CN108164961B - Preparation method of modified polycarbonate material for 3D printing - Google Patents
Preparation method of modified polycarbonate material for 3D printing Download PDFInfo
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- CN108164961B CN108164961B CN201711463998.9A CN201711463998A CN108164961B CN 108164961 B CN108164961 B CN 108164961B CN 201711463998 A CN201711463998 A CN 201711463998A CN 108164961 B CN108164961 B CN 108164961B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE 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
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Abstract
The invention relates to a preparation method of a modified polycarbonate material for 3D printing, which comprises the following steps: weighing the following raw material components in parts by weight: 100 parts of polycarbonate, 0-10 parts of thermotropic liquid crystal polymer, 10-25 parts of polycaprolactone, 8-15 parts of toughening agent, 0-2 parts of hydrophobic fumed silica, 0.2-0.5 part of hindered phenol antioxidant and 0.2-0.5 part of phosphite antioxidant, mixing the raw materials, adding the mixture into a double-screw extruder to extrude and granulate, drying the granules, adding the dried granules into a single-screw extruder to extrude 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 method is convenient, convenient and economic, and is suitable for mass production, the prepared modified polycarbonate material for 3D printing can be printed and molded at the temperature below 260 ℃, the tensile strength and the notch impact strength are high, thermal degradation is not easy to occur, and the printed product is not warped and has a smooth surface.
Description
Technical Field
The invention relates to a preparation method of a modified polycarbonate material for 3D printing, and belongs to the field 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), automotive, aerospace, dental and medical industries, education, geographic information systems, civil engineering, firearms, and other fields.
The polymer material is the material class with the largest use amount of the 3D printing technology, but the polymer materials most commonly used in the field of 3D printing, such as polylactic acid (PLA), acrylonitrile-butadiene-styrene copolymer (ABS), etc., have many problems, which limit the application of 3D printing in engineering. Specifically, PLA has a good printing effect, but the material is very brittle and often breaks in the 3D printing process, and in addition, the mechanical property and the heat resistance of PLA do not reach the level of real engineering plastics, so that the 3D printing technology is difficult to be pushed to the high-end manufacturing field; the ABS material then releases pungent smell in 3D prints fashioned high temperature to the warpage deformation easily appears in the printing, prints the success rate and hangs down, also is difficult to popularize and use in 3D printing technical field.
The polycarbonate material is an engineering plastic with wide application, has excellent mechanical property, heat resistance and processability, particularly has outstanding impact resistance, and can promote the further practicability of the 3D printing technology. However, the application of polycarbonate materials in 3D printing technology, especially Fused Deposition Modeling (FDM), has the following major problems: (1) the melting temperature of the polycarbonate is higher (240-270 ℃), the viscosity after melting is high, and high processing and printing temperatures are required, while the heating upper limit temperature which can be provided by most FDM type 3D printers at present is 250-260 ℃, and the temperature which is required for the polycarbonate material to keep enough melt flow rate is far more than 260 ℃; (2) the rigid molecular chain of the polycarbonate causes the product to be deformed and cracked due to internal stress, and the product is warped and deformed due to the adhesion problem of the polycarbonate material and the printer forming bottom plate, so that the dimensional accuracy of the product is reduced.
Therefore, there is a need to prepare a modified polycarbonate material so that it can be universally used for the FDM type 3D printing technology and has higher performance and printing effect.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in order to solve the technical problems that the polycarbonate material cannot be printed and molded at the temperature of below 260 ℃ and the printed product of the polycarbonate material is warped and deformed, the preparation method of the modified polycarbonate material 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 polycarbonate material for 3D printing comprises the following steps:
drying the polycarbonate, and then cooling to normal temperature for later use;
the following raw materials were weighed out in parts by weight: 100 parts of polycarbonate, 0-10 parts of thermotropic liquid crystal polymer, 10-25 parts of polycaprolactone, 8-15 parts of toughening agent, 0-2 parts of hydrophobic fumed silica, 0.2-0.5 part of hindered phenol antioxidant and 0.2-0.5 part of phosphite antioxidant, and stirring and mixing the weighed raw material components to obtain a premixed raw material;
adding the premixed raw materials into a double-screw extruder for extrusion granulation 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.
Preferably, the preparation method of the modified polycarbonate material for 3D printing comprises the following components in parts by weight: 100 parts of polycarbonate, 5-10 parts of thermotropic liquid crystal polymer, 12-20 parts of polycaprolactone, 10-12 parts of toughening agent, 1-2 parts of hydrophobic fumed silica, 0.3-0.5 part of hindered phenol antioxidant and 0.3-0.5 part of phosphite antioxidant.
Preferably, the toughening agent is a soft core-shell type core-shell copolymer taking methyl methacrylate as a shell, and is preferably a methyl methacrylate-styrene-butadiene core-shell copolymer or a methyl methacrylate-butyl acrylate core-shell copolymer.
Preferably, the polycarbonate comprises 65-100 wt% of general purpose polycarbonate and 0-35 wt% of optical disc grade polycarbonate, and the polycarbonate comprises 70-80 wt% of general purpose polycarbonate and 20-30 wt% of optical disc grade polycarbonate.
Preferably, the general purpose polycarbonate has a melt index at 300 ℃ and 1.2Kg pressure of not less than 20g/10 min.
Preferably, the thermotropic liquid crystalline polymer has a melting point of 260-280 ℃.
Preferably, the molecular weight of the polycaprolactone is 50000-70000.
Preferably, the hindered phenolic antioxidant is β -octadecyl (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] or 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene.
Preferably, the phosphite antioxidant is tris [2, 4-di-tert-butylphenyl ] phosphite or bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite.
Preferably, the temperatures of the zones of the twin-screw extruder are set as follows: the temperature of the first zone is 195-225 ℃, the temperature of the second zone is 225-240 ℃, the temperature of the third zone is 230-245 ℃, the temperature of the fourth zone is 232-248 ℃, the temperature of the fifth zone is 235-245 ℃, the temperature of the sixth zone is 232-240 ℃, the temperature of the seventh zone is 232-240 ℃, the temperature of the eighth zone is 230-240 ℃, the temperature of the ninth zone is 230-238 ℃, the temperature of the tenth zone is 230-235 ℃, the temperature of the head is 232-238 ℃, the rotation speed of the host is 300-500r/min, and the feeding frequency is 7-15r/min (the feeding frequency is the rotation speed of a screw at the bottom of the feeding hopper, and the material is added to the inlet of the double-screw extruder at a certain;
preferably, the temperatures of the heating sections of the single-screw extruder are set as follows: the first region 210-.
Preferably, the drying method of the polycarbonate comprises the following steps: drying at 100-120 ℃ until the water content is not more than 0.05 percent, wherein the drying method of the modified granules comprises the following steps: drying at 65-85 deg.C until water content is not more than 0.05%.
Preferably, the stirring and mixing method of the raw material components comprises the following steps: stirring and mixing for 10-20 minutes at the speed of 100-600 r/min.
The invention has the beneficial effects that:
the preparation method comprises the steps of mixing polycarbonate, thermotropic liquid crystal polymer, polycaprolactone, toughening agent, hydrophobic fumed silica, hindered phenol antioxidant and phosphite antioxidant in a certain proportion, adding premixed raw materials into a double-screw extruder for extrusion granulation, drying modified granules, adding the dried modified granules into a single-screw extruder for extrusion of plastic melt, and carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain a wire rod, wherein the method is convenient and economic, is suitable for large-batch production, and the prepared modified polycarbonate material for 3D printing can be printed and molded at the temperature of below 260 ℃, has good mechanical properties, high tensile strength and notch impact strength, is not easy to thermally degrade, and a printed product of the modified polycarbonate material can not generate warping deformation and crack and has a smooth and flat surface; the method has the following specific beneficial effects:
(1) the polycaprolactone is added into the polycarbonate, so that the processing temperature of the polycarbonate wire and the printing temperature during 3D printing can be reduced, and the melt flow rate of the modified polycarbonate material is greatly improved; on the other hand, the polycaprolactone can effectively reduce the internal stress of the polycarbonate matrix, improve the interlayer adhesion of the 3D printing supplies, reduce interlayer cracking of each layer caused by shrinkage stress, improve the bonding of the 3D printing product and the printer forming bottom plate, and reduce the warping and cracking of the printing product.
(2) The thermotropic liquid crystal polymer is easy to flow after being melted, and the melt viscosity of the polycarbonate matrix can be reduced by adding the thermotropic liquid crystal polymer, so that the flow rate of the melt is increased, and the processing performance is improved; and the shrinkage rate of the thermotropic liquid crystal polymer is extremely low, and the shrinkage rate of the polycarbonate material can be improved by adding the thermotropic liquid crystal polymer, so that the size of a printed product is more stable.
(3) The added soft-core hard-shell type core-shell copolymer taking methyl methacrylate as a shell is easy to be uniformly dispersed in a polycarbonate/polycaprolactone system by single particles, the toughening effect of the copolymer on a modified polycarbonate material is fully exerted, the impact strength of the polycarbonate/polycaprolactone system is effectively improved, and the hardness and modulus of the polycarbonate/polycaprolactone system are slightly changed due to the existence of hard shell methyl methacrylate.
(4) The mechanical property of the printed product can be effectively improved by adding the hydrophobic fumed silica, and the shrinkage rate of the 3D printed product can be reduced.
(5) Hindered phenol antioxidants and phosphite antioxidants are selected to be matched for use, and the compounded antioxidants complement each other in the aspect of oxidation resistance and can synergistically resist thermal oxidation degradation in high-temperature processing caused by the addition of polycaprolactone.
(6) The polycarbonate of choice preferably includes general purpose polycarbonates and disc grade polycarbonates because disc grade polycarbonates have higher melt flow properties but are not suitable for extrusion, and the use of a proportion of disc grade polycarbonate results in higher melt flow rates and allows the modified polycarbonate material system to be extruded properly.
Detailed Description
The present invention will now be described in further detail.
Example 1
The embodiment provides a preparation method of a modified polycarbonate material for 3D printing, which comprises the following steps:
baking the polycarbonate at 110 ℃ until the water content is not more than 0.05%, and then cooling to normal temperature for later use;
the following raw materials were weighed out in parts by weight: 100 parts of universal polycarbonate, 20 parts of polycaprolactone, 10 parts of a toughening agent, 0.5 part of hindered phenol antioxidant and 0.2 part of phosphite antioxidant, and stirring and mixing the weighed components at the speed of 400r/min for 10 minutes to obtain a premixed raw material; the universal polycarbonate is scientific wound
XT5010, the polycaprolactone is CapaTM6500 the toughening agent is methyl methacrylate-styrene-butadiene core-shell copolymer, the hindered phenol antioxidant is β - (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, and the phosphite antioxidant is tris [2, 4-di-tert-butylphenyl ] propionate]A phosphite ester;
adding the premixed raw materials into a double-screw extruder for extrusion granulation to obtain modified granules, wherein the temperature of each area of the double-screw extruder is sequentially set as follows: 195 ℃ in the first zone, 225 ℃ in the second zone, 230 ℃ in the third zone, 232 ℃ in the fourth zone, 235 ℃ in the fifth zone, 232 ℃ in the sixth zone, 232 ℃ in the seventh zone, 230 ℃ in the eighth zone, 230 ℃ in the ninth zone, 230 ℃ in the tenth zone, 230 ℃ in the eleventh zone, 232 ℃ in the head, 300r/min of the main machine rotation speed and 7r/min of the feeding frequency;
drying the modified granules at 70 ℃ 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, carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain wires, wherein the temperature of each heating interval of the single-screw extruder is set as follows: the first zone is 210 ℃, the second zone is 225 ℃, the third zone is 225 ℃, the fourth zone is 225 ℃, the fifth zone is 222 ℃, the sixth zone is 222 ℃, the temperature of hot water is 60 ℃ and the temperature of cold water is 35 ℃.
Example 2
The embodiment provides a preparation method of a modified polycarbonate material for 3D printing, which comprises the following steps:
baking the polycarbonate at 100 ℃ until the water content is not more than 0.05%, and then cooling to normal temperature for later use;
the following raw materials were weighed out in parts by weight: 100 parts of universal polycarbonate, 10 parts of thermotropic liquid crystal polymer, 25 parts of polycaprolactone, 12 parts of flexibilizer, 2 parts of hydrophobic fumed silica, 0.3 part of hindered phenol antioxidant and 0.2 part of phosphite antioxidant, and stirring and mixing the weighed components at the speed of 100r/min for 20 minutes to obtain a premixed raw material; the universal polycarbonate is Qimei PC-122, and the thermotropic liquid crystal polymer is of Seranian
A950, the polycaprolactone is CapaTM6506 the toughening agent is methyl methacrylate-styrene-butadiene core-shell copolymer, and the hydrophobic fumed silica is selected from Yingchuangtugsai hydrophobic fumed silica
R974, the hindered phenol antioxidant is β - (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, and the phosphite antioxidant is tris [2, 4-di-tert-butylphenyl]A phosphite ester;
adding the premixed raw materials into a double-screw extruder for extrusion granulation to obtain modified granules, wherein the temperature of each area of the double-screw extruder is sequentially set as follows: 195 ℃ in the first zone, 228 ℃ in the second zone, 235 ℃ in the third zone, 236 ℃ in the fourth zone, 235 ℃ in the fifth zone, 232 ℃ in the sixth zone, 232 ℃ in the seventh zone, 232 ℃ in the eighth zone, 230 ℃ in the ninth zone, 230 ℃ in the tenth zone, 230 ℃ in the eleventh zone, 232 ℃ in the head, 450r/min of the main engine speed and 10r/min of the feeding frequency;
drying the modified granules at 65 ℃ until the water content is not more than 0.05 percent to obtain dried granules, adding the dried granules into a single-screw extruder to extrude a plastic melt, carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain wires, wherein the temperature of each heating interval of the single-screw extruder is set as follows: 218 ℃ in the first zone, 228 ℃ in the second zone, 227 ℃ in the third zone, 225 ℃ in the fourth zone, 224 ℃ in the fifth zone, 224 ℃ in the sixth zone, 65 ℃ in the hot water and 40 ℃ in the cold water.
Example 3
The embodiment provides a preparation method of a modified polycarbonate material for 3D printing, which comprises the following steps:
baking the polycarbonate at 120 ℃ until the water content is not more than 0.05 percent, and then cooling to normal temperature for later use;
the following raw materials were weighed out in parts by weight: 80 parts of general polycarbonate, 20 parts of optical disc grade polycarbonate, 5 parts of thermotropic liquid crystal polymer, 15 parts of polycaprolactone, 8 parts of toughening agent, 2 parts of hydrophobic fumed silica, 0.5 part of hindered phenol antioxidant and 0.2 part of phosphite antioxidant, and stirring and mixing the weighed components at the speed of 600r/min for 15 minutes to obtain a premixed raw material; the universal polycarbonate is scientific wound
2405, the optical disk grade polycarbonate is Kostewa CD2005, and the thermotropic liquid crystal polymer is of Seranian
A900, the toughening agent is methyl methacrylate-butyl acrylate core-shell copolymer, and the polycaprolactone is CapaTM6500 the hydrophobic fumed silica is Yingchuangdegussa hydrophobic fumed silica
R972, wherein the hindered phenol antioxidant is tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester, wherein the phosphite antioxidant is bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite;
adding the premixed raw materials into a double-screw extruder for extrusion granulation to obtain modified granules, wherein the temperature of each area of the double-screw extruder is sequentially set as follows: the temperature of the first zone is 205 ℃, the temperature of the second zone is 230 ℃, the temperature of the third zone is 235 ℃, the temperature of the fourth zone is 240 ℃, the temperature of the fifth zone is 237 ℃, the temperature of the sixth zone is 237 ℃, the temperature of the seventh zone is 235 ℃, the temperature of the eighth zone is 235 ℃, the temperature of the ninth zone is 232 ℃, the temperature of the tenth zone is 230 ℃, the temperature of the head is 235 ℃, the rotating speed of the main machine is 500 r/min;
drying the modified granules at 75 ℃ 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, carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain wires, wherein the temperature of each heating interval of the single-screw extruder is set as follows: the temperature of the first zone is 210 ℃, the temperature of the second zone is 225 ℃, the temperature of the third zone is 228 ℃, the temperature of the fourth zone is 232 ℃, the temperature of the fifth zone is 227 ℃, the temperature of the sixth zone is 225 ℃, the temperature of the hot water is 55 ℃ and the temperature of the cold water is 30 ℃.
Example 4
The embodiment provides a preparation method of a modified polycarbonate material for 3D printing, which comprises the following steps:
baking the polycarbonate at 100 ℃ until the water content is not more than 0.05%, and then cooling to normal temperature for later use;
the following raw materials were weighed out in parts by weight: 65 parts of general polycarbonate, 35 parts of optical disc grade polycarbonate, 10 parts of thermotropic liquid crystal polymer, 12 parts of polycaprolactone, 15 parts of toughening agent, 1 part of hydrophobic fumed silica, 0.2 part of hindered phenol antioxidant and 0.5 part of phosphite antioxidant, and stirring and mixing the weighed components at the speed of 300r/min for 15 minutes to obtain a premixed raw material; the universal polycarbonate is Qimei PC-122, the optical disk grade polycarbonate is Qimei PC-175, and the thermotropic liquid crystal polymer is Qimei PC-175
B950, the toughening agent is a methyl methacrylate-butyl acrylate core-shell copolymerThe polycaprolactone is CapaTM6500D, the hydrophobic fumed silica is Yingchuangdegussa hydrophobic fumed silica
R974, wherein the hindered phenol antioxidant is 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, and the phosphite antioxidant is bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite;
adding the premixed raw materials into a double-screw extruder for extrusion granulation to obtain modified granules, wherein the temperature of each area of the double-screw extruder is sequentially set as follows: 225 ℃ in the first zone, 240 ℃ in the second zone, 245 ℃ in the third zone, 248 ℃ in the fourth zone, 245 ℃ in the fifth zone, 240 ℃ in the sixth zone, 240 ℃ in the seventh zone, 240 ℃ in the eighth zone, 238 ℃ in the ninth zone, 235 ℃ in the tenth zone, 235 ℃ in the eleventh zone, 238 ℃ in the head, the rotating speed of a main engine is 400r/min, and the feeding frequency is 9 r/min;
drying the modified granules at 85 ℃ 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, carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain wires, wherein the temperature of each heating interval of the single-screw extruder is set as follows: the temperature of the first zone is 225 ℃, the temperature of the second zone is 235 ℃, the temperature of the third zone is 235 ℃, the temperature of the fourth zone is 232 ℃, the temperature of the fifth zone is 230 ℃, the temperature of the sixth zone is 230 ℃, the temperature of the hot water is 60 ℃ and the temperature of the cold water is 35 ℃.
Example 5
The embodiment provides a preparation method of a modified polycarbonate material for 3D printing, which comprises the following steps:
baking the polycarbonate at 110 ℃ until the water content is not more than 0.05%, and then cooling to normal temperature for later use;
the following raw materials were weighed out in parts by weight: 70 parts of general polycarbonate and 30 parts of optical disk grade polycarbonate; 5 parts of thermotropic liquid crystal polymer, 10 parts of polycaprolactone, 10 parts of flexibilizer, 2 parts of hydrophobic fumed silica, 0.5 part of hindered phenol antioxidant and 0.3 part of phosphite antioxidant, and stirring and mixing the weighed components at the speed of 300r/min for 15 minutes to obtain a premixed raw material; the universal polycarbonate is scientific wound
2407, the optical disk grade polycarbonate is Kostechu DP1-1265, the thermotropic liquid crystal polymer is Jinfa science and technology Vicryst R8000NC001, and the polycaprolactone is CapaTM6500 the toughening agent is methyl methacrylate-styrene-butadiene core-shell copolymer, and the hydrophobic fumed silica is Wacker chemical hydrophobic fumed silica
H20, wherein the hindered phenol antioxidant is β - (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, and the phosphite antioxidant is tris [2, 4-di-tert-butylphenyl ]]A phosphite ester;
adding the premixed raw materials into a double-screw extruder for extrusion granulation to obtain modified granules, wherein the temperature of each area of the double-screw extruder is sequentially set as follows: the first zone is 210 ℃, the second zone is 235 ℃, the third zone is 239 ℃, the fourth zone is 242 ℃, the fifth zone is 238 ℃, the sixth zone is 238 ℃, the seventh zone is 236 ℃, the eighth zone is 236 ℃, the ninth zone is 233 ℃, the tenth zone is 233 ℃, the eleventh zone is 232 ℃, the head is 235 ℃, the rotating speed of the main machine is 400r/min, and the feeding frequency is 10 r/min;
drying the modified granules at 75 ℃ 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, carrying out hot water treatment, cold water cooling and shaping and air drying on the obtained plastic melt to obtain wires, wherein the temperature of each heating interval of the single-screw extruder is set as follows: the temperature of the first zone is 216 ℃, the temperature of the second zone is 228 ℃, the temperature of the third zone is 232 ℃, the temperature of the fourth zone is 232 ℃, the temperature of the fifth zone is 230 ℃, the temperature of the sixth zone is 228 ℃, the temperature of the hot water is 60 ℃ and the temperature of the cold water is 35 ℃.
The wires of examples 1 to 5 were printed on a test piece by an FDM type 3D printer to examine the printing effect and test the performance of the test piece under the conditions that the temperature of a printing nozzle was 250 ℃, the temperature of a base plate was 65 to 80 ℃, three and 190 gloss oil was sprayed on the base plate to increase the adhesion between the base plate and a printed article, the printing speed was 50mm/s, the tensile property of the sample piece was tested by standard ISO527, a type A sample piece in the standard was selected, and the notch impact property of the printed notch test piece was tested by standard ISO179, and the test piece was a notch test piece (type A notch) of 80mm × 10mm × 4mm, and the results are shown in Table 1.
TABLE 1 sample effects and Performance results for wire printing of examples 1-5
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 polycarbonate material for 3D printing is characterized by comprising the following steps:
drying the polycarbonate, and then cooling to normal temperature for later use;
the following raw materials were weighed out in parts by weight: 100 parts of polycarbonate, 5-10 parts of thermotropic liquid crystal polymer, 12-20 parts of polycaprolactone, 10-12 parts of toughening agent, 1-2 parts of hydrophobic fumed silica, 0.3-0.5 part of hindered phenol antioxidant and 0.3-0.5 part of phosphite antioxidant, and stirring and mixing the weighed raw material components to obtain a premixed raw material;
adding the premixed raw materials into a double-screw extruder for extrusion granulation 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 polycarbonate material for 3D printing according to claim 1, wherein the toughening agent is a soft core-hard shell type core-shell copolymer with methyl methacrylate as a shell.
3. The preparation method of the modified polycarbonate material for 3D printing according to claim 1 or 2, wherein the polycarbonate comprises 65-100 wt% of general purpose polycarbonate and 0-35 wt% of optical disc grade polycarbonate.
4. The preparation method of the modified polycarbonate material for 3D printing as claimed in claim 3, wherein the general purpose polycarbonate has a melt index of not less than 20g/10min at 300 ℃ and 1.2Kg pressure, the thermotropic liquid crystal polymer has a melting point of 260-280 ℃, and the polycaprolactone has a molecular weight of 50000-70000.
5. The method for preparing a modified polycarbonate material for 3D printing according to claim 1 or 2, wherein the hindered phenol antioxidant is β octadecyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] or 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, and the phosphite antioxidant is tris [2, 4-di-tert-butylphenyl ] phosphite or bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite.
6. The preparation method of the modified polycarbonate material for 3D printing as claimed in claim 1 or 2, wherein the temperatures of the zones of the twin-screw extruder are sequentially set as follows: the temperature of the first zone is 195-225 ℃, the temperature of the second zone is 225-240 ℃, the temperature of the third zone is 230-245 ℃, the temperature of the fourth zone is 232-248 ℃, the temperature of the fifth zone is 235-245 ℃, the temperature of the sixth zone is 232-240 ℃, the temperature of the seventh zone is 232-240 ℃, the temperature of the eighth zone is 230-240 ℃, the temperature of the ninth zone is 230-238 ℃, the temperature of the tenth zone is 230-235 ℃, the temperature of the eleventh zone is 230-235 ℃, the temperature of the head is 232-238 ℃, the rotation speed of the host is 300-500r/min, and the feeding frequency is 7-.
7. The method for preparing a modified polycarbonate material for 3D printing according to claim 1 or 2, wherein the temperature of each heating zone of the single-screw extruder is set as follows: the first region 210-.
8. The preparation method of the modified polycarbonate material for 3D printing according to claim 1 or 2, wherein the drying method of the polycarbonate comprises the following steps: drying at 100-120 ℃ until the water content is not more than 0.05 percent, wherein the drying method of the modified granules comprises the following steps: drying at 65-85 deg.C until water content is not more than 0.05%.
9. The preparation method of the modified polycarbonate material for 3D printing according to claim 1 or 2, wherein the raw material components are stirred and mixed by the following steps: stirring and mixing for 10-20 minutes at the speed of 100-600 r/min.
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| CN110964302B (en) * | 2018-09-27 | 2022-02-25 | 上海交通大学医学院附属新华医院 | Osteoid 3D printing material and osteoid 3D printing temporal bone model with osteoid structure and neurovascular structure |
| CN109535673B (en) * | 2018-10-22 | 2021-05-25 | 诺思贝瑞新材料科技（苏州）有限公司 | Heat-resistant impact-resistant high-transparency polylactic acid composite material and preparation method thereof |
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