CN104031262B - A kind of high molecular weight nylon powder body that can be applicable to 3D printing and preparation method thereof - Google Patents
A kind of high molecular weight nylon powder body that can be applicable to 3D printing and preparation method thereof Download PDFInfo
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Abstract
The high molecular weight nylon powder body that the present invention relates to a kind of 3D of can be used for printing is characterized in that, it is characterized in that, described powder composition is that the aggregated reaction of the raw material by following weight portion obtains, and on the basis of the weight portion of lactam monomers, wherein raw material includes: lactams: 100 weight portions；Base catalyst: 0.005 1 weight portions；Activator: 0.01 2 weight portions；Antioxidant: 0.1 1 weight portions.The present invention also provides for the preparation method and applications of above-mentioned powder composition.It is adjustable in 5～900,000 that the nylon powder body of the present invention has viscosity-average molecular weight, and powder particle particle diameter is controlled at 20～100 microns, and particle size distribution is homogeneous, production technology environmental protection, and the nylon powder body of preparation can be used for 3D and prints.
Description
Technical field
The present invention relates to a kind of high molecular weight nylon powder body and preparation method thereof, be specifically related to one and can be used for
High molecular weight nylon powder body that 3D prints and preparation method thereof.
Background technology
3D printing technique, also known as layered manufacturing technology, is a kind of emerging technology in rapid shaping field, it
A kind of based on mathematical model file, use powdery metal or plastics etc. can jointing material, logical
The technology of constructed object is carried out after the mode successively printed.Ultimate principle is layered manufacturing, successively increases material
Material generates the technology of 3D solid.At present, 3D printing technique is applied primarily to product prototype, mould
Tool manufactures and the field such as artistic creation, jewelry-making, substitutes the retrofit work that these tradition rely on
Skill.It addition, 3D printing technique is gradually applied to medical science, biological engineering, building, clothing, aviation etc.
Field, has opened up wide space for innovation.
The polymeric material that melted extrusion modeling forming technique is more common in the market is acrylonitrile one fourth
Diene one styrene copolymer (ABS), polylactic acid (PLA), nylon (PA) and Merlon (PC),
Wherein nylon is the printing raw material that current consumption is maximum.
3D printing technique mainly includes the techniques such as SLA, FDM, SLS, LOM.Wherein fused glass pellet
Technology (FDM) and selective laser sintering (SLS) technology all can use thermoplastic to beat as basic 3D
Printed material material.
Generally SLS technology and equipment uses transmitting focusing in the laser of the energy of target area.Producing parts
Target area in or the dusty material that soften melted in the effect lower part of the energy launched by laser.Behaviour
When making, powder is connect the quantity of irradiated laser energy and should be enough to quickly form part sheets, thus is implementing
Target sublimity must be heated by laser pre-irradiation, powder is preheating to the temperature of slightly less than its fusing point, so
After under the effect striking off rod, powder is paved；Laser beam is under the control of the computer according to layering cross section information
Sinter selectively, one layer complete after carry out next layer of sintering again, it is unnecessary to remove after all having sintered
Powder, then can obtain a part sintered.
Specifically, SLS equipment include a kind of before powder bed is exposed to laser energy on the target surface
Deposit that one layer smooth, the device of the dusty material of level.By a manipulation connecting CAD/CAM system
It is selected to control laser energy and launch and to be confined to that light is scanned the computer forming parts " thin slice "
Target area part.After dusty material irradiates the ground floor " thin slice " of formation parts, by dusty material
The second layer be deposited in target area.The laser handled by CAD/CAM program rescans target area
The part only exposed in territory, obtains the second layer " thin slice " of parts.Constantly repeat the method until parts "
Sheet connects a piece of " build up and form complete parts.
Owing to the various performances of sinterable powder are guaranteeing that selective laser sintering process exists in an action pane
There is very important effect.It is to say, make polymer beads soften under high temperature to a certain degree
Phenomenon reduce to bottom line so that powder can be stored in the target environment being heated and don't cause granule
There is melting phenomenon, until energy quickly to be concentrated by the laser beam scanned the granule being supplied to be heated later.
Owing to SLS forming method has manufacturing process simple, degree of flexibility is high, material selection range is wide, material
Low price, the features such as low cost, stock utilization are high, and shaping speed is fast, for above feature SLS method
It is mainly used in foundry industry, and can be used to directly make fast mould.
Exploitation is adapted to the raw material of above-mentioned 3D printing technique, has become the emphasis that current various countries are studied.
In nylon material, at present in only in the nylon 12 of low-molecular-weight be largely used to 3D and printed,
But the cost of nylon 12 powder is high.So other kind powder material of developing low-cost, high performance nylon
Material tool is of great significance.
Summary of the invention
Printing, for current 3D, the shortcoming that nylon powder body description of materials is few, the present invention utilizes anionic polymerization
Prepare the nylon powder body material that can be used for the high molecular that 3D prints.
An object of the present invention is to provide a kind of high molecular weight nylon powder body material that can be used for 3D printing.
The two of the purpose of the present invention are that lactam monomers carries out anionic polymerisation, the nylon of preparation high molecular
Powder body, thus provide a kind of and can be used for the high molecular weight nylon raw powder's production technology that 3D prints.
The present invention is to utilize anionic polymerisation principle, makes lactam monomers under conditions of base catalyst exists
There is polyreaction, prepare nylon powder.Powder body prepared by the method, can perform well in secondary
Type.Pulverize with low temperature powder, compared with solvent precipitation technique, there is low cost, the advantage such as pollution-free.The present invention
The nylon powder of the high molecular of preparation, viscosity-average molecular weight is adjustable in 5～900,000, and powder particle particle diameter exists
20～100 microns controlled, and particle size distribution is homogeneous, production technology environmental protection, the nylon powder body of preparation
It is applicable to 3D and prints technique.
The present invention is achieved through the following technical solutions:
A kind of nylon powder composition printed for 3D, it is characterised in that described powder body material is by following
The aggregated reaction of raw material of weight portion obtains, and on the basis of the weight portion of lactam monomers, wherein raw material includes:
According to the present invention, described powder composition is that the raw material by following weight portion carries out melting in situ after mixing
Melt anionic polymerisation to obtain.
Described lactams is selected from caprolactam, ten lactams, one or more in lauric lactam.
According to the present invention, described base catalyst selected from sodium hydroxide, potassium hydroxide, magnesium hydroxide,
One or more in Sodium ethylate and Feldalat NM.
According to the present invention, described activator selected to benzene 2,4-diisocyanate (TDI), lek receive glue,
Hexamethylene diisocyanate (HDI), '-diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate
One or several in cyanate (PAPI), triphenylmethane triisocyanate (JQ-1 glue) and diphenyl carbonate
Kind.
According to the present invention, described antioxidant is selected from antioxidant 1010: four [β-(3,5-di-t-butyl-4-hydroxy benzeness
Base) propanoic acid] pentaerythritol ester；Antioxidant 1096:IRGANOX B-1096；Antioxidant 1098:(N, N'-
Double-(3-(3,5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine) and phosphite ester kind antioxidant interworking thing；
Irgasfos 168: one or more in three [2.4-di-tert-butyl-phenyl] phosphite ester.Antioxidant is possible to prevent
In 3D print procedure, because high temperature causes the decomposition of nylon.
According to the present invention, in described nylon powder composition, the viscosity-average molecular weight of nylon is 5-90 ten thousand, macromolecule
Amount is conducive to the raising of the performances such as product mechanics.Preferably, the molecular weight of described nylon is 10-80 ten thousand, or
15-70 ten thousand, 20-60 ten thousand, it is also possible to for 30-40 ten thousand.
According to the present invention, in described nylon powder composition, the particle diameter of nylon is 20～100 microns, this particle diameter model
Enclose beneficially 3D processing technique.Particle diameter is preferably 25-90 micron, or 30-80 micron, 40-70 micron, also may be used
Think 50-60 micron.
According to the present invention, the amount of being preferably added to of described base catalyst is 0.007-0.8, it is also possible to for 0.05-0.5,
0.1-0.2 weight portion.
According to the present invention, the amount of being preferably added to of described antioxidant is: 0.2-0.8 weight portion, it is also possible to for 0.3-0.5
Weight portion.
According to the present invention, the amount of being preferably added to of described activator is 0.1-1.5 weight portion, 0.2-1 weight portion, also
It can be 0.5-0.8 weight portion.
The present invention also provides for the preparation method of a kind of above-mentioned nylon powder composition, it is characterised in that described side
Method includes:
(1) on the basis of the weight portion of lactam monomers, the lactam monomers of 100 weight portions is joined appearance
In device, it is dehydrated under vacuum conditions；
(2) it is subsequently adding base catalyst and the antioxidant of 0.1～1 weight portion of 0.005～1 weight portion, continues
Continuous evacuation, is warming up to 130～140 DEG C；
(3) insulation reaction 10～after 30 minutes, adds the activator of 0.01～2 weight portions, and stirring to mixing is all
Even；
(4) mixture after step (3) being stirred is poured into equipped with being pre-heated to 150～170 DEG C of solid particles
In container, after insulation is stirred vigorously a period of time, it is down to room temperature,
(5) passing through method for separating, it is thus achieved that molecular weight is 5～1,200,000, particle diameter is the heat conduction of 20～100 microns
Nylon powder composition.
According to the present invention, described method specifically includes following steps:
(1) on the basis of the weight portion of lactam monomers, the lactam monomers of 100 weight portions is joined appearance
In device, evacuation at temperature is 90～120 DEG C, it is dehydrated under vacuum conditions；
(2) pressure of the system shown in gauge < during 400Pa, releases vacuum, adds 0.005～1 weight
The base catalyst of part and the antioxidant of 0.1～1 weight portion, continue evacuation, be warming up to 130～140 DEG C；
(3) system shown by gauge pressure < during 400Pa, insulation reaction 10～30 minutes, solve
Except vacuum, add the activator of 0.01～2 weight portions, stir,
(4) mixture after step (3) being stirred is poured into equipped with the solid particle being preheated to 150～170 DEG C
Container in, be stirred vigorously 10～30 minutes, be naturally down to 25 DEG C；
(5) by method for separating, the viscosity-average molecular weight nylon powder composition at 5-90 ten thousand is obtained.
In said method, solid particle is used to will assist in lactam monomers in molecular weight propagation process, no
Can be mutually bonded.Simultaneously in the method for separating of step (5), solid particle can be sub-elected, thus
This granule is reused.
According to the present invention, described solid particle can be recycled.
According to the present invention, the particle diameter of described solid particle is 1～50 micron.
According to the present invention, the magnetic material powder such as described solid particle chosen from Fe, nickel, cobalt or selected from quartz
One or more in sand, silica dioxide granule and Machine-made Sand.
According to the present invention, the screening installation used in step (5) selected from Magnet Separater, suction type aspirator and
One in cycle winnowing device.
The present invention also provides for the application of above-mentioned nylon powder body, it is characterised in that described nylon powder body is applied to 3D
Printing technique, wherein, described nylon powder body is selected from the nylon powder body of the invention described above.
The present invention also provides for a kind of 3D Method of printing, it is characterised in that use the nylon powder body conduct of the present invention
Printed material.
According to the present invention, described Method of printing comprises the steps:
(1) the nylon powder composition of the present invention is deposited on carrier surface, and coverage goal region；
(2) described nylon powder composition is flattened, form a smooth surface；
(3) by energetic beam illumination to target area, described powder body is made to form an integral layer；With
(4) step (1)～(3) is repeated, to form overall and neighboring layers bonding other each layer, from
And obtain three-dimensional article.
The nylon powder body of the present invention, through lactams in the presence of base catalyst and activator, divides at solid
Forming through anionic polymerisation in scattered seed, compared with what slurry polymerization, the powder granule surface with preparation is miscellaneous
Matter is few, size tunable, and molecular weight is high, prints for 3D, the product mechanical property of preparation and dimensional stability
Can be more preferably.
Detailed description of the invention
Below by way of detailed description of the invention, the present invention is described in further detail, but should this be interpreted as
The scope of the present invention is only limitted to Examples below.In the case of without departing from said method thought of the present invention, root
The various replacements made according to ordinary skill knowledge and customary means or change, should be included in the present invention
In the range of.
Embodiment 1
On the basis of the weight portion of caprolactam monomer, the caprolactam monomer of 100 weight portions is joined appearance
In device, evacuation at temperature is 90 DEG C, it is dehydrated under vacuum conditions, the system shown in gauge
Pressure < during 400Pa, release vacuum, add the anti-of the sodium hydroxide of 0.005 weight portion and 0.1 weight portion
Oxygen agent 1010, continues evacuation, is warming up to 130 DEG C, the pressure < 400Pa of the system shown by gauge
Time, insulation reaction 10 minutes, add 0.01 weight portion to benzene 2,4-diisocyanate, stirring to mixing is all
Even, to pour into equipped with in the container of the quartz sand that particle diameter is 1 micron being pre-heated to 160 DEG C, insulation is stirred vigorously
10 minutes, it is naturally cooling to 25 DEG C, afterwards by using suction type aspirator method for separating, obtains viscosity-average molecular weight
Being 900,000, particle diameter is the nylon powder body of 20-30 micron, and by gained powder body, Method of printing comprises the steps:
(1) nylon powder composition is deposited on carrier surface, and coverage goal region；
(2) nylon powder composition is flattened, form a smooth surface；
(3) by energetic beam illumination to target area, described powder body is made to form an integral layer；With
(4) step (1)～(3) is repeated, to form overall and neighboring layers bonding other each layer, from
And obtain three-dimensional article.Its 3D prints product properties and is shown in Table 1.
Embodiment 2
On the basis of the weight portion of caprolactam monomer, the caprolactam monomer of 100 weight portions is joined appearance
In device, evacuation at temperature is 100 DEG C, it is dehydrated under vacuum conditions, the system shown in gauge
Pressure < during 400Pa, release vacuum, add the anti-of the potassium hydroxide of 0.007 weight portion and 0.5 weight portion
Oxygen agent 1096, continues evacuation, is warming up to 135 DEG C, the pressure < 400Pa of the system shown by gauge
Time, insulation reaction 10 minutes, add the lek of 0.15 weight portion and receive glue, stir to mix homogeneously, pour into
Equipped be pre-heated to 165 DEG C the ferrum that particle diameter is 10 microns, nickel, cobalt magnetisable material powder container in, protect
After temperature is stirred vigorously 10 minutes, being naturally cooling to 25 DEG C, insulation is stirred vigorously 10 minutes, is naturally cooling to
25 DEG C, afterwards by using Magnet Separater method for separating, obtaining molecular weight is 500,000, and particle diameter is that 20-40 is micro-
The nylon powder body of rice, the method that nylon powder body prepares 3D product is same as in Example 1, and its 3D prints goods
Performance is shown in Table 1.
Embodiment 3
On the basis of the weight portion of ten lactam monomers, ten lactam monomers of 100 weight portions are joined appearance
In device, evacuation at temperature is 120 DEG C, it is dehydrated under vacuum conditions, the system shown in gauge
Pressure < during 400Pa, release vacuum, add magnesium hydroxide and the irgasfos 168 of 1 weight portion of 1 weight portion,
Continuing evacuation, be warming up to 140 DEG C, < during 400Pa, insulation is anti-for the pressure of the system shown by gauge
Answer 20 minutes, add the hexamethylene diisocyanate of 2 weight portions, stir to mix homogeneously, pour into equipped with the most pre-
Hot to the container of the Machine-made Sand that particle diameter is 20 microns of 180 DEG C, after insulation is stirred vigorously 20 minutes, natural
Being cooled to 25 DEG C, afterwards by using cycle winnowing device method for separating, obtaining viscosity-average molecular weight is 400,000, particle diameter
For the nylon powder body of 30-50 micron, the method that nylon powder body prepares 3D product is same as in Example 1, its 3D
Print product properties and be shown in Table 1.
Embodiment 4
On the basis of the weight portion of ten lactam monomers, ten lactam monomers of 100 weight portions are joined appearance
In device, evacuation at temperature is 110 DEG C, it is dehydrated under vacuum conditions, the system shown in gauge
Pressure < during 400Pa, release vacuum, add Sodium ethylate and the antioxidant of 0.3 weight portion of 0.1 weight portion
1010, continue evacuation, the pressure being warming up to 135 DEG C and system shown by vacuometer < during 400Pa, is protected
Temperature reaction 30 minutes, adds the '-diphenylmethane diisocyanate of 1 weight portion, and stirring, to mix homogeneously, is poured into
Equipped with in the container of the quartz sand that particle diameter is 15 microns being pre-heated to 170 DEG C, insulation is stirred vigorously 30 minutes
After, it is naturally cooling to 25 DEG C, afterwards by using cycle winnowing device method for separating, obtaining viscosity-average molecular weight is 30
Ten thousand, particle diameter is the nylon powder body of 40-60 micron, and nylon powder body prepares method and embodiment 1 phase of 3D product
With, its 3D prints product properties and is shown in Table 1.
Embodiment 5
On the basis of the weight portion of lauric lactam monomer, the lauric lactam monomer of 100 weight portions is added
In container, evacuation at temperature is 100 DEG C, it is dehydrated under vacuum conditions, shown in gauge
The pressure of system < during 400Pa, releases vacuum, adds the Feldalat NM of 0.05 weight portion and the anti-of 0.8 weight portion
Oxygen agent 1096, continues evacuation, is warming up to 135 DEG C, the pressure < 400Pa of the system shown by gauge
Time, insulation reaction 15 minutes, add the poly methylene poly phenyl poly isocyanate of 0.5 weight portion, stirring is extremely
Mix homogeneously, pours into equipped with in the container of the silica dioxide granule that particle diameter is 10 microns being pre-heated to 170 DEG C,
After insulation is stirred vigorously 20 minutes, it is naturally cooling to 25 DEG C, afterwards by using cycle winnowing device method for separating,
Obtaining viscosity-average molecular weight is 300,000, and particle diameter is the nylon powder body of 50-70 micron, and nylon powder body is prepared 3D and produced
The method of product is same as in Example 1, and its 3D prints product properties and is shown in Table 1.
Embodiment 6
On the basis of the weight portion of lauric lactam monomer, the lauric lactam monomer of 100 weight portions is added
In container, evacuation at temperature is 115 DEG C, it is dehydrated under vacuum conditions, shown in gauge
The pressure of system < during 400Pa, releases vacuum, adds the sodium hydroxide of 0.5 weight portion and 0.1 weight portion
Irgasfos 168, continues evacuation, is warming up to 130 DEG C, the pressure < 400Pa of the system shown by gauge
Time, insulation reaction 30 minutes, add the triphenylmethane triisocyanate of 0.2 weight portion, stirring to mixing is all
Even, pour into equipped with in the container of the silica dioxide granule that particle diameter is 20 microns being pre-heated to 165 DEG C, be incubated
After being stirred vigorously 15 minutes, it is naturally cooling to 25 DEG C, afterwards by using cycle winnowing device method for separating, to obtain final product
Viscosity-average molecular weight is 150,000, and particle diameter is the nylon powder body of 60-80 micron, and nylon powder body prepares 3D product
Method is same as in Example 1, and its 3D prints product properties and is shown in Table 1.
Embodiment 7
On the basis of the weight portion of caprolactam monomer, the caprolactam monomer of 100 weight portions is joined container
In, evacuation at temperature is 120 DEG C, it is dehydrated under vacuum conditions, the system shown in gauge
Pressure < during 400Pa, release vacuum, add sodium hydroxide and the antioxidant 1010 of 1 weight portion of 0.2 weight portion,
Continue evacuation, be warming up to 140 DEG C, and the pressure of the system shown by gauge < during 400Pa, insulation reaction
20 minutes, adding the diphenyl carbonate of 0.8 weight portion, stirring, to mix homogeneously, is poured into equipped with being pre-heated to 170
DEG C the ferrum that particle diameter is 50 microns, nickel, cobalt magnetisable material powder container in, and be incubated 170 DEG C and be stirred vigorously,
Being naturally cooling to 25 DEG C, afterwards by using Magnet Separater method for separating, obtaining viscosity-average molecular weight is 50,000, grain
Footpath is the nylon powder body of 70-100 micron, and the method that nylon powder body prepares 3D product is same as in Example 1, its 3D
Print product properties and be shown in Table 1.
Table 1 performance data and method of testing
Claims (23)
1. the nylon powder composition printed for 3D, it is characterised in that described nylon powder composition
It is that the raw material by following weight portion obtains through the most melted anionic polymerisation, with the weight of lactam monomers
On the basis of Fen, wherein raw material includes:
Wherein, in described nylon powder body, the viscosity-average molecular weight of nylon is 5-90 ten thousand, the particle diameter of described nylon powder body
It is 20～100 microns,
The preparation method of described nylon powder composition includes:
(1) on the basis of the weight portion of lactam monomers, the lactam monomers of 100 weight portions is joined appearance
In device, it is dehydrated under vacuum conditions；
(2) it is subsequently adding base catalyst and the antioxidant of 0.1～1 weight portion of 0.005～1 weight portion, continues
Continuous evacuation, is warming up to 130～140 DEG C；
(3) insulation reaction 10～after 30 minutes, adds the activator of 0.01～2 weight portions, and stirring to mixing is all
Even；
(4) mixture after step (3) being stirred is poured into equipped with being pre-heated to 150～170 DEG C of solid particles
In container, after insulation is stirred vigorously a period of time, it is down to room temperature,
(5) passing through method for separating, it is thus achieved that molecular weight is 5～1,200,000, particle diameter is the heat conduction of 20～100 microns
Nylon powder composition；
In step (4), the particle diameter of described solid particle is 1～50 micron, chosen from Fe, nickel or cobalt magnetic
Material powder or one or more in quartz sand, silica dioxide granule and Machine-made Sand.
Compositions the most according to claim 1, it is characterised in that described lactams is selected from caprolactam, in ten
Amide, one or more in lauric lactam.
3. according to the compositions of claim 1 or 2, it is characterised in that described base catalyst is selected from hydrogen
One or more in sodium oxide, potassium hydroxide, magnesium hydroxide, Sodium ethylate and Feldalat NM；
Described activator is selected from benzene 2,4-diisocyanate (TDI), lek are received glue, hexamethylene diisocyanate
(HDI), '-diphenylmethane diisocyanate (MDI), poly methylene poly phenyl poly isocyanate (PAPI),
One or more in triphenylmethane triisocyanate (JQ-1 glue) and diphenyl carbonate；
Described antioxidant is selected from antioxidant 1010: four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] seasons penta
Four alcohol esters；Antioxidant 1096:IRGANOX B-1096；Antioxidant 1098:(N, N'-pair-(3-(3,5-bis-
Tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine) and phosphite ester kind antioxidant interworking thing；Irgasfos 168:
One or more in three [2.4-di-tert-butyl-phenyl] phosphite ester.
Compositions the most according to claim 3, it is characterised in that the addition of described base catalyst is
0.007-0.8 weight portion；
The addition of described activator is 0.1-1.5 weight portion；
The addition of described antioxidant is 0.2-0.8 weight portion.
Compositions the most according to claim 4, it is characterised in that the addition of described base catalyst is
0.05-0.5 weight portion；
The addition of described activator is 0.2-1 weight portion；
The addition of described antioxidant is 0.3-0.5 weight portion.
Compositions the most according to claim 5, it is characterised in that the addition of described base catalyst is
0.1-0.2 weight portion；The addition of described activator is 0.5-0.8 weight portion.
7. according to the compositions of any one of claim 1-2, it is characterised in that nylon in described nylon powder body
Viscosity-average molecular weight is 10-80 ten thousand.
Compositions the most according to claim 7, it is characterised in that the viscous equal molecule of nylon in described nylon powder body
Amount is 15-70 ten thousand.
Compositions the most according to claim 7, it is characterised in that the viscous equal molecule of nylon in described nylon powder body
Amount is 20-60 ten thousand.
Compositions the most according to claim 9, it is characterised in that in described nylon powder body, the viscous of nylon is divided equally
Son amount is 30-40 ten thousand.
11. compositionss according to claim 1, it is characterised in that the particle diameter of described nylon powder body is 25-90
Micron.
12. compositionss according to claim 11, it is characterised in that the particle diameter of described nylon powder body is 30-80
Micron.
13. compositionss according to claim 12, it is characterised in that the particle diameter of described nylon powder body is 40-70
Micron.
14. compositionss according to claim 13, it is characterised in that the particle diameter of described nylon powder body is 50-60
Micron.
The preparation method of the nylon powder composition of 15. any one of claim 1-14, it is characterised in that described
Method includes:
(1) on the basis of the weight portion of lactam monomers, the lactam monomers of 100 weight portions is joined appearance
In device, it is dehydrated under vacuum conditions；
(2) it is subsequently adding base catalyst and the antioxidant of 0.1～1 weight portion of 0.005～1 weight portion, continues
Continuous evacuation, is warming up to 130～140 DEG C；
(3) insulation reaction 10～after 30 minutes, adds the activator of 0.01～2 weight portions, and stirring to mixing is all
Even；
(4) mixture after step (3) being stirred is poured into equipped with being pre-heated to 150～170 DEG C of solid particles
In container, after insulation is stirred vigorously a period of time, it is down to room temperature,
(5) passing through method for separating, it is thus achieved that molecular weight is 5～1,200,000, particle diameter is the heat conduction of 20～100 microns
Nylon powder composition；
In step (4), the particle diameter of described solid particle is 1～50 micron, chosen from Fe, nickel or cobalt magnetic
Material powder or one or more in quartz sand, silica dioxide granule and Machine-made Sand.
16. methods according to claim 15, it is characterised in that described method comprises the steps:
(1) on the basis of the weight portion of lactam monomers, the lactam monomers of 100 weight portions is joined appearance
In device, evacuation at temperature is 90～120 DEG C, it is dehydrated under vacuum conditions；
(2) pressure of the system shown in gauge < during 400Pa, releases vacuum, adds 0.005～1 weight
The base catalyst of part and the antioxidant of 0.1～1 weight portion, continue evacuation, be warming up to 130～140 DEG C；
(3) system shown by gauge pressure < during 400Pa, insulation reaction 10～30 minutes, solve
Except vacuum, add the activator of 0.01～2 weight portions, stir,
(4) mixture after step (3) being stirred is poured into equipped with the solid particle being preheated to 150～170 DEG C
Container in, be stirred vigorously 10～30 minutes, be naturally down to 25 DEG C,
(5) by method for separating, the viscosity-average molecular weight nylon powder composition at 5-90 ten thousand is obtained.
17. according to the preparation method of claim 15 or 16, it is characterised in that described solid particle is capable of circulation
Use.
18. preparation methoies according to claim 15, it is characterised in that the particle diameter of described solid particle is 10-40
Micron.
19. according to the preparation method of claim 15 or 16, it is characterised in that described screening installation is selected from magnetic
Select the one in separator, suction type aspirator and cycle winnowing device.
The application of the nylon powder composition of 20. 1 kinds of any one of claim 1-14, it is characterised in that described
Nylon powder body is applied to 3D printing technique.
21. 1 kinds of 3D Method of printings, it is characterised in that use the nylon powder body of any one of claim 1-14
Compositions is as printed material.
22. 3D Method of printings according to claim 21, it is characterised in that described Method of printing includes as follows
Step:
(1) the nylon powder composition of any one of claim 1-14 is deposited on carrier surface, and covers
Target area；
(2) described nylon powder composition is flattened, form a smooth surface；
(3) by energetic beam illumination to target area, described powder body is made to form an integral layer；With
(4) step (1)～(3) is repeated, to form the overall two outer each layers bondd with neighboring layers, from
And obtain three-dimensional article.
23. 1 kinds of three-dimensional articles, it is characterised in that described three-dimensional article includes any one of claim 1-14
Nylon powder composition.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410181476.XA CN104031262B (en) | 2014-04-30 | A kind of high molecular weight nylon powder body that can be applicable to 3D printing and preparation method thereof | |
| PCT/CN2015/077350 WO2015165361A1 (en) | 2014-04-30 | 2015-04-24 | Nylon powder composition for 3d printing, and preparation method and use thereof |
| US15/507,662 US11472929B2 (en) | 2014-04-30 | 2015-04-24 | Nylon powder composition for 3D printing, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410181476.XA CN104031262B (en) | 2014-04-30 | A kind of high molecular weight nylon powder body that can be applicable to 3D printing and preparation method thereof |
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| CN104031262A CN104031262A (en) | 2014-09-10 |
| CN104031262B true CN104031262B (en) | 2016-11-30 |
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| CN1796457A (en) * | 2004-12-27 | 2006-07-05 | 上海杰事杰新材料股份有限公司 | Nylon fuel tank in use for automobiles and motorcycles, and preparation method |
| CN103205107A (en) * | 2013-04-03 | 2013-07-17 | 中山职业技术学院 | Three-dimensional printing forming material with toughness and high adhesive property and preparation method thereof |
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| CN1640936A (en) * | 2004-01-02 | 2005-07-20 | 上海杰事杰新材料股份有限公司 | Continuous long-fiber reaction-reinforced nylon resin and its making method |
| CN1718409A (en) * | 2004-07-29 | 2006-01-11 | 南京理工大学 | Preparation method of nylon composite gradient pipe |
| CN1796457A (en) * | 2004-12-27 | 2006-07-05 | 上海杰事杰新材料股份有限公司 | Nylon fuel tank in use for automobiles and motorcycles, and preparation method |
| CN103205107A (en) * | 2013-04-03 | 2013-07-17 | 中山职业技术学院 | Three-dimensional printing forming material with toughness and high adhesive property and preparation method thereof |
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