CN116285338B - Composite magnetic plastic and preparation method thereof - Google Patents
Composite magnetic plastic and preparation method thereof Download PDFInfo
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- CN116285338B CN116285338B CN202310406667.0A CN202310406667A CN116285338B CN 116285338 B CN116285338 B CN 116285338B CN 202310406667 A CN202310406667 A CN 202310406667A CN 116285338 B CN116285338 B CN 116285338B
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- 239000006247 magnetic powder Substances 0.000 claims abstract description 84
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 62
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- 239000007788 liquid Substances 0.000 claims abstract description 53
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 49
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- 239000004519 grease Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 14
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- 239000011248 coating agent Substances 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
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- 239000004640 Melamine resin Substances 0.000 claims description 10
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 6
- 238000007765 extrusion coating Methods 0.000 claims description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 6
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- LQLQDKBJAIILIQ-UHFFFAOYSA-N Dibutyl terephthalate Chemical compound CCCCOC(=O)C1=CC=C(C(=O)OCCCC)C=C1 LQLQDKBJAIILIQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004677 Nylon Substances 0.000 claims description 2
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 claims description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 2
- 229910001172 neodymium magnet Inorganic materials 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
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- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 11
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- 230000000052 comparative effect Effects 0.000 description 5
- 239000000696 magnetic material Substances 0.000 description 5
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
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- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
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- 235000019359 magnesium stearate Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/203—Solid polymers with solid and/or liquid additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2461/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08J2461/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
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- 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)
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to the technical field of functional magnetic polymer materials, in particular to a composite magnetic plastic and a preparation method thereof. The preparation method of the composite magnetic plastic comprises the steps of preparing a porous film, preparing a magnetic powder dispersion liquid and melamine fat solution, preparing the porous film filled with magnetic melamine fat, crushing, melting, extruding, granulating and drying in sequence. The invention adopts the process to prepare the magnetic plastic, on one hand, the agglomeration of the magnetic powder can be effectively avoided, the specific gravity difference between the magnetic powder and a plastic matrix can be reduced, and the layering of the magnetic powder can be reduced, on the other hand, the affinity between the resin polymer and the magnetic powder can be effectively improved, and the compatibility between the matrix resin and the inorganic magnetic powder can be improved, so that the magnetic performance and the processing performance of the magnetic plastic can be effectively improved, and the invention is suitable for the preparation and the application of the magnetic plastic.
Description
Technical Field
The invention relates to the technical field of functional magnetic polymer materials, in particular to a composite magnetic plastic and a preparation method thereof.
Background
The magnetic plastic is a novel high-molecular functional material for recording sound, light, electricity and other information, can synthesize the characteristics of plastic and magnetic materials, has the advantages of strong magnetism retention, small density, high impact strength and easy machining, is one of important basic materials in the technical field of modern science, and has been widely applied to the fields of magnetic materials such as electronics, motors, communication, instruments and meters and the like.
The magnetic plastics are divided into structural type and composite type according to the composition, and the structural type magnetic plastics refer to a magnet with strong magnetism of the polymer. The composite magnetic plastic is a magnet made by mixing and bonding plastic or rubber as an adhesive and magnetic powder. At present, most of magnetic plastics realizing commercial production are composite magnetic plastics, so that the composite magnetic plastics are still the main stream direction for developing magnetic plastics, and the yield and the demand are also improved year by year.
In the prior art, when magnetic material powder, polymer base material resin and other auxiliary materials are blended, stirring, dispersing and stirring and kneading modes are generally adopted. In actual operation, the stirring mode is adopted, and the stirring and processing processes are easy to have the phenomena of powder aggregation and uneven magnetic distribution due to fine granularity and large consumption of the magnetic powder, and the layering phenomenon caused by large specific gravity difference between the magnetic powder and the polymer base material is easy to occur, or the problems of poor compatibility between the magnetic powder and plastics and the like are solved, so that the performance of the magnetic plastic is influenced.
Disclosure of Invention
The invention aims to provide a preparation method of composite magnetic plastic, which can solve the problems of agglomeration, layering and uneven distribution of magnetic materials and poor compatibility of magnetic powder and plastic when the magnetic plastic is prepared and molded.
The invention also aims to provide the composite magnetic plastic, which has the advantages of uniform magnetic particle distribution, good compatibility with plastic, high magnetism and good processability, and can be directly used for preparing target products.
The preparation method of the composite magnetic plastic adopts the following technical scheme:
a preparation method of composite magnetic plastic comprises the following steps:
(1) Melting a polymer to prepare a film, stretching and shaping the film, and forming holes on the film by stretching and shaping to obtain a porous film; the thickness of the porous membrane is 50-100 mu m, and the porosity is 50% -80%; the aperture of the micropores in the porous membrane is 10-20 mu m;
(2) Placing magnetic powder, a plasticizer and a dispersing agent in absolute ethyl alcohol, stirring and performing ultrasonic dispersion to obtain a magnetic powder dispersion liquid;
adding melamine into an acidic formaldehyde solution for reaction, filtering after the reaction to obtain solid melamine grease, washing with water to be neutral, and stirring and ultrasonically dispersing by adopting absolute ethyl alcohol to obtain melamine grease solution;
stirring and mixing the magnetic powder dispersion liquid and the melamine fat solution to obtain a mixed dispersion liquid; in the mixed dispersion liquid, the mass ratio of the magnetic powder to the melamine grease is 10: (0.6-1.0);
(3) Uniformly coating the mixed dispersion liquid obtained in the step (2) on one side of the porous membrane obtained in the step (1), filling the mixed dispersion liquid into micropores of the porous membrane, removing the mixed dispersion liquid in other areas on the surface of the porous membrane, and further heating and curing to obtain the porous membrane filled with the magnetic melamine grease in the micropores;
(4) And crushing the porous membrane filled with the magnetic melamine grease, and then carrying out melt extrusion granulation and drying to obtain the composite magnetic plastic.
Preferably, in the step (1), the polymer is one or more of polyethylene, polypropylene, acrylonitrile-butadiene-styrene copolymer and nylon.
Further, in the step (1), the stretching and shaping treatment is specifically: the film is subjected to a first biaxial stretching treatment at 140-150 ℃, then is subjected to a first heat setting treatment at 150-170 ℃, then is subjected to a second biaxial stretching treatment at 130-140 ℃, and finally is subjected to a second heat setting treatment at 140-160 ℃ to obtain the porous film.
Before the magnetic powder is used, the required micron-sized granularity can be obtained through a ball milling process. Preferably, in the step (2), the magnetic powder is any one of ferroferric oxide magnetic powder and neodymium iron boron magnetic powder; the particle size of the magnetic powder is 2-4 mu m.
The dispersing agent is sodium dodecyl sulfate or polyacrylamide, and the dosage of the dispersing agent is 1-2% of the mass of the magnetic powder; the plasticizer is one or two of dioctyl phthalate, dibutyl phthalate and dibutyl terephthalate, and the dosage of the plasticizer is 2-4% of the mass of the magnetic powder.
Before mixing with melamine fat, the magnetic powder is dispersed in absolute ethyl alcohol to obtain dispersion liquid by ultrasonic treatment in order to avoid agglomeration of the magnetic powder in melamine fat solution. Preferably, the dosage ratio of the magnetic powder to the absolute ethyl alcohol is 1g: (0.5-0.6) mL.
By controlling the reaction parameters and conditions of formaldehyde and melamine, the micro-nano melamine grease which is easy to disperse and has good blending modification effect with magnetic powder can be prepared. Preferably, in the step (2), the pH value of the acidic formaldehyde solution is 1-4; the concentration of the formaldehyde solution is 35% -40%; the mole ratio of melamine to formaldehyde is 1: (0.5 to 0.8); the reaction is carried out for 1-2 h at 70-90 ℃; the dosage ratio of melamine fat to absolute ethyl alcohol is 1g: (1.2-1.8) mL.
Preferably, in the step (3), the coating is performed by extrusion coating, and the coating pressure is controlled so that the mixed dispersion liquid fills the micropores of the porous membrane, and the mixed dispersion liquid in other areas of the surface of the porous membrane is removed by extrusion.
Further, in the step (3), the curing temperature is 120-140 ℃ and the curing time is 5-10 min.
Preferably, in the step (4), the crushing treatment adopts a film crusher, and the granularity of the crushed discharged material is 3-5 mm.
The composite magnetic plastic is prepared by the preparation method of the composite magnetic plastic.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the composite magnetic plastic comprises the steps of preparing a porous membrane by adopting a polymer, preparing magnetic powder dispersion liquid and melamine fat solution, mixing the prepared magnetic powder dispersion liquid and the melamine fat solution to prepare mixed dispersion liquid, uniformly coating the mixed dispersion liquid on one side of the porous membrane, solidifying to obtain the porous membrane with the magnetic melamine fat filled in micropores, crushing the porous membrane, and finally carrying out melt extrusion granulation and drying to obtain the composite magnetic plastic.
According to the preparation method, the mixed dispersion liquid is uniformly coated on one side of the porous membrane, and the magnetic powder is uniformly distributed on the porous membrane after coating, so that agglomeration of the magnetic powder can be avoided, and the magnetic property of the magnetic plastic is improved. Meanwhile, the coating process is to coat the mixed dispersion liquid after the magnetic powder dispersion liquid and the melamine resin solution are mixed, and the magnetic melamine resin composite material with the melamine resin coated magnetic powder is filled in micropores of the cured porous film, so that the specific gravity difference between the magnetic powder and a plastic matrix can be reduced, the layering of the magnetic powder can be reduced, the affinity between a resin polymer and the magnetic powder can be effectively improved, the compatibility between matrix resin and inorganic magnetic powder can be improved, and the magnetic property and the processing property of the magnetic plastic can be comprehensively improved.
In addition, the porosity of the porous membrane can be effectively controlled through a processing technology, so that the magnetic powder with different dosages can be controllably adjusted according to actual use conditions during application, and the magnetic performance of the magnetic material can be more easily improved.
The composite magnetic plastic provided by the invention has excellent magnetic performance and good processing performance, is convenient to produce and package after being prepared into magnetic plastic particles, can be directly used for the preparation and application of downstream products, and has wide application prospects in the fields of magnetic plastic materials such as storage materials and wave-absorbing materials.
Drawings
FIG. 1 is a process flow diagram of a preparation method of composite magnetic plastic provided by the invention;
fig. 2 is a schematic diagram of an apparatus used in the coating process of step (3) of the preparation method of the composite magnetic plastic provided in embodiments 1 to 3 of the present invention;
in fig. 2: 100-hopper; 210-a first roller; 211-grinding Mao Buliao; 220-a second roller; 310-heat source; 400-porous membrane.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below in connection with specific embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The process flow chart of the preparation method of the composite magnetic plastic related in the following examples is shown in fig. 1, which sequentially includes the preparation of a porous film, the preparation of a magnetic powder dispersion and a melamine fat solution, the preparation of a porous film filled with magnetic melamine fat, and the steps of crushing, melt extrusion granulation, and drying. The process is described in detail below with reference to specific examples.
Example 1
In the composite magnetic plastic of the embodiment, the adopted polymer raw material is nylon 66, and the preparation process comprises the following steps:
(1) Nylon 66 is used as a polymer, a winding roller is used for stretching after melting to prepare a film, the film is subjected to a first biaxial stretching treatment at 140 ℃, then is subjected to a first heat setting treatment at 150 ℃, then is subjected to a second biaxial stretching treatment at 130 ℃, and finally is subjected to a second heat setting treatment at 140 ℃, and the porous film is obtained through the stretching and setting process to realize the opening of the film. The thickness of the obtained porous film was 80 μm and the porosity was 70%; the pore diameter of the micropores in the porous membrane is 10-20 mu m.
(2) Placing ferroferric oxide magnetic powder with the particle size of 2-4 mu m, a plasticizer dioctyl phthalate and a dispersing agent sodium dodecyl sulfate into absolute ethyl alcohol, stirring and ultrasonically dispersing to obtain a magnetic powder dispersion liquid; wherein, the consumption of the dispersing agent is 1% of the mass of the magnetic powder; the plasticizer is 3% of the mass of the magnetic powder; the dosage ratio of the magnetic powder to the absolute ethyl alcohol is 1g:0.6mL.
Melamine was also added to an acidic formaldehyde solution (37% concentration) at ph=2, with a molar ratio of melamine to formaldehyde of 1:0.6, reacting at 80 ℃ for 1.5h; filtering after reaction to obtain solid melamine grease, washing with deionized water for many times to neutrality, and stirring with absolute ethyl alcohol for ultrasonic dispersion, wherein the dosage ratio of the melamine grease to the absolute ethyl alcohol is 1g:1.5mL of a melamine lipid solution was obtained;
stirring and mixing the magnetic powder dispersion liquid and the melamine fat solution to obtain a mixed dispersion liquid; in the mixed dispersion liquid, the mass ratio of the magnetic powder to the melamine grease is 10:0.8.
(3) And (3) uniformly coating the mixed dispersion liquid obtained in the step (2) on one side of the porous membrane obtained in the step (1) by adopting an extrusion coating mode, filling the mixed dispersion liquid into micropores of the porous membrane, simultaneously removing the mixed dispersion liquid in other areas on the surface of the porous membrane by controlling extrusion pressure, further heating to 130 ℃, and curing for 8min to obtain the porous membrane filled with the magnetic melamine grease in the micropores.
(4) And crushing the porous film filled with the magnetic powder by adopting a film crusher, wherein the granularity of the crushed discharged material is 3-5 mm, and then carrying out melt extrusion granulation and drying to obtain the composite magnetic plastic.
Example 2
In the composite magnetic plastic of the embodiment, the adopted polymer raw material is polyethylene, and the preparation process comprises the following steps:
(1) The preparation method comprises the steps of taking a mixture of ultra-high molecular weight polyethylene with a molecular weight of 450 ten thousand and common molecular weight polyethylene with a molecular weight of 50 ten thousand in a mass ratio of 1:1 as a composite polymer, stretching the composite polymer by adopting a winding roller after melting to prepare a film, carrying out a first biaxial stretching treatment at 150 ℃, then carrying out a first heat setting treatment at 160 ℃, then carrying out a second biaxial stretching treatment at 140 ℃, finally carrying out a second heat setting treatment at 150 ℃, and carrying out stretching and setting processes to realize the opening of the film, thus obtaining the porous film. The thickness of the porous membrane is 60 μm, and the porosity is 65%; the pore diameter of the micropores in the porous membrane is 10-20 mu m.
(2) Placing ferroferric oxide magnetic powder with the particle size of 2-4 mu m, a plasticizer dioctyl phthalate and a dispersing agent sodium dodecyl sulfate into absolute ethyl alcohol, stirring and ultrasonically dispersing to obtain a magnetic powder dispersion liquid; wherein, the consumption of the dispersing agent is 1% of the mass of the magnetic powder; the plasticizer is 3% of the mass of the magnetic powder; the dosage ratio of the magnetic powder to the absolute ethyl alcohol is 1g:0.6mL.
Melamine was also added to an acidic formaldehyde solution (37% concentration) at ph=2, with a molar ratio of melamine to formaldehyde of 1:0.6, reacting at 80 ℃ for 1.5h; filtering after reaction to obtain solid melamine grease, washing with deionized water for many times to neutrality, and stirring with absolute ethyl alcohol for ultrasonic dispersion, wherein the dosage ratio of the melamine grease to the absolute ethyl alcohol is 1g:1.5mL of a melamine lipid solution was obtained;
stirring and mixing the magnetic powder dispersion liquid and the melamine fat solution to obtain a mixed dispersion liquid; in the mixed dispersion liquid, the mass ratio of the magnetic powder to the melamine grease is 10:0.8.
(3) And (3) uniformly coating the mixed dispersion liquid obtained in the step (2) on one side of the porous membrane obtained in the step (1) by adopting an extrusion coating mode, filling the mixed dispersion liquid into micropores of the porous membrane, simultaneously removing the mixed dispersion liquid in other areas on the surface of the porous membrane by controlling extrusion pressure, further heating to 140 ℃, and curing for 5min to obtain the porous membrane filled with the magnetic melamine grease in the micropores.
(4) And crushing the porous film filled with the magnetic powder by adopting a film crusher, wherein the granularity of the crushed discharged material is 3-5 mm, and then carrying out melt extrusion granulation and drying to obtain the composite magnetic plastic.
Example 3
In the composite magnetic plastic of the embodiment, the adopted polymer raw material is polypropylene, and the preparation process comprises the following steps:
(1) The method comprises the steps of taking a mixture of polypropylene with a molecular weight of 1000 and polypropylene with a molecular weight of 4000 in a mass ratio of 1:1 as a composite polymer, stretching the composite polymer by adopting a winding roller after melting to prepare a film, carrying out a first biaxial stretching treatment at 145 ℃, then carrying out a first heat setting treatment at 150 ℃, then carrying out a second biaxial stretching treatment at 145 ℃, finally carrying out a second heat setting treatment at 155 ℃, and carrying out a stretching and setting process to realize the opening of the film, thereby obtaining the porous film. The thickness of the porous film was 70 μm and the porosity was 75%; the pore diameter of the micropores in the porous membrane is 10-20 mu m.
(2) Placing ferroferric oxide magnetic powder with the particle size of 2-4 mu m, a plasticizer dioctyl phthalate and a dispersing agent sodium dodecyl sulfate into absolute ethyl alcohol, stirring and ultrasonically dispersing to obtain a magnetic powder dispersion liquid; wherein, the consumption of the dispersing agent is 1% of the mass of the magnetic powder; the plasticizer is 3% of the mass of the magnetic powder; the dosage ratio of the magnetic powder to the absolute ethyl alcohol is 1g:0.6mL.
Melamine was also added to an acidic formaldehyde solution (37% concentration) at ph=2, with a molar ratio of melamine to formaldehyde of 1:0.6, reacting at 80 ℃ for 1.5h; filtering after reaction to obtain solid melamine grease, washing with deionized water for many times to neutrality, and stirring with absolute ethyl alcohol for ultrasonic dispersion, wherein the dosage ratio of the melamine grease to the absolute ethyl alcohol is 1g:1.5mL of a melamine lipid solution was obtained.
Stirring and mixing the magnetic powder dispersion liquid and the melamine fat solution to obtain a mixed dispersion liquid; in the mixed dispersion liquid, the mass ratio of the magnetic powder to the melamine grease is 10:0.8.
(3) And (3) uniformly coating the mixed dispersion liquid obtained in the step (2) on one side of the porous membrane obtained in the step (1) by adopting an extrusion coating mode, filling the mixed dispersion liquid into micropores of the porous membrane, simultaneously removing the mixed dispersion liquid in other areas on the surface of the porous membrane by controlling extrusion pressure, further heating to 120 ℃, and curing for 10min to obtain the porous membrane filled with the magnetic melamine grease in the micropores.
(4) And crushing the porous film filled with the magnetic powder by adopting a film crusher, wherein the granularity of the crushed discharged material is 3-5 mm, and then carrying out melt extrusion granulation and drying to obtain the composite magnetic plastic.
In the above examples 1 to 3, the step (3) was carried out using an extrusion coating device. As shown in fig. 2, the coating device includes a bracket, a hopper 100, a first roller 210, a second roller 220, a heat source 310, and two first motors. The porous membrane 400 is horizontally placed on the support, the hopper 100 is arranged on the support, the lower end of the hopper 100 is provided with a discharge hole, and the first roller 210 and the second roller 220 are sequentially and horizontally arranged on the support from top to bottom and can axially rotate around the hopper. The first roller 210 is below the discharge port, the first roller 210 is above the porous membrane 400 and abuts against one side of the porous membrane 400, and the abrasive cloth 211 is disposed on the peripheral wall of the first roller 210. The second roller 220 is under the porous membrane 400 and abuts against the other side of the porous membrane 400. The output shafts of the two first motors are respectively connected to the first roller 210 and the second roller 220, and rotate the first roller 210 and the second roller 220 in opposite directions. A heat source 310 is installed on the support, and the heat source 310 is used to heat and cure the porous film 400 coated with the mixed solution.
In operation, the resulting mixed liquor is placed in the hopper 100, flows through the discharge port to the first roller 210, and is absorbed by the abrasive cloth 211 on the first roller 210. The two first motors are started to reversely rotate the first roller 210 and the second roller 220, so that the porous membrane 400 is driven to move towards the heat source 310. When the porous membrane 400 moves, the first roller 210 and the porous membrane 400 squeeze the mill Mao Buliao, the mixed dispersion liquid absorbed by the abrasive cloth 211 is uniformly coated into micropores of the porous membrane 400 by controlling the squeezing pressure, meanwhile, the mixed dispersion liquid in other areas on the surface of the porous membrane 400 is removed by a squeezing mode, then the porous membrane 400 coated with the mixed liquid is sent to the heat source 310 for heat curing reaction, and the mixed liquid is cured to obtain the porous membrane filled with the magnetic melamine resin in the micropores.
Comparative example
The composite magnetic plastic of the comparative example is prepared by adopting a stirring and mixing method in the prior art, and in order to improve the dispersion effect, a coupling agent phthalate and a lubricant magnesium stearate are additionally introduced into the system to serve as auxiliary dispersion materials. The dosage of the dispersant, the lubricant and the coupling agent is 1% of the mass of the magnetic powder; the proportions and amounts of the raw materials such as the polymer resin, the magnetic powder, the melamine resin and the like are the same as in example 1.
The specific process is as follows:
(1) Melting nylon 66 resin, melamine resin and plasticizer dioctyl phthalate, and dispersing for 20min at a stirring speed of 1000 r/min;
(2) Placing ferroferric oxide magnetic powder, a coupling agent phthalate, a lubricant magnesium stearate and a dispersant sodium dodecyl sulfate into absolute ethyl alcohol, and kneading for 20min at a stirring speed of 80 r/min;
(3) Adding the resin prepared in the step (1) into the magnetic powder dispersion liquid prepared in the step (2), kneading and stirring for 20min at 80r/min, curing, extruding, granulating and drying to obtain the composite magnetic plastic.
Performance testing
The composite magnetic plastics provided in examples 1 to 5 and comparative example are melted and then injected into a mold cavity, the melt in the cavity is magnetized, the cooling and solidification are carried out after pressure maintaining is carried out for 20min, the magnetic plastic sample with the same specification is prepared, and then the magnetic plastic sample is tested for the maximum magnetic energy product, coercive force, tensile strength and elongation at break. The results are shown in Table 1 below.
Table 1 properties of the magnetic plastics prepared in examples and comparative examples
As is clear from Table 1 above, examples 1 to 3 of the present invention have different material properties due to the use of different resin substrates. Compared with the magnetic plastic of the comparative example 1, the magnetic energy product, the coercive force, the tensile strength and the elongation at break of the material are obviously improved in the example 1. Therefore, compared with the existing stirring and mixing process, the invention adopts the mixed dispersion liquid obtained by mixing the magnetic powder dispersion liquid and the melamine resin solution to coat, so that the magnetic melamine resin composite material with the melamine resin coated magnetic powder is filled in the micropores of the cured porous film, on one hand, the agglomeration of the magnetic powder can be effectively avoided, the specific gravity difference between the magnetic powder and a plastic matrix is reduced, and the layering of the magnetic powder is reduced, on the other hand, the affinity between the resin polymer and the magnetic powder can be effectively improved, the compatibility between matrix resin and inorganic magnetic powder is improved, and the magnetic property and the processing performance of the magnetic plastic are comprehensively improved.
Claims (8)
1. The preparation method of the composite magnetic plastic is characterized by comprising the following steps:
(1) Melting a polymer to prepare a film, stretching and shaping the film, and forming holes on the film by stretching and shaping to obtain a porous film; the thickness of the porous membrane is 50-100 mu m, and the porosity is 50% -80%; the aperture of the micropores in the porous membrane is 10-20 mu m;
(2) Placing magnetic powder, a plasticizer and a dispersing agent in absolute ethyl alcohol, stirring and performing ultrasonic dispersion to obtain a magnetic powder dispersion liquid;
adding melamine into an acidic formaldehyde solution for reaction, filtering after the reaction to obtain solid melamine grease, washing with water to be neutral, and stirring and ultrasonically dispersing by adopting absolute ethyl alcohol to obtain melamine grease solution;
stirring and mixing the magnetic powder dispersion liquid and the melamine fat solution to obtain a mixed dispersion liquid; in the mixed dispersion liquid, the mass ratio of the magnetic powder to the melamine grease is 10: (0.6-1.0);
(3) Uniformly coating the mixed dispersion liquid obtained in the step (2) on one side of the porous membrane obtained in the step (1), filling the mixed dispersion liquid into micropores of the porous membrane, removing the mixed dispersion liquid in other areas on the surface of the porous membrane, and further heating and curing to obtain the porous membrane filled with the magnetic melamine grease in the micropores;
(4) Crushing the porous membrane filled with the magnetic melamine resin, and then carrying out melt extrusion granulation and drying to obtain the composite magnetic plastic;
wherein, in the step (2), the particle size of the magnetic powder is 2-4 mu m; the pH value of the acidic formaldehyde solution is 1-4; the concentration of the formaldehyde solution is 35% -40%; the mole ratio of melamine to formaldehyde is 1: (0.5 to 0.8); the reaction is carried out for 1-2 h at 70-90 ℃; the dosage ratio of solid melamine grease to absolute ethyl alcohol is 1g: (1.2-1.8) mL.
2. The method of claim 1, wherein in the step (1), the polymer is one or more of polyethylene, polypropylene, acrylonitrile-butadiene-styrene copolymer, and nylon.
3. The method of producing a composite magnetic plastic according to claim 1, wherein in step (1), the stretching and shaping process is specifically: the film is subjected to a first biaxial stretching treatment at 140-150 ℃, then is subjected to a first heat setting treatment at 150-170 ℃, then is subjected to a second biaxial stretching treatment at 130-140 ℃, and finally is subjected to a second heat setting treatment at 140-160 ℃ to obtain the porous film.
4. The method of producing a composite magnetic plastic according to claim 1, wherein in the step (2), the magnetic powder is any one of a ferroferric oxide magnetic powder and a neodymium iron boron magnetic powder; the dispersing agent is sodium dodecyl sulfate or polyacrylamide, and the dosage of the dispersing agent is 1-2% of the mass of the magnetic powder; the plasticizer is one or two of dioctyl phthalate, dibutyl phthalate and dibutyl terephthalate, and the dosage of the plasticizer is 2-4% of the mass of the magnetic powder; the dosage ratio of the magnetic powder to the absolute ethyl alcohol is 1g: (0.5-0.6) mL.
5. The method of producing a composite magnetic plastic according to any one of claims 1 to 4, wherein in the step (3), the coating is performed by extrusion coating, and the coating pressure is controlled so that the mixed dispersion is filled into the micropores of the porous membrane, and the mixed dispersion in other regions of the surface of the porous membrane is removed by extrusion.
6. The method of producing a composite magnetic plastic according to any one of claims 1 to 4, wherein in the step (3), the curing temperature is 120 to 140 ℃ for 5 to 10 minutes.
7. The method according to any one of claims 1 to 4, wherein in the step (4), the crushing treatment is performed by using a film crusher, and the crushed material has a particle size of 3 to 5mm.
8. A composite magnetic plastic, characterized in that it is prepared by the preparation method of the composite magnetic plastic according to any one of claims 1 to 7.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012167181A (en) * | 2011-02-14 | 2012-09-06 | Daicel Corp | Porous film containing inorganic particle, and method for producing the same |
| CN102820120A (en) * | 2010-04-30 | 2012-12-12 | 广东百顺纸品有限公司 | Magnetic plastic for disposable absorption product magnetic closed system and preparation method thereof |
| CN107574408A (en) * | 2017-08-18 | 2018-01-12 | 武汉华星光电半导体显示技术有限公司 | A kind of high polymer mask version and preparation method thereof and application |
| CN110975635A (en) * | 2019-11-11 | 2020-04-10 | 北京航空航天大学 | Magnetic fluid/porous net composite membrane and preparation method and application thereof |
| CN113698685A (en) * | 2021-08-16 | 2021-11-26 | 深圳市酷彼伴玩具有限公司 | Magnetic plastic and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102820120A (en) * | 2010-04-30 | 2012-12-12 | 广东百顺纸品有限公司 | Magnetic plastic for disposable absorption product magnetic closed system and preparation method thereof |
| JP2012167181A (en) * | 2011-02-14 | 2012-09-06 | Daicel Corp | Porous film containing inorganic particle, and method for producing the same |
| CN107574408A (en) * | 2017-08-18 | 2018-01-12 | 武汉华星光电半导体显示技术有限公司 | A kind of high polymer mask version and preparation method thereof and application |
| CN110975635A (en) * | 2019-11-11 | 2020-04-10 | 北京航空航天大学 | Magnetic fluid/porous net composite membrane and preparation method and application thereof |
| CN113698685A (en) * | 2021-08-16 | 2021-11-26 | 深圳市酷彼伴玩具有限公司 | Magnetic plastic and preparation method thereof |
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