CN106243705A - Long-chain nylon and the alloy powder material preparation method of nylon 6 for SLS - Google Patents
Long-chain nylon and the alloy powder material preparation method of nylon 6 for SLS Download PDFInfo
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- CN106243705A CN106243705A CN201610856397.3A CN201610856397A CN106243705A CN 106243705 A CN106243705 A CN 106243705A CN 201610856397 A CN201610856397 A CN 201610856397A CN 106243705 A CN106243705 A CN 106243705A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses the alloy powder material preparation method of a kind of long-chain nylon for SLS and nylon 6, it comprises the following steps: long-chain nylon and nylon 6 particulate material is mixed, pours in autoclave after adding mixed solvent, antioxidant and compatilizer；Heating, stirring make nylon mixture be dissolved in mixed solvent, are incubated a period of time；It is gradually cooling to room temperature, obtains the nylon alloy dusty material for SLS technology through vacuum filtration, dry, ball milling and screening.Alloy powder material mechanical property prepared by the inventive method is good, sintering window is big, form uniform and good fluidity, the paving powder of beneficially SLS technology and shaping, and this alloy material preparation cost is low simultaneously, has a good application prospect.
Description
Technical field
The invention belongs to advanced manufacturing technology and field of material preparation, more particularly, to a kind of long-chain Buddhist nun for SLS
Dragon and the alloy powder material preparation method of nylon 6.
Background technology
Selective laser sintering (Selective Laser Sintering, SLS) is a kind of important increasing material manufacturing technology,
It uses Layered manufacturing principle of stacking, by computer aided design and manufacture, utilizes laser to scan sintered powder selectively
Material, Layered manufacturing, successively superposition, be Three-dimensional Entity Components by dusty material direct forming.Compared with traditional processing method,
It is to utilize material cumulation to come processing and manufacturing macromolecular material, pottery, metal and the model of various composite and function zero
Part.SLS technology is not affected by drip molding complexity in theory, can manufacture the part of personalization, complicated shape, at utmost
Meet application demand.
Nylon is a kind of semicrystalline polymeric, has good sintering character and relatively low melt viscosity, can be straight by SLS
It is connected into that shape consistency is high, the preferable function part of mechanical property, thus becomes one of SLS moulding material of being most widely used.
The nylon being currently used for SLS technology mainly has nylon 11 and nylon 12 isometric strand polymer, accounts for SLS macromolecule on market
More than the 95% of material, long-chain nylon has big sintering temperature window, good powder apperance and extraordinary low temperature properties, easily
Machine-shaping, is highly suitable for SLS technology, but its intensity is the highest, and on the high side.
Nylon 6 is one of excellent performance in synthetic fibers, broad-spectrum kind, and it has many excellent performances, removes
Possessing outside the performances such as total corrosion-resistant, resistance to of synthetic fibers goes rotten, hydroscopicity is low, its main feature also resides in: fracture strength
Height, excellent in abrasion resistance, good springiness, elongate fiber response rate are high, and simultaneously relative to its moderate cost of long-chain nylon, the market price is about
30000 yuan/ton.But its shortcoming is: sintering temperature window is less, Young's modulus is little, be easily generated buckling deformation, heat resistance is bad,
Light fastness is poor, easily turn yellow under daylight or ultraviolet irradiate, these drawbacks limit its in the technical application of SLS.
The long-chain nylons such as nylon 11 and nylon 12 and nylon 6 are prepared as alloy material and can maximize both advantages
Organically combine, improve the combination properties such as the mechanical property of SLS nylon powder and sintering temperature window, strengthen, tenacity increased nylon SLS
Drip molding, can also reduce cost simultaneously, have preferable application prospect.Prepared by patent CN01132392 twin-screw extrusion method
The pellet of nylon alloy, due to long-chain nylon and nylon 6 difference in the physicochemical properties such as intensity, dissolubility, fusing point
Relatively big, it is difficult at present prepare the nylon alloy dusty material for SLS.
The preparation method of SLS nylon powder material mainly has three kinds, i.e. twin-screw extrusion-deep cooling crush method, directly gather
Legal and solvent deposition method.Twin-screw extrusion-deep cooling crush method by bi-material mix homogeneously, but cannot be able to be prepared
Small particle (10-100 micron) powder of one-tenth SLS technological requirement, and powder particle shape irregular, poor fluidity.Suspend
Strict with emulsion polymerization technological requirement, it is difficult to large-scale industrial production.Solvent precipitation applies in general to nylon composite powder
The preparation of powder material, such as, ZL200710053668.2 uses solvent precipitation preparation to strengthen for the inorganic nano-filler of SLS
Nylon composite materials；But the method is higher to physical property requirements such as the dissolubility of the characteristic of solvent and material, is generally used for
Prepare single nylon and composite thereof, owing to long-chain nylon and short chain nylon physical property difference are big, there is presently no use
The method prepares nylon alloy.
Summary of the invention
For disadvantages described above or the Improvement requirement of prior art, the invention provides a kind of for precinct laser sintering technology
The preparation method of nylon alloy dusty material, the present invention uses the method for solvent deposition at high temperature by nylon 11, nylon 12
Being dissolved in equably in alcohol solvent Deng long-chain nylon and nylon 6, the most gradually cooling separates out nylon alloy powder, thus solves
The problem that nylon powder material is single, mechanical strength is low, cost is high of current SLS.
For achieving the above object, the present invention proposes the alloy powder material of a kind of long-chain nylon for SLS and nylon 6
Preparation method, comprises the following steps:
(1) choose long-chain nylon and nylon 6 particulate material mechanical mixture that particle diameter is 3～5mm to mix to obtain nylon
Thing, wherein, the mass fraction of long-chain nylon is 30%-70%, and the mass fraction of nylon 6 is 30%-70%；
(2) in the described nylon mixture of step (1), add antioxidant, compatilizer and mixed solvent and pour into airtight
To obtain mixed solution in reactor, then by reactor sealing, evacuation, and pour inert protective gas, wherein, every 100
Gram nylon, the consumption of antioxidant is 0.1 gram～0.5 gram, and antioxidant can be that symmetrical phenolic antioxidant, asymmetric phenols resist
Oxygen agent, phosphite ester kind antioxidant, monothioester kind antioxidant, amine antioxidants or above-mentioned several being combined；Every 100 grams of Buddhist nuns
Dragon, the consumption of compatilizer is 0.1 gram～15 grams；Every 100 grams of nylon, the consumption of mixed solvent is 1L；
(3) mixed solution of step (2) gained is stirred, with the speed of 1～2 DEG C/min, mixed solution is heated to simultaneously
165～185 DEG C, so that nylon is dissolved completely in solvent, heat-insulation pressure keeping 2～3h afterwards；
(4) by the solution of step (3) gained under fast stirring, it is cooled to room temperature with the speed of 2～4 DEG C/min, is formed
Nylon alloy material powder suspension, carries out solid-liquid separation to described nylon alloy material powder suspension, obtains powder and assembles
Body；
(5) powder aggregates obtained is dried, grinds and sieves, it is thus achieved that particle diameter is 10 microns～100 microns
Long-chain nylon and the alloy material of nylon 6.
As it is further preferred that the compound antioxygen being made up of Hinered phenols and phosphorous acid esters selected by described antioxidant
Agent, its composition mass ratio is: Hinered phenols antioxidant 60～80%, remaining is phosphite ester kind antioxidant.
As it is further preferred that described compatilizer optimization styrene graft or Graft Polyolefin.
As it is further preferred that described mixed solvent is ethanol, ethylene glycol, propylene glycol and distilled water mixed solution, its
In: ethanol 70～85%, ethylene glycol 0.1～20%, propylene glycol 0.1～10%, distilled water 0.1～5%.
As the stirring speed it is further preferred that the mixing speed in step (3) is 400-500r/min, in step (4)
Degree is 400-500r/min.
As it is further preferred that step (4) carries out solid-liquid separation to described nylon alloy material powder suspension
Specifically comprises the processes of: sucking filtration solvent under vacuum conditions.
As it is further preferred that in step (5), the powder aggregates obtained is dried, grinds and is sieved is concrete
Technique is: being put into by product in vacuum drying oven and to dry 24h at 80 DEG C to constant weight, grind, 150 eye mesh screens sieve and obtain composite powder
Powder material.
As it is further preferred that described long-chain nylon is preferably nylon 1010, nylon 11, nylon 12, nylon 1212, Buddhist nun
One or more in dragon 1313, the more preferably fusing point nylon less than 200 DEG C.
In general, by the contemplated above technical scheme of the present invention compared with prior art, mainly possess following
Technological merit:
1. the present invention is by the nylon being dissolved in alcohol solvent, the homogeneously crystallized precipitation powder particle when Slow cooling
Mode prepares nylon alloy powder, and the nylon alloy powder particle flowing property obtained and discreteness are good, and form is uniform, sphericity
Good, particle diameter is 10-100 μm, is highly suitable for SLS technology, and the powder flowbility of this particle diameter is good, the SLS initial blank of shaping
Possesses degree of precision and intensity.
2. low due to semicrystalline polymeric nylon melt viscosity, use the SLS product of nylon 12 long-chain nylon mo such as grade
Intensity the highest, the present invention can ensure that it can be used for SLS skill by long-chain nylon and nylon 6 are made alloy powder material
It is effectively improved its mechanical strength while art, improves product mechanical property.
3. the market price of the nylon 6 used due to the present invention is the half of nylon 12, and itself and long-chain nylon are made conjunction
Gold copper-base alloy can significantly reduce the preparation cost of alloy powder, has a good application prospect.
Accompanying drawing explanation
Fig. 1 is the FB(flow block) of preparation method of the present invention.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, right
The present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, and
It is not used in the restriction present invention.If additionally, technical characteristic involved in each embodiment of invention described below
The conflict of not constituting each other just can be mutually combined.
First the present invention weighs a certain amount of long-chain nylon and nylon 6 granule, by nylon particles, antioxygen in hermetic container
The mixture heated and stirred of agent, compatilizer and mixed solvent, makes nylon particles be dissolved in solvent, the most gradually cools down, make
Nylon alloy crystallization, through solvent recovery, vacuum drying, ball milling, screening selects the powder of certain grain size distribution to be nylon
Alloy powder material.
Nylon is semicrystalline polymeric, and its melt viscosity is less, and the SLS initial blank of preparation can be made to have consistency
Greatly, intensity is high, form accuracy is good feature, nylon alloy can optimize the performance of different nylon.The preferred scope of long-chain nylon
For: nylon 1010, nylon 11, nylon 12, nylon 1212, one or more in nylon 1313, its most preferred scope
For the fusing point nylon less than 200 DEG C, material melting point is low the lowest to preheating temperature requirement during laser sintering (SLS), sintering easily control
System.The mass fraction of comprehensive physical performance and reduction production cost long-chain nylon for improving alloy powder can be 30%-
70%, the mass fraction of nylon 6 can be 30%-70%.
For preventing in high temperature environments, nylon oxidation stain, antioxidant need to be added, antioxidant is selected by Hinered phenols
With the composite antioxidant of phosphorous acid esters composition, it forms and mass ratio is: Hinered phenols antioxidant: 60～80%, remaining is
Phosphite ester kind antioxidant.
The preferable following material of Hinered phenols antioxidant: 1,3,5-trimethyl-2,4,6-tri-(3,5-di-t-butyl-4-hydroxyls
Base benzyl) benzene, 2,6-di-t-butyl-4-methyl-phenol, N, N '-two (3,5-di-tert-butyl-hydroxy phenyl propionic acid amide .), 2,
2 '-bis-(4-methyl-6-tert butyl-phenol) methane, 2,2 '-bis-(4-ethyl-6-t-butyl-phenol) methane etc..
The preferable following material of phosphite ester kind antioxidant: 2,2 '-ethylenebis (4,6-di-tert-butyl-phenyl) fluoro is sub-
Phosphate ester, four (2,4-di-tert-butyl-phenyls)-4,4 '-xenyl bis-phosphite etc..The consumption of antioxidant is: every 100 grams
Nylon adds 0.1 gram～0.5 gram of antioxidant.
Long-chain nylon and short chain nylon compatibility are poor, for making it the most well merge, and optimized alloy powder property, need
Adding compatilizer, compatilizer can be styrene-grafted thing or Graft Polyolefin, connects including acrylonitrile-butadiene-styrene (ABS)
Branch maleic anhydride, styrene-grafted maleic anhydride, ethylene-octene copolymer grafted maleic anhydride, styrene/ethylene-butylene/benzene
Ethylene block copolymer grafted maleic anhydride, polypropylene grafted maleic anhydride etc..The consumption of compatilizer is: in every 100 grams of nylon
Add 0.1 gram～15 grams of compatilizers.
Mixed solvent is the mixed solution of ethanol, ethylene glycol, propylene glycol and distilled water, wherein: ethanol: 70～85%, steams
Distilled water: 0.1～5%, ethylene glycol: 0.1～20%, propylene glycol: 0.1～10%, the consumption of mixed solvent is: every 100 grams of nylon,
Mixed solvent consumption is 1L.
The long-chain nylon for SLS technology of present invention offer and the preparation method of the alloy material of short chain nylon, specifically
Comprise the following steps:
(1) long-chain nylon that a certain amount of particle size range is 3～5mm and nylon 6 particulate material mechanical mixture are chosen；
(2) nylon mixture in step (1) is poured into closed reactor plus antioxidant, compatilizer and mixed solvent
In, sealing, evacuation, fill inert protective gas (such as nitrogen)；
(3) mixed solution of step (2) gained is stirred under 400-500r/min speed, simultaneously with 1～2 DEG C/min's
Mixed solution is heated to 165～185 DEG C by speed, to ensure that nylon is dissolved completely in solvent, and heat-insulation pressure keeping 2～3h afterwards；
(4) solution of step (3) gained is maintained under the speed of 400-500r/min stirring, with 2～4 DEG C/min gradually
It is cooled to room temperature, forms nylon alloy material powder suspension, described nylon alloy material powder suspension is carried out solid-liquid and divides
From, obtain powder aggregates, concrete, suspension sucking filtration under vacuum conditions is gone out solvent, recycling design, remaining for powder
Aggregation.
(5) last, the powder aggregates obtained is dried, grinds and sieves, it is thus achieved that particle diameter is 10 microns～100 micro-
The long-chain nylon of rice and the alloy material of nylon 6: powder aggregates is put into and dries 24h in vacuum drying oven at 80 DEG C to permanent
Weight, grinds, and 150 eye mesh screens sieve, and selects particle diameter to be distributed in 10 microns～the powder of 100 microns, the long-chain described in final acquisition
Nylon and the alloy material of nylon 6.
It is below the specific embodiment of the present invention:
Embodiment 1
(1) nylon 12 and nylon 6 particulate material, mixed solvent 3L and composite antioxidant that 150 gram particle footpaths are 3 millimeters are respectively taken
0.3 gram, compatilizer 0.3 gram puts in the rustless steel 50L reactor of jacketed, is sealed by reactor, evacuation, logical N2Gas is protected
Protect.
Wherein, the proportioning of mixed solvent is: 70% ethanol, 0.1% distilled water, 20% ethylene glycol, 9.9% propylene glycol；Multiple
The proportioning closing antioxidant is: 1,3,5-trimethyl-2, and 4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene is 80%, four (2,
4-di-tert-butyl-phenyl)-4,4 '-xenyl bis-phosphite is 20%；Compatilizer selects acrylonitrile-butadiene-styrene (ABS) to connect
Branch maleic anhydride.
(2) stir mixed solution with the speed of 500r/min, then with the speed of 1 DEG C/min, be gradually warmed up to 175 DEG C,
Nylon 12 is made to be dissolved completely in solvent, heat-insulation pressure keeping 2h.
(3) it is stirred vigorously with the speed of 500r/min, is gradually cooling to room temperature with 2 DEG C/min speed, makes nylon 12
Separate out with nylon 6, form nylon alloy powder suspension.
(4) in a kettle., being filtered by vacuum, the suspension cooled down is carried out solid-liquid separation, the solvent obtained can
To repeat to recycle, the powder aggregates obtained is stand-by.
(5) powder aggregates obtained is put into and is dried 24h in vacuum drying oven at 80 DEG C to constant weight, grinding, 150 eye mesh screens
Sieving, the powder selecting particle diameter to be distributed in 10 microns～100 microns i.e. obtains nylon alloy dusty material.
Embodiment 2
(1) take nylon 12 particulate material 90 grams that particle diameter is 4 millimeters and nylon 6 particulate material 210 grams, mixed solvent 3L and
Composite antioxidant 0.3 gram, compatilizer 20 grams puts in the rustless steel 50L reactor of jacketed, is sealed by reactor, evacuation,
Logical N2Gas shielded.
Wherein, the proportioning of mixed solvent is: 85% ethanol, 5% distilled water, 0.1% ethylene glycol, 9.9% propylene glycol；Compound
The proportioning of antioxidant is: 1,3,5-trimethyl-2, and 4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene is 60%, 2,2 '-sub-
Double (4, the 6-di-tert-butyl-phenyl) fluorophosphite of ethyl is 40%；Compatilizer selects styrene-grafted maleic anhydride.
(2) stir mixed solution with the speed of 400r/min, then with the speed of 1.5 DEG C/min, be gradually warmed up to 185
DEG C, make nylon 12 be dissolved completely in solvent, heat-insulation pressure keeping 2.5h.
(3) it is stirred vigorously with the speed of 430r/min, is gradually cooling to room temperature with 2 DEG C/min speed, makes nylon 12
Separate out with nylon 6, form nylon alloy powder suspension.
(4) in a kettle., being filtered by vacuum, the suspension cooled down is carried out solid-liquid separation, the solvent obtained can
To repeat to recycle, the powder aggregates obtained is stand-by.
(5) powder aggregates obtained is put into and is dried 24h in vacuum drying oven at 80 DEG C to constant weight, grinding, 150 eye mesh screens
Sieving, the powder selecting particle diameter to be distributed in 10 microns～100 microns i.e. obtains nylon alloy dusty material.
Embodiment 3
(1) nylon 12 particulate material 210 grams and nylon 6 particulate material 90 grams that particle diameter is 4.5 millimeters, mixed solvent 3L are taken
And composite antioxidant 1.0 grams, compatilizer 45 grams puts in the rustless steel 50L reactor of jacketed, is sealed by reactor, takes out true
Sky, logical N2Gas shielded.
Wherein, the proportioning of mixed solvent is: 76% ethanol, 4% distilled water, 10% ethylene glycol, 10% propylene glycol；Compound anti-
The proportioning of oxygen agent is: 2,6-di-t-butyl-4-methyl-phenol, N, N '-two (3,5-di-tert-butyl-hydroxy phenyl propionic acid amide .)
Being 70%, four (2,4-di-tert-butyl-phenyls)-4,4 '-xenyl bis-phosphite is 30%；Compatilizer selects ethylene-octene altogether
Polymers grafted maleic anhydride.
(2) stir mixed solution with the speed of 450r/min, then with the speed of 2 DEG C/min, be gradually warmed up to 165 DEG C,
Nylon 12 is made to be dissolved completely in solvent, heat-insulation pressure keeping 3h.
(3) it is stirred vigorously with the speed of 450r/min, is gradually cooling to room temperature with 3 DEG C/min speed, makes nylon 12
Separate out with nylon 6, form nylon alloy powder suspension.
(4) in a kettle., being filtered by vacuum, the suspension cooled down is carried out solid-liquid separation, the solvent obtained can
To repeat to recycle, the powder aggregates obtained is stand-by.
(5) powder aggregates obtained is put into and is dried 24h in vacuum drying oven at 80 DEG C to constant weight, grinding, 150 eye mesh screens
Sieving, the powder selecting particle diameter to be distributed in 10 microns～100 microns i.e. obtains nylon alloy dusty material.
Embodiment 4
(1) nylon 11 and nylon 6 particulate material, mixed solvent 3L and compound antioxygen that 150 gram particle footpaths are 3.5 millimeters are respectively taken
Agent 1.0 grams, compatilizer 0.3 gram puts in the rustless steel 50L reactor of jacketed, is sealed by reactor, evacuation, logical N2Gas is protected
Protect.
Wherein, the proportioning of mixed solvent is: 81.9% ethanol, 3% distilled water, 15% ethylene glycol, 0.1% propylene glycol；Multiple
The proportioning closing antioxidant is: 2,2 '-bis-(4-methyl-6-tert butyl-phenol) methane are 75%, four (2,4-di-tert-butyls
Base)-4,4 '-xenyl bis-phosphite is 25%；Compatilizer selects acrylonitrile-butadiene-styrene (ABS) grafted maleic anhydride.
(2) stir mixed solution with the speed of 480r/min, then with the speed of 1 DEG C/min, be gradually warmed up to 175 DEG C,
Nylon 11 is made to be dissolved completely in solvent, heat-insulation pressure keeping 2h.
(3) it is stirred vigorously with the speed of 400r/min, is gradually cooling to room temperature with 3 DEG C/min speed, makes nylon 11
Separate out with nylon 6, form nylon alloy powder suspension.
(4) in a kettle., being filtered by vacuum, the suspension cooled down is carried out solid-liquid separation, the solvent obtained can
To repeat to recycle, the powder aggregates obtained is stand-by.
(5) powder aggregates obtained is put into and is dried 24h in vacuum drying oven at 80 DEG C to constant weight, grinding, 150 eye mesh screens
Sieving, the powder selecting particle diameter to be distributed in 10 microns～100 microns i.e. obtains nylon alloy dusty material.
Embodiment 5
(1) take nylon 11 particulate material 90 grams that particle diameter is 5 millimeters and nylon 6 particulate material 210 grams, mixed solvent 3L and
Composite antioxidant 1.5 grams, compatilizer 20 grams puts in the rustless steel 50L reactor of jacketed, is sealed by reactor, evacuation,
Logical N2Gas shielded.
Wherein, the proportioning of mixed solvent is: 72% ethanol, 3% distilled water, 20% ethylene glycol, 5% propylene glycol；Compound anti-
The proportioning of oxygen agent is: 1,3,5-trimethyl-2, and 4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene is 65%, four (2,4-bis-
Tert-butyl-phenyl)-4,4 '-xenyl bis-phosphite is 35%；Compatilizer selects polypropylene grafted maleic anhydride.
(2) stir mixed solution with the speed of 460r/min, then with the speed of 1.5 DEG C/min, be gradually warmed up to 185
DEG C, make nylon 11 be dissolved completely in solvent, heat-insulation pressure keeping 2.5h.
(3) it is stirred vigorously with the speed of 500r/min, is gradually cooling to room temperature with 4 DEG C/min speed, makes nylon 11
Separate out with nylon 6, form nylon alloy powder suspension.
(4) in a kettle., being filtered by vacuum, the suspension cooled down is carried out solid-liquid separation, the solvent obtained can
To repeat to recycle, the powder aggregates obtained is stand-by.
(5) powder aggregates obtained is put into and is dried 24h in vacuum drying oven at 80 DEG C to constant weight, grinding, 150 eye mesh screens
Sieving, the powder selecting particle diameter to be distributed in 10 microns～100 microns i.e. obtains nylon alloy dusty material.
Embodiment 6
(1) take nylon 12 particulate material 210 grams that particle diameter is 3 millimeters and nylon 6 particulate material 90 grams, mixed solvent 3L and
Composite antioxidant 1.5 grams, compatilizer 45 grams puts in the rustless steel 50L reactor of jacketed, is sealed by reactor, evacuation,
Logical N2Gas shielded.
Wherein, the proportioning of mixed solvent is: 85% ethanol, 1% distilled water, 10% ethylene glycol, 4% propylene glycol；Compound anti-
The proportioning of oxygen agent is: 2,2 '-bis-(4-ethyl-6-t-butyl-phenol) methane are 80%, four (2,4-di-tert-butyl-phenyls)-4,
4 '-xenyl bis-phosphite is 20%；Compatilizer selects acrylonitrile-butadiene-styrene (ABS) grafted maleic anhydride.
(2) stir mixed solution with the speed of 490r/min, then with the speed of 2 DEG C/min, be gradually warmed up to 165 DEG C,
Nylon 12 is made to be dissolved completely in solvent, heat-insulation pressure keeping 3h.
(3) it is stirred vigorously with the speed of 490r/min, is gradually cooling to room temperature with 4 DEG C/min speed, makes nylon 12
Separate out with nylon 6, form nylon alloy powder suspension.
(4) in a kettle., being filtered by vacuum, the suspension cooled down is carried out solid-liquid separation, the solvent obtained can
To repeat to recycle, the powder aggregates obtained is stand-by.
(5) powder aggregates obtained is put into and is dried 24h in vacuum drying oven at 80 DEG C to constant weight, grinding, 150 eye mesh screens
Sieving, the powder selecting particle diameter to be distributed in 10 microns～100 microns i.e. obtains nylon alloy dusty material.
The present invention uses the method for solvent deposition, by the long-chain nylons such as nylon 11, nylon 12 and nylon 6 in high temperature environments
Being dissolved in equably in alcohol solvent, cooling separates out nylon alloy powder, and the powder alloy material mechanical property obtained is good, sintering
Window is big, form is uniform, good sphericity, good fluidity, the paving powder of beneficially SLS technology and shaping, and preparation cost is relatively low simultaneously,
There is good application prospect.
As it will be easily appreciated by one skilled in the art that and the foregoing is only presently preferred embodiments of the present invention, not in order to
Limit the present invention, all any amendment, equivalent and improvement etc. made within the spirit and principles in the present invention, all should comprise
Within protection scope of the present invention.
Claims (8)
1. the long-chain nylon for SLS and the alloy powder material preparation method of nylon 6, it is characterised in that include following
Step:
(1) long-chain nylon and nylon 6 particulate material mechanical mixture that particle diameter is 3～5mm are chosen to obtain nylon mixture, its
In, long-chain nylon accounts for the 30%～70% of total raw material quality；
(2) in the described nylon mixture of step (1), add antioxidant, compatilizer and mixed solvent and pour confined reaction into
To obtain mixed solution in still, then by reactor sealing, evacuation, and pour inert protective gas, wherein, every 100 grams of Buddhist nuns
The amount of antioxidant, compatilizer and mixed solvent added in dragon mixture be respectively 0.1 gram～0.5 gram, 0.1 gram～15 grams and
1L；
(3) mixed solution of step (2) gained is stirred, with the speed of 1～2 DEG C/min, mixed solution is heated to 165 simultaneously
～185 DEG C, so that nylon is dissolved completely in solvent, heat-insulation pressure keeping 2～3h afterwards；
(4) by the solution of step (3) gained under fast stirring, it is cooled to room temperature with the speed of 2～4 DEG C/min, forms nylon
Alloy material powder suspension, carries out solid-liquid separation to described nylon alloy material powder suspension, obtains powder aggregates；
(5) powder aggregates obtained is dried, grinds and sieves, it is thus achieved that particle diameter is 10 microns～the long-chain of 100 microns
Nylon and the alloy powder material of nylon 6.
2. the long-chain nylon for SLS as claimed in claim 1 and the alloy powder material preparation method of nylon 6, its feature
Being, the composite antioxidant being made up of Hinered phenols and phosphorous acid esters selected by described antioxidant, and its composition mass ratio is: be subject to
Resistance phenolic antioxidant 60～80%, remaining is phosphite ester kind antioxidant.
3. the long-chain nylon for SLS as claimed in claim 1 or 2 and the alloy powder material preparation method of nylon 6, it is special
Levy and be, described compatilizer optimization styrene graft or Graft Polyolefin.
4. the long-chain nylon for SLS as claimed in claim 3 and the alloy powder material preparation method of nylon 6, its feature
Being, described mixed solvent is ethanol, ethylene glycol, propylene glycol and distilled water mixed solution, wherein: ethanol 70～85%, second two
Alcohol 0.1～20%, propylene glycol 0.1～10%, distilled water 0.1～5%.
5. the long-chain nylon for SLS as claimed in claim 4 and the alloy powder material preparation method of nylon 6, its feature
Being, the mixing speed in step (3) and step (4) is 400-500r/min.
6. the long-chain nylon for SLS as claimed in claim 5 and the alloy powder material preparation method of nylon 6, its feature
It is, step (4) carries out solid-liquid separation to described nylon alloy material powder suspension specifically comprises the processes of: at vacuum ring
Sucking filtration solvent under border.
7. the long-chain nylon for SLS as claimed in claim 6 and the alloy powder material preparation method of nylon 6, its feature
It is, the powder aggregates obtained is dried, grinds and sieves by step (5) specifically comprises the processes of: the powder that will obtain
Aggregation is put in vacuum drying oven and to be dried 24h at 80 DEG C to constant weight, grinds, and 150 eye mesh screens sieve and obtain composite powder material.
8. the long-chain nylon for SLS as claimed in claim 7 and the alloy powder material preparation method of nylon 6, its feature
Being, described long-chain nylon is preferably the one or several in nylon 1010, nylon 11, nylon 12, nylon 1212, nylon 1313
Kind, the more preferably fusing point nylon less than 200 DEG C.
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| CN106832900A (en) * | 2017-01-06 | 2017-06-13 | 北京增材制造技术研究院有限公司 | Inexpensive selective laser sintering modification of nylon composite powder and its application method |
| CN107268111A (en) * | 2017-07-18 | 2017-10-20 | 广东银禧科技股份有限公司 | It is a kind of suitable for modification long-chain nylon silk material of fusion sediment and preparation method thereof |
| CN110272623A (en) * | 2019-06-25 | 2019-09-24 | 湖南华曙高科技有限责任公司 | A kind of laser sintered preparation method with the fire-retardant dusty material of polyamide |
| CN110724376A (en) * | 2019-10-08 | 2020-01-24 | 裕克施乐塑料制品（太仓）有限公司 | Efficient high-strength heat conducting fin and preparation method thereof |
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