CN106243705B - The alloy powder material preparation method of long-chain nylon and nylon 6 for SLS - Google Patents
The alloy powder material preparation method of long-chain nylon and nylon 6 for SLS Download PDFInfo
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- CN106243705B CN106243705B CN201610856397.3A CN201610856397A CN106243705B CN 106243705 B CN106243705 B CN 106243705B CN 201610856397 A CN201610856397 A CN 201610856397A CN 106243705 B CN106243705 B CN 106243705B
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- 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 the alloy powder material preparation methods of a kind of long-chain nylon for SLS and nylon 6 comprising following steps：Long-chain nylon and 6 particulate material of nylon are mixed, poured into autoclave after mixed solvent, antioxidant and compatilizer is added；Heating, stirring make nylon mixture be dissolved in the mixed solvent, heat preservation a period of time；It is gradually cooling to room temperature, the nylon alloy dusty material for SLS technologies is obtained through vacuum filter, drying, ball milling and screening.The alloy powder material mechanical property of the method for the present invention preparation is good, sintering window is big, form is uniform and good fluidity, is conducive to powdering and the forming of SLS technologies, while the alloy material manufacturing cost is low, has a good application prospect.
Description
Technical field
The invention belongs to advanced manufacturing technologies and field of material preparation, more particularly, to a kind of long-chain Buddhist nun for SLS
The alloy powder material preparation method of dragon and nylon 6.
Background technology
Selective laser sintering (Selective Laser Sintering, SLS) is a kind of important increases material manufacturing technology,
It uses Layered manufacturing principle of stacking, and by computer aided design and manufacture, sintering powder is selectively scanned using laser
Material, Layered manufacturing are successively superimposed, and are Three-dimensional Entity Components by dusty material direct forming.Compared with traditional processing method,
It is the model and function zero that high molecular material, ceramics, metal and various composite materials are fabricated using material cumulation
Part.Theoretically SLS technologies are not influenced by drip molding complexity, can manufacture personalized, complicated shape part, utmostly
Meet application demand.
Nylon is a kind of semicrystalline polymeric, has good sintering character and lower melt viscosity, can be straight by SLS
It is connected into shape consistency height, the preferable function part of mechanical property, thus as one of the SLS moulding materials being most widely used.
Nylon currently used for SLS technologies mainly has the long chains polymer such as nylon 11 and nylon 12, accounts for SLS macromolecules in the market
95% or more of material, long-chain nylon have big sintering temperature window, good powder apperance and extraordinary low temperature properties, easily
Machine-shaping is highly suitable for SLS technologies, but its intensity is not high, and on the high side.
Nylon 6 be had excellent performance in synthetic fibers, widely used one of kind, it have many excellent performances, remove
Have outside the performances such as shared corrosion-resistant, resistance to of synthetic fibers goes rotten, hydroscopicity is low, main feature also resides in：Fracture strength
Height, excellent in abrasion resistance, elasticity are good, elongate fiber response rate is high, while it is moderate relative to long-chain nylon, and the market price is about
30000 yuan/ton.But the disadvantage is that：Sintering temperature window is smaller, Young's modulus is small, be also easy to produce buckling deformation, heat resistance is bad,
Light fastness is poor, easily turns yellow under daylight or ultraviolet light irradiation, these defects limit it in the technical applications of SLS.
The long-chain nylons such as nylon 11 and nylon 12 and nylon 6 are prepared into alloy material and can maximized the advantage of the two
It organically combines, improves the comprehensive performances such as mechanical property and the sintering temperature window of SLS nylon powders, enhancing, tenacity increased nylon SLS
Drip molding, while cost can also be reduced, there is preferable application prospect.Patent CN01132392 is prepared with twin-screw extrusion method
The pellet of nylon alloy, due to the difference of long-chain nylon and nylon 6 in the physicochemical properties such as intensity, dissolubility, fusing point
It is larger, it is difficult to prepare the nylon alloy dusty material for SLS at present.
There are mainly three types of the preparation methods of SLS nylon powder materials, i.e. twin-screw extrusion-deep cooling crush method, directly poly-
Legal and solvent deposition method.Two kinds of materials can be uniformly mixed by twin-screw extrusion-deep cooling crush method, but can not be prepared
At small particle (10-100 microns) powder of SLS technological requirements, and powder particle shape irregular, poor fluidity.It suspends
It is stringent 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 enhances for example, ZL200710053668.2 is prepared using solvent precipitation for the inorganic nano-filler of SLS
Nylon composite materials；But this method is higher to the physical property requirements such as the characteristic of solvent and the solubility of material, is generally used for
Single nylon and its composite material are prepared, since long-chain nylon and short chain nylon physical property difference are big, there is presently no use
This method prepares nylon alloy.
Invention content
For the disadvantages described above or Improvement requirement of the prior art, the present invention provides one kind being used for precinct laser sintering technology
Nylon alloy dusty material preparation method, the present invention using solvent deposition method at high temperature by nylon 11, nylon 12
Equal long-chain nylons and nylon 6 are equably dissolved in alcohol solvent, then gradually cooling that nylon alloy powder is precipitated, and are thus solved
The problem that the nylon powder material of current SLS is single, mechanical strength is low, of high cost.
To achieve the above object, the present invention proposes a kind of alloy powder material of the long-chain nylon for SLS and nylon 6
Preparation method includes the following steps：
(1) long-chain nylon and 6 particulate material of nylon that grain size is 3~5mm are chosen and mechanical mixture is to obtain nylon mixing
Object, wherein the mass fraction of long-chain nylon is 30%-70%, and the mass fraction of nylon 6 is 30%-70%；
(2) antioxidant, compatilizer and mixed solvent are added in the nylon mixture of step (1) and pours into closed
To obtain mixed solution in reaction kettle, then reaction kettle is sealed, is vacuumized, and pours inert protective gas, wherein every 100
The dosage of gram nylon, antioxidant is 0.1 gram~0.5 gram, and antioxidant can be that symmetrical phenolic antioxidant, asymmetric phenols are anti-
Oxygen agent, phosphite ester kind antioxidant, thioester antioxidant, amine antioxidants or above-mentioned several compound；Every 100 grams of Buddhist nuns
The dosage of dragon, compatilizer is 0.1 gram~15 grams；The dosage of every 100 grams of nylon, mixed solvent is 1L；
(3) mixed solution obtained by step (2) is stirred, while is heated to mixed solution with the speed of 1~2 DEG C/min
165~185 DEG C, so that nylon is dissolved completely in solvent, 2~3h of heat-insulation pressure keeping later；
(4) under fast stirring by the solution obtained by step (3), it is cooled to room temperature, is formed with the speed of 2~4 DEG C/min
Nylon alloy material powder suspension carries out solid- liquid separation to the nylon alloy material powder suspension, obtains powder aggregation
Body；
(5) obtained powder aggregates are dried, ground and sieved, it is 10 microns~100 microns to obtain grain size
The alloy material of long-chain nylon and nylon 6.
As it is further preferred that the antioxidant selects the compound antioxygen being made of Hinered phenols and phosphorous acid esters
Agent, composition mass ratio are：Hinered phenols antioxidant 60~80%, remaining is phosphite ester kind antioxidant.
As it is further preferred that the compatilizer optimization styrene graft or Graft Polyolefin.
As it is further preferred that the mixed solvent be ethyl alcohol, ethylene glycol, propylene glycol and distillation water mixed solution,
In：Ethyl alcohol 70~85%, ethylene glycol 0.1~20%, propylene glycol 0.1~10%, distilled water 0.1~5%.
As it is further preferred that the mixing speed in step (3) is 400-500r/min, the stirring in step (4) is fast
Degree is 400-500r/min.
As it is further preferred that carrying out solid- liquid separation to the nylon alloy material powder suspension in step (4)
Concrete technology is：Solvent is filtered under vacuum conditions.
As it is further preferred that obtained powder aggregates being dried, grinding and being sieved in step (5) is specific
Technique is：Product is put into vacuum drying chamber at 80 DEG C and is dried for 24 hours to constant weight, is ground, 150 mesh screens are sieved to obtain composite powder
Powder material.
As it is further preferred that the long-chain nylon is preferably nylon 1010, nylon 11, nylon 12, nylon 1212, Buddhist nun
One or more of dragon 1313, further preferably fusing point are less than 200 DEG C of nylon.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, mainly have below
Technological merit：
1. the present invention is by the nylon being dissolved in alcohol solvent, the homogeneously crystallized precipitation powder particle in Slow cooling
Mode prepares nylon alloy powder, and obtained nylon alloy powder particle flowing property and discreteness is good, and form is uniform, sphericity
Good, grain size is 10-100 μm, is highly suitable for SLS technologies, the powder flowbility of the grain size is good, the SLS initial blanks of forming
Have degree of precision and intensity.
2. since semicrystalline polymeric nylon melt viscosity is low, the SLS products of the equal long-chains nylon mo of nylon 12 are used
Intensity it is not high, the present invention can be used for SLS skills by the way that alloy powder material is made in long-chain nylon and nylon 6 ensureing it
Its mechanical strength is effectively improved while art, improves product mechanical property.
3. since the market price of the nylon 6 of the invention used is the half of nylon 12, conjunction is made with long-chain nylon in it
Golden material can significantly reduce the manufacturing cost of alloy powder, have a good application prospect.
Description of the drawings
Fig. 1 is the flow diagram of preparation method of the present invention.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
It does not constitute a conflict with each other and can be combined with each other.
The present invention weighs 6 particle of a certain amount of long-chain nylon and nylon first, by nylon particles, antioxygen in closed container
The mixture heating stirring of agent, compatilizer and mixed solvent, makes nylon particles be dissolved in solvent, then gradually cooling, makes
Nylon alloy crystallization is precipitated, and through solvent recovery, vacuum drying, ball milling, the powder of screening selection certain grain size distribution is nylon
Alloy powder material.
Nylon is semicrystalline polymeric, and melt viscosity is smaller, and the SLS initial blanks of preparation can be made to have consistency
Greatly, the feature that intensity is high, form accuracy is good, 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 of nylon 1313, further preferred scope
Be less than 200 DEG C of nylon for fusing point, material melting point it is low to laser sintering (SLS) when preheating temperature require also low, be sintered and be easy control
System.Can be 30%- to improve the comprehensive physical performance of alloy powder and reducing the mass fraction of production cost long-chain nylon
70%, the mass fraction of nylon 6 can be 30%-70%.
To prevent under high temperature environment, nylon oxidation stain need to add antioxidant, and antioxidant is selected by Hinered phenols
With the composite antioxidant of phosphorous acid esters composition, composition and mass ratio are：Hinered phenols antioxidant：60~80%, remaining is
Phosphite ester kind antioxidant.
The preferably following material of Hinered phenols antioxidant：1,3,5- trimethyl -2,4, (3, the 5- di-t-butyl -4- hydroxyls of 6- tri-
Base benzyl) benzene, 2,6- di-t-butyl -4- methyl-phenols, N, N '-two (3,5- di-tert-butyl-hydroxy phenyl propionamide), 2,
2 '-bis- (4- methyl-6-terts butyl-phenol) methane, 2,2 '-bis- (4- ethyl -6- t-butyl-phenols) methane etc..
The preferably following material of phosphite ester kind antioxidant：2,2 '-ethylenebis (4,6- di-tert-butyl-phenyl) fluoro is sub-
Phosphate, four (2,4- di-tert-butyl-phenyl) -4,4 '-xenyl bis-phosphite etc..The dosage of antioxidant is：Every 100 grams
0.1 gram~0.5 gram antioxidant is added in nylon.
Long-chain nylon and short chain nylon compatibility are poor, and to make it, good fusion, optimized alloy powder property need in the solution
Compatilizer is added, compatilizer can be styrene-grafted object or Graft Polyolefin, including acrylonitrile-butadiene-styrene (ABS) connects
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 dosage of compatilizer is：In every 100 grams of nylon
0.1 gram~15 grams compatilizers are added.
Mixed solvent is the mixed solution of ethyl alcohol, ethylene glycol, propylene glycol and distilled water, wherein：Ethyl alcohol：70~85%, it steams
Distilled water：0.1~5%, ethylene glycol：0.1~20%, propylene glycol：0.1~10%, the dosage of mixed solvent is：Every 100 grams of nylon,
Mixed solvent dosage is 1L.
Provided by the present invention for the preparation method of the alloy material of the long-chain nylon and short chain nylon of SLS technologies, specifically
Include the following steps：
(1) long-chain nylon and 6 particulate material of nylon that a certain amount of particle size range is 3~5mm and mechanical mixture are chosen；
(2) nylon mixture in step (1) is poured into closed reactor plus antioxidant, compatilizer and mixed solvent
In, it seals, vacuumize, filling inert protective gas (such as nitrogen)；
(3) mixed solution obtained by step (2) is stirred under 400-500r/min speed, while 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, 2~3h of heat-insulation pressure keeping later；
(4) solution obtained by step (3) is maintained under the speed of 400-500r/min and is stirred, it is gradual with 2~4 DEG C/min
It is cooled to room temperature, forms nylon alloy material powder suspension, solid-liquid point is carried out to the nylon alloy material powder suspension
From obtaining powder aggregates, specifically, suspension is filtered out solvent under vacuum conditions, recycling design, remaining is powder
Aggregation.
(5) finally, obtained powder aggregates are dried, ground and sieved, it is 10 microns~100 micro- to obtain grain size
The alloy material of the long-chain nylon and nylon 6 of rice：Powder aggregates are put into vacuum drying chamber at 80 DEG C and are dried for 24 hours to permanent
Weight, grinding, the sieving of 150 mesh screens select powder of the particle diameter distribution at 10 microns~100 microns, final to obtain the long-chain
The alloy material of nylon and nylon 6.
It is specific embodiments of the present invention below：
Embodiment 1
(1) it is 3 millimeters of 6 particulate material of nylon 12 and nylon, mixed solvent 3L and composite antioxidant respectively to take 150 gram particle diameters
0.3 gram, 0.3 gram of compatilizer is put into the stainless steel 50L reaction kettles of jacketed, and reaction kettle is sealed, is vacuumized, and leads to N2Gas is protected
Shield.
Wherein, the proportioning of mixed solvent is：70% ethyl alcohol, 0.1% distilled water, 20% ethylene glycol, 9.9% propylene glycol；It is multiple
Close antioxidant proportioning be：1,3,5- trimethyl -2,4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene be 80%, four (2,
4- di-tert-butyl-phenyls) -4,4 '-xenyl bis-phosphites be 20%；Compatilizer selection acrylonitrile-butadiene-styrene (ABS) connects
Branch maleic anhydride.
(2) solution is stirred with the speed of 500r/min, then with the speed of 1 DEG C/min, is gradually warming up to 175 DEG C,
Nylon 12 is set to be dissolved completely in solvent, heat-insulation pressure keeping 2h.
(3) it is vigorously stirred with the speed of 500r/min, room temperature is gradually cooling to 2 DEG C/min speed, makes nylon 12
It is precipitated with nylon 6, forms nylon alloy powder suspension.
(4) in a kettle, by vacuum filter, solid- liquid separation is carried out to the suspension cooled down, obtained solvent can
To repeat to recycle, obtained powder aggregates are for use.
(5) powder aggregates obtained, which are put into vacuum drying chamber at 80 DEG C, dries for 24 hours to constant weight, grinding, 150 mesh screens
Sieving selects particle diameter distribution in 10 microns~100 microns of powder up to nylon alloy dusty material.
Embodiment 2
(1) take 210 grams of 90 grams of 12 particulate material of nylon and 6 particulate material of nylon that grain size is 4 millimeters, mixed solvent 3L and
0.3 gram of composite antioxidant, 20 grams of compatilizer put into the stainless steel 50L reaction kettles of jacketed, reaction kettle are sealed, is vacuumized,
Logical N2Gas shielded.
Wherein, the proportioning of mixed solvent is：85% ethyl alcohol, 5% distilled water, 0.1% ethylene glycol, 9.9% propylene glycol；It is compound
The proportioning of antioxidant is：1,3,5- trimethyl -2,4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene are 60%, and 2,2 '-is sub-
Bis- (4, the 6- di-tert-butyl-phenyl) fluorophosphites of ethyl are 40%；Compatilizer selects styrene-grafted maleic anhydride.
(2) solution is stirred with the speed of 400r/min, then with the speed of 1.5 DEG C/min, is gradually warming up to 185
DEG C, so that nylon 12 is dissolved completely in solvent, heat-insulation pressure keeping 2.5h.
(3) it is vigorously stirred with the speed of 430r/min, room temperature is gradually cooling to 2 DEG C/min speed, makes nylon 12
It is precipitated with nylon 6, forms nylon alloy powder suspension.
(4) in a kettle, by vacuum filter, solid- liquid separation is carried out to the suspension cooled down, obtained solvent can
To repeat to recycle, obtained powder aggregates are for use.
(5) powder aggregates obtained, which are put into vacuum drying chamber at 80 DEG C, dries for 24 hours to constant weight, grinding, 150 mesh screens
Sieving selects particle diameter distribution in 10 microns~100 microns of powder up to nylon alloy dusty material.
Embodiment 3
(1) 90 grams of 210 grams of 12 particulate material of nylon and 6 particulate material of nylon that grain size is 4.5 millimeters, mixed solvent 3L are taken
And 1.0 grams of composite antioxidant, 45 grams of compatilizer put into the stainless steel 50L reaction kettles of jacketed, reaction kettle are sealed, and take out true
Sky leads to N2Gas shielded.
Wherein, the proportioning of mixed solvent is：76% ethyl alcohol, 4% distilled water, 10% ethylene glycol, 10% propylene glycol；It is compound anti-
The proportioning of oxygen agent is：2,6- di-t-butyl -4- methyl-phenols, N, N '-two (3,5- di-tert-butyl-hydroxy phenyl propionamide)
It is 70%, four (2,4- di-tert-butyl-phenyl) -4,4 '-xenyl bis-phosphite is 30%；Compatilizer selects ethylene-octene total
Polymers grafted maleic anhydride.
(2) solution is stirred with the speed of 450r/min, then with the speed of 2 DEG C/min, is gradually warming up to 165 DEG C,
Nylon 12 is set to be dissolved completely in solvent, heat-insulation pressure keeping 3h.
(3) it is vigorously stirred with the speed of 450r/min, room temperature is gradually cooling to 3 DEG C/min speed, makes nylon 12
It is precipitated with nylon 6, forms nylon alloy powder suspension.
(4) in a kettle, by vacuum filter, solid- liquid separation is carried out to the suspension cooled down, obtained solvent can
To repeat to recycle, obtained powder aggregates are for use.
(5) powder aggregates obtained, which are put into vacuum drying chamber at 80 DEG C, dries for 24 hours to constant weight, grinding, 150 mesh screens
Sieving selects particle diameter distribution in 10 microns~100 microns of powder up to nylon alloy dusty material.
Embodiment 4
(1) it is 3.5 millimeters of 6 particulate material of nylon 11 and nylon, mixed solvent 3L and compound antioxygen respectively to take 150 gram particle diameters
1.0 grams of agent, 0.3 gram of compatilizer put into the stainless steel 50L reaction kettles of jacketed, reaction kettle are sealed, is vacuumized, and lead to N2Gas is protected
Shield.
Wherein, the proportioning of mixed solvent is：81.9% ethyl alcohol, 3% distilled water, 15% ethylene glycol, 0.1% propylene glycol；It is multiple
Close antioxidant proportioning be：2,2 '-bis- (4- methyl-6-terts butyl-phenol) methane are 75%, four (2,4- di-tert-butyls
Base) -4,4 '-xenyl bis-phosphites be 25%；Compatilizer selects acrylonitrile-butadiene-styrene (ABS) grafted maleic anhydride.
(2) solution is stirred with the speed of 480r/min, then with the speed of 1 DEG C/min, is gradually warming up to 175 DEG C,
Nylon 11 is set to be dissolved completely in solvent, heat-insulation pressure keeping 2h.
(3) it is vigorously stirred with the speed of 400r/min, room temperature is gradually cooling to 3 DEG C/min speed, makes nylon 11
It is precipitated with nylon 6, forms nylon alloy powder suspension.
(4) in a kettle, by vacuum filter, solid- liquid separation is carried out to the suspension cooled down, obtained solvent can
To repeat to recycle, obtained powder aggregates are for use.
(5) powder aggregates obtained, which are put into vacuum drying chamber at 80 DEG C, dries for 24 hours to constant weight, grinding, 150 mesh screens
Sieving selects particle diameter distribution in 10 microns~100 microns of powder up to nylon alloy dusty material.
Embodiment 5
(1) take 210 grams of 90 grams of the nylon 11 particulate material and 6 particulate material of nylon that grain size is 5 millimeters, mixed solvent 3L and
1.5 grams of composite antioxidant, 20 grams of compatilizer put into the stainless steel 50L reaction kettles of jacketed, reaction kettle are sealed, is vacuumized,
Logical N2Gas shielded.
Wherein, the proportioning of mixed solvent is：72% ethyl alcohol, 3% distilled water, 20% ethylene glycol, 5% propylene glycol；It is compound anti-
The proportioning of oxygen agent is：1,3,5- trimethyl -2,4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene are 65%, four (2,4- bis-
Tert-butyl-phenyl) -4,4 '-xenyl bis-phosphites be 35%；Compatilizer selects polypropylene grafted maleic anhydride.
(2) solution is stirred with the speed of 460r/min, then with the speed of 1.5 DEG C/min, is gradually warming up to 185
DEG C, so that nylon 11 is dissolved completely in solvent, heat-insulation pressure keeping 2.5h.
(3) it is vigorously stirred with the speed of 500r/min, room temperature is gradually cooling to 4 DEG C/min speed, makes nylon 11
It is precipitated with nylon 6, forms nylon alloy powder suspension.
(4) in a kettle, by vacuum filter, solid- liquid separation is carried out to the suspension cooled down, obtained solvent can
To repeat to recycle, obtained powder aggregates are for use.
(5) powder aggregates obtained, which are put into vacuum drying chamber at 80 DEG C, dries for 24 hours to constant weight, grinding, 150 mesh screens
Sieving selects particle diameter distribution in 10 microns~100 microns of powder up to nylon alloy dusty material.
Embodiment 6
(1) take 90 grams of 210 grams of 12 particulate material of nylon and 6 particulate material of nylon that grain size is 3 millimeters, mixed solvent 3L and
1.5 grams of composite antioxidant, 45 grams of compatilizer put into the stainless steel 50L reaction kettles of jacketed, reaction kettle are sealed, is vacuumized,
Logical N2Gas shielded.
Wherein, the proportioning of mixed solvent is：85% ethyl alcohol, 1% distilled water, 10% ethylene glycol, 4% propylene glycol；It is compound anti-
The proportioning of oxygen agent is：2,2 '-bis- (4- ethyl -6- t-butyl-phenols) methane are 80%, four (2,4- di-tert-butyl-phenyls) -4,
4 '-xenyl bis-phosphites are 20%；Compatilizer selects acrylonitrile-butadiene-styrene (ABS) grafted maleic anhydride.
(2) solution is stirred with the speed of 490r/min, then with the speed of 2 DEG C/min, is gradually warming up to 165 DEG C,
Nylon 12 is set to be dissolved completely in solvent, heat-insulation pressure keeping 3h.
(3) it is vigorously stirred with the speed of 490r/min, room temperature is gradually cooling to 4 DEG C/min speed, makes nylon 12
It is precipitated with nylon 6, forms nylon alloy powder suspension.
(4) in a kettle, by vacuum filter, solid- liquid separation is carried out to the suspension cooled down, obtained solvent can
To repeat to recycle, obtained powder aggregates are for use.
(5) powder aggregates obtained, which are put into vacuum drying chamber at 80 DEG C, dries for 24 hours to constant weight, grinding, 150 mesh screens
Sieving selects particle diameter distribution in 10 microns~100 microns of powder up to nylon alloy dusty material.
The method that the present invention uses solvent deposition, under high temperature environment by the long-chain nylons such as nylon 11, nylon 12 and nylon 6
It is equably dissolved in alcohol solvent, cooling precipitation nylon alloy powder, obtained powder alloy material mechanical property is good, is sintered
Window is big, form is uniform, good sphericity, good fluidity, is conducive to powdering and the forming of SLS technologies, while manufacturing cost is relatively low,
There is good application prospect.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all within the spirits and principles of the present invention made by all any modification, equivalent and improvement etc., should all include
Within protection scope of the present invention.
Claims (9)
1. the alloy powder material preparation method of a kind of long-chain nylon for SLS and nylon 6, which is characterized in that including following
Step：
(1) long-chain nylon and 6 particulate material of nylon that grain size is 3~5mm are chosen and mechanical mixture is to obtain nylon mixture,
In, long-chain nylon accounts for the 30%~70% of total raw material quality；
(2) antioxidant, compatilizer and mixed solvent are added in the nylon mixture of step (1) and pours into confined reaction
To obtain mixed solution in kettle, then reaction kettle is sealed, is vacuumized, and pours inert protective gas, wherein every 100 grams of Buddhist nuns
The amount of the antioxidant, compatilizer and the mixed solvent that are added in imperial mixture be respectively 0.1 gram~0.5 gram, 0.1 gram~15 grams and
1L, the mixed solvent are ethyl alcohol, ethylene glycol, propylene glycol and distillation water mixed solution；
(3) mixed solution obtained by step (2) is stirred, while mixed solution is heated to 165 with the speed of 1~2 DEG C/min
~185 DEG C, so that nylon is dissolved completely in solvent, 2~3h of heat-insulation pressure keeping later；
(4) under fast stirring by the solution obtained by step (3), 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 the nylon alloy material powder suspension, obtains powder aggregates；
(5) obtained powder aggregates are dried, ground and sieved, obtain the long-chain that grain size is 10 microns~100 microns
The alloy powder material of nylon and nylon 6.
2. the alloy powder material preparation method for the long-chain nylon and nylon 6 of SLS as described in claim 1, feature
It is, the antioxidant selects the composite antioxidant being made of Hinered phenols and phosphorous acid esters, forms mass ratio and is：By
Phenolic antioxidant 60~80% is hindered, remaining is phosphite ester kind antioxidant.
3. the alloy powder material preparation method for the long-chain nylon and nylon 6 of SLS as claimed in claim 1 or 2, special
Sign is that the compatilizer is styrene-grafted object or Graft Polyolefin.
4. the alloy powder material preparation method for the long-chain nylon and nylon 6 of SLS as claimed in claim 3, feature
It is, the in the mixed solvent ethyl alcohol 70~85%, ethylene glycol 0.1~20%, propylene glycol 0.1~10%, distilled water 0.1~
5%.
5. the alloy powder material preparation method for the long-chain nylon and nylon 6 of SLS as claimed in claim 4, feature
It is, the mixing speed in step (3) and step (4) is 400-500r/min.
6. the alloy powder material preparation method for the long-chain nylon and nylon 6 of SLS as claimed in claim 5, feature
It is, the concrete technology for carrying out solid- liquid separation in step (4) to the nylon alloy material powder suspension is：In vacuum ring
Solvent is filtered under border.
7. the alloy powder material preparation method for the long-chain nylon and nylon 6 of SLS as claimed in claim 6, feature
It is, is by the concrete technology that obtained powder aggregates are dried, grind and sieve in step (5)：The powder that will be obtained
Aggregation, which is put into vacuum drying chamber at 80 DEG C, dries for 24 hours to constant weight, grinds, 150 mesh screens are sieved to obtain composite powder material.
8. the alloy powder material preparation method for the long-chain nylon and nylon 6 of SLS as described in claim 1, feature
It is, the long-chain nylon is one or more of nylon 1010, nylon 11, nylon 12, nylon 1212, nylon 1313.
9. the alloy powder material preparation method for the long-chain nylon and nylon 6 of SLS as described in claim 1, feature
It is, the long-chain nylon is the nylon that fusing point is 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 |
| CN107268111B (en) * | 2017-07-18 | 2019-02-19 | 广东银禧科技股份有限公司 | A kind of modification long-chain nylon silk material and preparation method thereof suitable for fusion sediment |
| 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 |
| CN110272623B (en) * | 2019-06-25 | 2022-01-18 | 湖南华曙高科技有限责任公司 | Preparation method of polyamide flame-retardant powder material for laser sintering |
| CN110724376B (en) * | 2019-10-08 | 2022-06-03 | 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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| CN102140246A (en) * | 2010-12-21 | 2011-08-03 | 湖南华曙高科技有限责任公司 | Method for preparing nylon powder for selective laser sintering |
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