CN116238128A - Method for preparing 3D printing wire based on chain segment sequence structure regulation and control - Google Patents

Method for preparing 3D printing wire based on chain segment sequence structure regulation and control Download PDF

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CN116238128A
CN116238128A CN202310194996.3A CN202310194996A CN116238128A CN 116238128 A CN116238128 A CN 116238128A CN 202310194996 A CN202310194996 A CN 202310194996A CN 116238128 A CN116238128 A CN 116238128A
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polylactic acid
wire
printing
copolymer
caprolactone
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潘鹏举
潘咏葳
余承涛
郑映
胡海波
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HUAFON GROUP CO LTD
Zhejiang University ZJU
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HUAFON GROUP CO LTD
Zhejiang University ZJU
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05—Filamentary, e.g. strands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a 3D printing technology, and aims to provide a method for preparing a 3D printing wire based on regulation and control of a chain segment sequence structure. The method comprises the steps of uniformly mixing polylactic acid and a polylactic acid copolymer with a specific chain segment sequence structure, and then carrying out melt extrusion granulation and melt extrusion drafting shaping to obtain a polylactic acid-based 3D printing wire; the polylactic acid copolymer with a specific chain segment sequence structure refers to a polylactic acid-polycaprolactone-polylactic acid triblock copolymer or a poly (lactic acid-co-caprolactone) random copolymer formed by ring-opening copolymerization of lactide and caprolactone. The polylactic acid copolymer with a specific chain segment sequence structure in the product can keep the fusion property among different components, realize the adjustment of the strength and toughness of the printing wire, improve the toughness and interlayer binding force of the wire, and remarkably improve the printing efficiency. The preparation process is simple and easy to operate, and can realize large-scale industrial production.

Description

Method for preparing 3D printing wire based on chain segment sequence structure regulation and control
Technical Field
The invention relates to a 3D printing technology, in particular to a method for preparing a 3D printing wire based on regulation and control of a chain segment sequence structure.
Background
The 3D printing technology is a rapid prototyping technology developed in recent years, and is based on digital model files, and uses powdery metal or plastic and other bondable materials to construct objects in a layer-by-layer printing mode. The 3D printing technology can be applied to various fields such as aerospace, medical, industrial design, automobile manufacturing, etc. The Fused Deposition Modeling (FDM) technology is the most commonly applied 3D printing technology at present, has high product performance, no pollution and simple and flexible operation, and is suitable for use and design creation in families and offices.
Currently, in the field of degradable FDM materials, more than 95% of the materials used are polylactic acid. Polylactic acid is a common biodegradable plastic, has good degradability and biocompatibility, and can replace part of common plastics to be used in the fields of agriculture, packaging materials, clothing and the like. However, polylactic acid has many disadvantages for 3D printing materials, such as brittleness, low interlayer bonding force, and poor impact resistance. In order to improve the mechanical and heat resistance of polylactic acid and maintain the degradability of the material, researchers have carried out physical blending modification on the polylactic acid by adding natural fillers (such as natural fibers, chitosan, starch and the like). As patent application CN105295106A reports a method for preparing a 3D printing wire by compounding cellulose microfiber with modified polylactic acid, the mechanical property of the material is improved while the cost is reduced; patent application CN108822511a also reports that after alkali treatment and polyethylene oxide coating of cellulose nanocrystals, the cellulose nanocrystals are used as a modifier to improve the mechanical properties and thermal stability of polylactic acid-based 3D printing wires. Although the method improves the mechanical properties of the polylactic acid to a certain extent, the method does notThe interlayer bonding force of the printing device can be effectively improved. This is due to the FDM printing process being layer-by-layer extrusion build-up, the underlying plastic filaments being cooled over a period of time, the surface temperature may have been cooled to the glass transition temperature (T g ) The chain segment movement is stopped, the plastic wire just extruded from the upper layer is required to be transferred to the lower layer, and the surface temperature of the lower layer is heated to T again g The chain segment movement can be induced, and the chain segments on the upper layer and the lower layer are entangled together, so that a certain bonding strength is obtained after cooling. For wires generally containing fillers or fibers, the larger the filling rate, the smaller the area of the polymer contacts between the extruded filaments, and the fibers also prevent the movement of the polylactic acid chain segments, so that the bonding force between the layers of the PLA wires modified by common fibers is far lower than that of pure resin without the fillers or fibers.
In addition, the printing speed of the currently reported polylactic acid-based 3D printing wire is low, generally not more than 50mm/s, and the printing efficiency is low because a long time is required for printing a large model. If the printing speed of the common polylactic acid 3D printing wire rod is further improved to 250mm/s, the wire rod is easy to break and draw in the printing process, and the precision of a printing device is greatly reduced.
Therefore, the polylactic acid base material capable of being subjected to ultra-fast 3D printing is designed and developed, and the requirements of practical application are met.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a method for preparing a 3D printing wire based on regulation and control of a chain segment sequence structure.
In order to solve the technical problems, the invention adopts the following solutions:
the method for preparing the 3D printing wire based on the regulation and control of the chain segment sequence structure comprises the steps of uniformly mixing polylactic acid and a polylactic acid copolymer with a specific chain segment sequence structure, and then carrying out melt extrusion granulation and melt extrusion drawing shaping to obtain the polylactic acid-based 3D printing wire; the polylactic acid copolymer with a specific segment sequence structure refers to a polylactic acid-polycaprolactone-polylactic acid triblock copolymer (PLA-b-PCL-b-PLA) or a polylactic acid-co-caprolactone random copolymer (PLCL) which is formed by ring-opening copolymerization of lactide and caprolactone; in the polylactic acid copolymer, the mass fraction of lactide units is 80-95%, and the mass fraction of caprolactone units is 5-20%; the mass ratio of the polylactic acid to the polylactic acid copolymer is 80-95:5-20.
In a preferred embodiment of the present invention, in the poly (lactic acid-co-caprolactone) random copolymer (PLCL), the average segment length of the lactide unit (LLLL) is 5 to 20, and the average segment length of the caprolactone unit (CCCC) is 1 to 2.
As a preferred embodiment of the present invention, the method specifically comprises the steps of:
(1) Respectively weighing polylactic acid and polylactic acid copolymer according to the parts by mass, and uniformly mixing after drying treatment to obtain a blending raw material;
(2) Adding the mixed raw materials into a double-screw extruder, and obtaining a wire master batch through melt plasticization, extrusion and granulation;
(3) And adding the wire master batch into a single screw extruder, and obtaining the 3D printing wire with the wire diameter of 1.75mm plus or minus 0.05mm through melt plasticization, drafting shaping and wire winding.
As a preferable scheme of the invention, the working temperature of the double-screw extruder and the single-screw extruder is 180-230 ℃.
As a preferable scheme of the invention, any one or more of the following auxiliary materials or auxiliary agents are further mixed into the mixed raw materials or wire master batch: chain extenders, nucleating agents, plasticizers, antioxidants, anti-hydrolysis agents and pigments.
Description of the inventive principles:
when using a common polylactic acid-based 3D printing wire, the printing speed is generally not more than 50mm/s, and is not suitable for ultra-fast printing (printing speed is more than 250 mm/s), for the following reasons: (1) Because the FDM printing process is extrusion stacking layer by layer, the printing speed is accelerated, so that the curing time between stacking layers is shortened, and the corner of the model is easy to draw, so that the surface of the model is rough and is not attractive; (2) Because 3D prints and need adopt extrusion wheel clamp wire rod to send into the heating bush with it and melt, improve the wire rod consumption that printing rate can increase in the unit time, lead to extrusion wheel's conveying speed to increase for the wire rod is fragile to take place when receiving extrusion wheel's pulling, increases broken string probability.
Compared with the prior art that natural fillers (such as natural fibers, chitosan, starch and the like) or modifiers (such as cellulose nanocrystals are subjected to alkali treatment and polyethylene oxide coating) are used, the applicant changes the development thought and puts forward a brand new solution, adopts modified components with homology with polylactic acid which is a main raw material component of the printing wire to maintain the fusibility between different components, and simultaneously realizes the regulation and control of the strength and toughness of the printing wire.
The high molecular polylactic acid copolymer used as the modified component has a specific chain segment sequence structure and can obviously influence the T of the material g And mechanical properties. The concrete explanation is as follows:
in the polylactic acid triblock copolymer PLA-b-PCL-b-PLA, polycaprolactone is integrally embedded in the polylactic acid chain segment, and the polycaprolactone has lower melting point and T g Acting as a flexible chain segment, so that the motion capability of the polylactic acid chain segments at two ends of polycaprolactone is enhanced, and the toughness of the material is improved, and meanwhile, the T of the block copolymer is also realized g Reducing, prolonging the curing time and improving the interlayer binding force. Likewise, the length of the polycaprolactone sequences in the block copolymers or the mass fraction of the copolylactones has a significant influence on the printing effect. When the mass fraction of caprolactone units is 5% -20%, the prepared ultra-fast 3D printing wire has good interlayer binding force and toughness.
In the poly (lactic acid-co-caprolactone) random copolymer (PLCL), T of the copolymer is caused by addition of the comonomer caprolactone g And melting point reduction, so that curing time can be prolonged and toughness of the material can be increased. When the average segment length of the lactide units (LLLL) is short<5) The curing time is too long, the mechanical property is poor, and the printing precision is reduced. Therefore, the average chain segment length of the lactide units (LLLL) in the random copolymer PLCL is set to be 5-20, and the ultra-fast 3D printing wire prepared by blending the polylactic acid copolymer PLCL and the polylactic acid has better interlayer binding force and toughness.
According to the invention, the polylactic acid-based wire rod capable of being subjected to ultra-fast 3D printing is prepared through regulation and control of a chain segment sequence structure, so that wire rod winding, conveying of an extrusion wheel and interlayer binding force improvement can be realized; more importantly, the obtained product can be perfectly suitable for an ultra-fast 3D printing process, the printing speed can reach 250mm/s, and the printed product has higher strength and toughness.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention creatively provides a preparation method for optimizing a 3D printing wire, and the obtained product contains the polylactic acid copolymer with a specific chain segment sequence structure, so that the fusion property among different components can be maintained, the strength and toughness of the printing wire can be adjusted, and the toughness and interlayer binding force of the wire are improved.
2. The 3D printing wire rod prepared by the invention has the printing speed of 250mm/s in use, obviously improves the printing efficiency, and can effectively expand the application field of 3D printing.
3. The preparation process is simple and easy to operate, and can realize large-scale industrial production.
Drawings
FIG. 1 is a nuclear magnetic resonance carbon spectrum of a PLCL of a polylactic acid copolymer and a characteristic peak position of a typical sequence structure thereof;
fig. 2 is a standard spline for testing interlayer bonding force.
Detailed Description
The invention will be described in further detail with reference to the drawings and the detailed description, but the scope of the invention claimed is not limited to the scope expressed by examples.
The raw materials used in the examples of the present invention or comparative examples will be described first.
The polylactic acid copolymer with the specific chain segment sequence structure refers to polylactic acid-polycaprolactone-polylactic acid triblock copolymer (PLA-b-PCL-b-PLA) or poly (lactic acid-co-caprolactone) random copolymer (PLCL) formed by ring-opening copolymerization of lactide and caprolactone. In each example, the polylactic acid copolymer used was prepared by a known method using L-lactide and epsilon-caprolactone, and the molecular weight was about 10 ten thousand. The present invention is not particularly limited with respect to specific production conditions thereof. The L-lactide is purchased from Henan Jindan lactic acid technology Co., ltd, and the purity is more than 99%; epsilon-caprolactone and cellulose were purchased from ala Ding Gongsi; polylactic acid (trade name R190) was purchased from marine biological materials, inc.
In the preparation process of the printing wire rod, any one or more of the following auxiliary materials or auxiliary agents can be added according to the conventional process: chain extenders (e.g., joncry1ADR4300, joncry1ADR4368, or Joncry1ADR4370, etc.), nucleating agents (e.g., phenyl metal phosphate, diphenyl metal phosphate, or phenyl metal hypophosphite, etc.), plasticizers (e.g., acetyl tributyl citrate, or tributyl phthalate, etc.), antioxidants (e.g., antioxidant 1010, antioxidant 1076, etc.), anti-hydrolysis agents (e.g., carbodiimide, etc.), and pigments (e.g., organic pigments or inorganic pigments, etc.). The auxiliary materials or auxiliary agents can be prepared by a known method or can be obtained by direct purchase.
Example 1
Drying 10 parts by mass of random copolymer PLCL and 90 parts by mass of polylactic acid, and uniformly mixing; adding the mixture into a double-screw extruder, and extruding at 190 ℃ to prepare the wire master batch. Then adding the wire master batch into a single screw extruder, and extruding at 190 ℃; and obtaining the wire rod with the wire diameter of 1.75mm through melting plasticization, drafting shaping and winding.
Wherein the mass fraction of lactide units in the random copolymer PLCL is 95%, the mass fraction of caprolactone units is 5%, the average segment length of lactide units (LLLL) in the copolymer chain is 20, and the average segment length of caprolactone units is 2.
Example 2
Drying 10 parts by mass of random copolymer PLCL and 90 parts by mass of polylactic acid, and uniformly mixing; adding the mixture into a double-screw extruder, and extruding at 190 ℃ to prepare the wire master batch. Then adding the wire master batch into a single screw extruder, and extruding at 190 ℃; and obtaining the wire rod with the wire diameter of 1.75mm through melting plasticization, drafting shaping and winding.
Wherein the mass fraction of lactide units in the random copolymer PLCL is 90%, the mass fraction of caprolactone units is 10%, the average segment length of lactide units (LLLL) in the copolymer chain is 13, and the average segment length of caprolactone units is 1.
Example 3
Drying 10 parts by mass of random copolymer PLCL and 90 parts by mass of polylactic acid, and uniformly mixing; adding the mixture into a double-screw extruder, and extruding at 190 ℃ to prepare the wire master batch. Then adding the wire master batch into a single screw extruder, and extruding at 190 ℃; and obtaining the wire rod with the wire diameter of 1.75mm through melting plasticization, drafting shaping and winding.
Wherein the mass fraction of lactide units in the random copolymer PLCL is 85%, the mass fraction of caprolactone units is 15%, the average segment length of lactide units (LLLL) in the copolymer chain is 9, and the average segment length of caprolactone units is 1.5.
Example 4
Drying 10 parts by mass of random copolymer PLCL and 90 parts by mass of polylactic acid, and uniformly mixing; adding the mixture into a double-screw extruder, and extruding at 190 ℃ to prepare the wire master batch. Then adding the wire master batch into a single screw extruder, and extruding at 190 ℃; and obtaining the wire rod with the wire diameter of 1.75mm through melting plasticization, drafting shaping and winding.
Wherein the mass fraction of lactide units in the random copolymer PLCL is 80%, the mass fraction of caprolactone units is 20%, the average segment length of lactide units (LLLL) in the copolymer chain is 5, and the average segment length of caprolactone units is 1.3.
Example 5
Drying 5 parts by mass of random copolymer PLCL and 95 parts by mass of polylactic acid, and uniformly mixing; adding the mixture into a double-screw extruder, and extruding at 180 ℃ to prepare the wire master batch. Then adding the wire master batch into a single screw extruder, and extruding at 230 ℃; and obtaining the wire rod with the wire diameter of 1.75mm through melting plasticization, drafting shaping and winding.
Wherein the mass fraction of lactide units in the random copolymer PLCL is 85%, the mass fraction of caprolactone units is 15%, the average segment length of lactide units (LLLL) in the copolymer chain is 9, and the average segment length of caprolactone units is 1.5.
Example 6
Drying 20 parts by mass of random copolymer PLCL and 80 parts by mass of polylactic acid, and uniformly mixing; adding the mixture into a double-screw extruder, and extruding at 230 ℃ to prepare the wire master batch. Then adding the wire master batch into a single screw extruder, and extruding at 180 ℃; and obtaining the wire rod with the wire diameter of 1.75mm through melting plasticization, drafting shaping and winding.
Wherein the mass fraction of lactide units in the random copolymer PLCL is 85%, the mass fraction of caprolactone units is 15%, the average segment length of lactide units (LLLL) in the copolymer chain is 9, and the average segment length of caprolactone units is 1.5.
Example 7
10 parts by mass of triblock copolymer PLA-b-PCL-b-PLA and 90 parts by mass of polylactic acid are dried and then uniformly mixed; adding the mixture into a double-screw extruder, and extruding at 190 ℃ to prepare the wire master batch. Then adding the wire master batch into a single screw extruder, and extruding at 190 ℃; and obtaining the wire rod with the wire diameter of 1.75mm through melting plasticization, drafting shaping and winding.
Wherein the mass fraction of lactide units in the triblock copolymer PLA-b-PCL-b-PLA is 95%, and the mass fraction of caprolactone units is 5%.
Example 8
10 parts by mass of triblock copolymer PLA-b-PCL-b-PLA and 90 parts by mass of polylactic acid are dried and then uniformly mixed; adding the mixture into a double-screw extruder, and extruding at 190 ℃ to prepare the wire master batch. Then adding the wire master batch into a single screw extruder, and extruding at 190 ℃; and obtaining the wire rod with the wire diameter of 1.75mm through melting plasticization, drafting shaping and winding.
Wherein the mass fraction of lactide units in the triblock copolymer PLA-b-PCL-b-PLA is 90%, and the mass fraction of caprolactone units is 10%.
Example 9
10 parts by mass of triblock copolymer PLA-b-PCL-b-PLA and 90 parts by mass of polylactic acid are dried and then uniformly mixed; adding the mixture into a double-screw extruder, and extruding at 190 ℃ to prepare the wire master batch. Then adding the wire master batch into a single screw extruder, and extruding at 190 ℃; and obtaining the wire rod with the wire diameter of 1.75mm through melting plasticization, drafting shaping and winding.
Wherein the mass fraction of lactide units in the triblock copolymer PLA-b-PCL-b-PLA is 85%, and the mass fraction of caprolactone units is 15%.
Example 10
10 parts by mass of triblock copolymer PLA-b-PCL-b-PLA and 90 parts by mass of polylactic acid are dried and then uniformly mixed; adding the mixture into a double-screw extruder, and extruding at 190 ℃ to prepare the wire master batch. Then adding the wire master batch into a single screw extruder, and extruding at 190 ℃; and obtaining the wire rod with the wire diameter of 1.75mm through melting plasticization, drafting shaping and winding.
Wherein the mass fraction of lactide units in the triblock copolymer PLA-b-PCL-b-PLA is 80%, and the mass fraction of caprolactone units is 20%.
Example 11
Drying 5 parts by mass of triblock copolymer PLA-b-PCL-b-PLA and 95 parts by mass of polylactic acid, and uniformly mixing; adding the mixture into a double-screw extruder, and extruding at 180 ℃ to prepare the wire master batch. Then adding the wire master batch into a single screw extruder, and extruding at 230 ℃; and obtaining the wire rod with the wire diameter of 1.75mm through melting plasticization, drafting shaping and winding.
Wherein the mass fraction of lactide units in the triblock copolymer PLA-b-PCL-b-PLA is 85%, and the mass fraction of caprolactone units is 15%.
Example 12
Drying 20 parts by mass of triblock copolymer PLA-b-PCL-b-PLA and 80 parts by mass of polylactic acid, and uniformly mixing; adding the mixture into a double-screw extruder, and extruding at 230 ℃ to prepare the wire master batch. Then adding the wire master batch into a single screw extruder, and extruding at 180 ℃; and obtaining the wire rod with the wire diameter of 1.75mm through melting plasticization, drafting shaping and winding.
Wherein the mass fraction of lactide units in the triblock copolymer PLA-b-PCL-b-PLA is 85%, and the mass fraction of caprolactone units is 15%.
Comparative example 1
Drying 100 parts by mass of polylactic acid, adding the polylactic acid into a double-screw extruder, extruding at 190 ℃ to prepare a wire master batch, and adding the wire master batch into a single-screw extruder, and extruding at 190 ℃; and obtaining the wire rod with the wire diameter of 1.75mm for 3D printing through melt plasticization, drawing shaping and wire rod winding.
Comparative example 2
Uniformly mixing 10 parts by mass of cellulose and 90 parts by mass of polylactic acid after drying treatment, adding the mixture into a double-screw extruder, extruding at 190 ℃ to prepare a wire master batch, and adding the wire master batch into a single-screw extruder, and extruding at 190 ℃; and obtaining the wire rod with the wire diameter of 1.75mm for 3D printing through melt plasticization, drawing shaping and wire rod winding.
Performance testing and analysis
Melting point and glass transition temperature test: the test was carried out using a Differential Scanning Calorimeter (DSC) at a temperature of-50 to 200℃and a heating rate of 10℃per minute.
Elongation at break: the elongation at break of the wire was measured using a SUNS universal material tester at a tensile speed of 10mm/min and a test temperature of 25.+ -. 1 ℃. At least 5 parallel tests were used for each sample.
Interlayer binding force test: the prepared wire was loaded into a 3D printer (Shenzhen creative three-dimensional, CR 5060 pro) and dumbbell-shaped bars (125 mm. Times.10 mm. Times.5 mm) were printed at a nozzle temperature of 250℃and a hot bed temperature of 60℃at a printing speed of 250mm/s (as shown in FIG. 2). And then measuring the interlayer bonding force by using a SUNS universal material tester, namely, the maximum force in the spline stretching process is the interlayer bonding force, and the stretching speed is 10mm/min. At least 5 parallel tests were used for each sample.
The data of comparative examples 1 and 2 and 3D printed wires prepared in examples 1 to 9 were obtained through the test and are shown in table 1.
TABLE 1
Figure BDA0004106799620000081
From the contents of each example and comparative example, and the above data, it can be seen that:
compared with pure polylactic acid (comparative example 1), the conventional cellulose-added polylactic acid-based wire (comparative example 2) is not effective in improving interlayer bonding force, and the polylactic acid-based wire prepared by the method (examples 1 to 12) has excellent toughness and interlayer bonding force. Through practical use verification, the wire rod prepared by the invention can be used for preparing complex products at the printing speed of 250mm/s, and the printing effect is excellent.
In addition, as is clear from comparative examples 1 to 4, the average segment length of lactide units (LLLL) in the copolymer chain was reduced from 20 to 5 with the decrease in lactide content in the polylactic acid copolymer, and T of the strands g And the melting point is gradually reduced, and the toughness and interlayer binding force are increased. From example 4, it is understood that when the average segment length of the lactide unit (LLLL) in the polymer chain is 5, the elongation at break is as high as 273.1%, 49 times that of the pure polylactic acid, and the interlayer bonding force is as high as 412N, 2.4 times that of the pure polylactic acid, showing excellent toughness and interlayer bonding ability.
As is clear from comparative examples 7 to 10, T of the wire rod was decreased with the decrease of the lactide content in the triblock copolymer g The difference from the melting point is not great, and particularly the melting point can still be kept above 170 ℃, so that the toughness and interlayer binding force are increased. From example 10, it is understood that when the mass fraction of lactide units in the triblock copolymer is 80%, the elongation at break can be up to 112.5%, which is 20 times that of pure polylactic acid, and the interlayer bonding force can be up to 372N, which is 2.2 times that of pure polylactic acid, and excellent toughness and interlayer bonding ability are exhibited. As can be seen from a comparison of examples 1 to 12, the wires prepared from the random copolymer have toughness and interlayer bonding ability higher than those of wires prepared from the triblock copolymer at the same mass fraction.
Finally, it should be noted that the above list is only specific embodiments of the present invention. Obviously, the invention is not limited to the above embodiments, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.

Claims (5)

1. A method for preparing a 3D printing wire based on regulation and control of a chain segment sequence structure is characterized in that polylactic acid and a polylactic acid copolymer with a specific chain segment sequence structure are uniformly mixed, and then melt extrusion granulation and melt extrusion drawing shaping are carried out to obtain the polylactic acid-based 3D printing wire;
the polylactic acid copolymer with a specific chain segment sequence structure refers to a polylactic acid-polycaprolactone-polylactic acid triblock copolymer or a poly (lactic acid-co-caprolactone) random copolymer formed by ring-opening copolymerization of lactide and caprolactone; in the polylactic acid copolymer, the mass fraction of lactide units is 80-95%, and the mass fraction of caprolactone units is 5-20%; the mass ratio of the polylactic acid to the polylactic acid copolymer is 80-95:5-20.
2. The method according to claim 1, wherein in the poly (lactic acid-co-caprolactone) random copolymer, the average segment length of lactide units is 5 to 20 and the average segment length of caprolactone units is 1 to 2.
3. The method according to claim 1, characterized in that it comprises in particular the following steps:
(1) Respectively weighing polylactic acid and polylactic acid copolymer according to the parts by mass, and uniformly mixing after drying treatment to obtain a blending raw material;
(2) Adding the mixed raw materials into a double-screw extruder, and obtaining a wire master batch through melt plasticization, extrusion and granulation;
(3) And adding the wire master batch into a single screw extruder, and obtaining the 3D printing wire with the wire diameter of 1.75mm plus or minus 0.05mm through melt plasticization, drafting shaping and wire winding.
4. A process according to claim 3, wherein the twin screw extruder and the single screw extruder are operated at temperatures of 180 to 230 ℃.
5. A method according to claim 3, characterized in that in the blend stock or wire masterbatch, any one or more of the following adjuvants or auxiliaries are further incorporated: chain extenders, nucleating agents, plasticizers, antioxidants, anti-hydrolysis agents and pigments.
CN202310194996.3A 2023-03-03 2023-03-03 Method for preparing 3D printing wire based on chain segment sequence structure regulation and control Pending CN116238128A (en)

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