CN110396286B - Low-price excellent 3D printing consumable and preparation method thereof - Google Patents

Low-price excellent 3D printing consumable and preparation method thereof Download PDF

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CN110396286B
CN110396286B CN201910668370.5A CN201910668370A CN110396286B CN 110396286 B CN110396286 B CN 110396286B CN 201910668370 A CN201910668370 A CN 201910668370A CN 110396286 B CN110396286 B CN 110396286B
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pla
tpu
gma
pgu
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CN110396286A (en
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莫羡忠
谭登峰
魏福祥
庞锦英
党延辉
宁世川
梁家能
严镇坤
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Nanning Normal University
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • 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
    • 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
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

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Abstract

The invention discloses a3D printing consumable with excellent low price and a preparation method thereof. The 3D printing consumable provided by the invention comprises the following raw materials in parts by mass: 65-95 parts of polylactic acid (PLA), 5-35 parts of Thermoplastic Polyurethane (TPU), 0.1-30 parts of PLA-based compatibilizer (PGU) and 5-40 parts of thermoplastic starch (TPS). The 3D printing consumable material has the advantages of low cost, environmental protection, energy conservation and excellent performance.

Description

Low-price excellent 3D printing consumable and preparation method thereof
Technical Field
The invention belongs to the technical field of 3D printing consumables, and particularly relates to a3D printing consumable with excellent low price and a preparation method thereof.
Background
The 3D printing technique is also called additive manufacturing, and is a new model manufacturing method in recent times. 3D printing began in the 80's of the last century, and through continuous development and innovation in recent decades, 3D printing technology has become mature and widely applied to various fields. Fused Deposition Modeling (FDM) is one of the important technologies constituting 3D printing technology, and uses thermoplastic wire as the main raw material, and moves along the cross-sectional profile and filling track of a part through a hot melting head, and the molten material is sent to a designated position and is bonded and solidified to finally form a product. The materials used for 3D printing are typically in the form of powders, filament rolls, liquid plastics, etc. Commercially available 3D printing consumables mainly comprise thermoplastic plastics, and mainly comprise non-degradable plastics such as acrylonitrile-butadiene-styrene copolymer (ABS), Polystyrene (PS), nylon (PA), polyvinyl alcohol (PVA), polypropylene (PP) and the like, and degradable plastics such as PLA, PCL and the like. PLA is a high molecular material formed by polymerizing lactic acid generated after fermentation of biomass resources (such as sugarcane, cassava, beet and the like), is green and pollution-free in production process, and can be completely degraded into CO2And H2O, is a green environment-friendly degradable environment-friendly material, and PLA-based 3D printing consumables are also widely applied to FDM technology. Compared with the traditional petroleum-based plastics, the degradable high polymer material PLA is equivalent to the traditional petroleum-based plastics in processing performance and mechanical performance, can replace the use of petroleum-based plastics to a certain extent, and is considered to be the first substitute of the traditional plastic materials in the industry. PLA-based modified 3D printing consumables have become a current focus of research. Chen et al prepared a PLA base wire modified by a chain extender by using a Joncryl ADR 4370S chain extender as a modifier, and the PLA wire for 3D printing was obtained by melt extrusion molding, and the thermal properties, melt strength, mechanical properties and the like of the modified PLA were studied. The results show that: compared with unmodified PLA, the heat resistance, melt strength and mechanical property of PLA modified by adding ADR chain extender are all improved. When the ADR is used in an amount of 0.4%, the modified PLA filament has the best overall printing performance. Tangtongming et al prepared a novel PLA3D printing consumable with excellent thermal stability by improving the synthesis conditions of polylactic acid. Zhang Lanbo et al using melt blendingThe method prepares the TPU toughened PLA3D printing wire and researches the toughening effect of TPU with different contents on PLA and the rheological property of TPU/PLA composite material. The results show that the toughness of the composite material is improved and the rheological property of the composite material is reduced along with the increase of the TPU content in the components, and the rheological property of the composite material is suitable for being used as a3D printing consumable material when the TPU content is 10%. Rafael et al reinforced modified PLA with 60 μm carbon fiber and prepared 3D printing consumables. The results show that the tensile modulus and shear modulus of the PLA composite are increased by 1.25 times and 1.16 times, respectively, when the amount of carbon fiber added is 15%. Respectively using polyethylene glycol (PEG) and poly (butylene succinate) (PBS) as toughening agents and ammonium polyphosphate (APP) as a flame retardant to modify PLA, and preparing the PLA/PEG/APP/LCP toughening flame-retardant system 3D printing consumables. The result shows that the elongation at break of the composite material is increased from 4.2% to 72% by adding 15% of PEG, the limiting oxygen index of the composite material reaches 30.1% after adding 15% of APP, the rheological property of the composite material is obviously improved after adding LCP, and the MFR is improved from 7.01g/10min to 14.09g/10 min. Delphine et al [7 ]]The short bamboo fiber reinforced polylactic acid is used, the mechanical property of the polylactic acid-based 3D printing consumable material reinforced by the short bamboo fiber is studied, and the modulus of the polylactic acid-based printing consumable material reinforced by the short bamboo fiber with the length-diameter ratio of 1:4.1-1:4.7 can be enhanced to 230% of that of pure polylactic acid at most. Panda et al prepared PCL/PLA3D printing supplies with different ratios and found that when PCL: PLA is 70:30, the 3D printing supplies had optimal mechanical properties.
Although the bio-based renewable plastic PLA has various excellent performances, the toughness, the rheological property and the mechanical property of the 3D printing consumable prepared by matching different raw material components with the PLA are greatly influenced, and the toughness, the rheological property, the mechanical property and the like of the 3D printing consumable are hardly influenced by adding one raw material each time. Such as: in the toughening effect experiment of the TPU on the PLA, along with the increase of the content of the TPU in the components, the toughness of the composite material is improved while the rheological property of the composite material is reduced, and when the content of the TPU is 10%, the rheological property of the composite material is suitable for being used as a3D printing consumable, but the PLA and the TPU have the problems of poor compatibility and dispersibility, so that the thermal expansion ratio is high, and the comprehensive performance of the 3D printing consumable is influenced.
Thus, although bio-based renewable plastic PLA has a number of excellent properties, low toughness, high price are major drawbacks that limit its further applications. In applying PLA to 3D printing consumables, how to reduce the raw materials cost of preparation 3D printing consumables, can also possess good toughness, rheology nature, melt strength and the good 3D printing consumables of lower thermal expansion ratio, become the problem that needs to solve urgently.
Disclosure of Invention
Aiming at the technical problems, the invention provides a3D printing consumable with excellent performance, which can reduce cost, is environment-friendly and energy-saving, and has good toughness, rheological property and melt strength, low thermal expansion ratio and good surface performance.
The invention provides a3D printing consumable which is prepared from the following raw materials in parts by mass: 65-95 parts of polylactic acid (PLA), 5-35 parts of Thermoplastic Polyurethane (TPU), 0.1-30 parts of PLA-based compatibilizer (PGU) and 5-40 parts of thermoplastic starch (TPS).
Preferably, the thermoplastic starch (TPS) comprises 10-50 parts by mass of glycerol and 50-90 parts by mass of tapioca starch, and is prepared by mixing the glycerol and the tapioca starch for 5-15min by a high-speed mixer, swelling, taking out and standing for 15-30 h.
Preferably, the PLA-based compatibilizer (PGU) comprises the following raw materials in parts by mass: 65-97 parts of dried polylactic acid (PLA), 5-40 parts of Thermoplastic Polyurethane (TPU), 2-35 parts of Glycidyl Methacrylate (GMA) and 0.1-1.0 wt% of dicumyl peroxide (DCP)0.1-2.0 parts; and is prepared by the following preparation steps:
step one, firstly, 65-97 parts of dried polylactic acid (PLA) is firstly densified in an internal mixer at 180 ℃ for 2-10min at 50rpm, then 0.1-2.0 parts of dicumyl peroxide (DCP) are added, the reaction is continued for 2-15min, then 2-35 parts of Glycidyl Methacrylate (GMA) are added, the material is taken out after the reaction is carried out for 3-10min, and the PLA-g-GMA is prepared by washing, drying and crushing;
and step two, adding 2-35 parts of Glycidyl Methacrylate (GMA) into PLA-g-GMA in an internal mixer at 180 ℃ at 50rpm, continuously compacting for 3-10min, adding 5-40 parts of Thermoplastic Polyurethane (TPU), continuously reacting for 4-12min to enable the TPU to completely replace the GMA, taking out the materials, washing, drying and crushing to obtain a PLA-g-TPU copolymer, namely the PLA-based compatibilizer (PGU).
The invention also provides a preparation method of the 3D printing consumable, which comprises the following steps: adding 65-95 parts of dried polylactic acid (PLA), 5-35 parts of Thermoplastic Polyurethane (TPU), 0.1-30 parts of PLA-based compatibilizer (PGU) and 5-40 parts of thermoplastic starch (TPS) into a high-speed mixer, mixing for 5-10 min, adding the mixed materials into a double-screw extruder, wherein the temperature of each zone of the extruder is 190 ℃ at the highest temperature and 170 ℃ at the lowest temperature, and carrying out melt blending, extrusion, granulation, drying and bagging to obtain the 3D printing consumable.
The invention at least comprises the following beneficial effects:
according to the invention, the cassava starch which is low in price, wide in source and capable of being fully biodegraded is added to be thermoplastic starch (TPS), polylactic acid (PLA), Thermoplastic Polyurethane (TPU) and PLA-based compatibilizer (PGU), and the 3D printing consumable prepared by mixing the TPS, the PLA, the TPU and the PGU is low in cost, energy-saving, environment-friendly and capable of accelerating the degradation rate of the PLA/TPS composite material. Under the action of PLA-based compatibilizer (PGU), the compatibility of PLA phase and TPU phase in the composite material is improved, the toughness and the elongation at break of the composite material can be effectively improved, a certain amount of thermoplastic starch (TPS) is added, good rheological property, toughness and melt strength can still be kept, the thermal expansion ratio is low, the surface performance is good, the melting temperature is reduced, and the later-stage 3D printing temperature control is utilized.
Drawings
FIG. 1 is an infrared spectrum of PLA/PGU/TPU after dissolution in tetrahydrofuran solution;
FIG. 2 is a stress versus strain graph of PLA, PLA10, and PLA 20;
FIG. 3 is a bar graph of notched impact strength for PLA, PLA10 and PLA 20;
FIG. 4 is a DSC temperature rise profile for PLA, PLA10 and PLA 20;
FIG. 5 is a graph of the effect of making a standard wire of PLA10 and PLA 20;
fig. 6 is a diagram of the effect of the printed finished products of PLA10 and PLA 20.
Detailed Description
The present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It is to be noted that the experimental methods described in the following embodiments are all conventional methods unless otherwise specified, and the reagents and materials are commercially available unless otherwise specified.
Example 1
The 3D printing consumable provided by the invention comprises the following raw materials in parts by mass: 65 parts of polylactic acid (PLA), 5 parts of Thermoplastic Polyurethane (TPU), 0.1 part of PLA-based compatibilizer (PGU) and 5 parts of thermoplastic starch (TPS).
The 3D printing consumable with excellent low price is prepared by the following method, and the method adopts the raw materials in parts by mass and comprises the following steps:
adding 65 parts of dried polylactic acid (PLA), 5 parts of Thermoplastic Polyurethane (TPU), 0.1 part of PLA-based compatibilizer (PGU) and 5 parts of thermoplastic starch (TPS) into a high-speed mixer, mixing for 5min, adding the mixed materials into a double-screw extruder, wherein the temperature of each zone of the extruder is 190 ℃ at the highest temperature and 170 ℃ at the lowest temperature, and carrying out melt blending, extrusion, granulation, drying and bagging to obtain the 3D printing consumable.
The thermoplastic starch (TPS) comprises 10 parts by mass of glycerol and 50 parts by mass of cassava starch, and the glycerol and the cassava starch are mixed for 5min by a high-speed mixer, swelled, taken out and placed for 15h to obtain the thermoplastic starch.
The PLA-based compatibilizer (PGU) comprises the following raw materials in parts by mass: 65 parts of dried polylactic acid (PLA), 5 parts of Thermoplastic Polyurethane (TPU), 2 parts of Glycidyl Methacrylate (GMA) and 0.1 part of dicumyl peroxide (DCP); and is prepared by the following preparation steps:
firstly, 65 parts of dried polylactic acid (PLA) are firstly densified in an internal mixer at 180 ℃ at 50rpm for 2min, then 0.1 part of dicumyl peroxide (DCP) is added, the reaction is continued for 2min, then 2 parts of Glycidyl Methacrylate (GMA) are added, the material is taken out after the reaction is carried out for 3min, and the PLA-g-GMA is prepared by washing, drying and crushing;
and step two, continuously compacting PLA-g-GMA for 3min at 50rpm in an internal mixer at 180 ℃, adding 5 parts of Thermoplastic Polyurethane (TPU), continuously reacting for 4min to enable the TPU to completely replace the GMA, taking out the material, washing, drying and crushing to obtain a PLA-g-TPU copolymer, namely the PLA-based compatibilizer (PGU).
Example 2
The 3D printing consumable with low price and excellent performance is prepared by the following method:
step one, after 97 parts of dried polylactic acid (PLA) is firstly densified in an internal mixer at 180 ℃ and 50rpm for 10min, 2.0 parts of dicumyl peroxide (DCP) is added, the reaction is continued for 15min, 35 parts of Glycidyl Methacrylate (GMA) are added, the material is taken out after the reaction is carried out for 10min, and the PLA-g-GMA is prepared by washing, drying and crushing;
step two, continuously compacting PLA-g-GMA for 10min at 50rpm in an internal mixer at 180 ℃, adding 40 parts of Thermoplastic Polyurethane (TPU), continuously reacting for 12min to enable the TPU to thoroughly replace the GMA, taking out the material, washing, drying and crushing to obtain a PLA-g-TPU copolymer, namely a PLA-based compatibilizer (PGU);
mixing 50 parts by mass of glycerol and 90 parts by mass of cassava starch for 15min by using a high-speed mixer, swelling, taking out, and standing for 15-30h to obtain thermoplastic starch (TPS);
and step four, adding 95 parts of dried polylactic acid (PLA), 35 parts of Thermoplastic Polyurethane (TPU), 30 parts of PLA-based compatibilizer (PGU) and 40 parts of thermoplastic starch (TPS) into a high-speed mixer, mixing for 10min, adding the mixed materials into a double-screw extruder, wherein the highest temperature of each zone of the extruder is 190 ℃ and the lowest temperature is 170 ℃, and carrying out melt blending extrusion, granulation, drying and bagging to obtain the 3D printing consumable.
Example 3
The 3D printing consumable with low price and excellent performance is prepared by the following method:
firstly, 70 parts of dried polylactic acid (PLA) are firstly densified in an internal mixer at 180 ℃ for 5min at 50rpm, 1 part of dicumyl peroxide (DCP) is added, the reaction is continued for 10min, 15 parts of Glycidyl Methacrylate (GMA) are added, the material is taken out after the reaction is carried out for 8min, and the PLA-g-GMA is prepared by washing, drying and crushing;
secondly, continuously compacting PLA-g-GMA for 5min at 50rpm in an internal mixer at 180 ℃, adding 5-40 parts of Thermoplastic Polyurethane (TPU), continuously reacting for 5min to enable the TPU to thoroughly replace the GMA, taking out the material, washing, drying and crushing to obtain a PLA-g-TPU copolymer, namely a PLA-based compatibilizer (PGU);
mixing 20 parts by mass of glycerol and 60 parts by mass of cassava starch for 10min by using a high-speed mixer, swelling, taking out, and standing for 15-30h to obtain thermoplastic starch (TPS);
and step four, adding 70 parts of dried polylactic acid (PLA), 10 parts of Thermoplastic Polyurethane (TPU), 10 parts of PLA-based compatibilizer (PGU) and 30 parts of thermoplastic starch (TPS) into a high-speed mixer, mixing for 10min, adding the mixed materials into a double-screw extruder, wherein the highest temperature of each zone of the extruder is 190 ℃ and the lowest temperature is 170 ℃, and carrying out melt blending extrusion, granulation, drying and bagging to obtain the 3D printing consumable.
Example 4
The 3D printing consumable with low price and excellent performance is prepared by the following method:
firstly, 80 parts of PLA is firstly densified in an internal mixer at 180 ℃ and 50rpm for 5min, 1 part of DCP is added, the reaction is continued for 10min, 20 parts of GMA are added, the material is taken out after the reaction is carried out for 5min, and the PLA-g-GMA is prepared by washing, drying and crushing;
secondly, on the basis of the first step, continuously compacting PLA-g-GMA for 5min at 50rpm in an internal mixer at 180 ℃, adding 30 parts of TPU, continuously reacting for 10min to enable the TPU to thoroughly replace the GMA, taking out the material, washing, drying and crushing to obtain a PLA-g-TPU copolymer, namely a PLA-based compatibilizer (PGU);
step three, mixing 40 parts by mass of glycerin and 80 parts by mass of cassava starch for 10min by a high-speed mixer, swelling, taking out, and standing for 20h to obtain thermoplastic starch (TPS);
and step four, adding 70 parts of dried polylactic acid (PLA), 20 parts of Thermoplastic Polyurethane (TPU), 15 parts of PLA-based compatibilizer (PGU) and 35 parts of thermoplastic starch (TPS) into a high-speed mixer, mixing for 10min, adding the mixed materials into a double-screw extruder, wherein the highest temperature of each zone of the extruder is 190 ℃ and the lowest temperature is 170 ℃, and carrying out melt blending extrusion, granulation, drying and bagging to obtain the 3D printing consumable.
Example 5
The 3D printing consumable with low price and excellent performance is prepared by the following method:
firstly, 80 parts of PLA is firstly densified in an internal mixer at 180 ℃ and 50rpm for 5min, 1 part of DCP is added, the reaction is continued for 10min, 20 parts of GMA are added, the material is taken out after the reaction is carried out for 5min, and the PLA-g-GMA is prepared by washing, drying and crushing;
secondly, on the basis of the first step, continuously compacting PLA-g-GMA for 5min at 50rpm in an internal mixer at 180 ℃, adding 30 parts of TPU, continuously reacting for 10min to enable the TPU to thoroughly replace the GMA, taking out the material, washing, drying and crushing to obtain a PLA-g-TPU copolymer, namely a PLA-based compatibilizer (PGU);
mixing 20 parts by mass of glycerol and 90 parts by mass of cassava starch for 10min by using a high-speed mixer, swelling, taking out, and standing for 24h to obtain thermoplastic starch (TPS);
and step four, adding 80 parts of dried PLA, 20 parts of TPU, 10 parts of PGU and 10 parts of TPS into a high-speed mixer, mixing for 5min, adding the mixed materials into a double-screw extruder, melting, blending, extruding, granulating, drying and bagging to obtain the 3D printing consumable material, wherein the highest temperature of each zone of the extruder is 190 ℃ and the lowest temperature of each zone of the extruder is 170 ℃.
Example 6
The 3D printing consumable with low price and excellent performance is prepared by the following method:
firstly, 80 parts of PLA is firstly densified in an internal mixer at 180 ℃ and 50rpm for 5min, 1 part of DCP is added, the reaction is continued for 10min, 20 parts of GMA are added, the material is taken out after the reaction is carried out for 5min, and the PLA-g-GMA is prepared by washing, drying and crushing;
secondly, on the basis of the first step, continuously compacting PLA-g-GMA for 5min at 50rpm in an internal mixer at 180 ℃, adding 30 parts of TPU, continuously reacting for 10min to enable the TPU to thoroughly replace the GMA, taking out the material, washing, drying and crushing to obtain a PLA-g-TPU copolymer, namely a PLA-based compatibilizer (PGU);
mixing 20 parts by mass of glycerol and 90 parts by mass of cassava starch for 10min by using a high-speed mixer, swelling, taking out, and standing for 24h to obtain thermoplastic starch (TPS);
and step four, adding 80 parts of dried PLA, 20 parts of TPU, 10 parts of PGU and 20 parts of TPS into a high-speed mixer, mixing for 5min, adding the mixed materials into a double-screw extruder, melting, blending, extruding, granulating, drying and bagging to obtain the 3D printing consumable material, wherein the highest temperature of each zone of the extruder is 190 ℃ and the lowest temperature of each zone of the extruder is 170 ℃.
Test example:
composite PLA10 was prepared by example 5.
Composite PLA20 was prepared by example 6.
The PLA material is a pure polylactic acid PLA material, the preparation method is the same as the steps of the example 5, and the only difference is that no TPU, PGU and TPS are added, and the preparation method specifically comprises the following steps: adding PLA into a high-speed mixer, mixing for 5min, adding the mixed materials into a double-screw extruder, wherein the temperature of each zone of the extruder is 190 ℃ at the highest temperature and 170 ℃ at the lowest temperature, and performing melt blending extrusion, granulation, drying and bagging to obtain the pure PLA material.
The preparation method of the composite material PLA/PGU/TPU10 specifically comprises the following steps:
firstly, 80 parts of PLA is firstly densified in an internal mixer at 180 ℃ and 50rpm for 5min, 1 part of DCP is added, the reaction is continued for 10min, 20 parts of GMA are added, the material is taken out after the reaction is carried out for 5min, and the PLA-g-GMA is prepared by washing, drying and crushing;
secondly, on the basis of the first step, continuously compacting PLA-g-GMA for 5min at 50rpm in an internal mixer at 180 ℃, adding 30 parts of TPU, continuously reacting for 10min to enable the TPU to thoroughly replace the GMA, taking out the material, washing, drying and crushing to obtain a PLA-g-TPU copolymer, namely a PLA-based compatibilizer (PGU);
and step three, adding 80 parts of dried PLA, 10 parts of TPU and 10 parts of PGU into a high-speed mixer, mixing for 5min, adding the mixed materials into a double-screw extruder, wherein the highest temperature of each zone of the extruder is 190 ℃ and the lowest temperature of each zone of the extruder is 170 ℃, and carrying out melt blending extrusion, granulation, drying and bagging to obtain the composite material PLA/PGU/TPU 10.
The preparation steps of the composite material PLA/PGU/TPU 20 and the composite material PLA/PGU/TPU10 are the same, and the only difference is that the added amount of the TPU is different and is 20 parts.
The preparation steps of the composite material PLA/PGU/TPU30 and the composite material PLA/PGU/TPU10 are the same, and the only difference is that the added amount of the TPU is different and is 30 parts.
Test example 1
The results of earlier studies show that the tetrahydrofuran solution at 50 ℃ has a better dissolving capacity for pure TPU. And the pure TPU is 3695cm-1、3336cm-1、1731cm-1、1415cm-1There are distinct characteristic peaks, which are characteristic peaks of OH radicals, NH, C ═ O, CN and other groups in TPU. After PLA/PGU/TPU10, PLA/PGU/TPU 20 and PLA/PGU/TPU30 were dissolved in tetrahydrofuran solution, the IR spectra were measured and shown in FIG. 1, where the right box in FIG. 1 is 1415cm-1 to extract an enlarged portion. From FIG. 1 it can be seen that the three components PLA/PGU/TPU10, PLA/PGU/TPU10 and PLA/PGU/TPU30 were all found to represent characteristic peaks at 3336cm-1, 1415cm-1 for NH, CN in the TPU, indicating that the TPU had been successfully grafted onto the PLA/GMA. The structure of PLA-g-TPU was further demonstrated.
Test example 2
Pure polylactic acid PLA material, composite material PLA10, composite material PLA20 were respectively subjected to tensile experiments, and the stress-strain curves obtained are shown in FIG. 2. As can be seen from fig. 2, pure PLA has no yield point and exhibits brittle fracture. When the TPS is added to 10 parts, the mechanical property is kept excellent, the elongation at break can reach 10% -35%, and the performance requirement of the 3D printing consumables is met. When 20 parts of TPS is added, the elongation at break is reduced almost as same as that of pure PLA, but the 3D printing consumable material needs to have certain toughness and elongation at break, so the adding amount of TPS is limited, the optimal elongation at break is about 10 parts of TPS, and the cost is reduced by adding TPS, and meanwhile, the excellent performance of the 3D printing consumable material can be still maintained.
Test example 3
The results of notch impact strength tests on materials of PLA, PLA10 and PLA20 are shown in FIG. 3, and the results in FIG. 3 show that the impact strength increases with the increase of TPS, the brittleness of PLA can be improved by adding TPS, and the 3D printing consumables of PLA10 and PLA20 prepared by the invention have high impact strength, low brittleness and excellent performance.
Test example 4
The DSC temperature rise test was performed on the PLA, PLA10, and PLA20 materials, respectively, and the test results are shown in fig. 4, and it can be seen from the results in fig. 4 that the melting temperature of PLA is 174 ℃, the melting temperature of the PLA-based composite material after TPS addition is reduced, the melting temperatures of PLA10 and PLA20 are 168 ℃ and 164 ℃, respectively, and the temperature control of the later 3D printing is used. Because the printing temperature is a key factor in the later 3D printing, the printing temperature must be above the melting temperature and below the decomposition temperature, the melting temperature can be reduced by adding the TPS, namely, the temperature can be set to be lower than that of pure PLA in the later 3D printing, and the energy consumption can be saved.
Test example 5
The materials of PLA10 and PLA20 were subjected to standard wire preparation tests, respectively, fig. 5(a) is a graph of the effect of wires made of PLA10 material, and fig. 5(b) is a graph of the effect of wires made of PLA20 material. The diameter of the wire rod needs to be controlled to be kept within the range of 1.75mm +/-0.15 mm in the preparation process of the standard wire rod, and the surface of the wire rod is required to be smooth and uniform. The wire rod is extruded by a single screw extruder (or a double screw extruder), and then is wound into a coiled material by a coiled material device after being subjected to water cooling and diameter measurement. Therefore, there is a need for certain toughness, rheology and melt strength as a base material for 3D wire. As can be seen from the figure, both PLA10 and PLA20 components can be used in the preparation of 3D printing consumables for extrusion into a roll. The 3D printed wires after the addition of 10 and 20 parts of TPS still maintained a relatively uniform diameter, and it can be seen from fig. 5(a) and 5(b) that the 3D printed wires of PLA10 and PLA20 all printed samples with relatively smooth and uniform surfaces.
To further explore the accuracy of the 3D printed wire, 4 points were randomly selected on the 3D printed wire made of PLA20, the diameter of the selected point was measured using a vernier caliper and compared to the diameter standard set by the 3D printing consumables tester, the thermal expansion ratio was low, and the results are shown in table 1.
TABLE 13D comparison of diameter of randomly selected points of printed wire to set standard diameter
Figure RE-GDA0002203043670000121
Test example 6
Respectively performing finished product printing tests on the materials of PLA10 and PLA20, drawing a model of a table by using 3D One3 dimensional drawing software, then digitally slicing the drawn 3 dimensional model by using the same-creation three-dimensional digital slicing software, setting printing parameters, and finally printing the models with different sizes, for example, fig. 6 (a) is an effect diagram of printing the finished product by using the PLA10 material, and fig. 6(b) is an effect diagram of printing the finished product by using the PLA20 material. As is apparent from the printing effect of FIG. 6, the product printed by the 3D printing consumable material of the present invention is smooth, has no warpage, and has good printing effect, and the 3D printing consumable material of the present invention has excellent performance.
Test examples 5 and 6 were studied from the wire feeding condition of the printed wire and the surface properties of the printed sample. The printing consumables of each component do not find the conditions of material leakage and filament blockage in the printing process, which shows that the PLA-based printing consumables of each component meet the basic requirement on the rheological property of the wire in the 3D printing process. In addition, no warpage was found on the surface of the printed sample of each component.
In conclusion of test experiments, the 3D printing consumable material has the advantages of low cost, environmental protection, energy conservation and excellent performance.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.

Claims (2)

1. The 3D printing consumable is characterized by comprising the following raw materials in parts by mass: 65-95 parts of polylactic acid (PLA), 5-35 parts of Thermoplastic Polyurethane (TPU), 0.1-30 parts of PLA-based compatibilizer (PGU) and 5-40 parts of thermoplastic starch (TPS);
wherein the thermoplastic starch (TPS) comprises 10-50 parts by mass of glycerol and 50-90 parts by mass of tapioca starch, and is prepared by mixing the glycerol and the tapioca starch for 5-15min by a high-speed mixer, swelling, taking out and standing for 15-30 h;
the PLA-based compatibilizer (PGU) comprises the following raw materials in parts by mass: 65-97 parts of dried polylactic acid (PLA), 5-40 parts of Thermoplastic Polyurethane (TPU), 2-35 parts of Glycidyl Methacrylate (GMA) and 0.1-2.0 parts of dicumyl peroxide (DCP); and is prepared by the following preparation steps:
step one, firstly, 65-97 parts of dried polylactic acid (PLA) is firstly densified in an internal mixer at 180 ℃ for 2-10min at 50rpm, then 0.1-2.0 parts of dicumyl peroxide (DCP) are added, the reaction is continued for 2-15min, then 2-35 parts of Glycidyl Methacrylate (GMA) are added, the material is taken out after the reaction is carried out for 3-10min, and the PLA-g-GMA is prepared by washing, drying and crushing;
and step two, continuously compacting PLA-g-GMA for 3-10min at 50rpm in an internal mixer at 180 ℃, adding 5-40 parts of Thermoplastic Polyurethane (TPU), continuously reacting for 4-12min to enable the Thermoplastic Polyurethane (TPU) to completely replace Glycidyl Methacrylate (GMA), taking out the materials, washing, drying and crushing to obtain a PLA-g-TPU copolymer, namely the PLA-based compatibilizer (PGU).
2. The preparation method of the 3D printing consumable material according to claim 1, characterized by adding 65-95 parts of dried polylactic acid (PLA), 5-35 parts of Thermoplastic Polyurethane (TPU), 0.1-30 parts of PLA-based compatibilizer (PGU) and 5-40 parts of thermoplastic starch (TPS) into a high-speed mixer for mixing for 5-10 min, adding the mixed materials into a double-screw extruder, wherein the temperature of each zone of the extruder is 190 ℃ at the highest temperature and 170 ℃ at the lowest temperature, and carrying out melt blending extrusion, granulation, drying and bagging to obtain the 3D printing consumable material.
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