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CN-121973444-A - PBS-based bionic texture bio-based leather 3D printing preparation method

CN121973444ACN 121973444 ACN121973444 ACN 121973444ACN-121973444-A

Abstract

The invention relates to a preparation method of 3D printing of bionic texture bio-based leather based on PBS, which takes PBS as a base material, prepares special slurry for 3D printing by compounding bio-based toughening agent, compatilizer and the like, constructs a bionic leather texture structure through digital modeling, combines a fused deposition modeling technology to realize high-precision 3D printing molding of the bio-based leather, finally obtains the bionic bio-based leather with natural leather texture characteristics, excellent mechanical property and biodegradability through post-treatment optimization, solves the problems of complex production process, serious environmental pollution and low texture simulation degree of the traditional artificial leather, realizes green degradability of materials, and can be widely applied to the fields of bags, shoes, furniture and the like.

Inventors

  • WANG CHAO

Assignees

  • 北京碳和新材未来科技有限公司

Dates

Publication Date
20260505
Application Date
20260204

Claims (10)

  1. 1. The bionic texture bio-based leather 3D printing preparation method based on PBS comprises the following components, by weight, 60 parts of polybutylene succinate (PBS) resin with the number average molecular weight of 5-10 ten thousand, 20 parts of polylactic acid (bio-based toughening agent) with the weight average molecular weight of 8-12 ten thousand, 10 parts of maleic anhydride grafted PBS (grafting rate of 1.5-2.5%) compatilizer, 5 parts of zinc stearate lubricant, and 5 parts of antioxidant compounded by antioxidant 1010 and antioxidant 168 according to the mass ratio of 1:1; The method also comprises the following steps: Firstly, preparing slurry, namely premixing the raw materials in a high-speed mixer for 8 minutes at the speed of 1000r/min, adding the raw materials into a double-screw extruder for melt blending and granulating, wherein the temperature of a first area of the extruder is 130 ℃, the temperature of a second area of the extruder is 160 ℃, the temperature of a third area of the extruder is 170 ℃, the temperature of a fourth area of the extruder is 160 ℃, the rotating speed of a screw is 250r/min, and the extruded raw materials are subjected to water cooling and granulating to obtain PBS-based printing granules; Collecting the surface texture characteristics of natural leather by adopting a three-dimensional laser scanner (resolution: 50 μm), obtaining microscopic morphology data, constructing a three-dimensional model containing bionic textures by CAD software after noise reduction, splicing and curved surface reconstruction by using reverse engineering software, and performing layering slicing treatment according to the thickness of 0.1-0.3mm to generate a 3D printing path file in a G code format; 3D printing and forming, namely setting the printing temperature of the filamentous consumable material to 160-190 ℃, the printing speed to 30-60mm/s, the layer thickness to 0.1-0.3mm and the filling rate to 60-80% by adopting an FDM process, printing layer by layer according to a slicing file, and cooling to room temperature to obtain a bionic texture biological base leather blank; The method comprises the following steps of post-treatment, removing a supporting structure of a printing blank, polishing the printing blank with 700-mesh sand paper to be flat, putting the printing blank into a plasma treatment instrument, introducing argon, setting power to be 200W, carrying out surface modification for 10 minutes, then adopting a spraying mode to coat chitosan aqueous solution with the mass concentration of 8% and the deacetylation degree of more than or equal to 90%, airing the coating at room temperature, and finally putting the printing blank into an oven to carry out heat setting at 70 ℃ for 3 hours to obtain the finished bionic texture bio-based leather.
  2. 2. The preparation method of the bionic texture bio-based leather 3D printing based on the PBS according to claim 1, wherein in the first step, the bio-based toughening agent is atactic polylactic acid, the weight average molecular weight is 8-12 ten thousand, the melting temperature is 150-160 ℃, the compatilizer is maleic anhydride grafted PBS, the grafting rate is 1.5-2.5%, the lubricant is zinc stearate, the purity is more than or equal to 99%, the particle size is 10-20 mu m, the antioxidant is a compound combination of antioxidant 1010 and antioxidant 168 according to the mass ratio of 1:1, and the industrial purity is more than or equal to 98%.
  3. 3. The preparation method of the PBS-based bionic texture bio-based leather 3D printing according to claim 1, wherein the technological parameters of the double-screw extruder in the first step are that the temperature of a first area is 130 ℃, the temperature of a second area is 160 ℃, the temperature of a third area is 170 ℃, the temperature of a fourth area is 160 ℃, the rotating speed of a screw is 250r/min, and the drying treatment condition is that the drying is carried out for 5 hours at 90 ℃.
  4. 4. The PBS-based bionic texture bio-based leather 3D printing preparation method according to claim 1, wherein in the second step, a laser copolymerization Jiao Sanwei scanner (model: KEYENCEVK-X200K) is adopted for three-dimensional scanning, the scanning resolution is 50 μm, the scanning speed is 10-20mm/s, slicing software (such as Cura 5.0) is adopted for layering slicing, the layer thickness precision is +/-0.01 mm, and the deviation of the layer thickness parameter of the layering slicing and the layer thickness parameter of the 3D printing process is less than or equal to +/-0.02 mm.
  5. 5. The PBS-based bionic texture bio-based leather 3D printing preparation method according to claim 1, wherein the plasma surface modification process parameters in the fourth step are that the plasma power is 200W, the treatment time is 10 minutes, the gas is argon, the bio-based coating is a chitosan coating, and the heat setting treatment condition is that the heat setting is carried out for 3 hours at 70 ℃.
  6. 6. The 3D printing preparation method of the bionic texture bio-based leather based on the PBS according to any one of claims 1 to 5, wherein the tensile strength of the bio-based leather is more than or equal to 15MPa (tested according to the test conditions of film and sheet in the 3 rd part of the determination of plastic tensile properties), the elongation at break is more than or equal to 200% (tested according to the GB/T1040.3-2006), the surface texture reproduction accuracy is more than or equal to 90% (observed by a laser confocal microscope, the matching degree with the texture of the natural leather is analyzed according to ImageJ software), and the biodegradation rate is more than or equal to 90% in 180 days in the natural environment (the temperature is 25+/-2 ℃ and the humidity is 50+/-5%), thereby meeting the complete biodegradation requirements in the definition, classification, marking and degradation performance requirements of degraded plastics of GB/T20197-2006.
  7. 7. The preparation method of the bionic texture bio-based leather 3D printing based on the PBS according to claim 1, wherein the drying equipment in the first step comprises a vacuum drying oven (1), a stainless steel net drum (7) is coaxially arranged in the vacuum drying oven (1), the mesh aperture is 0.5-1.0mm, a bottom plate (8) is detachably connected to the bottom of the net drum (7) through bolts, a horizontal supporting plate (12) is arranged below the bottom plate (8), two symmetrically distributed connecting rods (10) are fixedly connected to two sides of the supporting plate (12), one end, far away from the supporting plate (12), of each connecting rod (10) is welded and fixed with the inner wall of the vacuum drying oven (1), and the length of each connecting rod (10) is 15-20cm.
  8. 8. The preparation method of the bionic texture bio-based leather 3D printing based on the PBS (phosphate buffer solution) according to claim 7, wherein a collecting frame (9) which is in sliding connection with the inner wall of the vacuum drying oven (1) is arranged below the supporting plate (12), a handle is fixedly connected to the front side surface of the collecting frame (9), an electric push rod (11) is fixedly connected to the top surface of the supporting plate (12), and the output end of the electric push rod (11) is in rotary connection with the bottom surface of the bottom plate (8) through a bearing.
  9. 9. The preparation method of the bionic texture bio-based leather 3D printing based on the PBS according to claim 8, wherein a material guiding table (13) is fixedly connected to the top surface of the bottom plate (8), a feeding pipe (2) communicated with the inside of the net drum (7) is fixedly connected to the top of the net drum (7), and the feeding pipe (2) penetrates through the top of the vacuum drying box (1) and is rotatably connected with a penetrating part through a sealing bearing.
  10. 10. The PBS-based bionic texture bio-based leather 3D printing preparation method is characterized in that a threaded cover (3) is connected to the top of a feeding pipe (2) in a threaded mode, a silicon rubber sealing gasket (14) is fixedly connected to the inner wall of the threaded cover (3), the thickness of the sealing gasket (14) is 3-5mm, a gear ring (4) is fixedly sleeved on the surface of the feeding pipe (2), the gear module is 2-3, a rotary gear (5) is connected to one side of the gear ring (4) in a meshed mode, a stepping motor (6) fixedly connected with a vacuum drying box (1) through bolts is arranged below the rotary gear (5), the model of the motor (6) is 57HS22, the rotating speed is 50-100r/min, and the output end of the motor (6) is fixedly connected with the rotary gear (5) through a coupler.

Description

PBS-based bionic texture bio-based leather 3D printing preparation method Technical Field The invention relates to the technical field of leather preparation, in particular to a PBS-based bionic texture bio-based leather 3D printing preparation method. Background The traditional artificial leather mostly uses polyvinyl chloride (PVC) and Polyurethane (PU) as raw materials, a large amount of organic solvents such as N, N-dimethylformamide and the like are needed in the production process (such as the preparation method of the PVC artificial leather), the volatilization rate of the organic solvents reaches 30-40%, serious atmospheric pollution is caused, the degradation period of the material in the natural environment exceeds 100 years, and white pollution is easy to form. Although the natural leather has excellent mechanical properties, the price is 5-8 times of that of artificial leather due to animal breeding and scarce resources, and chromium-containing wastewater (the total chromium emission limit value defined in GB21902-2008 'emission Standard of synthetic leather and artificial leather Industrial pollutants' is less than or equal to 1.5 mg/L) can be generated by a chromium salt tanning process in the processing process, so that the pollution treatment cost is high. Polybutylene succinate (PBS) is aliphatic polyester with good biodegradability and processability, is synthesized by taking renewable resources of succinic acid and butanediol as raw materials, and becomes an ideal choice for replacing the traditional petroleum-based high polymer material. However, the prior patent adopts a tape casting molding process, the texture simulation degree is only about 70%, the elongation at break is less than 150%, a mold is needed to be used for molding, and the customized production period is more than 7 days. The 3D printing technology can realize personalized molding of a complex structure, and can prepare leather products with high simulation degree by combining with bionic texture design, but at present, no related report exists that the FDM3D printing technology is combined with bionic texture digital modeling and is used for PBS-based bio-based leather preparation, and the prior art has the technical pain points of low texture simulation degree (less than or equal to 75 percent), insufficient mechanical property (less than or equal to 180 percent of elongation at break), long customization period (more than or equal to 5 days) and the like. Disclosure of Invention The invention provides a PBS-based bionic texture bio-based leather 3D printing preparation method, which solves the technical problems in the background technology. In order to solve the technical problems, the invention adopts the following technical scheme: The bionic texture bio-based leather 3D printing preparation method based on PBS comprises the following components, by weight, 60 parts of polybutylene succinate (PBS) resin with the number average molecular weight of 5-10 ten thousand, 20 parts of polylactic acid (bio-based toughening agent) with the weight average molecular weight of 8-12 ten thousand, 10 parts of maleic anhydride grafted PBS (grafting rate of 1.5-2.5%) compatilizer, 5 parts of zinc stearate lubricant, and 5 parts of antioxidant compounded by antioxidant 1010 and antioxidant 168 according to the mass ratio of 1:1; The method also comprises the following steps: Firstly, preparing slurry, namely premixing the raw materials in a high-speed mixer for 8 minutes at the speed of 1000r/min, adding the raw materials into a double-screw extruder for melt blending and granulating, wherein the temperature of a first area of the extruder is 130 ℃, the temperature of a second area of the extruder is 160 ℃, the temperature of a third area of the extruder is 170 ℃, the temperature of a fourth area of the extruder is 160 ℃, the rotating speed of a screw is 250r/min, and the extruded raw materials are subjected to water cooling and granulating to obtain PBS-based printing granules; Collecting the surface texture characteristics of natural leather by adopting a three-dimensional laser scanner (resolution: 50 μm), obtaining microscopic morphology data, constructing a three-dimensional model containing bionic textures by CAD software after noise reduction, splicing and curved surface reconstruction by using reverse engineering software, and performing layering slicing treatment according to the thickness of 0.1-0.3mm to generate a 3D printing path file in a G code format; 3D printing and forming, namely setting the printing temperature of the filamentous consumable material to 160-190 ℃, the printing speed to 30-60mm/s, the layer thickness to 0.1-0.3mm and the filling rate to 60-80% by adopting an FDM process, printing layer by layer according to a slicing file, and cooling to room temperature to obtain a bionic texture biological base leather blank; The method comprises the following steps of post-treatment, removing a supporting structu