CN108841146A - A kind of thermal conductivity polylactic acid 3D printing material and its preparation method and application - Google Patents
A kind of thermal conductivity polylactic acid 3D printing material and its preparation method and application Download PDFInfo
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- CN108841146A CN108841146A CN201810562858.5A CN201810562858A CN108841146A CN 108841146 A CN108841146 A CN 108841146A CN 201810562858 A CN201810562858 A CN 201810562858A CN 108841146 A CN108841146 A CN 108841146A
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- polylactic acid
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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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
- 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
- C08K2201/001—Conductive additives
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of thermal conductivity polylactic acid 3D printing materials and its preparation method and application, and the polylactic acid 3D printing material is grouped as by the group of following mass fraction：30~90 parts of polylactic acid, 10~25 parts of graphene oxide, 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 thermal conductivity polylactic acid 3D printing material and its system
Preparation Method and application.
Background technique
" fusion sediment " (Fused Deposition Modeling, FDM) rapid shaping technique is existed using plastic material
It is melted under high temperature, utilizes computer control layer layer accumulation molding.The system of random geometry can be almost formed using the technology
Part, 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 touches FDM and beats
Print technology, but being different industry is different to characteristic needed for consumptive material.Under the premise of not influencing to print object precision,
Multiple functions characteristic especially low-density, thermally conductive, electric conductivity polylactic acid 3D printing material are provided with before biggish application
Scape.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of thermal conductivity polylactic acid 3D printing material,
Polylactic acid 3D printing material provided by the invention have low-density, thermally conductive, electric conductivity, can satisfy market to high thermal conductivity, lead
The demand of electricity, the dedicated consumptive material of low-gravity 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 thermal conductivity polylactic acid 3D printing material, the polylactic acid 3D printing material by following mass fraction component
Composition：
Wherein, the molecular weight of the polylactic acid is 40000~100000.
The present invention is aided with antioxidant, dispersing agent and nucleation by the polylactic acid of selection graphene oxide and specified molecular weight
A kind of thermal conductivity polylactic acid 3D printing material is prepared in agent.Poly-lactic acid material provided by the invention have it is thermally conductive, conductive and
Low-gravity advantage, can effectively solve existing polylactic acid leads to model surface effect difference because cooling velocity is slow in printing
Problem.The wire rod that poly-lactic acid material provided by the invention is prepared has conducting function, and can be applied to electronic apparatus etc. needs
Antistatic occasion is wanted, and the specific gravity of polylactic acid wire rod obtained is lower, this advantageously reduces model weight, and model is made to reach light
The effect of matter.
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 graphite oxide
Alkene dispersion is uneven, reunites, seriously affects the thermally conductive and conductive characteristic of lactic acid composite material, while to the table of printer model
Effect generation in face significantly affects.The item of the polylactic acid of specified molecular weight and the graphene oxide of specified particle diameter is selected in the present invention
Under part, the dispersing agent preferentially selects polyethylene wax, polypropylene wax, EVA wax, ethylene bis stearic acid amide, POE wax, stearic acid
One of zinc, magnesium stearate, paraffin, ROWAXE wax, micro mist wax, oleamide, fluoropolymer or low molecular weight ionomer
Or it is several；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 special material for FDM technology further genralrlization
Solution.
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 thermal conductivity polylactic acid 3D printing material 1 of embodiment 1 and wire rod 1
A kind of thermal conductivity polylactic acid 3D printing material, the polylactic acid 3D printing material by following mass fraction component
Composition：Polylactic acid 65g, graphene oxide 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, graphene oxide, antioxidant, dispersing agent and nucleating agent are added in high-speed mixer, high speed
3min is mixed, the material mixed is added in the barrel of single screw extrusion machine, extrusion mixing under the conditions of 180 DEG C, air-dries, cuts
Grain obtains particles of polylactic acid 3D printing material.
Again plastic extruder will be added to after the drying of above-mentioned particles of polylactic acid 3D printing material, extruder temperature 180~
220 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,
It is fully cooled shape wire；It is rolled into dragger, by the size diameter of the fixed wire rod of pulling force, dragger is fixed after coming out
The wire rod of type, into two-wheel storage rack, buffering and storage pull out wire rod, and the wire rod that storage rack comes out enters coil winder, online
At polylactic acid 3D printing wire rod, gauge or diameter of wire needs to be customized automatic winding according to client in disk, error range ±
0.05mm。
A kind of thermal conductivity polylactic acid 3D printing material 2 of embodiment 2 and wire rod 2
A kind of thermal conductivity polylactic acid 3D printing material, the polylactic acid 3D printing material by following mass fraction component
Composition：Polylactic acid 30g, graphene oxide 25g, antioxidant 0.5g, dispersing agent 3g, nucleating agent 0.1g.
Wherein, the molecular weight 100000 of the polylactic acid.
A kind of thermal conductivity polylactic acid 3D printing material 3 of embodiment 3 and wire rod 3
A kind of thermal conductivity polylactic acid 3D printing material, the polylactic acid 3D printing material by following mass fraction component
Composition：Polylactic acid 90g, graphene oxide 15g, antioxidant 3g, dispersing agent 7g, nucleating agent 1g.
Wherein, the molecular weight of the polylactic acid is 60000.
A kind of thermal conductivity polylactic acid 3D printing material 4 of embodiment 4 and wire rod 4
A kind of thermal conductivity polylactic acid 3D printing material, the polylactic acid 3D printing material by following mass fraction component
Composition：Polylactic acid 55g, graphene oxide 20g, 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 thermal conductivity polylactic acid 3D printing material, which is characterized in that the polylactic acid 3D printing material is by following quality
The group of number is grouped as：
30~90 parts of polylactic acid；
10~25 parts of graphene oxide；
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；
15~20 parts of graphene oxide；
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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| CN201810562858.5A CN108841146A (en) | 2018-06-01 | 2018-06-01 | A kind of thermal conductivity polylactic acid 3D printing material and its preparation method and application |
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| CN201810562858.5A CN108841146A (en) | 2018-06-01 | 2018-06-01 | A kind of thermal conductivity polylactic acid 3D printing material and its preparation method and application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109971140A (en) * | 2019-03-20 | 2019-07-05 | 福建师范大学 | A kind of preparation method and its device with three dimentional heat conduction network chain composite material |
| CN110459342A (en) * | 2019-08-16 | 2019-11-15 | 戴洪卫 | It is a kind of with the composite high-molecular conductive material and preparation method thereof for stablizing conductivity |
| CN110452510A (en) * | 2019-08-20 | 2019-11-15 | 管彩琴 | A kind of 3D printing high strength easy-to-degrade material and preparation method thereof |
| WO2021095021A1 (en) * | 2019-11-15 | 2021-05-20 | Tor Corporation Ltd | Biodegradable polymer nanocomposite and method for production thereof |
-
2018
- 2018-06-01 CN CN201810562858.5A patent/CN108841146A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109971140A (en) * | 2019-03-20 | 2019-07-05 | 福建师范大学 | A kind of preparation method and its device with three dimentional heat conduction network chain composite material |
| CN109971140B (en) * | 2019-03-20 | 2021-12-31 | 福建师范大学 | Preparation method and device of composite material with three-dimensional heat conduction network chain |
| CN110459342A (en) * | 2019-08-16 | 2019-11-15 | 戴洪卫 | It is a kind of with the composite high-molecular conductive material and preparation method thereof for stablizing conductivity |
| CN110452510A (en) * | 2019-08-20 | 2019-11-15 | 管彩琴 | A kind of 3D printing high strength easy-to-degrade material and preparation method thereof |
| WO2021095021A1 (en) * | 2019-11-15 | 2021-05-20 | Tor Corporation Ltd | Biodegradable polymer nanocomposite and method for production thereof |
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