CN104029391B - A kind of 3D printing shaping polyolefine material and preparation method thereof - Google Patents
A kind of 3D printing shaping polyolefine material and preparation method thereof Download PDFInfo
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- CN104029391B CN104029391B CN201410182309.7A CN201410182309A CN104029391B CN 104029391 B CN104029391 B CN 104029391B CN 201410182309 A CN201410182309 A CN 201410182309A CN 104029391 B CN104029391 B CN 104029391B
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Abstract
A kind of method that the invention discloses 3D printing shaping polyolefine material, and the polyolefine material with the method molding.It is characterized in that: this 3D printing shaping method is a kind of new method dissolution method or swelling method combined with 3D printing technique, comprise the steps: vistanex, auxiliary agent adds mixing device with organic solvent in certain ratio, keep certain pressure and temperature, after mixing a period of time, the paste mixture obtained is transferred to feed arrangement, shower nozzle sprays said mixture according to CAD program, after solvent volatilizees, nozzle successively sprays according still further to the program set, repeat above-mentioned successively molding, after solvent volatilizees completely, obtain required polyolefine material.Method disclosed by the invention overcomes the hot conditions (more than polyolefin fusing point) that traditional diamond-making technique needs, and reduces energy consumption, has saved cost.
Description
Technical field
A kind of method that the present invention relates to 3D printing shaping polyolefine material, and with the method molding
Polyolefine material.
Background technology
Polyolefin, refers to by ethylene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 4-first
Alpha-olefins such as base-1-amylene and some cycloolefin is polymerized alone or combined polymerization and the analog thermoplastic that obtains
The general name of resin.Wherein, polyethylene, polypropylene are most common and most important two kinds of polyolefin.
The advantages such as polyolefin has abundant raw material, cheap, easy machine-shaping, high comprehensive performance.Poly-
Olefin product is of a great variety, such as hollow product, thin film, electric wire cladding material, fiber, single (flat)
Silk, molded plastic package container etc., it is widely used in transportation, industrial or agricultural thin film, household electrical appliances, doctor
The fields such as treatment, article of everyday use and furniture, packaging, construction material.
The forming method of polyolefin products has a lot, such as injection moulding, extrusion molding, blow molding,
Hollow blow molding, foaming, melt spinning etc..But these forming methods are required for polyene
Hydrocarbon is heated to more than its melt temperature, and energy consumption is higher.Over nearly twenties years, 3D printing technique, as
A kind of emerging technology in rapid shaping field, develops very fast, the most in Aero-Space, life
The fields such as thing medical science, defence and military, engineering education, new product development are applied.3D printing technique
Also known as increasing material manufacturing technology, different from traditional method removing materials processing, it is by successively heap
The mode of long-pending material directly manufactures product.3D printing technique utilizes three-dimensional CAD model on an equipment
Can rapidly and precisely produce parts with complex structures, thus realize " freely manufacturing ", solve tradition
Technique difficulty processes the limitation maybe cannot processed, and substantially reduces the process-cycle.According to material stacking side
Formula, 3D printing technique can be divided into photocuring in container, injection of material, and binding agent sprays, and material squeezes
Pressing formation, powder bed sintering/fusing, sheet is laminated into method, and oriented energy deposits seven kinds.
CN102093646A proposes a kind of material for rapid three dimensional printing forming and preparation side thereof
Method, rapid prototyping material includes modified powder materials A and binding agent B, wherein: modified powder materials A
Preparation: dusty material and the first solvent are joined ball mill or grinding machine for grinding, obtain powder
Pretreatment material；By surfactant, lubricant, organic resin gradually joins in the second solvent,
Dispersed with stirring 2-3h, obtains modification liquid；Dusty material pretreatment material is mixed with modification liquid, puts into and grind
In grinding machine, room temperature mixed grinding, it is dried, grinds, obtain modified powder materials A；During use,
1 part of modified powder materials A and 0.01-0.07 part binding agent B adapted.Although this patent employs solvent,
But its purpose is to dusty material is modified.In this patent, final utilization remains powder material
Material.
The shortcoming of the method that use powder carries out 3D printing shaping is that this needs specific auxiliary and sets
Standby and temperature higher than fusing point, this adds the cost of manufacture undoubtedly.Therefore, a kind of simple, soon
Speed, temperature is relatively low, and lower-cost 3D printing technique is to be badly in need of.
Summary of the invention
It is an object of the invention to overcome traditional molding methods must add in polyolefin fusing point implementation above
Work, processing temperature is higher, the defect that energy consumption is higher, it is provided that one can be prepared poly-at a lower temperature
The method of olefin material and the polyolefine material prepared by this method.
What the present invention provided prepares polyolefinic method is that dissolution method or swelling method are printed by one with 3D
The new method that technology combines, comprises the steps:
Vistanex, organic solvent and optional auxiliary agent are mixed, thus obtain paste mixture,
Being transferred in the feed arrangement of 3D printer by the paste mixture obtained, shower nozzle sprays according to CAD program
Go out said mixture, until solvent volatilize after, nozzle according still further to set program successively spray, repeat on
State successively molding, after solvent volatilizees completely, obtain required polyolefine material.
In said method, described polyolefin refers to by ethylene, propylene, 1-butylene, isobutene., 1-penta
Alkene, 1-hexene, vinyl chloride, styrene, 1-octene, 4-methyl-1-pentene and cyclopropylene, ring fourth
Alkene, cyclopentenes, cyclohexene, cycloheptene, 1,3-cyclohexadiene, 1,4-cyclohexadiene are polymerized alone or are total to
At least one in the TPO being polymerized and obtain.
Described vistanex can be pellet or powder.
The weight average molecular weight of described vistanex is 10,000-50 ten thousand, preferably 50,000-20 ten thousand.
Described organic solvent refers to polyolefinic good solvent or theta solvent.Concrete polyolefinic good solvent or θ
Solvent is known to the person skilled in the art, concretely hexamethylene, hexahydrotoluene, ethyl ring
Hexane, normal heptane, ether, diamyl ether, methyl phenyl ethers anisole, ethyl sulfide, isoamyl acetate, toluene, two
Toluene, chlorobenzene, halogenated hydrocarbons, tetrahydronaphthalene, ten change hydrogen naphthalenes, oxolane, dimethylformamide,
Higher fatty acid race esters, at least one of fatty ether apoplexy due to endogenous wind.
Described auxiliary agent can be inorganic filler, pigment, at least one in processing aid.
Preferably, described inorganic filler can be diameter or thickness be 1 nanometer to the granule between 100 microns,
Fiber or sheet material, concretely white carbon black, silicon, silicon dioxide, graphite, Muscovitum, Fe3O4、TiO2、
Cu2O、ZnO、CdS、CaCO3、BaCO3、BaSO4Or LiFePO4。
Described pigment can be inorganic pigment chromate, sulfate, silicate, borate, molybdate,
Phosphate, vanadate, ferricyanate, hydroxide, sulfide and organic pigment AZOpigments, phthalein
The polycyclic pigment such as cyanine pigment, anthraquinone, indigoids, quinacridone, diazine or virtue methaneseries pigment.
Described processing aid can be defoamer, lubricant, plasticizer, thickening agent, degasser, stable
Agent, dispersant, in age resistor, fire retardant at least one.
Described vistanex has no particular limits with the proportioning (by weight) of organic solvent, example
As being 1/10-10/1, preferably 1/3-3/1, condition is to obtain paste.Auxiliary agent and vistanex
Ratio can be 0/1000-1/1.
Vistanex can be carried out, such as under a certain pressure with the mixing of organic solvent and optional adjuvants
1-5 atmospheric pressure, preferably 1-4 atmospheric pressure, more preferably 1-3 atmospheric pressure.Mixing temperature can be
Room temperature is to 80 DEG C.Incorporation time can be 10min to 12h.
Gained paste viscosity at 25 DEG C has no particular limits, for example, 100-10000Pa s.,
It is preferably 500-5000Pa s, prints so that it is suitable to 3D.
The present invention also provides for polyolefine material prepared by as above method.
The present invention also provides for polyolefine material prepared by the as above method application in 3D prints.
The polyolefin paste of the present invention can be directly used for 3D and prints.In 3D print procedure, use institute
State paste and carry out 3D printing, wherein apply one layer of paste so that it is in solvent volatilization, the most again
Print last layer.Polyolefin in described paste coalesces together, thus while solvent volatilizees
After described layer applies, form 3D printing objects.
Compared with prior art, the invention has the beneficial effects as follows: will dissolve or swelling method prints skill with 3D
Art combines, it is not necessary to is heated to more than polyolefinic melt temperature and just can realize molding, reduces
Energy consumption, has saved cost.
Detailed description of the invention
Below by way of specific embodiment, the present invention is described, but embodiment is merely to illustrate, be not limiting as this
The scope of invention.Described method is conventional method if no special instructions.Described raw material is as without especially
Illustrate all to obtain from open commercial sources.
Embodiment 1 method of polypropylene material 3D printing shaping
1) by 65 parts of polypropylene powders (fusing point is about 172 DEG C) and 30 parts of hexamethylene, 5 parts of glycerol trihydroxies
Polyethers is invested in material-compound tank；
2) keeping normal pressure, temperature is 80 DEG C, to form cream after 1500rpm speed stirring mixing 30min
Shape mixture；
3) this paste mixture being transferred to feed arrangement, 3D printing head starts according to the program set
Eject 2) in paste mixture, treat that solvent volatilizees；
4) until 3) after the material that prints is completely dried, shower nozzle successively prints further according to setting program, treats
After solvent is completely dried, i.e. gained polypropylene material.
At normal pressure, under conditions of 80 DEG C, hexamethylene energy swells polypropylene pellet, swelling after polypropylene
The distance of molecule interchain increases, and the interaction of molecule interchain weakens, and the motor capacity of chain is greatly improved,
Molecule interchain is bonded together by entanglement effect.After solvent volatilization volatilization completely, the polypropylene obtained
Material.Use dissolving or swelling method first by polymer beads at least surface region soluble or swelling, improve
The interfacial interaction of material so that the polypropylene material of preparation has good mechanical strength and resistance to
Mill property.Additionally, glycerol trihydroxy polyethers is as defoamer, can effectively remove in raw material mixed process
The bubble produced, it is to avoid goods are uneven or porous reduces its mechanical performance.Plant and swelling method and 3D are beaten
The method of print combines the method forming temperature preparing polypropylene material far below polyacrylic melted temperature
Degree, reduces energy consumption, has saved cost.
Embodiment 2 method of fire-retardant polyethylene material 3D printing shaping
1) by 60 parts of polyethylene (low-density) homopolymer pellets and 25 parts of decahydronaphthalenes, 15 parts of APPs,
It is invested in material-compound tank；
2) keeping normal pressure, temperature is 60 DEG C, mixed to form paste after 1500rpm speed stirring mixing 5h
Compound；
3) this paste mixture being transferred to feed arrangement, 3D printing head starts according to the program set
Eject 2) in paste mixture, treat that solvent volatilizees；
4) until 3) after the material that prints is completely dried, more successively print according to setting program with shower nozzle,
After solvent is completely dried, i.e. gained polypropylene material.
At normal pressure, under the conditions of 60 DEG C, decahydronaphthalenes can dissolve Low Density Polyethylene, after stirring mixing 5h,
Mixture becomes paste.This paste mixture is successively printed according to setting program, treats that solvent volatilizees completely
After, the polyethylene products obtained has good mechanical performance.Use dissolving or swelling method first will be polymerized
Composition granule at least surface region soluble or swelling, improves the interfacial interaction of material, additionally,
Under the effect of the ammonium polyphosphate flame retardant of polyethylene, the oxygen index (OI) of prepared polythene material substantially carries
Height, effectively improves the fire resistance of polyethylene products.
Embodiment 3 method of polyethylene-propylene random copolymer material 3D printing shaping
1) by 50 parts of polyethylene-propylene random copolymer pellets and 25 parts of dimethylbenzene, 20 parts of nanoscales two
Silicon oxide, 5 points of silica dispersions EL-6226 are invested in material-compound tank；
2) keeping normal pressure, temperature is 120 DEG C, to form paste after 1500rpm speed stirring mixing 3h
Mixture；
3) this paste mixture being transferred to feed arrangement, 3D printing head starts according to the program set
Eject 2) in paste mixture, treat that solvent volatilizees；
4) until 3) after the material that prints is completely dried, more successively print according to setting program with shower nozzle,
After solvent is completely dried, i.e. gained polypropylene material.
At normal pressure, under the conditions of 120 DEG C, dimethylbenzene energy polyethylene dissolving-random copolymer of propylene pellet,
Nanometer silicon dioxide particle can well be dispersed in polyethylene-propylene randomly altogether under the effect of dispersant
In polymers/xylene solution, form the paste mixture that denseness is higher.Material is sprayed by printer, by
Layer prints.Compared with HOPP material, the addition of ethylene composition, make 3D print prepare poly-
The flexibility of ethylene, propylene random copolymer material improves, and tolerance to cold improves, and impact strength improves.
Embodiment 4 method of polyethylen-octene copolymer (POE) flexibilized polypropylene material 3D printing shaping
1) by 20 parts of polyethylen-octene copolymer powders, 20 parts of polypropylene granules, 30 parts of toluene, 10
Part nanometer grade calcium carbonate is invested in material-compound tank；
2) keeping 3 atmospheric pressure, temperature is 50 DEG C, to be formed after 1500rpm speed stirring mixing 6h
Paste mixture；
3) this paste mixture being transferred to feed arrangement, 3D printing head starts according to the program set
Eject 2) in paste mixture, treat that solvent volatilizees；
4) until 3) after the material that prints is completely dried, more successively print according to setting program with shower nozzle,
After solvent is completely dried, i.e. gained polyethylen-octene copolymer (POE) flexibilized polypropylene material.
Although polyethylene is a kind of crystalline material, but the addition of octene, destroy the knot of part polyethylene
Crystalline substance, and define elastic soft section, so, the copolymer of polyethylen-octene has the character of elastomer,
May be used for tenacity-increased profax.The existence of calcium carbonate acts not only as polyacrylic filler, simultaneously can
As reinforcing agent, to improve the tearing strength of POE.Use dissolving or swelling method first by polymer beads
At least surface region soluble or swelling, improves the interfacial interaction of material, can make to prepare
Intensity and the toughness of PP composite material are all greatly enhanced.Therefore, print by the method
The polypropylene material gone out has good mechanical performance, can serve as bumper.
Claims (4)
1. a method for 3D printing shaping polyolefine material, it comprises the steps: polyolefin
Resin, organic solvent and optional auxiliary agent are mixed together thus obtain paste mixture, by described paste
Mixture is transferred in the feed arrangement of 3D printer, and shower nozzle sprays this mixture according to CAD program,
After solvent volatilizees, nozzle successively sprays according still further to the program set, and repeats above-mentioned successively molding, treats
After solvent volatilizees completely, obtain required polyolefine material；Wherein said paste mixture is at 25 DEG C
Viscosity be 100-10000Pa s, described auxiliary agent is inorganic filler, pigment or processing aid；
It is blended under the pressure of 1-5 atmospheric pressure and carries out；
It is blended in room temperature to carry out at 80 DEG C；
Incorporation time be 10 minutes to 12h；
Described vistanex is pellet or powder, and the weight average molecular weight of described fluoropolymer resin is 10,000
-50 ten thousand.
Method the most according to claim 1, it is characterised in that: described organic solvent is polyolefin
Good solvent or theta solvent.
Method the most according to claim 2, it is characterised in that: described organic solvent is hexamethylene, first
Butylcyclohexane, ethyl cyclohexane, normal heptane, ether, diamyl ether, methyl phenyl ethers anisole, ethyl sulfide, acetic acid
Isopentyl ester, toluene, dimethylbenzene, chlorobenzene, halogenated hydrocarbons, naphthane, decahydronaphthalene, oxolane,
Dimethylformamide, higher fatty acid race ester or fatty ether.
Method the most according to claim 1, it is characterised in that: described vistanex is with organic
The part by weight of solvent is 1/10-10/1, and auxiliary agent is 0/1000-1/1 with the ratio of vistanex.
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| CN108164787A (en) * | 2017-12-18 | 2018-06-15 | 河南佳木新型环保材料有限公司 | A kind of material for 3D printing |
| CN111117228B (en) * | 2019-12-31 | 2023-03-10 | 湖南华曙新材料科技有限责任公司 | Preparation method of high polymer powder material for optical fiber laser sintering |
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