CN107304261A - Preparation method for the anti-static polyethylene toner of selective laser sintering - Google Patents
Preparation method for the anti-static polyethylene toner of selective laser sintering Download PDFInfo
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- CN107304261A CN107304261A CN201610256356.0A CN201610256356A CN107304261A CN 107304261 A CN107304261 A CN 107304261A CN 201610256356 A CN201610256356 A CN 201610256356A CN 107304261 A CN107304261 A CN 107304261A
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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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
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/14—Powdering or granulating by precipitation from solutions
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C08K3/36—Silica
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C08K2003/0812—Aluminium
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K2201/011—Nanostructured additives
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
Abstract
The invention provides a kind of preparation method of the anti-static polyethylene toner for selective laser sintering, comprise the following steps：A) at the heating temperature, polyvinyl resin is dissolved in C5‑C12At least one of alkane, obtains polyvinyl resin solution；B) the polyvinyl resin solution for obtaining step a) cools, and makes solid Precipitation, obtains solidliquid mixture；C) add after auxiliary agent and be well mixed in the solidliquid mixture that step b) is obtained, remove and dried after solvent, obtain the anti-static polyethylene toner for selective laser sintering；Wherein, the auxiliary agent includes antistatic additive, antioxidant and separator powder.Present invention also offers a kind of selective laser sintering method using the polyethylene powders that are prepared according to methods described as raw material.
Description
Technical field
The present invention relates to technical field of polymer processing, and in particular to a kind of for the anti-quiet of selective laser sintering
The preparation method of electric polyethylene resin powder and the application in terms of selective laser sintering.
Background technology
Selective laser sintering (Selective Laser Sintering, SLS) technology is a kind of rapid shaping technique, is
Most widely used and most market prospects technology in current increases material manufacturing technology, shows fast development in recent years
Trend.SLS technologies are that 3D solid is scanned first by computer, are then shone by high intensity laser beam
The material powder spread on workbench or parts optionally molten sintering layer by layer in advance is penetrated,
And then realize the technology being successively molded.SLS technologies have the design of height flexible, can produce accurate mould
Type and prototype, can be molded the parts that can directly use with reliable structure, and with short production cycle,
Technique is simple, is therefore particularly suited for the exploitation of new product.
The moulding material species that can be used in SLS technologies is relatively broad, including macromolecule, paraffin, metal, pottery
Porcelain and their composite.However, the performance of moulding material, character are that SLS technologies sintering is successful again
One key factor, it also directly affects the shaping speed of molding part, precision, and physics, chemical property and
Its combination property.Although applicable moulding material species is various, SLS technologies can be directly applied at present
And it is fresh successfully to produce the polymer powder powder stock for the moulded work that scale error is small, surface is regular, porosity is low
It is few.In the prior art, SLS powder stock is generally prepared using comminuting method, such as deep cooling crush method, this
Particular device is not only needed, the particles of powdered ingredient surface prepared is rougher, particle diameter not enough uniform, shape
Irregularly, it is unfavorable for the formation of sintered moulded body, and influences the performance of formed body.It is applied to SLS in the market
The polymer powder scarcity of raw material of technology, therefore the corresponding solid powder raw material of various type of polymer urgently opens
Hair.
Polyethylene is that a kind of use scope is very wide and consumption very big commodity polymer material, with good synthesis
Performance.However, polythene material is in use often due to carrying electrostatic and influenceing properties of product, even
Cause a variety of drawbacks, form harm.Therefore SLS anti-static polyethylene solid powder is developed, can both be met
Individual demand in practical application can meet requirement of the application field to material antistatic property again.
The content of the invention
Object of the present invention is to provide a kind of anti-static polyethylene resin suitable for selective laser sintering
The preparation method and application of powder.The polyethylene resin powder that the method provided according to the present invention is prepared, tool
There are good antistatic behaviour and powder flowbility, suitably sized size, suitable heap density, well-balanced particle
Profile and uniform particle diameter distribution, it is adaptable to which selective laser sintering prepares various moulded works.
The invention provides a kind of preparation side of the anti-static polyethylene toner for selective laser sintering
Method, comprises the following steps：
A) at the heating temperature, polyvinyl resin is dissolved in C5-C12At least one of alkane, is gathered
Vinyl solution；
B) the polyvinyl resin solution for obtaining step a) cools, and makes solid Precipitation, obtains solid-liquid mixing
Thing；
C) add after auxiliary agent and be well mixed in the solidliquid mixture that step b) is obtained, remove and dried after solvent,
Obtain the anti-static polyethylene toner for selective laser sintering；
Wherein, the auxiliary agent includes antistatic additive, antioxidant and separator powder.
According to the present invention, in step a), the C5-C12Alkane is preferably C5-C8Alkane, is more preferably wrapped
Include pentane, isopentane, n-hexane, 2- methylpentanes, 3- methylpentanes, 2,2- dimethylbutanes, 2,3- bis-
Methybutane, hexamethylene, normal heptane, 2- methyl hexanes, 3- methyl hexanes, 2,2- dimethyl pentanes, 2,3- bis-
In methylpentane, 2,4- dimethyl pentanes, 3,3- dimethyl pentanes, 3- ethylpentanes, 2,2,3- triptanes
At least one, most preferably n-hexane and/or normal heptane.
Although organic solvent deposit technology has been used for separating and purifying biochemical substances, especially protein, or
Person prepares crystal for precipitation.But, at present on being prepared using organic solvent precipitation method for selective laser
The report of the resin material powder of sintering technology is also seldom.Especially not yet have been reported that and be applied to selection for preparing
The laser sintered polyethylene resin powder of property.For organic solvent deposit technology, being selected from for solvent species is heavy to closing
Will.For specific high polymer material polyvinyl resin, the present inventor is by being constantly trying to and exploring
Research, finds to use C as described above5-C12Alkane, especially n-hexane and/or normal heptane are used as organic solvent
When dissolving simultaneously cryoprecipitation polyvinyl resin, the laser sintered polyethylene powders of being suitably selected for property are resulted in former
Material.
According to the present invention, in step a), the polyvinyl resin is preferably high density polyethylene (HDPE), low-density
At least one of polyethylene and LLDPE.The melt index of the polyvinyl resin at 190 DEG C,
20~100g/10min, preferably 30~80g/10min are determined as under 2.16kg carrying capacity.
The present inventor has found that the polyvinyl resin of melt index within the above range exists by many experiments
There is good mobility after melting, be conducive to laser sintering process.
Preferably, in step a), counted by 100 parts by weight of the polyvinyl resin, the C5-C12
Alkane consumption is 600~1200 parts by weight, preferably 800~1000 parts by weight.
The present inventor is further had found by substantial amounts of experimental exploring, as use C as described above5-C12Alkane
Hydrocarbon, such as n-hexane as polyvinyl resin solvent when, polyvinyl resin can be made with spherical and/or spherical
Character separate out, and with 30~150 μm, preferably 30~100 μm of particle diameter, surface is round and smooth, good dispersion,
Size Distribution is small, is particularly suitable for use in Selective Laser Sintering.
Work as C5-C12When the consumption of alkane is in aforementioned range, pattern, dispersiveness preferably polyethylene are resulted in
Toner.
, according to the invention it is preferred in step a), the heating-up temperature is 70~140 DEG C, preferably 80~120 DEG C,
More preferably 90~100 DEG C.
In a preferred embodiment, polyvinyl resin solution is kept for 30~90 minutes in heating-up temperature.
, according to the invention it is preferred to which in step b), average rate of temperature fall is 0.1 DEG C/min~1 DEG C/min.
Preferably, polyvinyl resin solution is cooled to cooling target temperature, and kept in cooling target temperature
30~90 minutes；The cooling target temperature is preferably 10~30 DEG C.
In the method that the present invention is provided, the temperature-fall period of polyvinyl resin solution can at the uniform velocity cool, can also
Stage cooling.The present inventor passes through substantial amounts of experimental exploring, find the present invention some are preferred
In embodiment, in step b), polyvinyl resin solution is cooled to one or more medium temperatures, and
Kept for 30~90 minutes in the medium temperature；The medium temperature is preferably 40~70 DEG C, preferably 50~60
℃.It is readily appreciated that, the medium temperature refers to step a) heating-up temperature and step b) cooling target temperature
Between temperature.Further, when medium temperature is, for example, any one temperature in 40~70 DEG C, step
A) temperature in should be more than the medium temperature.For example, in a specific embodiment, by polyvinyl resin
Solution from 110 DEG C of heating-up temperature be down to 60 DEG C when, in 60 DEG C of keeping temperatures 60 minutes；Or directly it is down to room
Temperature.In other preferred embodiments, when polyvinyl resin solution is down to 50~60 DEG C from heating-up temperature,
Insulation 30~90 minutes, results in and preferably separates out effect.
By the heating cooling method of invention, the acquisition uniform powder particle of particle diameter distribution is ensure that, thus it is special
The not laser sintered application of being suitably selected for property.
In the method that the present invention is provided, the antistatic behaviour of polyethylene resin powder is improved using antistatic additive
Energy.Antistatic additive be the powder with anti-static function, particle or fiber, specifically including carbon black, graphite,
At least one in graphene, the metal dust of CNT and conducting function, metallic fiber or metal oxide
Kind.Wherein, the carbon black is that acetylene carbon black, superconduction carbon black, spy lead at least one of carbon black；The graphite
For at least one of native graphite, expansible graphite；The CNT is single-walled carbon nanotube, many wall carbon
At least one of nanotube；The conducting metal and metallic fiber be containing gold, silver, copper, iron, aluminium, nickel,
Metal dust/fiber, alloy powder/fiber, the composite powder/fiber of the compositions such as stainless steel；The metal oxidation
Thing is at least one of titanium oxide, zinc oxide, tin oxide, indium oxide, cadmium oxide.
In step c), counted by 100 parts by weight of polyvinyl resin, the antistatic additive is preferably 0.05~15
Parts by weight, more preferably 0.25~5 parts by weight.
In step c), the antioxidant is preferably antioxidant 1010 and/or irgasfos 168, to prevent poly- second
Oxidation reaction occurs for olefine resin.Counted by 100 parts by weight of polyvinyl resin, the antioxidant 1010 consumption
Preferably 0.1~0.5 parts by weight, more preferably 0.2~0.4 parts by weight；Irgasfos 168 consumption is preferably
0.1~0.5 parts by weight, more preferably 0.2~0.4 parts by weight.
In a preferred embodiment, antioxidant by scope as defined above antioxidant 1010 and antioxidant
168 compounding compositions.
Polyvinyl resin obtained polyethylene powders easily jaundice in the presence of high temperature and organic solvent becomes fragile, unfavorable
In the raw material as selective laser sintering, long-term preservation is less useful for.In the method that the present invention is provided, adopt
Prevented with antioxidant polyvinyl resin occur oxidation reaction, it is possible to increase obtained polyethylene resin powder it is resistance to
Hot and service life, transparent color and luster is non-yellowing, it is adaptable to which selective laser sintering prepares the process of various product.
In the method that the present invention is provided, prevent to glue between polyethylene powders particle using separator powder
Knot.The separator powder can be metallic soap, i.e., alkali metal or alkali based on alkane monocarboxylic acid or dimeric dibasic acid
Earth metal, is preferably selected from least one of following material：It is odium stearate, potassium stearate, zinc stearate, hard
Resin acid calcium, lead stearate.The separator powder can also be nano-oxide or nano metal salt, preferably select
From at least one of following material：Silica, titanium dioxide, aluminum oxide, zinc oxide, zirconium oxide, carbon
Sour calcium, barium sulfate.Counted by 100 parts by weight of polyvinyl resin, the consumption of the separator powder is preferably
0.01~10 parts by weight, more preferably 0.1~5 parts by weight, most preferably 0.5~1 parts by weight.
It can prevent from bonding between polyethylene powders particle using separator powder, so that influence processability
Energy.On the other hand the bonding of antioxidant is also possible to prevent, its being dispersed in polyvinyl resin evenly is played
Antioxygenic property.Further, separator powder can also act synergistically with antioxidant, and especially its consumption is preceding
In the range of stating, dispersiveness and good fluidity, the polyvinyl resin for being suitable for selective laser sintering are resulted in
Powder.
It is used for the antistatic poly- of selective laser sintering present invention also offers what is prepared according to above method
Vinyl powder, the particle of the powder is spherical and/or spherical, and the particle size of particle is
30~150 μm, particle diameter distribution D10=45~69 μm, D50=66~97 μm, D90=85~120 μm.According to this
The polyethylene resin powder that invention is provided is particularly suitable for use in Selective Laser Sintering, and sintering success rate is high,
Obtained sintered products and predetermined prod scale error are small, and section cavity is few.
In addition, the present invention further provides a kind of selective laser sintering method, methods described is included by as above
Described method prepares polyethylene resin powder, to be used as sintered powder raw material.The choosing provided by the present invention
Selecting property laser sintering processes, can be prepared with irregular figure, the well-balanced smooth, satisfactory mechanical property in surface
Polyethylene molding product.
Provided by the present invention for the preparation method of the polyethylene resin powder of selective laser sintering, operating procedure
Simply, it is easily operated, by selecting suitable solvent, select under specific temperature and pressure, design is suitable
Heating and cooling method, so as to obtain the polyethylene that form, character etc. are particularly suitable for selective laser sintering
Toner raw material.In addition, another advantage protruded of the present invention is, by adding antistatic additive, powder
Interleaving agent and antioxidant, can obtain that size is moderate, surface is round and smooth, dispersed and good fluidity, particle diameter
Be evenly distributed, heap appropriate density, oxidation resistant polyethylene resin powder, for Selective Laser Sintering
When, it can easily prepare that scale error is small, hole is few, profile is well-balanced, good mechanical property moulded work.Thus,
The invention provides a kind of polyethylene resin powder raw material of good performance suitable for selective laser sintering and
Its preparation method, only selective laser sintering does not provide new qualified raw materials for sintering, is also polyethylene tree
The processing and application of fat provide new direction.
Embodiment
The present invention will be described further by specific embodiment below, it should be appreciated that the scope of the present invention
It is not limited to this.
The particle size and particle diameter distribution of polyethylene resin powder：Using laser particle analyzer (Mastersizer 2000,
Malvern companies of Britain) determine.
The volume resistance Rv of moulded work obtained by the chosen property laser sintering and moulding of polyethylene resin powder：According to state
Family standard GB/T 1410-2006, are determined using megger (ZC36).
Embodiment 1
By polyvinyl resin (the density 0.965g/cm of 100 parts by weight3, melt index (190 DEG C, 2.16kg)
For 30g/10min) and the n-hexane of 1000 parts by weight be placed in autoclave, be passed through high pure nitrogen extremely
0.2MPa.100 DEG C are then raised temperature to, at this temperature constant temperature 60 minutes.Constant temperature terminate after through cooling water with
1.0 DEG C/min speed is down to 60 DEG C, at this temperature constant temperature 60 minutes.Continue with 1.0 DEG C/min speed
It is down to room temperature.The CNT of 0.5 parts by weight is added in obtained solidliquid mixture, 0.25 parts by weight
After the irgasfos 168 of antioxidant 1010 and 0.25 parts by weight, and the calcium stearate of 0.5 parts by weight, warp
Centrifuge and the anti-static polyethylene toner suitable for selective laser sintering is obtained after being dried in vacuo.Will
Obtained polyethylene resin powder is used for selective laser sintering, obtains moulded work product.
Determined through laser particle analyzer, the particle size of obtained polyethylene resin powder is 35~115 μm, particle diameter
It is distributed as D10=45 μm, D50=71 μm, D90=92 μm.
Determined through megger, the molding obtained after the chosen property of gained anti-static polyethylene toner is laser sintered
The volume resistance Rv of product is：1.2×108Ω。
Embodiment 2
By polyvinyl resin (the density 0.947g/cm of 100 parts by weight3, melt index (190 DEG C, 2.16kg)
For 70g/10min) and the n-hexane of 800 parts by weight be placed in autoclave, be passed through high pure nitrogen extremely
0.3MPa.110 DEG C are then raised temperature to, at this temperature constant temperature 30 minutes.Constant temperature terminate after through cooling water with
1.0 DEG C/min speed is down to 55 DEG C, at this temperature constant temperature 60 minutes.It is down to 1.0 DEG C/min speed
20 DEG C, and kept for 60 minutes at 20 DEG C.The conductive black of 5 parts by weight is added in obtained solidliquid mixture,
The irgasfos 168 of the antioxidant 1010 of 0.25 parts by weight and 0.25 parts by weight, and 1 parts by weight
After zinc stearate, the poly- second suitable for selective laser sintering is obtained after material is centrifuged and is dried in vacuo
Olefine resin powder.Obtained polyethylene resin powder is used for selective laser sintering, moulded work product is obtained.
Determined through laser particle analyzer, the particle size of obtained polyethylene resin powder is 50~130 μm, particle diameter
It is distributed as D10=61 μm, D50=94 μm, D90=115 μm.
Determined through megger, the molding obtained after the chosen property of gained anti-static polyethylene toner is laser sintered
The volume resistance Rv of product is 6.2 × 107Ω。
Embodiment 3
By polyvinyl resin (the density 0.920g/cm of 100 parts by weight3, melt index (190 DEG C, 2.16kg)
For 50g/10min) and the n-hexane of 1200 parts by weight be placed in autoclave, be passed through high pure nitrogen extremely
0.1MPa.90 DEG C are then raised temperature to, at this temperature constant temperature 90 minutes.It is down to 0.1 DEG C/min speed
Room temperature.The conductive black of 2.5 parts by weight, the carbon nanometer of 0.1 parts by weight are added in obtained solidliquid mixture
The irgasfos 168 of pipe, the antioxidant 1010 of 0.1 parts by weight and 0.1 parts by weight, and 0.75 parts by weight
After several nano silicons, obtain being applied to selective laser burning after material is centrifuged and is dried in vacuo
The polyethylene resin powder of knot.Obtained polyethylene resin powder is used for selective laser sintering, molded
Product product.
Determined through laser particle analyzer, the particle size of obtained polyethylene resin powder is 30~100 μm, particle diameter
It is distributed as D10=46 μm, D50=66 μm, D90=85 μm.
Determined through megger, the molding obtained after the chosen property of gained anti-static polyethylene toner is laser sintered
The volume resistance Rv of product is：2.6×107Ω。
Embodiment 4
By polyvinyl resin (the density 0.915g/cm of 100 parts by weight3, melt index (190 DEG C, 2.16kg)
For 40g/10min) and the n-hexane of 1200 parts by weight be placed in autoclave, be passed through high pure nitrogen extremely
0.1MPa.90 DEG C are then raised temperature to, at this temperature constant temperature 90 minutes.Constant temperature terminate after through cooling water with 0.5
DEG C/min speed is down to 55 DEG C, constant temperature 60 minutes at this temperature.Room temperature is down to 0.1 DEG C/min speed,
Kept for 60 minutes at room temperature.The aluminium powder and 0.05 weight of 7.5 weight fractions are added in obtained solidliquid mixture
The irgasfos 168 of the CNT of fraction, the antioxidant 1010 of 0.3 weight fraction and 0.3 weight fraction is measured,
And 0.9 weight fraction nano zine oxide after, be centrifuged and obtained after being dried in vacuo be applied to selectivity
Laser sintered polyethylene resin powder.Obtained polyethylene resin powder is used for selective laser sintering, obtained
To moulded work product.
Determined through laser particle analyzer, the particle size of obtained polyethylene resin powder is 35~120 μm, particle diameter
It is distributed as D10=52 μm, D50=79 μm, D90=100 μm.
Determined through megger, the molding obtained after the chosen property of gained anti-static polyethylene toner is laser sintered
The volume resistance Rv of product is：3.7×107Ω。
Embodiment 5
By polyvinyl resin (the density 0.935g/cm of 100 parts by weight3, melt index (190 DEG C, 2.16kg)
For 60g/10min) and the n-hexane of 1000 parts by weight be placed in autoclave, be passed through high pure nitrogen extremely
0.3MPa.90 DEG C are then raised temperature to, at this temperature constant temperature 30 minutes.Constant temperature terminate after through cooling water with 0.5
DEG C/min speed is down to 30 DEG C, and kept for 30 minutes at 30 DEG C.0.5 is added in obtained solidliquid mixture
The irgasfos 168 of the graphene of weight fraction, the antioxidant 1010 of 0.2 weight fraction and 0.2 weight fraction,
And 0.6 weight fraction nano-calcium carbonate after, be centrifuged and obtained after being dried in vacuo be applied to selectivity
Laser sintered polyethylene resin powder.Obtained polyethylene resin powder is used for selective laser sintering, obtained
To moulded work product.
Determined through laser particle analyzer, the particle size of obtained polyethylene resin powder is 50~150 μm, particle diameter
It is distributed as D10=69 μm, D50=97 μm, D90=120 μm.
Determined through megger, the molding obtained after the chosen property of gained anti-static polyethylene toner is laser sintered
The volume resistance Rv of product is：7.3×107Ω。
Embodiment 6
By polyvinyl resin (the density 0.955g/cm of 100 parts by weight3, melt index (190 DEG C, 2.16kg)
For 45g/10min) and the normal heptane of 1200 parts by weight be placed in autoclave, be passed through high pure nitrogen extremely
0.2MPa.90 DEG C are then raised temperature to, at this temperature constant temperature 90 minutes.Constant temperature terminate after through cooling water with 0.5
DEG C/min speed is down to 50 DEG C, constant temperature 90 minutes at this temperature.Room temperature is down to 0.2 DEG C/min speed.
The expansible graphite of 1 weight fraction is added in obtained solidliquid mixture, the antioxidant of 0.15 weight fraction is added
The irgasfos 168 of 1010 and 0.15 weight fraction, and after the odium stearate of 0.8 weight fraction, through centrifugation point
From with the anti-static polyethylene toner suitable for selective laser sintering is obtained after vacuum drying.By what is obtained
Polyethylene resin powder is used for selective laser sintering, obtains moulded work product.
Determined through laser particle analyzer, the particle size of obtained polyethylene resin powder is 45~130 μm, particle diameter
It is distributed as D10=67 μm, D50=96 μm, D90=114 μm.
Determined through megger, the molding obtained after the chosen property of gained anti-static polyethylene toner is laser sintered
The volume resistance Rv of product is：4.5×108Ω。
Comparative example 1
By polyvinyl resin (the density 0.965g/cm of 100 parts by weight3, melt index (190 DEG C, 2.16kg)
For 30g/10min) and the n-hexane of 1000 parts by weight be placed in autoclave, be passed through high pure nitrogen extremely
0.2MPa.100 DEG C are then raised temperature to, at this temperature constant temperature 60 minutes.Constant temperature terminate after through cooling water with
1.0 DEG C/min speed is down to 60 DEG C, at this temperature constant temperature 60 minutes.Continue with 1.0 DEG C/min speed
It is down to room temperature.The antioxidant 1010 and 0.25 parts by weight of 0.25 parts by weight are added in obtained solidliquid mixture
After several irgasfos 168s, and the calcium stearate of 0.5 parts by weight, after being centrifuged and being dried in vacuo
To the anti-static polyethylene toner suitable for selective laser sintering.Obtained polyethylene resin powder is used
In selective laser sintering, moulded work product is obtained.
Compared with Example 1, due to there is no antistatic additive in comparative example 1, therefore the anti-of finished product can not be assigned
Antistatic property, can cause to influence the normal of product to use because of electrostatic interaction.Meanwhile, antistatic additive is added without,
It can also be caused due to the electrostatic interaction between polyethylene resin powder and between polyethylene resin powder and equipment
Powdering operation can not be smoothly completed.
Determined through megger, the body of the moulded work obtained after the chosen property of gained polyethylene resin powder is laser sintered
Accumulating resistance Rv is：7.8×1016Ω。
Comparative example 2
By polyvinyl resin (the density 0.965g/cm of 100 parts by weight3, melt index (190 DEG C, 2.16kg)
For 30g/10min) and the n-hexane of 1000 parts by weight be placed in autoclave.It is passed through high pure nitrogen extremely
0.2MPa.100 DEG C are then raised temperature to, at this temperature constant temperature 60 minutes.Constant temperature terminate after through cooling water with
1.0 DEG C/min speed is down to 60 DEG C, at this temperature constant temperature 60 minutes.Continue with 1.0 DEG C/min speed
It is down to room temperature.The CNT of 0.5 parts by weight, and 0.5 parts by weight are added in obtained solidliquid mixture
After several calcium stearates, it is centrifuged and is obtained after being dried in vacuo suitable for the antistatic of selective laser sintering
Polyethylene resin powder.
Compared with Example 1, due to not having antioxidant in comparative example 2, obtained polyethylene powders application is caused
It is heated when laser sintered degradable so that the mechanical property of moulded work is substantially reduced.
Comparative example 3
By polyvinyl resin (the density 0.965g/cm of 100 parts by weight3, melt index (190 DEG C, 2.16kg)
For 30g/10min) and the n-hexane of 1000 parts by weight be placed in autoclave.It is passed through high pure nitrogen extremely
0.2MPa.100 DEG C are then raised temperature to, at this temperature constant temperature 60 minutes.Constant temperature terminate after through cooling water with
1.0 DEG C/min speed is down to 60 DEG C, at this temperature constant temperature 60 minutes.Continue with 1.0 DEG C/min speed
It is down to room temperature.The CNT of 0.5 parts by weight is added in obtained solidliquid mixture, 0.25 parts by weight
After antioxidant 1010 and the irgasfos 168 of 0.25 parts by weight, it is centrifuged and is fitted after being dried in vacuo
Anti-static polyethylene toner for selective laser sintering.
Compared with Example 1, due to not having separator powder in comparative example 3, obtained polyethylene powders are caused
Easily bond, mobility is poor, it is impossible to preferably meet the requirement of laser sintering process.
Above example and comparative example explanation, the polyethylene resin powder obtained according to the present invention have good resist
It is static behaviour and inoxidizability, good powder flowbility, suitably sized size, suitable heap density, well-balanced
Particle profile and uniform particle diameter distribution, it is adaptable to selective laser sintering prepares various moulded works.Implement
The volume resistance of the moulded work obtained after example 1-6 addition antistatic additive is significantly lower than does not add antistatic additive accordingly
Result (for save length, the corresponding comparative examples of embodiment 2-6 are not enclosed).It is unmodified in such as comparative example 1
Volume resistance of the polyethylene resin powder through laser sintered moulded work is about 1016Ω, and the mould that embodiment 1 is obtained
The volume resistance of modeling product is about 107~108Ω.Compared with comparative example 1, embodiment 1 is modified by antistatic additive
Volume resistance of the polyethylene resin powder through laser sintered moulded work is substantially reduced, and modified effect substantially, illustrates this
The polyethylene resin powder that invention is provided has stronger antistatic property.
According to present invention also offers a kind of selective laser sintering method, methods described is included by as described above
Method prepare polyethylene resin powder, to be used as sintered powder raw material.The selectivity provided by the present invention
Laser sintering processes, can be prepared well-balanced smooth, satisfactory mechanical property poly- with irregular figure, surface
Ethene moulded work.
Although the present invention has been described in detail, it will be understood by those skilled in the art that in spirit of the invention and model
Modification in enclosing will be apparent.However, it should be understood that each side, difference that the present invention is recorded
The each several part of embodiment and the various features enumerated can be combined or all or part of exchange.Above-mentioned
Each embodiment in, those with reference to another embodiment embodiment can suitably with its
Its embodiment is combined, and this is will be to understand by those skilled in the art.In addition, those skilled in the art
It will be understood that, description above is only the mode of example, it is no intended to the limitation present invention.
Claims (12)
1. a kind of preparation method of anti-static polyethylene toner for selective laser sintering, including it is following
Step：
A) at the heating temperature, polyvinyl resin is dissolved in C5-C12At least one of alkane, is gathered
Vinyl solution；
B) the polyvinyl resin solution for obtaining step a) cools, and makes solid Precipitation, obtains solid-liquid mixing
Thing；
C) add after auxiliary agent and be well mixed in the solidliquid mixture that step b) is obtained, remove and dried after solvent,
Obtain the anti-static polyethylene toner for selective laser sintering；
Wherein, the auxiliary agent includes antistatic additive, antioxidant and separator powder.
2. according to the method described in claim 1, it is characterised in that in step a), the polyethylene tree
The melt index of fat is determined as 20~100g/10min, preferably 30~80g/10min under 190 DEG C, 2.16kg carrying capacity.
3. method according to claim 1 or 2, it is characterised in that in step a), with described poly-
Vinyl is 100 parts by weight meters, the C5-C12The consumption of alkane is 600~1200 parts by weight, excellent
Elect 800~1000 parts by weight as.
4. the method according to any one in claim 1-3, it is characterised in that in step a),
The C5-C12Alkane is C5-C8Alkane, preferably include pentane, isopentane, n-hexane, 2- methylpentanes,
3- methylpentanes, 2,2- dimethylbutanes, 2,3- dimethylbutanes, hexamethylene, normal heptane, 2- methyl hexanes,
3- methyl hexanes, 2,2- dimethyl pentanes, 2,3- dimethyl pentanes, 2,4- dimethyl pentanes, 3,3- dimethyl pentanes,
3- ethylpentanes, 2, more preferably at least one of 2,3- triptanes, n-hexane and/or normal heptane.
5. the method according to any one in claim 1-4, it is characterised in that in step a),
The heating-up temperature is 70~140 DEG C, more preferably preferably 80~120 DEG C, 90~100 DEG C；It is preferred that by polyethylene
Resin solution is kept for 30~90 minutes in the heating-up temperature.
6. the method according to any one in claim 1-5, it is characterised in that in step b),
Average rate of temperature fall is 0.1 DEG C/min~1 DEG C/min；Preferably, polyvinyl resin solution is cooled to cooling mesh
Temperature is marked, and is kept for 30~90 minutes in cooling target temperature；The cooling target temperature is preferably 10~30 DEG C.
7. the method according to any one in claim 1-6, it is characterised in that in step b),
Polyvinyl resin solution is cooled to one or more medium temperatures, and is kept for 30~90 points in the medium temperature
Clock；It is preferred that the medium temperature is 40~70 DEG C, more preferably 50~60 DEG C.
8. the method according to any one in claim 1-7, it is characterised in that in step c),
The antistatic additive includes metal dust, the gold of carbon black, graphite, graphene, CNT and conducting function
Belong at least one of fiber or metal oxide；Counted by 100 parts by weight of polyvinyl resin, it is described anti-quiet
Electric agent consumption is 0.05~15 parts by weight, preferably 0.25~5 parts by weight.
9. the method according to any one in claim 1-8, it is characterised in that in step c),
The separator powder is selected from alkali metal based on alkane monocarboxylic acid or dimeric dibasic acid or alkaline-earth metal, nano oxidized
At least one of thing and nano metal salt, are preferably selected from odium stearate, potassium stearate, zinc stearate, tristearin
Sour calcium, lead stearate, silica, titanium dioxide, aluminum oxide, zinc oxide, zirconium oxide, calcium carbonate and sulphur
At least one of sour barium；Counted by 100 parts by weight of polyvinyl resin, the separator powder consumption is
0.01~10 parts by weight, preferably 0.1~5 parts by weight, more preferably 0.5~1 parts by weight.
10. the method according to any one in claim 1-9, it is characterised in that in step c),
The antioxidant includes antioxidant 1010 and/or irgasfos 168；Counted by 100 parts by weight of polyvinyl resin,
The antioxidant 1010 consumption is 0.1~0.5 parts by weight, preferably 0.2~0.4 parts by weight；Irgasfos 168
Consumption is 0.1~0.5 parts by weight, preferably 0.2~0.4 parts by weight.
11. it is used for selective laser sintering according to what any one methods described in claim 1-10 was prepared
Antistatic behaviour polyethylene resin powder, the particle of the powder is spherical and/or spherical, and the particle diameter of particle is big
Small is 30~150 μm, particle diameter distribution D10=45~69 μm, D50=66~97 μm, D90=85~120 μm.
12. a kind of selective laser sintering method, methods described includes will be by any in such as claim 1-10
Polyethylene resin powder prepared by one methods described is used as sintered powder raw material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110467769A (en) * | 2019-08-26 | 2019-11-19 | 华南理工大学 | A kind of anti-oxidant high-density polyethylene composite material and preparation method thereof |
| WO2022043552A1 (en) | 2020-08-31 | 2022-03-03 | SETUP Performance SAS | Powder composition for additive process and printed parts thereof |
| CN114349988A (en) * | 2021-12-29 | 2022-04-15 | 湖南华曙高科技股份有限公司 | High polymer powder material for selective laser sintering and preparation method thereof |
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| CN102399371A (en) * | 2011-10-17 | 2012-04-04 | 湖南华曙高科技有限责任公司 | Preparation method of polyamide powder used for selective laser sintering |
| CN103951971A (en) * | 2014-05-12 | 2014-07-30 | 湖南华曙高科技有限责任公司 | Carbon fiber reinforced resin powder material for selective laser sintering |
| CN104497323A (en) * | 2014-12-17 | 2015-04-08 | 湖南华曙高科技有限责任公司 | Preparation method of nylon powder for selective laser sintering |
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| US3943115A (en) * | 1974-03-23 | 1976-03-09 | Ube Industries, Ltd. | Method for preparing finely divided ethylene polymer particles |
| CN102399371A (en) * | 2011-10-17 | 2012-04-04 | 湖南华曙高科技有限责任公司 | Preparation method of polyamide powder used for selective laser sintering |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110467769A (en) * | 2019-08-26 | 2019-11-19 | 华南理工大学 | A kind of anti-oxidant high-density polyethylene composite material and preparation method thereof |
| WO2022043552A1 (en) | 2020-08-31 | 2022-03-03 | SETUP Performance SAS | Powder composition for additive process and printed parts thereof |
| CN114349988A (en) * | 2021-12-29 | 2022-04-15 | 湖南华曙高科技股份有限公司 | High polymer powder material for selective laser sintering and preparation method thereof |
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Application publication date: 20171031 |