CN106147220A - Long-chain nylon and nylon66 fiber alloy powder material preparation method for SLS - Google Patents
Long-chain nylon and nylon66 fiber alloy powder material preparation method for SLS Download PDFInfo
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- CN106147220A CN106147220A CN201610859916.1A CN201610859916A CN106147220A CN 106147220 A CN106147220 A CN 106147220A CN 201610859916 A CN201610859916 A CN 201610859916A CN 106147220 A CN106147220 A CN 106147220A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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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
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- 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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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The invention discloses a kind of long-chain nylon for SLS and nylon66 fiber alloy powder material preparation method, it comprises the following steps: long-chain nylon and nylon66 fiber particulate material is mixed, pours in autoclave after adding mixed solvent, antioxidant and compatilizer；Heating, stirring make nylon mixture be dissolved in alcohol mixed solvent, are incubated a period of time；It is gradually cooling to room temperature, obtains nylon alloy dusty material through vacuum filtration, dry, ball milling and screening.Alloy powder material mechanical strength prepared by the inventive method is high, sintering window is big, form uniform and good fluidity, the paving powder of beneficially SLS technology and shaping, and this alloy material low cost, has a good application prospect simultaneously.
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 nylon66 fiber.
Background technology
Selective laser sintering (Selective LaserSintering, SLS) is a kind of application increasing material system widely
Making technology, it is based on discrete, the thought of stack shaping, uses laser to scan sintered powder material selectively, Layered manufacturing,
Successively superposition, forms physical model.From traditional Material removal, split shapes and to be forced to the processing methods such as shaping different, it is
Material cumulation is utilized to come processing and manufacturing macromolecular material, pottery, metal and the model of various composite and function part.
SLS technology is not affected by drip molding complexity, is therefore widely used in the fields such as biologic medical, Aero-Space, automobile, permissible
Make personalization, complex product efficiently.
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 shape consistency height, the preferable function part of mechanical property, thus becomes the SLS moulding material being most widely used.At present,
Nylon for SLS technology mainly has nylon 11 and nylon 12 isometric strand polymer, accounts for SLS macromolecular material on market
More than 95%, long-chain nylon has big sintering temperature window, good powder apperance and extraordinary low temperature properties, easily processes
Molding, is highly suitable for SLS technology, but its intensity is the highest, and price is higher.Nylon66 fiber has anti-wear performance and self lubricity
The feature that energy is good, mechanical strength is high, relative to its moderate cost of long-chain nylon, the market price about 30,000 yuan/ton, the most extensively uses
In the industry such as electronics and chemical industry.But the sintering temperature window of short chain nylon is less, is easily generated buckling deformation, there is water suction simultaneously
Rate toughness high, low temperature resistant is relatively low and the shortcoming such as environmental stress resistance difference, limits it in the technical application of SLS.
What the long-chain nylons such as nylon 11 and nylon 12 and nylon66 fiber be prepared as alloy material can maximize both is excellent
Gesture organically combines, and improves the combination properties such as the mechanical property of SLS nylon powder and sintering temperature window, strengthens, tenacity increased nylon
SLS drip molding, can also reduce cost simultaneously, have preferable application prospect.But due to long-chain nylon and the thing of nylon66 fiber
Physicochemical nature difference is bigger: both strength differences are big, dissolubility is different, and fusing point is different, is difficult at present prepare preferable Buddhist nun
Dragon alloy powder material.
At present, the preparation method of SLS nylon powder material mainly has three kinds, i.e. twin-screw extrusion-deep cooling crush method, straight
Connect polymerization and solvent deposition method.
(1) twin-screw extrusion-deep cooling crush method is by bi-material melt blending, extrusion first by double screw extruder
Pelletize, then use deep cooling crush preparation be suitable for SLS technique powder, although this method can by bi-material mix homogeneously,
As patent CN01132392 twin-screw extrusion method is prepared for the pellet of nylon alloy, but SLS technique cannot be prepared into
Small particle (10-100 micron) powder required, and powder particle shape irregular, poor fluidity.
(2) suspend and emulsion polymerization is with special polymerization technique, directly obtain powdered polymeric body from starting monomer.
Make the nylon molecules of formation assemble with micron or nanoscale by effects such as antistatic additive, anticoagulant and dispersants to exist.This method
Technological requirement is strict, it is difficult to large-scale industrial production.
(3) solvent precipitation applies in general to the preparation of nylon composite powder material, and such as, ZL200710053668.2 makes
The inorganic nano-filler prepared for SLS with solvent precipitation strengthens nylon composite materials.The method is to the characteristic of solvent and material
The physical property requirements such as dissolubility of material is higher, is generally used for preparing single nylon and composite thereof, due to long-chain nylon and
Short chain nylon physical property difference is big, there is presently no use the method and prepares nylon alloy.
Summary of the invention
For disadvantages described above or the Improvement requirement of prior art, the invention provides a kind of long-chain nylon for SLS with
The alloy powder material preparation method of nylon66 fiber, 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 nylon66 fiber, the most gradually cooling separates out nylon alloy powder, thus solves
Determine the problem that nylon powder material is single, mechanical strength is not enough and 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 nylon66 fiber
Preparation method for material, comprises the following steps:
(1) choose long-chain nylon and nylon66 fiber particulate material mechanical mixture that particle diameter is 3～5mm to mix to obtain nylon
Thing, wherein, 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 into airtight
To obtain mixed solution in reactor, then by reactor sealing, evacuation, and pour inert protective gas, wherein, every 100
The amount of the antioxidant, compatilizer and the mixed solvent that add in gram nylon mixture is respectively 0.1 gram～0.5 gram, 0.1 gram～15
Gram 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 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 nylon66 fiber.
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 prepares nylon by the way of homogeneously crystallized precipitation powder particle when the nylon of dissolving is at Slow cooling
Alloy powder, the nylon alloy powder particle obtained flowing property and discreteness are good, and form is uniform, and good sphericity, particle diameter is 10-
100 μm, are highly suitable for SLS technology, and the powder flowbility of this particle diameter is good, and 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 by long-chain nylon and nylon66 fiber are made alloy powder material
It is effectively improved its mechanical strength while technology, improves product mechanical property.
3. the market price of the nylon66 fiber 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 nylon66 fiber granule, by nylon particles, anti-in hermetic container
The mixture heated and stirred of oxidant, compatilizer and mixed solvent, makes nylon particles be dissolved in solvent, the most gradually cools down,
Making nylon alloy crystallization, through solvent recovery, vacuum drying, ball milling, screening selects the powder of certain grain size distribution to be Buddhist nun
Dragon 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, the feature that intensity is high, form accuracy is good.
The preferred scope of long-chain nylon is: nylon 1010, nylon 11, nylon 12, nylon 1212, the one in nylon 1313
Or several, its further preferably scope be the nylon that fusing point is less than 200 DEG C, low pre-to during laser sintering (SLS) of material melting point
Hot temperature requirement is also low, and sintering is easily controlled.Comprehensive physical performance and reduction production cost for improving alloy powder are long
The mass fraction of chain nylon is preferably 30%-70%, and the mass fraction of nylon66 fiber 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: every 100 grams of Buddhist nuns
Dragon 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 ethanol, ethylene glycol, propylene glycol and distilled water mixed solution, wherein: ethanol: 70～85%, and distillation
Water: 0.1～5%, ethylene glycol: 0.1～20%, propylene glycol: 0.1～10%, its consumption is: every 100 grams of nylon, and mixed solvent is used
Amount is 1L.
A kind of long-chain nylon for SLS of present invention offer and the alloy powder material preparation method of nylon66 fiber, including
Following steps:
(1) choose long-chain nylon and nylon66 fiber particulate material mechanical mixture that particle diameter is 3～5mm to mix to obtain nylon
Thing；
(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；
(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 the speed of 2～4 DEG C/min
Degree is cooled to room temperature, forms nylon alloy material powder suspension, described nylon alloy material powder suspension is carried out solid-liquid
Separate, obtain powder aggregates.Concrete, nylon alloy material powder suspension sucking filtration under vacuum conditions is gone out solvent, with
Realize the suspension cooled down is carried out solid-liquid separation, obtain powder aggregates and solvent, solvent recoverable.
(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 nylon66 fiber: powder aggregates is put in vacuum drying oven and to dry 24h at 80 DEG C to constant weight, grind
Mill, the 150 eye mesh screens selection particle diameter that sieves is distributed in 10 microns～the powder of 100 microns, final obtain described in long-chain nylon and
The alloy material of nylon66 fiber.
It is below the specific embodiment of the present invention:
Embodiment 1
(1) nylon 12 and nylon66 fiber particulate material, mixed solvent 3L and compound antioxygen that 150 gram particle footpaths are 3 millimeters are respectively taken
Agent 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 nylon66 fiber, 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) nylon 12 particulate material 90 grams and nylon66 fiber particulate material 210 grams that particle diameter is 4 millimeters, mixed solvent 3L are taken
And composite antioxidant 0.3 gram, compatilizer 20 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: 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 nylon66 fiber, 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 nylon66 fiber particulate material 90 grams that particle diameter is 4.5 millimeters, mixed solvent are taken
3L 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 nylon66 fiber, 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 nylon66 fiber particulate material that 150 gram particle footpaths are 3.5 millimeters are respectively taken, mixed solvent 3L and compound anti-
Oxygen agent 1.0 grams, compatilizer 0.3 gram puts in the rustless steel 50L reactor of jacketed, is sealed by reactor, evacuation, logical N2Gas
Protection.
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 nylon66 fiber, 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) nylon 11 particulate material 90 grams and nylon66 fiber particulate material 210 grams that particle diameter is 5 millimeters, mixed solvent 3L are taken
And composite antioxidant 1.5 grams, compatilizer 20 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: 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 nylon66 fiber, 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) nylon 12 particulate material 210 grams and nylon66 fiber particulate material 90 grams that particle diameter is 3 millimeters, mixed solvent 3L are taken
And composite antioxidant 1.5 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: 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 nylon66 fiber, 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 most equal to the long-chain nylons such as nylon 11, nylon 12 and nylon66 fiber
Even being dissolved in alcohol solvent, cooling separates out nylon alloy powder, and the powder alloy material mechanical property obtained is good, sintering window
Greatly, form uniform, good sphericity, good fluidity, the paving powder of beneficially SLS technology and shaping, environmentally safe, and cost are relatively
Low, 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 nylon66 fiber, it is characterised in that include following
Step:
(1) long-chain nylon and nylon66 fiber particulate material mechanical mixture that particle diameter is 3～5mm are chosen to obtain nylon mixture,
Wherein, 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 material of nylon66 fiber.
2. the long-chain nylon for SLS as claimed in claim 1 and the alloy powder material preparation method of nylon66 fiber, 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 nylon66 fiber, its
It is characterised by, 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 nylon66 fiber, 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 nylon66 fiber, 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 nylon66 fiber, 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 nylon66 fiber, 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 nylon66 fiber, 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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| CN108788123A (en) * | 2018-05-08 | 2018-11-13 | 苏州耐思特塑胶有限公司 | A kind of preparation method of metal die dusty material |
| CN110819104A (en) * | 2018-07-23 | 2020-02-21 | 上海杰事杰新材料(集团)股份有限公司 | High-dimensional-precision nylon powder for 3D printing and preparation method and application thereof |
| CN114149682A (en) * | 2021-12-09 | 2022-03-08 | 惠州鸿为新材料科技有限公司 | Thermoplastic extinction nylon powder and preparation method thereof |
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Application publication date: 20161123 Assignee: DONGGUAN SILVER AGE OPTOELECTRONICS SCI. & TECH. CO., LTD. Assignor: Guangdong Silverage Holdings Ltd. Contract record no.: X2019990000092 Denomination of invention: Preparation method for long-chain nylon and nylon 66 alloy powder material for SLS Granted publication date: 20180619 License type: Common License Record date: 20190920 |