CN113831704A - Biodegradable PHA composite material for 3D printer consumable and preparation method thereof - Google Patents
Biodegradable PHA composite material for 3D printer consumable and preparation method thereof Download PDFInfo
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- CN113831704A CN113831704A CN202110915585.XA CN202110915585A CN113831704A CN 113831704 A CN113831704 A CN 113831704A CN 202110915585 A CN202110915585 A CN 202110915585A CN 113831704 A CN113831704 A CN 113831704A
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- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 18
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 18
- 239000002023 wood Substances 0.000 claims abstract description 18
- 239000007822 coupling agent Substances 0.000 claims abstract description 13
- 238000010146 3D printing Methods 0.000 claims abstract description 12
- 239000002667 nucleating agent Substances 0.000 claims abstract description 10
- 229920001896 polybutyrate Polymers 0.000 claims abstract description 10
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 241000219000 Populus Species 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- PFNROQCAJVOSIR-UHFFFAOYSA-N oxiran-2-ylmethyl 2-methylprop-2-enoate;5-phenylpenta-2,4-dienenitrile Chemical compound CC(=C)C(=O)OCC1CO1.N#CC=CC=CC1=CC=CC=C1 PFNROQCAJVOSIR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 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 3
- 239000000155 melt Substances 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- -1 pentaerythritol ester Chemical class 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000007639 printing Methods 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 39
- 229920000903 polyhydroxyalkanoate Polymers 0.000 description 38
- 238000012360 testing method Methods 0.000 description 3
- 239000012620 biological material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 229920001587 Wood-plastic composite Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011155 wood-plastic composite Substances 0.000 description 1
Images
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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
Abstract
The invention discloses a biodegradable PHA composite material for 3D printer consumables and a preparation method thereof. A biodegradable PHA composite material for consumables of a3D printer, comprising, in parts by weight: PHA resin, PBAT resin, wood powder, a nucleating agent, a compatilizer, a coupling agent, an antioxidant and a lubricant. The invention has the beneficial effects that: the following problems are solved: the toughness of the PHA material is improved, so that the toughness meets the requirements of 3D printing consumables; the crystallinity of the PHA material is improved, the heat-resistant temperature is improved, the printing temperature can be improved from 150 ℃ to 180 ℃, and the heat-resistant temperature is improved, so that the processing and the use are facilitated; provides a PHA3D printing material with wood texture, and greatly improves the strength of the model.
Description
Technical Field
The invention relates to a biodegradable PHA composite material for 3D printer consumables and a preparation method thereof.
Background
Polyhydroxyalkanoate (PHA), an intracellular polyester synthesized by many microorganisms, is a natural high molecular biomaterial. PHA has good biocompatibility, biodegradability and thermal processing performance of plastics, can be used as biomedical materials and biodegradable packaging materials, and has become the most active research hotspot in the field of biomaterials in recent years.
PHA has good gas barrier property, and the performance of the PHA is comparable to that of products such as PET, PP and the like, and the PHA can be applied to fresh-keeping packaging of fresh products for a long time. PHA also has good hydrolytic stability and good ultraviolet stability. The excellent performances make it have wide application prospect in the fields of packaging materials, adhesive materials, spraying materials, clothing materials, appliance materials, electronic products, durable consumer goods, agricultural products and the like.
The application of PHA materials in the 3D industry is still in the first stage, and their material properties and processing techniques are not yet mature. For example, chinese patent application publication No. CN108485219A discloses a method for preparing a bio-based wood-plastic composite new material, and publication No. CN 112552654a discloses a PBAT/PHA/wood flour composition suitable for preparing a film, and preparation and application thereof, all of which mention modified preparation methods of PHA resins, but there are few patent reports of applying the same to the field of 3D printing industry.
At present, in the 3D printing industry, the PHA material as a printing material has the following problems: at present, the common PHA is used for preparing consumables of the 3D printer, and the consumables are poor in toughness and are brittle. The heat resistance of the material is not high enough, and the strength of the printed model is not sufficient. When overcoming the defects of the above material technologies, the PHA material can be modified to be a PHA composite material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a biodegradable PHA composite material for 3D printer consumables and a preparation method thereof, which solve the following problems: the toughness of the PHA material is improved, so that the toughness meets the requirements of 3D printing consumables; the crystallinity of the PHA material is improved, the heat-resistant temperature is improved, the printing temperature can be improved from 150 ℃ to 180 ℃, and the heat-resistant temperature is improved, so that the processing and the use are facilitated; provides a PHA3D printing material with wood texture, and greatly improves the strength of the model.
The technical scheme adopted by the invention is as follows:
a biodegradable PHA composite material for consumables of a3D printer, comprising, in parts by weight:
the molecular structure of the PHA resin is mP34HB 10, and the melt flow rate is 5-15g/10 min.
The PBAT resin is preferably one or more of C1100, C1200, C2224, BX7011, BX8145 and TH 801T.
The wood powder is poplar powder or oak powder, and the mesh number of the wood powder is larger than 300 meshes.
The nucleating agent is one or more of calcium carbonate, talcum powder and barium sulfate.
The compatilizer is one or more of styrene-acrylonitrile-glycidyl methacrylate, styrene-acrylonitrile-maleic anhydride copolymer and ethylene-acrylate-glycidyl ester copolymer.
The coupling agent is one or two of silane coupling agents KH550, KH560, KH570, titanate coupling agents and aluminate coupling agents.
The antioxidant is compounded by tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester serving as a main antioxidant and tri (2, 4-di-tert-butylphenyl) phosphite serving as an auxiliary antioxidant according to the mass ratio of 1: 2.
The lubricant is one or two of PE wax, mesoacid amide, white mineral oil and silicone oil.
A method for preparing a biodegradable PHA composite for 3D printer consumables, comprising the following steps:
(S1) firstly, carrying out surface treatment on the wood powder and the nucleating agent; placing the wood powder, the nucleating agent and the coupling agent into a high-speed mixer, and stirring for 3-10min at 65-80 ℃;
(S2) putting the PHA resin, the compatilizer and the antioxidant into a mixer according to the proportion, and stirring for 3-5 min; finally, adding the lubricant, and putting the mixture into a mixer to be stirred for 3-5min at the temperature of 65-80 ℃;
(S3) adding the mixed materials into a hopper of a double-screw extruder, and performing melt blending extrusion, water cooling and air drying to obtain the PHA composite material for the 3D printing consumable, wherein the temperature of the double-screw extruder is set as follows: a first area: 150-160 ℃; and a second zone: 160-170 ℃; and (3) three zones: 170 ℃ and 180 ℃; and (4) four areas: 170-180 ℃; and a fifth zone: 160-170 ℃; a sixth zone: 160-170 ℃; seven areas: 150-160 ℃; and eight regions: 150-160 ℃; zone 9: 160-170 ℃; head temperature: 160-170 ℃; the rotating speed of the screw is controlled to be 200-350 r/min; cooling requirements: the temperature requirement is 20 ℃ to 25 ℃; the automatic traction speed of the extrusion tractor is set to be 12-20 r/min; obtaining the PHA composite material for the 3D printing consumables.
The invention has the beneficial effects that: the following problems are solved: the toughness of the PHA material is improved, so that the toughness meets the requirements of 3D printing consumables; the crystallinity of the PHA material is improved, the heat-resistant temperature is improved, the printing temperature can be improved from 150 ℃ to 180 ℃, and the heat-resistant temperature is improved, so that the processing and the use are facilitated; provides a PHA3D printing material with wood texture, and greatly improves the strength of the model.
Drawings
FIG. 1 is a schematic flow chart of the steps of the present invention
Detailed Description
As shown in fig. 1, the biodegradable PHA composite material for consumable of 3D printer of the present invention comprises the following components by weight:
the molecular structure of the PHA resin is mP34HB 10, and the melt flow rate is 5-15g/10 min.
The PBAT resin is preferably one or more of C1100, C1200, C2224, BX7011, BX8145 and TH 801T.
The wood powder is poplar powder or oak powder, and the mesh number of the wood powder is larger than 300 meshes.
The nucleating agent is one or more of calcium carbonate, talcum powder and barium sulfate.
The compatilizer is one or more of styrene-acrylonitrile-glycidyl methacrylate, styrene-acrylonitrile-maleic anhydride copolymer and ethylene-acrylate-glycidyl ester copolymer.
The coupling agent is one or two of silane coupling agents KH550, KH560, KH570, titanate coupling agents and aluminate coupling agents.
The antioxidant is compounded by tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester serving as a main antioxidant and tri (2, 4-di-tert-butylphenyl) phosphite serving as an auxiliary antioxidant according to the mass ratio of 1: 2.
The lubricant is one or two of PE wax, mesoacid amide, white mineral oil and silicone oil.
A method for preparing a biodegradable PHA composite for 3D printer consumables, comprising the following steps:
(S1) firstly, carrying out surface treatment on the wood powder and the nucleating agent; placing the wood powder, the nucleating agent and the coupling agent into a high-speed mixer, and stirring for 3-10min at 65-80 ℃;
(S2) putting the PHA resin, the compatilizer and the antioxidant into a mixer according to the proportion, and stirring for 3-5 min; finally, adding the lubricant, and putting the mixture into a mixer to be stirred for 3-5min at the temperature of 65-80 ℃;
(S3) adding the mixed materials into a hopper of a double-screw extruder, and performing melt blending extrusion, water cooling and air drying to obtain the PHA composite material for the 3D printing consumable, wherein the temperature of the double-screw extruder is set as follows: a first area: 150-160 ℃; and a second zone: 160-170 ℃; and (3) three zones: 170 ℃ and 180 ℃; and (4) four areas: 170-180 ℃; and a fifth zone: 160-170 ℃; a sixth zone: 160-170 ℃; seven areas: 150-160 ℃; and eight regions: 150-160 ℃; zone 9: 160-170 ℃; head temperature: 160-170 ℃; the rotating speed of the screw is controlled to be 200-350 r/min; cooling requirements: the temperature requirement is 20 ℃ to 25 ℃; the automatic traction speed of the extrusion tractor is set to be 12-20 r/min; obtaining the PHA composite material for the 3D printing consumables.
Example 1
80% of PHA resin, 5% of PBAT resin, 5% of oak powder, 6% of calcium carbonate, 3% of styrene-acrylonitrile-glycidyl methacrylate, 0.2% of an antioxidant, and 0.5% of PE wax.
Example 2
70% of PHA resin, 5% of PBAT resin, 10% of oak powder, 11% of calcium carbonate, 3% of styrene-acrylonitrile-glycidyl methacrylate, 0.2% of an antioxidant, and 0.4% of PE wax.
Example 3
60% of PHA resin, 10% of PBAT resin, 15% of oak powder, 10% of calcium carbonate, 4% of ethylene-acrylate-glycidyl ester, 0.2% of antioxidant and 0.4% of PE wax.
Example 4
60% of PHA resin, 10% of PBAT resin, 20% of poplar powder, 5% of calcium carbonate, 4% of ethylene-acrylate-glycidyl ester, 0.2% of antioxidant and 0.4% of PE wax.
Example 5
50% of PHA resin, 10% of PBAT resin, 30% of poplar powder, 5% of calcium carbonate, 4% of ethylene-acrylate-glycidyl ester, 0.2% of antioxidant and 0.4% of PE wax.
The granulated materials of examples 1 to 5 were punched into a plate by an injection molding machine to prepare a standard mechanical test sample strip, and the mechanical properties were measured by a universal testing machine, and the test results are shown in table one.
Table-basic mechanical properties
The consumables of examples 1 to 5 were model-printed on an FDM 3D printer to evaluate their printing performance.
The invention has the beneficial effects that: the following problems are solved: the toughness of the PHA material is improved, so that the toughness meets the requirements of 3D printing consumables; the crystallinity of the PHA material is improved, the heat-resistant temperature is improved, the printing temperature can be improved from 150 ℃ to 180 ℃, and the heat-resistant temperature is improved, so that the processing and the use are facilitated; provides a PHA3D printing material with wood texture, and greatly improves the strength of the model.
Claims (10)
1. A biodegradable PHA composite material for 3D printer consumables, which is characterized by comprising the following components in parts by weight:
2. the PHA composite biodegradable material for a consumable of a3D printer according to claim 1, wherein: the molecular structure of the PHA resin is mP34HB 10, and the melt flow rate is 5-15g/10 min.
3. The PHA composite biodegradable material for a consumable of a3D printer according to claim 1, wherein: the PBAT resin is preferably one or more of C1100, C1200, C2224, BX7011, BX8145 and TH 801T.
4. The PHA composite biodegradable material for a consumable of a3D printer according to claim 1, wherein: the wood powder is poplar powder or oak powder, and the mesh number of the wood powder is larger than 300 meshes.
5. The PHA composite biodegradable material for a consumable of a3D printer according to claim 1, wherein: the nucleating agent is one or more of calcium carbonate, talcum powder and barium sulfate.
6. The PHA composite biodegradable material for a consumable of a3D printer according to claim 1, wherein: the compatilizer is one or more of styrene-acrylonitrile-glycidyl methacrylate, styrene-acrylonitrile-maleic anhydride copolymer and ethylene-acrylate-glycidyl ester copolymer.
7. The PHA composite biodegradable material for a consumable of a3D printer according to claim 1, wherein: the coupling agent is one or two of silane coupling agents KH550, KH560, KH570, titanate coupling agents and aluminate coupling agents.
8. The PHA composite biodegradable material for a consumable of a3D printer according to claim 1, wherein: the antioxidant is compounded by tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester serving as a main antioxidant and tri (2, 4-di-tert-butylphenyl) phosphite serving as an auxiliary antioxidant according to the mass ratio of 1: 2.
9. The PHA composite biodegradable material for a consumable of a3D printer according to claim 1, wherein: the lubricant is one or two of PE wax, mesoacid amide, white mineral oil and silicone oil.
10. Method for the preparation of a biodegradable PHA composite for consumables of 3D printers according to any of the claims from 1 to 9, characterized by the fact of comprising the following steps:
(1) firstly, carrying out surface treatment on wood powder and a nucleating agent; placing the wood powder, the nucleating agent and the coupling agent into a high-speed mixer, and stirring for 3-10min at 65-80 ℃;
(2) then putting the PHA resin, the compatilizer and the antioxidant into a mixer according to the proportion, and stirring for 3-5 min; finally, adding the lubricant, and putting the mixture into a mixer to be stirred for 3-5min at the temperature of 65-80 ℃;
(3) adding the mixed materials into a hopper of a double-screw extruder, and performing melt blending extrusion, water cooling and air drying to obtain the PHA composite material for the 3D printing consumables, wherein the temperature of the double-screw extruder is set as follows: a first area: 150-160 ℃; and a second zone: 160-170 ℃; and (3) three zones: 170 ℃ and 180 ℃; and (4) four areas: 170-180 ℃; and a fifth zone: 160-170 ℃; a sixth zone: 160-170 ℃; seven areas: 150-160 ℃; and eight regions: 150-160 ℃; zone 9: 160-170 ℃; head temperature: 160-170 ℃; the rotating speed of the screw is controlled to be 200-350 r/min; cooling requirements: the temperature requirement is 20 ℃ to 25 ℃; the automatic traction speed of the extrusion tractor is set to be 12-20 r/min; obtaining the PHA composite material for the 3D printing consumables.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110915585.XA CN113831704A (en) | 2021-08-10 | 2021-08-10 | Biodegradable PHA composite material for 3D printer consumable and preparation method thereof |
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| CN202110915585.XA CN113831704A (en) | 2021-08-10 | 2021-08-10 | Biodegradable PHA composite material for 3D printer consumable and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024067326A1 (en) * | 2022-09-26 | 2024-04-04 | 北京微构工场生物技术有限公司 | Straw and preparation method therefor |
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| CN106147168A (en) * | 2016-07-21 | 2016-11-23 | 芜湖凯奥尔环保科技有限公司 | A kind of straw is combined 3D printed material and preparation method thereof |
| CN106893285A (en) * | 2017-04-06 | 2017-06-27 | 华南协同创新研究院 | 3D printing reversible temperature-sensitive discoloration PHA material and its preparation method and application |
| CN107586441A (en) * | 2017-10-18 | 2018-01-16 | 四川理工学院 | A kind of multiple material of schlempe base and the technique for preparing 3D printing wire rod using the multiple material |
| CN112552654A (en) * | 2020-11-17 | 2021-03-26 | 中广核俊尔(浙江)新材料有限公司 | PBAT/PHA/wood flour composition suitable for preparing film and preparation and application thereof |
-
2021
- 2021-08-10 CN CN202110915585.XA patent/CN113831704A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106147168A (en) * | 2016-07-21 | 2016-11-23 | 芜湖凯奥尔环保科技有限公司 | A kind of straw is combined 3D printed material and preparation method thereof |
| CN106893285A (en) * | 2017-04-06 | 2017-06-27 | 华南协同创新研究院 | 3D printing reversible temperature-sensitive discoloration PHA material and its preparation method and application |
| CN107586441A (en) * | 2017-10-18 | 2018-01-16 | 四川理工学院 | A kind of multiple material of schlempe base and the technique for preparing 3D printing wire rod using the multiple material |
| CN112552654A (en) * | 2020-11-17 | 2021-03-26 | 中广核俊尔(浙江)新材料有限公司 | PBAT/PHA/wood flour composition suitable for preparing film and preparation and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024067326A1 (en) * | 2022-09-26 | 2024-04-04 | 北京微构工场生物技术有限公司 | Straw and preparation method therefor |
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Application publication date: 20211224 |
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