CN107304292A - nylon resin powder for selective laser sintering and preparation method thereof - Google Patents
nylon resin powder for selective laser sintering and preparation method thereof Download PDFInfo
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- CN107304292A CN107304292A CN201610256272.7A CN201610256272A CN107304292A CN 107304292 A CN107304292 A CN 107304292A CN 201610256272 A CN201610256272 A CN 201610256272A CN 107304292 A CN107304292 A CN 107304292A
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Abstract
The invention provides a kind of preparation method of the nylon resin powder for selective laser sintering, comprise the following steps：A) at the heating temperature, nylon resin is dissolved in amide-type and/or alcohol organic solvent, obtains nylon resin solution；B) the nylon resin solution for obtaining step a) cools, and makes solid Precipitation, obtains solidliquid mixture；C) auxiliary agent is added in the solidliquid mixture that step b) is obtained, be well mixed；D) separation of solid and liquid, drying solid is obtained for laser sintered nylon resin powder；Wherein, the auxiliary agent includes functional aid, separator powder and antioxidant.Present invention also offers a kind of selective laser sintering method using the nylon resin powder as raw material.
Description
Technical field
The present invention relates to technical field of polymer processing, and in particular to a kind of nylon for selective laser sintering
Toner and preparation method thereof and the application in terms of selective laser sintering.
Background technology
Selective laser sintering (Selective Laser Sintering, SLS) is a kind of rapid shaping technique, by calculating
Prow is first scanned to 3D solid, is then irradiated in advance on workbench or parts by high intensity laser beam
The material powder spread optionally molten sintering layer by layer, and then realize the technology being successively molded.
SLS has the design of height flexible, can produce accurate model and prototype, can be molded with reliable knot
The parts that can directly use of structure, and it is with short production cycle, and technique is simple, is therefore particularly suited for new production
The exploitation of product.At present, SLS is most widely used and most market prospects technology in increases material manufacturing technology, closely
The trend of fast development is showed over year.
Moulding material is to influence a key factor of SLS development, directly affects shaping speed, the essence of molding part
Degree, and physics, chemical property and its combination property.In moulding material, compared to ceramic powders and metal
Powder, polymer powder has the advantages that forming temperature is low, sintering laser power is small, precision is high.Patent US
The SLS methods that 3D solid is prepared using polymer powder are describe in detail in 6136948.Although being applicable
Moulding material species is various, but can directly apply to SLS technologies and successfully produce that scale error is small, table
The polymer powder powder stock of the regular moulded work in face is seldom.In the prior art, generally using comminuting method, it is such as deep
Cold comminuting method prepares SLS powder stock, and this not only needs particular device, the powder stock prepared
Particle surface is rougher, particle diameter is not uniform enough, in irregular shape, is unfavorable for the formation of sintered moulded body, and shadow
Ring the performance of formed body.It is applied to the polymer powder scarcity of raw material of SLS technologies in the market, thus it is various
The corresponding solid powder raw material of type of polymer is urgently developed.
Nylon isMoleculeThe thermoplasticity rolled into a ball on main chain containing recurring amide radicalResinGeneral name, it is nontoxic, with excellent
Mechanical strength, wearability and corrosion resistance, are widely used in industry, medical treatment and textile industry.But, with section
The development of skill, is being continuously increased to the demand with specific functionality nylon resin materials.Therefore exploitation SLS is used
Functional nylon toner, can meet personalization products application demand can meet people again to product
The requirement of the performances such as safety, health.
The content of the invention
Object of the present invention is to provide a kind of nylon resin powder suitable for selective laser sintering and its
Preparation method and application.Good inoxidizability is had according to the nylon resin powder that provides of the present invention, it is good
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 method of the nylon resin powder for selective laser sintering, the side
Method comprises the following steps：
A) at the heating temperature, nylon resin is dissolved in amide-type and/or alcohol organic solvent, obtains Buddhist nun
Imperial resin solution；
B) the nylon resin solution for obtaining step a) cools, and makes solid Precipitation, obtains solidliquid mixture；
C) auxiliary agent is added in the solidliquid mixture that step b) is obtained, be well mixed；
D) separation of solid and liquid, drying solid obtains being applied to laser sintered nylon resin powder；
Wherein, the auxiliary agent includes functional aid, separator powder and antioxidant.
According to the present invention, in step a), the nylon resin is nylon 56 or NYLON610.
Nylon is mainly produced by petrochemistry method, and such as nylon 56 is polymerized by adipic acid and pentanediamine.With
The reinforcement of increasingly exhausted and people's environmental consciousness of fossil resource, the biology produced by raw material of biomass resource
Geordie dragon, increasingly develops into scale industrial production and application.Nylon 56 is had been developed by lysine through biology
It is engineered to obtain 1,5- pentanediamines, bio-based nylon 56 partly or entirely can be made using 1,5- pentanediamines,
Environment-friendly advantage is had more compared to petroleum base nylon product.The obtained fiber of nylon 56 has high-hydroscopicity, good
Wearability and mechanical performance, traditional nylon 6 and nylon66 fiber can be substituted in industrial circle completely, especially spun
Knitting industry more has excellent application.
Preferably, in step a), counted by 100 parts by weight of the nylon resin, the organic solvent
Consumption is 700-1100 parts by weight, preferably 900-1000 parts by weight.
According to the present invention, the amide-type is preferably C1-C8Acid amides, is preferably selected from C2-C4Acid amides, be preferably
N,N-dimethylformamide and/or DMAC N,N' dimethyl acetamide.
According to the present invention, the alcohols is preferably C1-C9Fatty alcohol, is preferably selected from C1-C5Fatty alcohol, preferably
For methanol and/or ethanol.
In a preferred embodiment, the organic solvent be preferably DMF and/or
DMAC N,N' dimethyl acetamide.
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 nylon resin powder of property.For organic solvent deposit technology, being selected from for solvent species is most important.
For specific high polymer material nylon resin, the present inventor by being constantly trying to and exploratory development,
It was found that using organic solvent as described above, especially N,N-dimethylformamide and/or N, N- dimethylacetamide
When amine is as organic solvent dissolving and cryoprecipitation nylon resin, being suitably selected for property laser burning can be advantageously obtained
The nylon powder raw material of knot.
The present inventor is further had found by substantial amounts of experimental exploring, when using organic molten as described above
Agent, such as ethanol as nylon resin solvent when, nylon resin can be made with spherical and/or spherical character
Separate out, and with 15-150 μm of particle diameter, surface is round and smooth, and good dispersion, Size Distribution is small, especially fits
For Selective Laser Sintering.
When the consumption of organic solvent is in aforementioned range, pattern, dispersiveness preferably nylon resin powder are resulted in
End.
, according to the invention it is preferred to which in step a), the heating-up temperature is 150-220 DEG C, preferably 170-210
℃；It is preferred that nylon resin solution is kept for 60-180 minutes in the heating-up temperature.
Preferably, step a) is heated under an inert gas, preferably nitrogen；The inert gas pressure
For 0.1-0.5Mpa, preferably 0.2-0.3Mpa.
, according to the invention it is preferred to which in step b), average rate of temperature fall is 0.5 DEG C/min-1 DEG C/min.
Preferably, nylon resin solution is cooled to cooling target temperature, and 45-90 is kept in cooling target temperature
Minute；The cooling target temperature is preferably 15-30 DEG C.
Preferably, step b) is carried out at autogenous pressures.
Preferably, in step b), nylon resin solution is cooled to one or more medium temperatures, and
The medium temperature is kept for 45-90 minutes；The medium temperature is preferably 100-150 DEG C, preferably 110-130
℃。
According to the certain preferred embodiments of the present invention, in step b), nylon resin solution is cooled to one
Individual medium temperature.The method according to the invention, it is only necessary to a described medium temperature of experience, that is, only need to point
Two stages are cooled, it becomes possible to obtain good effect.
In the method that the present invention is provided, the temperature-fall period of nylon resin solution can at the uniform velocity cool, can also rank
Section property cooling.The present inventor passes through substantial amounts of experimental exploring, finds some preferred realities in the present invention
Apply in scheme, can be obtained by two steps or a step falling temperature method and preferably separate out effect., will in step b)
Nylon resin solution is cooled to one or more medium temperatures, and is kept for 45~90 minutes in the medium temperature；
The medium temperature is preferably 100-150 DEG C, preferably 110-130 DEG C.It is readily appreciated that, the medium temperature is
Refer to the temperature between step a) heating-up temperature and step b) cooling target temperature.Further, centre is worked as
When temperature is, for example, any one temperature in 100~150 DEG C, the temperature in step a) should be more than in the middle of this
Temperature.For example, in a specific embodiment, the resin solution of nylon 56 is down to for 200 DEG C from heating-up temperature
At 130 DEG C, in 130 DEG C of keeping temperatures 60 minutes；Or directly it is down to room temperature.In other sides of being preferable to carry out
In case, when the resin solution of nylon 56 is down to 100-120 DEG C from heating-up temperature, 45-90 minutes are incubated.Through big
The experiment of amount proves that the thermostatic process in the heating and temperature-fall period, which is resulted in, 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.
According to the present invention, in step c), the functional aid includes antiseptic, antistatic additive and ultrashort
At least one of glass fibre.According to step c), it can be needed to adjust nylon resin powder according to actual industrial
Antibacterial, antistatic and physical and mechanical properties.
According to the present invention, in step c), the antiseptic preferably includes support type antiseptic, inorganic antibacterial
At least one of agent, organic antibacterial agent and natural antibacterial agent.Counted by 100 parts by weight of nylon resin, institute
It is preferably 0.05~1.5 parts by weight to state antiseptic, more preferably 0.1~0.5 parts by weight.
In the present invention, term " support type antiseptic " refers to that antimicrobial component is supported on into realization on carrier resists
The one class antiseptic of bacterium effect.
The support type antiseptic preferably include with zeolite, basic zirconium phosphate, calcium phosphate, hydroxyapatite, glass and
It is anti-that at least one of activated carbon is carrier, load includes at least one of silver ion, zinc ion and copper ion
The antiseptic of bacterium composition.
The inorganic antiseptic comprises preferably the nano metal and/or metal oxide of antibacterial action.The nanometer
Metal preferably includes nanogold and/or Nano Silver.The metal oxide preferably includes zinc oxide and/or titanium dioxide
Titanium.
The organic antibacterial agent preferably includes organic guanidine, quaternary ammonium salt, pyridines, imidazoles, isothiazoline
At least one of ketone and organic metal class.Organic guanidine is preferably included as polyhexamethylene guanide, ten
At least one of dialkyl group guanidine acetate and phenformin hydrochloride.The quaternary ammonium salt preferably includes benzyl dimethyl
Cetyl chloro ammonium, methylacryoyloxyethyl-benzyl-dimethyl ammonium chloride, single pyridine quaternary ammonium salt, alkyl
At least one of metronidazole quaternary ammonium salt and the iodo- 2- propargyl butyl carbamates of 3-.The pyridines are preferred
For ZPT.The imidazoles preferably include at least one of probenazole, Bravo and carbendazim.Institute
State isothiazolinone and preferably include the ketone (OIT) of 2- n-octyl -4- isothiazole -3, the chloro- 2- n-octyls -4- of 4,5- bis-
Isothiazoline -3- ketone (DCOIT), 10,10'- oxygen connection phenoxazine pyrrole (OBPA) and normal-butyl BIT
At least one of (BBIT).The organic metal class preferably include organic mercury compound, organocopper compound,
At least one of organic zinc compound, organo-lead compound and organo-tin compound.
The natural antibacterial agent preferably includes chitosan, wooden mustard seed, sorbic acid and at least one of aloe.
According to the present invention, the ultrashort glass fibre is preferably 5~20 μm of diameter, the nothing that 100~500 μm of length
Alkali containing glass fibre, more preferably 5~15 μm of diameter, the alkali-free glass fibre that 100~250 μm of length.With nylon tree
Fat is 100 parts by weight meters, and the glass fibre is 5~60 parts by weight, preferably 10~50 parts by weight.
In the present invention, term " ultrashort glass fibre " refers to after glass fibre is crushed obtaining straight through screening
2-30 μm of footpath, a class glass fibre of 80-600 μm of length.
The antistatic additive is the powder with anti-static function, particle or fiber, specifically including carbon black, stone
In ink, graphene, metal dust, metallic fiber or the metal oxide of CNT and conducting function extremely
Few one kind.Wherein, the carbon black is that acetylene carbon black, superconduction carbon black, spy lead at least one of carbon black；It is described
Graphite is at least one of native graphite, expansible graphite；The CNT is single-walled carbon nanotube, many
At least one of wall carbon nano tube；The conducting metal and metallic fiber be containing gold, silver, copper, iron, aluminium,
Metal dust/fiber, alloy powder/fiber, the composite powder/fiber of the compositions such as nickel, stainless steel；The metal
Oxide is at least one of titanium oxide, zinc oxide, tin oxide, indium oxide, cadmium oxide.
Counted by 100 parts by weight of nylon resin, the antistatic additive is preferably 0.05~15 parts by weight, more
Preferably 0.25~5 parts by weight.
According to the present invention, in step c), the antioxidant is preferably antioxidant 1010 and/or irgasfos 168,
It is further preferred that being counted by 100 parts by weight of nylon resin, the antioxidant 1010 consumption is 0.2-0.5
Parts by weight, preferably 0.3-0.4 parts by weight；Irgasfos 168 consumption is 0.2-0.5 parts by weight, preferably
For 0.3-0.4 parts by weight.
In a preferred embodiment, antioxidant by scope as defined above antioxidant 1010 and antioxidant
168 compounding compositions.
Nylon resin has amide group, and its dissociation energy is relatively low, strand easy fracture, and amide group is
Chromophore, easily triggers the degraded of polymer in the presence of hyperpyrexia and organic solvent；It has stronger polarity,
It is hygroscopic, hydrolysis, ammonolysis and acidolysis easily occur at high temperature, so as to deteriorate toner in selective laser
Performance in sintering process, causes its service life to shorten.According to the present invention, when adding antioxidant, not only
The chain of oxidation reaction can be prevented to transmit, moreover it is possible to from improving stability of the nylon resin to light, slow down nylon resin hair
Raw oxidation reaction, improves the heat-resistant stability and processing stability of obtained nylon resin powder, reaches that extension makes
With the purpose in life-span.
According to the present invention, in step c), the separator powder can be metallic soap, i.e., based on alkane one
The alkali metal or alkaline-earth metal of first carboxylic acid or dimeric dibasic acid, be preferably selected from odium stearate, potassium stearate, zinc stearate,
At least one of calcium stearate and lead stearate.According to the present invention, the separator powder can be nano oxygen
Compound and/or nano metal salt, be preferably selected from silica, titanium dioxide, aluminum oxide, zinc oxide, zirconium oxide,
At least one of calcium carbonate and barium sulfate nanoparticles.
In the present invention, counted by 100 parts by weight of nylon resin, the separator powder consumption is 0.05-10
Parts by weight, preferably 0.2-5 parts by weight, preferably 0.6-1 parts by weight.
It can prevent from bonding between nylon powder particle using separator powder, so that influence processing characteristics.
On the other hand the bonding of antioxidant is also possible to prevent, its being dispersed in nylon resin evenly is played anti-oxidant
Performance.Further, separator powder can also act synergistically with antioxidant, and especially its consumption is in aforementioned range
It is interior, result in dispersiveness and good fluidity, the nylon resin powder for being suitable for selective laser sintering.
Present invention also offers the nylon resin for selective laser sintering prepared according to above method
Powder, the particle of the powder is spherical and/or spherical, and the particle size of particle is 15-150 μm, particle diameter
D10=40-70 μm, D50=60-100 μm, D90=70-130 μm of distribution.The nylon provided according to the present invention
Toner is particularly suitable for use in Selective Laser Sintering, and sintering success rate is high, obtained sintered products with it is pre-
Fixed output quota product scale error is 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 nylon resin powder, to be used as sintered powder raw material.The selection provided by the present invention
Property laser sintering processes, can be prepared well-balanced smooth, satisfactory mechanical property with irregular figure, surface
Nylon moulded work.
Provided by the present invention for the preparation method of the nylon resin powder of selective laser sintering, operating procedure letter
It is single, easily operated, by selecting suitable solvent, select under specific temperature and pressure, design is suitable
Heating and cooling method, so as to obtain the nylon resin that form, character etc. are particularly suitable for selective laser sintering
Powder stock.In addition, another advantage protruded of the present invention is, by adding antioxidant and separator powder,
It can obtain that size is moderate, surface is round and smooth, dispersed and good fluidity, particle diameter distribution are uniform, heap density
Suitably, oxidation resistant nylon resin powder, when for Selective Laser Sintering, can easily prepare chi
Very little error is small, hole is few, profile is well-balanced, good mechanical property moulded work.Thus, the invention provides one kind
It is of good performance suitable for nylon resin powder stock of selective laser sintering and preparation method thereof, be not only to select
Selecting property is laser sintered to provide new qualified raw materials for sintering, and the also processing for nylon resin and application provides new
Direction.
Brief description of the drawings
Fig. 1 is the SEM (SEM) of according to embodiments of the present invention 1 toner of nylon 56 provided
Figure.
Fig. 2 is the scanning electron microscope diagram for the powder of polyamide 12 for being commercially for selective laser sintering.Mesh
The preceding nylon powder commercially still rarely having for selective laser sintering, enclose herein in the market compared with
For the scanning electron microscope diagram of the powder of polyamide 12 for selective laser sintering generally circulated, it is used for
Contrasted with (Fig. 1) of the invention.
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.
In the examples below that, using laser particle analyzer (Mastersizer 2000, Malvern companies of Britain)
Characterize the particle size and particle diameter distribution of obtained nylon resin powder.
Embodiment 1
The ethanol of the resin of nylon 56 of 100 parts by weight and 1000 parts by weight is placed in autoclave.It is passed through
High pure nitrogen is to 0.2MPa；200 DEG C are then raised temperature to, at this temperature constant temperature 120 minutes；After constant temperature terminates
130 DEG C are down to 1.0 DEG C/min speed through cooling water, at this temperature constant temperature 60 minutes；Continue with 1.0
DEG C/min speed is down to room temperature.The basic zirconium phosphate that 0.5 weight fraction is added in obtained solidliquid mixture carries silver-colored anti-
Microbial inoculum, the CNT of 0.5 weight fraction, add 5 μm of the diameters of 10 weight fractions, 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 toner of nylon 56 of knot.Particle size, the particle diameter distribution result of the toner of nylon 56 obtained are shown in
Table 1.
Embodiment 2
The ethanol of the resin of nylon 56 of 100 parts by weight and 800 parts by weight is placed in autoclave.It is passed through
High pure nitrogen is to 0.3MPa；210 DEG C are then raised temperature to, at this temperature constant temperature 90 minutes；After constant temperature terminates
125 DEG C are down to 1.0 DEG C/min speed through cooling water, at this temperature constant temperature 60 minutes；With 1.0 DEG C/min
Speed be down to 20 DEG C, and kept for 60 minutes at 20 DEG C.0.05 weight point is added in obtained solidliquid mixture
Several ZPTs, the conductive black of 5 weight fractions, 250 μm of 10 μm of the diameter of 25 weight fractions, length
Ultrashort glass fibre, the irgasfos 168 of the antioxidant 1010 of 0.25 parts by weight and 0.25 parts by weight,
And 1 parts by weight zinc stearate after, obtained after material is centrifuged and is dried in vacuo be applied to selection
The laser sintered toner of nylon 56 of property.The particle size of the toner of nylon 56 obtained, particle diameter point
Cloth the results are shown in Table 1.
Embodiment 3
The ethanol of the resin of nylon 56 of 100 parts by weight and 1100 parts by weight is placed in autoclave.It is passed through
High pure nitrogen is to 0.1MPa；200 DEG C are then raised temperature to, at this temperature constant temperature 150 minutes；With 0.1 DEG C/min
Speed be down to room temperature.The nano zine oxide of 1.5 weight fractions, 2.5 weight are added in obtained solidliquid mixture
The CNT of the conductive black of fraction and 0.1 weight fraction, 15 μm of the diameter of 10 weight fractions, length
The irgasfos 168 of 200 μm of ultrashort glass fibre, the antioxidant 1010 of 0.1 parts by weight and 0.1 parts by weight,
And 0.75 parts by weight nano silicon after, be applicable after material is centrifuged and is dried in vacuo
In the toner of nylon 56 of selective laser sintering.The particle size of the toner of nylon 56 obtained,
Particle diameter distribution the results are shown in Table 1.
Embodiment 4
The ethanol of the resin of nylon 56 of 100 parts by weight and 1100 parts by weight is placed in autoclave.It is passed through
High pure nitrogen is to 0.1MPa；190 DEG C are then raised temperature to, at this temperature constant temperature 180 minutes；After constant temperature terminates
125 DEG C are down to 0.5 DEG C/min speed through cooling water, at this temperature constant temperature 60 minutes；With 0.1 DEG C/min
Speed be down to room temperature, at room temperature keep 60 minutes.0.3 weight fraction is added in obtained solidliquid mixture
Glass carries the CNT of silver-colored zinc antiseptic, the aluminium powder of 7.5 weight fractions and 0.05 weight fraction, 10 weight point
Several 15 μm of diameter, the ultrashort glass fibre of 200 μm of length, the antioxidant 1010 of 0.3 parts by weight and 0.3
After the irgasfos 168 of parts by weight, and the nano zine oxide of 0.9 parts by weight, material is centrifuged
With the toner of nylon 56 for obtaining being applied to selective laser sintering after vacuum drying.The nylon 56 obtained
Particle size, the particle diameter distribution of toner the results are shown in Table 1.
Embodiment 5
The methanol of the resin of nylon 56 of 100 parts by weight and 1000 parts by weight is placed in autoclave.It is passed through
High pure nitrogen is to 0.3MPa；210 DEG C are then raised temperature to, at this temperature constant temperature 60 minutes；After constant temperature terminates
30 DEG C are down to 0.5 DEG C/min speed through cooling water, and is kept for 30 minutes at 30 DEG C.Obtained solid-liquid is mixed
0.5 weight fraction carried by active carbon silver antibacterial agent, the graphene of 0.5 weight fraction, 35 weight point are added in compound
Several 15 μm of diameter, the ultrashort glass fibre of 500 μm of length, the antioxidant 1010 of 0.2 parts by weight and 0.2
After the irgasfos 168 of parts by weight, and the nano-calcium carbonate of 0.6 parts by weight, material is centrifuged
With the toner of nylon 56 for obtaining being applied to selective laser sintering after vacuum drying.The nylon 56 obtained
Particle size, the particle diameter distribution of toner the results are shown in Table 1.
Embodiment 6
The methanol of the resin of nylon 56 of 100 parts by weight and 1000 parts by weight is placed in autoclave.It is passed through
High pure nitrogen is to 0.2MPa；190 DEG C are then raised temperature to, at this temperature constant temperature 180 minutes；After constant temperature terminates
100 DEG C are down to 0.5 DEG C/min speed through cooling water, at this temperature constant temperature 90 minutes；With 0.2 DEG C/min
Speed be down to room temperature.The zeolite that 0.3 parts by weight are added in obtained solidliquid mixture carries silver-colored zinc antiseptic, 1
The expansible graphite of weight fraction, 5 μm of the diameter of 25 weight fractions, the ultrashort glass fibre of 150 μm of length,
The irgasfos 168 of the antioxidant 1010 of 0.20 parts by weight and 0.20 parts by weight, and 0.8 parts by weight
After odium stearate, the nylon suitable for selective laser sintering is obtained after material is centrifuged and is dried in vacuo
56 toners.Particle size, the particle diameter distribution of the toner of nylon 56 obtained the results are shown in Table 1.
Table 1
Comparative example 1
The N,N-dimethylformamide of the resin of nylon 56 of 100 parts by weight and 1000 parts by weight is placed in high pressure anti-
Answer in kettle.High pure nitrogen is passed through to 0.2MPa；200 DEG C are then raised temperature to, at this temperature constant temperature 120 minutes；
Constant temperature with 1.0 DEG C/min speed is down to 130 DEG C after terminating through cooling water, at this temperature constant temperature 60 minutes；
Continuation is down to room temperature with 1.0 DEG C/min speed.The anti-of 0.25 weight fraction is added in obtained solidliquid mixture
The irgasfos 168 of the weight fraction of oxygen agent 1010 and 0.25, and after the calcium stearate of 0.5 weight fraction, through from
The heart separates and obtained after being dried in vacuo the toner composition of nylon 56 suitable for selective laser sintering.
Compared with Example 1, due to there is no antiseptic, antistatic additive and ultrashort glass fibre in comparative example 1,
The moulded work for causing obtained functional nylon powder composition to be obtained when using selective laser sintering does not have
Specific functionality, it is impossible to meet demand of some fields to nylon resin materials performance.
Comparative example 2
The N,N-dimethylformamide of the resin of nylon 56 of 100 parts by weight and 1000 parts by weight is placed in high pressure anti-
Answer in kettle.High pure nitrogen is passed through to 0.2MPa；200 DEG C are then raised temperature to, at this temperature constant temperature 120 minutes；
Constant temperature with 1.0 DEG C/min speed is down to 130 DEG C after terminating through cooling water, at this temperature constant temperature 60 minutes；
Continuation is down to room temperature with 1.0 DEG C/min speed.The phosphoric acid of 0.5 weight fraction is added in obtained solidliquid mixture
Zirconium carrying silver antimicrobials, add the CNT of 0.5 weight fraction, add 5 μm of diameter, the length of 10 weight fractions
After the ultrashort glass fibre of 150 μm of degree, the calcium stearate of 0.5 weight fraction, it is centrifuged and is dried in vacuo
The toner composition of functional nylon 56 suitable for selective laser sintering is obtained afterwards.
Compared with Example 1, due to not having antioxidant in comparative example 2, obtained functional nylon powder is caused
Composition is heated degradable when being applied to laser sintered, and obtained moulded work easily shrinks and collapsed, it is impossible to preferably
Meet the requirement of laser sintering process.
Comparative example 3
The N,N-dimethylformamide of the resin of nylon 56 of 100 parts by weight and 1000 parts by weight is placed in high pressure anti-
Answer in kettle.High pure nitrogen is passed through to 0.2MPa；200 DEG C are then raised temperature to, at this temperature constant temperature 120 minutes；
Constant temperature with 1.0 DEG C/min speed is down to 130 DEG C after terminating through cooling water, at this temperature constant temperature 60 minutes；
Continuation is down to room temperature with 1.0 DEG C/min speed.The phosphoric acid of 0.5 weight fraction is added in obtained solidliquid mixture
Zirconium carrying silver antimicrobials, add the CNT of 0.5 weight fraction, add 5 μm of diameter, the length of 10 weight fractions
The antioxygen of the ultrashort glass fibre of 150 μm of degree, the antioxidant 1010 of 0.25 weight fraction and 0.25 weight fraction
After agent 168, it is centrifuged and the functional nylon 56 suitable for selective laser sintering is obtained after being dried in vacuo
Toner composition.
Compared with Example 1, due to not having interleaving agent in comparative example 3, obtained functional nylon powder is caused
Composition is easily bonded, and mobility is poor, it is impossible to preferably meet the requirement of laser sintering process.
Comparative example 4
The N,N-dimethylformamide of the resin of nylon 56 of 100 parts by weight and 1000 parts by weight is placed in high pressure anti-
Answer in kettle.High pure nitrogen is passed through to 0.2MPa；200 DEG C are then raised temperature to, at this temperature constant temperature 120 minutes；
Constant temperature with 1.0 DEG C/min speed is down to 130 DEG C after terminating through cooling water, at this temperature constant temperature 60 minutes；
Continuation is down to room temperature with 1.0 DEG C/min speed.Obtained solidliquid mixture adds the basic zirconium phosphate of 0.5 weight fraction
After carrying silver antimicrobials, the CNT of 0.5 weight fraction is added, 5 μm of diameter, the length of 10 weight fractions is added
After the ultrashort glass fibre of 150 μm of degree, it is centrifuged and obtains being applied to selective laser burning after being dried in vacuo
The toner composition of functional nylon 56 of knot.
Compared with Example 1, due to not having antioxidant and interleaving agent in comparative example 4, obtained feature is caused
Nylon powder composition is heated degradable when being applied to laser sintered, and obtained moulded work easily shrinks and collapsed, no
The requirement of laser sintering process can preferably be met；And causing it easily to bond, mobility is poor, it is impossible to preferably
Meet the requirement of laser sintering process.
Above example and comparative example explanation, the functional nylon toner group that the method according to the invention is obtained
Compound has good antibacterial, an antistatic and physical and mechanical properties, 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.For nylon resin materials, prepared and swashed for selectivity by the method for the present invention
The functional nylon toner composition of light sintering, obtains good effect.Further, by this hair
The selective laser sintering method of bright offer, can prepare with irregular figure, surface it is well-balanced it is smooth,
The functional nylon moulded work of satisfactory mechanical property.
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 (13)
1. a kind of preparation method of nylon resin powder for selective laser sintering, comprises the following steps：
A) at the heating temperature, nylon resin is dissolved in amide-type and/or alcohol organic solvent, obtains Buddhist nun
Imperial resin solution；
B) the nylon resin solution for obtaining step a) cools, and makes solid Precipitation, obtains solidliquid mixture；
C) auxiliary agent is added in the solidliquid mixture that step b) is obtained, be well mixed；
D) separation of solid and liquid, drying solid is obtained for laser sintered nylon resin powder；
Wherein, the auxiliary agent includes functional aid, separator powder and antioxidant.
2. according to the method described in claim 1, it is characterised in that in step a), the nylon resin
For nylon 56 or NYLON610.
3. method according to claim 1 or 2, it is characterised in that using the nylon resin as 100 weights
Number meter is measured, the consumption of organic solvent is 700-1100 parts by weight, preferably 900-1000 parts by weight.
4. the method according to any one in claim 1-3, it is characterised in that the amide-type is
C1-C8Acid amides, is preferably selected from C2-C4Acid amides, preferably DMF and/or N, N- dimethyl second
Acid amides；The alcohols is C1-C9Fatty alcohol, is preferably selected from C1-C5Fatty alcohol, preferably methanol and/or ethanol.
5. the method according to any one in claim 1-4, it is characterised in that in step a),
The heating-up temperature is 150-220 DEG C, preferably 170-210 DEG C；It is preferred that by nylon resin solution in the heating
Temperature is kept for 60-180 minutes.
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 0.5 DEG C/min-1 DEG C/min；Preferably, nylon resin solution is cooled to cooling target
Temperature, and kept for 45-90 minutes in cooling target temperature；It is preferred that the cooling target temperature is 15-30 DEG C.
7. the method according to any one in claim 1-6, it is characterised in that in step b),
Nylon resin solution is cooled to one or more medium temperatures, and kept for 45-90 minutes in the medium temperature；
It is preferred that the medium temperature is 100-150 DEG C, preferably 110-130 DEG C.
8. method according to claim 7, it is characterised in that in step b), nylon resin is molten
Liquid is cooled to a medium temperature.
9. the method according to any one in claim 1-8, it is characterised in that in step c),
The functional aid includes at least one of antiseptic, antistatic additive and ultrashort glass fibre；With nylon tree
Fat is 100 parts by weight meters, and the antiseptic consumption is 0.05~1.5 parts by weight, preferably 0.1~0.5 weight
Measure number；The antistatic additive is 0.05~15 parts by weight, preferably 0.25~5 parts by weight；It is described ultrashort
Glass fibre is 5~60 parts by weight, preferably 10~50 parts by weight.
10. the method according to any one in claim 1-9, it is characterised in that in step c),
The antioxidant is selected from antioxidant 1010 and/or irgasfos 168；Counted by 100 parts by weight of nylon resin,
The antioxidant 1010 consumption is 0.2-0.5 parts by weight, preferably 0.3-0.4 parts by weight；Irgasfos 168
Consumption is 0.2-0.5 parts by weight, preferably 0.3-0.4 parts by weight.
11. the method according to any one in claim 1-10, it is characterised in that in step c),
The separator powder is selected from as alkali metal or alkaline-earth metal, nano oxygen based on alkane monocarboxylic acid or dimeric dibasic acid
At least one of compound and nano metal salt, are preferably selected from odium stearate, potassium stearate, zinc stearate, hard
Resin acid calcium, lead stearate, silica, titanium dioxide, aluminum oxide, zinc oxide, zirconium oxide, calcium carbonate and
At least one of barium sulfate；Counted by 100 parts by weight of nylon resin, the separator powder consumption is
0.05-10 parts by weight, preferably 0.2-5 parts by weight, more preferably 0.6-1 parts by weight.
What 12. any one methods described was prepared in a kind of 1-11 according to claim is used for selective laser
The nylon resin powder of sintering, the particle of the powder is spherical and/or spherical, and the particle size of particle is
15-150 μm, D10=40-70 μm, D50=60-100 μm, D90=70-130 μm of particle diameter distribution.
13. a kind of selective laser sintering method, methods described includes will be by any in such as claim 1-11
Method described in prepares nylon resin powder as sintered powder raw material.
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