[go: up one dir, main page]

CN112442270B - A kind of nanomaterial composite polymer powder and preparation method thereof - Google Patents

A kind of nanomaterial composite polymer powder and preparation method thereof Download PDF

Info

Publication number
CN112442270B
CN112442270B CN201910827848.4A CN201910827848A CN112442270B CN 112442270 B CN112442270 B CN 112442270B CN 201910827848 A CN201910827848 A CN 201910827848A CN 112442270 B CN112442270 B CN 112442270B
Authority
CN
China
Prior art keywords
powder
nano
temperature
polymer
heating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910827848.4A
Other languages
Chinese (zh)
Other versions
CN112442270A (en
Inventor
马永梅
路兴婷
张京楠
曹新宇
郑鲲
叶钢
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Chemistry CAS
Original Assignee
Institute of Chemistry CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Chemistry CAS filed Critical Institute of Chemistry CAS
Priority to CN201910827848.4A priority Critical patent/CN112442270B/en
Publication of CN112442270A publication Critical patent/CN112442270A/en
Application granted granted Critical
Publication of CN112442270B publication Critical patent/CN112442270B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • 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
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • 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
    • 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
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K3/38—Boron-containing compounds
    • 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
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The invention discloses a nano-material composite polymer powder and a preparation method thereof, wherein the powder comprises a nano-material and a polar polymer, the nano-material and the polar polymer can be mixed, heated and dried in deionized water to prepare the powder, the particle size of the powder is measured by laser particle size, and the particle size range of the powder is 1-1000 mu m. The preparation method comprises the steps of mixing the polar polymer, the nano material and deionized water, heating the mixture to the heat preservation temperature at a certain speed, stirring, preserving heat for a certain time, taking out a cooled product after heat preservation, and performing suction filtration and drying to obtain powder. The invention provides a method for preparing nano material composite polymer powder in one step, which is characterized in that a polymer and a nano material are stirred in water under certain pressure and temperature conditions and then dried to prepare the powder.

Description

Nano material composite polymer powder and preparation method thereof
Technical Field
The invention belongs to the field of polymer composite materials, and particularly relates to nano-material composite polymer powder and a preparation method thereof.
Background
The polymer powder maintains the excellent physical and chemical properties of the polymer, has the advantages of large specific surface area, easy processing and the like, and can be applied to the fields of cosmetics, coatings, adsorbents, chromatographic media and the like. Along with the development of 3D printing, polymer powder is applied gradually in the 3D printing industry. According to different applications, different requirements are imposed on the particle size, sphericity and the like of the polymer powder.
The polymer powder is generally prepared by a dissolution precipitation method or a mechanical pulverization method.
The Chinese patent with the application number of 201010597529.8 provides a method for preparing nylon powder for selective laser sintering, which takes nylon granules as raw materials and comprises the following steps: A. in a certain solvent, under a certain pressure and a certain temperature, the nylon granules are stirred in a high-pressure container for a period of time under the condition of heat preservation and pressure maintaining, and then the materials are taken out and dried in vacuum to obtain the heat-treated nylon granules; B. adding a certain amount of the nylon granules obtained by the heat treatment in the step A, a crystallization assistant and a solvent into a high-pressure container, stirring and ultrasonically treating for a period of time at a certain temperature and under a certain pressure, then cooling and depressurizing to normal temperature and normal pressure, separating out powder, filtering, washing and drying to obtain nylon powder; C. and C, mixing the nylon powder obtained in the step B with a flow aid and an antioxidant according to a certain ratio, uniformly mixing, and screening to obtain the nylon powder for selective laser sintering. The scheme uses a dissolution precipitation method for preparing powder, and the prepared powder is used for 3D printing. However, the powder prepared by the dissolution precipitation method has irregular surface and poor sphericity, and a large amount of organic reagent is used as a solvent, so that great environmental pollution is caused.
Chinese patent with application number 201710834954.6 discloses a graphene composite nylon powder material, which comprises raw materials of nylon and graphene, wherein the graphene is a powdery graphene microchip, the diameter of the graphene microchip is less than or equal to 100 microns, and the thickness of the graphene microchip is less than or equal to 30 microns; in the obtained graphene composite nylon powder material, graphene exists on the surface of nylon powder in a flaky manner. The preparation method comprises the following steps: firstly, ultrasonically dispersing graphene in an organic solvent A to obtain a graphene dispersion liquid; mixing nylon and an organic solvent B, placing the mixture in a high-pressure reaction kettle, primarily heating until the nylon is completely dissolved, and cooling to obtain a nylon microparticle suspension after relieving high pressure; and finally, mixing the graphene dispersion liquid with the nylon microparticle suspension, heating for reaction, and then carrying out post-treatment. In the scheme, a dissolving precipitation method is firstly used for preparing nylon powder, and graphene is dispersed in a poor solvent of nylon to prepare graphene dispersion liquid. And then uniformly mixing and heating the prepared nylon powder and the graphene dispersion liquid, and adhering graphene to the nylon powder to obtain the graphene composite nylon powder. However, the nylon powder undergoes secondary processing, and the performance is affected by the number of processing times and is somewhat reduced.
The Chinese patent with the application number of 201710834954.6 discloses a preparation method of nylon micro powder for selective laser sintering, which is characterized by comprising the following steps: the preparation method comprises the following preparation steps: (1) adding a certain amount of nylon granules and a dispersant into a good solvent of the nylon granules and the dispersant, stirring and dissolving to obtain a homogeneous transparent solution; (2) adding a poor solvent of nylon in a certain proportion into the transparent solution obtained in the step (1), stirring, precipitating, and carrying out post-treatment to obtain nylon powder; (3) and (3) mixing the nylon powder obtained in the step (2) with a flow aid and an antioxidant according to a certain ratio, uniformly mixing, and sieving with a 120-mesh and 300-mesh sieve to obtain the nylon micro powder for selective laser sintering. The method needs more organic reagents, relatively accurately controls the phase separation process and has complex process.
In addition, the preparation of the polymer micro-powder also comprises methods such as a cryogenic grinding method and a melt dispersion method, but the cryogenic grinding method is not suitable for polymers with strong toughness and low embrittlement temperature, and has large consumption of liquid nitrogen and high cost; the melt dispersion method uses water as a solvent, and utilizes high-speed dispersion to prepare polymer powder in a short time, but a large amount of active agents need to be added in the process, and the active agents are difficult to resist high temperature and have high cost, so that the method is not suitable for popularization and use.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing polymer powder by using water as a dispersing agent, wherein the polymer powder comprises a polar polymer and a nano material, and in the preparation process, only water is added to be mixed with the polar polymer and the nano material, and the mixture is mixed under certain temperature and pressure conditions, so that the polymer powder with uniform granularity can be prepared. The preparation process of the powder only takes water as a dispersing medium, does not add an organic solvent, is simple, and can prepare the powder only by heating, stirring and drying in one step, thereby greatly shortening the process flow.
In order to solve the technical problems, the invention adopts the technical scheme that:
the invention provides a nano-material composite polymer powder, which comprises a nano-material and a polar polymer, wherein the nano-material and the polar polymer can be mixed, heated and dried in deionized water to prepare the powder, and the particle size of the powder is measured by laser particle size, and the particle size range of the powder is 1-1000 mu m.
The further scheme of the invention is as follows: the particle size of the powder particles is preferably 25-35 μm in D10, 70-75 μm in D50 and less than 150 μm in D90 through laser particle size measurement; the powder has an angle of repose of 24 to 42 degrees, preferably 24 to 34 degrees.
In the above scheme, the polymer powder provided by the application has relatively concentrated particle size distribution, and the powder shape is close to spherical, so that the polymer powder has better fluidity and higher bulk density, the surface of a workpiece taking the polymer powder as a raw material is smoother, and the preparation fineness is improved. The size of the angle of repose directly reflects the flowability of the powder, and the smaller the angle of repose, the better the flowability of the powder.
The invention also provides a preparation method of the nano-material composite polymer powder, which comprises the following steps: mixing polar polymer, nano material and deionized water, heating the mixture to the heat preservation temperature at a certain speed, stirring, preserving heat for a certain time, taking out the cooled product after heat preservation, and performing suction filtration and drying to obtain powder.
According to the preparation method, the lower limit of the heat preservation temperature is 70 ℃ lower than the melting point of the polymer, and the upper limit of the heat preservation temperature is 260 ℃; preferably, the lower limit of the heat preservation temperature is lower than the melting point of the polymer by 40 ℃, and the upper limit of the heat preservation temperature is higher than the melting point of the polymer by 30 ℃; more preferably, the lower limit of the holding temperature is lower than 40 ℃ of the melting point of the polymer, and the upper limit of the holding temperature is the melting point of the polymer.
According to the preparation method, the raw materials for preparing the powder comprise:
0.5 to 20 parts by weight of a polar polymer
0.1-5 parts by weight of nano material
100 parts of deionized water.
According to the preparation method, the raw materials also comprise an auxiliary agent, and the auxiliary agent is selected from an antioxidant or a nucleating agent.
According to the preparation method, the heating rate is 1-20 ℃/min, and the preferable heating rate is 5-10 ℃/min; the temperature rising process also comprises the step of not applying or applying low-speed stirring to the mixture, wherein the low-speed stirring can be 1 rpm-40 rpm.
In the preparation method, under the condition of higher temperature rise rate, the energy consumption of the whole process can be saved, the aging of the polymer material is prevented, in addition, the low-speed stirring is applied in the temperature rise process, the uniformity degree of the polymer and the nanometer material can be further improved, and the finally prepared powder has more uniform shape.
According to the preparation method, the rotation speed of stirring after the temperature reaches the heat preservation temperature is 100-20000 rpm, preferably 500-5000 rpm; the heat preservation time is 10min to 5h, and preferably 20min to 90 min.
In the above preparation method, the raw materials are continuously stirred during the heat preservation process.
According to the preparation method, the heating, stirring and heat preservation processes of the mixture are carried out in a reactor which is vacuumized or protected by gas, and the pressure in the heat preservation process is the saturated vapor pressure of the deionized water at the temperature, preferably 0.002-5 MPa; preferably, after evacuation, an inert atmosphere is introduced into the reactor, and the mixture is again heated, stirred and kept warm.
In the preparation method, the polymer is stirred and crushed into powder under the condition of heating in water and melting, can be coated and blocked by the nano material dispersed in water, weakens the merging behavior of the polymer, can keep high temperature and high pressure and relatively anaerobic environment by utilizing a high-pressure device, has short preparation time and large yield compared with the prior art, and can obtain the nano composite polymer powder only by one-step preparation.
According to the preparation method, the raw materials also comprise 1-50 parts by weight of glass beads, and the glass beads are removed after the product is subjected to suction filtration and drying to obtain powder.
In the preparation method, the method of adding the glass beads to simulate the ball milling process and assist the powdering can further promote the breaking of macromolecules, and simultaneously has a certain barrier effect, so that the particle size of the product is reduced, and the preparation time is shortened. The glass beads do not participate in the reaction, and screening is carried out after the step of drying and pulverizing.
According to the above preparation method, the polar polymer is one or two selected from the group consisting of polyamide, polyurethane, polycaprolactone, polymethyl methacrylate, polyhydroxyethyl methacrylate, poly beta-hydroxybutyrate, polyvinyl acetate, polylactic acid, polycycloamide resin, polysebacic acid m (p) phenylene dimethylene amine resin, polybutylene terephthalate, polyethylene-2, 6-naphthalene dicarboxylate, polycarbonate, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, acrylonitrile-butadiene-styrene copolymer.
According to the preparation method, the nano material is selected from one or more of zero-dimensional nano material, one-dimensional nano material and two-dimensional nano material, and is preferably selected.
In the above preparation method, the zero-dimensional nanomaterial and the one-dimensional nanomaterial include nano silicon oxide, nano titanium oxide, nano zirconium oxide, nano zinc oxide, nano aluminum oxide, nano nickel oxide, nano gold, nano silver, nano silicon, nano carbon black, carbon nanofiber, carbon nanotube, nano graphite, nano boron powder, nano sulfur, nano lanthanum oxide, nano neodymium oxide, nano erbium oxide, nano cerium oxide, nano praseodymium oxide, nano yttrium oxide, nano europium oxide, nano tungsten oxide, nano silicon carbide, nano tellurium oxide, nano niobium oxide, nano hafnium oxide, or nano molybdenum oxide; the two-dimensional nano material is mostly a layered nano material and comprises ionic and non-ionic layered materials, wherein the ionic layered nano material comprises cationic layered silicate, layered titanate, layered phosphate and anionic hydrotalcite compound, and specifically comprises one or more of nano montmorillonite, nano potassium titanate, kaolin, sepiolite and hydrotalcite. The non-ionic nano-layered material comprises: 1. carbon material: graphene, graphene oxide; 2. graphene analogs: elements of the fourth main group of the periodic table, such as silylene, germylene, boracene, arsylene, etc., black phosphorus; 3. transition Metal Sulfides (TMDs): transition Metal Sulfides (TMDs) can form insulators (HfS) based on the coordination environment and oxidation state of the metal atom2) Semiconductor (MoS)2) Semi-metal (TiSe)2) And all metals (NbSe)2) Transition Metal Sulfides (TMDs) may exhibit superconductivity even under low temperature conditions. The current literature reportsMore than 40 layered transition metal sulfides; 4. layered metal oxide: MoO3、V2O3、V2O5、Al2O3Chromium oxide, TiO2、BiOCl、MnO2(ii) a 5. Layered metal hydroxides, perovskite oxides; 6. metal nitrides, carbides: h-BN, nitrogen carbide (g-C)3N4) (ii) a 7. Two-dimensional metal-organic framework material: MOFs that have been stripped include: [ Cu2Br (IN)2]N (IN) and Zn-BDC (BDC) terephthalic acid), manganese-2, 2-dimethylsuccinic acid (MnDMS) was exfoliated IN ethanol, and [ Zn ] was exfoliated IN a mixed solvent of methanol and propanol2(bim)4](bim ═ benzimidazole) MOF growth was controlled by diffusion in a mixed solvent of N, N-dimethylformamide and acetonitrile to give ultrathin 2D CuBDC and ZnBDC MOF materials. M-TC thermoplastic vulcanized rubber ultrathin nanosheets (M ═ Zn, Cu, Cd, Co; TC thermoplastic vulcanized rubber ═ 5,10,15, 20-tetrakis (4-carboxyphenyl) porphine); 8. transition metal oxyhalides: LiCoO2FeOCl, and the like.
According to the preparation method, in the preparation method, the nano material is mixed with deionized water to prepare nano material dispersion liquid, and then the polar polymer is added to prepare a raw material mixture.
In the preparation method, the nano material and the deionized water are mixed in advance, so that the nano material can be dispersed in the water more uniformly, and the phenomena of agglomeration and the like in the subsequent heating and melting process are prevented.
According to the above preparation method, the preparation method of the polymer powder of the present invention specifically comprises:
(1) adding 0.1-5 parts by weight of nano material into 100 parts by weight of deionized water to prepare nano material dispersion liquid;
(2) adding 0.5-20 parts by weight of high-polarity polymer into the nano-material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing, introducing inert gas, starting heating, and starting low-speed stirring at 1-40 rpm;
(4) heating to the heat preservation temperature at the speed of 1-20 ℃/min, starting high-speed stirring at the stirring speed of 100-20000 rpm, and preserving heat for 10 min-5 h;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, and drying to obtain a polymer powder product.
After adopting the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. the polymer powder provided by the invention is compounded with uniform nano materials, has relatively average particle size and spherical morphology and relatively strong fluidity, and is suitable for improving the fineness of a processing member taking the powder as a raw material;
2. the preparation method of the polymer powder provided by the invention mainly takes water as a dispersion system, and is low in cost and environment-friendly;
3. in the preparation method of the polymer powder, aiming at polar polymers, the powder can be prepared under the condition of not adding other additives, and the components only comprise water, nano materials and polymers, so that the purity of the product is maintained.
4. In the preparation method of the polymer powder provided by the invention, the yield of the polymer powder is higher, and the secondary processing is omitted when the nano composite polymer powder is prepared in one step.
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention, are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention without limiting the invention to the right. It is obvious that the drawings in the following description are only some embodiments, and that for a person skilled in the art, other drawings can be derived from them without inventive effort. In the drawings:
FIG. 1 is a SEM photograph showing the structure of the fine particles of example 1 of the present invention;
FIG. 2 is a graph showing a particle size distribution in example 2 of the present invention;
FIG. 3 is an SEM image of the powder structure of example 3 of the present invention.
It should be noted that the drawings and the description are not intended to limit the scope of the inventive concept in any way, but to illustrate it by a person skilled in the art with reference to specific embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1
In this example, a polymer powder was prepared as follows:
(1) adding 0.8 weight part of nano montmorillonite into 100 weight parts of deionized water to prepare nano material dispersion liquid;
(2) adding 5 parts by weight of polyamide 6 into the nano-material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing, introducing inert gas, and simultaneously starting heating;
(4) heating to 220 deg.C at 20 deg.C/min, stirring at 1000rpm, and keeping the temperature for 40 min;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, and drying to obtain a polymer powder product.
Example 2
In this example, a polymer powder was prepared as follows:
(1) adding 1.0 part by weight of graphene into 100 parts by weight of deionized water to prepare a nano material dispersion liquid;
(2) adding 5 parts by weight of polyamide 66 into the nano-material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing, introducing inert gas, and simultaneously starting heating;
(4) heating to 220 deg.C at a speed of 20 deg.C/min, stirring at 1000rpm, heating to 230 deg.C under stirring, and maintaining for 20 min;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, and drying to obtain a polymer powder product.
Example 3
In this example, a polymer powder was prepared as follows:
(1) adding 0.7 weight part of nano silicon oxide into 100 weight parts of deionized water to prepare nano material dispersion liquid;
(2) adding 5 parts by weight of polyamide 6 into the nano-material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing, introducing inert gas, and simultaneously starting heating;
(4) heating to 220 deg.C at a speed of 10 deg.C/min, stirring at 1000rpm, heating to 230 deg.C under stirring, and maintaining for 40 min;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, and drying to obtain a polymer powder product.
Example 4
In this example, a polymer powder was prepared as follows:
(1) adding 0.8 weight part of nano montmorillonite into 100 weight parts of deionized water to prepare nano material dispersion liquid;
(2) adding 5 parts by weight of polyamide 6 into the nano-material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing, introducing inert gas, and simultaneously starting heating;
(4) heating to 210 ℃ at the speed of 5 ℃/min, starting stirring at the speed of 3000rpm, and keeping the temperature for 60 min;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, and drying to obtain a polymer powder product.
Example 5
In this example, a polymer powder was prepared as follows:
(1) adding 0.6 weight part of nano alumina into 100 weight parts of deionized water to prepare nano material dispersion liquid;
(2) adding 3 parts by weight of polycaprolactone into the nano material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing, introducing inert gas, and simultaneously starting heating;
(4) heating to 50 deg.C at a speed of 1 deg.C/min, stirring at 5000rpm, and keeping the temperature for 10 min;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, and drying to obtain a polymer powder product.
Example 6
In this example, a polymer powder was prepared as follows:
(1) adding 5 parts by weight of nano silicon carbide into 100 parts by weight of deionized water to prepare nano material dispersion liquid;
(2) adding 4 parts by weight of polyvinyl acetate into the nano material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing, introducing inert gas, and simultaneously starting heating;
(4) heating to 55 ℃ at the speed of 5 ℃/min, starting stirring at the speed of 500rpm, and keeping the temperature for 15 min;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, and drying to obtain a polymer powder product.
Example 7
In this example, a polymer powder was prepared as follows:
(1) adding 20 parts by weight of nano silicon oxide into 100 parts by weight of deionized water to prepare nano material dispersion liquid;
(2) adding 0.1 part by weight of polylactic acid into the nano material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing, introducing inert gas, and simultaneously starting heating;
(4) heating to 100 deg.C at 2 deg.C/min, stirring at 1500rpm, heating to 155 deg.C under stirring, and maintaining for 10 min;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, and drying to obtain a polymer powder product.
Example 8
In this example, a polymer powder was prepared as follows:
(1) adding 10 parts by weight of nano alumina into 100 parts by weight of deionized water to prepare nano material dispersion liquid;
(2) adding 2 parts by weight of polymethyl methacrylate and 1 part by weight of glass beads into the nano material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing, introducing inert gas, and simultaneously starting heating;
(4) heating to 100 deg.C at a speed of 10 deg.C/min, stirring at 5000rpm, heating to 135 deg.C under stirring, and maintaining for 2 hr;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, drying and screening the glass beads to obtain a polymer powder product.
Example 9
In this example, a polymer powder was prepared as follows:
(1) adding 3 parts by weight of graphene into 100 parts by weight of deionized water to prepare a nano material dispersion liquid;
(2) adding 3 parts by weight of poly beta-hydroxybutyrate and 20 parts by weight of poly beta-hydroxybutyrate into the nano-material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing, introducing inert gas, and simultaneously starting heating;
(4) heating to 105 ℃ at the speed of 5 ℃/min, starting stirring at the speed of 20000rpm, continuously heating to 175 ℃ in a stirring state, and keeping the temperature for 2 h;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, drying and screening the glass beads to obtain a polymer powder product.
Example 10
In this example, a polymer powder was prepared as follows:
(1) adding 1 part by weight of graphene into 100 parts by weight of deionized water to prepare a nano material dispersion liquid;
(2) adding 0.2 part by weight of polylactic acid and 0.3 part by weight of poly beta-hydroxybutyrate into the nano-material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing, introducing inert gas, and simultaneously starting heating;
(4) heating to 150 ℃ at the speed of 5 ℃/min, starting stirring at the speed of 20000rpm, and keeping the temperature for 90 min;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, and drying to obtain a polymer powder product.
Example 11
In this example, a polymer powder was prepared as follows:
(1) adding 1 part by weight of graphene into 100 parts by weight of deionized water to prepare a nano material dispersion liquid;
(2) adding 5 parts by weight of polycycloamide resin into the nano-material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing, introducing inert gas, and simultaneously starting heating;
(4) heating to 210 ℃ at a speed of 15 ℃/min, starting stirring at a speed of 2000rpm, continuously heating to 230 ℃ in a stirring state, and keeping the temperature for 20 min;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, and drying to obtain a polymer powder product.
Example 12
In this example, a polymer powder was prepared as follows:
(1) adding 0.8 part by weight of graphene into 100 parts by weight of deionized water to prepare a nano material dispersion liquid;
(2) adding 5 parts by weight of polyamide 1012 into the nano-material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing, introducing inert gas, and simultaneously starting heating;
(4) heating to 190 deg.C at 1 deg.C/min, stirring at 1000rpm, heating to 210 deg.C under stirring, and maintaining for 40 min;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, and drying to obtain a polymer powder product.
Example 13
In this example, a polymer powder was prepared as follows:
(1) adding 0.5 part by weight of graphene into 100 parts by weight of deionized water to prepare a nano material dispersion liquid;
(2) adding 5 parts by weight of polybutylene terephthalate into the nano material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing, introducing inert gas, and simultaneously starting heating;
(4) heating to 225 deg.C at 20 deg.C/min, stirring at 1000rpm, and keeping the temperature for 40 min;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, and drying to obtain a polymer powder product.
Example 14
In this example, a polymer powder was prepared as follows:
(1) adding 1 weight part of nano potassium titanate into 100 weight parts of deionized water to prepare nano material dispersion liquid;
(2) adding 2 parts by weight of polyethylene glycol terephthalate into the nano material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing and introducing inert gas, starting heating and starting low-speed stirring at the speed of 40 rpm;
(4) heating to 250 deg.C at a speed of 15 deg.C/min, stirring at 1000rpm for 5 hr;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, and drying to obtain a polymer powder product.
Example 15
In this example, a polymer powder was prepared as follows:
(1) adding 0.6 weight part of nano silicon oxide into 100 weight parts of deionized water to prepare nano material dispersion liquid;
(2) adding 0.5 part by weight of poly-2, 6-naphthalene dicarboxylic acid ethylene glycol into the nano material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing, introducing inert gas, and simultaneously starting heating;
(4) heating to 265 deg.C at a speed of 10 deg.C/min, stirring at 3000rpm, and keeping the temperature for 60 min;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, and drying to obtain a polymer powder product.
Example 16
In this example, a polymer powder was prepared as follows:
(1) adding 2 parts by weight of nano montmorillonite into 100 parts by weight of deionized water to prepare nano material dispersion liquid;
(2) adding 3 parts by weight of polycarbonate into the nano-material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing, introducing inert gas, and simultaneously starting heating;
(4) heating to 225 deg.C at 5 deg.C/min, stirring at 5000rpm, and keeping the temperature for 10 min;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, and drying to obtain a polymer powder product.
Example 17
In this example, a polymer powder was prepared as follows:
(1) adding 5 parts by weight of kaolin into 100 parts by weight of deionized water to prepare a nano material dispersion liquid;
(2) adding 4 parts by weight of acrylonitrile-butadiene-styrene copolymer into the nano material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing and introducing inert gas, starting heating and starting low-speed stirring at the speed of 20 rpm;
(4) heating to 120 ℃ at the speed of 5 ℃/min, starting high-speed stirring at the speed of 20000rpm, and keeping the temperature for 90min under the stirring state;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, and drying to obtain a polymer powder product.
Example 18
In this example, a polymer powder was prepared as follows:
(1) adding 20 parts by weight of carbon black into 100 parts by weight of deionized water to prepare a nano material dispersion liquid;
(2) adding 0.1 part by weight of ethylene-methyl acrylate copolymer into the nano material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing and introducing inert gas, starting heating and starting low-speed stirring at the rotating speed of 1 rpm;
(4) heating to 80 deg.C at 1 deg.C/min, stirring at 500rpm for 20 min;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, and drying to obtain a polymer powder product.
Example 19
In this example, a polymer powder was prepared as follows:
(1) adding 10 parts by weight of boron nitride into 100 parts by weight of deionized water to prepare a nano material dispersion liquid;
(2) adding 2 parts by weight of ethylene-vinyl acetate copolymer and 20 parts by weight of glass beads into the nano-material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing, introducing inert gas, and simultaneously starting heating;
(4) heating to 99 ℃ at a speed of 10 ℃/min, starting stirring at a speed of 5000rpm, and keeping the temperature for 2h in a stirring state;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, drying and screening the glass beads to obtain a polymer powder product.
Example 20
In this example, a polymer powder was prepared as follows:
(1) adding 3 parts by weight of nano titanium oxide into 100 parts by weight of deionized water to prepare nano material dispersion liquid;
(2) adding 0.8 part by weight of ethylene-ethyl acrylate copolymer and 1 part by weight of the ethylene-ethyl acrylate copolymer into the nano material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing and introducing inert gas, and simultaneously starting heating and low-speed stirring at the speed of 20 rpm;
(4) heating to 96 ℃ at the speed of 8 ℃/min, starting high-speed stirring at the speed of 20000rpm, and keeping the temperature for 40min under the stirring state;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, drying and screening the glass beads to obtain a polymer powder product.
Example 21
In this example, a polymer powder was prepared as follows:
(1) adding 1 part by weight of graphene oxide into 100 parts by weight of deionized water to prepare a nano material dispersion liquid;
(2) adding 0.2 part by weight of ethylene-vinyl acetate copolymer and 0.3 part by weight of ethylene-ethyl acrylate copolymer into the nano material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing, introducing inert gas, and simultaneously starting heating;
(4) heating to 99 ℃ at the speed of 5 ℃/min, starting stirring at the speed of 20000rpm, and keeping the temperature for 90min under the stirring state;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, and drying to obtain a polymer powder product.
Example 22
In this example, a polymer powder was prepared as follows:
(1) adding 0.8 weight part of nano montmorillonite into 100 weight parts of deionized water to prepare nano material dispersion liquid;
(2) adding 5 parts by weight of polyamide 6 into the nano-material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing and introducing inert gas, and simultaneously starting heating and stirring at a low speed of 20 rpm;
(4) heating to 220 ℃ at the speed of 1 ℃/min, starting stirring at the speed of 1000rpm, and keeping the temperature for 40min in a stirring state;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, and drying to obtain a polymer powder product.
Example 23
In this example, the temperature increase rate in the step (4) was changed to 5 ℃/min based on example 22, and other implementation methods in this example were the same as example 22.
Example 24
In this example, the temperature increase rate in the step (4) was changed to 10 ℃/min based on example 22, and other implementation methods in this example were the same as example 22.
Example 25
In this example, the temperature increase rate in the step (4) was changed to 15 ℃/min based on example 22, and other implementation methods in this example were the same as example 22.
Comparative example 1
In this comparative example, the powder was prepared by a dissolution precipitation method, and the preparation process was as follows:
(1) adding 0.8 weight part of nano montmorillonite into 100 weight parts of ethanol to prepare nano material dispersion liquid;
(2) adding 5 parts by weight of polyamide 6 into the nano-material dispersion liquid prepared in the step (1) to prepare a mixture;
(3) adding the mixture prepared in the step (2) into a high-pressure reaction kettle, vacuumizing and introducing inert gas, and simultaneously starting heating and stirring at a low speed of 20 rpm;
(4) heating to 220 ℃ at the speed of 1 ℃/min, starting stirring at the speed of 1000rpm, and keeping the temperature for 40min in a stirring state;
(5) and closing the heating, reducing the temperature and the pressure to a safe state, opening the kettle, performing suction filtration on a product in the reaction kettle, and drying to obtain a polymer powder product.
Comparative example 2
On the basis of the example 22, the step (1) is removed, and the polymer, the nano material and the deionized water are directly mixed and then are sent into a reaction kettle for mixing.
Test example 1
The angles of repose, the difference angles and the sphericity of the powders prepared in examples 1 to 25 and comparative examples 1 and 2 of the present application were measured, and the results are shown in the following table:
Figure BDA0002189696320000171
Figure BDA0002189696320000181
as can be seen from the above table, the powder of examples 1 to 25 of the present invention has a relatively uniform angle of repose and a relatively large difference angle, and the powder having a better sphericity has a relatively small angle of repose and a relatively large difference angle. The size of the angle of repose directly reflects the flowability of the powder, the smaller the angle of repose, the better the flowability of the powder, and the larger the difference angle, the stronger the flowability and the sprayability of the powder, and the more favorable the processing of the component. In the comparative example 1, the powder is prepared by adopting the traditional dissolution precipitation method, the angle of repose is larger, which indicates that the powder has poor fluidity and poor sphericity, which indicates that the powder cannot form uniform spheres and is not beneficial to processing; in contrast to comparative example 2 and example 22, the addition sequence of the raw materials in step (1) is modified, which results in a larger angle of repose, a smaller difference angle, and a poor sphericity, because the addition sequence of the raw materials is changed, the nano-materials and other components are partially agglomerated in the stirring and dispersing process, and the powder processing performance is reduced.
In addition, as can be seen from the study of examples 1 and 22 to 25 of the present application, the temperature increase rate during the temperature increase to the heat preservation process also has a certain influence on the sphericity of the powder.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (11)

1. A method for preparing a nano-material composite polymer powder, the method comprising: mixing a nano material with deionized water to prepare a nano material dispersion liquid, mixing the nano material dispersion liquid with a polar polymer to prepare a mixture, heating the mixture to a heat preservation temperature at a certain speed, stirring, preserving the heat for a certain time, taking out a cooled product after the heat preservation is finished, and performing suction filtration and drying to prepare powder;
the heating rate is 1-20 ℃/min; the temperature rise process also comprises the step of stirring the mixture at a low speed, wherein the low speed is 1-40 rpm;
heating, stirring and heat preservation processes of the mixture are carried out in a reactor which is vacuumized or protected by gas, and the pressure in the heat preservation process is the saturated vapor pressure of the deionized water under the condition;
the lower limit of the heat preservation temperature is lower than 70 ℃ of the melting point of the polar polymer, and the upper limit of the heat preservation temperature is 260 ℃;
the raw materials for preparing the powder comprise:
0.5 to 20 parts by weight of a polar polymer
0.1-5 parts by weight of nano material
100 parts by weight of deionized water;
the polar polymer is selected from one or two of polyamide, polyurethane, polycaprolactone, polymethyl methacrylate, polyhydroxyethyl methacrylate, poly beta-hydroxybutyrate, polyvinyl acetate, polylactic acid, polycycloamide resin, polysebacic acid m-phenylene dimethylene amine resin, polysebacic acid p-phenylene dimethylene amine resin, polybutylene terephthalate, polyethylene terephthalate, poly-2, 6-naphthalene dicarboxylic acid ethylene ester, polycarbonate, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer and acrylonitrile-butadiene-styrene copolymer;
the nano material is selected from one or more of zero-dimensional nano material, one-dimensional nano material and two-dimensional nano material.
2. The method for preparing powder of nanomaterial composite polymer according to claim 1, wherein the lower limit of the holding temperature is lower than 40 ℃ of the melting point of the polar polymer and the upper limit of the holding temperature is higher than 30 ℃ of the melting point of the polar polymer.
3. The method for preparing powder of nanomaterial composite polymer according to claim 2, wherein the lower limit of the holding temperature is lower than 40 ℃ of the melting point of the polar polymer, and the upper limit of the holding temperature is the melting point of the polar polymer.
4. The method for preparing the powder of the nano-composite polymer according to claim 1, wherein the temperature increase rate is 5 to 10 ℃/min; the rotating speed of stirring after the heat preservation temperature is reached is 100-20000 rpm; the heat preservation time is 10 min-5 h.
5. The method for preparing powder of nanomaterial composite polymer according to claim 4, wherein the rotation speed of stirring after the temperature reaches the holding temperature is 500-5000 rpm; the heat preservation time is 20-90 min.
6. The method for preparing the powder of the nano-composite polymer according to claim 1, wherein the pressure during the heat-preservation process is 0.002-5 MPa.
7. The method for preparing powder of nanomaterial composite polymer according to claim 1, wherein the reactor is filled with inert gas after evacuation, and the mixture is heated, stirred and kept warm.
8. The method for preparing the powder of the nano-composite polymer according to claim 1, wherein the raw material further comprises 1 to 50 parts by weight of glass beads, and the glass beads are removed after the product is subjected to suction filtration and drying to obtain the powder.
9. A nano-material composite polymer powder, characterized in that it is prepared by the method for preparing a nano-material composite polymer powder according to any one of claims 1 to 8; the particle size of the powder particles is 1-1000 mu m through laser particle size measurement, and the shape of the powder particles is close to a sphere.
10. The nano-material composite polymer powder according to claim 9, wherein the polymer powder has an angle of repose of 24 ° to 42 °.
11. The nano-material composite polymer powder according to claim 10, wherein the polymer powder has an angle of repose of 24 ° to 34 °.
CN201910827848.4A 2019-09-03 2019-09-03 A kind of nanomaterial composite polymer powder and preparation method thereof Active CN112442270B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910827848.4A CN112442270B (en) 2019-09-03 2019-09-03 A kind of nanomaterial composite polymer powder and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910827848.4A CN112442270B (en) 2019-09-03 2019-09-03 A kind of nanomaterial composite polymer powder and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112442270A CN112442270A (en) 2021-03-05
CN112442270B true CN112442270B (en) 2021-10-29

Family

ID=74735406

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910827848.4A Active CN112442270B (en) 2019-09-03 2019-09-03 A kind of nanomaterial composite polymer powder and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112442270B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114605825A (en) * 2022-04-11 2022-06-10 焦作市天益科技有限公司 Photosensitive antistatic composite material and preparation method thereof
CN115090334B (en) * 2022-07-06 2023-09-29 扬州工业职业技术学院 MOF-derived porous carbon-based nano composite photodegradable material

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1192760A (en) * 1995-08-11 1998-09-09 大金工业株式会社 Preparation method of modified polytetrafluoroethylene granular powder
CN1249766A (en) * 1997-03-17 2000-04-05 大金工业株式会社 Filled particulate powder of polytetrafluoroethylene and process for preparing same
CN101296955A (en) * 2005-10-24 2008-10-29 巴斯福涂料股份公司 Structurally viscous, curable, aqueous powder dispersions that are substantially or entirely devoid of organic solvents, method for producing them and their use
EP2607408A1 (en) * 2011-12-21 2013-06-26 Rhein Chemie Rheinau GmbH Method for dust-free manufacture of master batches containing nano-particles (CNT) in high viscosity rubbers by means of a three roll device
CN104262646A (en) * 2014-09-12 2015-01-07 中国科学院化学研究所 Controllable-shape long-carbon-chain polyamide powder base and controllable-shape high-conductivity composite powder material
CN105860105A (en) * 2016-06-03 2016-08-17 湖南华曙高科技有限责任公司 Preparation method of polyamide 6 powder for laser sintering
CN106751767A (en) * 2015-11-24 2017-05-31 中国科学院理化技术研究所 Nylon alloy composite micro powder for selective laser sintering and preparation method thereof
CN107236288A (en) * 2017-06-09 2017-10-10 湖南华曙高科技有限责任公司 Static resistant polyamide dusty material and preparation method for selective laser sintering
CN107236294A (en) * 2017-05-19 2017-10-10 湖南华曙高科技有限责任公司 A kind of selective laser sintering polyamide 66 powder material preparation method
CN107418003A (en) * 2017-08-16 2017-12-01 东莞市联洲知识产权运营管理有限公司 A kind of preparation method of the composite of nanometer of unmodified clay and polar rubber
CN107722612A (en) * 2017-09-15 2018-02-23 中广核俊尔新材料有限公司 Graphene nylon composite powder powder material and preparation method thereof and the application in 3D printing
CN108084627A (en) * 2017-12-27 2018-05-29 上海统慧科技发展有限公司 HIPS base conductive agglomerates based on carbon nanotubes and graphene compound system and preparation method thereof
CN109517370A (en) * 2018-09-10 2019-03-26 湖南华曙高科技有限责任公司 A kind of nylon powder material preparation method for selective laser sintering

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080152909A1 (en) * 2005-02-10 2008-06-26 Kaneka Corporation Process for Producing Spherical Polymer Powder and Spherical Powder Comprising (Meth)Acrylic Block Copolymer

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1192760A (en) * 1995-08-11 1998-09-09 大金工业株式会社 Preparation method of modified polytetrafluoroethylene granular powder
CN1249766A (en) * 1997-03-17 2000-04-05 大金工业株式会社 Filled particulate powder of polytetrafluoroethylene and process for preparing same
CN101296955A (en) * 2005-10-24 2008-10-29 巴斯福涂料股份公司 Structurally viscous, curable, aqueous powder dispersions that are substantially or entirely devoid of organic solvents, method for producing them and their use
EP2607408A1 (en) * 2011-12-21 2013-06-26 Rhein Chemie Rheinau GmbH Method for dust-free manufacture of master batches containing nano-particles (CNT) in high viscosity rubbers by means of a three roll device
CN104262646A (en) * 2014-09-12 2015-01-07 中国科学院化学研究所 Controllable-shape long-carbon-chain polyamide powder base and controllable-shape high-conductivity composite powder material
CN106751767A (en) * 2015-11-24 2017-05-31 中国科学院理化技术研究所 Nylon alloy composite micro powder for selective laser sintering and preparation method thereof
CN105860105A (en) * 2016-06-03 2016-08-17 湖南华曙高科技有限责任公司 Preparation method of polyamide 6 powder for laser sintering
CN107236294A (en) * 2017-05-19 2017-10-10 湖南华曙高科技有限责任公司 A kind of selective laser sintering polyamide 66 powder material preparation method
CN107236288A (en) * 2017-06-09 2017-10-10 湖南华曙高科技有限责任公司 Static resistant polyamide dusty material and preparation method for selective laser sintering
CN107418003A (en) * 2017-08-16 2017-12-01 东莞市联洲知识产权运营管理有限公司 A kind of preparation method of the composite of nanometer of unmodified clay and polar rubber
CN107722612A (en) * 2017-09-15 2018-02-23 中广核俊尔新材料有限公司 Graphene nylon composite powder powder material and preparation method thereof and the application in 3D printing
CN108084627A (en) * 2017-12-27 2018-05-29 上海统慧科技发展有限公司 HIPS base conductive agglomerates based on carbon nanotubes and graphene compound system and preparation method thereof
CN109517370A (en) * 2018-09-10 2019-03-26 湖南华曙高科技有限责任公司 A kind of nylon powder material preparation method for selective laser sintering

Also Published As

Publication number Publication date
CN112442270A (en) 2021-03-05

Similar Documents

Publication Publication Date Title
CN109019656B (en) Production method of nanometer rare earth oxide powder
CN108128815B (en) A kind of method for preparing nano metal oxide and nano metal powder
TWI401211B (en) Indium oxide powder and method for producing same
CN108298502B (en) A kind of method for preparing dispersed nanometer metal oxide and nanometer metal powder
CN112442270B (en) A kind of nanomaterial composite polymer powder and preparation method thereof
CN107722612B (en) Graphene composite nylon powder material and its preparation method and application in 3D printing
CN102585493A (en) Nano particle/polyamide composite material, preparation method and application thereof
CN104710169B (en) A kind of magnesium aluminate spinel superfine powder and preparation method thereof
CN101078068A (en) Method for preparing ultra-fine crystal grain tungsten-copper alloy and tungsten-copper alloy
CN108889959B (en) rGO/Cu composite material and preparation method thereof
Xia et al. Facile synthesis of inorganic nanoparticles by a precipitation method in molten ε-caprolactam solvent
CN115974550A (en) A preparation method of nano-doped zirconia ceramic powder material with particle size D50 less than 100nm and tetragonal crystal phase
CN101691302A (en) Method for preparing sheet-shaped alpha-alumina particles
CN107414070A (en) A kind of uniform-spherical graphene/monocrystalline copper composite powder and preparation method thereof
CN112442232B (en) Nano material composite polymer powder and preparation method thereof
CN113526534A (en) Preparation method of monodisperse nano boehmite
CN111453769A (en) Organic additive for controlling particle size of nano zirconia powder
Logutenko et al. A novel method to prepare copper microspheres via chemical reduction route
Qi et al. Synthesis of silver nanocubes with controlled size using water-soluble poly (amic acid) salt as the intermediate via a novel ion-exchange self-assembly technique
CN108409513A (en) A kind of method of ammonium salt induction crystallization
CN113354942A (en) Polymer powder and preparation method thereof
KR20220056852A (en) composite material
CN113337105A (en) Polymer powder and preparation method thereof
CN111171345A (en) Preparation method of polyamide microspheres
CN103466721B (en) Cobalt molybdate hollow ball powder body material preparation method and cobalt molybdate hollow ball powder body material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant