CN106601420B - A kind of polyphenyl ether based magnetic liquid - Google Patents
A kind of polyphenyl ether based magnetic liquid Download PDFInfo
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- CN106601420B CN106601420B CN201710036925.5A CN201710036925A CN106601420B CN 106601420 B CN106601420 B CN 106601420B CN 201710036925 A CN201710036925 A CN 201710036925A CN 106601420 B CN106601420 B CN 106601420B
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- magnetic
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- polyphenyl ether
- magnetic liquid
- anionic surfactant
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01F1/42—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of organic or organo-metallic materials, e.g. graphene
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Abstract
The invention discloses a kind of polyphenyl ether based magnetic liquids, and the magnetic liquid is by exposed Fe3O4Magnetic nanoparticle, anionic surfactant and polyphenyl ether base load liquid three parts composition, wherein anionic surfactant is o-, m-, is mixed in any proportion to one or more of the chemical substance representated by three kinds of structures using phenoxy undecanoic acid, adjacent phenoxy benzoic acid, polyphenyl ether base load liquid.Magnetic liquid saturation magnetization high even particle distribution, does not reunite, does not settle, with properties such as high heat decomposition temperature, good Oxidation Stability, excellent radiation resistance, low-steam pressures, it can be suitable under extreme particular surroundings, solve the problems, such as that aerospace, machinery, chemical industry etc. have the important equipment special seal under intense radiation operating mode.
Description
Technical field
The present invention relates to a kind of magnetic liquids, and in particular to a kind of polyphenyl ether based magnetic liquid.
Background technology
Magnetic liquid is a kind of Nano-function thin films, is the grain size 10nm or so coated by surfactant
Magnetic-particle be dispersed in base load liquid, formed a kind of nanoscale, the mixing of solid-liquid two-phase stable homogeneous soliquid,
Layering and precipitating does not occur under impressed field.Magnetic liquid be a kind of mobility having both liquid with solid magnetic material to magnetic field
A kind of new function material of response characteristic, has a wide range of applications in engineering field, and wherein magnetic fluid sealing is magnetic liquid
One of numerous applications of body.
Magnetic-particle can be divided into according to classification：Metal class has Fe, Co, Ni, Fe-Co, Fe-Ni alloy/C etc.；Nitrided iron class,
There are FeN, Fe3N, Fe4N, Fe16N2(or Fe8N) etc.；Metal oxide-type mainly has Fe3O4, γ-Fe2O3, MFe2O4(M=Co,
Mn, Ni etc.).Fe3O4Magnetic-particle can rapidly be magnetized outside plus under magnetic fields, magnetic and vertical after externally-applied magnetic field removes
It disappears, no coercivity and remanent magnetism show excellent superparamagnetism, thus have special physical and chemical performance and nanometer
Energy.
Surfactant can be divided by the structure difference of its hydrophilic group：Anionic surfactant has carboxylic acid type, sulphur
Hydrochlorate type, sulfuric acid (ester) salt form, phosphoric acid (ester) salt form；Cationic surface active agent, have amine salt, quaternary amine, heterocyclic, indirectly
Connecting-type；Amphoteric ionic surfactant has amino acids, betaines, imidazoline type, phosphate type, oxidation amine；It is non-
Ionic surfactant has polyoxyethylene-type, polyoxypropylene, polyol type, alkylolamides, polyethers.Using coprecipitated
The exposed Fe that shallow lake method is prepared3O4Magnetic nanoparticle adsorption has hydroxide ion, the present invention to use anionic table
Phenoxy undecanoic acid in the activating agent of face or adjacent phenoxy benzoic acid.
According to the difference of base load liquid, magnetic liquid can be divided into：Water base, keryl, ester group, Silicon-oil-based, fluorine ether oil base, silicon-carbon
Hydride based magnetic liquid.Used in patent CN103680798A perfluoropolyether carboxylic acids surfactant to average grain diameter for
The exposed Fe of 10nm3O4Magnetic-particle is modified, and the perfluoro polyether oil based magnetic liquid of stable homogeneous, perfluoropolyether are obtained
Oil-based magnetic liquid has resistant to chemical etching, high-low temperature resistant, the absolutely not properties such as burning；Shell is used in patent CN1702782A
Derivative-carboxymethyl chitosan of glycan is as synthesis of surfactant Fe3O4Magnetic-particle water-base magnetic liquid, the magnetism liquid
Body has biocompatibility, is suitable for medical domain；The Coated with Oleic Acid Fe in patent CN104091678A3O4Magnetic-particle disperses
In keryl, the Kerosene-Base Magnetic Fluid of a stabilization is obtained；The invention discloses a kind of silicon in patent CN104867642A
The preparation method of Oil-based magnetic liquid usesMethod is in Fe3O4Wrap up SiO in magnetic-particle surface2Shell obtains shell-core
Structure, ferrite nanometer particle are dispersed in silicone oil base fluid and obtain Polydimethylsiloxane--based Ferrofluids, which can be satisfied with high temperature resistant
With intensity of magnetization height, good airproof performance, bearing capacity is strong, and sealing life is long.Ferrite MFe is based in patent CN1545108A2O4
The ionization of (M=Mn, Fe, Co, Ni, Zn, Cu) microparticle surfaces itself forms ionic ferrofluid.
Water base, keryl, ester group, Silicon-oil-based, fluorine ether oil based magnetic liquid have reached the ripe practical stage, but these
For the magnetic liquid of type with the expansion of application, current magnetic liquid has some disadvantages, such as：High temperature is cannot be used for, is easy
Oxidation, can not radiation hardness, volatility is relatively high etc., and polyphenyl ether is benzene ring structure, chemical property due to its structure
Stablize, have unique property, the defect of above-mentioned particular surroundings can be overcome, there is high use value.
Invention content
The technical problem to be solved in the invention is：Overcome the problems, such as that existing magnetic liquid exists, provides a kind of with height
Heat decomposition temperature, good Oxidation Stability, excellent radiation resistance, low-steam pressure can be suitable for extreme environment
Polyphenyl ether based magnetic liquid.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of polyphenyl ether based magnetic liquid, including three magnetic nanoparticle, surfactant and base load liquid parts.
Above-mentioned magnetic nanoparticle is Fe3O4Magnetic nanoparticle is prepared using coprecipitation, average grain diameter 10nm.
Above-mentioned surfactant is anionic surfactant, generally uses phenoxy undecanoic acid, adjacent phenoxy group benzene
Formic acid.The selection of surfactant is that magnetic liquid prepares the critical issue primarily solved, because it was prepared in magnetic liquid
Discrete particles are played in journey, improve the effects that particle surface performance is molten with base load liquid phase, can be related to magnetic liquid be successfully prepared,
Can magnetic liquid be stabilized, and whether magnetic liquid has the problems such as application value.
Above-mentioned base load liquid is polyphenyl ether, and the selection of base load liquid must consider chemical structural formula, molecular weight, using temperature
The factors such as degree, and strictly match with above-mentioned anionic surfactant, it can stablize dissolve each other therewith, these are all prepared
The premise of magnetic liquid.
A kind of preparation method operation of polyphenyl ether based magnetic liquid is as follows：
(1) Fe is prepared2+And Fe3+Molysite precursor solution
Deionized water is added according to certain molar ratio and prepares Fe2+And Fe3+Molysite precursor solution.
(2) exposed Fe3O4The preparation of magnetic nanoparticle
Using coprecipitation, cardinal principle is：Fe2++2Fe3++8OH-=Fe3O4+4H2O adds to molysite precursor solution
Enter excessive aqueous slkali (NH3·H2O or NaOH etc.) it is used as precipitating reagent, under nitrogen environment protection and certain temperature condition
High-speed stirred is carried out, precipitation reaction is for a period of time to get to exposed Fe3O4Magnetic nanoparticle.
(3) anionic surfactant precursor solution is prepared
The surfactant that the present invention uses is phenoxy undecanoic acid, adjacent phenoxy benzoic acid anionic surface activity
Agent precursor solution is at normal temperatures solid-state, need to be dissolved in organic solvent and solution for standby is made.Organic solvent generally selects
Final experimental result will not be impacted with absolute ethyl alcohol because absolute ethyl alcohol is volatile.
(4) anionic surfactant is to exposed Fe3O4The coating decoration of magnetic nanoparticle
On the basis of above-mentioned steps (2), (3), anion is added in the ratio of exposed magnetic-particle and surfactant
Type surfactant precursor solution carries out high-speed stirred under the conditions of nitrogen environment protection and certain temperature, reacts one section
The Fe after cladding is made in time3O4Magnetic nanoparticle.
(5) Fe after coating3O4The processing of magnetic nanoparticle
On the basis of above-mentioned steps (4), obtained product is moved into large beaker, is settled under magnetic support, deionization is used in combination
Water washs 7~8 times repeatedly, until with examine washing lotion pH=7, noresidue Cl-And SO4 2-.Gained magnetic-particle is moved into surface plate
In, it is put into vacuum drying chamber and is dried.
(6) polyphenyl ether based magnetic liquid is made in high-energy ball milling or ultrasonic vibration
Magnetic-particle dry obtained by above-mentioned steps (5) is weighed and is mixed by a certain percentage with polyphenyl ether base load liquid.
Also can be supplemented into mixture be added anionic surfactant precursor solution, additional proportion according to exposed magnetic-particle with
The ratio of surfactant, further to modify the magnetic-particle for making up and not yet completely coating.Using high-energy ball milling or ultrasound shake
Swing and mixture prepared into polyphenyl ether based magnetic liquid crude product, can also use the two by the way of it is prepared by mixture
Go out polyphenyl ether based magnetic liquid crude product.Crude product is precipitated on magnetic support or high speed centrifugation removes what bottom settled down
This step 3~5 time are repeated in bulky grain, and it is polyphenyl ether based magnetic liquid to take upper layer black even mixed liquor.
A kind of performance characterization of polyphenyl ether based magnetic liquid includes：
Vibrating specimen magnetometer (VSM) tests magnetization curve, it can be seen that polyphenylene ether magnetism liquid from magnetization curve
Whether body has remanent magnetism, coercivity, if superparamagnetism and the intensity of magnetization of polyphenyl ether based magnetic liquid is presented.
Transmission electron microscope (TEM) test surfaces pattern, it can be seen that magnetic-particle exterior appearance, particle size and point
Cloth.
X-ray diffractometer (XRD) tests crystalline structure, and obtained diffracting spectrum is compared with standard diagram, can be with
Prove whether the obtained product of experiment is anionic surfactant cladding Fe3O4The polyphenylene ether magnetic of magnetic nanoparticle
Property liquid, because anionic surfactant is to Fe3O4The cladding of magnetic nanoparticle can't influence Fe3O4Magnetic Nano
The crystalline structure of particle.
Fourier infrared spectrograph (FTIR) tests anionic surfactant to Fe3O4The cladding of magnetic nanoparticle
Situation is modified, each peak value in Fourier infrared spectrograph corresponds to different chemical combination keys.
Beneficial effects of the present invention：
Overcome the problems, such as that existing magnetic liquid exists, prepare saturation magnetization height, even particle distribution, do not reunite,
Do not settle, with high heat decomposition temperature, good Oxidation Stability, excellent radiation resistance, low-steam pressure can
Polyphenyl ether based magnetic liquid suitable for extreme environment.So the magnetic liquid of the present invention can be suitable for extreme particular surroundings
Under, it solves the problems, such as the important equipment special seal of the industries such as aerospace, machinery, chemical industry, promotes national defence, army as critical material
The development of the fields such as work, manned space flight tip device, while also having widened the use environment of magnetic liquid and having used medium.
Description of the drawings
Fig. 1 polyparaphenylene base ether molecular structures.
Fig. 2 meta position polyphenyl ether molecular structures.
The ortho positions Fig. 3 polyphenyl ether molecular structure.
Fig. 4 phenoxy undecanoic acid molecular structures.
Fig. 5 neighbour's phenoxy benzoic acid molecular structure.
Fig. 6 magnetic liquids composition figure.
Specific implementation mode
Embodiment 1
(1) Fe is prepared2+And Fe3+Molysite precursor solution
According to Fe2+：Fe3+=1:1.75 molar ratio weighs 18.92gFeCl respectively3·6H2O、7.95gFeCl2·4H2O
400ml deionized waters are added and prepare Fe2+And Fe3+Molysite precursor solution, moves in reaction vessel, and control bath temperature is 25
DEG C, mixing speed is that 300r/min is complete to iron salt dissolved.
(2) exposed Fe3O4The preparation of magnetic nanoparticle
Using coprecipitation, cardinal principle is：Fe2++2Fe3++8OH-=Fe3O4+4H2O is slow to molysite precursor solution
The NH of slow addition 25%3·H2O aqueous slkalis 60ml is as precipitating reagent, and control bath temperature is 25 DEG C, and mixing speed is reduced to
200r/min, precipitation reaction time 60min are to get to exposed Fe3O4Magnetic nanoparticle.
(3) anionic surfactant precursor solution is prepared
1.53g phenoxy undecanoic acid anionic surfactant is dissolved in 10ml absolute ethyl alcohols, phenoxy group is made
Hendecanoic acid anionic surfactant precursor solution.
(4) anionic surfactant is to exposed Fe3O4The coating decoration of magnetic nanoparticle
On the basis of above-mentioned steps (2), (3), the phenoxy undecanoic acid anionic surfactant of 10ml is added
Precursor solution, control bath temperature is 50 DEG C, and mixing speed is increased to 300r/min, coating reaction time 90min, and packet is made
Fe after covering3O4Magnetic nanoparticle.
(5) Fe after coating3O4The processing of magnetic nanoparticle
On the basis of above-mentioned steps (4), obtained product is moved into 1000ml beakers, is settled under magnetic support, and spend
Ionized water washs 7~8 times repeatedly, until with examine washing lotion pH=7, noresidue Cl-And SO4 2-.Gained magnetic-particle is moved into table
It in the ware of face, is put into vacuum drying chamber and is dried, vacuum degree is -0.1Mpa, and heating temperature is 60 DEG C, and drying time is for 24 hours.
(6) polyphenyl ether based magnetic liquid is made in ultrasonic vibration
Magnetic-particle dry obtained by above-mentioned steps (5) is weighed ratio 1:10 mix with polyphenyl ether base load liquid.It adopts
Mixture is prepared into polyphenyl ether based magnetic liquid crude product with ultrasonic vibration, crude product is precipitated on magnetic support, goes to break off the base
The bulky grain that layer settles down, is repeated this step 5 time, and it is polyphenylene ether magnetism liquid to take upper layer black even mixed liquor
Body.
Embodiment 2
(1) Fe is prepared2+And Fe3+Molysite precursor solution
According to Fe2+：Fe3+=1:1.75 molar ratio weighs 18.92gFeCl respectively3·6H2O、7.95gFeCl2·4H2O
400ml deionized waters are added and prepare Fe2+And Fe3+Molysite precursor solution, moves in reaction vessel, and control bath temperature is 25
DEG C, mixing speed is that 300r/min is complete to iron salt dissolved.
(2) exposed Fe3O4The preparation of magnetic nanoparticle
Using coprecipitation, cardinal principle is：Fe2++2Fe3++8OH-=Fe3O4+4H2O is slow to molysite precursor solution
The NH of slow addition 25%3·H2O aqueous slkalis 60ml is as precipitating reagent, and control bath temperature is 25 DEG C, and mixing speed is reduced to
200r/min, precipitation reaction time 60min are to get to exposed Fe3O4Magnetic nanoparticle.
(3) anionic surfactant precursor solution is prepared
1.18g neighbour's phenoxy benzoic acid anionic surfactant is dissolved in 10ml absolute ethyl alcohols, adjacent benzene oxygen is made
Yl benzoic acid anionic surfactant precursor solution.
(4) anionic surfactant is to exposed Fe3O4The coating decoration of magnetic nanoparticle
On the basis of above-mentioned steps (2), (3), the adjacent phenoxy benzoic acid surfactant presoma that 10ml is added is molten
Liquid, control bath temperature is 50 DEG C, and mixing speed is increased to 300r/min, coating reaction time 90min, after cladding is made
Fe3O4Magnetic nanoparticle.
(5) Fe after coating3O4The processing of magnetic nanoparticle
On the basis of above-mentioned steps (4), obtained product is moved into 1000ml beakers, is settled under magnetic support, and spend
Ionized water washs 7~8 times repeatedly, until with examine washing lotion pH=7, noresidue Cl-And SO4 2-.Gained magnetic-particle is moved into table
It in the ware of face, is put into vacuum drying chamber and is dried, vacuum degree is -0.1Mpa, and heating temperature is 60 DEG C, and drying time is for 24 hours.
(6) polyphenyl ether based magnetic liquid is made in ultrasonic vibration
Magnetic-particle dry obtained by above-mentioned steps (5) is weighed ratio 1:10 mix with polyphenyl ether base load liquid.It adopts
Mixture is prepared into polyphenyl ether based magnetic liquid crude product with ultrasonic vibration, crude product is precipitated on magnetic support, goes to break off the base
The bulky grain that layer settles down, is repeated this step 5 time, and it is polyphenylene ether magnetism liquid to take upper layer black even mixed liquor
Body.
Claims (4)
1. a kind of polyphenyl ether based magnetic liquid, by exposed Fe3O4Magnetic nanoparticle, anionic surfactant and poly-
Phenyl ether base load liquid three parts form, it is characterised in that polyphenyl ether base load liquid has following structure：[C6H5C6H4OC6H4C6H5]
N, and this polyphenyl ether base load liquid have it is o-, m-, to three kinds of structures, polyphenyl ether base load liquid is representated by above-mentioned three kinds of structures
One or more of chemical substance mix in any proportion.
2. a kind of polyphenyl ether based magnetic liquid according to claim 1, it is characterised in that anionic surfactant
Using phenoxy undecanoic acid.
3. a kind of polyphenyl ether based magnetic liquid according to claim 1, it is characterised in that the magnetic liquid can be at 450 DEG C
At a temperature of steady operation.
4. a kind of polyphenyl ether based magnetic liquid according to claim 1, it is characterised in that the magnetic liquid is suitable for strong
Sealing, sensor under radiation working condition, field of shock absorption.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006253239A (en) * | 2005-03-08 | 2006-09-21 | Bando Chem Ind Ltd | Magnetic viscous fluid |
| CN105047350A (en) * | 2015-09-09 | 2015-11-11 | 重庆科技学院 | Binary magnetic liquid and preparing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0727813B2 (en) * | 1987-03-03 | 1995-03-29 | 日本精工株式会社 | Magnetic fluid composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006253239A (en) * | 2005-03-08 | 2006-09-21 | Bando Chem Ind Ltd | Magnetic viscous fluid |
| CN105047350A (en) * | 2015-09-09 | 2015-11-11 | 重庆科技学院 | Binary magnetic liquid and preparing method thereof |
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