3D printing consumable and preparation method thereof

Abstract

The invention discloses a 3D printing consumable and a preparation method thereof, the 3D printing consumable comprises PBS, PLA, PBAT, a PLA-b-PVP block copolymer, mica powder and a composite functional additive, the composite functional additive comprises a chain extender, an anti-hydrolysis agent and an antioxidant, PLA comprises L-PLA, the melt index of PBS is 3-8 g / 10 min, and the particle size of mica powder is 5-15 [mu] m. The preparation method comprises the following steps: a granulation step and a molding step, the granulation step comprises the following steps: mixing PBS, PLA, PBAT, a PLA-b-PVP block copolymer, mica powder and a composite functional auxiliary agent, heating to a molten state, then extruding particles, and drying at 60 DEG C for 6 hours after the particles are cooled and molded. The 3D printing consumable has the advantages of favorable bending strength, favorable bonding strength, high aging resistance, high light transmittance and favorable glossiness.

Description

Technical Field

[0001] The present invention relates to the field of electronic product accessories, and in particular to a 3D printing consumable and a preparation method thereof. Background Art

[0002] 3D printing filament is a commonly used 3D printing consumable. Patent publication CN105670255A discloses a method for preparing filament for 3D printing. This filament preparation method is made by extruding a combination of PLA, PBS and PBAT. The disadvantages of this material are low gloss, poor light transmittance, low bending strength and decreased adhesion. When the temperature of the base plate is high, the material adheres to the base plate very firmly and will contaminate the base plate. The printing temperature is relatively high, the vertical straightness of the printed model is relatively poor, and the dimensional stability is relatively poor. Summary of the invention

[0003] In view of the above problems, the present invention proposes a 3D printing consumable, which is prepared from PBS, PLA, PBAT, PLA-b-PVP block copolymer, mica powder and composite functional additives. The consumable has good bending strength and bonding strength, strong aging resistance, high material transmittance and good gloss.

[0004] The technical solution adopted by the present invention is as follows:

[0005] A 3D printing consumable material comprises PBS, PLA, PBAT, PLA-b-PVP block copolymer, mica powder and composite functional additives.

[0006] In the above formula, the functions of each ingredient are as follows.

[0007] The role of PBS is to ensure the heat resistance of the overall product, the role of PLA is to provide sufficient strength and printability, and the role of PBAT is to provide toughness. The PLA matrix in the PLA-b-PVP block copolymer has good biodegradability and biocompatibility. PVP is hydrophilic and easily reacts with minerals and polar additive powders to coat and disperse the powders, reducing the adverse effects of the powders on adhesion and printing performance. Therefore, the PLA-b-PVP block copolymer can improve the rigidity enhancement efficiency of the powder, thereby improving adhesion, printing performance, and dimensional stability.

[0008] The function of mica powder is to improve dimensional stability and flexural strength, and the function of composite functional additives is to improve the durability of materials.

[0009] In summary, this 3D printing consumable is prepared from PBS, PLA, PBAT, PLA-b-PVP block copolymer, mica powder and composite functional additives. The consumable has good bending strength and bonding strength, strong aging resistance, high material transmittance and good gloss.

[0010] Specifically, in this type of printing consumables, the content, by weight, is 5-15 parts of PBS, 70-80 parts of PLA, 3-7 parts of PBAT, 3-5 parts of PLA-b-PVP block copolymer, 4-6 parts of mica powder, and 3-7 parts of composite functional additives.

[0011] Optionally, the composite functional additive includes a chain extender, an anti-hydrolysis agent and an antioxidant.

[0012] Specifically, the chain extender is a polyepoxide functional group type, the anti-hydrolysis agent is a carbodiimide type, and the antioxidant is a hindered phenol type.

[0013] Optionally, the mass ratio of the chain extender, the anti-hydrolysis agent and the antioxidant is 1:2:1.

[0014] Optionally, the PLA includes but is not limited to left-handed PLA.

[0015] Optionally, the melting point of the PBS is 3-8 g / 10 min.

[0016] Optionally, the mica powder includes but is not limited to white mica powder, and the particle size of the mica powder is 5um~15um.

[0017] A method for preparing the 3D printing consumables as described above comprises the following steps:

[0018] Granulation step: PBS, PLA, PBAT, PLA-b-PVP block copolymer, mica powder and composite functional additives are mixed and heated to a molten state, and then extruded into particles, and after the particles are cooled and formed, they are placed at 60° C. and dried for 6 hours;

[0019] In the molding step, the particles are heated to a molten state and then extruded and cooled.

[0020] Optionally, PBAT is sprayed with an alcohol solution before granulation, and the spraying amount of the alcohol solution is one thousandth of the mass of PBAT.

[0021] The purpose of spraying the PBAT particles with alcohol solution before granulation is to allow the alcohol solution to evaporate and take away some of the residual low molecular weight migrants.

[0022] The beneficial effects of the present invention are: the consumables are prepared from PBS, PLA, PBAT, PLA-b-PVP block copolymer, mica powder and composite functional additives, have good bending strength and bonding strength, strong aging resistance, high material transmittance and good glossiness. DETAILED DESCRIPTION

[0023] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the following is a detailed description of the specific embodiments of the present invention.

[0024] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein, and those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0025] Example 1

[0026] A 3D printing consumable material comprises, by weight, 10 parts of PBS, 75 parts of PLA, 5 parts of PBAT, 4 parts of PLA-b-PVP block copolymer, 5 parts of mica powder and 1 part of a composite functional additive.

[0027] In this embodiment, the composite functional additive includes a chain extender, an anti-hydrolysis agent and an antioxidant, and the mass ratio of the chain extender, the anti-hydrolysis agent and the antioxidant is 1:2:1.

[0028] In this embodiment, PLA is left-handed PLA.

[0029] In this embodiment, the melting point of PBS is 3-8 g / 10 min.

[0030] In this embodiment, the mica powder is white mica powder, and the particle size of the mica powder is 5um~15um.

[0031] In this embodiment, the synthesis method of the PLA-b-PVP block copolymer is as follows: 2w-5w g / mol of PLA and 2w-4w g / mol of PVP are selected and dissolved in THF (styrene tetrahydrocarbon), and the temperature is set to 120-150°C under a nitrogen atmosphere. After the two are mixed, a catalyst butyl tin oxide (such as Sn(Oct)2) is added for catalytic reaction. After the reaction is completed, a terminator ethanol is added. Finally, the reaction mixture is precipitated, filtered, and extracted to remove unreacted monomers and solvents, washed with deionized water, and dried in a vacuum drying oven to obtain a PLA-b-PVP copolymer. The PLA-b-PVP copolymer prepared by this method provides regions of different polarities due to microphase separation at the molecular scale, so that it exhibits good compatibility on the surface of various substrates. The large number of carbonyl and polar pyrrolidone groups on the PVP molecules can attract water molecules through hydrogen bonding, thereby giving the copolymer good hydrophilicity. At the same time, the polar functional groups of PVP can form hydrogen bonds and van der Waals forces with a variety of surfaces to form good initial adhesion, and combined with the mechanical properties and structural support of PLA, the stability and adhesion durability of the overall material are enhanced. Therefore, it has good compatibility, hydrophilicity and adhesion. The consumables prepared by the PLA-b-PVP copolymer prepared by this method have good interlayer adhesion, high surface quality and smoothness, better toughness, excellent biocompatibility and environmental friendliness.

[0032] Example 2

[0033] A preparation method of 3D printing consumables comprises the following steps: 10 parts of PBS, 75 parts of PLA, 5 parts of PBAT, 4 parts of PLA-b-PVP block copolymer, 5 parts of mica powder and 1 part of composite functional additive are uniformly mixed and heated to a molten state, and then particles are extruded, and after the particles are cooled and formed, they are placed at 60°C for drying for 6 hours; the particles are heated to a molten state, extruded and then cooled.

[0034] In this embodiment, the PBAT is first sprayed with an alcohol solution and then granulated, and the spraying amount of the alcohol solution is one thousandth of the mass of the PBAT.

[0035] In this embodiment, the composite functional additives include a chain extender, an anti-hydrolysis agent and an antioxidant, and the mass ratio of the chain extender, the anti-hydrolysis agent and the antioxidant is 1:2:1. PLA is left-handed PLA. The melting point of PBS is 3-8g / 10min. The mica powder is white mica powder, and the particle size of the mica powder is 5um~15um.

[0036] Comparative Example 1

[0037] A preparation method of 3D printing consumables comprises the following steps: 10 parts of PBS, 75 parts of PLA and 5 parts of PBAT are uniformly mixed and heated to a molten state, and then particles are extruded, and after the particles are cooled and formed, they are placed at 60° C. for drying for 6 hours; the particles are heated to a molten state, extruded and then cooled.

[0038] In this embodiment, the PBAT is first sprayed with an alcohol solution and then granulated, and the spraying amount of the alcohol solution is one thousandth of the mass of the PBAT.

[0039] In this embodiment, PLA is left-handed PLA. The melting point of PBS is 3-8 g / 10 min. The mica powder is white mica powder, and the particle size of the mica powder is 5 um to 15 um.

[0040] Comparative Example 2

[0041] A preparation method of 3D printing consumables comprises the following steps: 10 parts of PBS, 75 parts of PLA, 5 parts of PBAT and 4 parts of PLA-b-PVP block copolymer are uniformly mixed and heated to a molten state, and then particles are extruded, and after the particles are cooled and formed, they are placed at 60° C. for drying for 6 hours; the particles are heated to a molten state, extruded and then cooled.

[0042] In this embodiment, the PBAT is first sprayed with an alcohol solution and then granulated, and the spraying amount of the alcohol solution is one thousandth of the mass of the PBAT.

[0043] In this embodiment, the composite functional additive includes a chain extender, an anti-hydrolysis agent and an antioxidant, and the mass ratio of the chain extender, the anti-hydrolysis agent and the antioxidant is 1:2:1. PLA is left-handed PLA. The melting point of PBS is 3-8g / 10min.

[0044] Comparative Example 3

[0045] A preparation method of 3D printing consumables comprises the following steps: 10 parts of PBS, 75 parts of PLA, 5 parts of PBAT, 4 parts of PLA-b-PVP block copolymer and 5 parts of mica powder are uniformly mixed and heated to a molten state, and then particles are extruded, and after the particles are cooled and formed, they are placed at 60°C for drying for 6 hours; the particles are heated to a molten state, extruded and then cooled.

[0046] In this embodiment, the PBAT is first sprayed with an alcohol solution and then granulated, and the spraying amount of the alcohol solution is one thousandth of the mass of the PBAT.

[0047] In this embodiment, PLA is left-handed PLA. The melting point of PBS is 3-8 g / 10 min. The mica powder is white mica powder, and the particle size of the mica powder is 5 um to 15 um.

[0048] Comparative Example 4

[0049] A preparation method of 3D printing consumables comprises the following steps: 10 parts of PBS, 75 parts of PLA, 5 parts of PBAT and 5 parts of mica powder are uniformly mixed and heated to a molten state, and then particles are extruded, and after the particles are cooled and formed, they are placed at 60° C. for drying for 6 hours; the particles are heated to a molten state, extruded and then cooled.

[0050] In this embodiment, the PBAT is first sprayed with an alcohol solution and then granulated, and the spraying amount of the alcohol solution is one thousandth of the mass of the PBAT.

[0051] In this embodiment, PLA is left-handed PLA. The melting point of PBS is 3-8 g / 10 min. The mica powder is white mica powder, and the particle size of the mica powder is 5 um to 15 um.

[0052] In the above-mentioned Example 2 and Control Examples 1 to 4, several test strips were printed in accordance with the requirements of "GB / T 1040.2--2022 5A Test Strip". During printing, the nozzle temperature was 220°C, the hot bed temperature was 55°C, the sample was printed upright, and the test strips were tested using a tensile testing machine.

[0053] The printed specimens were tested for breaking strength using a tensile testing machine (breaking strength can represent interlayer adhesion), and the shrinkage rates in the length, width and height directions were tested (the shrinkage rates in each direction can represent dimensional stability). Aging resistance tests were also carried out at a temperature of 60°C and a humidity of 85%. The test results are shown in Table 1 below.

[0054] Table 1

[0055] Material Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Breaking strength / (MPa) 35.45 37.88 38.14 35.86 31.17 Shrinkage in length direction (%) ±0.43 ±0.74 ±0.73 ±0.45 ±0.62 Shrinkage in width direction (%) ±0.17 ±0.39 ±0.41 ±0.16 ±0.31 Shrinkage rate in height direction (%) ±0.10 ±0.27 ±0.29 ±0.11 ±0.18 Tensile strength / (MPa) (60℃, 85% humidity, 144 hours aging) 41.10 9.87 9.36 8.25 5.13 Tensile strength / (MPa) (60℃, 85% humidity, 240 hours aging) 42.02 Unable to test Unable to test Unable to test Unable to test

[0056] The above-described embodiments only express some embodiments of the present invention, and the description is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that for those skilled in the art, it is still possible to modify the technical solutions recorded in the above-mentioned embodiments, or to replace some of the technical features therein with equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A 3D printing consumable, characterized in that: Including PBS, PLA, PBAT, PLA-b-PVP block copolymer, mica powder and composite functional additives.

2. A 3D printing consumable according to claim 1, characterized in that: The composite functional additives include a chain extender, an anti-hydrolysis agent and an antioxidant.

3. A 3D printing consumable according to claim 2, characterized in that: The mass ratio of the chain extender, the anti-hydrolysis agent and the antioxidant is 1:2:

1.

4. A 3D printing consumable according to claim 1, characterized in that: The PLA includes left-handed PLA.

5. A 3D printing consumable according to claim 1, characterized in that: The melting point of the PBS is 3-8 g / 10 min.

6. A 3D printing consumable according to claim 1, characterized in that: The mica powder includes white mica powder, and the particle size of the mica powder is 5um~15um.

7. A method for preparing a 3D printing consumable according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: a granulation step, in which PBS, PLA, PBAT, PLA-b-PVP block copolymer, mica powder and a composite functional additive are mixed and heated to a molten state, and then particles are extruded, and after the particles are cooled and formed, they are placed at 60° C. and dried for 6 hours; and a forming step, in which the particles are heated to a molten state, extruded and then cooled.

8. The preparation method according to claim 7, characterized in that: Granulation is performed after spraying PBAT with an alcohol solution, and the spraying amount of the alcohol solution is one thousandth of the mass of PBAT.