CN108164945B - Preparation method of modified polylactic acid material with metal effect for 3D printing - Google Patents

Preparation method of modified polylactic acid material with metal effect for 3D printing Download PDF

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CN108164945B
CN108164945B CN201711461396.XA CN201711461396A CN108164945B CN 108164945 B CN108164945 B CN 108164945B CN 201711461396 A CN201711461396 A CN 201711461396A CN 108164945 B CN108164945 B CN 108164945B
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polylactic acid
metal
parts
coupling agent
zone
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CN108164945A (en
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李振
茅伟华
熊文治
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North Bridge New Material Technology Suzhou Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00Materials specially adapted for additive manufacturing
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • C08K2003/0812Aluminium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • C08K2003/085Copper
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/005Additives being defined by their particle size in general
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/014Additives containing two or more different additives of the same subgroup in C08K
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/53Core-shell polymer

Abstract

The invention relates to a preparation method of a modified polylactic acid material with a metal effect for 3D printing, which comprises the following steps: preparing the following raw materials in parts by weight: 100 parts of polylactic acid, 80-150 parts of metal powder, 1-5 parts of metal pigment, 8-18 parts of a methyl methacrylate shell soft core-shell type core-shell copolymer toughening agent, 0.5-2 parts of a coupling agent, 0.5-1.5 parts of a lubricant, 0.2-0.8 part of a hindered phenol antioxidant and 0.1-0.5 part of a phosphite or thioester antioxidant, wherein the metal powder and the metal pigment are mixed and simultaneously sprayed into a coupling agent solution, the mixture is dried, the modified metal powder, the metal pigment, the polylactic acid, the toughening agent, the lubricant and the antioxidant are mixed and then added into a double-screw extruder for extrusion granulation and drying, the dried granules are added into a single-screw extruder for extrusion, and the wire rod is obtained after hot water, cold water treatment and air drying. The modified polylactic acid material prepared by the invention has the advantages of metal effect, good toughness and difficult degradation.

Description

Preparation method of modified polylactic acid material with metal effect for 3D printing
Technical Field
The invention relates to a preparation method of a modified polylactic acid material with a metal effect for 3D printing, and belongs to the technical field of preparation of materials for 3D printing.
Background
3D printing technology is changing the progress of modern manufacturing industry deeply, and is a technology for constructing objects by printing layer by layer using bondable materials such as powdered metals or plastics based on digital model files without the need for conventional tools, jigs and machines, and is applied to jewelry, footwear, industrial design, construction, engineering and construction (AEC), automobiles, aerospace, dental and medical industries, education, geographic information systems, civil engineering, firearms, and other fields.
Due to good heat fluidity, rapid cooling cohesiveness and higher mechanical strength of the polymer material, the polymer material is rapidly applied and developed in the field of 3D printing manufacturing, and particularly, polylactic acid as a new green, environment-friendly and biodegradable material has particularly excellent printing effects of high interlayer adhesion, difficulty in warping deformation, smooth and flat surface of a printed part and the like, so that the polylactic acid is widely applied to 3D printing materials and is favored by people in the 3D printing industry. However, common polylactic acid consumables are brittle and have poor toughness and a single effect, and if a large amount of fillers with special effects and purposes (such as metal powder or metal pigment) are added, the polylactic acid consumables are brittle, layers of a printed product are difficult to fuse, the printed product is easy to crack, and the final effect or purpose is difficult to realize; in addition, common PLA (polylactic acid) consumables have the disadvantage of easy degradation during high-temperature processing besides biodegradation, the performance of the consumables is seriously reduced by long-time or multiple times of thermoforming processing, and the thermal degradation phenomenon is more obvious when a large amount of metal powder and metal pigment are filled.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in order to solve the problems of brittleness, single effect and easy degradation of the existing polylactic acid consumables, especially the technical problems of excessive embrittlement, easy cracking and easy degradation after the filler is added, the preparation method of the modified polylactic acid material with the metal effect for 3D printing is provided.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a modified polylactic acid material with a metal effect for 3D printing comprises the following steps:
preparing the following preparation raw materials in parts by weight: 100 parts of polylactic acid, 80-150 parts of metal powder, 1-5 parts of metal pigment, 8-18 parts of toughening agent, 0.5-2 parts of coupling agent, 0.5-1.5 parts of lubricant, 0.2-0.8 part of hindered phenol antioxidant and 0.1-0.5 part of phosphite or thioester antioxidant, wherein the toughening agent is a soft core-hard shell type core-shell copolymer taking methyl methacrylate as a shell;
preparing a coupling agent solution;
mixing metal powder and metal pigment, spraying a coupling agent solution, drying the obtained metal powder and metal pigment with the surface soaked with the coupling agent, and cooling to normal temperature to obtain modified metal powder and metal pigment;
mixing the modified metal powder, the metal pigment, the polylactic acid, the toughening agent, the lubricant and the antioxidant to obtain a premixed raw material;
adding the premixed raw materials into a double-screw extruder, and extruding and granulating to obtain modified granules;
and drying the modified granules to obtain dried granules, adding the dried granules into a single-screw extruder to extrude a plastic melt, and carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain the wire.
The metal powder of 80-150 parts is selected because the metal powder can not be bonded when the 3D printing molding is carried out, the bonding mainly passes through the polylactic acid matrix, so that the metal powder is difficult to disperse in the polylactic acid matrix due to excessive amount, the embrittlement problem is caused, the interlayer bonding is difficult in the 3D printing, the product is easy to crack, and the metal texture of the product is poor due to too small amount of the added metal powder.
Preferably, the preparation raw material comprises the following components in parts by weight: 100 parts of polylactic acid, 120 parts of metal powder, 2-3 parts of metal pigment, 10-15 parts of toughening agent, 0.8-1.2 parts of coupling agent, 0.7-1.2 parts of lubricant, 0.3-0.6 part of hindered phenol antioxidant and 0.2-0.4 part of phosphite or thioester antioxidant.
The metal powder of 80-150 parts is selected because the metal powder can not be bonded when the 3D printing molding is carried out, the bonding mainly passes through the polylactic acid matrix, so that the metal powder is difficult to disperse in the polylactic acid matrix due to excessive amount, the embrittlement problem is caused, the interlayer bonding is difficult in the 3D printing, the product is easy to crack, and the metal texture of the product is poor due to too small amount of the added metal powder.
Preferably, the soft core-shell type core-shell copolymer taking methyl methacrylate as a shell is at least one of a methyl methacrylate-butyl acrylate core-shell copolymer, an organosilicon modified methyl methacrylate-butyl acrylate core-shell copolymer and a methyl methacrylate-butadiene-styrene core-shell copolymer.
The soft core-hard shell type core-shell copolymer taking methyl methacrylate as a shell is selected as a toughening agent of the polylactic acid material for 3D printing, and the non-industrial common styrene-butadiene-styrene thermoplastic elastomer, ethylene propylene diene monomer, ethylene-vinyl acetate copolymer, polyolefin elastomer POE (such as Dow POE 8411 and Dow POE 8402) and maleic anhydride grafted products thereof are selected as the toughening agent for the following reasons: (1) the toughening agent can exert the toughening effect only by reaching a proper size in the matrix and being uniformly dispersed in the matrix, and the original particle size of the soft-core hard-shell type core-shell copolymer taking methyl methacrylate as the shell is less than 0.5 micron, particularly the solubility parameters of methyl methacrylate and polylactic acid are similar, so that the soft-core hard-shell type core-shell copolymer taking methyl methacrylate as the shell is easily uniformly dispersed in the polylactic acid by single particles, the toughening effect of the copolymer on the polylactic acid material can be fully exerted, and the toughening agent commonly used in the industry has poor compatibility with the polylactic acid, poor dispersibility in melt processing and insignificant toughening effect; (2) the soft core-hard shell type core-shell copolymer taking methyl methacrylate as a shell can enable indexes such as modulus, hardness, heat-resisting temperature and the like of the polylactic acid material to change very little due to the existence of hard shell methyl methacrylate, and a toughening agent commonly used in the industry can enable the hardness, modulus, heat distortion temperature and the like of the polylactic acid material to be greatly reduced; (3) because the core-shell copolymer of the soft core and the hard shell, which takes methyl methacrylate as a shell layer, is of a spherical structure, the entanglement of the toughening agent and the molecular chain of the polylactic acid material of the matrix is weakened, the reduction of the melt flow rate is less, and the toughening agent commonly used in the industry can cause the great reduction of the melt flow rate of the polylactic acid material.
Preferably, the metal powder is at least one of 400-mesh 800-mesh granular stainless steel powder, copper powder, bronze powder, brass powder and aluminum powder, and the metal pigment is at least one of 500-mesh 700-mesh scaly aluminum silver powder, copper powder, bronze powder and copper-gold powder.
Preferably, the coupling agent is a silane coupling agent or a titanate coupling agent; the general formula of the silane coupling agent is YSiX3X is methoxy or ethoxy, Y contains amino, mercapto or epoxy, preferably gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane or gamma-mercaptopropyl trimethoxy silane; the titanate coupling agent is at least one of monoalkoxy titanate coupling agent, chelating titanate coupling agent and ligand titanate coupling agent, preferably tri (dioctyl pyrophosphoryl oxy) isopropyl titanate and tetraoctyloxy titanium [ di (tridecyl phosphite ester)]Or tetraoctyloxy titanium [ di (dilauryl phosphite)]。
Preferably, the hindered phenol antioxidant is octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] or 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, the phosphite antioxidant is tris [2, 4-di-tert-butylphenyl ] phosphite or bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite, and the thioester antioxidant is dioctadecyl thiodipropionate or pentaerythritol (3-n-decylthiopropionate).
Because a plurality of short-time high-temperature processing are carried out in the preparation process of the polylactic acid material, in this case, although the hindered phenol antioxidant can prevent the polylactic acid from being oxidized at different stages to a certain extent, in order to control the dosage of a single antioxidant and further enhance the antioxidant effect of the polylactic acid, the invention selects the phosphite antioxidant or the thioester antioxidant to be matched with the hindered phenol antioxidant for use, and the two antioxidants complement each other in the antioxidant aspect of the polylactic acid and can synergistically resist the degradation of the polylactic acid during high-temperature processing.
Preferably, the lubricant is at least one of ethylene bis stearamide, pentaerythritol stearate and polyester hyperbranched resin.
Preferably, the preparation method of the modified polylactic acid material with the metal effect for 3D printing comprises the following steps:
preparing a coupling agent solution; when the coupling agent is a silane coupling agent, the coupling agent is preferably prepared into a coupling agent solution with the content of 10-20 wt% by using an organic solvent or water, and the pH value of the coupling agent solution is adjusted to be 4-5.5; when the coupling agent is titanate coupling agent, the coupling agent is preferably prepared into coupling agent solution with the content of 10-20 wt% by using organic solvent;
stirring and mixing the metal powder and the metal pigment at the speed of 100-;
stirring and mixing the modified metal powder, the metal pigment, the polylactic acid, the toughening agent, the lubricant and the antioxidant for 10-15 minutes at the speed of 100-400r/min to obtain a premixed raw material;
adding the premixed raw materials into a double-screw extruder, and extruding and granulating to obtain modified granules;
and drying the modified granules at 50-60 ℃ until the water content is not more than 0.05% to obtain dried granules, adding the dried granules into a single-screw extruder to extrude a plastic melt, and carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain the wire rod.
The coupling agent solution is sprayed in an atomizing mode while the metal powder and the metal pigment are stirred and mixed, so that the coupling agent can be more uniform on the surface of the filler; when the coupling agent is a titanate coupling agent, only the organic solvent is selected to prepare the coupling agent solution, because the coupling effect of the titanate coupling agent with the surfaces of the metal powder and the metal pigment in water is poor, the titanate coupling agent solution cannot be prepared by water.
Preferably, the temperature of each section of the twin-screw extruder is set as follows: the first zone is 160-plus-175 ℃, the second zone is 165-plus-178 ℃, the third zone is 170-plus-185 ℃, the fourth zone is 173-plus-185 ℃, the fifth zone is 175-plus-188 ℃, the sixth zone is 175-plus-188 ℃, the seventh zone is 173-plus-188 ℃, the eighth zone is 173-plus-185 ℃, the ninth zone is 173-plus-185 ℃, the tenth zone is 172-plus-185 ℃, the eleventh zone is 172-plus-185 ℃, the head is 175-plus-195 ℃, the rotation speed of the host is 300-plus-450 r/min, and the feeding frequency is 6-10r/min (the feeding frequency is the rotation speed of the screw at the bottom of the feeding hopper, and the material is added to the inlet of the double-screw extruder at a.
Preferably, the temperature of each heating zone of the single-screw extruder is set to 150-.
The invention has the beneficial effects that:
the preparation method of the invention comprises the steps of firstly mixing the metal powder and the metal pigment, simultaneously spraying the coupling agent solution, drying, mixing the modified metal powder, the metal pigment, the polylactic acid, the flexibilizer, the lubricant and the antioxidant according to a certain proportion, adding the mixture into a double-screw extruder for extrusion granulation and drying, adding the dried granules into a single-screw extruder for extrusion, treating the granules with hot water and cold water, the prepared modified polylactic acid material solves the problems of brittleness, single effect and easy degradation of the existing polylactic acid material, especially solves the technical problems of excessive embrittlement, easy cracking and easy degradation of a printed product after the filler is added, and the prepared wire rod and the printed product have good metal effects, good toughness and difficult degradation and have excellent printing effects when applied to 3D printing; the method has the following specific beneficial effects:
(1) the soft core-hard shell type core-shell copolymer taking methyl methacrylate as a shell is selected as a toughening agent of the polylactic acid material for 3D printing, and the following beneficial effects are brought: a. the soft-core hard-shell type core-shell copolymer taking methyl methacrylate as the shell is easy to be uniformly dispersed in polylactic acid as single particles, and can fully exert the toughening effect on the polylactic acid material; b. due to the existence of the hard shell layer methyl methacrylate, the indexes such as modulus, hardness, heat-resistant temperature and the like of the polylactic acid material can be changed very little, and the excellent performances such as molding stability, hardness, heat resistance and the like of a printing piece of the polylactic acid material are ensured; c. the reduction of the melt flow rate is less, and the surface smoothness of the printing piece of the polylactic acid material is ensured.
(2) The addition of 80-150 parts by weight of 400-800 mesh granular metal powder to 100 parts by weight of polylactic acid can effectively disperse the metal powder in the polylactic acid matrix, so that the layers of the printed product are well fused, the product is difficult to crack, the toughness is good, and good metal texture is generated.
(3) The scaly metal pigment added in the preparation method of the invention can be arranged on the outer side of the produced product during extrusion processing, thereby enhancing the visual metal luster of the modified polylactic acid material.
(4) According to the invention, the phosphite or thioester antioxidant and the hindered phenol antioxidant are selected to be matched for use, the compounded antioxidants complement each other in the antioxidation aspect of the polylactic acid, and the degradation of the polylactic acid material during a plurality of short-time high-temperature processing is synergistically resisted, so that the polylactic acid can be efficiently prevented from being oxidized.
(5) According to the preparation method disclosed by the invention, the silane coupling agent or titanate coupling agent is added, so that the dispersibility of the metal powder and the metal pigment in the polylactic acid can be increased, the agglomeration of the metal powder and the metal pigment is prevented, the interface combination of the metal powder, the metal pigment and the polylactic acid is increased, and the problems of mechanical property and easiness in cracking of the metal powder filled polylactic acid material during 3D printing forming are effectively solved.
(6) The preparation method of the invention selects the lubricant as the internal lubricant of the polylactic acid, the lubricant can increase the flow rate of the melt, improve the surface smoothness of the produced wire rod, also can assist the plasticization of the polylactic acid particles in the double-screw extruder and the dispersion of the pigment, improve the interlayer adhesion of the printing piece to a certain extent, and the reasonable adding amount of the lubricant can also avoid the product warping phenomenon caused by the precipitation of the lubricant.
Detailed Description
The present invention will now be described in further detail.
Example 1
The embodiment provides a preparation method of a modified polylactic acid material with a metal effect for 3D printing, which comprises the following steps:
preparing the following preparation raw materials in parts by weight: 100 parts of polylactic acid, 100 parts of metal powder, 2 parts of metal pigment, 10 parts of toughening agent, 0.5 part of coupling agent, 0.5 part of lubricant, 0.3 part of hindered phenol antioxidant and 0.2 part of phosphite antioxidant; the polylactic acid is selected from 4032D (polylactic acid can be applied to the invention as long as the polylactic acid is a polylactic acid grade suitable for extrusion), the metal powder is 500-mesh granular copper powder, the metal pigment is 500-mesh flaky copper powder, the toughening agent is methyl methacrylate-butadiene-styrene core-shell copolymer, the coupling agent gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, the lubricant is ethylene bis stearamide, the hindered phenol antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, and the phosphite antioxidant is tris [2, 4-di-tert-butylphenyl ] phosphite;
preparing a coupling agent into a coupling agent solution with the content of 10 wt% by using ethanol, and adjusting the pH value of the coupling agent solution to be 4-5.5;
stirring and mixing metal powder and metal pigment at the speed of 400r/min, simultaneously atomizing and spraying a coupling agent solution, continuing stirring for 5 minutes after the coupling agent solution is sprayed, drying the obtained metal powder and metal pigment with the coupling agent soaked on the surface at the temperature of 80 ℃ for 3 hours, and cooling to normal temperature to obtain modified metal powder and metal pigment;
stirring and mixing the modified metal powder, the metal pigment, the polylactic acid, the toughening agent, the lubricant and the antioxidant at the speed of 400r/min for 10 minutes to obtain a premixed raw material;
adding the premixed raw materials into a double-screw extruder, and extruding and granulating to obtain modified granules, wherein the temperature of each section of the double-screw extruder is set as follows: the first zone is 165 ℃, the second zone is 172 ℃, the third zone is 175 ℃, the fourth zone is 178 ℃, the fifth zone is 180 ℃, the sixth zone is 180 ℃, the seventh zone is 178 ℃, the eighth zone is 178 ℃, the ninth zone is 178 ℃, the tenth zone is 176 ℃, the eleventh zone is 176 ℃, the head is 180 ℃, the main machine rotation speed is 300r/min, and the feeding frequency is 6 r/min;
drying the modified granules at 50 ℃ until the water content is not more than 0.05 percent to obtain dried granules, then adding the dried granules into a single-screw extruder to extrude a plastic melt, and carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain wires, wherein the temperatures of heating sections of the single-screw extruder are set to be 152 ℃ in a first zone, 156 ℃ in a second zone, 158 ℃ in a third zone, 162 ℃ in a fourth zone, 162 ℃ in a fifth zone, 160 ℃ in a sixth zone, the hot water temperature is 45 ℃ and the cold water temperature is 25 ℃.
Example 2
The embodiment provides a preparation method of a modified polylactic acid material with a metal effect for 3D printing, which comprises the following steps:
preparing the following preparation raw materials in parts by weight: 100 parts of polylactic acid, 120 parts of metal powder, 3 parts of metal pigment, 10 parts of toughening agent, 0.8 part of coupling agent, 0.5 part of lubricant, 0.3 part of hindered phenol antioxidant and 0.2 part of phosphite antioxidant; the polylactic acid is 4043D of natureworks company, the metal powder is 400-mesh granular bronze powder, the metal pigment is 500-mesh flaky bronze powder, the toughening agent is methyl methacrylate-butyl acrylate core-shell copolymer, the coupling agent is tetraoctyloxy titanium [ di (dilauryl phosphite) ], the lubricant is pentaerythritol stearate, the hindered phenol antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the phosphite antioxidant is bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite;
preparing a coupling agent into a coupling agent solution with the content of 20 wt% by using ethanol;
stirring and mixing metal powder and metal pigment at the speed of 200r/min, simultaneously atomizing and spraying a coupling agent solution, continuing stirring for 10 minutes after the coupling agent solution is sprayed, drying the obtained metal powder and metal pigment with the coupling agent soaked on the surfaces at 105 ℃ for 2 hours, and cooling to normal temperature to obtain modified metal powder and metal pigment;
stirring and mixing the modified metal powder, the metal pigment, the polylactic acid, the toughening agent, the lubricant and the antioxidant for 15 minutes at the speed of 200r/min to obtain a premixed raw material;
adding the premixed raw materials into a double-screw extruder, and extruding and granulating to obtain modified granules, wherein the temperature of each section of the double-screw extruder is set as follows: 160 ℃ in the first zone, 170 ℃ in the second zone, 185 ℃ in the third zone, 185 ℃ in the fourth zone, 188 ℃ in the fifth zone, 188 ℃ in the sixth zone, 178 ℃ in the seventh zone, 178 ℃ in the eighth zone, 173 ℃ in the ninth zone, 172 ℃ in the tenth zone, 172 ℃ in the eleventh zone, 175 ℃ in the head, 450r/min of the rotating speed of the main machine and 10r/min of feeding frequency;
drying the modified granules at 60 ℃ until the water content is not more than 0.05 percent to obtain dried granules, then adding the dried granules into a single-screw extruder to extrude a plastic melt, and carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain wires, wherein the temperatures of heating sections of the single-screw extruder are set to be 150 ℃ in a first zone, 155 ℃ in a second zone, 158 ℃ in a third zone, 158 ℃ in a fourth zone, 155 ℃ in a fifth zone, 155 ℃ in a sixth zone, the hot water temperature is 55 ℃ and the cold water temperature is 30 ℃.
Example 3
The embodiment provides a preparation method of a modified polylactic acid material with a metal effect for 3D printing, which comprises the following steps:
preparing the following preparation raw materials in parts by weight: 100 parts of polylactic acid, 80 parts of metal powder, 5 parts of metal pigment, 8 parts of toughening agent, 2 parts of coupling agent, 1.5 parts of lubricant, 0.2 part of hindered phenol antioxidant and 0.4 part of thioester antioxidant; the polylactic acid is REVODE190 of Zhejiang Haizhen biomaterial GmbH, the metal powder is 800-mesh granular aluminum powder, the metal pigment is 600-mesh flaky aluminum powder, the toughening agent is an organic silicon modified methyl methacrylate-butyl acrylate core-shell copolymer, the coupling agent is tri (dioctyl pyrophosphoryl oxy) isopropyl titanate, the lubricant is polyester hyperbranched resin, the hindered phenol antioxidant is 4, 6-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, and the thioester antioxidant is dioctadecyl thiodipropionate;
preparing a coupling agent into a coupling agent solution with the content of 15 wt% by using ethanol;
stirring and mixing metal powder and metal pigment at the speed of 200r/min, simultaneously atomizing and spraying a coupling agent solution, continuously stirring for 7 minutes after the coupling agent solution is sprayed, drying the obtained metal powder and metal pigment with the coupling agent soaked on the surfaces for 2.5 hours at the temperature of 100 ℃, and cooling to normal temperature to obtain modified metal powder and metal pigment;
stirring and mixing the modified metal powder, the metal pigment, the polylactic acid, the toughening agent, the lubricant and the antioxidant at the speed of 200r/min for 12 minutes to obtain a premixed raw material;
adding the premixed raw materials into a double-screw extruder, and extruding and granulating to obtain modified granules, wherein the temperature of each section of the double-screw extruder is set as follows: 175 ℃ in the first zone, 178 ℃ in the second zone, 180 ℃ in the third zone, 180 ℃ in the fourth zone, 185 ℃ in the fifth zone, 185 ℃ in the sixth zone, 188 ℃ in the seventh zone, 185 ℃ in the eighth zone, 185 ℃ in the ninth zone, 185 ℃ in the tenth zone, 185 ℃ in the eleventh zone, 195 ℃ at the head, 400r/min at the rotating speed of a main machine and 8r/min at the feeding frequency;
drying the modified granules at 55 ℃ until the water content is not more than 0.05 percent to obtain dried granules, then adding the dried granules into a single-screw extruder to extrude a plastic melt, and carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain wires, wherein the temperatures of heating sections of the single-screw extruder are set to be 156 ℃ in a first zone, 170 ℃ in a second zone, 172 ℃ in a third zone, 172 ℃ in a fourth zone, 168 ℃ in a fifth zone, 168 ℃ in a sixth zone, the hot water temperature is 50 ℃ and the cold water temperature is 20 ℃.
Example 4
The embodiment provides a preparation method of a modified polylactic acid material with a metal effect for 3D printing, which comprises the following steps:
preparing the following preparation raw materials in parts by weight: 100 parts of polylactic acid, 150 parts of metal powder, 1 part of metal pigment, 15 parts of toughening agent, 1.5 parts of coupling agent, 0.7 part of lubricant, 0.6 part of hindered phenol antioxidant and 0.1 part of thioester antioxidant; the polylactic acid is selected from 4032D brand of natureworks company, the metal powder is 600-mesh granular brass powder, the metal pigment is 600-mesh flaky copper gold powder, the toughening agent is methyl methacrylate-butyl acrylate core-shell copolymer, the coupling agent is tetraoctyloxy titanium [ di (tridecyl phosphite) ], the lubricant is ethylene bis stearamide, the hindered phenol antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the thioester antioxidant is pentaerythritol (3-n-decylthiopropionate);
preparing a coupling agent into a coupling agent solution with the content of 10 wt% by using ethanol;
stirring and mixing metal powder and metal pigment at the speed of 100r/min, simultaneously atomizing and spraying a coupling agent solution, continuously stirring for 8 minutes after the coupling agent solution is sprayed, drying the obtained metal powder and metal pigment with the coupling agent soaked on the surfaces at 90 ℃ for 3 hours, and cooling to normal temperature to obtain modified metal powder and metal pigment;
stirring and mixing the modified metal powder, the metal pigment, the polylactic acid, the toughening agent, the lubricant and the antioxidant for 15 minutes at the speed of 100r/min to obtain a premixed raw material;
adding the premixed raw materials into a double-screw extruder, and extruding and granulating to obtain modified granules, wherein the temperature of each section of the double-screw extruder is set as follows: the first zone is 165 ℃, the second zone is 165 ℃, the third zone is 170 ℃, the fourth zone is 173 ℃, the fifth zone is 175 ℃, the sixth zone is 175 ℃, the seventh zone is 173 ℃, the eighth zone is 173 ℃, the ninth zone is 173 ℃, the tenth zone is 172 ℃, the eleventh zone is 172 ℃, the head is 185 ℃, the rotating speed of the main machine is 350r/min, and the feeding frequency is 7 r/min;
drying the modified granules at 60 ℃ until the water content is not more than 0.05 percent to obtain dried granules, then adding the dried granules into a single-screw extruder to extrude a plastic melt, and carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain wires, wherein the temperatures of heating sections of the single-screw extruder are set to be 150 ℃ in a first zone, 155 ℃ in a second zone, 160 ℃ in a third zone, 160 ℃ in a fourth zone, 156 ℃ in a fifth zone, 156 ℃ in a sixth zone, the hot water temperature is 50 ℃ and the cold water temperature is 25 ℃.
Example 5
The embodiment provides a preparation method of a modified polylactic acid material with a metal effect for 3D printing, which comprises the following steps:
preparing the following preparation raw materials in parts by weight: 100 parts of polylactic acid, 110 parts of metal powder, 3 parts of metal pigment, 12 parts of toughening agent, 1.2 parts of coupling agent, 1.2 parts of lubricant, 0.5 part of hindered phenol antioxidant and 0.3 part of phosphite antioxidant; the polylactic acid is selected from 4032D brand of natureworks company, the metal powder is 600-mesh granular stainless steel powder, the metal pigment is 600-mesh flaky aluminum silver powder, the toughening agent is methyl methacrylate-butadiene-styrene core-shell copolymer, the coupling agent is gamma-mercaptopropyl trimethoxy silane, the lubricant is ethylene bis stearamide, the hindered phenol antioxidant is octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and the phosphite antioxidant is tris [2, 4-di-tert-butylphenyl ] phosphite;
preparing a coupling agent into a coupling agent solution with the content of 15 wt% by using water, and adjusting the pH value of the coupling agent solution to be 4-5.5;
stirring and mixing metal powder and metal pigment at the speed of 300r/min, simultaneously atomizing and spraying a coupling agent solution, continuing stirring for 10 minutes after the coupling agent solution is sprayed, drying the obtained metal powder and metal pigment with the coupling agent soaked on the surface at the temperature of 100 ℃ for 3 hours, and cooling to normal temperature to obtain modified metal powder and metal pigment;
stirring and mixing the modified metal powder, the metal pigment, the polylactic acid, the toughening agent, the lubricant and the antioxidant for 15 minutes at the speed of 200r/min to obtain a premixed raw material;
adding the premixed raw materials into a double-screw extruder, and extruding and granulating to obtain modified granules, wherein the temperature of each section of the double-screw extruder is set as follows: the first zone is 165 ℃, the second zone is 172 ℃, the third zone is 175 ℃, the fourth zone is 178 ℃, the fifth zone is 185 ℃, the sixth zone is 185 ℃, the seventh zone is 183 ℃, the eighth zone is 183 ℃, the ninth zone is 183 ℃, the tenth zone is 181 ℃, the eleventh zone is 181 ℃, the head is 180 ℃, the main machine rotation speed is 400r/min, and the feeding frequency is 8 r/min;
drying the modified granules at 55 ℃ until the water content is not more than 0.05 percent to obtain dried granules, then adding the dried granules into a single-screw extruder to extrude a plastic melt, and carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain wires, wherein the temperatures of heating sections of the single-screw extruder are set to be 158 ℃ in a first zone, 162 ℃ in a second zone, 166 ℃ in a third zone, 170 ℃ in a fourth zone, 168 ℃ in a fifth zone, 165 ℃ in a sixth zone, the hot water temperature is 50 ℃ and the cold water temperature is 25 ℃.
Example 6
The only difference from example 5 is that the toughening agent is a methyl methacrylate-butyl acrylate core-shell copolymer.
Example 7
The difference from example 5 is only that the toughening agent is an organosilicon modified methyl methacrylate-butyl acrylate core-shell copolymer.
Comparative example 1
The only difference from example 5 is that the toughening agent is a styrene-butadiene-styrene thermoplastic elastomer.
Comparative example 2
The only difference from example 5 is that the toughening agent is ethylene propylene diene monomer.
Comparative example 3
The only difference from example 5 is that the toughening agent is Dow POE 8411.
Comparative example 4
The difference from example 5 is only that the toughening agent is 0.8 parts of hindered phenol antioxidant octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and no phosphite antioxidant.
Comparative example 5
The only difference from example 5 is that the metal powder content is 160 parts.
The wires prepared in examples 1 to 7 and comparative examples 1 to 5 were used to prepare 80mm × 10mm × 4mm test specimens using a MakerBot repeater 2 printer from MakerBot, and the bending properties and unnotched impact properties of the test specimens were measured in accordance with standards ISO178 and ISO179, respectively; further, a notched specimen (type A notch) of 80 mm. times.10 mm. times.4 mm was prepared by printing, and the notched specimen was tested for notched impact properties in accordance with ISO179 standard, with the results shown in Table 1.
TABLE 1 Performance results of the wire and printed samples of examples 1-7 and comparative examples 1-5
The wire rods prepared in the embodiments 1-7 of the invention have good metal effect, good forming, no degradation phenomenon, obvious metal effect of the printed sample and no cracking phenomenon, and the printed sample prepared by the modified polylactic acid wire rod has good toughness and good mechanical property as can be seen from the performance measurement result of the printed sample.
The results of the performance measurements of the printed samples prepared from the wires of examples 5 to 7 and comparative examples 1 to 3 can be seen: compared with the commonly used styrene-butadiene-styrene thermoplastic elastomer, ethylene propylene diene monomer and Dow POE 8411 in the industry as the toughening agent, the soft core-hard shell type core-shell copolymer taking methyl methacrylate as the shell has obvious toughening effect on printed products, greatly improves the embrittlement phenomenon of the polylactic acid materials, particularly the polylactic acid materials added with metal powder, and can effectively resist external force impact or heavy pressure.
It can be seen from the wires prepared in example 5 and comparative example 4 that: the phosphite antioxidant and the hindered phenol antioxidant are selected to be matched for use, so that the degradation of the polylactic acid material during a plurality of short-time high-temperature processing can be synergistically resisted, the polylactic acid is efficiently prevented from being oxidized, and the wire rod is well formed; and the hindered phenol antioxidant is used alone, so that the polylactic acid material is degraded, and the wire extrusion molding effect is poor.
As can be seen from the results of measuring the properties of the printed samples prepared from the wires of example 5 and comparative example 5: excessive metal powder is difficult to disperse in polylactic acid, and the heat conductivity of metal powder makes the polylactic acid base member melt faster when extrusion processing, and the friction between the metal powder produces extra heat and shearing force and also makes polylactic acid have bigger decomposition tendency, and this viscosity and melt strength when all will making the wire rod extrude are low, and stability variation, in addition, too much metal powder also does not benefit to the bonding between printing piece layer and layer, and the final wire rod shaping that makes comparative example 5 is relatively poor, and it is poor to print sample impact strength, has the interlaminar fracture phenomenon.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (9)

1. A preparation method of a modified polylactic acid material with a metal effect for 3D printing is characterized by comprising the following steps:
preparing the following preparation raw materials in parts by weight: 100 parts of polylactic acid, 80-150 parts of metal powder, 1-5 parts of metal pigment, 8-18 parts of toughening agent, 0.5-2 parts of coupling agent, 0.5-1.5 parts of lubricant, 0.2-0.8 part of hindered phenol antioxidant and 0.1-0.5 part of phosphite or thioester antioxidant, wherein the toughening agent is a soft core-hard shell type core-shell copolymer taking methyl methacrylate as a shell; the metal powder is at least one of 400-mesh 800-mesh granular stainless steel powder, copper powder, bronze powder, brass powder and aluminum powder, and the metal pigment is at least one of 500-mesh 700-mesh flaky aluminum powder, copper powder, bronze powder and copper-gold powder;
preparing a coupling agent solution;
mixing metal powder and metal pigment, spraying a coupling agent solution, drying the obtained metal powder and metal pigment with the surface soaked with the coupling agent, and cooling to normal temperature to obtain modified metal powder and metal pigment;
mixing the modified metal powder, the metal pigment, the polylactic acid, the toughening agent, the lubricant and the antioxidant to obtain a premixed raw material;
adding the premixed raw materials into a double-screw extruder, and extruding and granulating to obtain modified granules;
and drying the modified granules to obtain dried granules, adding the dried granules into a single-screw extruder to extrude a plastic melt, and carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain the wire.
2. The preparation method of the modified polylactic acid material with the metal effect for 3D printing according to claim 1, wherein the preparation raw material comprises the following components in parts by weight: 100 parts of polylactic acid, 120 parts of metal powder, 2-3 parts of metal pigment, 10-15 parts of toughening agent, 0.8-1.2 parts of coupling agent, 0.7-1.2 parts of lubricant, 0.3-0.6 part of hindered phenol antioxidant and 0.2-0.4 part of phosphite or thioester antioxidant.
3. The preparation method of the modified polylactic acid material with the metal effect for 3D printing according to claim 1 or2, wherein the soft core-hard shell type core-shell copolymer taking methyl methacrylate as a shell is at least one of a methyl methacrylate-butyl acrylate core-shell copolymer, an organosilicon modified methyl methacrylate-butyl acrylate core-shell copolymer and a methyl methacrylate-butadiene-styrene core-shell copolymer.
4. The preparation method of the modified polylactic acid material with metal effect for 3D printing according to claim 1 or2, wherein the coupling agent is a silane coupling agent or a titanate coupling agent; the general formula of the silane coupling agent is YSiX3X is methoxy or ethoxy, Y contains amino, sulfydryl or epoxy; the titanate coupling agent is at least one of a monoalkoxy titanate coupling agent, a chelating titanate coupling agent and a ligand titanate coupling agent.
5. The method of preparing a modified polylactic acid material for 3D printing having a metal effect according to claim 1 or2, wherein the hindered phenolic antioxidant is octadecyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] or 4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, the phosphite antioxidant is tris [2, 4-di-t-butylphenyl ] phosphite or bis (2, 4-di-t-butylphenol) pentaerythritol diphosphite, and the thioester antioxidant is dioctadecyl thiodipropionate or pentaerythritol (3-n-decylthiopropionate).
6. The method for preparing the modified polylactic acid material with the metal effect for 3D printing according to claim 1 or2, wherein the lubricant is at least one of ethylene bis stearamide, pentaerythritol stearate and polyester hyperbranched resin.
7. The method for preparing the modified polylactic acid material with metal effect for 3D printing according to claim 1 or2,
the method for preparing the modified metal powder and the metal pigment comprises the following steps: stirring and mixing the metal powder and the metal pigment at the speed of 100-400r/min, simultaneously atomizing and spraying the coupling agent solution, continuing stirring for 5-10 minutes after spraying the coupling agent solution, drying the obtained metal powder and the metal pigment with the coupling agent soaked on the surfaces at the temperature of 80-105 ℃ for 2-3 hours, and cooling to the normal temperature;
the mixing method for preparing the premixed raw materials comprises the following steps: stirring and mixing for 10-15 minutes at the speed of 100-400 r/min;
the drying method for preparing the dried granules comprises the following steps: drying at 50-60 deg.C until water content is not more than 0.05%.
8. The preparation method of the modified polylactic acid material with the metal effect for 3D printing as claimed in claim 1 or2, wherein the temperature of each section of the twin-screw extruder is set as follows: the first zone is 160-year-round region at 175 ℃, the second zone is 165-year-round region at 178 ℃, the third zone is 170-year-round region at 185 ℃, the fourth zone is 173-year-round region at 185 ℃, the fifth zone is 175-year-round region at 188 ℃, the sixth zone is 175-year-round region at 188 ℃, the seventh zone is 173-year-round region at 188 ℃, the eighth zone is 173-year-round region at 185 ℃, the ninth zone is 173-year-round region at 185 ℃, the tenth zone is 172-year-round region at 185 ℃, the head is 175-year-round region at 195 ℃, the rotation speed.
9. The method for preparing the modified polylactic acid material with metal effect for 3D printing as claimed in claim 1 or2, wherein the temperature of each heating zone of the single screw extruder is set as 150-.
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