CN105462244B - A kind of preparation method of selective laser sintering carbon fiber reinforced nylon composite micro-powder - Google Patents
A kind of preparation method of selective laser sintering carbon fiber reinforced nylon composite micro-powder Download PDFInfo
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- CN105462244B CN105462244B CN201410458111.7A CN201410458111A CN105462244B CN 105462244 B CN105462244 B CN 105462244B CN 201410458111 A CN201410458111 A CN 201410458111A CN 105462244 B CN105462244 B CN 105462244B
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Abstract
The present invention discloses a kind of preparation method of selective laser sintering carbon fiber reinforced nylon composite micro-powder.Carbon fiber powder is first carried out surface preparation by this method, it is added in together in the polymer good solvent containing dispersant with nylon pellet, after heated stirring makes polymer fully dissolve, the poor solvent for adding in nylon so that gradually crystallization is coated on carbon fiber surface to nylon using carbon fiber as nucleus, then it by suction filtration, drying, sieves, add in the acquisition of other auxiliary agents suitable for selective laser sintering carbon fiber reinforced nylon composite powder.The present invention is without high-temperature high-pressure apparatus compared with prior art, simple process, economical and effective, environmental-friendly, easy implementation.Prepared material sintering character is excellent, and carbon fiber content is controllable in material, and gained SLS molded parts have a distinct increment compared to the SLS molded parts of base resin material in terms of mechanical property.
Description
Technical field
The present invention relates to the technical fields of selective laser sintering material.It is burnt more particularly, to a kind of selective laser
The preparation method of knot carbon fiber reinforced nylon composite micro-powder.
Background technology
Selective laser sintering (SLS) is a kind of important technology of 3D printing-increasing material manufacturing.Profit is computerizedd control infrared
Laser beam, is sintered solid powder demixing scan with certain speed and energy density, and layer upon layer eventually forms drip molding.
Material property is the key link of SLS technologies development, it directly affects forming speed, precision and physics, the chemistry of sintered specimen
Performance.With nylon 12 for representative polymer powder and its modified material have water absorption rate is low, fusing point is low, density is low, shrinking percentage
The advantages that low, heat-resisting, easily molded is the widely used a kind of important source material of current Selective Laser Sintering.But such material
Expect intensity and rigidity it is relatively low, by SLS technologies institute shaped article cannot meet certain molded part measuring mechanical property requirements or
The performance requirement used directly as final products.Nylon composite powder is prepared by the means such as modification, compound, can be sintered
To the sintered part of nylon composite materials.These Composite Sintering parts can change the performance of original pure nylon sintered part, so as to
Can meet the needs of different occasions, purposes are to plastic functional piece performance, extend its application field.
Carbon fiber is swollen with low-density, high intensity, high-modulus, high temperature resistant, resist chemical, low resistance, high heat conduction, low-heat
The characteristics such as swollen, chemically-resistant radiation and good biocompatibility.In addition, also there is the distinctive flexibility of fiber and programmable, it
Specific strength and specific modulus be superior to other inorfils.Therefore, it is compound that resin, carbon, metal, ceramics, cement base are mainly used as
The reinforcement of material.It is equal by polyamide (nylon) material of fibre reinforced, mechanical strength, dimensional stability and heat resistance etc.
It increases significantly, and with more good rub resistance and abrasion performance, belongs to self-lubricating material, axis can be made
It holds, the friction members such as gear.
Preparing selective laser sintering composite powder, the most commonly used is mechanical mixings.As its name suggests, just referring to need to
The powder of two or more to be mixed different component carries out the mixing of machinery, mixes such as in high-speed mixer or in the ball mill
It closes, the method as described in patent CN 103951971A.Due to two or more powder phases of different nature during mechanical mixture
To being individually present, density is different, and form is different, it is easy to composition cluster phenomenon is generated, so as to cause the part finally shaped
In uneven components, so as to further influence the various aspects of performance of part.The present invention prepares carbon using solvent precipitation
Fibre-reinforced nylon powder by nylon matrix material dissolving-precipitation process, makes nylon gradually be crystallized using carbon fiber as nucleus
Carbon fiber surface is coated on, two kinds of different components of realization be combined with each other.The degree of being uniformly dispersed of gained composite powder is much larger than
Mechanical mixture powder, SLS molded parts mechanical property also have very big promotion.
Invention content
The technical problem to be solved in the present invention is to provide a kind of selective laser sintering carbon fiber reinforced nylon is compound micro-
The preparation method of powder, this method prepare the nylon powder of fibre reinforced using solvent precipitation, pass through nylon matrix material
Dissolving-precipitation process, making nylon, gradually crystallization is coated on carbon fiber surface using carbon fiber as nucleus, two kinds of different components of realization
It is combined with each other.Much larger than mechanical mixture powder, SLS molded parts mechanical property also has very the degree that is uniformly dispersed of gained composite powder
It is big to be promoted.
In order to solve the above technical problems, the present invention uses following technical proposals：
A kind of preparation method of selective laser sintering carbon fiber reinforced nylon composite micro-powder prepares step including following
Suddenly：
(1) carbon fiber powder is subjected to chemical oxidation pre-treatment or graft pre-processes；
(2) it will be added in the good solvent of nylon pellet by the carbon fiber powder, nylon pellet and dispersant of pretreatment, stirring
Being heated to certain temperature makes nylon and dispersant all dissolve；
(3) into the mixed liquor of step (2) add in nylon pellet poor solvent, stirring, make nylon using carbon fiber powder as
Nucleus be precipitated sediment, and by drying precipitate, screening, obtain carbon fiber-nylon micron particles；
(4) carbon fiber-nylon micron particles obtained by step (3) and flow promortor and antioxidant are mixed, obtains selectivity
It is laser sintered to use carbon fiber reinforced nylon composite micro-powder.
Preferably, step (1) described chemical oxidation pre-treatment includes the following steps：
Carbon fiber powder is placed in Soxhlet extractor, after acetone extraction 24-48 hours, vacuum drying；Then it uses
14mol/L nitric acid is aoxidized, and 300 mesh screens are crossed after washing is dry.
Preferably, step (1) the graft pretreatment includes the following steps：
Carbon fiber powder is placed in Soxhlet extractor, after acetone extraction 24-48 hours, vacuum drying；Then silane is used
Coupling agent is grafted in toluene solvant, and 300 mesh screens are crossed after dry.
Carbon fiber powder surface is aoxidized or is grafted pretreatment by using nitric acid or silane coupling agent, its surface can be made
Carboxyl, hydroxyl isoreactivity group are generated, while increases the polarity for improving fiber surface, improves the infiltration of fiber and resin
Property, be conducive to fiber and resin boundary surface combines.
Preferably, step (1) described carbon fiber powder is 7-10 microns a diameter of, and length is 10-50 microns.
Preferably, step (2) the nylon pellet is selected from nylon 6, nylon66 fiber, nylon 11, nylon 12, nylon 1010 or Buddhist nun
Dragon one or more of 1212.
Preferably, step (2) described dispersant is selected from polyvinylpyrrolidone, polyacrylic acid or hydroxypropyl cellulose, gathers
One or more of vinyl alcohol, ethylenebisstearamide or the excellent amide of ethylenebis.
Dispersant is introduced into the good solvent of nylon, through cryoprecipitation, utilizes the phase of dispersant and polymer chain in system
Interaction and for particle stability protection effect enable nylon base-material be uniformly wrapped in carbon fiber surface finally with
Carbon fiber is precipitated for core.The degree that is uniformly dispersed of gained overlay film powder is much larger than standard machinery mixed-powder.
Preferably, step (2) described good solvent is one or more of trifluoroacetic acid, acetic acid, formic acid.
Preferably, step (2) temperature in room temperature between 120 DEG C.
Preferably, the mass ratio of step (2) carbon fiber powder and nylon pellet is 1: 1~1: 20；The nylon pellet
Weight ratio with solvent is 1: 2~1: 200；The weight proportion of the dispersant and total solvent is 1: 2~1: 100.
Preferably, step (3) described poor solvent, which refers to, is poor solvent to nylon pellet and is good solvent to dispersant；
It is highly preferred that the poor solvent is selected from one or more of ethyl alcohol, ethylene glycol, acetone or water；
It is highly preferred that the volume ratio of poor solvent described in step (3) and step (2) described good solvent is 0~5: 1.
Preferably, step (4) described flow promortor be selected from nano carborundum powder, nano silicon dioxide, nano aluminium oxide or
One or more of nano-titanium oxide；
The antioxidant is selected from the composite antioxidant that Hinered phenols antioxidant and phosphite ester kind antioxidant form；It is described by
Hinder the 60-80% that phenolic antioxidant dosage is composite antioxidant total weight；
It is highly preferred that the Hinered phenols antioxidant is selected from 2,2'- di-2-ethylhexylphosphine oxides-(4- methyl-6-tert-butylphenols), 1,
3,5- trimethyls -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene, 2,6- di-t-butyl -4- methyl-phenols, N, N ' -
Two (3,5- di-tert-butyl-hydroxy phenyls propionamides), 2,2 '-bis- (4- methyl-6-terts butyl-phenol) methane or 2,2 '-bis-
One or more of (4- ethyl -6- t-butyl-phenols) methane；
It is highly preferred that the phosphite ester kind antioxidant is selected from 2,2 '-ethylenebis (4,6- di-tert-butyl-phenyl) fluoro
One or more of phosphite ester or four (2,4- di-tert-butyl-phenyls) -4,4 '-xenyl bis-phosphites.
Preferably, the dosage of step (4) described flow promortor for selective laser sintering nylon micro mist 0.1%~
5%, the dosage of the antioxidant is the 0.1%~5% of selective laser sintering nylon micro mist.
Solvent for use of the present invention may be recovered after use to be recycled, and the present invention is without high compared with prior art
Press equipment, simple process, environmental-friendly, easy implementation.
Beneficial effects of the present invention are as follows：
The present invention is aoxidized or is grafted pretreatment to carbon fiber powder surface by using nitric acid and silane coupling agent, can be made
Its surface generates carboxyl, hydroxyl isoreactivity group, while increases and improve the polarity of fiber surface, improves fiber and resin
Wellability, is conducive to fiber and resin boundary surface combines.In addition, the dispersants such as polyvinylpyrrolidone are introduced nylon by the present invention
In good solvent, through cryoprecipitation, the interaction using polymer chain in dispersant and system and the stability for particle
Protective effect nylon base-material to be uniformly wrapped in carbon fiber surface finally to be precipitated by core of carbon fiber.Gained overlay film
The degree that is uniformly dispersed of powder is much larger than standard machinery mixed-powder.
Solvent for use of the present invention may be recovered after use to be recycled, and the present invention is without high compared with prior art
Press equipment, simple process, environmental-friendly, easy implementation.It can obtain that there is excellent physicochemical property using method provided by the invention
Carbon fiber reinforced nylon powder.Material sintering character prepared by the present invention is excellent, and carbon fiber-nylon content can in material
Control, gained SLS molded parts are obviously improved compared to the SLS molded parts of base resin material in mechanical property.
Specific embodiment
In order to illustrate more clearly of the present invention, with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection domain of invention.
Embodiment 1
(1) commercially available 1.5kg carbon fiber powders in Soxhlet extractor are used into acetone extraction 48h, 1.0L is added in after vacuum drying
In a concentration of 14mol/L nitric acid, it is heated to reflux 5h and is aoxidized.It is filtered by vacuum, is washed to neutrality after distilled water dilution, it is dry,
Cross 300 mesh screens.
(2) by carbon fiber powder 1kg processed in step (1) and 12 pellet 3kg of nylon, polyvinylpyrrolidone 2kg mono-
It rises and is added in 15L formic acid, 80 DEG C of heating stirring 2h make 12 pellet of nylon fully dissolve.
(3) it is vigorously stirred while 10L absolute ethyl alcohols is added in into step (2), precipitation is precipitated after standing.It filters, ethyl alcohol is washed
After washing, drying, sieved with 200 mesh screens.
(4) carbon fiber-nylon powder 4kg and flow promortor nano silicon dioxide 20g, antioxidant obtained by step (3) are taken
2,2'- di-2-ethylhexylphosphine oxides-(4- methyl-6-tert-butylphenols) 10g, stirring and mixing 1h in vertical stirrer obtain selectivity and swash
Light sintering carbon fiber reinforced nylon composite micro-powder.
Embodiment 2
(1) it is molten to add in toluene with acetone extraction 48h in Soxhlet extractor for commercially available 1.5kg carbon fiber powders after vacuum drying
It is dispersed with stirring in liquid, adds in the ethanol solution of Silane coupling agent KH550, led to nitrogen, be heated to reflux 1h, be filtered by vacuum, washed, done
It is dry, cross 300 mesh screens.
(2) by carbon fiber powder 1kg processed in step (1) and 12 pellet 3kg of nylon, polyvinylpyrrolidone 2kg mono-
It rises and is added in 15L formic acid, 80 DEG C of heating stirring 2h make 12 pellet of nylon fully dissolve.
(3) it is vigorously stirred while 10L absolute ethyl alcohols is added in into step (2), precipitation is precipitated after standing.It filters, ethyl alcohol is washed
After washing, drying, sieved with 200 mesh screens.
(4) carbon fiber-nylon powder 4kg and flow promortor nano silicon dioxide 20g, antioxidant obtained by step (3) are taken
2,2'- di-2-ethylhexylphosphine oxides-(4- methyl-6-tert-butylphenols) 10g, stirring and mixing 1h in vertical stirrer obtain selectivity and swash
Light sintering carbon fiber reinforced nylon composite micro-powder.
Embodiment 3
(1) commercially available 1.5kg carbon fiber powders, with acetone extraction 48h, 14mol/ are added in after vacuum drying in Soxhlet extractor
In L nitric acid, it is heated to reflux 5h and is aoxidized.It is filtered by vacuum, is washed to neutrality after distilled water dilution, it is dry, cross 300 mesh screens.
(2) by carbon fiber powder 1kg processed in step (1) and nylon66 fiber pellet 3kg, polyvinylpyrrolidone 2kg mono-
It rises and is added in 18L acetic acid, 100 DEG C of heating stirring 2h make nylon66 fiber pellet fully dissolve.
(3) it is vigorously stirred while 10L absolute ethyl alcohols is added in into step (2), precipitation is precipitated after standing.It filters, ethyl alcohol is washed
After washing, drying, sieved with 200 mesh screens.
(4) carbon fiber-nylon powder 4kg and flow promortor nano silicon dioxide 20g, antioxidant obtained by step (3) are taken
2,2'- di-2-ethylhexylphosphine oxides-(4- methyl-6-tert-butylphenols) 10g, stirring and mixing 1h in vertical stirrer obtain selectivity and swash
Light sintering carbon fiber reinforced nylon composite micro-powder.
Embodiment 4：
(1) it is molten to add in toluene with acetone extraction 48h in Soxhlet extractor for commercially available 1.5kg carbon fiber powders after vacuum drying
It is dispersed with stirring in liquid, adds in the ethanol solution of Silane coupling agent KH550, led to nitrogen, be heated to reflux 1h, be filtered by vacuum, washed, done
It is dry, cross 300 mesh screens.
(2) by carbon fiber powder 1kg processed in step 1) together with nylon66 fiber pellet 3kg, polyvinylpyrrolidone 2kg
It is added in 18L acetic acid, 100 DEG C of heating stirring 2h make nylon66 fiber pellet fully dissolve.
(3) it is vigorously stirred while 10L absolute ethyl alcohols is added in into step (2), precipitation is precipitated after standing.It filters, ethyl alcohol is washed
After washing, drying, sieved with 200 mesh screens.
(4) step 3 gained carbon fiber-nylon powder 4kg and flow promortor nano silicon dioxide 20g, antioxidant 2 are taken,
2'- di-2-ethylhexylphosphine oxides-(4- methyl-6-tert-butylphenols) 10g, the stirring and mixing 1h in vertical stirrer obtains selective laser
Sintering carbon fiber reinforced nylon composite micro-powder.
Embodiment 5,6,7,8：
Repeating embodiment 1-4, it the difference is that only, carbon fiber quality is 2kg in step (2).
Embodiment 9,10,11,12：
Repeating embodiment 1-4, it the difference is that only, carbon fiber quality is 3kg in step (2).
Embodiment 13：
(1) commercially available 1.5kg carbon fiber powders | acetone extraction is used in Soxhlet extractor 48 hours, first is added in after vacuum drying
It is dispersed with stirring in benzole soln, adds in the ethanol solution of Silane coupling agent KH550, led to nitrogen, be heated to reflux 1h, be filtered by vacuum, wash
It washs, it is dry, cross 300 mesh screens.
(2) by carbon fiber powder 1kg processed in step 1) together with nylon66 fiber pellet 3kg, polyvinylpyrrolidone 2kg
It is added in 18L acetic acid, 100 DEG C of heating stirring 2h make nylon66 fiber pellet fully dissolve.
(3) it is vigorously stirred while 10L absolute ethyl alcohols is added in into step (2), precipitation is precipitated after standing.It filters, ethyl alcohol is washed
After washing, drying, sieved with 200 mesh screens.
(4) step 3 gained carbon fiber-nylon powder 4kg and flow promortor nano silicon dioxide 20g, Hinered phenols are taken
The composite antioxidant 10g of antioxidant and phosphite ester kind antioxidant composition, the stirring and mixing 1h in vertical stirrer are selected
Property it is laser sintered use nylon micro mist.
The Hinered phenols antioxidant dosage is the 60% of composite antioxidant total weight；The Hinered phenols antioxidant is 2,
2'- di-2-ethylhexylphosphine oxides-(4- methyl-6-tert-butylphenols), the phosphite ester kind antioxidant are 2,2 '-ethylenebis (4,6- bis-
Tert-butyl-phenyl) fluorophosphite.
Embodiment 14,15：
Embodiment 8 is repeated, the difference is that only, the Hinered phenols antioxidant dosage is respectively that composite antioxidant is total
The 70% of weight or 80%.
Performance test：
Obtained selective laser sintering carbon fiber reinforced nylon composite micro-powder its fusing point, knot in the embodiment of the present invention
Brilliant degree is tested using the differential scanning calorimeter DSC of Mettler TAGS companies；Powder diameter passes through Mastersizer 3000
Laser particle analyzer is tested；The mechanical property of molded part is tested by Instron3365 types universal testing machine, and testing standard is
GB/T 1040-92。
1 preparation method of comparative example：By 12 pellet of 50g nylon, 20g polyvinylpyrrolidones (PVP), 500ml formic acid, add in
80 DEG C are warming up in reaction kettle, stirring 2h makes material fully dissolve, and then adds in the stirring of 700ml ethyl alcohol, powder is precipitated, filter,
Washing, drying, obtain pure nylon micro mist；Addition flow promortor nano silicon dioxide 0.25g, antioxidant 2,2' methylene bis-
(4- methyl-6-tert-butylphenols) 0.13g, the stirring and mixing 1h in vertical stirrer, material cross 200 mesh screens after being mixed evenly
Obtain 12 micro mist of composite nylon.
Comparative example 2 be by 12 micro mist of nylon pure in comparative example 1 and 0.5wt% flow promortors nano silicon dioxide,
0.25wt% antioxidant 2,2' methylene bis-(4- methyl-6-tert-butylphenols) and 40wt% are by nitric acid oxidation processing
Carbon fiber powder adds in mechanical mixture 2h in vertical stirrer and obtains 12 micro mist of nylon of fibre reinforced together.
1 the performance test results of table
As can be seen from the above table, the present invention is micro- by obtained carbon fiber reinforced nylon by the method for dissolving-precipitation
Its SLS selective laser sintering of powder material is functional, prepared its molded part mechanical property phase of composite powder in embodiment
Than being remarkably reinforced in no comparative example 1 for adding in carbon fiber.It is also significantly better than in comparative example 2 through the side of mechanical mixture simultaneously
Carbon fiber reinforced nylon composite micro-powder prepared by method.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention for those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is every to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the row of protection scope of the present invention.
Claims (12)
1. a kind of selective laser sintering preparation method of carbon fiber reinforced nylon composite micro-powder, which is characterized in that including with
Lower preparation process：
（1）Carbon fiber powder is subjected to chemical oxidation pre-treatment or graft pretreatment；
（2）Pretreated carbon fiber powder, nylon pellet and dispersant are added in the good solvent of nylon pellet, are heated with stirring to
Certain temperature makes nylon and dispersant all dissolve；
（3）To step（2）Mixed liquor in add in nylon pellet poor solvent, stirring, make nylon using carbon fiber powder as nucleus
Sediment is precipitated, and drying precipitate, excessively 200-300 mesh screens are sieved, obtains carbon fiber-nylon micron particles；
（4）By step（3）Gained carbon fiber-nylon micron particles are mixed with flow promortor and antioxidant, obtain selective laser
Sintering carbon fiber reinforced nylon composite micro-powder；
The good solvent is one or more of trifluoroacetic acid, acetic acid, formic acid；
The poor solvent, which refers to, to be poor solvent to nylon pellet and is good solvent to dispersant；
The poor solvent is selected from one or more of ethyl alcohol, ethylene glycol, acetone or water.
2. the selective laser sintering according to claim 1 preparation method of carbon fiber reinforced nylon composite micro-powder,
It is characterized in that, step（1）The chemical oxidation pre-treatment includes the following steps：
Carbon fiber powder is placed in Soxhlet extractor, after acetone extraction 24-48 hours, vacuum drying；Then 14mol/L nitre is used
Acid is aoxidized, washing, and 300 mesh screens are crossed after dry.
3. the selective laser sintering according to claim 1 preparation method of carbon fiber reinforced nylon composite micro-powder,
It is characterized in that, step（1）The graft pretreatment includes the following steps：
Carbon fiber powder is placed in Soxhlet extractor, after acetone extraction 24-48 hours, vacuum drying；Then with silane coupled
Agent is grafted in toluene solvant, and 300 mesh screens are crossed after dry.
4. the selective laser sintering according to claim 1 preparation method of carbon fiber reinforced nylon composite micro-powder,
It is characterized in that：Step（1）The carbon fiber powder is 7-10 microns a diameter of, and length is 10-50 microns.
5. the selective laser sintering according to claim 1 preparation method of carbon fiber reinforced nylon composite micro-powder,
It is characterized in that：Step（2）The nylon pellet is selected from nylon 6, nylon66 fiber, nylon 11, nylon 12, nylon 1010 or nylon 1212
One or more of；
Step（2）The dispersant is selected from polyvinylpyrrolidone, polyacrylic acid or hydroxypropyl cellulose, polyvinyl alcohol, sub- second
One or more of base bis-stearamides.
6. the selective laser sintering according to claim 1 preparation method of carbon fiber reinforced nylon composite micro-powder,
It is characterized in that：Step（2）The temperature is in room temperature between 120 DEG C.
7. the selective laser sintering according to claim 1 preparation method of carbon fiber reinforced nylon composite micro-powder,
It is characterized in that：Step（2）The mass ratio of the carbon fiber powder and nylon pellet is 1: 1~1: 20；The nylon pellet and solvent
Weight ratio be 1: 2~1: 200；The weight proportion of the dispersant and total solvent is 1: 2~1: 100.
8. the selective laser sintering according to claim 1 preparation method of carbon fiber reinforced nylon composite micro-powder,
It is characterized in that：
Step（3）Described in poor solvent and step（2）The volume ratio of the good solvent is 0~5, wherein not including 0.
9. the selective laser sintering according to claim 1 preparation method of carbon fiber reinforced nylon composite micro-powder,
It is characterized in that：Step（4）The flow promortor is selected from nano carborundum powder, nano silicon dioxide, nano aluminium oxide or nanometer two
One or more of titanium oxide；
The antioxidant is selected from the composite antioxidant that Hinered phenols antioxidant and phosphite ester kind antioxidant form；The hindered phenol
Kind antioxidant dosage is the 60-80% of composite antioxidant total weight.
10. the selective laser sintering according to claim 9 preparation method of carbon fiber reinforced nylon composite micro-powder,
It is characterized in that：The Hinered phenols antioxidant is selected from 2,2' methylene bis-(4- methyl-6-tert-butylphenols), 1,3,5- front threes
Base -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene, 2,6- di-t-butyl -4- methyl-phenols, the N, (3,5- of N '-two
Di-tert-butyl-hydroxy phenyl propionamide), 2,2 '-bis- (4- methyl-6-terts butyl-phenol) methane or 2,2 '-bis- (4- ethyls-
One or more of 6- t-butyl-phenols) methane.
11. the selective laser sintering according to claim 9 preparation method of carbon fiber reinforced nylon composite micro-powder,
It is characterized in that：The phosphite ester kind antioxidant is selected from 2,2 '-ethylenebis (4,6- di-tert-butyl-phenyls) fluorophosphite
Or four one or more of (2,4- di-tert-butyl-phenyls) -4,4 '-xenyl bis-phosphite.
12. the selective laser sintering according to claim 1 preparation method of carbon fiber reinforced nylon composite micro-powder,
It is characterized in that：Step（4）The dosage of the flow promortor is the 0.1%~5% of selective laser sintering nylon micro mist, described
The dosage of antioxidant is the 0.1%~5% of selective laser sintering nylon micro mist.
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