CN110684348B - Polyamide material with metal texture and preparation method thereof - Google Patents
Polyamide material with metal texture and preparation method thereof Download PDFInfo
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- CN110684348B CN110684348B CN201911084331.7A CN201911084331A CN110684348B CN 110684348 B CN110684348 B CN 110684348B CN 201911084331 A CN201911084331 A CN 201911084331A CN 110684348 B CN110684348 B CN 110684348B
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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
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- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention provides a polyamide material and a preparation method thereof, wherein the core-shell structure metal toner spraying-free polyamide material is prepared from the following raw materials: low-viscosity polyamide 6 resin, high-viscosity polyamide 6 low resin, an antioxidant, a lubricant, a thermal oxygen aging resistant agent and core-shell structure metal toner. The spraying-free polyamide material prepared from the core-shell structure metal toner has excellent mechanical properties and processability, and can be applied to the fields of automobiles and household appliances, such as automobile exterior trims, air conditioner decorative strips, small household appliance exterior decorative structures and the like.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a polyamide material with metal texture and a preparation method thereof.
Background
Polyamide, also known as nylon, is used as an engineering plastic, has excellent mechanical properties, thermal oxidative aging resistance, self-lubricity and the like, and is easy to process, so that the polyamide is used in the fields of electrical tools, machinery, rail transit and the like. Conventional plastic surface coatings, while having good decorative properties, also inevitably cause environmental pollution and increase the cost of the system. Therefore, in recent years, a material having a metallic texture free from painting has been produced.
Because the inorganic component is used in the spray-free material, the compatibility of the spray-free material with the polymer is poor, and the incompatibility is one of important reasons for causing the problems of flow marks, welding marks and the like of the spray-free material in the actual use process. Therefore, during the actual use of the spray-free paint, the formula of the paint often contains a dispersing agent, a compatilizer, a coupling agent and the like.
Chinese patents CN201810443420.5, CN201810443419.2 and CN201811129257.1 are high-fluidity spray-free polyamide materials prepared by selecting PA6 resin as a matrix, adding a silane coupling agent or titanate as a coupling agent and selecting a polymer grafted maleic anhydride compatilizer, and thus obtaining the high-fluidity spray-free metallic silver polyamide composition. Chinese patent CN201711026449.5 discloses a spraying-free polyamide resin compound and a preparation method thereof, wherein 2-10 parts of polymer grafted maleic anhydride is also added as a compatilizer, and finally a spraying-free material with excellent weather resistance is prepared. Chinese patents CN201711021228.9, CN201711026436.8, cn201711021321.x all disclose environmentally friendly low odor spray-free polyamide compositions and methods of making the same, which reduce the gas generated during the production and/or molding process of nylon materials, thereby obtaining better appearance. Chinese patent CN201810638847.0 is a polyamide resin composition with high metal texture and a preparation method thereof, and the polyamide resin composition is used for modifying a nylon material of a spraying-free aesthetic plastic by utilizing a maleic acid dibutyl tin-methyl methacrylate-sodium methacrylate copolymer.
The main trend of the existing spraying-free material is to add an auxiliary agent to assist the metal toner in the processing process, but the dispersion efficiency is relatively low, and more auxiliary agent needs to be added, aiming at the problem, the metal toner adopts a pretreatment process, Chinese patent CN201810328618.9 uses phosphoric acid to pretreat aluminum powder, then uses a silane coupling agent to carry out organic modification, and a workpiece after injection molding is placed in a water-soluble polishing solution of a plasma generation device, and a strong metal texture is obtained by using a plasma state. Chinese patent CN201810135037.3 reports that organic toner can be prepared by introducing a substance containing chlorine active groups to the surface of a system containing common pearlescent pigment, introducing an active fragment containing epoxy vinyl based on the substance, and then adding an initiator and a fluorine-containing olefin substance. However, these problems such as flow marks and weld marks in the field of spray coating are still not effectively controlled and solved, and it is difficult to achieve a balance between metallic texture, good mechanical properties, and surface properties.
Disclosure of Invention
Based on the above, the invention aims to provide a polyamide material and a preparation method thereof, and the polyamide material free from spraying metallic toner is prepared, so that the polyamide material has high metallic texture and good mechanical property and surface property.
The specific technical scheme is as follows:
the polyamide material comprises the following raw materials in parts by weight:
the preparation method of the metal toner with the core-shell structure comprises the following steps: mixing the metal toner pretreated by acrylic acid or polyacrylic acid solution with acrylate monomer and initiator, and polymerizing.
The invention also provides a preparation method of the polyamide material with metal texture, which comprises the following specific technical scheme:
a preparation method of a polyamide material comprises the steps of weighing low-viscosity polyamide 6 resin, high-viscosity polyamide 6 resin, an antioxidant, a lubricant and a thermal-resistant oxygen aging agent according to weight fractions, mixing by using a high-speed stirrer, and adding into a double-screw extruder through a main feed; and adding the metal toner with the core-shell structure into a double-screw extruder through side feeding, and then performing melt extrusion granulation to obtain the metal toner.
Based on the technical scheme, the invention has the following beneficial effects:
according to the invention, the metal toner with the core-shell structure is prepared, wherein the metal toner is used as a core, the polymer formed by polyacrylic acid and polyacrylate is used as a shell, the metal toner with the core-shell structure is designed through the special structure, and is matched with two polyamide 6 resins with different viscosities to be mixed in a proper proportion, and the antioxidant, the lubricant and the heat-resistant aging agent in a proper proportion are compounded, so that the compatibility of the metal toner with the core-shell structure and the polyamide 6 resin is improved on the premise of not influencing the metal texture and luster, the dispersibility of the metal toner in the polyamide material is greatly improved, the prepared material avoids flow marks and mark welding, has good metal texture, and simultaneously ensures the processing performance of a polyamide material system and the mechanical performance of the processed and molded material.
The preparation method of the polyamide resin material with metal texture, disclosed by the invention, has the advantages of simple preparation process, easiness in control and low requirement on equipment, all the used equipment are general polymer processing equipment, and the prepared polyamide 6 has excellent mechanical property and processing property and can be applied to the fields of automobiles and household appliances such as automobile exterior decorations, air conditioner decorative strips, small household appliance external decorative structures and the like.
Drawings
Fig. 1 is a flow chart of a preparation process of a spraying-free polyamide material of core-shell structure metallic toner according to an embodiment of the present invention;
FIG. 2 is a drawing of the part of example 7 with a wire drawing effect;
fig. 3 shows the part with wire drawing effect of the external crank of comparative example 2, and the circled part is the position where the flow mark appears.
Detailed Description
In order that the invention may be more readily understood, reference will now be made to the following more particular description of the invention, examples of which are set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete. It is to be understood that the experimental procedures in the following examples, where specific conditions are not noted, are generally in accordance with conventional conditions, or with conditions recommended by the manufacturer. The various reagents used in the examples are commercially available.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The polyamide material comprises the following raw materials in parts by weight: 20-50 parts of low-viscosity polyamide 6 resin; 50-80 parts of high-viscosity polyamide 6 resin; the sum of the parts by weight of the low-viscosity polyamide 6 resin and the high-viscosity polyamide 6 resin is 100 parts; 0.5-1 part of antioxidant; 0.5-1 part of lubricant; 0.5-1 part of thermal oxygen aging resistant agent; 0.3-2 parts of core-shell structure metal toner; the preparation method of the metal toner with the core-shell structure comprises the following steps: mixing the metal toner pretreated by acrylic acid or polyacrylic acid solution with acrylate monomer and initiator, and polymerizing.
The components solve the problems of flow marks, welding marks and the like caused by uneven dispersion of metal toner in the existing spraying-free polyamide material. The metal toner with the core-shell structure is synthesized, so that the compatibility of the metal toner and the matrix resin polyamide 6 is obviously improved, and the mechanical property and the processing property of the polyamide 6 are ensured by compounding and using the polyamide 6 resin with high viscosity and low viscosity. By compounding and using the antioxidant, the lubricant and the heat aging resistant agent, the processing performance and the heat resistance of the spraying-free polyamide material of the core-shell structure metal toner can be obviously improved.
Preferably, the low viscosity polyamide 6 resin has a relative viscosity of 2.3 to 2.6; the relative viscosity of the high-viscosity polyamide 6 resin is 2.8-3.2. More preferably, the low viscosity polyamide 6 resin has a relative viscosity of 2.35 to 2.55; the relative viscosity of the high-viscosity polyamide 6 resin is 2.85-3.15. Further preferably, the low viscosity polyamide 6 resin has a relative viscosity of 2.5; the relative viscosity of the high-viscosity polyamide 6 resin was 3.0.
Preferably, the weight part of the low-viscosity polyamide 6 resin is 25-45 parts, and the weight part of the high-viscosity polyamide 6 resin is 55-75 parts; the sum of the parts by weight of the low-viscosity polyamide 6 resin and the high-viscosity polyamide 6 resin is 100 parts.
Preferably, the preparation method of the metal toner with the core-shell structure is as follows: 1) dissolving acrylic acid or polyacrylic acid in water to prepare an aqueous solution with the concentration of 0.001g/L-1 g/L; 2) adding the metallic toner into the aqueous solution obtained in the step 1) according to the ratio of 0.001g/L-1g/L, stirring and filtering to obtain pretreated metallic toner; 3) dissolving an acrylate monomer in an organic solvent to prepare a solution of 0.001g/L-1 g/L; 4) and (3) mixing the pretreated metallic toner with the solution and the initiator in the step 3), and carrying out polymerization reaction to obtain the metallic toner with the core-shell structure.
Preferably, the mass ratio of the acrylic acid or polyacrylic acid to the metal toner and the acrylate monomer is (0.1-2): (0.1-2): 1. more preferably (0.5-1.5): (0.5-1.5):1. Further preferred is a 1: 1.
preferably, in the method for preparing the metal toner with the core-shell structure, in the step 1), acrylic acid or polyacrylic acid is dissolved in water to prepare an aqueous solution of acrylic acid or polyacrylic acid with a concentration of 0.005g/L-1 g/L. More preferably, it is prepared as an aqueous acrylic acid solution or an aqueous polyacrylic acid solution having a concentration of 0.005g/L to 0.1 g/L. More preferably, it is formulated into an aqueous acrylic acid solution or an aqueous polyacrylic acid solution at a concentration of 0.005g/L to 0.015 g/L. More preferably 0.01g/L of an aqueous acrylic acid solution or an aqueous polyacrylic acid solution.
Preferably, in the method for preparing the core-shell structure metal toner, the metal toner in the step 2) is added into the acrylic acid aqueous solution or the polyacrylic acid aqueous solution at a ratio of 0.005g/L-1 g/L. More preferably, the metallic toner is added to the aqueous acrylic acid solution or the aqueous polyacrylic acid solution at 0.005g/L to 0.1 g/L. More preferably, the metallic toner is added to the acrylic acid aqueous solution or the polyacrylic acid aqueous solution at 0.005g/L to 0.015 g/L. Further preferably, the metallic toner is added to an aqueous acrylic acid solution or an aqueous polyacrylic acid solution at 0.01 g/L.
Preferably, in the preparation method of the core-shell structure metal toner, in the step 3), the acrylate monomer is dissolved in the organic solvent to prepare a solution of 0.001g/L to 1g/L of the acrylate monomer. More preferably, a solution of 0.001g/L to 0.1g/L of an acrylate monomer is prepared. More preferably, a solution of 0.001g/L to 0.015g/L of an acrylate monomer is prepared. Further preferably, a solution of 0.01g/L of an acrylic monomer is prepared.
Preferably, the metallic toner is at least one of aluminum powder, copper powder, gold powder, silver powder, zinc powder, tin powder, iron powder and nickel powder.
Preferably, the weight average molecular weight of the polyacrylic acid is 20000-500000. More preferably, the polyacrylic acid has a weight average molecular weight of 20000-30000.
Optionally, the organic solvent is at least one of ethanol, acetone, ethyl acetate, diethyl ether and benzene.
Optionally, the acrylate monomer is at least one of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-methyl methacrylate and 2-ethyl methacrylate; and/or
Optionally, the initiator is at least one of benzoyl peroxide, tert-butyl peroxybenzoate, azobisisobutyronitrile, and azobisisoheptonitrile.
Preferably, the antioxidant is at least one of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid N-octadecyl ester, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) phosphite. The antioxidant improves the processing stability of matrix resin in the processing process of polyamide, and avoids the problems of material degradation and the like caused by a high-temperature processing process, thereby improving the overall performance of the material.
Preferably, the lubricant is at least one of silicone powder, pentaerythritol stearate, calcium stearate, zinc stearate, aluminum stearate, and ethylene bisstearamide. The lubricant has good thermal stability and is not easy to decompose in the processing process of polyamide 6. Meanwhile, in order to improve the processability of the material and reduce the comprehensive energy consumption by considering the high-viscosity polyamide 6 in the formula composition, a lubricant is introduced, and the two are matched with each other in a proper ratio so as to obviously reduce the torque of the material in the processing process.
Preferably, the heat-resistant oxygen aging agent is at least one of sodium bromide, sodium iodide, calcium bromide, calcium iodide, copper iodide, magnesium bromide, potassium bromide and potassium iodide. On one hand, the heat-resistant oxygen aging agent has a remarkable inhibiting effect on heat aging in a processing process, and on the other hand, after the heat-resistant oxygen aging agent is introduced and is matched with other components in a specific proportion, the service life of the material in the actual use process can be greatly prolonged.
The preparation method of the polyamide material comprises the steps of weighing the raw materials of any one of the low-viscosity polyamide 6 resin, the high-viscosity polyamide 6 resin, the antioxidant, the lubricant and the thermal oxygen aging resistant agent according to the weight fraction, mixing the raw materials by using a high-speed stirrer, and adding a main feed into a double-screw extruder; and adding the metal toner with the core-shell structure into a double-screw extruder through side feeding, and then performing melt extrusion granulation to obtain the metal toner.
Preferably, the mixing speed of the high-speed stirrer is 500-1200 rpm. Preferably, the process parameters of the double-screw extruder for melt extrusion granulation are as follows: the temperature of the first zone is 245-265 ℃, the temperature of the second zone is 250-270 ℃, the temperature of the third zone is 250-270 ℃, the temperature of the fourth zone is 255-275 ℃, the temperature of the fifth zone is 255-275 ℃, the temperature of the sixth zone is 250-270 ℃, the temperature of the seventh zone is 250-270 ℃, the temperature of the eighth zone is 250-270 ℃, the temperature of the die head is 250-270 ℃, the rotating speed of the screw is 200-500 rpm, and the vacuum degree is-0.05-0.08 MPa.
More preferably, the ratio L/D of the length L and the diameter D of the screw of the double-screw extruder is 35-50; the screw is provided with more than 1-2 meshing block areas and more than 1-2 reverse thread areas.
The raw material components and sources thereof used in the specific embodiment of the present invention are as follows:
low viscosity polyamide 6 resin (relative viscosity of 2.3), low viscosity polyamide 6 resin (relative viscosity of 2.5), low viscosity polyamide 6 resin (relative viscosity of 2.6), purchased from south Henan Mars Nylon chemical Limited;
high viscosity polyamide 6 resin (relative viscosity of 2.8), high viscosity polyamide 6 resin (relative viscosity of 3.0), high viscosity polyamide 6 resin (relative viscosity of 3.2), purchased from the country of the Hunan province, the country of the mountain, the country of China of the petrochemical company;
antioxidant: octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], purchased from Beijing very easily available chemical Co., Ltd;
antioxidant: n, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) phosphite, purchased from beijing Tiangang adjuncts, llc;
lubricant silicone powder, purchased from Chuanhua chemical industry technologies, Inc., Guangzhou;
lubricant pentaerythritol stearate, purchased from Guangzhou Reynaud technologies, Inc.;
lubricant calcium stearate, lubricant zinc stearate, purchased from zichuan ruifeng plastics auxiliaries factory;
ethylene bis stearamide, a lubricant, was purchased from one chemical technology ltd, guangzhou;
sodium bromide, sodium iodide and calcium bromide as heat resisting oxygen aging resisting agents, which are purchased from chemical reagents of national medicine group, Inc.;
metallic toner, available from new color plastics industries, llc, of the shude district, mountain, fo;
polyacrylic acid available from sigma aldrich trade ltd;
methyl methacrylate, initiator azobisisoheptonitrile, selected from sigma aldrich trade ltd.
The present invention will be described in detail with reference to specific examples.
Example 1
The core-shell structure metal toner spraying-free polyamide material comprises the following components in parts by weight:
the core-shell structure method of the core-shell structure metal toner comprises the following steps: 1) firstly, adding acrylic acid into water to prepare an aqueous solution with the concentration of 0.001 g/L; 2) adding the metallic toner silver powder into the acrylic acid aqueous solution in the step 1) according to the concentration of 0.001g/L, stirring for 0.5h, filtering, washing and drying to obtain pretreated metallic toner; 3) adding methyl acrylate monomer into ethanol to prepare 0.001g/L solution; 4) adding the pretreated metallic toner into the solution in the step 3), adding azodiisoheptonitrile at the same time, heating to 60 ℃ under the stirring condition to initiate polymerization, reacting for 0.5h, filtering, washing and drying to finally obtain the metallic toner with the core-shell structure.
The core-shell structure metal toner spraying-free polyamide material and the preparation method thereof comprise the following steps:
1) the polyamide 6 was dried at 80 ℃ for 4 hours and then cooled. And weighing the raw material components of the cooled polyamide 6 resin, the antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl), the lubricant silicone powder and the heat-resistant oxygen aging agent sodium bromide according to parts by weight, and uniformly mixing by using a high-speed stirrer at the rotating speed of 500 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding metal toner with a core-shell structure into the parallel double-screw extruder (total eight zones) in the lateral direction, performing melt extrusion, and granulating, wherein the process parameters are as follows: the temperature of the first zone was 245 ℃, the temperature of the second zone was 250 ℃, the temperature of the third zone was 250 ℃, the temperature of the fourth zone was 255 ℃, the temperature of the fifth zone was 255 ℃, the temperature of the sixth zone was 250 ℃, the temperature of the seventh zone was 250 ℃, the temperature of the eighth zone was 250 ℃, the temperature of the die head was 250 ℃, the rotation speed of the screw was 200rpm, and the vacuum degree was-0.05 MPa.
The ratio L/D of the length L of the screw to the diameter D is 35; and the screw is provided with 1 meshing block area and 1 reverse thread area.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the granular spraying-free polyamide material.
Example 2
The core-shell structure metal toner spraying-free polyamide material comprises the following components in parts by weight:
the core-shell structure method of the core-shell structure metal toner comprises the following steps: 1) firstly, adding polyacrylic acid with molecular weight of 20000 into water to prepare an aqueous solution with the concentration of 0.01 g/L; 2) adding metallic toner iron powder into the polyacrylic acid aqueous solution in the step 1) according to the concentration of 0.01g/L, stirring for 3 hours, filtering, washing and drying to obtain pretreated metallic toner; 3) adding an ethyl acrylate monomer into acetone to prepare a solution of 0.01 g/L; 4) adding the pretreated metallic toner into the solution in the step 3), adding benzoyl peroxide, heating to 70 ℃ under the stirring condition to initiate polymerization, reacting for 3 hours, filtering, washing and drying to finally obtain the metallic toner with the core-shell structure.
The core-shell structure metal toner spraying-free polyamide material and the preparation method thereof comprise the following steps:
1) the polyamide 6 was dried at 90 ℃ for 6 hours and then cooled. And weighing the raw material components of the cooled polyamide 6 resin, the antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl), the lubricant pentaerythritol stearate and the heat-resistant oxygen aging agent calcium bromide according to parts by weight, and uniformly mixing by using a high-speed stirrer at the rotating speed of 1000 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding metal toner with a core-shell structure into the parallel double-screw extruder (total eight zones) in the lateral direction, performing melt extrusion, and granulating, wherein the process parameters are as follows: the temperature of the first zone was 255 ℃, the temperature of the second zone was 260 ℃, the temperature of the third zone was 260 ℃, the temperature of the fourth zone was 265 ℃, the temperature of the fifth zone was 265 ℃, the temperature of the sixth zone was 260 ℃, the temperature of the seventh zone was 260 ℃, the temperature of the eighth zone was 260 ℃, the temperature of the die head was 260 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.07 MPa.
The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the granular spraying-free polyamide material.
Example 3:
the core-shell structure metal toner spraying-free polyamide material comprises the following components in parts by weight:
the core-shell structure method of the core-shell structure metal toner comprises the following steps: 1) firstly, adding polyacrylic acid with the molecular weight of 500000 into water to prepare aqueous solution with the concentration of 1 g/L; 2) adding the metallic toner aluminum powder into the solution in the step 1) according to the concentration of 1g/L, stirring for 5 hours, filtering, washing and drying to obtain pretreated metallic toner; 3) adding an acrylate monomer into ethyl acetate to prepare a solution of 1 g/L; 4) adding the pretreated metallic toner into the solution in the step 3), adding tert-butyl peroxybenzoate at the same time, heating to 80 ℃ under the stirring condition to initiate polymerization, reacting for 5 hours, filtering, washing and drying to finally obtain the metallic toner with the core-shell structure.
The core-shell structure metal toner spraying-free polyamide material and the preparation method thereof comprise the following steps:
1) the polyamide 6 was dried at 110 ℃ for 8 hours and then cooled. Weighing the cooled polyamide 6 resin, the antioxidant N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) phosphite ester, the lubricant calcium stearate and the heat-resistant oxygen aging agent magnesium bromide according to parts by weight, and uniformly mixing by using a high-speed stirrer at the rotating speed of 1200 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding metal toner with a core-shell structure into the parallel double-screw extruder (total eight zones) in the lateral direction, performing melt extrusion, and granulating, wherein the process parameters are as follows: the temperature of the first zone was 265 deg.C, the temperature of the second zone was 70 deg.C, the temperature of the third zone was 270 deg.C, the temperature of the fourth zone was 275 deg.C, the temperature of the fifth zone was 275 deg.C, the temperature of the sixth zone was 2670 deg.C, the temperature of the seventh zone was 270 deg.C, the temperature of the eighth zone was 270 deg.C, the temperature of the die head was 270 deg.C, the screw speed was 500rpm, and the vacuum was-0.08 MPa.
The ratio L/D of the length L of the screw to the diameter D of the screw is 50; and the screw is provided with 2 meshing block areas and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the granular spraying-free polyamide material.
Example 4
The core-shell structure metal toner spraying-free polyamide material comprises the following components in parts by weight:
the core-shell structure method of the core-shell structure metal toner comprises the following steps: 1) firstly, adding polyacrylic acid with molecular weight of 20000 into water to prepare an aqueous solution with the concentration of 0.01 g/L; 2) adding metallic toner iron powder into the solution obtained in the step 1) according to the concentration of 0.01g/L, stirring for 3 hours, filtering, washing and drying to obtain pretreated metallic toner; 3) adding an ethyl acrylate monomer into acetone to prepare a solution of 0.01 g/L; 4) adding the pretreated metallic toner into the solution in the step 3), adding benzoyl peroxide, heating to 70 ℃ under the stirring condition to initiate polymerization, reacting for 3 hours, filtering, washing and drying to finally obtain the metallic toner with the core-shell structure.
The core-shell structure metal toner spraying-free polyamide material and the preparation method thereof comprise the following steps:
1) the polyamide 6 was dried at 90 ℃ for 6 hours and then cooled. And weighing the raw material components of the cooled polyamide 6 resin, the antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl), the lubricant pentaerythritol stearate and the heat-resistant oxygen aging agent calcium bromide according to parts by weight, and uniformly mixing by using a high-speed stirrer at the rotating speed of 1000 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding metal toner with a core-shell structure into the parallel double-screw extruder (total eight zones) in the lateral direction, performing melt extrusion, and granulating, wherein the process parameters are as follows: the temperature of the first zone was 255 ℃, the temperature of the second zone was 260 ℃, the temperature of the third zone was 260 ℃, the temperature of the fourth zone was 265 ℃, the temperature of the fifth zone was 265 ℃, the temperature of the sixth zone was 260 ℃, the temperature of the seventh zone was 260 ℃, the temperature of the eighth zone was 260 ℃, the temperature of the die head was 260 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.07 MPa.
The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the granular spraying-free polyamide material.
Example 5:
the core-shell structure metal toner spraying-free polyamide material comprises the following components in parts by weight:
the core-shell structure method of the core-shell structure metal toner comprises the following steps: 1) firstly, adding polyacrylic acid with molecular weight of 20000 into water to prepare an aqueous solution with the concentration of 0.01 g/L; 2) adding metallic toner iron powder into the solution obtained in the step 1) according to the concentration of 0.01g/L, stirring for 3 hours, filtering, washing and drying to obtain pretreated metallic toner; 3) adding an ethyl acrylate monomer into acetone to prepare a solution of 0.01 g/L; 4) adding the pretreated metallic toner into the solution in the step 3), adding benzoyl peroxide, heating to 70 ℃ under the stirring condition to initiate polymerization, reacting for 3 hours, filtering, washing and drying to finally obtain the metallic toner with the core-shell structure.
The core-shell structure metal toner spraying-free polyamide material and the preparation method thereof comprise the following steps:
1) the polyamide 6 was dried at 90 ℃ for 6 hours and then cooled. And weighing the raw material components of the cooled polyamide 6 resin, the antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl), the lubricant pentaerythritol stearate and the heat-resistant oxygen aging agent calcium bromide according to parts by weight, and uniformly mixing by using a high-speed stirrer at the rotating speed of 1000 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding metal toner with a core-shell structure into the parallel double-screw extruder (total eight zones) in the lateral direction, performing melt extrusion, and granulating, wherein the process parameters are as follows: the temperature of the first zone was 255 ℃, the temperature of the second zone was 260 ℃, the temperature of the third zone was 260 ℃, the temperature of the fourth zone was 265 ℃, the temperature of the fifth zone was 265 ℃, the temperature of the sixth zone was 260 ℃, the temperature of the seventh zone was 260 ℃, the temperature of the eighth zone was 260 ℃, the temperature of the die head was 260 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.07 MPa.
The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the granular spraying-free polyamide material.
Example 6:
the core-shell structure metal toner spraying-free polyamide material comprises the following components in parts by weight:
the core-shell structure method of the core-shell structure metal toner comprises the following steps: 1) firstly, adding polyacrylic acid with molecular weight of 20000 into water to prepare an aqueous solution with the concentration of 0.01 g/L; 2) adding metallic toner iron powder into the solution obtained in the step 1) according to the concentration of 0.01g/L, stirring for 3 hours, filtering, washing and drying to obtain pretreated metallic toner; 3) adding an ethyl acrylate monomer into acetone to prepare a solution of 0.01 g/L; 4) adding the pretreated metallic toner into the solution in the step 3), adding benzoyl peroxide, heating to 70 ℃ under the stirring condition to initiate polymerization, reacting for 3 hours, filtering, washing and drying to finally obtain the metallic toner with the core-shell structure.
The core-shell structure metal toner spraying-free polyamide material and the preparation method thereof comprise the following steps:
1) the polyamide 6 was dried at 90 ℃ for 6 hours and then cooled. And weighing the raw material components of the cooled polyamide 6 resin, the antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl), the lubricant pentaerythritol stearate and the heat-resistant oxygen aging agent calcium bromide according to parts by weight, and uniformly mixing by using a high-speed stirrer at the rotating speed of 1000 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding metal toner with a core-shell structure into the parallel double-screw extruder (total eight zones) in the lateral direction, performing melt extrusion, and granulating, wherein the process parameters are as follows: the temperature of the first zone was 255 ℃, the temperature of the second zone was 260 ℃, the temperature of the third zone was 260 ℃, the temperature of the fourth zone was 265 ℃, the temperature of the fifth zone was 265 ℃, the temperature of the sixth zone was 260 ℃, the temperature of the seventh zone was 260 ℃, the temperature of the eighth zone was 260 ℃, the temperature of the die head was 260 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.07 MPa.
The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the granular spraying-free polyamide material.
Example 7:
the core-shell structure metal toner spraying-free polyamide material comprises the following components in parts by weight:
the core-shell structure method of the core-shell structure metal toner comprises the following steps: 1) firstly, adding polyacrylic acid with molecular weight of 20000 into water to prepare an aqueous solution with the concentration of 0.01 g/L; 2) adding metallic toner iron powder into the solution obtained in the step 1) according to the concentration of 0.01g/L, stirring for 3 hours, filtering, washing and drying to obtain pretreated metallic toner; 3) adding an ethyl acrylate monomer into acetone to prepare a solution of 0.01 g/L; 4) adding the pretreated metallic toner into the solution in the step 3), adding benzoyl peroxide, heating to 70 ℃ under the stirring condition to initiate polymerization, reacting for 3 hours, filtering, washing and drying to finally obtain the metallic toner with the core-shell structure.
The core-shell structure metal toner spraying-free polyamide material and the preparation method thereof comprise the following steps:
1) the polyamide 6 was dried at 90 ℃ for 6 hours and then cooled. And weighing the raw material components of the cooled polyamide 6 resin, the antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl), the lubricant pentaerythritol stearate and the heat-resistant oxygen aging agent calcium bromide according to parts by weight, and uniformly mixing by using a high-speed stirrer at the rotating speed of 1000 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding metal toner with a core-shell structure into the parallel double-screw extruder (total eight zones) in the lateral direction, performing melt extrusion, and granulating, wherein the process parameters are as follows: the temperature of the first zone was 255 ℃, the temperature of the second zone was 260 ℃, the temperature of the third zone was 260 ℃, the temperature of the fourth zone was 265 ℃, the temperature of the fifth zone was 265 ℃, the temperature of the sixth zone was 260 ℃, the temperature of the seventh zone was 260 ℃, the temperature of the eighth zone was 260 ℃, the temperature of the die head was 260 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.07 MPa.
The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the granular spraying-free polyamide material.
Comparative example 1:
the core-shell structure metal toner spraying-free polyamide material comprises the following components in parts by weight:
the core-shell structure method of the core-shell structure metal toner comprises the following steps: 1) firstly, adding polyacrylic acid with molecular weight of 20000 into water to prepare an aqueous solution with the concentration of 0.01 g/L; 2) adding metallic toner iron powder into the solution obtained in the step 1) according to the concentration of 0.01g/L, stirring for 3 hours, filtering, washing and drying to obtain pretreated metallic toner; 3) adding an ethyl acrylate monomer into acetone to prepare a solution of 0.01 g/L; 4) adding the pretreated metallic toner into the solution in the step 3), adding benzoyl peroxide, heating to 70 ℃ under the stirring condition to initiate polymerization, reacting for 3 hours, filtering, washing and drying to finally obtain the metallic toner with the core-shell structure.
The core-shell structure metal toner spraying-free polyamide material and the preparation method thereof comprise the following steps:
1) the polyamide 6 was dried at 90 ℃ for 6 hours and then cooled. And weighing the raw material components of the cooled polyamide 6 resin, the antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl), the lubricant pentaerythritol stearate and the heat-resistant oxygen aging agent calcium bromide according to parts by weight, and uniformly mixing by using a high-speed stirrer at the rotating speed of 1000 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding metal toner with a core-shell structure into the parallel double-screw extruder (total eight zones) in the lateral direction, performing melt extrusion, and granulating, wherein the process parameters are as follows: the temperature of the first zone was 255 ℃, the temperature of the second zone was 260 ℃, the temperature of the third zone was 260 ℃, the temperature of the fourth zone was 265 ℃, the temperature of the fifth zone was 265 ℃, the temperature of the sixth zone was 260 ℃, the temperature of the seventh zone was 260 ℃, the temperature of the eighth zone was 260 ℃, the temperature of the die head was 260 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.07 MPa.
The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the granular spraying-free polyamide material.
Comparative example 2:
the core-shell structure metal toner spraying-free polyamide material comprises the following components in parts by weight:
the spraying-free polyamide material for the metallic toner and the preparation method thereof comprise the following steps:
1) the polyamide 6 was dried at 90 ℃ for 6 hours and then cooled. And weighing the raw material components of the cooled polyamide 6 resin, the antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl), the lubricant pentaerythritol stearate and the heat-resistant oxygen aging agent calcium bromide according to parts by weight, and uniformly mixing by using a high-speed stirrer at the rotating speed of 1000 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding metal toner with a core-shell structure into the parallel double-screw extruder (total eight zones) in the lateral direction, performing melt extrusion, and granulating, wherein the process parameters are as follows: the temperature of the first zone was 255 ℃, the temperature of the second zone was 260 ℃, the temperature of the third zone was 260 ℃, the temperature of the fourth zone was 265 ℃, the temperature of the fifth zone was 265 ℃, the temperature of the sixth zone was 260 ℃, the temperature of the seventh zone was 260 ℃, the temperature of the eighth zone was 260 ℃, the temperature of the die head was 260 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.07 MPa.
The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the granular spraying-free polyamide material.
Comparative example 3:
the core-shell structure metal toner spraying-free polyamide material comprises the following components in parts by weight:
the core-shell structure method of the core-shell structure metal toner comprises the following steps: 1) firstly, adding polyacrylic acid with molecular weight of 20000 into water to prepare an aqueous solution with the concentration of 0.01 g/L; 2) adding metallic toner iron powder into the solution obtained in the step 1) according to the concentration of 0.01g/L, stirring for 3 hours, filtering, washing and drying to obtain pretreated metallic toner; 3) adding an ethyl acrylate monomer into acetone to prepare a solution of 0.01 g/L; 4) adding the pretreated metallic toner into the solution in the step 3), adding benzoyl peroxide, heating to 70 ℃ under the stirring condition to initiate polymerization, reacting for 3 hours, filtering, washing and drying to finally obtain the metallic toner with the core-shell structure.
The core-shell structure metal toner spraying-free polyamide material and the preparation method thereof comprise the following steps:
1) the polyamide 6 was dried at 90 ℃ for 6 hours and then cooled. And weighing the raw material components of the cooled polyamide 6 resin, the antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl), the lubricant pentaerythritol stearate and the heat-resistant oxygen aging agent calcium bromide according to parts by weight, and uniformly mixing by using a high-speed stirrer at the rotating speed of 1000 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding metal toner with a core-shell structure into the parallel double-screw extruder (total eight zones) in the lateral direction, performing melt extrusion, and granulating, wherein the process parameters are as follows: the temperature of the first zone was 255 ℃, the temperature of the second zone was 260 ℃, the temperature of the third zone was 260 ℃, the temperature of the fourth zone was 265 ℃, the temperature of the fifth zone was 265 ℃, the temperature of the sixth zone was 260 ℃, the temperature of the seventh zone was 260 ℃, the temperature of the eighth zone was 260 ℃, the temperature of the die head was 260 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.07 MPa.
The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the granular spraying-free polyamide material.
Comparative example 4:
the core-shell structure metal toner spraying-free polyamide material comprises the following components in parts by weight:
the core-shell structure method of the core-shell structure metal toner comprises the following steps: 1) firstly, adding polyacrylic acid with molecular weight of 20000 into water to prepare an aqueous solution with the concentration of 0.01 g/L; 2) adding metallic toner iron powder into the solution obtained in the step 1) according to the concentration of 0.01g/L, stirring for 3 hours, filtering, washing and drying to obtain pretreated metallic toner; 3) adding an ethyl acrylate monomer into acetone to prepare a solution of 0.01 g/L; 4) adding the pretreated metallic toner into the solution in the step 3), adding benzoyl peroxide, heating to 70 ℃ under the stirring condition to initiate polymerization, reacting for 3 hours, filtering, washing and drying to finally obtain the metallic toner with the core-shell structure.
The core-shell structure metal toner spraying-free polyamide material and the preparation method thereof comprise the following steps:
1) the polyamide 6 was dried at 90 ℃ for 6 hours and then cooled. And weighing the raw material components of the cooled polyamide 6 resin, the antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl), the lubricant pentaerythritol stearate and the heat-resistant oxygen aging agent calcium bromide according to parts by weight, and uniformly mixing by using a high-speed stirrer at the rotating speed of 1000 revolutions per minute.
2) Adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, adding metal toner with a core-shell structure into the parallel double-screw extruder (total eight zones) in the lateral direction, performing melt extrusion, and granulating, wherein the process parameters are as follows: the temperature of the first zone was 255 ℃, the temperature of the second zone was 260 ℃, the temperature of the third zone was 260 ℃, the temperature of the fourth zone was 265 ℃, the temperature of the fifth zone was 265 ℃, the temperature of the sixth zone was 260 ℃, the temperature of the seventh zone was 260 ℃, the temperature of the eighth zone was 260 ℃, the temperature of the die head was 260 ℃, the rotation speed of the screw was 300rpm, and the vacuum was-0.07 MPa.
The ratio L/D of the length L of the screw to the diameter D is 45; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
And carrying out melt extrusion and granulation by a double-screw extruder under the process conditions to obtain the granular spraying-free polyamide material.
The following is a list of raw material compositions of examples and comparative examples (table 1).
TABLE 1 summary of the composition parts by weight of the raw materials of the examples and comparative examples
Remarking: a, the relative viscosity of the low-viscosity polyamide 6 resin is 2.5; b, the relative viscosity of the high-viscosity polyamide 6 resin was 3.0.
The organic metallic toner spray-free polyamide material prepared in the above example was subjected to the following performance tests:
tensile property: testing according to GB/T1040-2006 standard, wherein the stretching speed is 50 mm/min;
impact properties: according to the test of GB/T1843-2008 standard, the thickness of the sample strip is 4 mm;
melt index: testing according to GB/T3682-2000 standard, wherein the testing temperature is 280 ℃, and the load is 5 kg;
gloss: testing according to GB/T8807-1988 standard, and selecting an angle of 60 degrees;
the flow marks are judged by using a curved surface mold, and the mold adopts a curved surface design, so that the flow marks are easy to observe in the injection molding process; the weld mark is designed by using a ring, and the molten resin is finally fused at the end of the ring, so that the condition of the weld mark is easy to observe. The two are evaluated separately, and the worst evaluation is used as a classification basis. I represents that the surface effect is excellent and no flow mark or weld mark exists; II represents that the surface effect is between I and III; III indicates that the surface effect is moderate and slight flow marks or welding marks exist; IV is between III and V; v indicates that the surface effect is poor and that there are serious flow marks and weld marks.
The results of the performance tests are shown in table 2.
TABLE 2 Properties of the spray-free polyamide materials of the examples and comparative examples
In examples 1 to 7, the proportions of the low-viscosity polyamide 6 resin, the high-viscosity polyamide 6 resin, the antioxidant, the lubricant, the thermal antioxidant and the organic metallic toner were adjusted, and it can be seen from the table that as the proportion of the low-viscosity polyamide 6 resin decreases, the tensile strength and the melt index of the resin tend to decrease, while the notched impact strength tends to increase. The addition amount of the organic metal toner is increased, the surface glossiness of the organic metal toner can be effectively improved, meanwhile, the relative viscosity of the resin matrix can also influence the final spraying-free glossiness, welding marks, flow marks and other effects, and the effect is better the lower the viscosity is. By comparison, the overall performance of example 7 is best.
Comparative example 1 compared with example 7, comparative example 1 uses more low viscosity polyamide 6 resin, and the proportion of the low viscosity polyamide 6 resin is higher than that of the high viscosity polyamide 6 resin, at the moment, the mechanical property of the material is obviously reduced, and the material is not suitable for being used in actual products; comparative example 2 the gloss and flow marks, weld marks were very severe in comparative example 2 compared to example 7, because the conventional metallic toner used in comparative example 2, which did not prepare a core shell structure, was poorly dispersed in the matrix resin, thus resulting in very severe flow marks, as shown in fig. 2 and 3. Fig. 2 shows example 7, fig. 3 shows comparative example 2, and the surface of fig. 2 is relatively uniform and no obvious flow mark appears, but the surface of fig. 3, two circled parts, shows very obvious flow mark. Meanwhile, the glossiness is further influenced by the dispersion problem; comparative examples 3 and 4 compared with example 7, the amount of the organic metal toner added in comparative example 3 was too low, and thus the glossiness thereof was greatly affected. In contrast, in comparative example 4, the addition amount of the organic metallic toner was too large, and although the glossiness was remarkably improved, the dispersion problem was also affected due to the increase in the addition amount, and thus, flow marks and weld marks were more remarkably generated.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, however, as long as there is no contradiction between the combinations of the technical features, the scope of the present description should be considered as being described in the present specification.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The polyamide material is characterized by comprising the following raw materials in parts by weight:
20-50 parts of low-viscosity polyamide 6 resin;
50-80 parts of high-viscosity polyamide 6 resin;
the sum of the parts by weight of the low-viscosity polyamide 6 resin and the high-viscosity polyamide 6 resin is 100 parts;
the preparation method of the metal toner with the core-shell structure comprises the following steps:
1) dissolving acrylic acid or polyacrylic acid in water to prepare an aqueous solution with the concentration of 0.005g/L-1 g/L;
2) adding the metallic toner into the aqueous solution obtained in the step 1) according to the proportion of 0.005g/L-1g/L, stirring and filtering to obtain pretreated metallic toner;
3) dissolving an acrylate monomer in an organic solvent to prepare a solution of 0.001g/L-1 g/L;
4) mixing the pretreated metallic toner with the solution and the initiator in the step 3), and carrying out polymerization reaction to obtain a metallic toner with a core-shell structure;
the mass ratio of the acrylic acid or polyacrylic acid to the metallic toner to the acrylate monomer is (0.5-1.5): (0.5-1.5):1.
2. The polyamide material as claimed in claim 1, wherein the low viscosity polyamide 6 resin has a relative viscosity of 2.3 to 2.6; the relative viscosity of the high-viscosity polyamide 6 resin is 2.8-3.2.
3. The polyamide material as claimed in claim 1, wherein the low viscosity polyamide 6 resin is 25 to 45 parts by weight, and the high viscosity polyamide 6 resin is 55 to 75 parts by weight;
the sum of the parts by weight of the low-viscosity polyamide 6 resin and the high-viscosity polyamide 6 resin is 100 parts.
4. The polyamide material as claimed in any one of claims 1 to 3, wherein the mass ratio of the acrylic acid or polyacrylic acid to the metallic toner and the acrylate monomer is 1: 1:1.
5. The polyamide material as claimed in claim 4, wherein the metallic toner is at least one of aluminum powder, copper powder, gold powder, silver powder, zinc powder, tin powder, iron powder, and nickel powder.
6. Polyamide material according to claim 4, characterized in that the polyacrylic acid has a weight average molecular weight of 20000-500000; and/or
The organic solvent is at least one of ethanol, acetone, ethyl acetate, diethyl ether and benzene; and/or
The acrylate monomer is at least one of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-methyl methacrylate and 2-ethyl methacrylate; and/or
The initiator is at least one of benzoyl peroxide, tert-butyl peroxybenzoate, azobisisobutyronitrile and azobisisoheptonitrile.
7. The polyamide material according to any one of claims 1 to 3, wherein the antioxidant is at least one of N-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) phosphite; and/or
The lubricant is at least one of silicone powder, pentaerythritol stearate, calcium stearate, zinc stearate, aluminum stearate and ethylene bisstearamide; and/or
The heat-resistant oxygen aging agent is at least one of sodium bromide, sodium iodide, calcium bromide, calcium iodide, copper iodide, magnesium bromide, potassium bromide and potassium iodide.
8. A method for preparing a polyamide material, characterized in that the raw materials according to any one of claims 1 to 7 are weighed according to weight fraction as low viscosity polyamide 6 resin, high viscosity polyamide 6 resin, antioxidant, lubricant, thermal oxygen aging resistant agent, mixed by a high speed mixer, and added into a double screw extruder through a main feed; and adding the metal toner with the core-shell structure into a double-screw extruder through side feeding, and then performing melt extrusion granulation to obtain the metal toner.
9. The method as claimed in claim 8, wherein the mixing speed of the high speed mixer is 500-1200 rpm; and/or
The technological parameters of the double-screw extruder for melt extrusion granulation are as follows: the temperature of the first zone is 245-265 ℃, the temperature of the second zone is 250-270 ℃, the temperature of the third zone is 250-270 ℃, the temperature of the fourth zone is 255-275 ℃, the temperature of the fifth zone is 255-275 ℃, the temperature of the sixth zone is 250-270 ℃, the temperature of the seventh zone is 250-270 ℃, the temperature of the eighth zone is 250-270 ℃, the temperature of the die head is 250-270 ℃, the rotating speed of the screw is 200-500 rpm, and the vacuum degree is-0.05-0.08 MPa.
10. The production method according to claim 8 or 9, wherein the ratio L/D of the screw length L and the diameter D of the twin-screw extruder is 35 to 50; the screw is provided with more than 1-2 meshing block areas and more than 1-2 reverse thread areas.
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