CN106893311A - A kind of magnetic Nano polymer composite and preparation method thereof - Google Patents
A kind of magnetic Nano polymer composite and preparation method thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- 239000006249 magnetic particle Substances 0.000 claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 239000004952 Polyamide Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 229920002647 polyamide Polymers 0.000 claims abstract description 9
- 239000012190 activator Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000006392 deoxygenation reaction Methods 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 44
- 239000002122 magnetic nanoparticle Substances 0.000 claims description 41
- 239000011553 magnetic fluid Substances 0.000 claims description 26
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical group O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 19
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 18
- 150000003951 lactams Chemical class 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 11
- 229920002292 Nylon 6 Polymers 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 11
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 11
- 230000005415 magnetization Effects 0.000 claims description 9
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 229910002518 CoFe2O4 Inorganic materials 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 7
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 6
- 229920000299 Nylon 12 Polymers 0.000 claims description 6
- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 claims description 6
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 5
- 229920001007 Nylon 4 Polymers 0.000 claims description 5
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 5
- 150000001263 acyl chlorides Chemical class 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910021281 Co3O4In Inorganic materials 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000007493 shaping process Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- 229920002521 macromolecule Polymers 0.000 description 12
- 238000009835 boiling Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 239000002114 nanocomposite Substances 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229920006351 engineering plastic Polymers 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 229910003321 CoFe Inorganic materials 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910000828 alnico Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/01—Magnetic additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Hard Magnetic Materials (AREA)
Abstract
The invention discloses a kind of magnetic Nano polymer composite, including the magnetic particle and mass percent that mass percent is 1-30wt% are the polyamide of 70-99wt%.The invention also discloses a kind of preparation method of the magnetic Nano polymer composite：First, 100 parts of high polymer monomers and 1-50 parts of magnetic presoma are well mixed, vacuumize in confined conditions, leads to nitrogen circulation deoxygenation, gradually heating up makes magnetic presoma be substantially dissolved in high polymer monomer；Then the reflow treatment under high temperature, vacuum condition；Nitrogen to standard atmospheric pressure is passed through, is lowered the temperature, add 0.5-8.0 parts of alkali to heat up, reflow treatment under vacuum condition；Cooling, adds 0.2-2.5 parts of polymerization activator to be uniformly mixed, and carries out polymerisation；Finally crush, extracting, dry, obtain the magnetic Nano polymer composite, have the advantages that good mechanical property, magnetic stability, wearability be high, easy processing shaping.
Description
Technical field
The invention belongs to Functional polymer materials technology field, it is related to a kind of magnetic Nano polymer composite and preparation method thereof.
Background technology
Magnetic Nano polymer composite is the class material being composited with magnetic nano-particle with macromolecule as matrix.It is micro-
Quantum effect and skin effect that the less size of nano-particle, big specific surface area are produced, assign its many special property,
Such as enhancing, toughness reinforcing, wear-resisting, high temperature resistant and improve processing characteristics.The macromolecules such as magnetic and plastics or rubber are combined, are obtained
Macromolecule magnetic material relative density it is small, and easy processing is high into dimensional accuracy and the product of complicated shape, overcomes original magnetic
The defect that material ferrite lattice, rare earth element magnet and alnico alloy magnet are present：Hard and crisp, poor in processability, cannot be made
The complicated, product of precise shape.
At present, conventional preparation method has blending method, sol-gel process, situ aggregation method.Blending is that filler is total to by solution
The modes such as mixed, emulsion blending, melt blending, mechanical blending mix with sizing material.The advantage of blending method is easy, economic, nanometer
Particle is carried out with the synthesis substep of material, can control form, the size of nano-particle.But magnetic nano-particle is small-sized,
The apparent density of aggregation is very low, and the viscosity of rubber is higher, is difficult to be mixed into and dispersed, it will usually substantially reduce composite wood
The mechanical performance of material.In order to improve the compatibility of nano-particle and macromolecule matrix, generally it is modified using surface, to promote nanometer
The dispersed and inorganic/organic interface active force of enhancing of particle.Process of Surface Modification not only takes time and effort, and also is difficult to reach
Ideal effect.
Sol-gel process refers to for magnetic presoma forming homogeneous solution in certain organic solvent, and solute hydrolyzes to form nanometer
Level particle simultaneously turns into colloidal sol, then colloidal sol is changed into gel through treatment such as solvent volatilization or heating.Prepared using sol-gel process
During magnetic Nano polymer composite, first, magnetic presoma is incorporated into macromolecule matrix, then by hydrolyzing and contracting
Conjunction directly generates dispersed nano-particle, so that introducing magnetic species in macromolecule.The method feature is can be gentle
Carried out under reaction condition, two-phase dispersed phase is more uniform than blending method.During its weak point is gel drying, solvent, small molecule,
The volatilization of water may cause Material shrinkage embrittlement.In addition, magnetic presoma is difficult largely to be incorporated into macromolecule matrix, therefore,
Usual magnetic nano-particle content and saturation magnetization be not high.
Situ aggregation method is that directly filler is added in liquid macroimolecule monomer, is polymerized under certain condition, makes whole filler/height
Molecule monomer system condenses to form composite.The method is a kind of conventional means of synthesizing magnetic nano polymer composite material,
Have the advantages that magnetic nano-particle filler is completely independent controllable, macromolecule matrix range of choice wide, but, situ aggregation method is still
It is difficult to reach the ideal dispersion of nanometer inorganic filler, and, the magnetic nano-particle production cost as raw material is generally higher, steady
It is qualitative poor, bring very big difficulty to the industrialized production of magnetic Nano polymer composite.
The content of the invention
It is multiple it is an object of the invention to provide a kind of magnetic Nano polymer composite for the defect for overcoming prior art to exist
Condensation material has the advantages that good mechanical property, magnetic stability, wearability be high, easy processing is molded.
It is a further object to provide a kind of preparation method of the magnetic Nano polymer composite, with raw material into
The advantages of this low, magnetic nano particle molecular dispersivity high, size tunable, mass fraction high.
To achieve the above object, the present invention uses following technical scheme：
A kind of magnetic Nano polymer composite, including mass percent for 1-30wt% magnetic particle and mass percent be
The polyamide of 70-99wt%.
The polyamide be by caprolactam, alpha-pyrrolidone, lauric lactam monovalent anion ring-opening polymerisation formed it is equal
Polymers or copolymer.The polyamide is selected from least one in nylon 4, nylon 6, nylon 12, nylon 6/12.
The magnetic particle is Fe3O4、Ni3O4、CoFe2O4、Co3O4In at least one.
The particle diameter of the magnetic particle is 2-100nm.
The saturation magnetization of the magnetic Nano polymer composite is 0.5-20emu/g, and composite is in -50-150 DEG C of air
Magnetic long-time stable in atmosphere.
A kind of preparation method of the magnetic Nano polymer composite, comprises the following steps：
(1) magnetic presoma/high polymer monomer solution is prepared
100 parts of high polymer monomers and 1-50 parts of magnetic presoma are well mixed, are vacuumized in confined conditions, led to nitrogen circulation
Deoxygenation, gradually heating up makes magnetic presoma be substantially dissolved in high polymer monomer；
(2) magnetic presoma/high polymer monomer solution water removal removal of impurity
Magnetic presoma/high polymer monomer solution prepared by step (1) reflow treatment under high temperature, vacuum condition；
(3) magnetic nanoparticle/high polymer monomer magnetic fluid is prepared
Nitrogen to standard atmospheric pressure is passed through in the deimpurity magnetic presoma/high polymer monomer solution of water removal to step (2) acquisition,
Cooling, adds 0.5-8.0 parts of alkali to heat up, and reflow treatment obtains magnetic nanoparticle/high polymer monomer magnetic fluid under vacuum condition；
(4) magnetic nanoparticle/high polymer monomer magnetic fluid in-situ polymerization
The magnetic nanoparticle that step (3) is obtained/high polymer monomer magnetic fluid cooling, adds 0.2-2.5 parts of polymerization activator
It is uniformly mixed, carries out polymerisation；
(5) material disintegrating, extracting, the drying for obtaining step (4), obtain the magnetic Nano polymer composite.
Magnetic presoma is M in the step (1)2+Divalence soluble salt or M3+The mixture of trivalent soluble salt, wherein：M2+
With M3+Mol ratio is (0.3-1.0):1；Preferably 0.67:1；The M2+Or M3+Be in magnetic metal Fe, Co, Ni extremely
Few one kind；The magnetic presoma is preferably NiSO4、Fe(NO3)2、CoCl2·6H2O、Fe2(SO4)3、Ni(NO3)2、
FeCl2·4H2O、FeCl3·6H2At least one in O.
High polymer monomer is at least one in caprolactam, alpha-pyrrolidone, lauric lactam in the step (1).
The temperature heated up in the step (1) is 80-180 DEG C, and it is 0.1-2h to hold time.
The temperature of step (2) high temperature is 100-200 DEG C, and it is 10-60min to hold time.
Alkali is selected from least one in alkali metal, alkali metal hydroxide or alkali metal alcoholates in the step (3), preferably
Na、K、NaOH、KOH、NaOC2H5、KOC2H5At least one in.
The temperature of cooling is 80-200 DEG C in the step (3).
The temperature heated up in the step (3) is 100-200 DEG C.
The time of reflow treatment is 0.5-6h under vacuum condition in the step (3).
Cooling refers to be down to temperature for 50~200 DEG C in the step (4).
The temperature of polymerisation is 50-200 DEG C in the step (4), and the time is 0.2-24h.
Polymerization activator is selected from least one in acyl chlorides, isocyanates in the step (4), wherein：The isocyanates
Activator is Toluene-2,4-diisocyanate, 4- diisocyanate (TDI)；The acyl chlorides is chlorobenzoyl chloride.
Extracting is to extract 10~14h with water in the step (5).
Dry temperature is 100~140 DEG C in the step (5).
There is advantages below and beneficial effect due to using above-mentioned technical proposal, the present invention：
The raw materials used low cost of the method for the present invention, production equipment are simple, route environmental protection, are adapted to large-scale industrial production.
The magnetic Nano polymer composite prepared using the method has advantages below：1. the molecular weight polymeric in composite is high,
There is good mechanical performance；2. magnetic nano-particle is dispersed in macromolecule matrix, can improve composite mechanical property,
Improve hot property, enhancing wearability；3., by controlling the concentration of magnetic presoma, particle diameter can regulate and control between 2nm to 100nm,
The content of corresponding magnetic particle changes between 1wt% to 30wt%, meanwhile, the saturation magnetization of composite is in 0.5emu/g
Change between 20emu/g.Magnetic Nano polymer composite of the invention can be widely applied to electronics, electric, instrument instrument
The various fields such as table, communication, culture and education, health care and daily life.
Specific embodiment
With reference to embodiment, the present invention is further detailed explanation.
The inventive method is uniformly to mix magnetic presoma with high polymer monomer；A certain amount of alkali is added, magnetic presoma is in high score
Sub- monomer situ generates magnetic nanoparticle；Polymerization activator is added, initiation is dispersed with the high polymer monomer of magnetic nanoparticle
In-situ polymerization generates magnetic Nano polymer composite.
Embodiment 1
Fe3O4The preparation method of/cast magnetic Nano the polymer composite of nylon 6, comprises the following steps：
(1) 250ml there-necked flasks are fixed in heating mantle, thermometer, air set pipe, logical nitrogen are mixed respectively for three mouthfuls and connect
Head, condenser pipe top connects vacuum extractor joint, it is ensured that the good air-tightness of package unit.Weigh and add 100g caprolactams,
3.2g FeCl2·4H2O and 6.5g FeCl3·6H2O is in flask, vacuumizing, logical nitrogen deoxygenation 3 times, is warming up to caprolactam
80 DEG C of fusing point, and 30min is maintained, make FeCl2·4H2O and FeCl3·6H2O is substantially dissolved in caprolactam, forms deep brown
Color solution.Step (1) in, add magnetic presoma amount determine target magnetic Nano polymer composite in magnetic nanoparticle
Particle diameter, weight/mass percentage composition and saturation magnetization.The amount of magnetic presoma is more, and the particle diameter of magnetic nanoparticle is bigger, matter
Amount fraction is higher, and composite saturation magnetization is bigger.
(2)FeCl2·4H2O and FeCl3·6H2The water removal of O/ caprolactam solutions, the removal of impurity.
Solution prepared by step (1) vacuumizes reflow treatment 20min at 150 DEG C, remove a small amount of water contained in raw material and
Low boiling impurity.
(3) Fe is prepared3O4Magnetic nanoparticle/caprolactam magnetic fluid.
By the FeCl after step (2) fully water removal2·4H2O and FeCl3·6H2O/ caprolactam solutions, are passed through nitrogen big to standard
Air pressure, is cooled to 90 DEG C, is sealed rapidly after adding 5g NaOH powder, vacuumizes and be warming up to 150 DEG C, air setting backflow
Treatment 1.5h, obtains Fe3O4Magnetic nanoparticle/caprolactam magnetic fluid.
In the process, solution eventually becomes mass colour fluid by dark brown gradually blackening, i.e., containing magnetic nanoparticle/macromolecule list
Body magnetic fluid.Gained magnetic fluid is down to more than high polymer monomer fusing point after 10 DEG C, is taken and is put into glassware on a small quantity, in room
24h is stood under the conditions of temperature, obvious sediment segregation phenomenon is not observed, illustrate that magnetic nano-particle can be dispersed in this with stable and uniform
In the selected high polymer monomer of invention.In addition, one piece of ndfeb magnet is placed on the outside of the glassware for containing magnetic fluid, stream
Black suspension particle is enriched in the glassware inwall near magnet in body；Fluid color is gradually become by original ink black simultaneously
It is close with high polymer monomer color；The particle transmission electron microscope observing particle diameter of enrichment is 20nm-100nm monodisperse spherical particles,
Illustrate to have obtained the magnetic nanoparticle high polymer monomer magnetic fluid of stable dispersion.
(4)Fe3O4Magnetic nanoparticle/caprolactam magnetic fluid in-situ polymerization.
System is passed through nitrogen to standard atmospheric pressure, temperature is under the conditions of 150 DEG C, to add 0.5g Toluene-2,4-diisocyanates, 4- diisocyanate
(TDI) it is transferred to after, being well mixed rapidly in 30s in the mould of nitrogen protection, in 170 DEG C of polymerisation 0.5h.Polymerisation is complete
Cheng Hou, is down to the room temperature demoulding, can directly obtain Fe3O4/ cast magnetic Nano composite engineering plastics the part of nylon 6, is applied to
Various fields.
(5) extract 12h with water after the material disintegrating for preparing step (4), remove unpolymerized high polymer monomer, oligomer,
Solvable inorganic salts, fully dry at 120 DEG C, obtain Fe3O4The polymer composite of magnetic nanoparticle/nylon 6, yield is
98%.Composite after purification can apply to the field higher to purity requirement, such as medical magnetic macromolecule, and be conducive to
Following process is molded.
Magnetic Nano polymer composite includes that mass percent is the magnetic particle Fe of 5.2wt%3O4It is with mass percent
The polyamide nylon 6 of 94.8wt%, the particle diameter of magnetic particle is 20nm, the saturation magnetic of magnetic Nano polymer composite
Change intensity is 3emu/g.
Embodiment 2
Fe3O4The preparation of the magnetic Nano composite high-molecular material of/nylon 4
(1) change caprolactam into alpha-pyrrolidone, according to the identical device of embodiment 1 and operating condition, FeCl is obtained2·4H2O
And FeCl3·6H2O/ alpha-pyrrolidone solution.
(2) according to a small amount of water and low boiling impurity contained in the identical device of embodiment 1 and operating condition removing raw material.
(3) Fe is prepared according to the identical device of embodiment 1 and operating condition3O4Magnetic nanoparticle/alpha-pyrrolidone magnetic fluid.
(4)Fe3O4Magnetic nanoparticle/alpha-pyrrolidone magnetic fluid in-situ polymerization.System is passed through nitrogen to standard atmospheric pressure,
2.5g chlorobenzoyl chlorides are added after being down to 80 DEG C, 24h is reacted at this temperature after being well mixed.
(5) polymerizate crushing extracts 12h with water, unpolymerized alpha-pyrrolidone, oligomer, solvable inorganic salts is removed, at 120 DEG C
Fully dry, obtain Fe3O4The polymer composite of magnetic nanoparticle/nylon 4, macromolecule yield is 40%.
Magnetic Nano polymer composite includes that mass percent is the magnetic particle Fe of 12wt%3O4It is with mass percent
The polyamide nylon 4 of 88wt%, the particle diameter of magnetic particle is 15nm, the saturated magnetization of magnetic Nano polymer composite
Intensity is 6.8emu/g.
Embodiment 3
Fe3O4The preparation method of/cast magnetic Nano the polymer composite of nylon 12, comprises the following steps：
(1) 250ml there-necked flasks are fixed in heating mantle, three mouthfuls are mixed thermometer, air set pipe, logical nitrogen respectively
Joint, condenser pipe top connects vacuum extractor joint, it is ensured that the good air-tightness of package unit.Weigh and add acyl in 100g 12
Amine, 1.6g FeCl2·4H2O and 3.2g FeCl3·6H2O is in flask, vacuumizing, logical nitrogen deoxygenation 3 times, is warming up to 180 DEG C,
And 30min is maintained, make FeCl2·4H2O and FeCl3·6H2O is substantially dissolved in lauric lactam, forms deep brown solution.
(2)FeCl2·4H2O and FeCl3·6H2The water removal of O/ lauric lactams solution, the removal of impurity.
Solution prepared by step (1) vacuumizes reflow treatment 20min at 180 DEG C, remove a small amount of water contained in raw material and
Low boiling impurity.
(3) Fe is prepared3O4Magnetic nanoparticle/lauric lactam magnetic fluid.
By the FeCl after step (2) fully water removal2·4H2O and FeCl3·6H2O/ lauric lactam solution, is passed through nitrogen to standard
Atmospheric pressure, is cooled to 180 DEG C, is sealed rapidly after adding 3g NaOH powder, vacuumizes and be warming up to 200 DEG C, air setting
Reflow treatment 1.5h, obtains Fe3O4Magnetic nanoparticle/lauric lactam magnetic fluid.
(4)Fe3O4Magnetic nanoparticle/lauric lactam magnetic fluid in-situ polymerization.
System is passed through nitrogen to standard atmospheric pressure, temperature is under the conditions of 180 DEG C, to add 0.5g Toluene-2,4-diisocyanates, 4- diisocyanate
(TDI) it is transferred to after, being well mixed rapidly in 30s in the mould of nitrogen protection, in 180 DEG C of polymerisation 0.5h.Polymerisation is complete
Cheng Hou, is down to the room temperature demoulding, can directly obtain Fe3O4/ cast magnetic Nano composite engineering plastics the part of nylon 12, is applied to
Various fields.
(5) material for preparing step (4), 12h is extracted after crushing with boiling water, removes unpolymerized high polymer monomer, oligomeric
Thing, solvable inorganic salts, fully dry at 120 DEG C, obtain Fe3O4The polymer composite of magnetic nanoparticle/nylon 12, produces
Rate is 99%.
Magnetic Nano polymer composite includes that mass percent is the magnetic particle Fe of 2.6wt%3O4It is with mass percent
The polyamide nylon 12 of 97.4wt%, the particle diameter of magnetic particle is 30nm, the saturation magnetic of magnetic Nano polymer composite
Change intensity is 1.8emu/g.
Embodiment 4
Fe3O4The preparation method of/cast magnetic Nano the polymer composite of nylon 6/12, comprises the following steps：
(1) 250ml there-necked flasks are fixed in heating mantle, thermometer, air set pipe, logical nitrogen are mixed respectively for three mouthfuls and connect
Head, condenser pipe top connects vacuum extractor joint, it is ensured that the good air-tightness of package unit.Weigh add 50g caprolactams and
50g lauric lactams, 1.6g FeCl2·4H2O and 3.2g FeCl3·6H2O is in flask, vacuumizing, logical nitrogen deoxygenation 3 times,
180 DEG C are warming up to, and maintain 30min, make FeCl2·4H2O and FeCl3·6H2O is substantially dissolved in acyl in caprolactam/12
In amine, deep brown solution is formed.
(2)FeCl2·4H2O and FeCl3·6H2O/ caprolactams/lauric lactam solution water removal, the removal of impurity.
Solution prepared by step (1) vacuumizes reflow treatment 20min at 180 DEG C, remove a small amount of water contained in raw material and
Low boiling impurity.
(3) Fe is prepared3O4Magnetic nanoparticle/caprolactam/lauric lactam magnetic fluid.
By the FeCl after step (2) fully water removal2·4H2O and FeCl3·6H2O/ caprolactams/lauric lactam solution, are passed through nitrogen
Gas is cooled to 160 DEG C to standard atmospheric pressure, is sealed rapidly after adding 3g NaOH powder, vacuumizes and be warming up to 180 DEG C,
Air setting reflow treatment 1.5h, obtains Fe3O4Magnetic nanoparticle/caprolactam/lauric lactam magnetic fluid.
(4)Fe3O4Magnetic nanoparticle/caprolactam/lauric lactam magnetic fluid in-situ polymerization.
System is passed through nitrogen to standard atmospheric pressure, temperature is under the conditions of 180 DEG C, to add 0.2g Toluene-2,4-diisocyanates, 4- diisocyanate
(TDI) it is transferred to after, being well mixed rapidly in 30s in the mould of nitrogen protection, in 170 DEG C of polymerisation 0.5h.Polymerisation is complete
Cheng Hou, is down to the room temperature demoulding, can directly obtain Fe3O4/ cast magnetic Nano composite engineering plastics the part of nylon 6/12, application
In various fields.
(5) material for preparing step (4), 12h is extracted after crushing with boiling water, removes unpolymerized high polymer monomer, oligomeric
Thing, solvable inorganic salts, fully dry at 120 DEG C, obtain Fe3O4The polymer composite of magnetic nanoparticle/nylon 6/12,
Yield is 97%.
Magnetic Nano polymer composite includes that mass percent is the magnetic particle Fe of 2.8wt%3O4It is with mass percent
The polyamide nylon 6/12 of 97.2wt%, the particle diameter of magnetic particle is 25nm, the saturation of magnetic Nano polymer composite
The intensity of magnetization is 1.9emu/g.
Embodiment 5
CoFe2O4The preparation method of/cast magnetic Nano the polymer composite of nylon 6, comprises the following steps：
(1) 250ml there-necked flasks are fixed in heating mantle, thermometer, air set pipe, logical nitrogen are mixed respectively for three mouthfuls and connect
Head, condenser pipe top connects vacuum extractor joint, it is ensured that the good air-tightness of package unit.Weighing addition 100g caprolactams,
4.2g CoCl2·6H2O and 8g FeCl3·6H2O is in flask, vacuumizing, logical nitrogen deoxygenation 3 times, is warming up to 80 DEG C, and tie up
30min is held, makes CoCl2·6H2O and FeCl3·6H2O forms solution in being substantially dissolved in caprolactam.
(2)CoCl2·6H2O and FeCl3·6H2The water removal of O/ caprolactam solutions, the removal of impurity.
Solution prepared by step (1) vacuumizes reflow treatment 20min at 140 DEG C, remove a small amount of water contained in raw material and
Low boiling impurity.
(3) CoFe is prepared2O4Magnetic nanoparticle/caprolactam magnetic fluid.
By the CoFe after step (2) fully water removal2O4And FeCl3·6H2O/ caprolactam solutions, are passed through nitrogen to normal atmosphere
Pressure, is cooled to 140 DEG C, is sealed rapidly after adding 6g KOH powder, vacuumizes and be warming up to 140 DEG C, at air setting backflow
Reason 1.5h, obtains CoFe2O4Magnetic nanoparticle/caprolactam magnetic fluid.
(4)CoFe2O4Magnetic nanoparticle/caprolactam magnetic fluid in-situ polymerization.
System is passed through nitrogen to standard atmospheric pressure, temperature is under the conditions of 160 DEG C, to add 0.5g Toluene-2,4-diisocyanates, 4- diisocyanate
(TDI) it is transferred to after, being well mixed rapidly in 30s in the mould of nitrogen protection, in 170 DEG C of polymerisation 0.5h.Polymerisation is complete
Cheng Hou, is down to the room temperature demoulding, can directly obtain CoFe2O4/ cast magnetic Nano composite engineering plastics the part of nylon 6, application
In various fields.
(5) material for preparing step (4), 12h is extracted after crushing with boiling water, removes unpolymerized high polymer monomer, oligomeric
Thing, solvable inorganic salts, fully dry at 120 DEG C, obtain CoFe2O4The polymer composite of magnetic nanoparticle/nylon 6,
Yield is 96%.
Magnetic Nano polymer composite includes magnetic particle of the mass percent for 6.4wt% to CoFe2O4And mass percent
It is the polyamide nylon 6 of 93.6wt%, the particle diameter of magnetic particle is 14nm, the saturation of magnetic Nano polymer composite
The intensity of magnetization is 2.7emu/g.
The above-mentioned description to embodiment is to be understood that and apply the present invention for ease of those skilled in the art.It is familiar with
The personnel of art technology obviously can easily make various modifications to these embodiments, and should General Principle described herein
Use in other embodiment without by performing creative labour.Therefore, the invention is not restricted to embodiment here, this area skill
Art personnel announcement of the invention, does not depart from improvement that scope made and modification all should be in protection model of the invention
Within enclosing.
Claims (10)
1. a kind of magnetic Nano polymer composite, it is characterised in that：It is the magnetic particle of 1-30wt% including mass percent
It is the polyamide of 70-99wt% with mass percent.
2. magnetic Nano polymer composite according to claim 1, it is characterised in that：The polyamide be by
Homopolymers or copolymer that caprolactam, alpha-pyrrolidone, the ring-opening polymerisation of lauric lactam monovalent anion are formed；
Preferably, the polyamide is selected from least one in nylon 4, nylon 6, nylon 12, nylon 6/12.
3. magnetic Nano polymer composite according to claim 1, it is characterised in that：The magnetic particle is Fe3O4、
Ni3O4、CoFe2O4、Co3O4In at least one；
Preferably, the particle diameter of the magnetic particle is 2-100nm；
Preferably, the saturation magnetization of the magnetic Nano polymer composite is 0.5-20emu/g.
4. the preparation method of any described magnetic Nano polymer composite of a kind of claims 1 to 3, it is characterised in that：
Comprise the following steps：
(1) magnetic presoma/high polymer monomer solution is prepared
100 parts of high polymer monomers and 1-50 parts of magnetic presoma are well mixed, are vacuumized in confined conditions, led to nitrogen circulation
Deoxygenation, gradually heating up makes magnetic presoma be substantially dissolved in high polymer monomer；
(2) magnetic presoma/high polymer monomer solution water removal removal of impurity
Magnetic presoma/high polymer monomer solution prepared by step (1) reflow treatment under high temperature, vacuum condition；
(3) magnetic nanoparticle/high polymer monomer magnetic fluid is prepared
Nitrogen to standard atmospheric pressure is passed through in the deimpurity magnetic presoma/high polymer monomer solution of water removal to step (2) acquisition,
Cooling, adds 0.5-8.0 parts of alkali to heat up, and reflow treatment obtains magnetic nanoparticle/high polymer monomer magnetic fluid under vacuum condition；
(4) magnetic nanoparticle/high polymer monomer magnetic fluid in-situ polymerization
The magnetic nanoparticle that step (3) is obtained/high polymer monomer magnetic fluid cooling, adds 0.2-2.5 parts of polymerization activator
It is uniformly mixed, carries out polymerisation；
(5) material disintegrating, extracting, the drying for obtaining step (4), obtain the magnetic Nano polymer composite.
5. the preparation method of magnetic Nano polymer composite according to claim 4, it is characterised in that：The step
(1) magnetic presoma is M in2+Divalence soluble salt or M3+The mixture of trivalent soluble salt, wherein：M2+With M3+Mol ratio is
(0.3-1.0):1；Preferably 0.67:1；Preferably, the M2+Or M3+It is at least in magnetic metal Fe, Co, Ni
Kind；The magnetic presoma is preferably NiSO4、Fe(NO3)2、CoCl2·6H2O、Fe2(SO4)3、Ni(NO3)2、FeCl2·4H2O、
FeCl3·6H2At least one in O.
6. the preparation method of magnetic Nano polymer composite according to claim 4, it is characterised in that：The step
(1) high polymer monomer is at least one in caprolactam, alpha-pyrrolidone, lauric lactam in；
Preferably, the temperature for being heated up in the step (1) is 80-180 DEG C, and it is 0.1-2h to hold time.
7. the preparation method of magnetic Nano polymer composite according to claim 4, it is characterised in that：The step
(2) temperature of high temperature is 100-200 DEG C, and it is 10-60min to hold time.
8. the preparation method of magnetic Nano polymer composite according to claim 4, it is characterised in that：The step
(3) in alkali be selected from alkali metal, alkali metal hydroxide or alkali metal alcoholates at least one, preferably Na, K, NaOH,
KOH、NaOC2H5、KOC2H5In at least one；
Preferably, the temperature of cooling is 80-200 DEG C in the step (3)；
Preferably, the temperature for being heated up in the step (3) is 100-200 DEG C；
Preferably, the time of reflow treatment is 0.5-6h under vacuum condition in the step (3).
9. the preparation method of magnetic Nano polymer composite according to claim 4, it is characterised in that：The step
(4) cooling refers to be down to temperature for 50~200 DEG C in；
Preferably, the temperature of polymerisation is 50-200 DEG C in the step (4), and the time is 0.2-24h；
Preferably, polymerization activator is selected from least one in acyl chlorides, isocyanates in the step (4), it is preferred that described
Isocyanates activator is Toluene-2,4-diisocyanate, 4- diisocyanate；Preferably, the acyl chlorides is chlorobenzoyl chloride.
10. the preparation method of magnetic Nano polymer composite according to claim 4, it is characterised in that：The step
Suddenly extracting is to extract 10~14h with water in (5)；
Preferably, dry temperature is 100~140 DEG C in the step (5).
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108504087A (en) * | 2018-05-10 | 2018-09-07 | 重庆新康意安得达尔新材料有限公司 | A kind of High Polymer Magnetic composite material and its preparation process |
| CN109054364A (en) * | 2018-07-11 | 2018-12-21 | 桐城市新瑞建筑工程有限公司 | A kind of magnetism nylon material and preparation method thereof |
| CN114437543A (en) * | 2022-01-11 | 2022-05-06 | 滁州杰事杰新材料有限公司 | Strong magnetic nylon 66 composition and preparation method thereof |
| CN114456372A (en) * | 2022-01-11 | 2022-05-10 | 滁州杰事杰新材料有限公司 | Cast nylon composite material and preparation method thereof |
| CN115232302A (en) * | 2022-08-30 | 2022-10-25 | 杭州聚合顺新材料股份有限公司 | Method for simply and rapidly preparing nylon 66 nano composite material |
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| CN102532523A (en) * | 2010-12-30 | 2012-07-04 | 上海杰事杰新材料(集团)股份有限公司 | Method for preparing magnetic polyamide composite material through in-situ hydrolysis |
| CN102585493A (en) * | 2010-12-28 | 2012-07-18 | 上海杰事杰新材料(集团)股份有限公司 | Nano particle/polyamide composite material, preparation method and application thereof |
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| CN102585493A (en) * | 2010-12-28 | 2012-07-18 | 上海杰事杰新材料(集团)股份有限公司 | Nano particle/polyamide composite material, preparation method and application thereof |
| CN102532523A (en) * | 2010-12-30 | 2012-07-04 | 上海杰事杰新材料(集团)股份有限公司 | Method for preparing magnetic polyamide composite material through in-situ hydrolysis |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108504087A (en) * | 2018-05-10 | 2018-09-07 | 重庆新康意安得达尔新材料有限公司 | A kind of High Polymer Magnetic composite material and its preparation process |
| CN109054364A (en) * | 2018-07-11 | 2018-12-21 | 桐城市新瑞建筑工程有限公司 | A kind of magnetism nylon material and preparation method thereof |
| CN114437543A (en) * | 2022-01-11 | 2022-05-06 | 滁州杰事杰新材料有限公司 | Strong magnetic nylon 66 composition and preparation method thereof |
| CN114456372A (en) * | 2022-01-11 | 2022-05-10 | 滁州杰事杰新材料有限公司 | Cast nylon composite material and preparation method thereof |
| CN115232302A (en) * | 2022-08-30 | 2022-10-25 | 杭州聚合顺新材料股份有限公司 | Method for simply and rapidly preparing nylon 66 nano composite material |
| CN115232302B (en) * | 2022-08-30 | 2024-01-05 | 杭州聚合顺新材料股份有限公司 | Method for simply, conveniently and rapidly preparing nylon 66 nanocomposite |
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