CN108912629A - A kind of polylactic acid 3D printing material and its preparation method and application - Google Patents
A kind of polylactic acid 3D printing material and its preparation method and application Download PDFInfo
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- CN108912629A CN108912629A CN201810562859.XA CN201810562859A CN108912629A CN 108912629 A CN108912629 A CN 108912629A CN 201810562859 A CN201810562859 A CN 201810562859A CN 108912629 A CN108912629 A CN 108912629A
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- polylactic acid
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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
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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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
- C08L2201/04—Antistatic
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
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Abstract
The present invention relates to a kind of polylactic acid 3D printing material and its preparation method and application, the polylactic acid 3D printing material is grouped as by the group of following mass fraction：30~90 parts of polylactic acid, 10~30 parts of nitrogen-doped graphene, 0.5~3 part of antioxidant, 3~7 parts of dispersing agent, 0.1~1 part of nucleating agent；Wherein, the molecular weight of the polylactic acid is 40000~100000.Polylactic acid 3D printing material provided by the invention has low-density, thermally conductive, electric conductivity, can satisfy market to high thermal conductivity, conduction, the demand of the dedicated consumptive material of low-gravity FDM.
Description
Technical field
The present invention relates to 3D printing Material Fields, and in particular to a kind of polylactic acid 3D printing material and preparation method thereof and
Using.
Background technique
" fusion sediment " (FusedDepositionModeling, FDM) rapid shaping technique is using plastic material in height
The lower melting of temperature, utilizes computer control layer layer accumulation molding.The product of random geometry can be almost formed using the technology,
Including the mold of various complicated shapes, industrial part, palm etc. needed for industrial production.
The applicable high molecular material range of " fusion sediment " rapid shaping technique is very wide, including low temperature material
(TPU, EVA, rubber, silicon rubber), common high molecular material (PP, PE, ABS), heat-resisting material (PC, PA, PEEK, PI,
PEI), biological degradation polyalcohol material (PCL, PLA, PHA) etc..At present be usually used in FDM forming technique material have polylactic acid,
ABS, nylon etc., wherein polylactic acid is widely used in FDM printing because biodegradable, printing shaping effect are good；But at present
Mainstream polylactic acid consumptive material is all to do different colours or carry out toughening to polylactic acid in the market, and there is no thermally conductive or conductive etc. special
Function.
Being constantly progressive and popularizing with FDM printing technique, the related personnel of more and more industries touch FDM printing
Technology, but being different industry is different to characteristic needed for consumptive material.Under the premise of not influencing to print object precision, mention
There is biggish application prospect for multiple functions characteristic especially low-density, thermally conductive, electric conductivity polylactic acid 3D printing material.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of polylactic acid 3D printing material, the present invention is mentioned
The polylactic acid 3D printing material of confession has low-density, thermally conductive, electric conductivity, can satisfy market to high thermal conductivity, conduction, low-gravity
The demand of the dedicated consumptive material of FDM.
Another object of the present invention is to provide the preparation methods of above-mentioned thermal conductivity polylactic acid 3D printing material.
Another object of the present invention is to provide above-mentioned thermal conductivity polylactic acid 3D printing materials in electric, industrial mould
Application in type or field of circuit boards.
A kind of polylactic acid 3D printing material, the polylactic acid 3D printing material are grouped as by the group of following mass fraction：
Wherein, the molecular weight of the polylactic acid is 40000~100000.
The present invention by select nitrogen-doped graphene and specified molecular weight polylactic acid, be aided with antioxidant, dispersing agent and at
A kind of polylactic acid 3D printing material is prepared in core agent.Poly-lactic acid material provided by the invention has thermally conductive, conductive and low-gravity
Advantage, can effectively solve existing polylactic acid leads to the problem of model surface effect difference because cooling velocity is slow in printing.
The wire rod that poly-lactic acid material provided by the invention is prepared have conducting function, can be applied to electronic apparatus etc. need to resist it is quiet
The occasion of electricity, and the specific gravity of polylactic acid wire rod obtained is lower, this advantageously reduces model weight, and model is made to reach the effect of lightweight
Fruit.
Preferably, the polylactic acid 3D printing material is grouped as by the group of following mass fraction：
In the present invention, the molecular weight of polylactic acid has large effect to the performance of 3D printing material.The molecule of polylactic acid
Amount influences whether the characteristics such as mechanical property, the mobility of polymer.The more low easier degradation of polylactic acid molecule amount, impact strength
Also poorer, the polylactic acid of low molecular weight is made into after wire rod, and the phenomenon that wire rod fractures, Jin Erying are easy to appear in print procedure
Ring the success rate of printing；The molecular weight of polylactic acid is excessive, and the mobility of polylactic acid can be caused to be substantially reduced, the resistance that when printing is subject to
Power can be larger, is easy to appear printing wire vent and has some setbacks, leads to model surface out-of-flatness.It is preferred that the molecule of the polylactic acid
Amount is 60000~80000.
Preferably, the antioxidant is Hinered phenols antioxidant and/or phosphite ester antioxidant；It is further preferable that institute
State the composite antioxidant that antioxidant is Hinered phenols antioxidant and phosphite ester antioxidant forms.
In the present invention, the Hinered phenols antioxidant and phosphite ester antioxidant can choose the anti-of this field routine
Oxygen agent；Preferably, the Hinered phenols antioxidant is 1,3,5- trimethyls -2,4, (3, the 5- di-t-butyl -4- hydroxyl benzyls of 6- tri-
Base) benzene, 2,6- di-t-butyl -4- methyl-phenol, N, N- bis- (3,5- di-tert-butyl-hydroxy phenyl propionamide), 2,2 '-is bis-
(4- methyl-6-tert butyl-phenol) methane, 2, one or more of 2 '-bis- (4- ethyl -6- t-butyl-phenol) methane,
Dosage is the 60~80% of composite antioxidant total weight.The phosphite ester antioxidant is 2,2 '-ethylenebis (4,6- bis- uncles
Butyl phenyl) fluorophosphite, one of four (2,4- di-tert-butyl-phenyl) -4,4 '-xenyl bis-phosphites or several
Kind；The phosphite ester antioxidant accounts for the 10~60% of composite antioxidant total weight, it is preferable that the phosphorous acid esters antioxygen
Agent accounts for the 20~40% of composite antioxidant gross mass.
In the present invention, the selection of dispersing agent is also most important, and dispersant selection is improper, is easy to cause N doping stone
Black alkene dispersion is uneven, reunites, seriously affects the thermally conductive and conductive characteristic of lactic acid composite material, while to printer model
Surface effect generation significantly affects.The polylactic acid of specified molecular weight and the nitrogen-doped graphene of specified particle diameter are selected in the present invention
Under conditions of, the dispersing agent preferentially selects polyethylene wax, polypropylene wax, EVA wax, ethylene bis stearic acid amide, POE wax, hard
In resin acid zinc, magnesium stearate, paraffin, ROWAXE wax, micro mist wax, oleamide, fluoropolymer or low molecular weight ionomer
It is one or more of；It is further preferable that the dispersing agent is one or more of EVA wax, POE wax, ROWAXE wax or micro mist wax.
The nucleating agent is talcum powder, silica, T-ZnO whisker, montmorillonite, MgSO4Whisker, nanofiber, graphite,
One or more of magnesia, hydrazides and amides, metal carboxylate, organic phosphate compound, further, nucleating agent is excellent
The dedicated nucleating agent of polyester/polylactic acid, such as organic hydrazides or amides nucleating agent are selected, it can more effectively promote PLA nucleation and crystallization.
The present invention also provides the preparation method of above-mentioned thermal conductivity polylactic acid 3D printing material, the method is the side
Method is that extruding pelletization will be mixed and be added in single screw extrusion machine after each raw material drying up to thermal conductivity polylactic acid 3D printing
Material.
Preferably, the processing temperature of the single screw extrusion machine is 160~230 DEG C, and screw speed is in 20~150rpm.
Method preparation FDM well known in the art can be used in the polylactic acid 3D printing material that the above method of the present invention is prepared
Printing polylactic acid wire rod.
Preparation method provided by the invention carries out extrusion modification to polylactic acid first, improves thermally conductive, the electric conductivity of polylactic acid
It can and reduce the specific gravity of polylactic acid；It is squeezed out again by single screw rod, by the adjustment of production technology, line footpath, surface spy is prepared
Property meet the lactic acid composite material that FDM printing requires, the line footpath of resulting polylactic acid wire rod be 1.75 or 2.85mm or other
Specification, the diameter error of wire rod that the polylactic acid 3D printing material in the present invention is prepared is ± 0.05mm.
Application of the above-mentioned thermal conductivity polylactic acid 3D printing material in electric, industry pattern or field of circuit boards.
Compared with prior art, the present invention has the advantages that：
Compared with existing conventional poly-lactic acid material in the market, poly-lactic acid material provided by the invention has thermally conductive, conductive
And the advantage that specific gravity is low, can satisfy conventional polylactic acid can not be applied to antistatic and thermally conductive field of electronics；And
The model surface that poly-lactic acid material provided by the invention prints is smooth, light weight, plug and wire vent does not occur in print procedure
The problems such as having some setbacks can guarantee the printing of material over time high quality, provide the solution of special material for FDM technology further genralrlization
Certainly scheme.
The product that polylactic acid 3D printing file printing provided by the invention obtains has excellent physical and chemical performance, mechanical property
And presentation quality, can meet the needs of electric equal special dimensions are to conductive, thermally conductive and light specific gravity material, there is biggish city
Field value.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.These embodiments are retouched to typical case of the invention
It states, however, the present invention is not limited thereto.Test method as used in the following examples unless otherwise specified, is conventional method, is made
Raw material, reagent etc., unless otherwise specified, being can raw materials and reagents obtained from commercial sources such as regular market purchases.
A kind of polylactic acid 3D printing material 1 of embodiment 1 and wire rod 1
A kind of polylactic acid 3D printing material, the polylactic acid 3D printing material are grouped as by the group of following mass fraction：It is poly-
Lactic acid 65g, nitrogen-doped graphene 10g, antioxidant 0.5g, dispersing agent 4g, nucleating agent 0.5g.
Wherein, the molecular weight of the polylactic acid is 40000.
The polylactic acid of drying, nitrogen-doped graphene, antioxidant, dispersing agent and nucleating agent are added in high-speed mixer, it is high
Speed mixing 3min, the material mixed is added in the barrel of single screw extrusion machine, extrusion mixing under the conditions of 180 DEG C, is air-dried,
Pelletizing obtains particles of polylactic acid 3D printing material.
Again plastic extruder, extruder temperature 180~220 will be added to after the drying of above-mentioned particles of polylactic acid 3D printing material
DEG C, 30~60RPM of screw speed squeezes out raw material, and plastic cement lines enter the sink for having ice water of 6 meters of long 10~15 DEG C, sufficiently
It is cooled and shaped wire rod；It is rolled into dragger, the size diameter of wire rod is fixed by pulling force, what dragger was formed after coming out
Wire rod, into two-wheel storage rack, buffering and storage pull out wire rod, and the wire rod that storage rack comes out enters coil winder, in drum
Automatic winding needs to be customized at polylactic acid 3D printing wire rod, gauge or diameter of wire according to client, and error range is in ± 0.05mm.
A kind of polylactic acid 3D printing material 2 of embodiment 2 and wire rod 2
A kind of polylactic acid 3D printing material, the polylactic acid 3D printing material are grouped as by the group of following mass fraction：It is poly-
Lactic acid 30g, nitrogen-doped graphene 30g, antioxidant 0.5g, dispersing agent 3g, nucleating agent 0.1g.
Wherein, the molecular weight 100000 of the polylactic acid.
A kind of polylactic acid 3D printing material 3 of embodiment 3 and wire rod 3
A kind of polylactic acid 3D printing material, the polylactic acid 3D printing material are grouped as by the group of following mass fraction：It is poly-
Lactic acid 90g, nitrogen-doped graphene 15g, antioxidant 3g, dispersing agent 7g, nucleating agent 1g.
Wherein, the molecular weight of the polylactic acid is 60000.
A kind of polylactic acid 3D printing material 4 of embodiment 4 and wire rod 4
A kind of polylactic acid 3D printing material, the polylactic acid 3D printing material are grouped as by the group of following mass fraction：It is poly-
Lactic acid 55g, nitrogen-doped graphene 25g, antioxidant 2g, dispersing agent 5g, nucleating agent 1g.
Wherein, the molecular weight 80000 of the polylactic acid.
The physical property for the polylactic acid 3D printing wire rod that Examples 1 to 4 is prepared is tested, polylactic acid wire rod
The test method of energy is as follows, and test result see the table below 1.
(1) sheet resistance measures
It is tested using sheet resistance analyzer；
(2) Determination of conductive coefficients
It is measured using thermal conductivity measuring apparatus；
(3) specific gravity tester
It is tested using specific gravity tester.
The polylactic acid 3D printing wire rod that Examples 1 to 4 is prepared is printed on FDM machine, preparation process ginseng
Number is：180~220 DEG C of print temperature, -55 DEG C of baseplate temp room temperature, 0.1~0.2mm of interlamellar spacing presses gained FDM molded part
ASTM standard is tested for the property, and test method is as follows, and test result is shown in Table 2.
(1) tensile strength
It is measured according to the method for ASTM D638；
(2) bending strength
It is measured according to the method for ASTM D790；
(3) impact strength
It is measured according to the method for ASTMD256；
(4) printout specific gravity
It is tested using specific gravity tester.
The quantitative measurement for the 3D printing wire rod that 1 Examples 1 to 4 of table is prepared
Printout performance test made of the 3D printing wire rod that 2 Examples 1 to 4 of table is prepared
Claims (8)
1. a kind of polylactic acid 3D printing material, which is characterized in that the polylactic acid 3D printing material by following mass fraction group
It is grouped as：
30~90 parts of polylactic acid；
10~30 parts of nitrogen-doped graphene；
0.5~3 part of antioxidant；
3~7 parts of dispersing agent；
0.1~1 part of nucleating agent；
Wherein, the molecular weight of the polylactic acid is 40000~100000.
2. thermal conductivity polylactic acid 3D printing material according to claim 1, which is characterized in that the polylactic acid 3D printing material
Material is grouped as by the group of following mass fraction：
45~80 parts of polylactic acid；
15~25 parts of nitrogen-doped graphene；
0.5~2 part of antioxidant；
4~6 parts of dispersing agent；
0.5~0.8 part of nucleating agent.
3. thermal conductivity polylactic acid 3D printing material according to claim 1, which is characterized in that the molecular weight of the polylactic acid
It is 60000~80000.
4. thermal conductivity polylactic acid 3D printing material according to claim 1, which is characterized in that the antioxidant is hindered phenol
Kind antioxidant and/or phosphite ester antioxidant.
5. thermal conductivity polylactic acid 3D printing material according to claim 1, which is characterized in that the dispersing agent is polyethylene
It is wax, polypropylene wax, EVA wax, ethylene bis stearic acid amide, POE wax, zinc stearate, magnesium stearate, paraffin, ROWAX E wax, micro-
One or more of powder wax, oleamide, fluoropolymer or low molecular weight ionomer.
6. thermal conductivity polylactic acid 3D printing material according to claim 1, which is characterized in that the nucleating agent is talcum
Powder, silica, T-ZnO whisker, montmorillonite, MgSO4Whisker, nanofiber, graphite, magnesia, organic phosphate or fragrant acyl
One or more of aminated compounds.
7. the preparation method of any thermal conductivity polylactic acid 3D printing material of claim 1~6, which is characterized in that described
Method is that will mix and be added to extruding pelletization in single screw extrusion machine to beat up to thermal conductivity polylactic acid 3D after each raw material drying
Print material.
8. any thermal conductivity polylactic acid 3D printing material of claim 1~6 is in electric, industry pattern or circuit board
Application in field.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810562859.XA CN108912629A (en) | 2018-06-01 | 2018-06-01 | A kind of polylactic acid 3D printing material and its preparation method and application |
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| CN201810562859.XA CN108912629A (en) | 2018-06-01 | 2018-06-01 | A kind of polylactic acid 3D printing material and its preparation method and application |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111607129A (en) * | 2020-05-29 | 2020-09-01 | 上海交通大学 | Formaldehyde-removing 3D printing wire rod containing axial orientation pore structure and preparation method thereof |
| CN111647320A (en) * | 2020-06-04 | 2020-09-11 | 广东康烯科技有限公司 | Preparation method of PTC graphene-based conductive ink and PTC graphene-based conductive ink |
| WO2021095021A1 (en) * | 2019-11-15 | 2021-05-20 | Tor Corporation Ltd | Biodegradable polymer nanocomposite and method for production thereof |
-
2018
- 2018-06-01 CN CN201810562859.XA patent/CN108912629A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021095021A1 (en) * | 2019-11-15 | 2021-05-20 | Tor Corporation Ltd | Biodegradable polymer nanocomposite and method for production thereof |
| CN111607129A (en) * | 2020-05-29 | 2020-09-01 | 上海交通大学 | Formaldehyde-removing 3D printing wire rod containing axial orientation pore structure and preparation method thereof |
| CN111647320A (en) * | 2020-06-04 | 2020-09-11 | 广东康烯科技有限公司 | Preparation method of PTC graphene-based conductive ink and PTC graphene-based conductive ink |
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Application publication date: 20181130 |