Degradable resin composition for 3D printing, degradable material prepared from degradable resin composition and application of degradable material

Abstract

The invention relates to a degradable resin composition for 3D printing, a degradable material prepared from the degradable resin composition and application of the degradable material. The degradable resin composition is prepared from the following components in parts by weight: 70 to 90 parts of degradable resin, 5 to 20 parts of polyethylene glycol terephthalate-1, 4-cyclohexanedimethanol ester (PETG) resin, 1 to 10 parts of filler and 1.4 to 18 parts of additive, wherein the total weight of the composition is 100 parts by weight. The degradable material prepared from the degradable resin composition has the advantages that the toughness and the heat resistance of the material are enhanced, and the forming quality is improved, so that the degradable material has a wide application prospect when being used as a 3D printing material.

Description

Technical Field

[0001] This application relates to the field of resin composition technology, and more specifically to a biodegradable resin composition for 3D printing, biodegradable materials prepared therefrom, and their uses. Background Technology

[0002] Polypropylene carbonate (PPC) is a biodegradable and environmentally friendly plastic synthesized from carbon dioxide and propylene oxide. Compared with other polyesters, PPC has advantages such as low price and complete biodegradability, making it suitable for applications in packaging materials and medical fields. Compared with PLA, it has a lower melting temperature, making it easier to use in 3D printing and consuming less energy. However, PPC's low glass transition temperature, poor heat resistance, and poor toughness limit its application range. Existing toughening methods for PPC include blending with polyolefin elastomers, but this type of modification affects its biodegradability and does not significantly reduce shrinkage. Developing high-performance biodegradable resins for 3D printing requires overcoming these problems. Summary of the Invention

[0003] Technical Purpose The technical objective of this application is to provide a biodegradable resin composition for 3D printing, which can be used to provide a biodegradable material with high mechanical properties, toughness, and low shrinkage.

[0004] Another technical objective of this application is to provide a biodegradable material prepared from the above-described biodegradable resin composition.

[0005] Another technical objective of this application is to provide the application of the aforementioned biodegradable materials in 3D printing.

[0006] Technical solution In one aspect, the present invention provides a biodegradable resin composition, comprising, based on 100 parts by weight of the total composition: 70-90 parts of biodegradable resin 5-20 parts of polyethylene terephthalate-1,4-cyclohexanediol (PETG) resin, 1-10 parts of filler Additives: 1.4 to 18 parts.

[0007] In a specific embodiment, the additives include one or more of chain extenders, lubricants, coupling agents, compatibilizers, and antioxidants.

[0008] In a specific embodiment, based on 100 parts by weight of the total composition, the biodegradable resin composition comprises: 70-90 parts of biodegradable resin 5-20 parts of polyethylene terephthalate-1,4-cyclohexanediol (PETG) resin, 1-10 parts of filler Chain extender 0.1-3 parts, Lubricant 0.1 to 2 parts, Coupling agent 0.1 to 1 part, 1-10 parts compatibilizer Antioxidant 0.1 to 2 parts. In a specific embodiment, the biodegradable resin is a carbon dioxide-based copolymer, preferably selected from one or more of propylene oxide / carbon dioxide / phthalic anhydride terpolymer and propylene oxide / carbon dioxide / phthalic anhydride / cyclohexane quaternary copolymer. More preferably, the biodegradable resin is a combination of propylene oxide / carbon dioxide / phthalic anhydride terpolymer and propylene oxide / carbon dioxide / phthalic anhydride / cyclohexane quaternary copolymer.

[0009] In a specific embodiment, the glass transition temperature (Tg) of the terpolymer is ≥50℃, and the glass transition temperature (Tg) of the tetrpolymer is ≥60℃. In a specific embodiment, based on 100 parts by weight of the total composition, the biodegradable resin composition comprises 35-45 parts of propylene oxide / carbon dioxide / phthalic anhydride terpolymer, 35-45 parts of propylene oxide / carbon dioxide / phthalic anhydride / cyclohexane tetrpolymer, 5-20 parts of PETG resin, 1-10 parts of filler, 0.1-3 parts of chain extender, 0.1-2 parts of lubricant, 0.1-1 parts of coupling agent, 1-10 parts of compatibilizer, and 0.1-2 parts of antioxidant.

[0010] In a specific embodiment, the PETG resin contains 1,4 The content of cyclohexanediethanol is 20 wt% to 45 wt%.

[0011] In a specific embodiment, the filler is calcium carbonate with a particle size of 200-1500 mesh.

[0012] In a specific embodiment, the chain extender is ADR. 4368, ADR 4400, ADR One or more of 4370.

[0013] In a specific embodiment, the lubricant is a stearic acid, preferably EBS.

[0014] In a specific embodiment, the coupling agent is one or more of titanate coupling agents and aluminate coupling agents.

[0015] In a specific embodiment, the compatibilizer is PE. g MAH (polyethylene grafted maleic anhydride), PP g MAH (polypropylene grafted with maleic anhydride), ethylene Acrylates, glycidyl methacrylate, SEBS g MAH (styrene-ethylene-butene-styrene block copolymer grafted with maleic anhydride), POE g One or more of GMA (polyolefin elastomer grafted glycidyl methacrylate).

[0016] In a specific embodiment, the antioxidant is one or more of antioxidant 1010, antioxidant 1098, and antioxidant 168.

[0017] In a specific embodiment, based on 100 parts by weight of the total composition, the biodegradable resin composition comprises 35-45 parts of propylene oxide / carbon dioxide / phthalic anhydride terpolymer, 35-45 parts of propylene oxide / carbon dioxide / phthalic anhydride / cyclohexane quaternary copolymer, 5-20 parts of PETG resin, 1-10 parts of calcium carbonate with a particle size of 200-1500 mesh, 0.1-3 parts of ADR-4368, 0.1-2 parts of EBS, 0.1-1 parts of aluminate coupling agent, 1-10 parts of PP-g-MAH, 0.3-0.6 parts of antioxidant 1010, and 0.3-0.6 parts of antioxidant 168.

[0018] On the other hand, the present invention provides a method for preparing biodegradable materials using the above-mentioned biodegradable resin composition, the method comprising the following steps: S1: Place the biodegradable resin, PETG resin, filler, and additives into a mixer and stir for 3 minutes. After 5 minutes, a mixture was obtained. S2: The mixture obtained in S1 is added to an extruder, and the mixture is melt-blended, extruded, water-cooled, air-dried, and drawn to obtain a biodegradable material.

[0019] In a specific embodiment, the extruder is a twin-screw extruder, wherein the temperature zones one through six of the twin-screw extruder are set sequentially to 150°C. 190℃, 190 230℃, 210 250℃, 210 250℃, 190 250℃, 170 230℃; its main engine speed is 2 30 rpm In a specific embodiment, the extruder is a twin-screw extruder, wherein the temperature zones one to six of the twin-screw extruder are set to 170℃, 210℃, 230℃, 230℃, 210℃, and 170℃ respectively; and its main extruder speed is 20 rpm.

[0020] In another aspect, the present invention provides biodegradable materials prepared by the above method.

[0021] In a specific embodiment, the tensile strength of the biodegradable material is in the range of 50-55 MPa, and the notched impact strength is in the range of 6-8 KJ / m. 2 Within the range, the shrinkage rate is in the range of 0.6-0.8%.

[0022] In another aspect, the present invention provides a 3D printed article made from the above-mentioned biodegradable material by 3D printing.

[0023] Beneficial effects The biodegradable material for 3D printing provided in this application has at least the following beneficial effects: (1) Enhanced toughness and heat resistance: In the composition of this application, PETG is used as a toughening component and is blended with polypropylene carbonate (PPC) to significantly improve the toughness, impact performance and heat resistance of the material, and also has good mechanical properties, thus expanding its application range.

[0024] (2) Improve molding quality: After the biodegradable composition is blended and modified, the resulting biodegradable material has a low shrinkage rate. When used for 3D printing, the product does not warp significantly and exhibits high molding quality. Detailed Implementation

[0025] The technical solutions of this application are described in detail below through specific embodiments, so that those skilled in the art can better understand the technical content of this application. However, the provision of these embodiments is not intended to limit the scope of protection of this application.

[0026] Materials and methods Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0027] PETG: Purchased from China Resources Chemical, CR-5083.

[0028] Chain extender ADR-4368: purchased from BASF.

[0029] Calcium carbonate: 500 mesh, purchased from Shandong Yuxin Nanotechnology Co., Ltd.

[0030] Antioxidants 1010 and 168: purchased from BASF.

[0031] The lubricant was EBS, purchased from Shandong Xinheng Chemical Co., Ltd.

[0032] The coupling agent is an aluminate coupling agent: purchased from Nanjing Herun Coupling Agent Co., Ltd.

[0033] Compatibilizer PP g MAH: Purchased from Ningbo Nengzhiguang New Materials Co., Ltd.

[0034] Other materials and reagents, unless otherwise specified, can be obtained commercially.

[0035] In the following examples, The preparation process of the propylene oxide / carbon dioxide / phthalic anhydride copolymer (carbon dioxide-based terpolymer) used is as follows: Under anhydrous and oxygen-free conditions, 4 mol of propylene oxide, 1 mol of phthalic anhydride, and 10 mmol of triethylboron catalyst were added to a 500 ml stainless steel reactor, and carbon dioxide was introduced at 1 MPa. The reaction was carried out at 70 °C for 8 hours, then cooled to 25 °C, while unreacted carbon dioxide was slowly released. The reaction was terminated by adding an appropriate amount of acetic acid aqueous solution dropwise, and the polymer was precipitated from ethanol. The washed product was then dried in a vacuum oven to obtain the propylene oxide / carbon dioxide / phthalic anhydride terpolymer (glass transition temperature Tg ≥ 50 °C). The preparation process of the propylene oxide / carbon dioxide / phthalic anhydride / cyclohexane oxide copolymer (carbon dioxide-based quaternary copolymer) used is as follows: Under anhydrous and oxygen-free conditions, 4 mol of propylene oxide, 1 mol of phthalic anhydride, 100 mmol of cyclohexane oxide, and 10 mmol of triethylboron catalyst were added to a 500 ml stainless steel reactor, and carbon dioxide was introduced at 1.1 MPa. The reaction was carried out at 70 °C for 8 hours, then cooled to 25 °C, during which unreacted carbon dioxide was slowly released. The reaction was terminated by adding an appropriate amount of aqueous acetic acid solution, and the polymer precipitated from ethanol. The washed product was then dried in a vacuum oven to obtain a propylene oxide / carbon dioxide / phthalic anhydride / cyclohexane oxide tetromer (glass transition temperature Tg ≥ 60 °C).

[0036] The formulations of the embodiments and comparative examples of the present invention are shown in Table 1 below.

[0037] Table 1

[0038] Example 1 (1) According to the formulation of Example 1# listed in Table 1, put the biodegradable resin, PETG resin, filler, additives, etc. into a mixer and stir for 5 minutes to obtain a mixture; (2) The mixture obtained in step 1 is added to an extruder and subjected to melt blending extrusion, water cooling, air drying and traction to obtain a biodegradable material for 3D printing. The extruder is a twin-screw extruder, and the temperature zones one to six of the twin-screw extruder are set to 170℃, 210℃, 230℃, 230℃, 210℃ and 170℃ respectively. The main engine speed is 20 rpm.

[0039] Example 2 (1) According to the formulation of Example 2# listed in Table 1, put the biodegradable resin, PETG resin, filler, additives, etc. into a mixer and stir for 5 minutes to obtain a mixture; (2) The mixture obtained in step 1 is added to an extruder and subjected to melt blending extrusion, water cooling, air drying and traction to obtain a biodegradable material for 3D printing. The extruder is a twin-screw extruder, and the temperature zones one to six of the twin-screw extruder are set to 170℃, 210℃, 230℃, 230℃, 210℃ and 170℃ respectively. The main engine speed is 20 rpm.

[0040] Comparative Example 1 (1) According to the formulation of Comparative Example 1# listed in Table 1, put the biodegradable resin, filler, additives, etc. into a mixer and stir for 5 minutes to obtain a mixture; (2) The mixture obtained in step 1 is added to an extruder and subjected to melt blending extrusion, water cooling, air drying and traction to obtain a biodegradable material for 3D printing. The extruder is a twin-screw extruder, and the temperature zones one to six of the twin-screw extruder are set to 170℃, 210℃, 230℃, 230℃, 210℃ and 170℃ respectively. The main engine speed is 20 rpm.

[0041] Comparative Example 2 (1) According to the formulation of Comparative Example 2# listed in Table 1, put the biodegradable resin, additives, etc. into a mixer and stir for 5 minutes to obtain a mixture; (2) The mixture obtained in step 1 is added to an extruder and subjected to melt blending extrusion, water cooling, air drying and traction to obtain a biodegradable material for 3D printing. The extruder is a twin-screw extruder, and the temperature zones one to six of the twin-screw extruder are set to 170℃, 210℃, 230℃, 230℃, 210℃ and 170℃ respectively. The main engine speed is 20 rpm.

[0042] Test case The products obtained from the above embodiments and comparative examples were subjected to performance tests using the following methods.

[0043] (1) Tensile strength: The tensile strength was tested according to GB / T1040-2006, with a tensile rate of 50 mm / min.

[0044] (2) Notched impact strength: The notched impact strength shall be tested in accordance with GB / T 1043-1993.

[0045] (3) Shrinkage rate: Tested according to GB / T17037-2003, using small square test pieces.

[0046] (4) Vicat softening point (characterizing heat resistance): tested according to GB / T1633-2000.

[0047] The product performance test results of the examples and comparative examples are shown in Table 2 below.

[0048] Table 2

[0049] As can be seen from the data in Table 2 above, the biodegradable material with added PETG resin in this application exhibits superior performance in terms of tensile strength, notched impact strength, shrinkage rate, and Vicat softening point compared to the biodegradable material without added PETG resin. Therefore, the biodegradable material for 3D printing prepared by this invention has higher mechanical properties, toughness, lower shrinkage rate, and better heat resistance compared to the unmodified material, thus expanding the application range of biodegradable materials.

Claims

1. A biodegradable resin composition, comprising, based on 100 parts by weight of the total composition: 70-90 parts of biodegradable resin 5-20 parts of polyethylene terephthalate-1,4-cyclohexanediol (PETG) resin, 1-10 parts of filler Additives: 1.4 to 18 parts.

2. The biodegradable resin composition according to claim 1, wherein, The additives include chain extenders, lubricants, coupling agents, compatibilizers, and antioxidants.

3. The biodegradable resin composition according to claim 1, wherein, Based on 100 parts by weight of the total composition, the biodegradable resin composition comprises: 70-90 parts of biodegradable resin 5-20 parts of polyethylene terephthalate-1,4-cyclohexanediol (PETG) resin, 1-10 parts of filler Chain extender 0.1-3 parts, Lubricant 0.1 to 2 parts, Coupling agent 0.1 to 1 part, 1-10 parts compatibilizer Antioxidant 0.1 to 2 parts.

4. The biodegradable resin composition according to any one of claims 1-3, wherein, The biodegradable resin is a carbon dioxide-based copolymer, preferably selected from one or more of propylene oxide / carbon dioxide / phthalic anhydride terpolymer and propylene oxide / carbon dioxide / phthalic anhydride / cyclohexane quaternary copolymer. More preferably, the biodegradable resin is a combination of propylene oxide / carbon dioxide / phthalic anhydride terpolymer and propylene oxide / carbon dioxide / phthalic anhydride / cyclohexane quaternary copolymer.

5. The biodegradable resin composition according to claim 4, wherein, The glass transition temperature (Tg) of the terpolymer is ≥50℃, and the glass transition temperature (Tg) of the quaternary copolymer is ≥60℃.

6. The biodegradable resin composition according to any one of claims 1-3, wherein, Based on a total weight of 100 parts by weight, the biodegradable resin composition comprises 35-45 parts of a propylene oxide / carbon dioxide / phthalic anhydride terpolymer, 35-45 parts of a propylene oxide / carbon dioxide / phthalic anhydride / cyclohexane tetrpolymer, 5-20 parts of PETG resin, 1-10 parts of filler, 0.1-3 parts of chain extender, 0.1-2 parts of lubricant, 0.1-1 parts of coupling agent, 1-10 parts of compatibilizer, and 0.1-2 parts of antioxidant. The PETG resin contains 1,4 The content of cyclohexanediethanol is 20 wt% to 45 wt%. The filler is calcium carbonate with a particle size of 200-1500 mesh; The chain extender is ADR. 4368, ADR 4400, ADR One or more of 4370; The lubricant is a stearic acid, preferably EBS; The coupling agent is one or more of titanate coupling agents and aluminate coupling agents; The compatibilizer is PE. g MAH, PP g MAH, ethylene Acrylates, glycidyl methacrylate, SEBS g MAH, POE g One or more of GMA; The antioxidant is one or more of antioxidant 1010, antioxidant 1098, and antioxidant 168.

7. The biodegradable resin composition according to any one of claims 1-3, wherein, Based on 100 parts by weight of the total composition, the biodegradable resin composition comprises 35-45 parts of propylene oxide / carbon dioxide / phthalic anhydride terpolymer, 35-45 parts of propylene oxide / carbon dioxide / phthalic anhydride / cyclohexane tetrpolymer, 5-20 parts of PETG resin, 1-10 parts of calcium carbonate with a particle size of 200-1500 mesh, 0.1-3 parts of ADR-4368, 0.1-2 parts of EBS, 0.1-1 parts of aluminate coupling agent, 1-10 parts of PP-g-MAH, 0.3-0.6 parts of antioxidant 1010, and 0.3-0.6 parts of antioxidant 168.

8. A method for preparing a biodegradable material using a biodegradable resin composition as described in any one of claims 1-7, the method comprising the following steps: S1: Place the biodegradable resin, PETG resin, filler, and additives into a mixer and stir for 3 minutes. After 5 minutes, a mixture was obtained. S2: The mixture obtained in S1 is added to an extruder, and the mixture is melt-blended, extruded, water-cooled, air-dried, and drawn to obtain a biodegradable material.

9. The method according to claim 8, wherein, The extruder is a twin-screw extruder, wherein the temperature zones one through six of the twin-screw extruder are set to 150°C respectively. 190℃, 190 230℃, 210 250℃, 210 250℃, 190 250℃, 170 230℃; main unit speed is 2 30 rpm Preferably, the temperature zones one through six of the twin-screw extruder are set as follows: 170℃, 210℃, 230℃, 230℃, 210℃, and 170℃; the main extruder speed is 20 rpm.

10. A biodegradable material prepared by the method of claim 8 or 9.

11. A 3D printed article, which is made by 3D printing from the biodegradable material of claim 10.

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