CN107304262A - Preparation method for the polyethylene resin powder of selective laser sintering - Google Patents
Preparation method for the polyethylene resin powder of selective laser sintering Download PDFInfo
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Abstract
The invention provides a kind of preparation method of the fiberglass reinforced polyethylene resin powder 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 fiberglass reinforced polyethylene resin powder for selective laser sintering；Wherein, the auxiliary agent includes glass fibre, antioxidant and separator powder.Present invention also offers the 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 glass for selective laser sintering
Strengthen polyethylene resin powder and preparation method thereof 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 (PE) is that a kind of use scope is very wide and consumption very big commodity polymer material, with good
Combination property.However, polythene material is frequently encountered in use, physical and mechanical properties is poor to ask
Topic, is restricted in application process.Therefore SLS fiberglass reinforced polyethylene solids powder is developed, both may be used
Requirement of the application field to material mechanical performance can be met again by meeting the individual demand in practical application.
The content of the invention
Object of the present invention is to provide a kind of fiberglass reinforced polyethylene tree suitable for selective laser sintering
Cosmetics end and its preparation method and application.The polyvinyl resin powder that the method provided according to the present invention is prepared
End, with good mechanical property and 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.
The invention provides a kind of preparation of the fiberglass reinforced polyethylene resin powder 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 fiberglass reinforced polyethylene resin powder for selective laser sintering；
Wherein, the auxiliary agent includes glass fibre, 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.Preferably, step a) is heated under inert gas, such as nitrogen atmosphere.
Preferably, step b) is carried out at autogenous pressures.
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 Physical Mechanical of polyethylene resin powder is improved using glass fibre
Energy.The glass fibre is preferably ultrashort glass fibre, more preferably 5~20 μm of diameter, 100~500 μm of length
Alkali-free glass fibre, 5~15 μm of most preferred diameters, the alkali-free glass fibre that 100~250 μm of length.With poly-
Vinyl is 100 parts by weight meters, and the glass fibre is 5~60 parts by weight, preferably 10~50 weights
Measure number.
In the present invention, term " ultrashort glass fibre " refers to 1~50 μm of diameter, 50~1000 μm of length
Glass fibre.
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.
Present invention also offers the fiberglass reinforced for selective laser sintering prepared according to above method
Polyethylene resin 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 glass fibre, 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) characterize measure.
The mechanical property of moulded work obtained by the chosen property laser sintering and moulding of polyethylene resin powder：According to national standard
ISO 527 determines tensile strength and characterized.
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.Added in obtained solidliquid mixture 5 μm of the diameters of 10 parts by weight, 150 μm of length it is super
The irgasfos 168 of short glass fiber, the antioxidant 1010 of 0.25 parts by weight and 0.25 parts by weight, and
After the calcium stearate of 0.5 parts by weight, it is centrifuged and obtains being applied to selective laser burning after being dried in vacuo
The fiberglass reinforced polyethylene resin powder of knot.Obtained polyethylene resin powder is used for selective laser sintering,
Obtain moulded work product.
Determined through laser particle analyzer, the particle size of obtained polyethylene resin powder is 30~105 μm, particle diameter
It is distributed as D10=42 μm, D50=67 μm, D90=90 μm.
After measured, the tensile strength of the polyethylene resin powder moulded work obtained is 38MPa.
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.Added in obtained solidliquid mixture 20 parts by weight 10 μm of diameter,
The ultrashort glass fibre of 250 μm of length, the antioxidant 1010 of 0.25 parts by weight and 0.25 parts by weight it is anti-
After oxygen agent 168, and the zinc stearate of 1 parts by weight, obtained after material is centrifuged and is dried in vacuo
Suitable for the polyethylene resin powder of selective laser sintering.Obtained polyethylene resin powder is used for selectivity
It is laser sintered, obtain moulded work product.
Determined through laser particle analyzer, the particle size of obtained polyethylene resin powder is 45~135 μm, particle diameter
It is distributed as D10=67 μm, D50=89 μm, D90=115 μm.
After measured, the tensile strength of the polyethylene resin powder moulded work obtained is 26MPa.
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.15 μm of diameter, the ultrashort glass of 200 μm of length of 10 parts by weight are added in obtained solidliquid mixture
Glass fiber, the CNT of 0.1 parts by weight, the antioxidant 1010 of 0.1 parts by weight and 0.1 parts by weight
After irgasfos 168, and the nano silicon of 0.75 parts by weight, material is centrifuged to do with vacuum
The polyethylene resin powder suitable for selective laser sintering is obtained after dry.Obtained polyethylene resin powder is used
In selective laser sintering, moulded work product is obtained.
Determined through laser particle analyzer, the particle size of obtained polyethylene resin powder is 35~100 μm, particle diameter
It is distributed as D10=44 μm, D50=68 μm, D90=87 μm.
After measured, the tensile strength of the polyethylene resin powder moulded work obtained is 17MPa.
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.5 μm of diameter, the length of 50 parts by weight are added in obtained solidliquid mixture
The irgasfos 168 of 150 μm of ultrashort glass fibre, the antioxidant 1010 of 0.3 parts by weight and 0.3 parts by weight,
And 0.9 parts by weight 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 40~125 μm, particle diameter
It is distributed as D10=55 μm, D50=86 μm, D90=110 μm.
After measured, the tensile strength of the polyethylene resin powder moulded work obtained is 16MPa.
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.35 are added in obtained solidliquid mixture
The ultrashort glass fibre of 15 μm of the diameter of parts by weight, 500 μm of length, the antioxidant 1010 of 0.2 parts by weight
After the irgasfos 168 of 0.2 parts by weight, and the nano-calcium carbonate of 0.6 parts by weight, be centrifuged and
The polyethylene resin powder suitable for selective laser sintering is obtained after vacuum drying.By obtained polyvinyl 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 45~150 μm, particle diameter
It is distributed as D10=66 μm, D50=91 μm, D90=125 μm.
After measured, the tensile strength of the polyethylene resin powder moulded work obtained is 22MPa.
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.
5 μm of diameter, the ultrashort glass fibre of 150 μm of length of 25 parts by weight are added in obtained solidliquid mixture,
The irgasfos 168 of the antioxidant 1010 of 0.15 parts by weight and 0.15 parts by weight, and 0.8 parts by weight
After odium stearate, it is centrifuged and obtains gathering suitable for the fiberglass reinforced of selective laser sintering after being dried in vacuo
Vinyl 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 50~135 μm, particle diameter
It is distributed as D10=68 μm, D50=98 μm, D90=118 μm.
After measured, the tensile strength of the polyethylene resin powder moulded work obtained is 35MPa.
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 polyethylene resin powder suitable for selective laser sintering.Obtained polyethylene resin powder is used to select
Property is laser sintered, obtains moulded work product.
After measured, the tensile strength of the polyethylene resin powder moulded work obtained is 28MPa.
Compared with Example 1, due to there is no ultrashort glass fibre in comparative example 1, therefore can not be to obtained mould
Modeling product play humidification, cause the mechanical property of the moulded work of comparative example 1 to be deteriorated compared with the mechanical property of embodiment 1.
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.Added in obtained solidliquid mixture 5 μm of the diameters of 10 parts by weight, 150 μm of length it is super
After short glass fiber, and the calcium stearate of 0.5 parts by weight, it is centrifuged and is fitted after being dried in vacuo
Fiberglass reinforced polyethylene resin powder for selective laser sintering.Obtained polyethylene resin powder is used for
Selective laser sintering, obtains moulded work product.
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.Added in obtained solidliquid mixture 5 μm of the diameters of 10 parts by weight, 150 μm of length it is super
After the irgasfos 168 of short glass fiber, the antioxidant 1010 of 0.25 parts by weight and 0.25 parts by weight, warp
Centrifuge and the fiberglass reinforced polyethylene resin powder suitable for selective laser sintering is obtained after being dried in vacuo.
Obtained polyethylene resin powder is used for selective laser sintering, moulded work product is obtained.
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, have good power according to the polyethylene resin powder that the present invention is obtained
Learn performance and inoxidizability, it is 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.Although
Because polyethylene raw material does not have the tensile strength for the moulded work that different density cause embodiment 1-6 to obtain not
Together, but generally speaking, the tensile strength of the moulded work obtained after the ultrashort glass fibre of embodiment 1-6 additions is obvious
Higher than the result for not adding ultrashort glass fibre accordingly (to save length, embodiment 2-6 phases are not enclosed and are tackled
Ratio).Particularly with the polyethylene raw material compared with low-density, the moulded work obtained after the ultrashort glass fibre of addition
Tensile strength is significantly increased, and the tensile strength that such as the corresponding comparative example of embodiment 4 is obtained is only 10MPa, very greatly
The mechanical property for the moulded work that polyethylene powders are obtained after laser sintered is improved in degree, is expanded before application
Scape.
Present invention also offers a kind of selective laser sintering method, methods described is included by side as described above
Method prepares polyethylene resin powder, to be used as sintered powder raw material.The selective laser provided by the present invention
Sintering method, can be prepared with irregular figure, well-balanced smooth, satisfactory mechanical property the polyethylene in surface
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 fiberglass reinforced polyethylene resin powder for selective laser sintering, including with
Lower 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 fiberglass reinforced polyethylene resin powder for selective laser sintering；
Wherein, the auxiliary agent includes glass fibre, 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 glass fibre is at least one of ultrashort glass fibre, preferably 5~20 μm of diameter, length
100~500 μm of alkali-free glass fibre, more preferably 5~15 μm of diameter, the alkali-free glass that 100~250 μm of length
Fiber；Counted by 100 parts by weight of polyvinyl resin, the glass fibre consumption is 5~60 parts by weight,
Preferably 10~50 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
Fiberglass reinforced 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110481014A (en) * | 2019-08-26 | 2019-11-22 | 华南理工大学 | A kind of high density polyethylene (HDPE) Complex Different Shape pipe fitting selective laser sintering forming method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104830053A (en) * | 2015-01-08 | 2015-08-12 | 杭州师范大学 | Caprolactam-laurolactam co-polymer modified by glass fiber and preparation method of powder thereof |
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2016
- 2016-04-22 CN CN201610258318.9A patent/CN107304262A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104830053A (en) * | 2015-01-08 | 2015-08-12 | 杭州师范大学 | Caprolactam-laurolactam co-polymer modified by glass fiber and preparation method of powder thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110481014A (en) * | 2019-08-26 | 2019-11-22 | 华南理工大学 | A kind of high density polyethylene (HDPE) Complex Different Shape pipe fitting selective laser sintering forming method |
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