CN106928671A - A kind of high-strength shape memory 3D printing biological plastics and preparation method - Google Patents
A kind of high-strength shape memory 3D printing biological plastics and preparation method Download PDFInfo
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- CN106928671A CN106928671A CN201710119919.6A CN201710119919A CN106928671A CN 106928671 A CN106928671 A CN 106928671A CN 201710119919 A CN201710119919 A CN 201710119919A CN 106928671 A CN106928671 A CN 106928671A
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- 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
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/12—Shape memory
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- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
Abstract
The invention discloses a kind of high-strength shape memory 3D printing biological plastics, it is by PLLA, PCL, CaCO3Compound and be made, it is 25% 80% that wherein PLLA accounts for material total mass ratio, and PCL accounts for 17% the 72% of material gross mass, CaCO3Account for the 3% of total quality of materials, it is obtained through fused glass pellet, it is blended by PLLA and PCL, its good biocompatibility can be ensured while enhancing PCL mechanical strengths, PLLA can also show shape memory characteristic after being processed through over mechanical processing or cross-linking radiation, after with PCL blending extrusions also can reserved materials shape memory, and a small amount of CaCO3Addition can not only play compatibilization, avoid mixing the hydraulic performance decline for causing, the mechanical strength of material can also further be improved, and also disclose the preparation method of high-strength shape memory 3D printing biological plastics, the method is easily operated, process conditions and production equipment requirement are low, can realize promoting the use of on a large scale, with wide application scenario.
Description
Technical field
The present invention relates to 3D printing field of material technology, a kind of biological modeling of high-strength shape memory 3D printing is specifically related to
Material.
Background technology
3D printing technique is referred to as rapid shaping technique, also referred to as increases material manufacturing technology, is one kind with mathematical model file
Based on, with powdery metal, plastics etc. can jointing material, come the rapid shaping of constructed object by way of successively printing
Technology.Compared with traditional manufacturing technology, 3D printing need not in advance manufacture mould, it is not necessary to remove substantial amounts of material in the fabrication process
Material, also can be obtained by final products without going through complicated forging technology, therefore, can be realized in production structure optimization,
Save material and save energy.
3D printing material is the important substance basis of 3D printing technique development, and to a certain extent, the development of material is determined
Can 3D printing technique wider application space, at present, the biomaterial used by fusion sediment (FDM) 3D printing technique
Mechanical strength is poor, and the product that traditional 3D printing biomaterial is printed lacks shape memory function, it is impossible to realize variable modeling
Shape, influences simulation quality and flexibility, and without shape memory, limit it in medical industry in the application of medical field
Range of application and practicality.
Traditional 3D printing biomaterial is based on PLA wire rods, but the impact strength of PLA is poor, and printed product is easily damaged
Go bad and do not possess shape memory, also there is the printing wire rod with PCL as base to come out in recent years, but its tensile strength and bending strength
Medical industry application demand can not all be met.
Thus, urgent need works out a kind of high-strength shape memory 3D printing biological plastics to solve the above problems.
The content of the invention
Not enough for more than, the invention provides a kind of high-strength shape memory 3D printing biological plastics, its feature exists
In：It is by PLLA, PCL, CaCO3It is combined and is made, wherein PLLA accounts for material total mass ratio for 25%-80%, and PCL accounts for material
Expect the 17%-72%, CaCO of gross mass3Account for the 3% of total quality of materials.
In order to further realize the present invention, the PLLA materials account for material total mass ratio for 50%-80%, and the PCL is accounted for
The 17%-47% of material gross mass, the CaCO3Account for the 3% of total quality of materials.
In order to further realize the present invention, it is 57% that the PLLA materials account for material total mass ratio, and it is total that the PCL accounts for material
The 40% of quality, the CaCO3Account for the 3% of total quality of materials.
In order to further realize the present invention, the CaCO3It is Nano-meter CaCO33。
In order to further realize the present invention, comprise the steps of,
(1) treatment of raw material：By PLLA, PCL in vacuum drying 24h, the moisture evaporation in PLLA, PCL will be remained in；
(2) batch mixing：By PLLA/PCL/CaCO3It is uniform according to aforementioned proportion mechanical mixture；
(3) melting extrusion：By in the compound system addition double screw extruder in (3), charging rate keeps uniformly smooth,
Ensure not produce betting contest in extrusion, wire vent stabilization is smooth,
(4) cool drying：Extrusion line is cooled down by first section, adopted immediately via three coolings, wire rod from after extruder extrusion
It is finally air-cooled via room temperature while playing desiccation then via room temperature cycles water-cooled with 70~80 DEG C of recirculated water coolings；
(5) by winder take-up after wire rod cool drying, winder configuration laser diameter measurement equipment adjusts take-up speed to protect
Barrier gauge or diameter of wire is 1.75 ± 0.005mm, often furls line about 340m；
(6) dry：Wire rod is vacuum dried 24h in the vacuum drying oven at 45 DEG C after the completion of take-up, you can for 3D printing
Equipment.
In order to further realize the present invention, step 1) in the drying temperature by PLLA be 55 DEG C, the drying temperature of PCL is
Room temperature.
In order to further realize the present invention, the step 3) in twin screw extrusion point three sections of temperature controls, melt temperature
It it is 190 DEG C, extrusion temperature is 185 DEG C, extrusion die temperature is 185 DEG C, extrusion die internal diameter is 2mm.
Beneficial effect：
1st, PLLA has good mechanical property, and stretch modulus is larger, and rigidity is strong, but shock resistance is poor, PCL toughness pole
It is good, with good biocompatibility and degradability, drug permeability and shape memory etc., when stretch modulus is higher and quality
After PCL blendings hard crisp PLLA splendid with the relatively low true toughness of stretch modulus, can both ensure the drop of the composite after blending
Solution performance and biocompatibility, can mutually learn from other's strong points to offset one's weaknesses in mechanical property again, finally realize the improvement of comprehensive mechanical property,
Carbonic acid calcium source is easy to get, and pollutes small, and whiteness is high, and loading is big and mixed refining process performance is good, nano-calcium carbonate can increase-volume can also
Activeness and quietness, main reason is that the specific properties of nano material, after particle size enters nanometer scale, the surface of nano-particle
, simultaneously because lacking adjacent atom around surface atom, there can be many dangling bonds with Surface binding energy increase, there is unsaturation
Property, show active surface.The high activity of nano-particle so that it is easy to macromolecular chain in matrix and produces bonding, again can be with
There is chemical bond and reaction with macromolecular chain.
2nd, PLLA (PLLA) has excellent stretching and bending strength, is blended by PLLA and PCL, strengthens PCL
Can ensure that its good biocompatibility, PLLA also can after being processed through over mechanical processing or cross-linking radiation while mechanical strength
Show shape memory characteristic, after with PCL blending extrusions also can reserved materials shape memory, and a small amount of CaCO3Plus
Entering can not only play compatibilization, it is to avoid the hydraulic performance decline that mixing is caused, additionally it is possible to further improve the mechanical strength of material.
3rd, preparation method of the invention, it is easy to operate, process conditions and equipment requirement are low, can realize large-scale life
Produce, with wide market scenario.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
The protection domain being not intended to limit the present invention.
A kind of high-strength shape memory 3D printing biological plastics, by PLLA, PCL, CaCO3Combine, wherein PLLA is carried
For the rigidity of material, PCL provides the toughness of material, CaCO3The effect of increase-volume is played in mixed system, while it is whole to improve material
The rigidity and toughness of body.CaCO in composite system3Content is 3%, PLLA and the content of PCL can be entered according to the actual requirements
Row regulation and control, the content of PLLA is increased when rigidity higher is needed, and when needing to increase toughness of material, improves PCL contents, PLLA
Material total mass ratio is accounted for for 25%-80%, PCL mass contents account for 17%-72%.
CaCO3It is preferred that using Nano-meter CaCO33。
Embodiment 1
The fused glass pellet of the present embodiment PLLA materials account for material total mass ratio for 25%, PCL accounts for material gross mass
72%, CaCO3Account for the 3% of total quality of materials；
The preparation method of the high-strength shape memory 3D printing biological plastics of the present embodiment, comprises the following steps：
(1) treatment of raw material：PLLA is vacuum dried 24h at 55 DEG C, PCL is vacuum dried 24h, will remain at room temperature
Moisture evaporation in PLLA, PCL；
(2) batch mixing：By PLLA/PCL/CaCO3It is uniform according to aforementioned proportion mechanical mixture；
(3) melting extrusion：By in the compound system addition double screw extruder in (3), charging rate keeps uniformly smooth,
Ensure not produce betting contest in extrusion, wire vent stabilization is smooth, three sections of temperature controls of twin screw extrusion point, melt temperature is
190 DEG C, extrusion temperature is 185 DEG C, and extrusion die temperature is 185 DEG C, and extrusion die internal diameter is 2mm；
(4) cool drying：Extrusion line is cooled down by first section, adopted immediately via three coolings, wire rod from after extruder extrusion
It is finally air-cooled via room temperature while playing desiccation then via room temperature cycles water-cooled with 70~80 DEG C of recirculated water coolings；
(5) by winder take-up after wire rod cool drying, winder configuration laser diameter measurement equipment adjusts take-up speed to protect
Barrier gauge or diameter of wire is 1.75 ± 0.005mm, often furls line about 340m；
(6) dry：Wire rod is vacuum dried 24h in the vacuum drying oven at 45 DEG C after the completion of take-up, you can for 3D printing
Equipment.
Embodiment 2
The fused glass pellet of the present embodiment PLLA materials account for material total mass ratio for 57%, PCL accounts for material gross mass
40%, CaCO3Account for the 3% of total quality of materials；
The preparation method of the high-strength shape memory 3D printing biological plastics of the present embodiment, comprises the following steps：
(1) treatment of raw material：PLLA is vacuum dried 24h at 55 DEG C, PCL is vacuum dried 24h, will remain at room temperature
Moisture evaporation in PLLA, PCL；
(2) batch mixing：By PLLA/PCL/ CaCO3It is uniform according to aforementioned proportion mechanical mixture；
(3) melting extrusion：By in the compound system addition double screw extruder in (3), charging rate keeps uniformly smooth,
Ensure not produce betting contest in extrusion, wire vent stabilization is smooth, three sections of temperature controls of twin screw extrusion point, melt temperature is
190 DEG C, extrusion temperature is 185 DEG C, and extrusion die temperature is 185 DEG C, and extrusion die internal diameter is 2mm；
(4) cool drying：Extrusion line is cooled down by first section, adopted immediately via three coolings, wire rod from after extruder extrusion
It is finally air-cooled via room temperature while playing desiccation then via room temperature cycles water-cooled with 70~80 DEG C of recirculated water coolings；
(5) by winder take-up after wire rod cool drying, winder configuration laser diameter measurement equipment adjusts take-up speed to protect
Barrier gauge or diameter of wire is 1.75 ± 0.005mm, often furls line about 340m；
(6) dry：Wire rod is vacuum dried 24h in the vacuum drying oven at 45 DEG C after the completion of take-up, you can for 3D printing
Equipment.
Embodiment 3
The fused glass pellet of the present embodiment PLLA materials account for material total mass ratio for 70%, PCL accounts for material gross mass
27%, CaCO3Account for the 3% of total quality of materials；
The preparation method of the high-strength shape memory 3D printing biological plastics of the present embodiment, comprises the following steps：
(1) treatment of raw material：PLLA is vacuum dried 24h at 55 DEG C, PCL is vacuum dried 24h, will remain at room temperature
Moisture evaporation in PLLA, PCL；
(2) batch mixing：By PLLA/PCL/ CaCO3It is uniform according to aforementioned proportion mechanical mixture；
(3) melting extrusion：By in the compound system addition double screw extruder in (3), charging rate keeps uniformly smooth,
Ensure not produce betting contest in extrusion, wire vent stabilization is smooth, three sections of temperature controls of twin screw extrusion point, melt temperature is
190 DEG C, extrusion temperature is 185 DEG C, and extrusion die temperature is 185 DEG C, and extrusion die internal diameter is 2mm；
(4) cool drying：Extrusion line is cooled down by first section, adopted immediately via three coolings, wire rod from after extruder extrusion
It is finally air-cooled via room temperature while playing desiccation then via room temperature cycles water-cooled with 70~80 DEG C of recirculated water coolings；
(5) by winder take-up after wire rod cool drying, winder configuration laser diameter measurement equipment adjusts take-up speed to protect
Barrier gauge or diameter of wire is 1.75 ± 0.005mm, often furls line about 340m；
(6) dry：Wire rod is vacuum dried 24h in the vacuum drying oven at 45 DEG C after the completion of take-up, you can for 3D printing
Equipment.
Embodiment 4
The fused glass pellet of the present embodiment PLLA materials account for material total mass ratio for 80%, PCL accounts for material gross mass
17%, CaCO3Account for the 3% of total quality of materials；
The preparation method of the high-strength shape memory 3D printing biological plastics of the present embodiment, comprises the following steps：
(1) treatment of raw material：PLLA is vacuum dried 24h at 55 DEG C, PCL is vacuum dried 24h, will remain at room temperature
Moisture evaporation in PLLA, PCL；
(2) batch mixing：By PLLA/PCL/ CaCO3It is uniform according to aforementioned proportion mechanical mixture；
(3) melting extrusion：By in the compound system addition double screw extruder in (3), charging rate keeps uniformly smooth,
Ensure not produce betting contest in extrusion, wire vent stabilization is smooth, three sections of temperature controls of twin screw extrusion point, melt temperature is
190 DEG C, extrusion temperature is 185 DEG C, and extrusion die temperature is 185 DEG C, and extrusion die internal diameter is 2mm；
(4) cool drying：Extrusion line is cooled down by first section, adopted immediately via three coolings, wire rod from after extruder extrusion
It is finally air-cooled via room temperature while playing desiccation then via room temperature cycles water-cooled with 70~80 DEG C of recirculated water coolings；
(5) by winder take-up after wire rod cool drying, winder configuration laser diameter measurement equipment adjusts take-up speed to protect
Barrier gauge or diameter of wire is 1.75 ± 0.005mm, often furls line about 340m；
(6) dry：Wire rod is vacuum dried 24h in the vacuum drying oven at 45 DEG C after the completion of take-up, you can for 3D printing
Equipment.
Better embodiment of the invention is the foregoing is only, the invention is not limited in above-mentioned implementation method, is being implemented
During there may be local small structural modification, if not departing from essence of the invention to various changes of the invention or modification
God and scope, and within the scope of belonging to claim of the invention and equivalent technologies, then the present invention is also intended to be changed comprising these
And modification.
Claims (7)
1. a kind of high-strength shape memory 3D printing biological plastics, it is characterised in that：It is by PLLA, PCL, CaCO3It is compound and
It is made, wherein PLLA accounts for material total mass ratio for 25%-80%, and PCL accounts for the 17%-72% of material gross mass, CaCO3Account for total
The 3% of quality of materials.
2. a kind of high-strength shape memory 3D printing biological plastics according to claim 1, it is characterised in that：It is described
PLLA materials account for material total mass ratio for 50%-80%, and the PCL accounts for the 17%-47% of material gross mass, the CaCO3Account for
The 3% of total quality of materials.
3. a kind of high-strength shape memory 3D printing biological plastics according to claim 1, it is characterised in that：It is described
It is 57% that PLLA materials account for material total mass ratio, and the PCL accounts for the 40% of material gross mass, the CaCO3Account for total quality of materials
3%.
4. a kind of high-strength shape memory 3D printing biological plastics according to claim 1, it is characterised in that：It is described
CaCO3It is Nano-meter CaCO33。
5. the preparation method of a kind of high-strength shape memory 3D printing biological plastics according to claim 1-3, it is special
Levy and be：Comprise the steps of,
(1) treatment of raw material：By PLLA, PCL in vacuum drying 24h, the moisture evaporation in PLLA, PCL will be remained in；
(2) batch mixing：By PLLA/PCL/CaCO3It is uniform according to aforementioned proportion mechanical mixture；
(3) melting extrusion：By in the compound system addition double screw extruder in (3), charging rate keeps uniformly smooth, it is ensured that
Betting contest is not produced in extrusion, wire vent stabilization is smooth,
(4) cool drying：Via three coolings, wire rod is cooled down extrusion line by first section immediately from after extruder extrusion, using 70
~80 DEG C of recirculated water coolings, it is finally air-cooled via room temperature while playing desiccation then via room temperature cycles water-cooled；
(5) by winder take-up after wire rod cool drying, winder configuration laser diameter measurement equipment adjusts take-up speed with security system
A diameter of 1.75 ± the 0.005mm of material, often furls line about 340m；
(6) dry：Wire rod is vacuum dried 24h in the vacuum drying oven at 45 DEG C after the completion of take-up, you can for 3D printing equipment.
6. a kind of preparation method of high-strength shape memory 3D printing biological plastics according to claim 5, its feature
It is：Step 1) in the drying temperature by PLLA be 55 DEG C, the drying temperature of PCL is room temperature.
7. a kind of preparation method of high-strength shape memory 3D printing biological plastics according to claim 5, its feature
It is：The step 3) in twin screw extrusion point three sections of temperature controls, melt temperature is 190 DEG C, and extrusion temperature is 185 DEG C,
Extrusion die temperature is 185 DEG C, and extrusion die internal diameter is 2mm.
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Cited By (4)
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| CN109880328A (en) * | 2019-03-14 | 2019-06-14 | 吉林大学 | A kind of preparation method of 3D printing intelligence structure polylactic acid-base composite material |
| CN109878070A (en) * | 2019-03-14 | 2019-06-14 | 吉林大学 | A kind of preparation method of the thermotropic shape memory lactic acid composite material of 3D printing |
| DE102018003274A1 (en) | 2018-04-23 | 2019-10-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Polymer blend with shape memory and / or with thermoresponsive properties |
| CN112920570A (en) * | 2021-01-28 | 2021-06-08 | 深圳光华伟业股份有限公司 | Biodegradable 4D printing shape memory material and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102018003274A1 (en) | 2018-04-23 | 2019-10-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Polymer blend with shape memory and / or with thermoresponsive properties |
| DE102018003274B4 (en) | 2018-04-23 | 2022-08-18 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Polymer blend with shape memory and/or thermoresponsive properties based on thermoplastic polyurethanes and polyolefins, polymer molding and method for programming the polymer blend of such a molding |
| CN109880328A (en) * | 2019-03-14 | 2019-06-14 | 吉林大学 | A kind of preparation method of 3D printing intelligence structure polylactic acid-base composite material |
| CN109878070A (en) * | 2019-03-14 | 2019-06-14 | 吉林大学 | A kind of preparation method of the thermotropic shape memory lactic acid composite material of 3D printing |
| CN112920570A (en) * | 2021-01-28 | 2021-06-08 | 深圳光华伟业股份有限公司 | Biodegradable 4D printing shape memory material and preparation method thereof |
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Application publication date: 20170707 |