A biodegradable polyester composition, and a method for preparing and using the same

Abstract

The application discloses a biodegradable polyester composition and a preparation method and application thereof, and belongs to the technical field of biodegradable materials. The biodegradable polyester composition comprises the following components in parts by mass: 48-77 parts of polylactic acid, 1-16 parts of biodegradable copolyester, 18-42 parts of talcum powder, 0.05-2.6 parts of erucic acid amide and 0.005-0.08 parts of silicone. The talcum powder has a D 95 Particle size of less than or equal to 17 microns. The biodegradable polyester composition has excellent mechanical properties and processing performance. The injection molding cycle of the biodegradable polyester composition is short, and the production efficiency is improved.

Description

Technical Field

[0001] This invention belongs to the field of biodegradable materials technology, and particularly relates to a biodegradable polyester composition, its preparation method and application. Background Technology

[0002] The selection of biodegradable and bio-based materials is an important approach to solving environmental pollution problems. It can not only fundamentally address the issue of "white pollution" (plastic pollution), but also significantly reduce the consumption of petroleum by the materials industry, alleviating pressure on petrochemical resources. Among these, polylactic acid (PLA) materials, possessing both biodegradability and bio-based advantages, are one of the most important new materials currently available.

[0003] Polylactic acid (PLA) materials have broad application prospects in industries such as product packaging, 3D printing, and injection molding due to their reliable biosafety, biodegradability, environmental friendliness, good mechanical properties, and ease of processing. However, PLA materials have problems such as poor crystallization ability, slow crystallization speed, and difficulty in demolding, which create extremely unfavorable situations in the actual processing during production and limit its application in the injection molding field to a certain extent. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a biodegradable polyester composition with excellent mechanical properties, good crystallinity, and a short molding cycle, as well as its preparation method and application.

[0005] To achieve the above objectives, in a first aspect of the present invention, the present invention provides a biodegradable polyester composition comprising the following components in parts by weight: 48-77 parts of polylactic acid, 1-16 parts of biodegradable copolyester, 18-42 parts of talc, 0.05-2.6 parts of erucamide, and 0.005-0.08 parts of silicone. The D of the talc 95 Particle size ≤17μm.

[0006] The present invention provides a biodegradable polyester composition by selecting appropriate mass proportions of components, particularly by adding erucamide and silicone to a biodegradable copolyester, and further, by combining appropriate D... 95 Talc powder with a particle size within a specific range, in combination with other components, can effectively improve the crystallinity of biodegradable polyester compositions, thereby shortening the injection molding cycle of biodegradable polyester compositions, improving the processing performance of the compositions, and the resulting products also have excellent mechanical properties.

[0007] The D of the talc 95The particle size was obtained by testing with a laser particle size analyzer. Specifically, the sample was prepared by a wet method. The talc powder to be tested and ethanol were mixed to form a particle suspension and then added to the measuring cell of the laser particle size analyzer for testing. The instrument used for testing was the LS-POP(6) of Zhuhai Omec Instrument Co., Ltd.

[0008] As a preferred embodiment of the biodegradable polyester composition of the present invention, the talc powder has a D... 95 The particle size is 10-14 μm.

[0009] For example, the D of the talc powder 95 The particle size can be any point value or any two points between 10-14 μm, such as 10.52-13.21 μm, or 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, etc.

[0010] For example, the polylactic acid can be any point value or any two-point range between 48 and 77 parts by weight, such as 50-75 parts, or 48, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 72, 74, 76, 77 parts, etc.; the biodegradable copolyester can be any point value or any two-point range between 1 and 16 parts, such as 3-15 parts, or 1, 3, 4, 6, 8, 10, 12, 14, 16 parts, etc.; the talc can be any point value or any two-point range between 18 and 42 parts, such as 20-40 parts, or 18, 20, 22, 25 parts, etc. 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, etc.; the mass fraction of erucamide can be any point value or any two-point range value between 0.05-2.6 parts, for example, it can be 0.1-2.5 parts, or 0.05 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.5 parts, 0.8 parts, 1.0 parts, 1.4 parts, 1.8 parts, 2.0 parts, 2.4 parts, 2.5 parts, etc.; the mass fraction of silicone can be any point value or any two-point range value between 0.005-0.08 parts, for example, it can be 0.01-0.07 parts, or 0.005 parts, 0.01 parts, 0.02 parts, 0.03 parts, 0.04 parts, 0.05 parts, 0.06 parts, 0.07 parts, 0.08 parts, etc.

[0011] Preferably, in the biodegradable polyester composition, the mass percentage of polylactic acid is ≥43% and the mass percentage of talc is ≥14%.

[0012] Preferably, the mass ratio of erucamide to silicone is (9-36):1.

[0013] For example, the mass ratio of erucamide to silicone can be any point value or any two points within a range of (9-36):1, such as 9:1, 10:1, 15:1, 20:1, 25:1, 30:1, 36:1, etc.

[0014] More preferably, the mass ratio of erucamide to silicone is (18-22):1.

[0015] The silicone used in this invention includes at least one of polysiloxane and silicone powder.

[0016] This invention does not impose any particular restrictions on the selection of polysiloxane or silicone powder. The polysiloxane can be dimethyl silicone oil, and the silicone powder can be BZSP001 or SY-306.

[0017] As a preferred embodiment of the biodegradable polyester composition of the present invention, the biodegradable polyester composition comprises the following components in parts by weight: 60-65 parts of polylactic acid, 8-10 parts of biodegradable polyester, 23-28 parts of talc, 0.4-1.2 parts of erucamide, and 0.02-0.03 parts of silicone.

[0018] The present invention has found that the proportions of biodegradable polyester and erucamide in a biodegradable polyester composition affect the overall performance of the product, and the proportions of other components also have a certain impact on the performance of the product. When the mass proportions of the components are further selected within the above range, the overall performance of the product is better.

[0019] As a preferred embodiment of the biodegradable polyester composition of the present invention, the biodegradable copolyester has a melt flow rate of 1-35 g / 10 min at 190°C and 2.16 kg.

[0020] The melt flow rate of the biodegradable copolyester at 190°C and 2.16 kg was tested according to ISO-1133-1:2011. It should be noted that the melt flow rate of the biodegradable copolyester may fluctuate by approximately ±12% during the testing process. For example, a biodegradable copolyester with a measured value of 30 g / 10 min may show results fluctuating between 26 and 33 g / 10 min in different batches.

[0021] The melt flow rate of the biodegradable copolyester at 190°C and 2.16 kg can be any point value or any two-point range between 1 and 35 g / 10 min, such as 2-30 g / 10 min, 2-20 g / 10 min, 20-25 g / 10 min, 20-30 g / 10 min, etc., or 1 g / 10 min, 2 g / 10 min, 4 g / 10 min, 6 g / 10 min, 8 g / 10 min, 10 g / 10 min, 12 g / 10 min, 14 g / 10 min, 16 g / 10 min, 18 g / 10 min, 20 g / 10 min, 22 g / 10 min, 24 g / 10 min, 26 g / 10 min, 28 g / 10 min, 30 g / 10 min, 32 g / 10 min, 35 g / 10 min, etc.

[0022] In a preferred embodiment of the biodegradable polyester composition of the present invention, the mass ratio of talc to biodegradable copolyester is (3-4):1.

[0023] For example, the mass ratio of talc to biodegradable copolyester can be any point value or any two points between (3-4):1, such as 3.0:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4.0:1, etc.

[0024] This invention has found that the mass ratio of talc to biodegradable copolyester affects the injection molding cycle and mechanical properties of the product. When the mass ratio of the two is further selected to be (3-4):1, the resulting product has better crystallinity, that is, a shorter injection molding cycle and better mechanical properties.

[0025] As a preferred embodiment of the biodegradable polyester composition of the present invention, the polylactic acid has a dextrorotatory D monomer molar content of ≤8%.

[0026] The molar content of the dextrorotatory D monomer of polylactic acid was obtained by gas chromatography. Specifically, the gas chromatography test was conducted using an Agilent 8860 gas chromatograph with a CP7502 column, an FID detector temperature of 200°C, a hydrogen flow rate of 45 mL / min, an air flow rate of 450 mL / min, and a split ratio of 5:1.

[0027] For example, the molar content of the dextrorotatory D monomer of polylactic acid can be any point value or any two points within the range of ≤8%, such as 0.5-8.0%, 0.5-3.7%, 0.5-1.4%, etc., or 0.5%, 1%, 1.4%, 1.5%, 2%, 2.5%, 3%, 3.5%, 3.7%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, etc.

[0028] This invention has found that when the molar content of the dextrorotatory D monomer of polylactic acid is further selected within the above-mentioned range, it can better cooperate with other components, resulting in a product with better crystallization performance and a shorter injection molding cycle.

[0029] As a preferred embodiment of the biodegradable polyester composition of the present invention, the biodegradable copolyester includes at least one of polybutylene adipate terephthalate, polybutylene sebacate terephthalate, polybutylene azelaate terephthalate, polybutylene terephthalate succinate, and polybutylene succinate.

[0030] Preferably, in the biodegradable copolyester, the molar ratio of fatty carboxylic acids to aromatic carboxylic acids is (1-2):1. Within the above range, its biodegradable characteristics can be met.

[0031] In a second aspect, the present invention also provides a method for preparing the biodegradable polyester composition, the method comprising the following steps: weighing the dried raw materials, mixing and extruding them, and granulating them to obtain the biodegradable polyester composition.

[0032] In a preferred embodiment of the preparation method described in this invention, the extrusion temperature is 150-240°C.

[0033] In a third aspect, the present invention also provides the use of the biodegradable polyester composition in the preparation of injection-molded products.

[0034] For example, the injection-molded products include any one of disposable knives, disposable forks, and disposable spoons.

[0035] Compared with the prior art, the beneficial effects of the present invention are as follows: The present invention provides a biodegradable polyester composition by selecting appropriate mass proportions of components, especially by adding a specific type of slip agent and a biodegradable copolyester within a specific melt flow rate range, and further limiting the D of talc powder. 95Within a specific particle size range, the resulting product exhibits excellent mechanical properties and a shorter injection molding cycle; specifically, the tensile strength of the obtained product is above 46.2 MPa, the elongation at break is above 4.5%, and the notched cantilever beam impact strength is above 4.0 KJ / m. 2 The injection molding cycle is less than 19 seconds. Detailed Implementation

[0036] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0037] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in the field.

[0038] Polybutylene succinate 1 (PBS1): The measured melt flow rate under the conditions of A200 SF NC801, 190℃, and 2.16kg was 30.0g / 10min. Zhuhai Kingfa Biomaterials Co., Ltd. Polybutylene succinate 2 (PBS2): The measured melt flow rate under the conditions of PBS FZ71PM, 190℃, and 2.16kg was 20.0g / 10min, Mitsubishi Chemical Corporation; Polybutylene adipate terephthalate 1 (PBAT1): A400 SF NC801, 190℃, 2.16kg, the measured melt flow rate was 20.0g / 10min, Zhuhai Kingfa Biomaterials Co., Ltd. Polybutylene adipate terephthalate 1 (PBAT2): A400 LF NC801, 190℃, 2.16kg, the measured melt flow rate was 2.0g / 10min, Zhuhai Kingfa Biomaterials Co., Ltd. Polylactic acid 1: PLA L105, the molar content of dextrorotatory D monomer was determined by gas chromatography to be 0.5%, TotalEnergies Corbion; Polylactic acid 2: PLA 3251D, the molar content of dextrorotatory D monomer was determined by gas chromatography to be 1.4% (Natureworks). Polylactic acid 3:FY204, the molar content of dextrorotatory D monomer was determined by gas chromatography to be 3.7%, Fengyuan Biotechnology; Polylactic acid 4: LX930, the molar content of dextrorotatory D monomer was determined by gas chromatography to be 8.0%, TotalEnergiesCorbion; The measured melt flow rate of a mixture of biodegradable copolyester 1:PBS1 and PBAT1 in a 1:1 mass ratio was 25 g / 10 min at 190 °C and 2.16 kg. The measured melt flow rate of biodegradable copolyester 2:PBS2 at 190℃ and 2.16kg was 20g / 10min. The measured melt flow rate of biodegradable copolyester 3:PBAT1 at 190℃ and 2.16kg was 20g / 10min. The measured melt flow rate of biodegradable copolyester 4: PBAT2 at 190℃ and 2.16kg was 2g / 10min. Talc 1: SD-9649, D 95 Particle size 5 is 10.52 μm, Liaoning Xinda Talc Group; Talc 2: T-2, D 95 Particle size 5 is 13.21 μm, Suzhou Youkuang Plastic New Material Co., Ltd.; Talc 3: SL92-10-A, D 95 Particle size 16.81μm, Guangxi Longsheng Huamei Talc Development Co., Ltd.; Talc 4: SD-9462, D 95 Particle size 5 is 8.75 μm, Liaoning Xinda Talc Group; Talc 5:T6,D 95 Particle size of 19.85μm, Suzhou Youkuang Plastic New Material Co., Ltd.; Erucamide: Commercially available; Silicone powder 1: BZSP001, Chongqing Baozhuan New Material Technology Co., Ltd.; Silicone powder 2: SY-306, Dongguan Shanyi Plastic Co., Ltd.

[0039] Examples 1-13 and Comparative Examples 1-7 The present invention provides a biodegradable polyester composition in the embodiments and comparative examples. The component content (parts by weight) of the biodegradable polyester composition is shown in Table 1-2. In Table 1-2, the mass part of silicone 1 refers to the mass part of silicone corresponding to the added silicone powder 1, and the mass part of silicone 2 refers to the mass part of silicone corresponding to the added silicone powder 2. Table 1 Table 2 The preparation method of the biodegradable polyester composition provided in Example 1 is as follows: After drying, the raw materials are weighed and added to a twin-screw extruder for mixing, extrusion, and granulation to obtain a biodegradable polyester composition. During the extrusion process, the temperature in the solid conveying zone is 130-160℃, the temperature in the melting zone is 160-210℃, and the temperature in the melt conveying zone is 210-220℃.

[0040] The preparation methods of the biodegradable polyester compositions provided in Examples 2-13 and Comparative Examples 1-7 are consistent with those in Example 1. If the relevant components are not available, they can be omitted. In Table 1-2, " / " indicates that the component is not added.

[0041] Example of effect The performance of the products prepared in the embodiments and comparative examples of this invention is verified by the following test items: 1. Tensile strength: The test shall be conducted in accordance with the requirements of GB / T 1040.1-2022, the specimen type shall refer to the A1 type specimen in GB / T 37426-2019, and the test speed shall be 50 mm / min; 2. Elongation at break: The test shall be conducted in accordance with the requirements of GB / T 1040.2-2022, and the specimen type shall refer to the A1 type specimen in GB / T 37426-2019. The test speed shall be 50 mm / min. 3. Cantilever beam notched impact strength: Injection molded specimens were prepared according to GB / T 1843-2008. Specimen dimensions: length b = (80±2) mm, width b = (10.0±0.2) mm, thickness h = (4.0±0.2) mm, and remaining notch width b. N =(8.0±0.2)mm. The notch type is Type A. The sample was conditioned for 88 hours in a test environment with a temperature of (23±2)℃ and a humidity of (50±10)% according to GB / T 2918-2018, and then a pendulum with a storage energy of 2.75J was selected for testing; 4. Injection cycle: When mass production is carried out at the same terminal, the total time required to complete one injection molding.

[0042] The test results are shown in Table 3. Table 3 As can be seen from Table 4, when the technical solution of the present invention is adopted, the obtained product has excellent mechanical properties and crystallinity; specifically, the tensile strength of the obtained biodegradable polyester composition is above 46.2 MPa, the elongation at break is above 4.5%, and the notched impact strength of the cantilever beam is above 4.0 KJ / m. 2 The injection molding cycle time is less than 19 seconds. As can be seen from Examples 1, 10-12, and Comparative Example 1, the choice of talc powder affects the performance of the product. When the D of the talc powder in Comparative Example 1... 95When the particle size is outside the range given in this invention, the resulting product not only has a significantly increased injection molding cycle, but also exhibits a significant downward trend in mechanical properties. As can be seen from Example 1 and Comparative Examples 2-4, erucamide and silicone are indispensable. Whether they are not added or replaced with other similar components, the injection molding cycle of the resulting product is significantly increased. As can be seen from Examples 1 and 5, the mass fraction of biodegradable polyester also affects the performance of the product. When the mass fraction of biodegradable polyester in Comparative Example 5 is too high, the overall performance of the obtained product decreases significantly. As can be seen from Examples 1 and 6, the mass fraction of erucamide also affects the performance of the product. When the mass fraction of erucamide in Comparative Example 6 is outside the range, the injection molding cycle of the obtained product increases significantly. As can be seen from Examples 1 and 7, the mass fraction of silicone also affects the performance of the product. When the mass fraction of silicone is outside the range of the present invention, the cantilever beam notched impact strength of the obtained product decreases significantly, and the injection molding cycle increases significantly.

[0043] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of the present invention and not to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A biodegradable polyester composition, characterized in that, The biodegradable polyester composition comprises the following components in parts by weight: Polylactic acid 48-77 parts, biodegradable polyester 1-16 parts, talc 18-42 parts, erucamide 0.05-1.2 parts, silicone 0.005-0.08 parts; The D of the talc 95 Particle size ≤17μm; The biodegradable polyester is at least one of polybutylene adipate terephthalate, polybutylene sebacic acid terephthalate, polybutylene azelaic acid terephthalate, polybutylene terephthalate succinate, and polybutylene succinate.

2. The biodegradable polyester composition according to claim 1, characterized in that, The biodegradable polyester composition comprises the following components in parts by weight: 60-65 parts polylactic acid, 8-10 parts biodegradable polyester, 23-28 parts talc, 0.4-1.2 parts erucamide, and 0.02-0.03 parts silicone.

3. The biodegradable polyester composition according to claim 1, characterized in that, The biodegradable polyester has a melt flow rate of 1-35 g / 10 min at 190°C and 2.16 kg.

4. The biodegradable polyester composition according to claim 1, characterized in that, The D of the talc 95 The particle size is 10-14 μm.

5. The biodegradable polyester composition according to claim 1, characterized in that, The mass ratio of talc to biodegradable polyester is (3-4):

1.

6. The biodegradable polyester composition according to claim 1, characterized in that, The polylactic acid has a dextrorotatory D monomer molar content of ≤8%.

7. The method for preparing the biodegradable polyester composition according to any one of claims 1-6, characterized in that, The preparation method includes the following steps: weighing the dried raw materials, mixing and extruding them, and granulating them to obtain a biodegradable polyester composition.

8. The use of the biodegradable polyester composition according to any one of claims 1-6 in the preparation of injection-molded products.

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