CN117106291A - Degradable antibacterial material for 3D printing and preparation method thereof - Google Patents
Degradable antibacterial material for 3D printing and preparation method thereof Download PDFInfo
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- CN117106291A CN117106291A CN202311058077.XA CN202311058077A CN117106291A CN 117106291 A CN117106291 A CN 117106291A CN 202311058077 A CN202311058077 A CN 202311058077A CN 117106291 A CN117106291 A CN 117106291A
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- 239000000463 material Substances 0.000 title claims abstract description 120
- 238000010146 3D printing Methods 0.000 title claims abstract description 66
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000835 fiber Substances 0.000 claims abstract description 110
- 239000000203 mixture Substances 0.000 claims abstract description 74
- 239000011256 inorganic filler Substances 0.000 claims abstract description 12
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 12
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 claims abstract description 9
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 7
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 5
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 124
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- 238000001035 drying Methods 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- HIAAVKYLDRCDFQ-UHFFFAOYSA-L calcium;dodecanoate Chemical compound [Ca+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O HIAAVKYLDRCDFQ-UHFFFAOYSA-L 0.000 claims description 7
- 239000008041 oiling agent Substances 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 claims description 6
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- 239000012466 permeate Substances 0.000 claims description 5
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- GPLYJGXNFXKEIH-UHFFFAOYSA-N 4-(2-hydroxypropyl)-3-piperazin-1-ylquinoline-2-carboxylic acid 2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(O)Cc1c(N2CCNCC2)c(nc2ccccc12)C(O)=O GPLYJGXNFXKEIH-UHFFFAOYSA-N 0.000 claims description 3
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- 244000198134 Agave sisalana Species 0.000 claims description 2
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- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
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- 229910052791 calcium Inorganic materials 0.000 claims description 2
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229940098697 zinc laurate Drugs 0.000 claims description 2
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 claims description 2
- 238000013461 design Methods 0.000 abstract description 5
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- 238000004458 analytical method Methods 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
- D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The application belongs to the technical field of 3D printing materials, and particularly provides a degradable antibacterial material for 3D printing and a preparation method thereof, wherein the degradable antibacterial material for 3D printing comprises the following components in parts by weight: 500-700 parts of PLA, 100-300 parts of PBS, 10-150 parts of inorganic filler, 5-10 parts of fiber composition, 50-150 parts of heat stabilizer, 0.01-0.05 part of compatibilizer, 1-3 parts of antibacterial agent and natural fiber and modified natural fiber. According to the application, the natural degradable material is adopted for component design, the PLA and PBS blend is prepared as a base material, the fiber composition and the inorganic filler are doped, the bridging sliding framework is constructed by utilizing the micro characteristics of the natural fiber, the mechanical property of the material is remarkably improved, the natural material has good degradability and antibacterial property, and is safer and more environment-friendly, and the problem that the 3D printing material in the prior art is difficult to have the mechanical property, the flexibility, the antibacterial property and the degradability simultaneously is effectively solved.
Description
Technical Field
The application belongs to the technical field of 3D printing materials, and particularly provides a degradable antibacterial material for 3D printing and a preparation method thereof.
Background
The 3D printing technology, namely the additive manufacturing technology, is a rapid additive manufacturing technology which takes a computer as a three-dimensional design model as a basis, and generates a three-dimensional entity by adding a stacking material layer by layer through metal powder or polymer materials, and the conventional 3D printing material has the advantages of being capable of rapidly manufacturing a complex irregular model, saving the time and the material cost of a casting mould, being incapable of degrading and easy to pollute the environment.
PLA (polylactic acid) is a polyester polymer obtained by taking lactic acid as a main raw material for polymerization, is a novel biodegradable material, has good thermal stability, better biocompatibility, glossiness and transparency, can be used as a biomedical material, but PLA does not have better toughness, is unfavorable for processing and material use, PBS (polybutylene succinate) is a white semi-crystalline polymer, also has good biodegradability, and the PBS material has excellent mechanical property, good heat resistance and relatively low price, and natural fibers have good mechanical property and degradability, can play a bridging role, and improve the extensibility of the material.
In the food and medical industries, plastic packaging materials are often required, the packaging materials in the fields have good mechanical properties, ensure the use function of the materials, have good antibacterial property and degradability, and can meet the requirements of safety and environmental protection, while the 3D printing materials in the prior art generally have difficulty in meeting the requirements of the performances, and the prior art lacks a 3D printing material which has excellent mechanical properties and flexibility, has good antibacterial property and can be efficiently degraded.
Disclosure of Invention
Aiming at the situation, in order to overcome the defects of the prior art, the application provides the degradable material for 3D printing and the preparation method thereof, which adopts the natural degradable material for component design, prepares PLA and PBS blend as a base material, and mixes fiber composition and inorganic filler as a network skeleton, so that the mechanical property and flexibility of the material are obviously improved, and the micro-characteristics of the material are utilized to construct a bridging sliding skeleton, so that the performance of the material is obviously improved.
In order to achieve the above purpose, the technical scheme adopted by the application is as follows:
the application provides a degradable antibacterial material for 3D printing, which comprises the following components in parts by weight: 500-700 parts of PLA, 100-300 parts of PBS, 10-150 parts of inorganic filler, 5-10 parts of fiber composition, 50-150 parts of heat stabilizer, 0.01-0.05 part of compatibilizer and 1-3 parts of antibacterial agent.
Preferably, the PLA molecular weight is: 50000-70000, the molecular weight of the PBS is: 8000-12000.
Further, the fiber composition comprises natural fibers and modified natural fibers, wherein the mass ratio of the natural fibers to the modified natural fibers is 1:1.
Further, the natural fiber adopts one of bamboo fiber, sisal fiber and cotton fiber, and the modified natural fiber adopts one of coconut fiber, cotton fiber and bamboo fiber as a raw material and is prepared by an oiling agent treatment process.
Preferably, in order to facilitate the preparation of the material, the natural fiber adopts the bamboo fiber, the modified natural fiber adopts the bamboo fiber as a raw material, the bamboo fiber is prepared into the modified bamboo fiber through an oiling agent treatment process, the length of the bamboo fiber is 5-15mm, and the diameter of the bamboo fiber is 20-50 mu m.
The preparation method of the bamboo fiber comprises the following steps:
step Z1: taking a bamboo pole, removing bamboo roots, bamboo tips, tabasheer and bamboo green, cutting the bamboo pole by a cutting machine to form bamboo rings, wherein the height of the bamboo rings is 0.5-1.5cm, and mechanically crushing the bamboo rings by a crusher to form bamboo chip particles with the particle size of 0.3-1.5 cm;
step Z2: the bamboo chip particles in the step Z1 are immersed and softened by adopting an immersion liquid, and the immersion liquid is formed by stirring and mixing the following raw materials in parts by weight: 3 parts of NaOH, 0.5 part of fatty alcohol polyoxyethylene ether and 96.5 parts of water; placing bamboo chip particles in impregnating solution, keeping the impregnating and softening processing temperature at 50-60 ℃, slowly stirring the mixture of the impregnating solution and the bamboo chip particles in a mechanical stirring mode, and accelerating the impregnating and softening process;
step Z3: filtering and collecting the immersed and softened bamboo chip particles, and sending the bamboo chip particles into a rolling grinder for opening and separating silk;
step Z4: and (3) carrying out fluffing dispersion on the bamboo chip particles subjected to the fluffing and filament dividing treatment by adopting an airflow dispersing machine, and feeding hot air in the fluffing dispersion process to evaporate water to prepare the bamboo fibers.
The oil treatment process comprises the following steps:
step Y1: preparing an oil mixture, wherein the oil mixture comprises the following raw materials in parts by weight: 30 parts of anionic surfactant and 70 parts of ester compound, wherein the anionic surfactant adopts linear sodium alkylbenzenesulfonate (LAS), the ester compound adopts isopropyl propionate, 30 parts of linear sodium alkylbenzenesulfonate (LAS) and 70 parts of isopropyl propionate are placed in a constant-temperature stirrer to be stirred and emulsified, the stirring and emulsifying temperature is controlled to be 60+/-5 ℃, and the stirring and emulsifying time is 10 minutes, so that an oil mixture is prepared;
step Y2: oiling the bamboo fibers by adopting a slow stirring and pressurizing pressing mode, placing a constant-temperature stirrer into a pressurizing box, keeping the oil mixture in the constant-temperature stirrer, adding the bamboo fibers into the oil mixture, slowly stirring by the constant-temperature stirrer, keeping the stirring temperature at 60+/-5 ℃, pressurizing the pressurizing box to 0.2MPa, promoting the oil mixture to permeate and adhere to the bamboo fibers, slowly stirring for 5min, and taking out the material mixture in the constant-temperature stirrer;
step Y3: and (3) centrifugally filtering the material mixture by a centrifugal machine, and then fluffing, dispersing and drying by an airflow dispersing machine to obtain the modified bamboo fiber.
Preferably, the inorganic filler is one of nano silicate, carbonate, mesoporous silica and talcum powder.
Preferably, the heat stabilizer is one of calcium laurate soap, zinc laurate soap, calcium fatty acid soap and zinc fatty acid soap.
Further, in the scheme, the inorganic filler adopts mesoporous silica, the external diameter size of the mesoporous silica is 14-16nm, and the pore volume of the mesoporous silica is 2.31cm 3 /g。
In the scheme, the heat stabilizer adopts calcium laurate soap.
In this embodiment, the compatibilizer is DCP (dicumyl peroxide).
In this embodiment, the antimicrobial agent is HPQM (2-hydroxypropyl-3-piperazinyl-quinoline carboxylic acid methacrylate).
The application also provides a preparation method of the degradable antibacterial material for 3D printing, which comprises the following steps:
(1) Drying PLA and PBS raw materials in a hot air box;
(2) Mixing 500-700 parts of PLA, 100-300 parts of PBS, 50-150 parts of mesoporous silica, 50-150 parts of lauric acid calcium soap, 0.01-0.04 part of DCP and 1-3 parts of HPQM by using a constant temperature stirrer to prepare a substrate mixture, wherein the rotating speed of the constant temperature stirrer is set to 1000-1200rpm, the stirring time of the constant temperature stirrer is set to 10-15min, and the temperature of the constant temperature stirrer is set to 80+/-5 ℃;
(3) Adding 5-10 parts of fiber composition into a base material mixture, continuously stirring and mixing by a constant temperature stirrer, and preparing a fiber-doped mixture, wherein the rotating speed of the constant temperature stirrer is set to 400-500rpm, the stirring time of the constant temperature stirrer is set to 10-15min, and the temperature of the constant temperature stirrer is set to 80+/-5 ℃;
(4) Extruding, drawing and winding the fiber-doped mixture in the step (3) by using a double-screw extruder;
(5) The extrusion product is a degradable antimicrobial material that can be used in 3D printing.
Further, in the step (1), the temperature of the hot air box is set to be 60+/-5 ℃, and the working time of the hot air box is 24 hours;
further, in the step (4), the temperature of the head of the twin-screw extruder is set to 190-200 ℃, and the rotational speed of the twin-screw extruder is set to 60-100rpm.
The raw bamboo fiber material has excellent mechanical strength, the surface of the raw bamboo fiber is rugged, oval pores are fully distributed, the bonding and the permeation of the substrate mixture are facilitated, and the raw bamboo fiber can be mutually meshed and connected with the substrate mixture through the pores on the surface, so that the toughness of the material is remarkably improved;
when the modified bamboo fiber material is prepared, the oiling agent mixture can also quickly and efficiently permeate into the inside of the bamboo fiber and adhere to the surface of the bamboo fiber, so that the roughness of the surface of the bamboo fiber is reduced, after the modified bamboo fiber is mixed with the substrate mixture, the modified bamboo fiber and the substrate mixture are kept in a sliding connection state, when the degradable antibacterial material for 3D printing prepared by the scheme is deformed under the action of load, the modified bamboo fiber and the substrate mixture slide relatively, the modified bamboo fiber plays a bridging role, the modified bamboo fiber is prevented from being excessively elongated to break, the substrate mixture can be deformed and cannot break, and therefore the toughness of the material can be remarkably improved;
and the surface pore characteristics of the bamboo fiber enable the bamboo fiber to have the capacity of sterilizing the bamboo fiber in 24 hours by more than 75 percent.
The beneficial effects obtained by the application are as follows:
(1) The application adopts the natural degradable material to carry out component design, fully exerts the mechanical property of the natural material, utilizes the microscopic characteristics of the material to construct the bridging sliding framework, thereby obviously improving the performance of the material, and compared with the traditional 3D printing material, the material has good degradability and is more environment-friendly;
(2) The surface characteristics of the bamboo fiber, PLA and PBS enable the material to have high-efficiency antibacterial performance, and the antibacterial rate of the degradable antibacterial material for 3D printing provided by the application is more than 90% through experimental comparison analysis, so that the degradable antibacterial material has excellent antibacterial performance and can be safely applied to the fields of foods and medicines;
(3) The natural bamboo fiber has good tensile strength, the pore characteristics on the surface of the natural fiber are convenient for the substrate mixture to bond and permeate the natural bamboo fiber to be mutually meshed and connected with the substrate mixture through the pores on the surface, so that the toughness of the material is obviously improved, and therefore, the natural bamboo fiber used in the application can form a net-shaped framework in the material, and the mechanical property of the material is improved;
(4) The modified natural fiber treated by the oiling agent has good slip bridging performance, and when the material is stretched, slip is generated between the modified natural fiber and the base material mixture, but excessive slip is avoided, and the modified natural fiber can play a bridging role, so that the elongation at break of the material is obviously improved;
(5) The pore characteristics of the surface of the bamboo fiber are more convenient for oil treatment, and the oil is easier to adhere to the surface of the bamboo fiber;
(6) The DCP is added in the PLA/PBS blend for material compatibilization, so that the tensile strength of the material is improved, and the processability of the 3D printing process is better met
(7) According to the application, mesoporous silica is added into the PLA/PBS blend as a filler, so that the tensile strength of the material is further remarkably improved;
(8) According to the application, the HPQM antibacterial material is added into the PLA/PBS blend, so that the antibacterial performance of the material is greatly improved;
(9) By combining the beneficial effects, the degradable antibacterial material for 3D printing prepared by the application can be used for preparing medical or food materials with complex shapes and high requirements on antibacterial performance, and realizes new application of the materials.
Drawings
FIG. 1 is a schematic illustration of the profile of a tensile test piece used in the tensile property test of the present application;
FIG. 2 is a schematic diagram of a bridging slip model between a modified natural fiber and a substrate mixture according to the present application.
In fig. 2, 1 represents modified natural fibers, and 2 represents a base material mixture.
The accompanying drawings are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate the application and together with the embodiments of the application, serve to explain the application.
Detailed Description
The following description of the embodiments of the present application will be made in detail, but clearly, the embodiments are illustrative only and not all embodiments; all other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the present application. The preferred methods and materials described herein are illustrative only and should not be construed as limiting the application.
The experimental methods in the following examples are all conventional methods unless otherwise specified; the test materials used in the examples described below, unless otherwise specified, were all commercially available, wherein polylactic acid (PLA), polybutylene succinate (PBS), dicumyl peroxide (DCP) were all purchased from Aba Ding Shiji (Shanghai) Inc., mesoporous Silica (SiO) 2 ) And 2-hydroxypropyl-3-piperazinyl-quinoline carboxylic acid methacrylate (HPQM) were purchased from Sigma Aldrich (Shanghai) Inc.
The scheme provides a degradable antibacterial material for 3D printing, which comprises the following components in parts by weight: 500-700 parts of PLA, 100-300 parts of PBS, 10-150 parts of mesoporous silica, 2.5-5 parts of bamboo fibrils, 2.5-5 parts of modified bamboo fibrils, 50-150 parts of lauric acid calcium soap, 0.01-0.05 part of DCP and 1-3 parts of HPQM.
The raw bamboo fiber is treated by an oiling agent treatment process to prepare the modified raw bamboo fiber.
The preparation method of the bamboo fiber comprises the following steps:
step Z1: taking a bamboo pole, removing bamboo roots, bamboo tips, tabasheer and bamboo green, cutting the bamboo pole by a cutting machine to form bamboo rings, wherein the height of the bamboo rings is 0.5-1.5cm, and mechanically crushing the bamboo rings by a crusher to form bamboo chip particles with the particle size of 0.3-1.5 cm;
step Z2: the bamboo chip particles in the step Z1 are immersed and softened by adopting an immersion liquid, and the immersion liquid is formed by stirring and mixing the following raw materials in parts by weight: 3 parts of NaOH, 0.5 part of fatty alcohol polyoxyethylene ether and 96.5 parts of water; placing bamboo chip particles in impregnating solution, keeping the impregnating and softening processing temperature at 50-60 ℃, slowly stirring the mixture of the impregnating solution and the bamboo chip particles in a mechanical stirring mode, and accelerating the impregnating and softening process;
step Z3: filtering and collecting the immersed and softened bamboo chip particles, and sending the bamboo chip particles into a rolling grinder for opening and separating silk;
step Z4: and (3) carrying out fluffing dispersion on the bamboo chip particles subjected to the fluffing and filament dividing treatment by adopting an airflow dispersing machine, and feeding hot air in the fluffing dispersion process to evaporate water to prepare the bamboo fibers.
The oil treatment process comprises the following steps:
step Y1: preparing an oil mixture, wherein the oil mixture comprises the following raw materials in parts by weight: 30 parts of anionic surfactant and 70 parts of ester compound, wherein the anionic surfactant adopts linear sodium alkylbenzenesulfonate (LAS), the ester compound adopts isopropyl propionate, 30 parts of linear sodium alkylbenzenesulfonate (LAS) and 70 parts of isopropyl propionate are placed in a constant-temperature stirrer to be stirred and emulsified, the stirring and emulsifying temperature is controlled to be 60+/-5 ℃, and the stirring and emulsifying time is 10 minutes, so that an oil mixture is prepared;
step Y2: oiling the bamboo fibers by adopting a slow stirring and pressurizing pressing mode, placing a constant-temperature stirrer into a pressurizing box, keeping the oil mixture in the constant-temperature stirrer, adding the bamboo fibers into the oil mixture, slowly stirring by the constant-temperature stirrer, keeping the stirring temperature at 60+/-5 ℃, pressurizing the pressurizing box to 0.2MPa, promoting the oil mixture to permeate and adhere to the bamboo fibers, slowly stirring for 5min, and taking out the material mixture in the constant-temperature stirrer;
step Y3: and (3) centrifugally filtering the material mixture by a centrifugal machine, and then fluffing, dispersing and drying by an airflow dispersing machine to obtain the modified bamboo fiber.
The scheme also provides a preparation method of the degradable antibacterial material for 3D printing, which specifically comprises the following steps:
(1) Drying PLA and PBS raw materials in a hot air box;
(2) Mixing 500-700 parts of PLA, 100-300 parts of PBS, 50-150 parts of mesoporous silica, 50-150 parts of lauric acid calcium soap, 0.01-0.04 part of DCP and 1-3 parts of HPQM by using a constant temperature stirrer to prepare a substrate mixture, wherein the rotating speed of the constant temperature stirrer is set to 1000-1200rpm, the stirring time of the constant temperature stirrer is set to 10-15min, and the temperature of the constant temperature stirrer is set to 80+/-5 ℃;
(3) Adding 2.5-5 parts of bamboo fibers and 2.5-5 parts of modified bamboo fibers into a base material mixture, and continuously stirring and mixing by a constant temperature stirrer to prepare a fiber-doped mixture, wherein the rotating speed of the constant temperature stirrer is set to 400-500rpm, the stirring time of the constant temperature stirrer is set to 10-15min, and the temperature of the constant temperature stirrer is set to 80+/-5 ℃;
(4) Extruding, drawing and winding the fiber-doped mixture in the step (3) by using a double-screw extruder, wherein the temperature of a head of the double-screw extruder is set to be 190-200 ℃, and the rotating speed of the double-screw extruder is set to be 60-100rpm;
(5) The extrusion product is a degradable antimicrobial material that can be used in 3D printing.
A simplified component proportioning table is designed through an orthogonal design method, and a degradable antibacterial material for 3D printing with various component proportions is prepared, wherein the proportions are shown in table 1.
TABLE 1 component proportioning table
Example 1: the present example uses the raw material components of group 1 in table 1:
the embodiment provides a degradable antibacterial material for 3D printing, which comprises the following components in parts by weight: 500 parts of PLA, 300 parts of PBS, 50 parts of mesoporous silica, 5 parts of bamboo fiber, 5 parts of modified bamboo fiber, 150 parts of lauric acid calcium soap, 0.04 part of DCP and 1.5 parts of HPQM.
The embodiment also provides a preparation method of the degradable antibacterial material for 3D printing, which comprises the following steps:
(1) Drying PLA and PBS raw materials in a hot air box, wherein the temperature of the hot air box is set to be 60 ℃, and the drying time is 24 hours;
(2) Mixing 500 parts of PLA, 300 parts of PBS, 50 parts of mesoporous silica, 150 parts of lauric acid calcium soap, 0.04 part of DCP and 1.5 parts of HPQM by using a constant temperature stirrer, preparing a substrate mixture, setting the rotating speed of the constant temperature stirrer to 1000rpm, setting the stirring time of the constant temperature stirrer to 10min, and setting the temperature of the constant temperature stirrer to 80 ℃;
(3) Adding 5 parts of bamboo fibers and 5 parts of modified bamboo fibers into a base material mixture, continuously stirring and mixing by a constant-temperature stirrer, and preparing a fiber-doped mixture, wherein the rotating speed of the constant-temperature stirrer is set to 400rpm, the stirring time of the constant-temperature stirrer is set to 10min, and the temperature of the constant-temperature stirrer is set to 80 ℃;
(4) Extruding, drawing and winding the fiber-doped mixture in the step (3) by using a double-screw extruder, wherein the temperature of a head of the double-screw extruder is set to 190 ℃, and the rotating speed of the double-screw extruder is set to 60rpm;
(5) The extrusion product is a degradable antimicrobial material that can be used in 3D printing.
The degradable antibacterial material for 3D printing prepared in the steps (1) - (5) is used for printing a product with a complex shape, the material is fully dissolved in the printing process, the printing is smooth, the surface of the printed product is smooth, the supporting structure is firm, the size is stable and deformation-free, the requirement of the 3D printing material can be met, and the material has a good inhibition effect on escherichia coli.
Example 2: the present example uses the raw material composition of group 2 in table 1:
the embodiment provides a degradable antibacterial material for 3D printing, which comprises the following components in parts by weight: 500 parts of PLA, 300 parts of PBS, 150 parts of mesoporous silica, 2.5 parts of bamboo fibrils, 2.5 parts of modified bamboo fibrils, 50 parts of calcium laurate soap, 0.02 part of DCP and 2.5 parts of HPQM.
This example also provides a method of preparing a degradable antimicrobial material for 3D printing, the method of preparing being performed with reference to example 1.
Example 3: the present example uses the raw material composition of group 3 in table 1:
the embodiment provides a degradable antibacterial material for 3D printing, which comprises the following components in parts by weight: 700 parts of PLA, 100 parts of PBS, 150 parts of mesoporous silica, 5 parts of bamboo fiber, 5 parts of modified bamboo fiber, 50 parts of lauric acid calcium soap, 0.04 part of DCP and 1.5 parts of HPQM.
This example also provides a method of preparing a degradable antimicrobial material for 3D printing, the method of preparing being performed with reference to example 1.
Example 4: the present example uses the raw material composition of group 4 in table 1:
the embodiment provides a degradable antibacterial material for 3D printing, which comprises the following components in parts by weight: 700 parts of PLA, 100 parts of PBS, 50 parts of mesoporous silica, 2.5 parts of bamboo fibrils, 2.5 parts of modified bamboo fibrils, 150 parts of calcium laurate soap, 0.02 part of DCP and 2.5 parts of HPQM.
This example also provides a method of preparing a degradable antimicrobial material for 3D printing, the method of preparing being performed with reference to example 1.
Comparative example 1: comparative example 1 the effect of the compatibilizer on the tensile properties and fracture toughness of the material was verified by eliminating the inclusion of the compatibilizer compared to example 1, and the remainder was identical to example 1.
The comparative example provides a degradable antibacterial material for 3D printing, which comprises the following components in parts by weight: 500 parts of PLA, 300 parts of PBS, 50 parts of mesoporous silica, 5 parts of bamboo fiber, 5 parts of modified bamboo fiber, 150 parts of lauric acid calcium soap and 1.5 parts of HPQM.
This comparative example also provides a preparation method for 3D printing of a degradable antibacterial material, which is performed with reference to example 2.
Comparative example 2: comparative example 2 was conducted to verify the effect of the inorganic filler on the tensile properties of the material by omitting the incorporation of the inorganic filler as compared with example 1, and the rest was the same as in example 1.
The comparative example provides a degradable antibacterial material for 3D printing, which comprises the following components in parts by weight: 500 parts of PLA, 300 parts of PBS, 5 parts of bamboo fiber, 5 parts of modified bamboo fiber, 150 parts of lauric acid calcium soap, 0.04 part of DCP and 1.5 parts of HPQM.
This comparative example also provides a preparation method for 3D printing of a degradable antibacterial material, which is performed with reference to example 1.
Comparative example 3: comparative example 3 the antibacterial property of the degradable antibacterial material for 3D printing in this scheme was verified by omitting the incorporation of the antibacterial agent with respect to example 1, and the rest is the same as example 1.
The comparative example provides a degradable antibacterial material for 3D printing, which comprises the following components in parts by weight: 500 parts of PLA, 300 parts of PBS, 50 parts of mesoporous silica, 5 parts of bamboo fiber, 5 parts of modified bamboo fiber, 150 parts of lauric acid calcium soap and 0.04 part of DCP.
This comparative example also provides a preparation method for 3D printing of a degradable antibacterial material, which is performed with reference to example 1.
Comparative example 4: comparative example 4 the mechanical properties and antibacterial properties of the degradable antibacterial material for 3D printing in this scheme were verified by omitting the incorporation of the bamboo fibrils and the modified bamboo fibrils relative to comparative example 3, and the rest is the same as comparative example 3.
The comparative example provides a degradable antibacterial material for 3D printing, which comprises the following components in parts by weight: 500 parts of PLA, 300 parts of PBS, 50 parts of mesoporous silica, 150 parts of calcium laurate soap and 0.04 part of DCP.
The present comparative example also provides a preparation method for a 3D printing degradable antibacterial material, which is performed with reference to step (1), step (2), step (4) and step (5) in example 1.
Tensile Property test
The degradable antibacterial materials for 3D printing of the examples 1-4 and the comparative examples 1-4 are respectively printed to prepare tensile test pieces with standard sizes, 3 tensile test pieces are prepared in each group, the thickness of each tensile test piece is 8mm, the outline of each tensile test piece is shown in figure 1, then standard tensile test tests are carried out on the tensile test pieces of the examples 1-4 and the comparative examples 1-4 according to the detection standards related to plastic tensile property measurement of the national standards GB/T1040.1-2018 and the national standards GB/T1040.2-2022, the test is carried out by adopting a MTS Landmark 370 high-performance fatigue tester, and the tensile process is carried out by adopting a displacement control mode with the tensile rate of 2mm/min.
The tensile properties include tensile strength and elongation at break, the tensile strength is calculated by using tensile data of a MTS Landmark 370 high-performance fatigue tester and the loaded cross-sectional area of a tensile test piece, the elongation at break is calculated by using travel data of the MTS Landmark 370 high-performance fatigue tester and the tensile area size of the tensile test piece, and after invalid data which obviously does not accord with material properties due to defects of the test piece and human factors in the test process are removed, the average tensile strength and elongation at break test results of the 3D printing degradable antibacterial materials of examples 1-4 and comparative examples 1-4 are shown in Table 2.
Antibacterial property test
The antibacterial test is carried out by adopting a film pasting method, smooth and flat test pieces are respectively prepared by using the degradable antibacterial materials for 3D printing in the examples 1-4 and the comparative examples 1-4, the sizes of the test pieces are 50 mm multiplied by 50 multiplied by mm multiplied by 5 multiplied by mm (length multiplied by width multiplied by thickness), quartz pieces with the same size are purchased to be used as comparison pieces, two identical test pieces are used as a group, and two identical comparison pieces are used as a group;
the test strain adopts escherichia coli (SHBCC D80636) ordered from Shanghai preservation biotechnology center, the escherichia coli is resuscitated and cultured for 24 hours, and a proper amount of escherichia coli is selected and placed in sterile physiological saline for mixing and dilution to form bacterial suspension;
sterilizing, cleaning and drying all the test pieces and the control pieces for later use;
respectively taking a single test specimen and a control specimen, placing the test specimen and the control specimen in a sterile culture plate, sucking bacterial suspension by using a dropper, respectively dripping 0.05ml of bacterial suspension on the upper surfaces of the test specimen and the control specimen, respectively taking two identical test specimens, one for carrying the bacterial suspension in the culture plate, and the other for covering the bacterial suspension, namely, stacking the two test specimens or the control specimens of the same group up and down, placing the bacterial suspension in a gap between the two test specimens or the control specimens, covering a culture plate cover, and placing a sample in a constant-temperature incubator for culturing for 24 hours;
the equal amount of eluent is utilized to elute the bacterial colonies in each test specimen and each control specimen respectively, the living bacteria number in the eluent is counted and the bacteriostasis rate is calculated by referring to the disinfection technical Specification, the calculation result of each test specimen is shown in the table 2, the bacterial colony number on each control specimen is not reduced, but is increased, and therefore, the 24h bacteriostasis rate of the quartz plate is 0.
Degradation Performance test
Referring to annex C in GB/T19277.1 2011, degradation tests were performed on the degradable antibacterial materials for 3D printing of examples 1-4 and comparative examples 1-4 by artificial composting, and mass losses of 7D and 15D were measured, the test temperature was maintained at 50+ -5deg.C, the 7D decomposition rate and the 15D decomposition rate were calculated, and the calculation results are shown in Table 2.
TABLE 2 Performance test results
According to the performance test data in the table 2, the degradable antibacterial material for 3D printing provided by the scheme has good mechanical properties, antibacterial properties and degradability, the natural materials PLA and PBS are used as main materials, the PLA and PBS have good degradability, the tensile strength of the material is obviously improved by adding the compatibilizer DCP and the inorganic filler mesoporous silica, the residual mesoporous silica is nontoxic and harmless after the material is degraded, the material is not influenced by the environment, the natural fibers and the modified natural fibers are used for modifying the material, the bridging slip capacity of the modified natural fibers is utilized to obviously improve the breaking elongation of the material, the material is more flexible, when the substrate mixture is broken, the bridging slip model between the modified bamboo fibers and the substrate mixture is shown in the figure 2, and the natural fibers have antibacterial and bacteriostatic properties by the surface characteristics of the natural fibers, meanwhile, the natural fibers are easy to degrade and cannot pollute the environment.
In summary, as shown by the verification of the examples and the comparative examples, the degradable antibacterial material for 3D printing is prepared by organic mixing of natural materials, and the DCP and the mesoporous silica doped by the application have the obvious effect of improving the tensile strength of the material, so that the material has better processing performance, the material has excellent loading capacity after 3D printing, the extensibility of the material is obviously improved by doping natural fibers, and the application realizes good antibacterial effect by virtue of the pore characteristics of the surface of the natural material, so that the application can be widely and safely applied to medical or food packaging materials.
Although embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the application, the scope of which is defined in the appended claims and their equivalents.
The application and its embodiments have been described above with no limitation, and the application is illustrated in the figures of the accompanying drawings as one of its embodiments, without limitation in practice. In summary, those skilled in the art, having benefit of this disclosure, will appreciate that the application can be practiced without the specific details disclosed herein.
Claims (10)
1. The degradable antibacterial material for 3D printing is characterized by comprising the following raw materials in parts by weight: 500-700 parts of PLA, 100-300 parts of PBS, 10-150 parts of inorganic filler, 5-10 parts of fiber composition, 50-150 parts of heat stabilizer, 0.01-0.05 part of compatibilizer and 1-3 parts of antibacterial agent.
2. A degradable antimicrobial material for 3D printing as claimed in claim 1, wherein: a degradable antimicrobial material for 3D printing according to claim 1, wherein the PLA molecular weight is: 50000-70000, the molecular weight of the PBS is: 8000-12000.
3. A degradable antimicrobial material for 3D printing as claimed in claim 1, wherein: the degradable antibacterial material for 3D printing according to claim 1, wherein the fiber composition comprises natural fibers and modified natural fibers, and the mass ratio of the natural fibers to the modified natural fibers is 1:1.
4. The degradable antibacterial material for 3D printing according to claim 3, wherein the natural fiber is one of bamboo fiber, sisal fiber and cotton fiber, and the modified natural fiber is one of coconut fiber, cotton fiber and bamboo fiber, and is prepared by an oiling agent treatment process.
5. The degradable antibacterial material for 3D printing according to claim 4, wherein the natural fibers are bamboo fibrils, the modified natural fibers are made of bamboo fibrils, the bamboo fibrils are made into modified cotton fibers by an oiling agent treatment process, the length of the bamboo fibrils is 5-15mm, and the diameter of the bamboo fibrils is 20-50 μm.
6. The degradable antibacterial material for 3D printing according to claim 5, wherein the preparation method of the bamboo fiber comprises the following steps:
step Z1: taking a bamboo pole, removing bamboo roots, bamboo tips, tabasheer and bamboo green, cutting the bamboo pole by a cutting machine to form bamboo rings, wherein the height of the bamboo rings is 0.5-1.5cm, and mechanically crushing the bamboo rings by a crusher to form bamboo chip particles with the particle size of 0.3-1.5 cm;
step Z2: the bamboo chip particles in the step Z1 are immersed and softened by adopting an immersion liquid, and the immersion liquid is formed by stirring and mixing the following raw materials in parts by weight: 3 parts of NaOH, 0.5 part of fatty alcohol polyoxyethylene ether and 96.5 parts of water; placing bamboo chip particles in impregnating solution, keeping the impregnating and softening processing temperature at 50-60 ℃, slowly stirring the mixture of the impregnating solution and the bamboo chip particles in a mechanical stirring mode, and accelerating the impregnating and softening process;
step Z3: filtering and collecting the immersed and softened bamboo chip particles, and sending the bamboo chip particles into a rolling grinder for opening and separating silk;
step Z4: and (3) carrying out fluffing dispersion on the bamboo chip particles subjected to the fluffing and filament dividing treatment by adopting an airflow dispersing machine, and feeding hot air in the fluffing dispersion process to evaporate water to prepare the bamboo fibers.
7. A degradable antimicrobial material for 3D printing as claimed in claim 6, wherein: the oil treatment process comprises the following steps:
step Y1: preparing an oil mixture, wherein the oil mixture comprises the following raw materials in parts by weight: 30 parts of anionic surfactant and 70 parts of ester compound, wherein the anionic surfactant adopts linear sodium alkylbenzenesulfonate (LAS), the ester compound adopts isopropyl propionate, 30 parts of linear sodium alkylbenzenesulfonate (LAS) and 70 parts of isopropyl propionate are placed in a constant-temperature stirrer to be stirred and emulsified, the stirring and emulsifying temperature is controlled to be 60+/-5 ℃, and the stirring and emulsifying time is 10 minutes, so that an oil mixture is prepared;
step Y2: oiling the bamboo fibers by adopting a slow stirring and pressurizing pressing mode, placing a constant-temperature stirrer into a pressurizing box, keeping the oil mixture in the constant-temperature stirrer, adding the bamboo fibers into the oil mixture, slowly stirring by the constant-temperature stirrer, keeping the stirring temperature at 60+/-5 ℃, pressurizing the pressurizing box to 0.2MPa, promoting the oil mixture to permeate and adhere to the bamboo fibers, slowly stirring for 5min, and taking out the material mixture in the constant-temperature stirrer;
step Y3: and (3) centrifugally filtering the material mixture by a centrifugal machine, and then fluffing, dispersing and drying by an airflow dispersing machine to obtain the modified bamboo fiber.
8. The degradable antibacterial material for 3D printing according to claim 1, wherein the inorganic filler is one of nano silicate, carbonate, mesoporous silica and talcum powder, and the heat stabilizer is one of calcium laurate soap, zinc laurate soap, calcium fatty acid soap and zinc fatty acid soap.
9. The degradable antibacterial material for 3D printing according to claim 8, wherein the inorganic filler is mesoporous silica, the external diameter of the mesoporous silica is 14-16nm, and the pore volume of the mesoporous silica is 2.31cm 3 And/g, wherein the heat stabilizer adopts calcium laurate soap, the compatibilizer adopts DCP (dicumyl peroxide), and the antibacterial agent adopts HPQM (2-hydroxypropyl-3-piperazinyl-quinoline carboxylic acid methacrylate).
10. The method for preparing a degradable antibacterial material for 3D printing according to any one of claims 1 to 9, characterized in that it comprises the following steps:
(1) Drying PLA and PBS raw materials in a hot air box;
(2) Mixing 500-700 parts of PLA, 100-300 parts of PBS, 50-150 parts of mesoporous silica, 50-150 parts of lauric acid calcium soap, 0.01-0.04 part of DCP and 1-3 parts of HPQM by using a constant temperature stirrer to prepare a substrate mixture, wherein the rotating speed of the constant temperature stirrer is set to 1000-1200rpm, the stirring time of the constant temperature stirrer is set to 10-15min, and the temperature of the constant temperature stirrer is set to 80+/-5 ℃;
(3) Adding 5-10 parts of fiber composition into a base material mixture, continuously stirring and mixing by a constant temperature stirrer, and preparing a fiber-doped mixture, wherein the rotating speed of the constant temperature stirrer is set to 400-500rpm, the stirring time of the constant temperature stirrer is set to 10-15min, and the temperature of the constant temperature stirrer is set to 80+/-5 ℃;
(4) Extruding, drawing and winding the fiber-doped mixture in the step (3) by using a double-screw extruder;
(5) The extrusion product can be used for 3D printing of degradable antibacterial materials;
in the step (1), the temperature of the hot air box is set to be 60+/-5 ℃, and the working time of the hot air box is 24 hours;
in the step (4), the temperature of the head of the double-screw extruder is set to be 190-200 ℃, and the rotating speed of the double-screw extruder is set to be 60-100rpm.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002223A (en) * | 2010-11-02 | 2011-04-06 | 奇瑞汽车股份有限公司 | Full-biodegradable polylactic acid composite material and preparation method thereof |
| CN102875986A (en) * | 2012-10-09 | 2013-01-16 | 扬州大学 | Preparation method of biodegradable high-polymer alloy material |
| CN104356426A (en) * | 2014-12-01 | 2015-02-18 | 贵州凯科特材料有限公司 | High-performance long-fiber reinforced polylactic acid composite material and preparation method thereof |
| CN104530669A (en) * | 2014-12-18 | 2015-04-22 | 陈梓煜 | Modified polylactic material for 3D (three dimensional) printing and preparation method thereof |
| CN105237977A (en) * | 2015-11-06 | 2016-01-13 | 福州市福塑科学技术研究所有限公司 | Bamboo fiber reinforced degradable PLA material and preparation method thereof |
| WO2016026920A1 (en) * | 2014-08-21 | 2016-02-25 | Styrolution Group Gmbh | Polylactic acid composites with natural fibers |
| CN106752012A (en) * | 2017-01-10 | 2017-05-31 | 东北林业大学 | A kind of high-performance Wood-plastic material for 3D printing shaping and preparation method thereof |
| CN111748185A (en) * | 2020-07-21 | 2020-10-09 | 苏州环诺新材料科技有限公司 | Antibacterial plant fiber toughened PLA composite material and preparation method thereof |
| CN113512275A (en) * | 2020-04-10 | 2021-10-19 | 上海茗露新材料科技有限公司 | High-melt-strength compostable degradable material and preparation method thereof |
| CN115785634A (en) * | 2022-12-20 | 2023-03-14 | 赖玲华 | Bamboo fiber based degradable environment-friendly material and preparation method thereof |
-
2023
- 2023-08-22 CN CN202311058077.XA patent/CN117106291B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002223A (en) * | 2010-11-02 | 2011-04-06 | 奇瑞汽车股份有限公司 | Full-biodegradable polylactic acid composite material and preparation method thereof |
| CN102875986A (en) * | 2012-10-09 | 2013-01-16 | 扬州大学 | Preparation method of biodegradable high-polymer alloy material |
| WO2016026920A1 (en) * | 2014-08-21 | 2016-02-25 | Styrolution Group Gmbh | Polylactic acid composites with natural fibers |
| CN104356426A (en) * | 2014-12-01 | 2015-02-18 | 贵州凯科特材料有限公司 | High-performance long-fiber reinforced polylactic acid composite material and preparation method thereof |
| CN104530669A (en) * | 2014-12-18 | 2015-04-22 | 陈梓煜 | Modified polylactic material for 3D (three dimensional) printing and preparation method thereof |
| CN105237977A (en) * | 2015-11-06 | 2016-01-13 | 福州市福塑科学技术研究所有限公司 | Bamboo fiber reinforced degradable PLA material and preparation method thereof |
| CN106752012A (en) * | 2017-01-10 | 2017-05-31 | 东北林业大学 | A kind of high-performance Wood-plastic material for 3D printing shaping and preparation method thereof |
| CN113512275A (en) * | 2020-04-10 | 2021-10-19 | 上海茗露新材料科技有限公司 | High-melt-strength compostable degradable material and preparation method thereof |
| CN111748185A (en) * | 2020-07-21 | 2020-10-09 | 苏州环诺新材料科技有限公司 | Antibacterial plant fiber toughened PLA composite material and preparation method thereof |
| CN115785634A (en) * | 2022-12-20 | 2023-03-14 | 赖玲华 | Bamboo fiber based degradable environment-friendly material and preparation method thereof |
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