CN106009351A - High-molecular polymer material for 3D printing and preparing method thereof - Google Patents
High-molecular polymer material for 3D printing and preparing method thereof Download PDFInfo
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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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/30—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by oxidation
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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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- 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
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Abstract
The invention relates to a high-molecular polymer material for 3D printing. The material is prepared from paraffin hydrocarbon oil, o-cresol formaldehyde epoxy resin, talcum powder, polydimethylsiloxane, oxidized polyethlene wax, triethylene glycol di-2-ethylhexoate, tributyl citrate, dibasic lead phthalate, polystyrene resin, thioxanthone, graphite fiber, polystyrene resin, cottonseed oil polyphenylenevinylene, graphene, tartaric acid, barium stearate and polyamide resin. The prepared material has high tensile strength and tensile modulus, high tenacity, and high elongation at break and impact strength; heat resistance is high, and usability is good.
Description
Technical field
The present invention relates to a kind of 3D printing macromolecule polymer material and preparation method thereof, belong to 3D printed material technology
Field.
Background technology
Part macromolecule polymer material (polyether-ether-ketone, polyimides etc.), as a kind of important structural material, has
Higher-strength, higher hardness, the advantage such as wear-resistant, corrosion-resistant, have at the numerous areas such as Aero-Space, biomedicine
And be widely applied.But for complex-shaped high score component, then need to make it shape by complicated mould.But
It is that complicated mould needs higher manufacturing cost and longer manufacturing cycle, and meanwhile, mould has once manufactured, just
Again size, pattern and other parameters of high score component product cannot be modified, and constrain prototype and little
The production of the high score component of batch.Being growing more intense in the market competition, product renewing hastens the today day by day accelerated, this life
Occurrence condition does not the most adapt to the existence of modern enterprise and the needs of development.
Summary of the invention
It is an object of the invention to provide a kind of 3D printing macromolecule polymer material and preparation method thereof, in order to more preferably
Ground improves to produce prepares effect, conveniently the most preferably uses.
To achieve these goals, technical scheme is as follows.
A kind of 3D printing macromolecule polymer material, is made up of the material of following mass fraction: paraffin hydrocarbon ils 18～22
Part, o-cresol formaldehyde epoxy resin 20～24 parts, Pulvis Talci 16～20 parts, polydimethylsiloxane 14～18 parts, oxygen
Change Tissuemat E 20～24 parts, 2,2'-ethylenedioxybis(ethanol). two tricaprylate 16～20 parts, tributyl citrate 14～18 parts, disalt
Base lead phthalate 20～24 parts, Pulvis Talci 16～20 parts, polystyrene resin 14～18 parts, the double first of Benzoinum
Ether 20～24 parts, graphite fibre 16～20 parts, polystyrene resin 16～20 parts, Oleum Gossypii semen polyphenylene ethylene 14～
18 parts, Graphene 20～24 parts, tartaric acid 16～20 parts, barium stearate 14～18 parts, polyamide 20～24
Part.
Further, above-mentioned 3D printing macromolecule polymer material, it is made up of the material of following mass fraction: paraffin
Hydrocarbon ils 18 parts, o-cresol formaldehyde epoxy resin 20 parts, Pulvis Talci 16 parts, polydimethylsiloxane 14 parts, aoxidize poly-second
20 parts of alkene wax, 2,2'-ethylenedioxybis(ethanol). two tricaprylate 16 parts, tributyl citrate 14 parts, Dythal 20 parts,
Pulvis Talci 16 parts, polystyrene resin 14 parts, benzoin dimethylether 20 parts, graphite fibre 16 parts, polystyrene tree
16 parts of fat, Oleum Gossypii semen polyphenylene ethylene 14 parts, Graphene 20 parts, 16 parts of tartaric acid, barium stearate 14 parts, poly-
Amide resin 20 parts.
Further, above-mentioned 3D printing macromolecule polymer material, it is made up of the material of following mass fraction: paraffin
Hydrocarbon ils 20 parts, o-cresol formaldehyde epoxy resin 22 parts, Pulvis Talci 18 parts, polydimethylsiloxane 16 parts, aoxidize poly-second
22 parts of alkene wax, 2,2'-ethylenedioxybis(ethanol). two tricaprylate 18 parts, tributyl citrate 16 parts, Dythal 22 parts,
Pulvis Talci 18 parts, polystyrene resin 16 parts, benzoin dimethylether 22 parts, graphite fibre 18 parts, polystyrene tree
18 parts of fat, Oleum Gossypii semen polyphenylene ethylene 16 parts, Graphene 22 parts, 18 parts of tartaric acid, barium stearate 16 parts, poly-
Amide resin 22 parts.
Further, above-mentioned 3D printing macromolecule polymer material, it is made up of the material of following mass fraction: paraffin
Hydrocarbon ils 22 parts, o-cresol formaldehyde epoxy resin 24 parts, Pulvis Talci 20 parts, polydimethylsiloxane 18 parts, aoxidize poly-second
24 parts of alkene wax, 2,2'-ethylenedioxybis(ethanol). two tricaprylate 20 parts, tributyl citrate 18 parts, Dythal 24 parts,
Pulvis Talci 20 parts, polystyrene resin 18 parts, benzoin dimethylether 24 parts, graphite fibre 20 parts, polystyrene tree
20 parts of fat, Oleum Gossypii semen polyphenylene ethylene 18 parts, Graphene 24 parts, 20 parts of tartaric acid, barium stearate 18 parts, poly-
Amide resin 24 parts.
Further, the above-mentioned polymeric material printed for 3D, its preparation method, comprise the steps:
1), after the material of above-mentioned mass fraction being mixed, add and extrude pelletizing after being blended uniformly in double screw extruder, obtain standby
Use material；The temperature of double screw extruder one district, 2nd district, 3rd district and die head is respectively 170～190 DEG C, 200～210 DEG C,
220～230 DEG C, 240～250 DEG C；Engine speed is 80～200rpm；
2) described lay-by material is joined in single screw extrusion machine, use traction machine drawing-off after extrusion, make and beat for 3D
The wire rod of print；The temperature of single screw extrusion machine one district, 2nd district, 3rd district and die head is respectively 236～240 DEG C, 242～250 DEG C,
255～265 DEG C, 265～275 DEG C；Screw speed is 10～20rpm, and the draw ratio of traction machine is 2.2～3.2.
This beneficial effect of the invention is: the 3D printing macromolecule polymer material in the present invention, by paraffin hydrocarbon ils,
O-cresol formaldehyde epoxy resin, Pulvis Talci, polydimethylsiloxane, OPE, 2,2'-ethylenedioxybis(ethanol). two tricaprylate, lemon
Lemon acid tributyl, Dythal, Pulvis Talci, polystyrene resin, benzoin dimethylether, graphite fibre,
Polystyrene resin, Oleum Gossypii semen polyphenylene ethylene, Graphene, tartaric acid, barium stearate, polyamide form, institute
The material of preparation has higher hot strength and stretch modulus, and remains good toughness, its elongation at break and
The performance indications such as impact strength are good；Not only having at a relatively high toughness, also have higher thermostability, serviceability is good.
Detailed description of the invention
Below in conjunction with embodiment, the detailed description of the invention of the present invention is described, in order to be better understood from the present invention.
Embodiment
3D printing macromolecule polymer material in the present embodiment, is made up of the material of following mass fraction: paraffin hydrocarbon
Oil 18 parts, o-cresol formaldehyde epoxy resin 20 parts, Pulvis Talci 16 parts, polydimethylsiloxane 14 parts, oxidic polyethylene
20 parts of wax, 2,2'-ethylenedioxybis(ethanol). two tricaprylate 16 parts, tributyl citrate 14 parts, Dythal 20 parts,
Pulvis Talci 16 parts, polystyrene resin 14 parts, benzoin dimethylether 20 parts, graphite fibre 16 parts, polystyrene tree
16 parts of fat, Oleum Gossypii semen polyphenylene ethylene 14 parts, Graphene 20 parts, 16 parts of tartaric acid, barium stearate 14 parts, poly-
Amide resin 20 parts.
The above-mentioned polymeric material printed for 3D, its preparation method, comprise the steps:
1), after the material of above-mentioned mass fraction being mixed, add and extrude pelletizing after being blended uniformly in double screw extruder, obtain standby
Use material；The temperature of double screw extruder one district, 2nd district, 3rd district and die head is respectively 170 DEG C, 200 DEG C, 220 DEG C,
240℃；Engine speed is 80rpm；
2) described lay-by material is joined in single screw extrusion machine, use traction machine drawing-off after extrusion, make and beat for 3D
The wire rod of print；The temperature of single screw extrusion machine one district, 2nd district, 3rd district and die head is respectively 236 DEG C, 242 DEG C, 255 DEG C,
265℃；Screw speed is 10rpm, and the draw ratio of traction machine is 2.2.
Embodiment 2
3D printing macromolecule polymer material in the present embodiment, is made up of the material of following mass fraction: paraffin hydrocarbon
Oil 20 parts, o-cresol formaldehyde epoxy resin 22 parts, Pulvis Talci 18 parts, polydimethylsiloxane 16 parts, oxidic polyethylene
22 parts of wax, 2,2'-ethylenedioxybis(ethanol). two tricaprylate 18 parts, tributyl citrate 16 parts, Dythal 22 parts,
Pulvis Talci 18 parts, polystyrene resin 16 parts, benzoin dimethylether 22 parts, graphite fibre 18 parts, polystyrene tree
18 parts of fat, Oleum Gossypii semen polyphenylene ethylene 16 parts, Graphene 22 parts, 18 parts of tartaric acid, barium stearate 16 parts, poly-
Amide resin 22 parts.
The above-mentioned polymeric material printed for 3D, its preparation method, comprise the steps:
1), after the material of above-mentioned mass fraction being mixed, add and extrude pelletizing after being blended uniformly in double screw extruder, obtain standby
Use material；The temperature of double screw extruder one district, 2nd district, 3rd district and die head is respectively 180 DEG C, 205 DEG C, 225 DEG C,
245℃；Engine speed is 140rpm；
2) described lay-by material is joined in single screw extrusion machine, use traction machine drawing-off after extrusion, make and beat for 3D
The wire rod of print；The temperature of single screw extrusion machine one district, 2nd district, 3rd district and die head is respectively 238 DEG C, 246 DEG C, 260 DEG C,
270℃；Screw speed is 15rpm, and the draw ratio of traction machine is 2.7.
Embodiment 3
3D printing macromolecule polymer material in the present embodiment, is made up of the material of following mass fraction: paraffin hydrocarbon
Oil 22 parts, o-cresol formaldehyde epoxy resin 24 parts, Pulvis Talci 20 parts, polydimethylsiloxane 18 parts, oxidic polyethylene
24 parts of wax, 2,2'-ethylenedioxybis(ethanol). two tricaprylate 20 parts, tributyl citrate 18 parts, Dythal 24 parts,
Pulvis Talci 20 parts, polystyrene resin 18 parts, benzoin dimethylether 24 parts, graphite fibre 20 parts, polystyrene tree
20 parts of fat, Oleum Gossypii semen polyphenylene ethylene 18 parts, Graphene 24 parts, 20 parts of tartaric acid, barium stearate 18 parts, poly-
Amide resin 24 parts.
The above-mentioned polymeric material printed for 3D, its preparation method, comprise the steps:
1), after the material of above-mentioned mass fraction being mixed, add and extrude pelletizing after being blended uniformly in double screw extruder, obtain standby
Use material；The temperature of double screw extruder one district, 2nd district, 3rd district and die head is respectively 190 DEG C, 210 DEG C, 230 DEG C,
250℃；Engine speed is 200rpm；
2) described lay-by material is joined in single screw extrusion machine, use traction machine drawing-off after extrusion, make and beat for 3D
The wire rod of print；The temperature of single screw extrusion machine one district, 2nd district, 3rd district and die head is respectively 240 DEG C, 250 DEG C, 265 DEG C,
275℃；Screw speed is 20rpm, and the draw ratio of traction machine is 3.2.
Reference examples
The polymeric material that this reference examples prints for 3D, its raw material consists of the poly-succinic fourth two of 100 mass fractions
Ester and the titanium dioxide of 6 mass fractions.
Its preparation process is as follows:
1) poly-succinic fourth diester is dried at 60 DEG C 15h；
2) by the poly-succinic fourth diester of 100 weight portions, after the titanium dioxide premix of 1 part, cut by double screw extruder extrusion
After Li, obtain lay-by material；The temperature of double screw extruder one district, 2nd district, 3rd district and die head is respectively 140～150 DEG C,
165～170 DEG C, 180～185 DEG C, 180～185 DEG C, engine speed is 40rpm.
Above-described embodiment 1, embodiment 2, embodiment 3 and matched group material are carried out performance test comparison, in test,
Tensile property is pressed ASTMD638 and is measured, and selects II pattern bar, and during test, draw speed is 50mm/min；Impact strength is pressed
ASTMD648 measures；Melt viscosity is at 160 DEG C, and strain is to use frequency scanning 0.01～100Hz mensuration for 1% time.
Performance test comparing result is as shown in table 1:
Table 1 performance test comparing result
| The performance test results | Embodiment 1 | Embodiment 2 | Embodiment 3 | Matched group |
| Hot strength/MPa | 66.6 | 69.9 | 65.3 | 29.6 |
| Stretch modulus/MPa | 1649.6 | 1815.6 | 1865 | 825.3 |
| Elongation at break/% | 95 | 99 | 94 | 286 |
| Impact strength/kJ m-2 | 17.8 | 19.9 | 18.9 | 9.8 |
| Zero shear viscosity/Pa s | 3924 | 3995 | 3797 | 952 |
From the present embodiment, product of the present invention, its hot strength, stretch modulus and impact strength significantly improve, 3D
Printing goods buckling deformation to significantly improve, dimensional accuracy improves.
The above is the preferred embodiment of the present invention, it is noted that come for those skilled in the art
Saying, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also regard
For protection scope of the present invention.
Claims (5)
1. a 3D printing macromolecule polymer material, it is characterised in that: it is made up of the material of following mass fraction:
Paraffin hydrocarbon ils 18～22 parts, o-cresol formaldehyde epoxy resin 20～24 parts, Pulvis Talci 16～20 parts, polydimethylsiloxanes
Alkane 14～18 parts, OPE 20～24 parts, 2,2'-ethylenedioxybis(ethanol). two tricaprylate 16～20 parts, tributyl citrate
14～18 parts, Dythal 20～24 parts, Pulvis Talci 16～20 parts, polystyrene resin 14～18
Part, benzoin dimethylether 20～24 parts, graphite fibre 16～20 parts, polystyrene resin 16～20 parts, Oleum Gossypii semen
Polyphenylene ethylene 14～18 parts, Graphene 20～24 parts, tartaric acid 16～20 parts, barium stearate 14～18 parts, poly-
Amide resin 20～24 parts.
3D printing macromolecule polymer material the most according to claim 1, it is characterised in that: described 3D beats
Print macromolecule polymer material, is made up of the material of following mass fraction: paraffin hydrocarbon ils 18 parts, o-cresol formaldehyde epoxy
Resin 20 parts, Pulvis Talci 16 parts, polydimethylsiloxane 14 parts, OPE 20 parts, 2,2'-ethylenedioxybis(ethanol). two are different pungent
Acid esters 16 parts, tributyl citrate 14 parts, Dythal 20 parts, Pulvis Talci 16 parts, polystyrene
Resin 14 parts, benzoin dimethylether 20 parts, graphite fibre 16 parts, polystyrene resin 16 parts, Oleum Gossypii semen polyhenylene
Ethylene 14 parts, Graphene 20 parts, 16 parts of tartaric acid, barium stearate 14 parts, polyamide 20 parts.
3D printing macromolecule polymer material the most according to claim 1, it is characterised in that: described 3D beats
Print macromolecule polymer material, is made up of the material of following mass fraction: paraffin hydrocarbon ils 20 parts, o-cresol formaldehyde epoxy
Resin 22 parts, Pulvis Talci 18 parts, polydimethylsiloxane 16 parts, OPE 22 parts, 2,2'-ethylenedioxybis(ethanol). two are different pungent
Acid esters 18 parts, tributyl citrate 16 parts, Dythal 22 parts, Pulvis Talci 18 parts, polystyrene
Resin 16 parts, benzoin dimethylether 22 parts, graphite fibre 18 parts, polystyrene resin 18 parts, Oleum Gossypii semen polyhenylene
Ethylene 16 parts, Graphene 22 parts, 18 parts of tartaric acid, barium stearate 16 parts, polyamide 22 parts.
3D printing macromolecule polymer material the most according to claim 1, it is characterised in that: described 3D beats
Print macromolecule polymer material, is made up of the material of following mass fraction: paraffin hydrocarbon ils 22 parts, o-cresol formaldehyde epoxy
Resin 24 parts, Pulvis Talci 20 parts, polydimethylsiloxane 18 parts, OPE 24 parts, 2,2'-ethylenedioxybis(ethanol). two are different pungent
Acid esters 20 parts, tributyl citrate 18 parts, Dythal 24 parts, Pulvis Talci 20 parts, polystyrene
Resin 18 parts, benzoin dimethylether 24 parts, graphite fibre 20 parts, polystyrene resin 20 parts, Oleum Gossypii semen polyhenylene
Ethylene 18 parts, Graphene 24 parts, 20 parts of tartaric acid, barium stearate 18 parts, polyamide 24 parts.
3D printing macromolecule polymer material the most according to claim 1, it is characterised in that: described for 3D
The polymeric material printed, its preparation method, comprise the steps:
1), after the material of above-mentioned mass fraction being mixed, add and extrude pelletizing after being blended uniformly in double screw extruder, obtain standby
Use material；The temperature of double screw extruder one district, 2nd district, 3rd district and die head is respectively 170～190 DEG C, 200～210 DEG C,
220～230 DEG C, 240～250 DEG C；Engine speed is 80～200rpm；
2) described lay-by material is joined in single screw extrusion machine, use traction machine drawing-off after extrusion, make and beat for 3D
The wire rod of print；The temperature of single screw extrusion machine one district, 2nd district, 3rd district and die head is respectively 236～240 DEG C, 242～250 DEG C,
255～265 DEG C, 265～275 DEG C；Screw speed is 10～20rpm, and the draw ratio of traction machine is 2.2～3.2.
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Cited By (1)
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| CN106916469A (en) * | 2017-03-26 | 2017-07-04 | 广西丰达三维科技有限公司 | A kind of environment-friendly materials with high tensile, preparation method and applications |
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Application publication date: 20161012 |