CN104910616A - Low-temperature nylon powder material for selective laser sintering and preparation method thereof - Google Patents
Low-temperature nylon powder material for selective laser sintering and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of polymer composites and particularly relates to a low-temperature nylon powder material for selective laser sintering. The low-temperature nylon powder material mainly comprises nylon 12 particles, dodecanedioic acid, double amino-terminated polyethylene glycol, deuterated trifluoroacetic acid, an antioxidant, a solvent, a nucleating agent, a plasticizer and a silane coupling agent. The low-temperature nylon powder material is prepared by the following steps: uniformly mixing the dodecanedioic acid and nylon 12 particles and putting into a reaction kettle; adding the double amino-terminated polyethylene glycol and deuterated trifluoroacetic acid into the reaction kettle; heating and starting stirring to obtain a product; putting the product together with the antioxidant, solvent, nucleating agent, plasticizer and silane coupling agent into the reaction kettle, and closing the kettle with a cover; vacuumizing the reaction kettle and introducing nitrogen displacement for protection; starting stirring and reducing the temperature of the kettle body to room temperature; taking out the materials, drying and performing ball milling; and drying the powder to obtain powder with good sphericity and fluidity. The low-temperature nylon powder material provided by the invention has the characteristics of low preheating temperature, wide preheating window, good aging resistance and adaptability to table boards of various specifications.
Description
Technical field
The present invention relates to technical field of polymer composite materials, be specifically related to a kind of low temperature nylon powder material for selective laser sintering and preparation method thereof.
Background technology
Increase the novel advanced manufacturing technology that material manufacture (be commonly called as 3D to print, be also called rapid shaping & and manufacture) technology relates to many science such as computer, control, machinery, material.It has broken traditional technology mode that material deformation is shaping and removal is shaping, adopts and successively manufactures and the increasing material forming method superposed, can produce the Three-dimensional Entity Components of any complexity in theory.
Selective laser sintering (Selective Laser Sintering, SLS) technology is a kind of increasing material manufacturing technology of current main flow.Polymer material and engineering be apply the earliest, be also maximum SLS materials, in laser sintered process, there is melting or softening, crystallization and densification occur in process of cooling and causes volumetric shrinkage, affecting the precision of drip molding.The amorphism macromolecular material of exploitation both at home and abroad comprises polystyrene (PS), polycarbonate (PC), acrylonitrile-butadiene-styrene copolymer (ABS) etc. at present, the density of its SLS profiled member is low, mechanical property is not high yet, needs just to can be used as the not high function part of mechanical property requirements through aftertreatment.Not only there is the densification volumetric shrinkage of similar amorphism material in hemicrystalline macromolecular material, and the volume change caused by melting recrystallization also can cause larger volumetric shrinkage in SLS process.Therefore, the buckling deformation that volumetric shrinkage causes is very large, and technological process is wayward, and research and development difficulty is large.But the density of its SLS drip molding is high, intensity and toughness very well, directly can be used as function part.Therefore, adopt this type of material to carry out SLS to manufacture and will have huge development potentiality.At present, the crystalline polymer material for SLS mainly contains nylon (PA), polyethylene wax etc.
Nylon 12 (Polyamide12, PA12) is a kind of semi-crystalline thermoplastic, and fusing point is 170 ~ 180 DEG C, and forming process is easy, mold temperature a wider range.Nylon 12 snappiness, chemical stability, oil-proofness, wear resistance are all better, are widely used in water flowmeter and other business equipment, as optical fiber, cable joint-box, mechanical cam, automobile, slide mechanism and bearing etc.Nylon 12 powder, through the laser sintered profiled member that can obtain high-compactness, high strength, directly can be used as functional part.But nylon 12 preheating temperature in SLS forming process is high, very easily degradation with aging occurs; Preheating temperature window narrows (1 ~ 2 DEG C) in addition, profiled member is buckling deformation very easily.This just causes nylon 12SLS complex forming technology, is difficult to promote, and more can not be applied on domestic large table top SLS equipment.
The shaping nylon plastic functional part of SLS has that intensity is high, speed fast, without the need to advantages such as aftertreatments, therefore nylon powder material has become the Main way of SLS material development.But the SLS preheating temperature of existing commercial nylon powder is high, preheating temperature window narrows, at home still unrealized commercialization, and Problems existing is embodied in:
(1) preheating temperature too high (160-180 DEG C), causes the also corresponding rising of the bulk temperature of SLS equipment.And laser and galvanometer scanning system etc. thereof generally all require to work under lesser temps (room temperature), high temperature preheating is very unfavorable to the stability of SLS equipment, very easily causes galvanometer laser scanning system to occur the problems such as temperature drift.
(2) preheating temperature window narrows (1 ~ 2 DEG C), requires the powder bed homogeneous temperature of SLS equipment, and can accurate temperature controlling.This not only significantly improves the cost of SLS equipment, also very difficult on technology realizes.The equipment of the Direct Laser sintered nylon that 3D Systems, EOS release is subtable face, still can not realize laser sintered on large counter-top device of nylon, and the SLS equipment that quick manufacturing center of the Central China University of Science and Technology sells in recent years is the SLS equipment of large work top.
(3) under high temperature, nylon powder is easily aging, causes the mechanical property of SLS product to decline to a great extent, laser sintered penalty.Aging for avoiding, all there is strict requirement, all at N to atmosphere when laser sintered nylon abroad
2carry out under gas shielded, and the oxygen level in strict controlled atmosphere.Nonetheless, the new powder at least adding 30% is still required.The price of nylon powder is high, and it is a kind of waste seriously that a large amount of powder can not recycle, domestic enterprise's this high working cost beyond affordability, makes SLS technology lose competitive edge directly preparing in plastic functional piece.The SLS equipment of existing domestic-developed is all run in air atmosphere, therefore more cannot meet the requirement of laser sintered nylon powder.
(4) warm up time before nylon powder shaping is long, and the cooling program after shaping is also very strict, thus makes forming period long, reduces the utilization ratio of SLS equipment.
(5) because preheating temperature is close to the fusing point of nylon, the crystallization enthalpy of nylon is very huge, during shaping, the storage effect of heat is fairly obvious, sintered compact surrounding powder is fusing or caking very easily therefore, unnecessary heat is taken away by body of must ventilating, and laser power, preheating temperature all will change with the change of sintering cross-sectional shape structure, operate very complicated, can not automatization be realized, be difficult to be generalized in production.
The disclosed patented technology about selective laser sintering nylon powder has at present:
1, a kind of method-application number preparing selective laser sintering nylon powder: 201010597529.8
2. for the nylon powder powder material – application number of speed laser sintered products: 02110361.5
3. nylon composite powder material-the application number for selective laser sintering: 201010239448.0
4. based on the nylon/aluminum powder composite powdery material-application number of selective laser sintering: 201010251726.4
5. preparation method-the application number of a nylon coating film metal powder material: 200710051795.9
6. preparation method-the application number of a nylon tectorial membrane ceramics powder material: 200710051863.1
All cannot reach above requirement.For these reasons, the commercialization of existing nylon powder on home equipment be realized still very difficult.
Summary of the invention
The object of the invention is for above-mentioned deficiency of the prior art, provide a kind of low temperature nylon powder material for selective laser sintering, it has, and low, the pre-thermal window of preheating temperature is wide, ageing resistance good, is applicable to the feature of all size table top.
Another goal of the invention of the present invention is to provide a kind of preparation method of the low temperature nylon powder material for selective laser sintering, and it has, and output is high, good toughness, uniform particle sizes, the feature of good sphericity.
Object of the present invention is achieved through the following technical solutions:
For a low temperature nylon powder material for selective laser sintering, be made up of the raw material of following weight part:
100 parts, nylon 12 particle,
SL-AH 0.5-2 part,
Amino-end peg 10-20 part,
Deuterated trifluoroacetic acid 5-15 part,
Oxidation inhibitor 0.1-0.5 part,
Solvent 101-135 part,
Nucleator 0.1-0.5 part,
Softening agent 5-15 part,
Silane coupling agent 0.5-1 part.
The present invention utilizes SL-AH, amino-end peg, deuterated trifluoroacetic acid can synthetic nylon soft section of polymkeric substance, synthesizes obtain a kind of nylon elastomer with nylon, tensile strength and impact strength at low temperature high, snappiness is good, and elastic recovery rate is high; Second-order transition temperature is low, under the low temperature environment of-40 ~ 0 DEG C, shock strength and snappiness still can be kept not to change; Flexibility change is little, and fusing point is high, and vicat softening temperature is high.
Further, a kind of low temperature nylon powder material for selective laser sintering, is made up of the raw material of following weight part:
100 parts, nylon 12 particle
SL-AH 1-1.5 part
Amino-end peg 13-18 part
Deuterated trifluoroacetic acid 8-12 part
Oxidation inhibitor 0.2-0.4 part
Solvent 105-120 part.
Nucleator 0.2-0.4 part
Softening agent 8-13 part
Silane coupling agent 0.7-1 part.
Wherein, described oxidation inhibitor is made up of phenols or phosphorous acid lipid or thioesters class.The present invention with the addition of specific oxidation inhibitor, effectively can slow down the ageing progress of material, and laser sintered through repeatedly of material of the present invention, still has good shock strength and tensile strength.Phenolic antioxidant is antioxidant 1010 or antioxidant 1076, and phosphite kind antioxidant is oxidation inhibitor 3010, and sulphur ester antioxidant is anti-oxidant DLTP.
Wherein, described solvent is made up of ethanol, butanone, glycol ether, water.Solvent of the present invention combines organic solvent and inorganic solvent, effectively can improve mobility and the consistency of material when building-up reactions, makes the overall performance of material more stable.
Wherein, ethanol 90 ~ 100 parts in described solvent, butanone 5 ~ 15 parts, glycol ether 1 ~ 5 part, 5 ~ 15 parts, water, the specific blending ratio of ethanol, butanone, glycol ether and water can improve mixing uniformity and the stability of material further.
Wherein, described softening agent is one or more the mixture in hexylene glycol, glycerine, p-Hydroxybenzoate, sulphonamide.The present invention, can the flexural strength of strongthener in conjunction with softening agent, improves the mechanical property of material.
Wherein, described nucleator is any one in silicon-dioxide, oildag, lithium fluoride, boron nitride, aluminum borate.Being added with of nucleator is beneficial to the one-tenth nuclear reaction of various component and the mixing of material, improves the stability of material.
For a preparation method for the low temperature nylon powder material of selective laser sintering, comprise following preparation process:
Step one, SL-AH and nylon 12 mix particles evenly to be loaded in reactor, add in reactor by amino-end peg, deuterated trifluoroacetic acid, sealing, vacuumizes, is filled with carbonic acid gas, and make reactor original pressure be 0.1-0.3MPa.
Step 2: heating, makes reactor be warming up to 170-190 DEG C gradually, opens and stirs, continue to be warming up to 190-210 DEG C, opens drain tap, still internal pressure is down to 1.3-1.5 MPa, keeps 0.4-0.6 hour.Slowly uniform step-down, made reacting kettle inner pressure be down to normal pressure in 1.8-2.2 hour, kept 0.4-0.7 hour at ambient pressure, stopped stirring, and was taken out by product and put into cold rinse bank, finally dried and obtained product.
Step 3: above-mentioned product and oxidation inhibitor, solvent, nucleator, softening agent are dropped in reactor together with silane coupling agent; close kettle cover, process is vacuumized to reactor, and passes into nitrogen replacement protection; reactor is slowly warming up to 150-190 DEG C, and is incubated 2-3 hour.
Step 4: open to stir and kettle temperature is down to room temperature, take out material, in powder, add displacer after dry 10-12 hour in atmosphere and carry out ball milling 3-4 hour, then the powder crossed by ball milling is put into vacuum drying oven and dried 46-48 hour, can obtain the powder of sphericity, good fluidity.
Wherein, described displacer is one or both the mixing with water in acetone or methyl alcohol, preferably, and acetone in displacer: methyl alcohol=2:3:8.
More specifically, a kind of preparation method of the low temperature nylon powder material for selective laser sintering: comprise following preparation process:
Step one, SL-AH and nylon 12 mix particles evenly to be loaded in reactor, add in reactor by amino-end peg, deuterated trifluoroacetic acid, sealing, vacuumizes, is filled with carbonic acid gas, and make reactor original pressure be 0.2MPa.
Step 2: heating, make reactor be warming up to 180 DEG C gradually, open and stir, continue to be warming up to 200 DEG C, open drain tap, still internal pressure is down to 1.4MPa, keeps slowly uniform step-down in 0.5 hour, make reacting kettle inner pressure be down to normal pressure in 2 hours, keep 0.5 hour at ambient pressure, stop stirring, product is taken out and puts into cold rinse bank, finally dry and obtain product.
Step 3: by above-mentioned product and oxidation inhibitor, solvent, nucleator, softening agent and silane coupling agent; close kettle cover, process is vacuumized to reactor, and pass into nitrogen and pass into nitrogen replacement and protect for 3 times; reactor is slowly warming up to 150-190 DEG C, and is incubated 2-3 hour.
Step 4: open to stir and kettle temperature is down to room temperature, take out material, in powder, add displacer after dry 10-12 hour in atmosphere and carry out ball milling 4 hours, then the powder crossed by ball milling puts into vacuum drying oven oven dry 48 hours, can obtain the powder of sphericity, good fluidity.
Beneficial effect of the present invention is: a kind of low temperature nylon powder material for selective laser sintering of the application, there is sectional type block nylon copolymer and the nylon elastomer of soft section, for selective laser sintering, material of the present invention has following characteristic: tensile strength and impact strength at low temperature high, snappiness is good, and elastic recovery rate is high; Second-order transition temperature is low, under the low temperature environment of-40 ~ 0 DEG C, shock strength and snappiness still can be kept not to change; Flexibility change is little, and fusing point is high, and vicat softening temperature is high.Therefore, be suitable at high temperature using, under the thermoplastic elastomer of other kind even can not carry out the hot conditions of testing, nylon elastomer of the present invention still can keep good tensile property.Concrete, the present invention also has the following advantages:
1. preheating temperature: have lower preheating temperature (120-150 DEG C) and wider preheating temperature window (20-40 DEG C), add the recovery utilization rate of powder largely, low to the accuracy requirement of SLS equipment, the cost of SLS equipment can be reduced, and more can maintain the stability of SLS equipment.
2. anti-aging: to have stronger antioxidant, add the recovery utilization rate of powder largely, reduce production cost, enhance productivity.
3. high tenacity.
4. uniform particle sizes, good sphericity.
Another beneficial effect of the present invention is: present method has prepared a kind of sectional type block nylon copolymer and nylon elastomer with soft section, for selective laser sintering, production capacity is high, the excellent combination property of nylon material, is applicable to the countertop fixture of existing all size size.
Embodiment
For the ease of the understanding of those skilled in the art, below in conjunction with embodiment, the present invention is further illustrated, and the content that embodiment is mentioned not is limitation of the invention.
embodiment 1
A kind of preparation method of the low temperature nylon powder material for selective laser sintering: comprise following preparation process:
Step one, SL-AH and nylon 12 mix particles evenly to be loaded in reactor, add in reactor by amino-end peg, deuterated trifluoroacetic acid, sealing, vacuumizes, is filled with carbonic acid gas, and make reactor original pressure be 0.2MPa.
Step 2: heating, make reactor be warming up to 180 DEG C gradually, open and stir, continue to be warming up to 200 DEG C, open drain tap, still internal pressure is down to 1.4MPa, keeps slowly uniform step-down in 0.5 hour, make reacting kettle inner pressure be down to normal pressure in 2 hours, keep 0.5 hour at ambient pressure, stop stirring, product is taken out and puts into cold rinse bank, finally dry and obtain product.
Step 3: by above-mentioned product and oxidation inhibitor, solvent, nucleator, softening agent and silane coupling agent; close kettle cover, process is vacuumized to reactor, and pass into nitrogen and pass into nitrogen replacement and protect for 3 times; reactor is slowly warming up to 150 DEG C, and is incubated 3 hours.
Step 4: open to stir and kettle temperature is down to room temperature, take out material, in powder, add displacer after dry 10 hours in atmosphere and carry out ball milling 4 hours, then the powder crossed by ball milling puts into vacuum drying oven oven dry 48 hours, can obtain the powder of sphericity, good fluidity.
The each ingredients weight parts of the present embodiment is respectively:
100 parts, nylon 12 particle
SL-AH 0.5 part
Amino-end peg 20 parts
Deuterated trifluoroacetic acid 5 parts
Antioxidant 1010 0.5 part
Solvent 101 parts, comprises ethanol 90 parts, butanone 5 parts, glycol ether 1 part, 5 parts, water
Silicon-dioxide 0.1 part
Hexylene glycol 15 parts
Silane coupling agent 1 part.
embodiment 2
A kind of preparation method of the low temperature nylon powder material for selective laser sintering: comprise following preparation process:
Step one, SL-AH and nylon 12 mix particles evenly to be loaded in reactor, add in reactor by amino-end peg, deuterated trifluoroacetic acid, sealing, vacuumizes, is filled with carbonic acid gas, and make reactor original pressure be 0.3MPa.
Step 2: heating, make reactor be warming up to 190 DEG C gradually, open and stir, continue to be warming up to 210 DEG C, open drain tap, still internal pressure is down to 1.3MPa, keeps slowly uniform step-down in 0.4 hour, make reacting kettle inner pressure be down to normal pressure in 1.8 hours, keep 0.7 hour at ambient pressure, stop stirring, product is taken out and puts into cold rinse bank, finally dry and obtain product.
Step 3: by above-mentioned product and oxidation inhibitor, solvent, nucleator, softening agent and silane coupling agent; close kettle cover, process is vacuumized to reactor, and pass into nitrogen and pass into nitrogen replacement and protect for 3 times; reactor is slowly warming up to 150 DEG C, and is incubated 2 hours.
Step 4: open to stir and kettle temperature is down to room temperature, take out material, in powder, add displacer after dry 10 hours in atmosphere and carry out ball milling 4 hours, then the powder crossed by ball milling puts into vacuum drying oven oven dry 48 hours, can obtain the powder of sphericity, good fluidity.
The each ingredients weight parts of the present embodiment is respectively:
100 parts, nylon 12 particle
SL-AH 2 parts
Amino-end peg 10 parts
Deuterated trifluoroacetic acid 15 parts
3,010 0.1 parts, oxidation inhibitor
Solvent 135 parts, comprises ethanol 100 parts, butanone 15 parts, glycol ether 5 parts, 15 parts, water
Lithium fluoride 0.5 part
P-Hydroxybenzoate 5 parts
Silane coupling agent 0.5 part.
embodiment 3
A kind of preparation method of the low temperature nylon powder material for selective laser sintering: comprise following preparation process:
Step one, SL-AH and nylon 12 mix particles evenly to be loaded in reactor, add in reactor by amino-end peg, deuterated trifluoroacetic acid, sealing, vacuumizes, is filled with carbonic acid gas, and make reactor original pressure be 0.1MPa.
Step 2: heating, make reactor be warming up to 170 DEG C gradually, open and stir, continue to be warming up to 190 DEG C, open drain tap, still internal pressure is down to 1.5MPa, keeps slowly uniform step-down in 0.6 hour, make reacting kettle inner pressure be down to normal pressure in 2.2 hours, keep 0.4 hour at ambient pressure, stop stirring, product is taken out and puts into cold rinse bank, finally dry and obtain product.
Step 3: by above-mentioned product and oxidation inhibitor, solvent, nucleator, softening agent and silane coupling agent; close kettle cover, process is vacuumized to reactor, and pass into nitrogen and pass into nitrogen replacement and protect for 3 times; reactor is slowly warming up to 190 DEG C, and is incubated 2 hours.
Step 4: open to stir and kettle temperature is down to room temperature, take out material, in powder, add displacer after dry 12 hours in atmosphere and carry out ball milling 3 hours, then the powder crossed by ball milling puts into vacuum drying oven oven dry 46 hours, can obtain the powder of sphericity, good fluidity.
The each ingredients weight parts of the present embodiment is respectively:
100 parts, nylon 12 particle
SL-AH 1.5 parts
Amino-end peg 18 parts
Deuterated trifluoroacetic acid 8 parts
Anti-oxidant DLTP 0.2 part
Solvent 105 parts, comprises ethanol 90 parts, butanone 8 parts, glycol ether 2 parts, 5 parts, water
Aluminum borate 0.2 part
Sulphonamide 13 parts
Silane coupling agent 0.7 part.
embodiment 4
A kind of preparation method of the low temperature nylon powder material for selective laser sintering: comprise following preparation process:
Step one, SL-AH and nylon 12 mix particles evenly to be loaded in reactor, add in reactor by amino-end peg, deuterated trifluoroacetic acid, sealing, vacuumizes, is filled with carbonic acid gas, and make reactor original pressure be 0.3MPa.
Step 2: heating, make reactor be warming up to 175 DEG C gradually, open and stir, continue to be warming up to 205 DEG C, open drain tap, still internal pressure is down to 1.4MPa, keeps slowly uniform step-down in 0.5 hour, make reacting kettle inner pressure be down to normal pressure in 2 hours, keep 0.6 hour at ambient pressure, stop stirring, product is taken out and puts into cold rinse bank, finally dry and obtain product.
Step 3: by above-mentioned product and oxidation inhibitor, solvent, nucleator, softening agent and silane coupling agent; close kettle cover, process is vacuumized to reactor, and pass into nitrogen and pass into nitrogen replacement and protect for 3 times; reactor is slowly warming up to 170 DEG C, and is incubated 2.5 hours.
Step 4: open to stir and kettle temperature is down to room temperature, take out material, in powder, add displacer after dry 12 hours in atmosphere and carry out ball milling 3 hours, then the powder crossed by ball milling puts into vacuum drying oven oven dry 48 hours, can obtain the powder of sphericity, good fluidity.
The each ingredients weight parts of the present embodiment is respectively:
100 parts, nylon 12 particle
SL-AH 1 part
Amino-end peg 13 parts
Deuterated trifluoroacetic acid 12 parts
Antioxidant 1076 0.4 part
Solvent 120 parts, comprises alcohol 95 part, butanone 10 parts, glycol ether 5 parts, 10 parts, water
Oildag 0.4 part
Glycerine 8 parts
Silane coupling agent 1 part.
performance test 1:
Low temperature nylon powder material the present invention prepared carries out agglutinating test on the equipment of varying mesa dimensions, obtains following experimental data:
Upper table describes the contrast of nylon elastomer preheating temperature and agglomeration temperature on the table top of different size, and nylon material of the present invention is applicable all equally at the worktable of large table top or little table top, and preheating temperature is low, and pre-thermal window money is wide.
performance test 2:
Pure PA12 and low temperature nylon powder material of the present invention are sintered into table sample and test it by SLS equipment, obtains following experimental data:
| Kind | Sintered density (g/cm 3） | Tensile strength (MPa) | Shock strength (KJ/m 2) | Flexural strength (MPa) | Modulus in flexure (GPa) |
| Pure nylon 12 | 0.96 | 44.0 | 37.2 | 50.8 | 1.14 |
| Nylon alloy | 0.93 | 29.8 | 48.6 | 34.9 | 0.87 |
The density of the sintered specimen of low temperature nylon powder material of the present invention, tensile strength, flexural strength, modulus in flexure can be obtained compared with pure nylon 12 SLS sample according to upper table, there is significant decline, but shock strength rises, and nylon powder of the present invention has obvious toughening effect to integral piece.
performance test 3:
Carry out 3 processing experiments to low temperature nylon powder material of the present invention, test-results is as follows:
As can be seen from above table, nylon powder of the present invention, laser sintered through three times, still keeps good mechanical property.
Above-described embodiment is the present invention's preferably implementation, and in addition, the present invention can also realize by alternate manner, and any apparent replacement is all within protection scope of the present invention without departing from the inventive concept of the premise.
Claims (10)
1., for a low temperature nylon powder material for selective laser sintering, it is characterized in that: be made up of the raw material of following weight part:
100 parts, nylon 12 particle
SL-AH 0.5-2 part
Amino-end peg 10-20 part
Deuterated trifluoroacetic acid 5-15 part
Oxidation inhibitor 0.1-0.5 part
Solvent 101-135 part
Nucleator 0.1-0.5 part
Softening agent 5-15 part
Silane coupling agent 0.5-1 part.
2. a kind of low temperature nylon powder material for selective laser sintering according to claim 1, is characterized in that: be made up of the raw material of following weight part:
100 parts, nylon 12 particle
SL-AH 1-1.5 part
Amino-end peg 13-18 part
Deuterated trifluoroacetic acid 8-12 part
Oxidation inhibitor 0.2-0.4 part
Solvent 105-120 part
Nucleator 0.2-0.4 part
Softening agent 8-13 part
Silane coupling agent 0.7-1 part.
3. a kind of low temperature nylon powder material for selective laser sintering according to claim 1, is characterized in that: described oxidation inhibitor is made up of phenols and phosphorous acid lipid or phenols and thioesters class.
4. a kind of low temperature nylon powder material for selective laser sintering according to claim 1, is characterized in that: described solvent is made up of ethanol, butanone, glycol ether, water.
5. a kind of low temperature nylon powder material for selective laser sintering according to claim 4, is characterized in that: ethanol 90 ~ 100 parts in described solvent, butanone 5 ~ 15 parts, glycol ether 1 ~ 5 part, 5 ~ 15 parts, water.
6. a kind of low temperature nylon powder material for selective laser sintering according to claim 1, is characterized in that: described softening agent is one or more the mixture in hexylene glycol, glycerine, p-Hydroxybenzoate, sulphonamide.
7. a kind of low temperature nylon powder material for selective laser sintering according to claim 1, is characterized in that: described nucleator is any one in silicon-dioxide, oildag, lithium fluoride, boron nitride, aluminum borate.
8. the preparation method of a kind of low temperature nylon powder material for selective laser sintering described in claim 1-7 any one, is characterized in that: comprise following preparation process:
Step one, SL-AH and nylon 12 mix particles evenly to be loaded in reactor, add in reactor by amino-end peg, deuterated trifluoroacetic acid, sealing, vacuumizes, is filled with carbonic acid gas, and make reactor original pressure be 0.1-0.3MPa;
Step 2: heating, makes reactor be warming up to 170-190 DEG C gradually, opens and stirs, continue to be warming up to 190-210 DEG C, open drain tap, still internal pressure is down to 1.3-1.5 MPa, keep 0.4-0.6 hour, slowly uniform step-down, make reacting kettle inner pressure be down to normal pressure in 1.8-2.2 hour, keep 0.4-0.7 hour at ambient pressure, stop stirring, product is taken out from reactor and puts into cold rinse bank, finally dry and obtain product;
Step 3: above-mentioned product and oxidation inhibitor, solvent, nucleator, softening agent are dropped in reactor together with silane coupling agent, close kettle cover, process is vacuumized to reactor, and passes into nitrogen replacement protection, reactor is slowly warming up to 150-190 DEG C, and is incubated 2-3 hour;
Step 4: open to stir and kettle temperature is down to room temperature, take out material, in powder, add displacer after dry 10-12 hour in atmosphere, carry out ball milling 3-4 hour, again the powder that ball milling is crossed is put into vacuum drying oven and dry 46-48 hour, obtain powder-product.
9. the preparation method of a kind of low temperature nylon powder material for selective laser sintering according to claim 8, is characterized in that: described displacer is one or both the mixing with water in acetone or methyl alcohol.
10. the preparation method of a kind of low temperature nylon powder material for selective laser sintering according to claim 8, is characterized in that: comprise following preparation process:
Step one, SL-AH and nylon 12 mix particles evenly to be loaded in reactor, add in reactor by amino-end peg, deuterated trifluoroacetic acid, sealing, vacuumizes, is filled with carbonic acid gas, and make reactor original pressure be 0.2MPa;
Step 2: heating, makes reactor be warming up to 180 DEG C gradually, opens and stirs, continue to be warming up to 200 DEG C, open drain tap, still internal pressure is down to 1.4MPa, keeps after 0.5 hour, continue slowly uniform step-down, make reacting kettle inner pressure be down to normal pressure in 2 hours, keep 0.5 hour at ambient pressure, stop stirring, product is taken out and puts into cold rinse bank, finally dry and obtain product;
Step 3: above-mentioned product and remaining reaction thing oxidation inhibitor, solvent, nucleator, softening agent, silane coupling agent are dropped in reactor together, close kettle cover, process is vacuumized to reactor, and pass into nitrogen and pass into nitrogen replacement and protect for 3 times, reactor is slowly warming up to 150-190 DEG C, and is incubated 2-3 hour;
Step 4: open to stir and kettle temperature is down to room temperature, take out material, add displacer after dry 10-12 hour in powder in atmosphere and carry out ball milling 4 hours, then the powder crossed by ball milling puts into vacuum drying oven oven dry 48 hours, obtains powder-product.
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| PCT/CN2016/088738 WO2017000923A1 (en) | 2015-06-30 | 2016-07-05 | Low-temperature nylon powder material for selective laser sintering and preparation method therefor |
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