CN110669180A - High-performance anti-deformation 3D printing material and preparation method thereof - Google Patents
High-performance anti-deformation 3D printing material and preparation method thereof Download PDFInfo
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- CN110669180A CN110669180A CN201910977155.3A CN201910977155A CN110669180A CN 110669180 A CN110669180 A CN 110669180A CN 201910977155 A CN201910977155 A CN 201910977155A CN 110669180 A CN110669180 A CN 110669180A
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- parts
- pcl
- printing
- printing material
- maleic anhydride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
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- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention provides a high-performance anti-deformation 3D printing material which comprises the following raw materials in parts by weight: 50-60 parts of PA, 10-20 parts of PCL, 1-3 parts of maleic anhydride compatilizer and 2-6 parts of grafted olefin. The invention also provides a preparation method thereof, grafting the grafting olefin onto PA in the PCL molten liquid, pre-crosslinking the components, and extruding by a double-screw extruder. The 3D printing material has good fluidity in a molten state, can be used for a 3D printing technology, and has good mechanical properties.
Description
Technical Field
The invention belongs to the field of 3D printing consumable manufacturing, and particularly relates to a high-performance anti-deformation 3D printing material and a preparation method thereof.
Background
3D printing is a technology for manufacturing a three-dimensional product by adding materials layer by layer through a 3D printing device according to a designed 3D model. This layer-by-layer build-up forming technique is also known as additive manufacturing. The 3D printing integrates advanced technologies in a plurality of fields such as a digital modeling technology, an electromechanical control technology, an information technology, material science and chemistry, is one of rapid prototyping technologies, and is known as a core technology of the third industrial revolution.
The 3D printing material is an important material basis for the development of the 3D printing technology, and the development of the material determines whether the 3D printing can be widely applied or not to some extent. In recent years, 3D printing technology has been rapidly developed, and the practical application fields thereof have been gradually increased. However, the supply situation of 3D printing materials is not optimistic, and the supply situation becomes a bottleneck that restricts the development of the 3D printing industry. In 3D printing consumables with limited quantity, the problems of low strength and elongation, poor deformation resistance or toxic and harmful gas release of materials in the preparation process are also common.
CN108034208A describes a high performance anti-deformation 3D printing polymer material, which is prepared by blending and extruding inorganic ceramic substrates such as hydroxyapatite, calcium carbonate and surface modified ceramic particle powder with a polymer composition, and due to the limitation of equipment, inaccurate shape is caused during the extrusion process, and during printing, due to the separation of organic and inorganic components caused by hot melting, the density of the printed product is not uniform, and the surface has floating powder and the deformation resistance is not outstanding.
Disclosure of Invention
In order to solve the above problems, the present invention provides a deformation-resistant material entirely composed of organic matter and a method for preparing the same.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a high-performance anti-deformation 3D printing material comprises the following raw materials in parts by weight:
50-60 parts of PA
PCL10-20 parts
1-3 parts of maleic anhydride compatilizer
2-6 parts of a grafted olefin.
Preferably, the raw materials are:
50-60 parts of PA
10-15 parts of PCL
2-3 parts of maleic anhydride compatilizer
3-6 parts of a grafted olefin.
In some embodiments:
PA 55 portion
15 portions of PCL
2 parts of maleic anhydride compatilizer
4 parts of a grafted olefin.
Preferably, the grafted olefin is polyethylene, polypropylene, isoprene, vinyl chloride, styrene.
The preparation method of the 3D printing material comprises the following steps:
1) heating PCL to 80-100 ℃, and dissolving PA in PCL in batches;
2) adding a maleic anhydride compatilizer into the mixture, heating to 120 ℃, adding the grafted olefin, and stirring at a high speed until the reaction is complete;
3) cooling, filtering and drying;
4) adding the mixture into a double-screw extruder for extrusion, wherein the temperature of the double-screw extruder is 160-225 ℃.
Further, the temperature of each zone of the double-screw extruder is as follows: a first area: 160-170 ℃; and a second zone: 170-180 ℃; and (3) three zones: 180-190 ℃; and (4) four areas: 190-200 ℃; extrusion temperature: 210-225 ℃.
The present printing materials may be used in Fused Deposition Modeling (FDM) printing techniques.
The invention has the beneficial effects that:
the PCL has high toughness, can dissolve PA, accelerates the reaction rate of grafting another high-toughness polar molecular olefin to the PA in a PCL liquid environment, synergistically improves the mechanical property of a printing material, reduces the dosage of an additive, and ensures the deformation resistance of a product.
The material disclosed by the invention has good fluidity in a molten state, and can be used for a 3D printing technology.
The invention has few raw material types, does not contain toxic additive, and can be used for manufacturing biomedical products with complex structures.
The method has the advantages of simple process flow, energy conservation, emission reduction, easy degradation and environmental friendliness.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Examples 1 to 6 a high-performance deformation-resistant 3D printing material, comprising the following raw materials in parts by weight:
table 1 raw material proportioning table of examples
Examples 1-5 methods of making printing materials the methods of making were:
1) heating PCL to 100 ℃, and dissolving PA in PCL in batches;
2) adding a maleic anhydride compatilizer into the mixture, heating to 120 ℃, adding the grafted olefin, and stirring at a high speed until the reaction is complete;
3) cooling, filtering and drying;
4) adding the mixture into a double-screw extruder for extrusion, wherein the temperature of each area of the double-screw extruder is as follows: a first area: 160 ℃; and a second zone: 170 ℃; and (3) three zones: 180 ℃; and (4) four areas: 190 ℃; extrusion temperature: at 210 ℃.
Example 6 preparation of a printing material the preparation method was:
1) heating PCL to 80 ℃, and dissolving PA in PCL in batches;
2) adding a maleic anhydride compatilizer into the mixture, heating to 120 ℃, adding the grafted olefin, and stirring at a high speed until the reaction is complete;
3) cooling, filtering and drying;
4) adding the mixture into a double-screw extruder for extrusion, wherein the temperature of each area of the double-screw extruder is as follows: a first area: 170 ℃; and a second zone: 180 ℃; and (3) three zones: 190 ℃; and (4) four areas: 200 ℃; extrusion temperature: 225 ℃ is adopted.
The printing materials obtained in examples 1 to 6 were used to prepare filamentous materials with a diameter of 1.7mm, which were printed in a 3D printer with a print head at 200 ℃ and a print speed of 5mm/s, and the physical properties of the printing materials were measured as shown in Table 2:
table 2 physical properties of the examples
The present invention is described in detail in order to make those skilled in the art understand the content and practice the invention, and the invention is not limited to the above embodiments, and all equivalent changes or modifications made according to the spirit of the invention should be covered by the scope of the invention.
Claims (7)
1. The high-performance anti-deformation 3D printing material is characterized by comprising the following raw materials in parts by weight:
50-60 parts of PA
10-20 parts of PCL
1-3 parts of maleic anhydride compatilizer
2-6 parts of a grafted olefin.
2. The printing material according to claim 1, comprising the following raw materials in parts by weight:
50-60 parts of PA
10-15 parts of PCL
2-3 parts of maleic anhydride compatilizer
3-6 parts of a grafted olefin.
3. The printing material according to claim 1 or 2, comprising the following raw materials in parts by weight:
PA 55 portion
15 portions of PCL
2 parts of maleic anhydride compatilizer
4 parts of a grafted olefin.
4. The printed material of claim 1, wherein the phase-grafted olefin is polyethylene, polypropylene, isoprene, vinyl chloride, styrene.
5. A method of preparing a 3D printed material according to any of claims 1, 2 or 4, comprising the steps of:
1) heating PCL to 80-100 ℃, and dissolving PA in PCL in batches;
2) adding a maleic anhydride compatilizer into the mixture, heating to 120 ℃, adding the grafted olefin, and stirring at a high speed until the reaction is complete;
3) cooling, filtering and drying;
4) adding the mixture into a double-screw extruder for extrusion, wherein the temperature of the double-screw extruder is 160-225 ℃.
6. The process according to claim 5, wherein the temperatures in the zones of the twin-screw extruder are: a first area: 160-170 ℃; and a second zone: 170-180 ℃; and (3) three zones: 180-190 ℃; and (4) four areas: 190-200 ℃; extrusion temperature: 210-225 ℃.
7. Use of the 3D printed material according to any of claims 1 or 2 or 4 in the field of 3D printing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910977155.3A CN110669180A (en) | 2019-10-15 | 2019-10-15 | High-performance anti-deformation 3D printing material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910977155.3A CN110669180A (en) | 2019-10-15 | 2019-10-15 | High-performance anti-deformation 3D printing material and preparation method thereof |
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| CN110669180A true CN110669180A (en) | 2020-01-10 |
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| CN201910977155.3A Pending CN110669180A (en) | 2019-10-15 | 2019-10-15 | High-performance anti-deformation 3D printing material and preparation method thereof |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5446109A (en) * | 1993-02-23 | 1995-08-29 | Teijin Limited | Polyamide/aliphatic polyester block copolymer, process for the production thereof, and blend containing the same |
| CN101469069A (en) * | 2007-12-24 | 2009-07-01 | 上海杰事杰新材料股份有限公司 | Random block polyamide material |
| CN104479349A (en) * | 2014-12-18 | 2015-04-01 | 陈梓煜 | Flame-retardant composite material for 3D printing and preparation method thereof |
| CN106349661A (en) * | 2015-07-20 | 2017-01-25 | 黑龙江鑫达企业集团有限公司 | Polycaprolactone (PCL) material for 3D printing |
| CN106543662A (en) * | 2015-09-18 | 2017-03-29 | 黑龙江鑫达企业集团有限公司 | A kind of 3D printing PLA/PCL bio-based materials |
| CN106832833A (en) * | 2017-02-13 | 2017-06-13 | 艾伯尔三氐生物科技（重庆）有限公司 | A kind of 3D printing shape memory resin material, preparation method and applications |
| US20190143582A1 (en) * | 2016-05-04 | 2019-05-16 | Covestro Deutschland Ag | Copolycarbonate as a supporting material in 3-d printing |
| WO2019097179A1 (en) * | 2017-11-17 | 2019-05-23 | Arkema France | Block copolymer exhibiting improved abrasion resistance and improved tear resistance |
-
2019
- 2019-10-15 CN CN201910977155.3A patent/CN110669180A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5446109A (en) * | 1993-02-23 | 1995-08-29 | Teijin Limited | Polyamide/aliphatic polyester block copolymer, process for the production thereof, and blend containing the same |
| CN101469069A (en) * | 2007-12-24 | 2009-07-01 | 上海杰事杰新材料股份有限公司 | Random block polyamide material |
| CN104479349A (en) * | 2014-12-18 | 2015-04-01 | 陈梓煜 | Flame-retardant composite material for 3D printing and preparation method thereof |
| CN106349661A (en) * | 2015-07-20 | 2017-01-25 | 黑龙江鑫达企业集团有限公司 | Polycaprolactone (PCL) material for 3D printing |
| CN106543662A (en) * | 2015-09-18 | 2017-03-29 | 黑龙江鑫达企业集团有限公司 | A kind of 3D printing PLA/PCL bio-based materials |
| US20190143582A1 (en) * | 2016-05-04 | 2019-05-16 | Covestro Deutschland Ag | Copolycarbonate as a supporting material in 3-d printing |
| CN106832833A (en) * | 2017-02-13 | 2017-06-13 | 艾伯尔三氐生物科技（重庆）有限公司 | A kind of 3D printing shape memory resin material, preparation method and applications |
| WO2019097179A1 (en) * | 2017-11-17 | 2019-05-23 | Arkema France | Block copolymer exhibiting improved abrasion resistance and improved tear resistance |
Non-Patent Citations (2)
| Title |
|---|
| 孔子明: "《最新新型工程材料生产新技术应用与新产品开发研制及行业技术标准实用大全 2 橡胶与塑料卷》", 30 November 2004, 学苑音像出版社 * |
| 王澜等: "《高分子材料》", 31 January 2009, 中国轻工业出版社 * |
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Application publication date: 20200110 |