CN111378262B - Polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material, preparation method thereof and application thereof in 3D printing consumables - Google Patents
Polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material, preparation method thereof and application thereof in 3D printing consumables Download PDFInfo
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Abstract
The invention discloses a polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material, a preparation method thereof and application thereof in 3D printing consumables, and belongs to the technical field of 3D printing. The composite material comprises the following raw material components in parts by mass: polylactic acid: 60-90 parts; polylactic acid-based thermoplastic polyurethane: 3-20 parts of a solvent; inorganic filler: 1-5 parts; a crosslinking agent: 1-5 parts; a stabilizer: 0.2-1 part; wherein the structural general formula of the polylactic acid-based thermoplastic polyurethane is as follows:
wherein, the group R in the structural general formula 1 Selected from polyalkyl ethers; radical R 2 One selected from linear hexyl or methane diphenyl; the mesh number of the inorganic filler is 3000-5000 meshes. The 3D printing performance of the composite material is good, and the printing precision is high.
Description
Technical Field
The invention relates to a composite material, belongs to the technical field of 3D printing, and particularly relates to a polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material, a preparation method thereof and application thereof in 3D printing consumables.
Background
The 3D printing technology is a high and new technology which utilizes continuous superposition of physical layers and applies related materials to carry out layer-by-layer superposition to finally generate a three-dimensional entity. It needs no machining or any mould, and directly utilizes the computer graphic data imaging principle to produce the parts with any shape, so that it can greatly shorten the development period of product, raise production rate and reduce production cost. 3D printing is generally divided into three types according to different printing modes: fused Deposition (FDM) printing, stereo photo-curing (SLA) printing, selective Laser Sintering (SLS) printing/Selective Laser Melting (SLM) printing, where FDM is the most commonly used technology, and the material currently used in this technology is mainly polylactic acid (PLA), however, PLA has its own limitations for 3D printing material.
Polylactic acid (PLA) has the advantages of no toxicity, no pungent smell, lower melting temperature, degradability, no pollution, small cooling shrinkage, transparency, easy dyeing and the like, and the characteristics all meet the requirements of 3D printing technology on polymer materials, but the PLA material is brittle, can generate gaps and damages mostly when dropped or impacted, can be easily broken when bent in a thin place, and greatly limits the range of 3D printing application.
The document "preparation of thermoplastic polyurethane toughened lactic acid elastic fiber and performance research thereof" selects polylactic acid grafted maleic anhydride prepared by reactive melt blending as a compatilizer and environment-friendly Thermoplastic Polyurethane (TPU) as a toughener, prepares the PLA fiber with high elasticity by adopting a melt spinning method, and characterizes the thermal property and thermal stability of fiber master batches and the section morphology and mechanical properties of the fiber. The DSC result shows that PLA and TPU are incompatible systems, the enthalpy of fusion of the composite master batch is reduced by adding TPU, the TG result shows that the initial degradation temperature of the composite master batch is reduced by adding TPU, when the content of TPU is 20wt%, the initial degradation temperature of the composite master batch is reduced by 9 ℃, and the FESEM photo shows that no obvious interface is formed between the PLA and the TPU. The interaction force between the two phases is good, in addition, the addition of the TPU effectively improves the breaking elongation of the fiber, when the addition amount of the TPU is 10wt%, the breaking elongation of the fiber is improved to 203.9% from 2.2% of pure PLA, however, the thermoplastic polyurethane toughened lactic acid elastic fiber is mainly characterized in that the symmetry of PLA molecular chains is destroyed and the crystallinity of the PLA molecular chains is reduced by grafting the PLA, then the TPU is introduced to entangle the two molecular chains, so that the interaction force between the PLA and the TPU is improved, the mechanical property of the composite fiber is improved, and the maleic anhydride plays a key role in the grafting of the PLA in the synthesis process. Without grafting PLA first, TPU is not well compatible with PLA and phase separation occurs resulting in agglomeration and failure to spin.
Disclosure of Invention
In order to solve the technical problems, the invention provides a polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material, a preparation method thereof and application thereof in 3D printing consumables. The composite material has certain toughness, and wires drawn out by a printer during printing have stable diameter, good roundness, smooth surface without impurities, and the prepared product has high precision.
In order to achieve the purpose, the invention discloses a polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material, which comprises the following raw material components in parts by mass:
polylactic acid: 60-90 parts;
polylactic acid-based thermoplastic polyurethane: 3-20 parts;
inorganic filler: 1-5 parts;
a crosslinking agent: 1-5 parts;
a stabilizer: 0.2-1 part;
wherein the polylactic acid-based thermoplastic polyurethane has the following structural general formula:
wherein, the group R in the structural general formula 1 Selected from polyalkyl ethers; radical R 2 One selected from linear hexyl or methane diphenyl;
the mesh number of the inorganic filler is 3000-5000 meshes.
Further, the synthetic route of the polylactic acid-based thermoplastic polyurethane is as follows:
further, the group R 1 Is selected from one of polyethylethyl ether, polypropylpropyl ether and polybutylbutyl ether.
Further, the inorganic filler comprises a mixture of one of graphene with 1-10 layers or carbon nanotubes with the length of 10-100 nm and inorganic nano particles.
Further, the inorganic nano-particles comprise any one of nano-silica, nano-calcium carbonate or graphite particles.
Further, the polylactic acid-based thermoplastic polyurethane has a number average molecular weight of 2 to 50 ten thousand and a melt flow index of 5 to 50g/10min (200 ℃,5 Kg).
In order to better realize the technical purpose of the invention, the invention also discloses a preparation method of the polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material, which comprises the following steps:
1) Preparing modified polylactic acid polyol: taking one of polyglycol or polyether diol, lactide and a first catalyst to carry out ring-opening polymerization to obtain modified polylactic acid polyol; the chemical structural formula is as follows:
2) Preparation of polylactic acid-based thermoplastic polyurethane: reacting the modified polylactic acid polyol prepared in the step 1), diisocyanate, butanediol and a second catalyst to obtain polylactic acid-based thermoplastic polyurethane with the following chemical structural formula;
3) Preparing a polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material, mixing the polylactic acid-based thermoplastic polyurethane prepared in the step 2) with polylactic acid, inorganic filler, a cross-linking agent and a stabilizer according to the following mixture ratio:
polylactic acid: 60-90 parts;
polylactic acid-based thermoplastic polyurethane: 3-20 parts of a solvent;
inorganic filler: 1-5 parts;
a crosslinking agent: 1-5 parts;
a stabilizer: 0.2-1 part;
and extruding and granulating the obtained mixture by a double-screw extruder to obtain the composite material.
Further, the first catalyst includes zinc compounds such as zinc powder, zinc oxide, zinc acetate, and diethyl zinc, or tin compounds such as dibutyltin dilaurate, stannous octoate, stannous chloride, and tin lactate, and the second catalyst includes tin compounds such as dibutyltin dilaurate, stannous octoate, stannous chloride, and tin lactate.
Further, the inorganic filler comprises a mixture of one of graphene with 1-10 layers or carbon nanotubes with the length of 10-100 nm and inorganic nano particles. The inorganic filler is uniformly loaded on the surface or inside of a three-dimensional framework formed by crosslinking polylactic acid-based thermoplastic polyurethane and polylactic acid, and is favorable for ensuring that a product has certain rigidity and low density on the basis of ensuring excellent toughness of the composite material.
In addition, the invention also discloses application of the polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material in 3D printing consumables. For example, in the fields of toys, automobile parts, educational and teaching equipment parts and the like.
The beneficial effects of the invention are mainly embodied in the following aspects:
1. the modified polylactic acid polyol designed by the invention takes PTMEG polyol as a center, HO-PLA-PTMEG-PLA-OH triblock polyol with certain molecular weight is gradually formed through chain growth, and the molecular weight and the structure can be adjusted according to the toughening effect of the finally prepared polylactic acid-based thermoplastic polyurethane.
2. The polylactic acid composite 3D printing material toughened by polylactic acid-based thermoplastic polyurethane has good toughness, the drawn wire rod has stable wire diameter and good roundness, the surface is smooth and free of impurities, a product printed by the 3D printing technology is stable in size, free of edge warping and not prone to brittle failure, the wire is smooth in the printing process, and the precision can reach 0.2mm.
3. The polylactic acid-based thermoplastic polyurethane toughened polylactic acid composite 3D printing material provided by the invention can be well compatible without adding a compatilizer in the processing process, and the polylactic acid can be grafted to an elastomer to further improve the compatibility by forming crosslinking after introducing the crosslinking agent.
4. According to the preparation method of the polylactic acid-based thermoplastic polyurethane and the toughened polylactic acid composite 3D printing material, the defects of brittleness, poor toughness and the like of PLA are overcome by using the special performance of the polylactic acid-based thermoplastic polyurethane as an elastomer, and the toughening effect of the toughened polylactic acid composite 3D printing material has long-term stability.
Detailed Description
The invention discloses a preparation method of a polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material, which comprises the following steps:
1) Preparing modified polylactic acid polyol: taking polyether polyol or polyglycol, lactide and a first catalyst to carry out ring-opening polymerization to obtain modified polylactic acid polyol; wherein the modified polylactic acid polyol has the following chemical structural general formula;
the first catalyst comprises one or more of zinc compounds such as zinc powder, zinc oxide, zinc acetate, diethyl zinc and the like, or tin compounds such as dibutyltin dilaurate, stannous octoate, stannous chloride, tin lactate and the like.
2) Preparation of polylactic acid-based thermoplastic polyurethane: reacting the modified polylactic acid polyol prepared in the step 1), diisocyanate, a chain extender and a second catalyst to obtain polylactic acid-based thermoplastic polyurethane with the following chemical structural formula;
The specific synthetic route is as follows:
the prepared polylactic acid-based thermoplastic polyurethane has the number average molecular weight of 2-50 ten thousand and the melt flow index of 5-50 g/10min (200 ℃,5 Kg). The polylactic acid-based thermoplastic polyurethane is cross-linked to form a target product with a three-dimensional space structure under the condition of better compatibility with polylactic acid, and is favorable for improving the toughness and the impact resistance of the target product.
3) Preparing a polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material, mixing the polylactic acid-based thermoplastic polyurethane prepared in the step 2) with polylactic acid, inorganic filler, a cross-linking agent and a stabilizing agent according to the following mixture ratio:
polylactic acid: 60-90 parts;
polylactic acid-based thermoplastic polyurethane: 3-20 parts of a solvent;
inorganic filler: 1-5 parts;
a crosslinking agent: 1-5 parts;
a stabilizer: 0.2-1 part;
extruding and granulating the obtained mixture by a double-screw extruder to obtain a composite material; the temperature of the screw is 75-180 ℃, the rotating speed of the screw is 20-180 r/min, the temperature of the feeding area is 75-90 ℃, the temperature of the reaction area is 110-180 ℃, and the temperature of the extrusion area is 130-160 ℃.
The mesh number of the inorganic filler is controlled to be 3000-5000 meshes, and specifically, the inorganic filler is a mixture of one of graphene with 1-10 layers or carbon nano tubes with the length of 10-100 nm and inorganic nano particles. The inorganic nano-particles comprise any one of nano-silica, nano-calcium carbonate or graphite particles.
The polylactic acid has a number average molecular weight of 6 to 40 ten thousand.
The number average molecular weight of the polyethylene glycol is 200-1500.
The polypropylene glycol has a number average molecular weight of 400 to 1000.
The number average molecular weight of the polytetrahydrofuran is 250-1400.
The cross-linking agent comprises any one of benzoyl peroxide and tetraalkyl butyl acrylate.
The stabilizer comprises any one of phosphite esters and calcium zinc stabilizers.
The polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material prepared by the invention is a particulate matter with the particle size of 3-4 mm.
In order to better explain the invention, the following embodiments further illustrate the main content of the invention, but the invention is not limited to the following embodiments.
Example 1
The embodiment discloses a preparation method of polylactic acid-based thermoplastic polyurethane, which comprises the following steps:
1) Preparing modified polylactic acid polyol: taking 130 parts of polytetrahydrofuran (with the number average molecular weight of 650), 270 parts of lactide, performing pre-dehydration treatment in different devolatilization kettles respectively, then uniformly mixing with 0.02 part of catalyst (diethyl zinc) in a reaction kettle, heating the reaction kettle to 120-180 ℃, reacting for 3-5 h, and performing devolatilization treatment for 1-2 h to obtain the modified polylactic acid polyol (wherein the number average molecular weight of the modified polylactic acid polyol is 2000).
2) Preparation of polylactic acid-based thermoplastic polyurethane: injecting the modified polylactic acid polyol prepared in the step 1), 1, 6-hexamethylene diisocyanate and butanediol in a molar ratio of 1. The specific synthetic route is as follows:
the polylactic acid-based thermoplastic polyurethane had a number average molecular weight of 62178 and a melt flow index of 18.2g/10min (200 ℃ C., 5 Kg).
Examples 2 to 6 (depending on the type of polyether polyol, polyether diol, or diisocyanate).
Example 2 Polytetrahydrofuran (number average molecular weight 1000) was selected, and otherwise the same as in example 1, to prepare a polylactic acid-based thermoplastic polyurethane having a number average molecular weight of 65412 and a melt flow index of 16.9g/10min (200 ℃ C., 5 Kg).
EXAMPLE 3 selection of Polytetrahydrofuran (number average molecular weight 1400), preparation of polylactic acid-based thermoplastic polyurethane having a number average molecular weight of 69362 and a melt flow index of 16.3g/10min (200 ℃,5 Kg), in the same manner as in example 1
Example 4A polylactic acid-based thermoplastic polyurethane having a number average molecular weight of 65116 and a melt flow index of 17.2g/10min (200 ℃ C., 5 Kg) was prepared by selecting polyethylene glycol (number average molecular weight 1000) and the same procedure as in example 1. The specific synthetic route is as follows:
example 5A polylactic acid-based thermoplastic polyurethane was prepared by selecting polypropylene glycol (number average molecular weight 600) and having a number average molecular weight of 63154 and a melt flow index of 17.9g/10min (200 ℃ C., 5 Kg) in the same manner as in example 1. The specific synthetic route is as follows:
example 6A polylactic acid-based thermoplastic polyurethane having a number average molecular weight of 63178 and a melt flow index of 18.4g/10min (200 ℃ C., 5 Kg) was prepared by selecting diphenylmethane diisocyanate, otherwise the same as in example 1.
The specific synthetic route is as follows:
example 7
A preparation method of a polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material comprises the steps of taking 3 parts of the polylactic acid-based thermoplastic polyurethane prepared in the embodiment 1, 60 parts of polylactic acid, 5 parts of an inorganic filler (a mixture of nano-silica and graphene with 1-10 layers), 1 part of a cross-linking agent benzoyl peroxide and 0.2 part of a stabilizer phosphite ester, wherein the particle size of the inorganic filler is 3500 meshes; and after the polylactic acid-based thermoplastic polyurethane toughened polylactic acid composite 3D printing material is fully dried, uniformly mixing the materials by using a high-speed mixer, then extruding the materials by using a double-screw extruder for granulation, feeding the granulated product into a single-screw extruder again, cooling and forming a stay wire to obtain a formed wire, and rolling the formed wire to obtain the polylactic acid-based thermoplastic polyurethane toughened polylactic acid composite 3D printing material.
Examples 8 to 12
Different from example 7, the addition type of the polylactic acid-based thermoplastic polyurethane is controlled.
Specifically, example 8 includes 3 parts of the polylactic acid-based thermoplastic polyurethane prepared in example 2, 60 parts of polylactic acid, 5 parts of an inorganic filler (a mixture of nano-silica and graphene having 1 to 10 layers), 1 part of a crosslinking agent benzoyl peroxide, and 0.2 part of a stabilizer phosphite, and the particle size of the inorganic filler is 3500 mesh.
Specifically, example 9 includes mixing 3 parts of the polylactic acid-based thermoplastic polyurethane prepared in example 3, 60 parts of polylactic acid, 5 parts of an inorganic filler (a mixture of nano-silica and graphene having 1 to 10 layers), 1 part of a crosslinking agent benzoyl peroxide, and 0.2 part of a stabilizer phosphite, and the particle size of the inorganic filler is 3500 mesh.
Specifically, example 10 includes taking 3 parts of the polylactic acid-based thermoplastic polyurethane prepared in example 4, 60 parts of polylactic acid, 5 parts of an inorganic filler (a mixture of nano-silica and graphene having 1 to 10 layers), 1 part of a crosslinking agent benzoyl peroxide, and 0.2 part of a stabilizer phosphite, and the particle size of the inorganic filler is 3500 mesh.
Specifically, example 11 includes mixing 3 parts of the polylactic acid-based thermoplastic polyurethane prepared in example 5, 60 parts of polylactic acid, 5 parts of an inorganic filler (a mixture of nano-silica and graphene having 1 to 10 layers), 1 part of a crosslinking agent benzoyl peroxide, and 0.2 part of a stabilizer phosphite, and the particle size of the inorganic filler is 3500 mesh.
Specifically, example 12 includes mixing 3 parts of the polylactic acid-based thermoplastic polyurethane prepared in example 6, 60 parts of polylactic acid, 5 parts of an inorganic filler (a mixture of nano-silica and graphene having 1 to 10 layers), 1 part of a crosslinking agent benzoyl peroxide, and 0.2 part of a stabilizer phosphite, and the particle size of the inorganic filler is 3500 mesh.
Examples 13 to 16
The difference from example 7 is that the amount of the polylactic acid-based thermoplastic polyurethane added was controlled.
Specifically, the example 13 comprises the following raw material components in parts by mass: polylactic acid: 60 parts; polylactic acid-based thermoplastic polyurethane: 2 parts of (1); inorganic filler: 5 parts of a mixture; a crosslinking agent: 1 part; a stabilizer: 0.2 part.
Specifically, the example 14 comprises the following raw material components in parts by mass: polylactic acid: 60 parts; polylactic acid-based thermoplastic polyurethane: 4 parts; inorganic filler: 5 parts of a mixture; a crosslinking agent: 1 part; a stabilizer: 0.2 part.
Specifically, the example 15 comprises the following raw material components in parts by mass: polylactic acid: 60 parts; polylactic acid-based thermoplastic polyurethane: 6 parts of (1); inorganic filler: 5 parts of a mixture; a crosslinking agent: 1 part; a stabilizer: 0.2 part.
Specifically, the example 16 comprises the following raw material components in parts by mass: polylactic acid: 60 parts; polylactic acid-based thermoplastic polyurethane: 8 parts of a mixture; inorganic filler: 5 parts of a mixture; a crosslinking agent: 1 part; a stabilizer: 0.2 part.
Example 17
A preparation method of polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material comprises the steps of taking 3 parts of the polylactic acid-based thermoplastic polyurethane prepared in the embodiment 2, 60 parts of polylactic acid, 2 parts of inorganic filler (a mixture of nano calcium carbonate and carbon nano tubes with the average length of 50 nm), 1 part of cross-linking agent benzoyl peroxide and 0.2 part of stabilizer phosphite ester, wherein the granularity of the inorganic filler is 4000 meshes; and after fully drying, uniformly mixing by using a high-speed mixer, then extruding and granulating by using a double-screw extruder, feeding the granulated product into a single-screw extruder again, cooling and forming a stay wire to obtain a formed wire, and rolling to obtain the polylactic acid-based thermoplastic polyurethane toughened polylactic acid composite 3D printing material.
Examples 18 to 21
The difference from example 17 was that the amount of the inorganic filler added was controlled.
Specifically, the example 18 comprises the following raw material components in parts by mass: polylactic acid: 60 parts; polylactic acid-based thermoplastic polyurethane: 3 parts of a mixture; inorganic filler: 3 parts of a mixture; a crosslinking agent: 1 part; a stabilizer: 0.2 part.
Specifically, the example 19 comprises the following raw material components in parts by mass: polylactic acid: 60 parts; polylactic acid-based thermoplastic polyurethane: 3 parts of a mixture; inorganic filler: 4 parts of a mixture; a crosslinking agent: 1 part; a stabilizer: 0.2 part.
Specifically, the example 20 comprises the following raw material components in parts by mass: polylactic acid: 60 parts; polylactic acid-based thermoplastic polyurethane: 3 parts of a mixture; inorganic filler: 4.5 parts; a crosslinking agent: 1 part; a stabilizer: 0.2 part.
Specifically, the example 21 comprises the following raw material components in parts by mass: polylactic acid: 60 parts; polylactic acid-based thermoplastic polyurethane: 3 parts of a mixture; inorganic filler: 5 parts of a mixture; a crosslinking agent: 1 part; a stabilizer: 0.2 part.
Example 22
A preparation method of polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material comprises the steps of taking 5 parts of polylactic acid-based thermoplastic polyurethane prepared in the embodiment 2, 60 parts of polylactic acid, 3 parts of inorganic filler (a mixture of graphite particles and carbon nano tubes with the average length of 50 nm), 1 part of cross-linking agent benzoyl peroxide and 0.2 part of stabilizer phosphite ester, wherein the particle size of the inorganic filler is 4000 meshes; and after fully drying, uniformly mixing by using a high-speed mixer, then extruding and granulating by using a double-screw extruder, feeding the granulated product into a single-screw extruder again, cooling and forming a stay wire to obtain a formed wire, and rolling to obtain the polylactic acid-based thermoplastic polyurethane toughened polylactic acid composite 3D printing material.
Example 23
A preparation method of polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material comprises the steps of taking 5 parts of polylactic acid-based thermoplastic polyurethane prepared in the embodiment 2, 60 parts of polylactic acid, 4 parts of inorganic filler (mixture of nano-silica and carbon nano-tubes with the average length of 50 nm), 1 part of cross-linking agent benzoyl peroxide and 0.2 part of stabilizer phosphite ester, wherein the particle size of the inorganic filler is 4000 meshes; and after fully drying, uniformly mixing by using a high-speed mixer, then extruding and granulating by using a double-screw extruder, feeding the granulated product into a single-screw extruder again, cooling and forming a stay wire to obtain a formed wire, and rolling to obtain the polylactic acid-based thermoplastic polyurethane toughened polylactic acid composite 3D printing material.
Example 24
A preparation method of polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material comprises the steps of taking 7 parts of polylactic acid-based thermoplastic polyurethane prepared in the embodiment 2, 60 parts of polylactic acid, 4.5 parts of inorganic filler (a mixture of nano calcium carbonate and graphene with 1-10 layers), 1 part of cross-linking agent benzoyl peroxide and 0.2 part of stabilizer phosphite, wherein the granularity of the inorganic filler is 4000 meshes; and after fully drying, uniformly mixing by using a high-speed mixer, then extruding and granulating by using a double-screw extruder, feeding the granulated product into a single-screw extruder again, cooling and forming a stay wire to obtain a formed wire, and rolling to obtain the polylactic acid-based thermoplastic polyurethane toughened polylactic acid composite 3D printing material.
Comparative example 1
In comparison with example 22 above, the polylactic acid based thermoplastic polyurethane was not added, and the rest remained the same.
Comparative example 2
In contrast to example 23 above, the polylactic acid-based thermoplastic polyurethane was replaced with another elastomer such as Wanhua 1495B, all of which remained the same.
Comparative example 3
The inorganic filler was replaced with nano silica, all other things remaining unchanged compared to example 24 above.
The properties of the composite 3D printed materials prepared in examples 7 to 24 and comparative examples 1 to 3 above are listed as follows:
the preparation process discovers that the polylactic acid composite 3D printing material toughened by the polylactic acid-based thermoplastic polyurethane has good toughness, the drawn wire rod is stable in wire diameter, good in roundness and smooth in surface without impurities, a product printed by the 3D printing technology is stable in size, free of edge warping and not prone to brittle failure, and the wire is smooth in the printing process. And further exploring the printing precision, and finding that the printing precision can reach 0.2mm.
The above examples are merely preferred examples and are not intended to limit the embodiments of the present invention. In addition to the above embodiments, the present invention has other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.
Claims (5)
1. A polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material comprises the following raw material components in parts by weight:
polylactic acid: 60-90 parts;
polylactic acid-based thermoplastic polyurethane: 3-20 parts of a solvent;
inorganic filler: 1-5 parts;
a crosslinking agent: 1-5 parts;
a stabilizer: 0.2-1 part;
wherein the polylactic acid-based thermoplastic polyurethane has the following structural general formula:
wherein, the group R in the structural general formula 1 Selected from polyalkyl ethers; radical R 2 One selected from linear hexyl or methane diphenyl; wherein the polyalkyl ether is selected from any one of polyethylene ethyl ether, polypropylene propyl ether and polybutylene butyl ether;
the mesh number of the inorganic filler is 3000-5000 meshes; the inorganic filler comprises a mixture of one of graphene with 1-10 layers or carbon nano tubes with the length of 10-100 nm and inorganic nano particles; the inorganic nano-particles comprise any one of nano-silica, nano-calcium carbonate or graphite particles;
the polylactic acid-based thermoplastic polyurethane has the number average molecular weight of 2-50 ten thousand, and the melt flow index of 5-50 g/10min per 5kg at 200 ℃;
the synthetic route of the polylactic acid-based thermoplastic polyurethane is as follows:
2. a preparation method of polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material comprises the following steps:
1) Preparing modified polylactic acid polyol: taking one of polydiol or polyether diol, lactide and a first catalyst to perform ring-opening polymerization to obtain modified polylactic acid polyol; the chemical structural formula is as follows:
2) Preparation of polylactic acid-based thermoplastic polyurethane: reacting the modified polylactic acid polyol prepared in the step 1), diisocyanate, butanediol and a second catalyst to obtain polylactic acid-based thermoplastic polyurethane with the following chemical structural formula;
3) Preparing a polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material, mixing the polylactic acid-based thermoplastic polyurethane prepared in the step 2) with polylactic acid, inorganic filler, a cross-linking agent and a stabilizing agent according to the following mixture ratio:
polylactic acid: 60-90 parts;
polylactic acid-based thermoplastic polyurethane: 3-20 parts of a solvent;
inorganic filler: 1-5 parts;
a crosslinking agent: 1-5 parts;
a stabilizer: 0.2-1 part;
and extruding and granulating the obtained mixture by a double-screw extruder to obtain the composite material.
3. The method for preparing the polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material according to claim 2, wherein the method comprises the following steps: the first catalyst comprises zinc compounds such as zinc powder, zinc oxide, zinc acetate and diethyl zinc or tin compounds such as dibutyltin dilaurate, stannous octoate, stannous chloride and tin lactate, and the second catalyst comprises tin compounds such as dibutyltin dilaurate, stannous octoate, stannous chloride and tin lactate.
4. The method for preparing a polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material according to claim 2 or 3, wherein: the inorganic filler comprises a mixture of one of graphene with 1-10 layers or carbon nano tubes with the length of 10-100 nm and inorganic nano particles.
5. The application of the polylactic acid-based thermoplastic polyurethane modified polylactic acid composite material of claim 1 in 3D printing consumables.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004027136A (en) * | 2002-06-28 | 2004-01-29 | Yamagata Univ Research Institute | Polylactic acid-based resin composition, process for producing the same and processed product using polylactic acid-based resin composition as stock material |
| CN106433052A (en) * | 2015-08-20 | 2017-02-22 | 黑龙江鑫达企业集团有限公司 | PLA/PCL material for 3D printing |
| CN108059806A (en) * | 2016-11-07 | 2018-05-22 | 黑龙江鑫达企业集团有限公司 | A kind of 3D printing PLA/TPU composite materials |
| CN109486142A (en) * | 2018-12-26 | 2019-03-19 | 福建省易启云互联网科技有限公司 | A kind of polylactic acid-polycaprolactone composite material and preparation method thereof for 3D printing |
| CN110627985A (en) * | 2019-09-09 | 2019-12-31 | 北京化工大学 | Polylactic acid-based thermoplastic polyurethane elastomer material and preparation method thereof |
-
2020
- 2020-04-16 CN CN202010301872.7A patent/CN111378262B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004027136A (en) * | 2002-06-28 | 2004-01-29 | Yamagata Univ Research Institute | Polylactic acid-based resin composition, process for producing the same and processed product using polylactic acid-based resin composition as stock material |
| CN106433052A (en) * | 2015-08-20 | 2017-02-22 | 黑龙江鑫达企业集团有限公司 | PLA/PCL material for 3D printing |
| CN108059806A (en) * | 2016-11-07 | 2018-05-22 | 黑龙江鑫达企业集团有限公司 | A kind of 3D printing PLA/TPU composite materials |
| CN109486142A (en) * | 2018-12-26 | 2019-03-19 | 福建省易启云互联网科技有限公司 | A kind of polylactic acid-polycaprolactone composite material and preparation method thereof for 3D printing |
| CN110627985A (en) * | 2019-09-09 | 2019-12-31 | 北京化工大学 | Polylactic acid-based thermoplastic polyurethane elastomer material and preparation method thereof |
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