyltriethoxysilanes, realize in the inert metal oxide layer of ferromagnetic nanoparticle or tree
Grafting hydroxyl, amino or sulfydryl scion grafting group in lipid layer；Either to be dispersed in water or organic solvent in ferromagnetism
A kind of and formaldehyde in polymerizable resorcinol, bisphenol-A, melamine, one kind in furfural are added in nano particle in acid
Or polymerization forms stable resin bed on the surface of ferromagnetic nanoparticle in the presence of alkali；Or to being dispersed in water or
It is anti-that methyl acrylate, ethyl acrylate, methacrylic acid heating stirring are added in ferromagnetic nanoparticle in person's organic solvent
Should, realize and form resin bed on the surface of ferromagnetic nanoparticle；Pass through the ferromagnetic nano to being coated with resin bed again
Grain, which is hydrolyzed, makes its surface carry carboxyl；Or ferromagnetic nanoparticle is coated from epoxy resin and curing agent；
3) being coated with the ferromagnetic nanoparticle of inert metal oxide layer and resin bed of being obtained in step 2) is added
17 fluorine decyl trimethoxy silanes, 17 fluorine decyl triethoxysilanes, ten difluoro heptyl propyl trimethoxy silicanes, 12
Fluorine heptyl propyl-triethoxysilicane can will contain fluorocarbon chain and be directly linked to magnetic particle surface；Or according to ferromagnetic nano
Functional group's selection fluorocarbon on grain surface is realized in ferromagnetic nanoparticle surface scion grafting carbon fluorine chain.
Further, it is being coated with the step 3) when the surface of ferromagnetic nanoparticle carries amino and hydroxyl
Perfluoro-octanoyl, perfluor caproyl chloride, perfluoro capryl sulphonyl are added in the ferromagnetic nanoparticle of inert metal oxide layer and resin bed
One kind in fluorine and perfluoro hexyl sulfuryl fluoride, or add perfluoro caprylic acid or perfluor caproic acid and phosphorus pentachloride, POCl3, chlorination
The mixture of any one in sulfoxide.
Further, in the step 3) when the surface of ferromagnetic nanoparticle carries sulfydryl, it is being coated with inertia gold
Belong in the ferromagnetic nanoparticle of oxide layer and resin bed and adding in perfluorohexyl ethylene, perfluorooctyl ethylene or 14 fluorine octenes
It is a kind of or any several, while realized under ultraviolet light by the scion grafting of carbon fluorine chain on the surface of ferromagnetic nanoparticle.
Further, in the step 3) when the surface of ferromagnetic nanoparticle carries carboxyl, it is being coated with inertia gold
Belong in the ferromagnetic nanoparticle of oxide layer and resin bed and adding in perfluor octylame, perfluor hexylamine, perfluorooctanol, perfluor hexanol
It is a kind of or it is any it is several reacted with carboxyl, realize the scion grafting carbon fluorine chain on the surface of ferromagnetic nanoparticle.
Compared with prior art, the present invention has the advantage that：
(1) the defects of present invention is directed to conventional magnetic fluid, there is provided a kind of novel magnetic encapsulant, as in magnetic fluid
Magnetic particle so that magnetic particle can form stable magnetic fluid with Direct Uniform stable being distributed in carrier fluid, solve
The problem of existing magnetic particle can not be distributed in carrier fluid by existing surfactant.
(2) scion grafting carbon fluorine chain after magnetic nanometer particles are coated is passed through in the present invention so that magnetic nanometer particles are straight
Connect being dispersed in carrier fluid for stable and uniform；On the one hand avoid and fc-surfactant is used in magnetic fluid, on the other hand
Solving after using fc-surfactant, magnetic nanometer particles are distributed in carrier fluid, the stability of magnetic fluid becomes extreme difference,
Also there is the problems such as phenomenon reunited and settled in magnetic particle so that the stability of magnetic fluid is good so that the magnetic seal of magnetic fluid
Effect is more preferable, and meets the requirement under the mal-conditions such as high temperature, high pressure.
Brief description of the drawings
The TEM figures of Fig. 1 modified magnetic particulates；
The SEM figures of Fig. 2 modified magnetic particulates；
The magnetic hysteresis loop of Fig. 3 magnetic materials；
The XRD of the particulate of Fig. 4 examples 4；
Photo in Fig. 5 examples 3 after particulate 3000rpm centrifugations；
Photo in Fig. 6 examples 5 after particulate 3000rpm centrifugations.
Embodiment
The present invention is described in further detail with reference to specific embodiment.
Embodiment 1
The ferroferric oxide magnetic nano particulate of coated with silica perfluoro caprylic acid grafting.Take 27.8g seven hydrated sulfuric acids
Ferrous and 3.99g iron chloride is configured to 50mL solution, then add 200mL ammonia spirits (100mL concentrated ammonia liquors and 100mL go from
Sub- water), with 300rpm speed mechanical agitation 2h.Then mixture is transferred in beaker, and beaker is placed on magnet
Side, makes ferroferric oxide magnetic nanoparticle be deposited to the bottom of beaker rapidly, outwells the water and impurity on top, and using go from
Sub- water cleans the 2-3 ferroferric oxide magnetic nano particulate for obtaining high-purity；By the ferroferric oxide magnetic nano particulate point
It is scattered in 100mL ethanol and the mixed solution of 200mL deionized waters formation, 15min is stirred with 300rpm speed at 50 DEG C
30mL concentrated ammonia liquors are added at 50 DEG C afterwards, 20g tetraethyl orthosilicates are added after 20min, 0.5g ammonia third is added after reacting 1h
Base front three silicyl oxide after being kept stirring for speed and reaction temperature 90min, will be coated with silicon oxide in system using magnet
Magnetic nanometer particles removing washes clean after, at 110 DEG C dry 8h；Then the magnetic nanometer particles of preparation are dispersed in
In 200mL dichloromethane, 1.5g perfluoro caprylic acid is added at 40 DEG C, after stirring 15min with 400rpm speed, adds 5mL's
Thionyl chloride, and 2.5m pyridines are added as acid binding agent, 2h is reacted in the case where keeping stable and stirring, then utilizes magnet
The magnetic nanometer particles of preparation are separated from system, 8h is dried at 100 DEG C after scrubbed, is obtained with ferroso-ferric oxide
Particulate is the magnetic nanometer particles that core can be dispersed in fluorine ether oil, and its transmission electron microscope photo is as shown in figure 1, core is in figure
The particulate of magnetic, outer layer is inertia clad, and has the carbon fluorine chain for dissolving in PFPE in surface grafting.
Embodiment 2
The ferroferric oxide magnetic nano particulate of coated with silica perfluor caproic acid grafting.Take 27.8g seven hydrated sulfuric acids
Ferrous and 3.99g iron chloride is configured to 50mL solution, then add 200mL ammonia spirits (100mL concentrated ammonia liquors and 100mL go from
Sub- water), with 300rpm speed mechanical agitation 2h.Then mixture is transferred in beaker, and beaker is placed on magnet
Side, makes magnetic ferroferric oxide be deposited to the bottom of beaker rapidly, outwells the water and impurity on top, and clean using deionized water
The 2-3 ferriferrous oxide nano particulate for obtaining high-purity.The ferroferric oxide magnetic nano particulate is distributed to 100mL ethanol
In the mixed solution formed with 200mL deionized waters, to add 30mL concentrated ammonia liquors after 300rpm speed stirring 15min, after
20g tetraethyl orthosilicates are added after 20min, 0.5g aminopropyl front three silicyl oxides is added in system after reacting 1h, keeps stirring
After mixing speed and reaction temperature 90min, after the magnetic nanometer particles being coated with silicon oxide are removed into washes clean using magnet,
8h. is dried at 110 DEG C and then the magnetic nanometer particles of preparation are disperseed into 200mL in dichloromethane, is added at 40 DEG C
1.2g perfluor caproic acid, after stirring 15min with 400rpm speed, 5mL thionyl chloride is added, and add the conduct of 2.5m pyridines and tie up
Sour agent, 2h is reacted in the case where keeping stable and stirring, then isolated from system magnetic nanometer particles using magnet
Come, 8h is dried at 100 DEG C after scrubbed, obtains the magnetic that can be dispersed in using ferroferric oxide particle as core in fluorine ether oil
Nanoparticle, the ESEM of particulate is as shown in Fig. 2 be that magnetic particle is spherical particle diameter between 5-10nm in Fig. 2.
Embodiment 3
The ferroferric oxide magnetic nano particulate of coated with silica fluorine ether acid grafting.Take 27.8g seven hydrated sulfuric acids sub-
Iron and 3.99g iron chloride are configured to 50mL solution, then add 200mL ammonia spirit (100mL concentrated ammonia liquors and 100mL deionizations
Water), with 300rpm speed mechanical agitation 2h.Then mixture is transferred in beaker, and beaker is placed into above magnet,
Magnetic ferroferric oxide is deposited to the bottom of beaker rapidly, outwell the water and impurity on top, and utilize deionized water cleaning 2-3
The secondary ferroferric oxide magnetic nano particulate for obtaining high-purity.The ferroferric oxide magnetic nano particulate is distributed to 100mL second
It is dense to add 30mL after 300rpm speed stirring 15min at 50 DEG C in the mixed solution that alcohol and 200mL deionized waters are formed
Ammoniacal liquor, 20g tetraethyl orthosilicates are added after 20min, 0.5g aminopropyl front three silicyl oxides are added in system after reacting 1h
In, it is using magnet that the magnetic particle being coated with silicon oxide removing washing is dry after being kept stirring for speed and reaction temperature 90min
After net, 8h is dried at 110 DEG C, then the magnetic nanometer particles of preparation are dispersed in 200mL dichloromethane, added at 40 DEG C
Enter 2.5g fluorine ether acid, after stirring 15min with 400rpm speed, add 5mL thionyl chloride, and add the conduct of 2.5m pyridines and tie up
Sour agent, 2h is reacted in the case where keeping stable and stirring, is then separated the magnetic nanometer particles from system using magnet
Out, 8h is dried after scrubbed at 100 DEG C, obtains the magnetic that can be dispersed in using ferroferric oxide particle as core in fluorine ether oil
Property nanoparticle, the magnetization curve of material are as shown in figure 3, as can be seen from the figure the magnetic particle has superparamagnetic characteristic
Typical superparamagnetism.
Embodiment 4
The ferroferric oxide magnetic nano particulate of coated with silica perfluorooctane sulfonate grafting.The seven of 27.8g is taken to be hydrated sulphur
Sour ferrous and 3.99g iron chloride is configured to 50mL solution, and then adding 200mL ammonia spirits, (100mL concentrated ammonia liquors and 100mL are gone
Ionized water), with 300rpm speed mechanical agitation 2h.Then mixture is transferred in beaker, and beaker is placed into magnet
Top, magnetic ferroferric oxide is deposited to the bottom of beaker rapidly, outwell the water and impurity on top, and it is clear using deionized water
Wash the 2-3 ferroferric oxide magnetic nano particulate for obtaining high-purity.The ferroferric oxide magnetic nano particulate is distributed to
In the mixed solution that 100mL ethanol and 200mL deionized waters are formed, add after stirring 15min at 50 DEG C with 300rpm speed
Enter 30mL concentrated ammonia liquors, 20g tetraethyl orthosilicates are added after 20min, 0.5g aminopropyl front three silica is added after reacting 1h
Alkane is in system, after being kept stirring for speed and reaction temperature 90min, is taken off the magnetic particle being coated with silicon oxide using magnet
After washes clean, 8h is dried at 110 DEG C；Then the magnetic nanometer particles of preparation are dispersed in 200mL dichloromethane,
1.5g perfluoro-octanoyl fluorine is added at 40 DEG C, after stirring 15min with 400rpm speed, adds 5mL thionyl chloride, and add
2.5g triethanolamine is reacted 2h in the case where keeping stable and stirring, is then received magnetic using magnet as catalyst
Rice particulate is separated from system, 8h is dried at 100 DEG C after scrubbed, obtaining can by core of ferroferric oxide particle
The magnetic nanometer particles being dispersed in fluorine ether oil, the X ray diffracting spectrum of particulate are shown in Fig. 4, Fig. 4 and standard gallery are contrasted
The thing for confirming particulate is mutually ferroso-ferric oxide.
Embodiment 5
The ferroferric oxide magnetic nano particulate of the pungent sulfonyl grafting of coated with silica perfluor.Take 27.8g seven hydrations
Ferrous sulfate and 3.99g iron chloride are configured to 50mL solution, then add 200mL ammonia spirits (100mL concentrated ammonia liquors and 100mL
Deionized water), with 300rpm speed mechanical agitation 2h；Then mixture is transferred in beaker, and beaker is placed into magnetic
Above iron, magnetic ferroferric oxide is deposited to the bottom of beaker rapidly, outwell the water and impurity on top, and utilize deionized water
Clean the 2-3 ferroferric oxide magnetic nano particulate for obtaining high-purity；The ferroferric oxide magnetic nano particulate is distributed to
In the mixed solution that 100mL ethanol and 200mL deionized waters are formed, add after stirring 15min at 50 DEG C with 300rpm speed
Enter 30mL concentrated ammonia liquors, 20g tetraethyl orthosilicates are added after 20min, 0.5g aminopropyl front three silica is added after reacting 1h
Alkane is in system, using magnet that the magnetic Nano being coated with silicon oxide is micro- after being kept stirring for speed and reaction temperature 90min
After grain removing washes clean, 8h is dried at 110 DEG C；Then the magnetic nanometer particles of preparation are dispersed in 200mL dichloromethane
In, 1.5g Perfluorooctanesulfonyl fluoride is added at 40 DEG C, after stirring 15min with 400rpm speed, adds 5mL thionyl chloride,
And the triethanolamine for adding 2.5g reacts 2h in the case where keeping stablizing and stirring, then utilizes magnet will as catalyst
Magnetic nanometer particles are separated from system, and 8h is dried at 100 DEG C after scrubbed, is obtained using ferroferric oxide particle as core
The heart can be dispersed in the magnetic nanometer particles in fluorine ether oil.
Embodiment 6
The cobalt magnetic nanometer particles of coated with silica perfluoro caprylic acid grafting.23.79g CoCL2 6H2Os are taken to be dissolved in
In 100mL deionized waters, then add 3g monoethanolamine, then with 300rpm speed mechanical agitation 30min after, add 50mL
The sodium borohydride aqueous solution (sodium borohydride concentration is 1mol/L) of sodium hydroxide and then stir 2h under conditions of 50 DEG C；Then will
Mixture is transferred in beaker, and beaker is placed into above magnet, cobalt nanoparticle is deposited to the bottom of beaker rapidly, is fallen
Fall the water and impurity on top, and the 2-3 cobalt magnetic nanometer particles for obtaining high-purity are cleaned using deionized water.By the cobalt magnetic
In the mixed solution that nanoparticle is distributed to 50mL ethanol and 100mL deionized waters are formed, with 300rpm speed at 50 DEG C
15mL concentrated ammonia liquors are added after stirring 15min, 10g tetraethyl orthosilicates are added after 20min, 0.25g ammonia is added after reacting 1h
Propyl group front three silicyl oxide is in system, and after being kept stirring for speed and reaction temperature 90min, titanium dioxide will be coated with using magnet
After the cobalt magnetic nanometer particles removing washes clean of silicon, 8h is dried at 110 DEG C；Then by the cobalt magnetic nanometer particles point of preparation
It is dispersed in 200mL dichloromethane, 0.75g perfluoro caprylic acid is added at 40 DEG C, after stirring 15min with 400rpm speed, adds
2.5mL thionyl chloride, and 2.5mL pyridines are added as acid binding agent, 2h is reacted in the case where keeping stable and stirring, then
Cobalt magnetic nanometer particles are separated from system using magnet, 8h is dried at 100 DEG C after scrubbed, is obtained with cobalt nanometer
Particulate is the magnetic nanometer particles that core can be dispersed in fluorine ether oil.
Embodiment 7
The cobalt magnetic nanometer particles of phenolic resin cladding perfluoro caprylic acid grafting.23.79g CoCL2 6H2Os are taken to be dissolved in
In 100mL deionized waters, then add 3g monoethanolamine, then with 300rpm speed mechanical agitation 30min after, add 50mL
The sodium borohydride aqueous solution (sodium borohydride concentration is 1mol/L) of sodium hydroxide and then stir 2h under conditions of 50 DEG C.Then will
Mixture is transferred in beaker, and beaker is placed into above magnet, magnetic cobalt magnetic nanometer particles is deposited to beaker rapidly
Bottom, outwell the water and impurity on top, and utilize deionized water to clean the 2-3 cobalt magnetic nanometer particles for obtaining high-purity.
The cobalt magnetic nanometer particles are distributed in the mixed solution that 100mL ethanol and 50mL deionized waters are formed, at 50 DEG C with
15mL concentrated ammonia liquors are added after 300rpm speed stirring 15min, 6g resorcinols and 10g (37%) are added after 20min
Formalin, it is using magnet that the cobalt magnetic Nano for being coated with phenolic resin is micro- after being kept stirring for speed and reaction temperature 90min
After grain removing washes clean, 8h is dried at 110 DEG C, the cobalt magnetic nanometer particles of preparation are then dispersed in 200mL dichloromethanes
In alkane, 0.75g perfluor iodo-octane is added at 40 DEG C, and adds 1.2mL pyridines as acid binding agent, is keeping stable and stirring
In the case of react 2h, then cobalt magnetic nanometer particles are separated from system using magnet, it is scrubbed after at 100 DEG C
8h is dried, obtains the magnetic nanometer particles that can be dispersed in using cobalt nanoparticle as core in fluorine ether oil.
Embodiment 8
The ferroplatinum magnetic nanometer particles of phenolic resin cladding PFO grafting.Take 1.62g iron chloride and 0.41g chlorine
Platinic acid in 20mL deionized waters, then add 0.1g tartaric acid, then with 300rpm speed mechanical agitation 30min after,
Add the sodium borohydride aqueous solution (sodium borohydride concentration is 1mol/L) of 2mL sodium hydroxides and then stirred under conditions of 50 DEG C
2h.Then mixture is transferred in beaker, and beaker is placed into above magnet, make magnetic pt-fe alloy magnetic nanometer particles
The rapid bottom for being deposited to beaker, outwells the water and impurity on top, and is cleaned 2-3 times using deionized water and obtain high purity platinum iron
Alloy magnetic nanometer particles.By the mixing that pt-fe alloy magnetic nanometer particles are distributed to 10mL ethanol and 5mL deionized waters are formed
In solution, to add 1.5mL concentrated ammonia liquors after 300rpm speed stirring 15min at 50 DEG C, after between addition 0.6g after 20min
The formalin of benzenediol and 1g (37%), after being kept stirring for speed and reaction temperature 90min, phenolic aldehyde will be coated with using magnet
After the pt-fe alloy magnetic nanometer particles removing washes clean of resin, 8h is dried at 110 DEG C；Then by the pt-fe alloy of preparation
Magnetic nanometer particles are dispersed in 200mL dichloromethane, and 0.1g perfluor iodo-octane is added at 40 DEG C, and add 0.1mL pyrroles
Pyridine reacts 2h as acid binding agent in the case where keeping stable and stirring, then using magnet that pt-fe alloy magnetic Nano is micro-
Grain is separated from system, and 8h is dried at 100 DEG C after scrubbed, obtains to be dispersed in by core of pt-fe alloy particulate
Magnetic nanometer particles in fluorine ether oil.
Embodiment 9
The ferroplatinum magnetic nanometer particles of melamine resin cladding perfluoro capryl grafting.Take 1.62g iron chloride and 0.41g chlorine
Platinic acid in 20mL deionized waters, then add 0.1g tartaric acid, then with 300rpm speed mechanical agitation 30min after,
Add the sodium borohydride aqueous solution (sodium borohydride concentration is 1mol/L) of 2mL sodium hydroxides and then stirred under conditions of 50 DEG C
2h；Then mixture is transferred in beaker, and beaker is placed into above magnet, make pt-fe alloy magnetic nanometer particles rapid
The bottom of beaker is deposited to, outwells the water and impurity on top, and cleaned 2-3 times using deionized water and obtain high purity platinum ferroalloy
Magnetic nanometer particles.By the mixed solution that pt-fe alloy magnetic nanometer particles are distributed to 10mL ethanol and 5mL deionized waters are formed
In, to utilize hydrochloric acid conditioning solution pH to 3.5 after 300rpm speed stirring 15min at 50 DEG C, added after 20min
The formalin of 0.6g melamines and 1g (37%), after being kept stirring for speed and reaction temperature 90min, it will be coated using magnet
After having the pt-fe alloy magnetic nanometer particles removing washes clean of melamine resin, 8h is dried at 110 DEG C；Then by the platinum of preparation
Ferroalloy magnetic nanometer particles are dispersed in 200mL dichloromethane, and 0.1g perfluor iodo-octane is added at 40 DEG C, and are added
0.1mL pyridines react 2h as acid binding agent in the case where keeping stable and stirring, then using magnet by the material from system
In separate, it is scrubbed after at 100 DEG C dry 8h, obtain the magnetic that can be dispersed in using pt-fe alloy as core in fluorine ether oil
Property nanoparticle.
Embodiment 10
The ferroplatinum magnetic nanometer particles of alchlor cladding perfluoro capryl grafting.Take 1.62g iron chloride and 0.41g chlorine
Platinic acid in 20mL deionized waters, then add 0.1g tartaric acid, then with 300rpm speed mechanical agitation 30min after,
Add the sodium borohydride aqueous solution (sodium borohydride concentration is 1mol/L) of 2mL sodium hydroxides and then stirred under conditions of 50 DEG C
2h.Then mixture is transferred in beaker, and beaker is placed into above magnet, make pt-fe alloy magnetic nanometer particles rapid
The bottom of beaker is deposited to, outwells the water and impurity on top, and cleaned 2-3 times using deionized water and obtain high purity platinum ferroalloy
Magnetic nanometer particles；By the mixed solution that pt-fe alloy magnetic nanometer particles are distributed to 10mL ethanol and 20mL deionized waters are formed
In, to add 2g aluminium isopropoxides after 300rpm speed stirring 15min at 50 DEG C, it is kept stirring for speed and reaction temperature
After 30min, after adding 02g aminopropyl trimethoxysilane, and 1.5g ammoniacal liquor reaction 2h, three oxidations will be coated with using magnet
After the pt-fe alloy magnetic nanometer particles removing washes clean of aluminium resin, 8h is dried at 110 DEG C；Then by the material of preparation point
200mL is dissipated in dichloromethane, 0.1g perfluor iodo-octane is added at 40 DEG C, and adds 0.1mL pyridines as acid binding agent,
Keep reacting 2h in the case of stable and stirring, then separated the material from system using magnet, it is scrubbed after
8h is dried at 100 DEG C；Obtain the magnetic nanometer particles that can be dispersed in using pt-fe alloy as core in fluorine ether oil.
Embodiment 11
The ferroplatinum magnetic nanometer particles of coated by titanium dioxide perfluoro capryl grafting.Take 1.62g iron chloride and 0.41g chlorine
Platinic acid in 20mL deionized waters, then add 0.1g tartaric acid, then with 300rpm speed mechanical agitation 30min after,
Add the sodium borohydride aqueous solution (sodium borohydride concentration is 1mol/L) of 2mL sodium hydroxides and then stirred under conditions of 50 DEG C
2h.Then mixture is transferred in beaker, and beaker is placed into above magnet, make pt-fe alloy magnetic nanometer particles rapid
The bottom of beaker is deposited to, outwells the water and impurity on top, and cleaned 2-3 times using deionized water and obtain high purity platinum ferroalloy
Magnetic nanometer particles；By the mixed solution that pt-fe alloy magnetic nanometer particles are distributed to 10mL ethanol and 20mL deionized waters are formed
In, to add 2g tetra isopropyl titanates after 300rpm speed stirring 15min at 50 DEG C, it is kept stirring for speed and reaction temperature
After spending 30min, after adding 02g aminopropyl trimethoxysilane, and 1.5g ammoniacal liquor reaction 2h, three oxygen will be coated with using magnet
After the pt-fe alloy magnetic nanometer particles removing washes clean for changing aluminium resin, 8h is dried at 110 DEG C；Then by the material of preparation
Scattered 200mL adds 0.1g perfluor iodo-octane in dichloromethane at 40 DEG C, and adds 0.1mL pyridines as acid binding agent,
2h is reacted in the case where keeping stable and stirring, is then separated the material from system using magnet, after scrubbed
8h is dried at 100 DEG C；Obtain the magnetic nanometer particles that can be dispersed in using pt-fe alloy as core in fluorine ether oil.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail good embodiment, it will be understood by those within the art that, can be to the skill of the present invention
Art scheme is modified or equivalent substitution, and without departing from the objective and scope of technical solution of the present invention, it all should cover at this
Among the right of invention.
Claims (10)
1. a kind of novel magnetic encapsulant, it is characterised in that the magnetic seal material is by core-shell structure copolymer particulate and scion grafting group structure
Into；The core is superparamagnetic nano particle, and the particle diameter of the magnetic nanoparticle is 5~100nm；The shell is to be coated on core
The inert layer of oxide or resin bed on surface；And hydroxyl, carboxyl, amino or the sulfydryl on the shell being capable of chemical scion grafting bases
Group；The thickness of the shell is 1~100nm；The scion grafting group is scion grafting on inert metal oxides layer or resin bed
Carbon fluorine chain, coverage of the carbon fluorine chain on shell surface are 5~95%, a length of 4-15 carbon atom of chain.
2. novel magnetic encapsulant according to claim 1, it is characterised in that the ferromagnetic nanoparticle is
Fe3O4、γ-Fe2O3Magnetic metal oxide nanoparticle is either iron, cobalt, nickel metallic nano-particle or is cobalt-neodymium, platinum-
Iron, palladium-magnetic alloy nanoparticle.
3. novel magnetic encapsulant according to claim 1, it is characterised in that the superparamagnetic nano particle it is micro-
Sight pattern is spherical, bar-shaped, cube shaped, cuboid, hexagon or nanometer flower-shaped structure.
4. novel magnetic encapsulant according to claim 1, it is characterised in that the inert layer of oxide is by titanium dioxide
A kind of surface for being coated on ferromagnetic nanoparticle in silicon, alchlor or titanium dioxide is formed.
5. novel magnetic encapsulant according to claim 1, it is characterised in that the resin bed is by phenolic resin, close
A kind of surface for being coated on superparamagnetic nano particle in polyimide resin, polyacrylic resin and epoxy resin is formed.
6. novel magnetic encapsulant according to claim 1, it is characterised in that the carbon fluorine chain be perfluorooctanoyl,
The pungent sulfonyl of perfluor, perfluor caproyl, the own sulfonyl of perfluor, fluorine ether acid, perfluorooctanol, perfluor octylame, PFO base, perfluor
One or both of carbon fluorine chain such as hexyl.
7. the preparation method of the novel magnetic encapsulant described in claim 1-6 any one, it is characterised in that specific steps
It is as follows：
1) preparation of ferromagnetic nanoparticle；Synthesized by coprecipitation, solvent-thermal method, emulsion synthetic method and sol-gal process
Obtain Fe3O4、γ-Fe2O3Magnetic metal oxide nanoparticle；Or by the precipitation method, solvent-thermal method, emulsion synthetic method with
And sol-gal process synthesizes to obtain the metal oxide nanoparticles or cobalt-neodymium of iron, cobalt, nickel, platinum-iron, the alloy oxidation of palladium-iron
After thing nanoparticle, then by obtained iron, cobalt, nickel metal oxide nanoparticles or cobalt-neodymium, platinum-iron, the alloy of palladium-iron
Oxides nanoparticles be reduced to iron, cobalt, nickel metallic nano-particle or be cobalt-neodymium, platinum-iron, the magnetic alloy such as palladium-iron is received
Rice particulate；
2) modification of superparamagnetic nano particle and cladding；By the ferromagnetic nanoparticle obtained in step 1) be dispersed in water or
In organic solvent, then again to be dispersed in water or organic solvent in superparamagnetic nano particle in add positive silicic acid tetrem
Ester, positive quanmethyl silicate, tetraisopropyl titanate, one kind of butyl titanate or aluminium isopropoxide, and be stirred in magnetic Nano
Inert layer of oxide is coated on particle surface；Ethene is added during inert layer of oxide is coated on ferromagnetic nanoparticle
Base trimethoxy silane, aminopropyl front three silicyl oxide, 3- mercaptopropyl trimethoxysilanes, VTES, ammonia
One or more in the ethoxyquin silane of propyl group three or 3- mercaptopropyltriethoxysilanes, are realized in superparamagnetic nano particle
Grafting hydroxyl, amino or sulfydryl scion grafting group in inert metal oxide layer or resin bed；Either to being dispersed in water or
The one kind and first added in ferromagnetic nanoparticle in organic solvent in polymerizable resorcinol, bisphenol-A, melamine
Polymerization forms stable resin bed on a kind of surface in the presence of acid or alkali in magnetic nanoparticle in aldehyde, furfural；Or
Person to be dispersed in water or organic solvent in magnetic nanoparticle in add methyl acrylate, ethyl acrylate, methyl
Acrylic acid heating stirring is reacted, and is realized and is formed resin bed on the surface of ferromagnetic nanoparticle；Again by being coated with resin
The magnetic nanoparticle of layer, which is hydrolyzed, makes its surface carry carboxyl；Or from epoxy resin and curing agent to ferromagnetic nano
Particle is coated, and magnetic particle surface is contained the remaining amido of curing agent.
3) it is coated with addition 17 in the ferromagnetic nanoparticle of inert metal oxide layer and resin bed by what is obtained in step 2)
Fluorine decyl trimethoxy silane, 17 fluorine decyl triethoxysilanes, ten difluoro heptyl propyl trimethoxy silicanes, ten difluoro heptan
Base propyl-triethoxysilicane can will contain fluorocarbon chain and be directly linked to magnetic particle surface；Or according to magnetic nanoparticle surface
Functional group selection fluorocarbon realize in magnetic nanoparticle surface scion grafting carbon fluorine chain.
8. the preparation method of novel magnetic encapsulant according to claim 7, it is characterised in that in the step 3) when
When the surface of superparamagnetic nano particle carries amino and hydroxyl, received in the superparamagnetism for being coated with inertia oxide layer and resin bed
The one kind added in rice grain in perfluoro-octanoyl, perfluor caproyl chloride, full-fluorine octyl sulfuryl fluoride and perfluoro hexyl sulfuryl fluoride, Huo Zhejia
Enter the mixture of any one in perfluoro caprylic acid or perfluor caproic acid and phosphorus pentachloride, POCl3, thionyl chloride.
9. the preparation method of novel magnetic encapsulant according to claim 7, it is characterised in that in the step 3) when
When the surface of ferromagnetic nanoparticle carries sulfydryl, the ferromagnetic nanoparticle of inert metal oxide layer and resin bed is being coated with
It is middle to add perfluorohexyl ethylene, perfluorooctyl ethylene or one kind or any several in 14 fluorine octenes, while in ultraviolet light
Lower realization is by the scion grafting of carbon fluorine chain on the surface of ferromagnetic nanoparticle.
10. the preparation method of novel magnetic encapsulant according to claim 7, it is characterised in that in the step 3)
When the surface of superparamagnetic nano particle carries carboxyl, the magnetic Nano of inert metal oxide layer and resin bed is being coated with
Added in grain perfluor octylame, perfluor hexylamine, perfluorooctanol, one kind in perfluor hexanol or it is any it is several reacted with carboxyl,
Realize the scion grafting carbon fluorine chain on the surface of ferromagnetic nanoparticle.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108735410A (en) * | 2018-06-08 | 2018-11-02 | 苏州大学 | A kind of double optics property intellectual material and preparation method thereof and application |
| CN109686526A (en) * | 2019-02-22 | 2019-04-26 | 株洲伟大科技发展有限责任公司 | Stable magnetic fluid and preparation method thereof under the conditions of a kind of high-intensity magnetic field |
| CN113921222A (en) * | 2021-10-27 | 2022-01-11 | 南京晶脉科技有限公司 | Magnetic fluid material, preparation method, fluid dynamic sealing method and application thereof |
| CN114890477A (en) * | 2022-04-08 | 2022-08-12 | 东南大学 | Organic solvent response type magnetic bead, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106000325A (en) * | 2016-06-14 | 2016-10-12 | 四川理工学院 | Magnetic decoloration material and preparation method thereof |
| CN106000355A (en) * | 2016-06-14 | 2016-10-12 | 四川理工学院 | Novel technology for recycling fluorinated surfactant in water |
-
2017
- 2017-09-01 CN CN201710778089.8A patent/CN107446546B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106000325A (en) * | 2016-06-14 | 2016-10-12 | 四川理工学院 | Magnetic decoloration material and preparation method thereof |
| CN106000355A (en) * | 2016-06-14 | 2016-10-12 | 四川理工学院 | Novel technology for recycling fluorinated surfactant in water |
Non-Patent Citations (1)
| Title |
|---|
| 韩调整等: ""磁流体的制备及应用"", 《材料开发与应用》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108735410A (en) * | 2018-06-08 | 2018-11-02 | 苏州大学 | A kind of double optics property intellectual material and preparation method thereof and application |
| CN108735410B (en) * | 2018-06-08 | 2020-11-10 | 苏州大学 | Dual-optical property intelligent material and preparation method and application thereof |
| CN109686526A (en) * | 2019-02-22 | 2019-04-26 | 株洲伟大科技发展有限责任公司 | Stable magnetic fluid and preparation method thereof under the conditions of a kind of high-intensity magnetic field |
| CN113921222A (en) * | 2021-10-27 | 2022-01-11 | 南京晶脉科技有限公司 | Magnetic fluid material, preparation method, fluid dynamic sealing method and application thereof |
| CN113921222B (en) * | 2021-10-27 | 2022-06-21 | 南京晶脉科技有限公司 | Magnetic fluid material, preparation method, fluid dynamic sealing method and application thereof |
| CN114890477A (en) * | 2022-04-08 | 2022-08-12 | 东南大学 | Organic solvent response type magnetic bead, preparation method and application thereof |
| CN114890477B (en) * | 2022-04-08 | 2024-04-05 | 东南大学 | Organic solvent response type magnetic bead, preparation method and application thereof |
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