Special resin material for 3D printing, preparation method thereof and 3D printed product

Abstract

The invention relates to the field of 3D printing materials, in particular to a resin material special for 3D printing, a preparation method of the resin material and a 3D printing product. According to the preparation method provided by the invention, the TMPTA and the ADR chain extender are used for modifying the inorganic filler into the multifunctional filler containing acrylics and epoxy groups under the action of the aluminate coupling agent, so that the compatibility of the inorganic filler with biodegradable high-molecular materials such as PLA and PBAT is improved, the phase structure is regulated and controlled, and the biodegradability of the biodegradable high-molecular materials is improved. The 3D printing manufacturability of the obtained material can also be ensured while high-content addition of the inorganic filler is realized, and subsequently, the improved inorganic filler, PLA, PBAT and auxiliaries are co-extruded and irradiated, so that the special resin material for 3D printing with excellent appearance and performance can be obtained; a 3D printing product prepared from the material has excellent mechanical properties and good apparent properties, can meet production and life requirements, and realizes organic unification of cost, use performance and degradability.

Description

Technical Field

[0001] The present invention relates to the field of 3D printing materials, and particularly to a special resin material for 3D printing, a preparation method thereof, and a 3D printed product. Background Art

[0002] At present, China's 3D printing industry is in a stage of steady growth, and 3D printing technology has been applied to a certain extent in the military, aerospace, mechanical manufacturing, and consumer fields. Compared with traditional printing and manufacturing processes, the advantages of 3D printing are as follows: 1) The operation process is simple, without redundant post-processing operations, and the production efficiency is high; 2) The product quality is high, the accuracy can reach the 0.01 mm level, no mold is required, and it can be quickly repaired, etc. 3D printing will promote the development of China's manufacturing industry by 5 - 10 years and has also become an industrial revolution in China.

[0003] Polylactic acid (PLA) is the most commonly used material for 3D printing materials at present. However, its main defects are high cost, low toughness, crystallinity, melt strength, and heat resistance. High melt strength PLA has excellent rheological properties, a wide processing window, and a stable processing state, which can meet the requirements of various molding and processing processes and help to expand the application fields of PLA. In order to make full use of the development of this biodegradable material, PLA, in the field of 3D printing, a large number of researchers have carried out functional modification on PLA. Among them, CN103980683B and CN104530669B blend PLA with aliphatic polycarbonate, use peroxide as an initiator, and use triallyl isocyanurate (TAIC) and a mixture of a terpolymer of GMA - methyl acrylate as crosslinking agents respectively to obtain modified polylactic acid, and then complete the preparation of 3D printed product; while CN111234279A uses the method of irradiating and crosslinking TAIC multi - functional monomers to improve the PLA / PBAT blend system to obtain a film product with excellent water vapor barrier performance, where PBAT is poly(butylene adipate - co - terephthalate).

[0004] However, Zhang Wei et al. (Polymer Bulletin, 2020, No2, p1-7) pointed out that the use of organic peroxides to induce free radical reactions in PLA easily leads to the formation of cross-linked structures (appearance of "gels") in modified PLA, resulting in poor fluidity and even loss of melt processability, and the appearance of "fish-eye" defects in the products. Moreover, the decomposition products of organic peroxides contain a large amount of small molecular substances with high toxicity and irritation (such as acetophenone, acetone, methyl ethyl ketone, and methanol, etc.), which limits the application of modified PLA in the fields of daily necessities, tableware, packaging, shopping bags, etc. In addition, cross-linking agents such as TAIC required for modifying PLA with peroxides are small molecular compounds containing terminal double bonds, which have strong volatility, irritation, and certain toxicity. Therefore, it is necessary to develop a biodegradable polylactic acid composite material that can meet the requirements of 3D printing. Summary of the Invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide a special resin material for 3D printing, its preparation method, and 3D printing products. The polylactic acid composite material provided by the present invention is a biodegradable material with high mechanical properties and good processing performance. As a 3D printing material, it can ensure the processability of 3D printing, and the obtained 3D printing products also have excellent mechanical properties and good appearance.

[0006] The present invention provides a special resin material for 3D printing, which is prepared from the following components:

[0007] 50 - 70 parts by weight of PLA;

[0008] 15 - 30 parts by weight of PBAT;

[0009] 10 - 20 parts by weight of modified inorganic filler, and the modified inorganic filler is prepared from aluminate coupling agent, TMPTA, ADR chain extender, and inorganic filler;

[0010] 0.6 - 2 parts by weight of additives.

[0011] The modified inorganic filler of the present invention is prepared from aluminate coupling agent, TMPTA, ADR chain extender, and inorganic filler. Among them, the inorganic filler includes one or more of calcium carbonate or talcum powder; the TMPTA is trimethylolpropane triacrylate; the epoxy equivalent of the ADR chain extender is 250 g / mol - 500 g / mol. The molecular weight of the ADR chain extender of the present invention is 6000 - 8000. The ADR chain extender of the present invention is preferably the ADR chain extender from Shanxi Research Institute of Chemical Industry, with the model ADR4368, its molecular weight is 6800, and its epoxy equivalent is 285 g / mol.

[0012] The mass ratio of the aluminate coupling agent, TMPTA, ADR chain extender, and inorganic filler in the present invention is (1-2):(1-5):(1-5):100. Preferably, the masses of TMPTA and the ADR chain extender are equal; non-limiting examples include the mass ratio of the aluminate coupling agent, TMPTA, ADR chain extender, and inorganic filler being (1-2):1:1:100, or (1-2):2:2:100, or (1-2):3:3:100, or (1-2):4:4:100, or (1-2):5:5:100.

[0013] The modified inorganic filler in the present invention is prepared by kneading and granulating the aluminate coupling agent, TMPTA, ADR chain extender, and inorganic filler in sequence. In certain embodiments of the present invention, the aluminate coupling agent, TMPTA, ADR chain extender, and inorganic filler are initially kneaded in an enclosed mixer, and then air-cooled rotary cutting granulation is performed by a granulator to obtain the modified inorganic filler. The temperature of the kneading in the present invention is 100°C - 130°C, and the time of the kneading is 10 min - 60 min.

[0014] In the present invention, the TMPTA and the ADR chain extender are coated on the surface of the inorganic filler by a physical adsorption method under the action of the aluminate coupling agent, so that the inorganic filler is modified into a multifunctional filler containing acrylate and epoxy groups, improving the compatibility of the inorganic filler with biodegradable polymer materials such as PLA and PBAT, regulating the phase structure, enabling high-content addition of the inorganic filler while also ensuring the 3D printing processability of the resulting material. Subsequently, the improved inorganic filler, PLA, PBAT, and additives are co-extruded and irradiated to obtain a 3D printing special resin material with excellent appearance and performance.

[0015] The additives in the present invention include 0.4 - 1 part by weight of a lubricant and 0.2 - 1 part by weight of an antioxidant; wherein, the lubricant is preferably calcium stearate, and the antioxidant is preferably one or more of antioxidant 1010 (pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]) and antioxidant 168 (tris(2,4-di-tert-butylphenyl) phosphite). In certain embodiments of the present invention, the 3D printing special resin material is prepared from the following components: 50 - 70 parts by weight of PLA; 15 - 30 parts by weight of PBAT; 10 - 20 parts by weight of the modified inorganic filler, the modified inorganic filler is prepared from the aluminate coupling agent, TMPTA, ADR chain extender, and inorganic filler, and the ADR chain extender is ADR4368; 0.3 - 0.5 part by weight of calcium stearate; 0.1 - 0.5 part by weight of antioxidant 1010; 0.1 - 0.5 part by weight of antioxidant 168. The 3D printing special resin material provided by the present invention contains a large amount of inorganic filler, reducing the cost of the 3D printing special resin material.

[0016] The present invention provides a method for preparing the 3D printing special resin material described in any of the above technical solutions, including the following steps: After extruding and granulating PLA, PBAT, modified inorganic filler and additives, irradiating the obtained material after granulation to obtain the 3D printing special resin material.

[0017] Specifically, mix PLA, PBAT, modified inorganic filler and additives at room temperature for 4 min to 6 min, then use a twin-screw extruder to carry out co-blending, melting extrusion and granulation on the mixed material, and then dry the obtained material after granulation and then carry out electron beam irradiation to obtain the 3D printing special resin. The present invention uses a twin-screw extruder to extrude and granulate the mixed material at a temperature of 180 °C to 200 °C. The dose of the irradiation described in the present invention is 10 kGy to 100 kGy.

[0018] The 3D printing special resin material obtained by the present invention is a bio-degradable 3D printing material with low cost and excellent properties, and is specifically used as a 3D printing material. In some embodiments of the present invention, the obtained 3D printing special resin is subjected to wire melting extrusion through a single-screw extruder equipped with a laser diameter limiting device, and a 3D printing special resin wire with a diameter of 1.75 ± 0.01 mm is obtained through a winding process. The present invention further enhances the compatibility between components through a reactive extrusion method and electron beam irradiation, ensuring that the obtained special resin has good fluidity, so as to ensure the smooth implementation of the 3D printing process, and at the same time has good mechanical properties. Moreover, the obtained 3D printing special resin material has good diameter uniformity after being further made into a wire. During the process of printing the wire into a product, the product has a fast cooling rate, a low shrinkage rate, does not warp, does not crack and has a smooth appearance, and can meet various 3D printing requirements.

[0019] The present invention also provides a 3D printed product, which is made of the 3D printing special resin material described in any of the above technical solutions. The 3D printing special resin material described in the present invention has good economy, bio-degradability, excellent mechanical properties and 3D printing processability, and the 3D printed product made of it also has excellent mechanical properties and good appearance.

[0020] The present invention provides a special resin material for 3D printing, a preparation method thereof, and a 3D printing product. In the preparation method provided by the present invention, an inorganic filler which is previously modified to contain acrylate and epoxy groups, biodegradable polymer materials such as PLA and PBAT, and other additives are subjected to a co-blending reaction extrusion by a twin-screw extruder with a threaded component arrangement that enhances shear force, achieving high plasticization and high compatibility of each component, and regulating the phase structure; finally, chain extension and cross-linking of PLA and PBAT are further achieved after electron beam irradiation, not only improving the melt strength of PLA and PBAT themselves, but also realizing chain entanglement of PLA and PBAT during the chain extension and cross-linking process, thereby further strengthening the compatibility between the components of the blend system, making the properties of the obtained material better, and finally realizing the addition of a high content of inorganic filler while ensuring the 3D printing processability of the obtained material; the 3D printing product prepared from the obtained special resin material for 3D printing has excellent mechanical properties and good appearance, can meet the production and living needs, and realizes the organic unity of cost, service performance, and degradability, thereby meeting the needs of economic and social development. Detailed Embodiments

[0021] The present invention discloses a special resin material for 3D printing, a preparation method thereof, and a 3D printing product. Those skilled in the art can draw on the content of this article and appropriately modify the process parameters to achieve it. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art, and they are all considered to be included in the present invention. The methods and applications of the present invention have been described through preferred embodiments, and those skilled in the art can obviously make changes or appropriate modifications and combinations to the methods and applications in this article without departing from the content, spirit, and scope of the present invention to implement and apply the technology of the present invention.

[0022] All ADR4368 used in the detailed embodiments of the present invention are ADR4368 from Shanxi Research Institute of Chemical Industry, with a molecular weight of 6800 and an epoxy equivalent of 285 g / mol.

[0023] The present invention is further illustrated below in conjunction with embodiments:

[0024] Example 1

[0025] Preparation of modified talc powder: 100 g of talc powder, 1 g of TMPTA, 1 g of ADR4368, 0.5 g of aluminate coupling agent, in a closed mixer at 110 ± 5 °C, mixed for 30 min, and then the material was transferred to a granulator at the same temperature. The granulator is fed by a high-power double rotor, single-screw extrusion, and air-cooled rotary cutting granulation to obtain modified talc powder pellets.

[0026] A preparation method of a low-cost biodegradable special resin for 3D printing is as follows: 60 g of PLA, 25 g of PBAT, 15 g of modified talcum powder, 0.4 g of calcium stearate, 0.1 g of antioxidant 1010, and 0.1 g of antioxidant 168. Weigh them according to the weight parts, add them to a blender, and mix at room temperature for 5 minutes. Then, use a twin-screw extruder to perform extrusion, granulation, and drying procedures. After electron beam irradiation, the special resin material is obtained. The temperatures of the 15 zones of the twin-screw extruder are 120 °C, 175 °C, 180 °C, 185 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 185 °C, and 180 °C respectively.

[0027] The electron beam irradiation of a low-cost biodegradable special resin for 3D printing mentioned in the present invention uses China General Nuclear Power Group Co., Ltd. (irradiation device system, DD5.0 - 30), and the irradiation dose is 10 kGy.

[0028] The special resin for 3D printing mentioned in the present invention is extruded into a wire through a single-screw extruder equipped with a laser diameter limiting device to obtain a wire with a diameter of 1.75 ± 0.01 mm.

[0029] Example 2

[0030] Preparation of modified calcium carbonate: 100 g of calcium carbonate, 2 g of TMPTA, 2 g of ADR4368, 0.5 g of aluminate coupling agent. In a closed mixer, mix at 110 ± 5 °C for 30 minutes. Then, transfer the material to a granulator at the same temperature. The granulator is fed by a high-power double rotor, extruded by a single screw, and air-cooled and rotary cut for granulation to obtain modified calcium carbonate pellets.

[0031] A preparation method of a low-cost biodegradable special resin for 3D printing is as follows: 65 g of PLA, 20 g of PBAT, 15 g of modified calcium carbonate, 0.4 g of calcium stearate, 0.1 g of antioxidant 1010, and 0.1 g of antioxidant 168. Weigh them according to the weight parts, add them to a blender, and mix at room temperature for 5 minutes. Then, use a twin-screw extruder to perform extrusion, granulation, and drying procedures. After electron beam irradiation, the special resin material is obtained. The temperatures of the 15 zones of the twin-screw extruder are 120 °C, 175 °C, 180 °C, 185 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 185 °C, and 180 °C respectively.

[0032] A low-cost biodegradable special resin for 3D printing uses electron beam irradiation from China General Nuclear Power Group Co., Ltd. (irradiation device system, DD5.0-30), and the irradiation dose is 15 kGy.

[0033] A low-cost biodegradable special resin for 3D printing is extruded into wire through a single-screw extruder equipped with a laser diameter limiting device to obtain a wire with a diameter of 1.75 ± 0.01 mm.

[0034] Example 3

[0035] Preparation of modified talcum powder: 100 g of talcum powder, 1.5 g of TMPTA, 1.5 g of ADR4368, 0.5 g of aluminate coupling agent. In a closed mixer at 110 ± 5 °C for 30 min, then transfer the material to a granulator at the same temperature. The granulator is fed by a high-power double rotor, single-screw extruded, and air-cooled rotary cutting granulation to obtain modified talcum powder pellets.

[0036] A preparation method of a low-cost biodegradable special resin for 3D printing is as follows: 70 g of PLA, 15 g of PBAT, 15 g of modified talcum powder, 0.4 g of calcium stearate, 0.2 g of antioxidant 1010, and 0.2 g of antioxidant 168. Weigh according to the weight parts and add them to a mixer and mix at room temperature for 5 min. Then use a twin-screw extruder for extrusion, granulation, and drying procedures, and after electron beam irradiation, the special resin material is obtained. The temperatures of the 15 zones of the twin-screw extruder are 120 °C, 175 °C, 180 °C, 185 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 185 °C, 180 °C respectively.

[0037] A low-cost biodegradable special resin for 3D printing uses electron beam irradiation from China General Nuclear Power Group Co., Ltd. (irradiation device system, DD5.0-30), and the irradiation dose is 5 kGy.

[0038] A low-cost biodegradable special resin for 3D printing is extruded into wire through a single-screw extruder equipped with a laser diameter limiting device to obtain a wire with a diameter of 1.75 ± 0.01 mm.

[0039] Example 4

[0040] Preparation of modified calcium carbonate: 100 g of calcium carbonate, 1.8 g of TMPTA, 1.8 g of ADR4368, 0.6 g of aluminate coupling agent. In a closed mixer at 110 ± 5 °C, knead for 30 min, then transfer the material to a granulator at the same temperature. The granulator is fed by a high-power double rotor, single-screw extruded, and air-cooled rotary cutting granulation to obtain modified calcium carbonate pellets.

[0041] A preparation method of a low-cost biodegradable special resin for 3D printing is as follows: 50 g of PLA, 30 g of PBAT, 20 g of modified calcium carbonate, 0.4 g of calcium stearate, 0.1 g of antioxidant 1010, and 0.1 g of antioxidant 168. Weigh according to the weight parts and add them to a mixer, mix at room temperature for 5 min, then use a twin-screw extruder for extrusion, granulation, and drying processes. After electron beam irradiation, the special resin material is obtained. The temperatures of the 15 zones of the twin-screw extruder are 120 °C, 175 °C, 180 °C, 185 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 185 °C, 180 °C respectively.

[0042] The electron beam irradiation of the low-cost biodegradable special resin for 3D printing mentioned in the present invention uses China General Nuclear Power Group Co., Ltd. (irradiation device system, DD5.0 - 30), and the irradiation dose is 15 kGy.

[0043] The low-cost biodegradable special resin for 3D printing mentioned in the present invention is extruded into a wire through a single-screw extruder equipped with a laser diameter limiting device to obtain a wire with a diameter of 1.75 ± 0.01 mm.

[0044] Example 5

[0045] Preparation of modified calcium carbonate: 100 g of calcium carbonate, 2 g of TMPTA, 2 g of ADR4368, 0.5 g of aluminate coupling agent. In a closed mixer at 110 ± 5 °C, knead for 30 min, then transfer the material to a granulator at the same temperature. The granulator is fed by a high-power double rotor, single-screw extruded, and air-cooled rotary cutting granulation to obtain modified calcium carbonate pellets.

[0046] A preparation method of a low-cost biodegradable special resin for 3D printing is as follows: 55 g of PLA, 25 g of PBAT, 20 g of modified calcium carbonate, 0.4 g of calcium stearate, 0.1 g of antioxidant 1010, and 0.1 g of antioxidant 168. Weigh them according to the weight parts and add them to a blender, mix at room temperature for 5 minutes, then use a twin-screw extruder for extrusion, granulation, and drying procedures. After electron beam irradiation, the special resin material is obtained. The temperatures of the 15 zones of the twin-screw extruder are 120 °C, 175 °C, 180 °C, 185 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 185 °C, 180 °C respectively.

[0047] The electron beam irradiation of a low-cost biodegradable special resin for 3D printing mentioned in the present invention uses the irradiation device system (DD5.0 - 30) of China General Nuclear Power Group Co., Ltd., and the irradiation dose is 20 kGy.

[0048] The special resin for 3D printing mentioned in the present invention is extruded into wire through a single-screw extruder equipped with a laser diameter limiting device to obtain a wire with a diameter of 1.75 ± 0.01 mm.

[0049] Example 6

[0050] Preparation of modified talc powder: 100 g of talc powder, 1 g of TMPTA, 1 g of ADR4368, 0.5 g of aluminate coupling agent. In a closed mixer, mix at 110 ± 5 °C for 30 minutes, then transfer the material to a granulator at the same temperature. The granulator is fed by a high-power double rotor, single-screw extruded, and air-cooled rotary cut granulation to obtain modified talc powder pellets.

[0051] A preparation method of a low-cost biodegradable special resin for 3D printing is as follows: 60 g of PLA, 20 g of PBAT, 20 g of modified talc powder, 0.4 g of calcium stearate, 0.1 g of antioxidant 1010, and 0.1 g of antioxidant 168. Weigh them according to the weight parts and add them to a blender, mix at room temperature for 5 minutes, then use a twin-screw extruder for extrusion, granulation, and drying procedures. After electron beam irradiation, the special resin material is obtained. The temperatures of the 15 zones of the twin-screw extruder are 120 °C, 175 °C, 180 °C, 185 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 185 °C, 180 °C respectively.

[0052] A low-cost biodegradable special resin for 3D printing uses electron beam irradiation from China General Nuclear Power Group Co., Ltd. (irradiation device system, DD5.0 - 30), and the irradiation dose is 10 kGy.

[0053] A low-cost biodegradable special resin for 3D printing is extruded into wire through a single-screw extruder equipped with a laser diameter limiting device to obtain a wire with a diameter of 1.75 ± 0.01 mm.

[0054] Example 7

[0055] Preparation of modified talc powder: 100 g of talc powder, 1 g of TMPTA, 1 g of ADR4368, 0.5 g of aluminate coupling agent. In a closed mixer at 110 ± 5 °C for 30 min, then transfer the material to a granulator at the same temperature. The granulator is fed by a high-power double rotor, single-screw extruded, and air-cooled rotary cutting granulation to obtain modified talc powder pellets.

[0056] A preparation method of a low-cost biodegradable special resin for 3D printing is as follows: 60 g of PLA, 30 g of PBAT, 10 g of modified talc powder, 0.4 g of calcium stearate, 0.5 g of antioxidant 1010, and 0.5 g of antioxidant 168. Weigh according to the weight parts and add them to a mixer and mix at room temperature for 5 min, then use a twin-screw extruder for extrusion, granulation, drying and other processes, and obtain the special resin material after electron beam irradiation. The temperatures of the 15 zones of the twin-screw extruder are 120 °C, 175 °C, 180 °C, 185 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 185 °C, 180 °C respectively.

[0057] A low-cost biodegradable special resin for 3D printing uses electron beam irradiation from China General Nuclear Power Group Co., Ltd. (irradiation device system, DD5.0 - 30), and the irradiation dose is 15 kGy.

[0058] A low-cost biodegradable special resin for 3D printing is extruded into wire through a single-screw extruder equipped with a laser diameter limiting device to obtain a wire with a diameter of 1.75 ± 0.01 mm.

[0059] Example 8

[0060] Preparation of modified talcum powder: 100 g of talcum powder, 1 g of TMPTA, 1 g of ADR4368, 0.5 g of aluminate coupling agent. In a closed mixer, at 110 ± 5 °C, mix for 30 min, then transfer the material to a granulator at the same temperature. The granulator is fed by a high-power double rotor, single-screw extruded, and air-cooled rotary cutting granulation to obtain modified talcum powder pellets.

[0061] A preparation method of a low-cost biodegradable special resin for 3D printing is as follows: 65 g of PLA, 25 g of PBAT, 10 g of modified talcum powder, 0.4 g of calcium stearate, 0.1 g of antioxidant 1010, 0.1 g of antioxidant 168. Weigh according to the weight parts and add them to a mixer, mix at room temperature for 5 min, then use a twin-screw extruder for extrusion, granulation, drying and other procedures, and obtain the special resin material after electron beam irradiation. The temperatures of the 15 zones of the twin-screw extruder are 120 °C, 175 °C, 180 °C, 185 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 185 °C, 180 °C respectively.

[0062] The electron beam irradiation of a low-cost biodegradable special resin for 3D printing mentioned in the present invention adopts China General Nuclear Power Group Co., Ltd. (irradiation device system, DD5.0 - 30), and the irradiation dose is 15 kGy.

[0063] The low-cost biodegradable special resin for 3D printing mentioned in the present invention is extruded into wire through a single-screw extruder equipped with a laser diameter limiting device to obtain a wire with a diameter of 1.75 ± 0.01 mm.

[0064] Comparative Example 1

[0065] The preparation of the comparative sample resin of Comparative Example 1 is carried out according to the following steps: 60 g of PLA, 30 g of PBAT, 10 g of talcum powder, 0.1 g of TMPTA, 0.1 g of ADR4368, 0.05 g of aluminate coupling agent, 0.4 g of calcium stearate, 0.5 g of antioxidant 1010, 0.5 g of antioxidant 168. Weigh according to the weight parts and add them to a mixer, mix at room temperature for 5 min, then use a twin-screw extruder for extrusion, granulation, drying and other procedures to obtain the special resin material. The temperatures of the 15 zones of the twin-screw extruder are 120 °C, 175 °C, 180 °C, 185 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 185 °C, 180 °C respectively.

[0066] Comparative Example 1: The comparative sample resin was extruded into a wire through a single-screw extruder equipped with a laser diameter limiting device to obtain a wire with a diameter of 1.75 ± 0.01 mm.

[0067] Comparative Example 2

[0068] Preparation of modified talc powder: 100 g of talc powder, 1 g of TMPTA, 1 g of ADR4368, 0.5 g of aluminate coupling agent. In a closed mixer, at 110 ± 5 °C, knead for 30 min, then transfer the material to a granulator at the same temperature. The granulator is fed by a high-power double rotor, single-screw extruded, and air-cooled rotary cutting granulation to obtain modified talc powder pellets.

[0069] The preparation method of the comparative sample resin of Comparative Example 2 was carried out as follows: 60 g of PLA, 30 g of PBAT, 10 g of modified talc powder, 0.1 g of TMPTA, 0.1 g of ADR4368, 0.05 g of aluminate coupling agent, 0.4 g of calcium stearate, 0.5 g of antioxidant 1010, and 0.5 g of antioxidant 168. Weigh according to the weight parts and add them to a mixer and mix at room temperature for 5 min, then use a twin-screw extruder for extrusion, granulation, drying and other procedures to obtain the resin special material. The temperatures of the 15 zones of the twin-screw extruder are 120 °C, 175 °C, 180 °C, 185 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 185 °C, 180 °C respectively.

[0070] The comparative sample resin of Comparative Example 2 was extruded into a wire through a single-screw extruder equipped with a laser diameter limiting device to obtain a wire with a diameter of 1.75 ± 0.01 mm.

[0071] Comparative Example 3

[0072] The preparation method of the comparative sample resin of Comparative Example 3 was carried out as follows: 60 g of PLA, 30 g of PBAT, 10 g of talc powder, 0.1 g of TMPTA, 0.1 g of ADR4368, 0.05 g of aluminate coupling agent, 0.4 g of calcium stearate, 0.5 g of antioxidant 1010, and 0.5 g of antioxidant 168. Weigh according to the weight parts and add them to a mixer and mix at room temperature for 5 min, then use a twin-screw extruder for extrusion, granulation, drying and other procedures to obtain the resin special material. The temperatures of the 15 zones of the twin-screw extruder are 120 °C, 175 °C, 180 °C, 185 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 190 °C, 185 °C, 180 °C respectively.

[0073] The electron beam irradiation of a low-cost biodegradable special resin for 3D printing mentioned in the present invention uses the irradiation device system (DD5.0-30) of China General Nuclear Power Group Co., Ltd., and the irradiation dose is 15 kGy.

[0074] For Comparative Example 3, the comparative sample resin was extruded into a wire through a single-screw extruder equipped with a laser diameter limiting device to obtain a wire with a diameter of 1.75 ± 0.01 mm.

[0075] The properties of the sheets prepared in the above Examples 1-8 and Comparative Examples 1-3 were tested, and the results are shown in Table 1:

[0076] Table 1

[0077]

[0078] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, making equivalent substitutions or changes, shall be covered by the protection scope of the present invention.

Claims

1. A special resin material for 3D printing, characterized in that, It is prepared from the following components: 50 - 70 parts by weight of PLA; 15 - 30 parts by weight of PBAT; 10 - 20 parts by weight of modified inorganic filler, and the modified inorganic filler is prepared from aluminate coupling agent, TMPTA, ADR chain extender and inorganic filler; 0.6 - 2 parts by weight of additives.

2. The 3D printing special resin material according to claim 1, characterized in that, The epoxy equivalent of the ADR chain extender is 250 g / mol - 500 g / mol.

3. The 3D printing special resin material according to claim 1, characterized in that The inorganic filler includes calcium carbonate or talcum powder; The additives include 0.4 - 1 part by weight of lubricant and 0.2 - 1 part by weight of antioxidant.

4. The 3D printing special resin material according to claim 1, characterized in that The mass ratio of the aluminate coupling agent, TMPTA, ADR chain extender and inorganic filler is (1 - 2):(1 - 5):(1 - 5):

100.

5. The 3D printing special resin material according to claim 4, wherein The masses of TMPTA and the ADR chain extender are equal.

6. The 3D printing special resin material according to claim 1, wherein The modified inorganic filler is prepared by kneading and granulating the aluminate coupling agent, TMPTA, ADR chain extender and inorganic filler in sequence. The temperature of the kneading is 100°C - 130°C, and the time of the kneading is 10 min - 60 min.

7. The 3D printing special resin material according to any one of claims 1 to 6, characterized in that It is prepared from the following components: 50 - 70 parts by weight of PLA; 15 - 30 parts by weight of PBAT; 10 - 20 parts by weight of modified inorganic filler, and the modified inorganic filler is prepared from aluminate coupling agent, TMPTA, ADR chain extender and inorganic filler, and the ADR chain extender is ADR4368; 0.4 - 1 part by weight of calcium stearate; 0.1 - 0.5 part by weight of antioxidant 1010; 0.1 - 0.5 part by weight of antioxidant 168.

8. The preparation method of the 3D printing special resin material according to any one of claims 1 to 7, characterized in that, It includes the following steps: After extruding and granulating PLA, PBAT, modified inorganic filler and additives, irradiate the obtained material after granulation to obtain a 3D printing special resin material.

9. The preparation method according to claim 8, characterized in that, The dose of the irradiation is 10 kGy - 100 kGy.

10. A 3D printed article, characterized in that, It is prepared from the 3D printing special resin material according to any one of claims 1 - 7.

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