CN103980485B - A kind of highly viscous nylon powder body that can be used for 3D printing and preparation method thereof - Google Patents
A kind of highly viscous nylon powder body that can be used for 3D printing and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of highly viscous nylon composite granule compositions, it is characterized in that, described compositions is obtained by reacting by the raw material of following weight portion is aggregated, with the weight portion of amidic-salt for benchmark, wherein said raw material includes: amidic-salt 100 weight portion, catalyst 0.02～0.8 weight portion; Molecular weight regulator 5～30 weight portion; Strand stabilizer 0.01～1 weight portion; Antioxidant 0.1-1 weight portion. The present invention also provides for preparation method and the application thereof of above-mentioned composition. Nylon powder body prepared by the present invention, relative viscosity is adjustable at 4-20, and particle diameter is controlled and narrow diameter distribution at 20-100 micron. The preparation method of the present invention, a step can prepare nylon powder body, with traditional, nylon chips carries out deep cooling crush and solvent precipitated phase ratio, and the method is simpler, and energy consumption is low.
Description
Technical field
The present invention relates to a kind of highly viscous nylon powder body and preparation method thereof, be specifically related to a kind of highly viscous nylon powder body that can be used for 3D printing 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, and it is a kind of based on mathematical model file, use powdery metal or plastics etc. can jointing material, carried out the technology of constructed object by the mode successively printed. Ultimate principle is layered manufacturing, successively increases material and generates the technology of 3D solid. At present, 3D printing technique is applied primarily to product prototype, Making mold and the field such as artistic creation, jewelry-making, substitutes the retrofit technique that these tradition rely on. It addition, 3D printing technique is applied to the fields such as medical science, biological engineering, building, clothing, aviation gradually, open up wide space for innovation.
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 as basic 3D printed material.
Usual SLS technology and equipment adopt transmitting focusing in the laser of the energy of target area. The dusty material melting in the effect lower part of the energy launched by laser or softening in the target area producing parts. During operation, powder is connect the quantity of irradiated laser energy should be enough to quickly form part sheets, thus target sublimity must be heated implementing laser pre-irradiation, powder is preheating to the temperature being slightly less than its fusing point, then under the effect striking off rod, powder is paved; Laser beam sinters selectively according to layering cross section information under the control of the computer, one layer complete after carry out next layer of sintering again, remove unnecessary powder after all having sintered, then can obtain a part sintered.
Specifically, SLS equipment includes a kind of depositing before powder bed is exposed to laser energy that one layer smooth, the device of the dusty material of level on the target surface.The computer being scanned being formed parts " thin slice " by the manipulation light connecting CAD/CAM system controls laser energy and launches and be confined to selected target area part. After irradiating, at dusty material, the ground floor " thin slice " forming parts, the second layer of dusty material is deposited in target area. The laser handled by CAD/CAM program rescans the part only exposed in target area, obtains the second layer " thin slice " of parts. Constantly repeat the method until parts " a piece of connect a piece of " build up and form complete parts.
Owing to the various performances of sinterable powder have very important effect in guaranteeing selective laser sintering process one action pane of existence. That is, polymer beads is made to occur the phenomenon of softening to reduce to bottom line under high temperature to a certain degree, making powder can be stored in the target environment being heated and don't cause granule generation melting phenomenon, being supplied to, until quickly being concentrated by energy by the laser beam scanned later, the granule being heated.
Owing to SLS forming method has manufacturing process simple, the features such as degree of flexibility is high, material selection range is wide, material price is cheap, and cost is low, stock utilization is high, and shaping speed is fast, it is mainly used in foundry industry for above feature SLS method, 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.
Summary of the invention
The inventors discovered that, with middle low-molecular-weight nylon material powder body material, using 3D to print technique, the goods of preparation, mechanical strength is inadequate, toughness is bad and the shortcoming of poor dimensional stability. For overcoming above-mentioned deficiency, the present invention provides a kind of highly viscous nylon powder, utilizes the technique that 3D prints, can prepare the goods that mechanical property is more excellent. Product size good stability.
An object of the present invention is to provide a kind of highly viscous nylon powder body material that can be used for 3D printing.
Amidic-salt is carried out slurry polymerization, the nylon powder body of preparation highly viscous by the two of the purpose of the present invention, thus providing a kind of to can be used for the 3D highly viscous nylon raw powder's production technology printed.
The present invention utilizes slurry polymerization principle, makes amidic-salt be polymerized in a solvent, stirs into powder body during discharging. Powder prepared by the method, tool molecular weight is high, and diameter of particle is controlled. The nylon powder body of highly viscous prepared by the present invention is applicable to 3D and prints technique.
The present invention is achieved through the following technical solutions:
A kind of highly viscous nylon composite granule compositions, it is characterised in that described powder composition is obtained by reacting by the raw material of following weight portion is aggregated, and with the weight portion of amidic-salt for benchmark, wherein said raw material includes:
According to the present invention, one or more in nylon salt, NYLON610 salt and nylon 612 salt of described amidic-salt.
According to the present invention, described powder body carries out slurry polymerization after mixing by described raw material and obtains.
According to the present invention, the relative viscosity of described highly viscous nylon powder body is 4-20, it is preferable that 5-18, more preferably 6-15, it is also possible to for 8-10.
According to the present invention, the particle diameter of described nylon powder body is 20～100 microns, and this particle size range is beneficial to 3D processing technique. Particle diameter is preferably 30-90 micron or 40-80 micron, it is also possible to for 50-70 micron.
According to the present invention, described molecular weight regulator is selected from one or both in adipic acid and dodecanedioic acid. Preferably, the addition of described molecular weight regulator is 10-25 weight portion, more preferably 15-20 weight portion.
According to the present invention, described strand stabilizer is selected from one or both in benzoic acid and acetic acid. Preferably, the addition of described strand stabilizer is 0.1-0.8 weight portion, it is also possible to for 0.3-0.5 weight portion.
According to the present invention, described catalyst is selected from one or both in ortho phosphorous acid and N-vinylcaprolactam. Preferably, the addition of described catalyst is 0.1-0.6 weight portion, it is also possible to for 0.2-0.5 weight portion.
According to the present invention, described antioxidant is selected from antioxidant 1010: four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester; Antioxidant 1096:IRGANOXB-1096; Antioxidant 1098:(N, N'-pair-(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.
Preferably, the addition of described antioxidant is 0.2-0.8 weight portion, it is also possible to for 0.3-0.5 weight portion.
The preparation method that the present invention also provides for a kind of highly viscous nylon composite granule compositions, it is characterised in that described method comprises the steps:
(1) the high temperature resistant atent solvent of 100～600 weight portions is joined in reactor, by the amidic-salt of 100 weight portions in whipping process, the molecular weight regulator of 5～30 weight portions, stirring is to mix homogeneously, in reactor, add strand stabilizer that weight portion is 0.01～1, weight portion be 0.02～0.8 catalyst and the antioxidant of 0.1～1 weight portion, stirring is to mix homogeneously;
(2) temperature of reactor carrying out at least two sections of intensifications, being first uniformly heating to temperature within a certain period of time by room temperature is 180～220 DEG C, maintains between 1.5～2MPa by the pressure in reactor simultaneously; Continuing reacting by heating still afterwards, making the temperature of reactor be 180～220 DEG C by temperature within a period of time, to be warming up to temperature be 280～285 DEG C, and reduces pressure in reactor to 1.01MPa; After temperature is 270～285 DEG C of insulations 30～60 minutes, evacuation, the pressure in reactor is reduced to 0.3Pa, and continues 1～4 hour under this pressure;
(3) opening the outlet valve discharging of reactor to container, be stirred vigorously 10～100 minutes, centrifugation, dry, prepared relative viscosity is 4～20, and particle diameter is at the composite heat-conducting nylon powder body of 20-100 micron.
According to the present invention, described method specifically includes following steps:
(1) the high temperature resistant atent solvent of 100～600 weight portions is joined in reactor, under agitation, molecular weight regulator by the amidic-salt of 100 weight portions, 5～30 weight portions, stirring is to mix homogeneously, in reactor, add strand stabilizer that weight portion is 0.01～1, weight portion be 0.02～0.5 catalyst and the antioxidant of 0.1～1 weight portion, stirring is to mix homogeneously;
(2) reactor is carried out inflated with nitrogen and evacuation processes to discharge the air in reactor; Then in reactor, it is filled with nitrogen, makes the initial pressure in reactor maintain between 0.2～0.5MPa;
(3) by 25 DEG C, the temperature of reactor being uniformly heating in 90～120 minutes temperature is 180～220 DEG C, and is incubated 30～60 minutes, maintains between 1.5～2MPa by the pressure in reactor simultaneously; Then proceed to reacting by heating still so that the temperature of reactor was 180～220 DEG C by temperature in 120～180 minutes, and to be warming up to temperature be 280～285 DEG C, during this period, at the uniform velocity discharge gas reactor, reduce pressure in reactor to 1.01MPa;After temperature is 270～285 DEG C of insulations 30～60 minutes, evacuation, the pressure in reactor is reduced to 0.3Pa, and continues 1～4 hour under this pressure;
(4) stirring is stopped, it is filled with nitrogen in reactor, the pressure in reactor is made to be increased to 0.2～0.5MPa by 0.3Pa, open the outlet valve discharging of reactor to container, it is stirred vigorously 10～100 minutes, centrifugation, dry, prepared relative viscosity is 4～20, and particle diameter is at the composite heat-conducting nylon powder body of 20-100 micron.
According to the present invention, one or more in silicone oil or phenyl silicone oil of described high temperature resistant atent solvent.
The present invention also provides for the application of above-mentioned nylon powder composition, it is characterised in that described nylon powder composition is applied to 3D printing technique, and 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 of the present invention as 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) on energetic beam illumination to target area, described powder body will be made to form an integral layer; With
(4) step (1)～(3) are repeated, to form overall and neighboring layers bonding other each layer, thus obtaining three-dimensional article.
The present invention also provides for a kind of three-dimensional article, it is characterised in that described three-dimensional article includes the nylon powder composition of the present invention.
The nylon powder body of the present invention utilizes slurry polymerization process, is formed by amidic-salt polycondensation in high boiling solvent, nylon powder body prepared by the present invention, and relative viscosity is adjustable at 4-20, and particle diameter is controlled at 20-100 micron. There is highly viscous, the feature that diameter of particle is controlled. With traditional, nylon chips carrying out deep cooling crush and solvent precipitated phase ratio, the method is simpler, and energy consumption is low. Processing technology is simple, and its powder body prepared meets the demand of 3D printed product.
Detailed description of the invention
Below by way of detailed description of the invention, the present invention is described in further detail, but this should not being interpreted as, the scope of the present invention is only limitted to Examples below. When without departing from said method thought of the present invention, the various replacements made according to ordinary skill knowledge and customary means or change, should be included in the scope of the present invention.
Comparative example 1:
Common nylon powder body, particle diameter 30-50 μm, relative viscosity is the material of 3, carries out 3D printing, and its technique is as follows:
(1) nylon powder composition is deposited on carrier surface, and coverage goal region;
(2) nylon powder composition is flattened, form a smooth surface;
(3) on energetic beam illumination to target area, described powder body will be made to form an integral layer; With
(4) repeating step (1)～(3), to form overall and neighboring layers bonding other each layer, thus obtaining three-dimensional article, its properties of product are in Table 1.
Embodiment 1
The high temperature resistant atent solvent silicone oil of 100 weight portions is joined in reactor, by the nylon salt of 100 weight portions in whipping process, the adipic acid of 5 weight portions, stirring is to mix homogeneously, in reactor, add benzoic acid that weight portion is 0.01, weight portion be 0.02 ortho phosphorous acid and the antioxidant 1010 of 0.1 weight portion, stirring is to mix homogeneously; Reactor is carried out inflated with nitrogen and evacuation processes to discharge the air in reactor; Then in reactor, it is filled with nitrogen, makes the initial pressure in reactor maintain between 0.2～0.5MPa;By 25 DEG C, the temperature of reactor was uniformly heating in 90 minutes temperature is 180～190 DEG C, and is incubated 30 minutes, maintains between 1.5～2MPa by the pressure in reactor simultaneously; Continue reacting by heating still afterwards, make the temperature of reactor be 180～190 DEG C by temperature in 180 minutes and be warming up to 280～285 DEG C, during this period, at the uniform velocity discharge gas reactor, reduce pressure in reactor to 1.01MPa; After temperature is 270 DEG C of insulations 30 minutes, evacuation, the pressure in reactor is reduced to 0.3Pa, and continues 1 hour under this pressure; Stop stirring, it is filled with nitrogen in reactor, make the pressure in reactor be increased to 0.2～0.5MPa by 0.3Pa, open the outlet valve discharging of reactor to container, be stirred vigorously 10 minutes, centrifugation, dry, prepared relative viscosity is 20, and particle diameter is at the composite heat-conducting nylon powder body of 80-100 micron, by gained powder body, 3D Method of printing is used to prepare product, its preparation process:
(1) nylon powder composition is deposited on carrier surface, and coverage goal region;
(2) nylon powder composition is flattened, form a smooth surface;
(3) on energetic beam illumination to target area, described powder body will be made to form an integral layer; With
(4) repeating step (1)～(3), to form overall and neighboring layers bonding other each layer, thus obtaining three-dimensional article, its 3D printed product performance test is in Table 1.
Embodiment 2
The high temperature resistant atent solvent phenyl silicone oil of 100 weight portions is joined in reactor, by the NYLON610 salt of 100 weight portions in whipping process, the dodecanedioic acid of 10 weight portions, stirring is to mix homogeneously, in reactor, add acetic acid that weight portion is 0.1, weight portion be 0.1 N-vinylcaprolactam and the antioxidant 1096 of 0.5 weight portion, stirring is to mix homogeneously; Reactor is carried out inflated with nitrogen and evacuation processes to discharge the air in reactor; Then in reactor, it is filled with nitrogen, makes the initial pressure in reactor maintain between 0.2～0.5MPa; By 25 DEG C, the temperature of reactor was uniformly heating in 100 minutes temperature is 190～200 DEG C, and is incubated 40 minutes, maintains between 1.5～2MPa by the pressure in reactor simultaneously; Continue reacting by heating still afterwards, make the temperature of reactor be 190～200 DEG C by temperature in 140 minutes and be warming up to 280～285 DEG C, during this period, at the uniform velocity discharge gas reactor, reduce pressure in reactor to 1.01MPa; After temperature is 280 DEG C of insulations 40 minutes, evacuation, the pressure in reactor is reduced to 0.3Pa, and continues 2 hours under this pressure; Stop stirring, it is filled with nitrogen in reactor, the pressure in reactor is made to be increased to 0.2～0.5MPa by 0.3Pa, open the outlet valve discharging of reactor to container, be stirred vigorously 30 minutes, centrifugation, dry, prepared relative viscosity is 18, particle diameter is at the composite heat-conducting nylon powder body of 60-80 micron, and its 3D product preparation method is identical with embodiment 1, and printed product performance test is in Table 1.
Embodiment 3
The high temperature resistant atent solvent silicone oil of 600 weight portions is joined in reactor, by the nylon 612 salt of 100 weight portions in whipping process, the adipic acid of 30 weight portions, stirring is to mix homogeneously, in reactor, add benzoic acid that weight portion is 1, weight portion be 0.5 ortho phosphorous acid and the irgasfos 168 of 1 weight portion, stirring is to mix homogeneously; Reactor is carried out inflated with nitrogen and evacuation processes to discharge the air in reactor; Then in reactor, it is filled with nitrogen, makes the initial pressure in reactor maintain between 0.2～0.5MPa;By 25 DEG C, the temperature of reactor was uniformly heating in 120 minutes temperature is 210～220 DEG C, and is incubated 60 minutes, maintains between 1.5～2MPa by the pressure in reactor simultaneously; Continue reacting by heating still afterwards, make the temperature of reactor be 210～220 DEG C by temperature in 120 minutes and be warming up to 280～285 DEG C, during this period, at the uniform velocity discharge gas reactor, reduce pressure in reactor to 1.01MPa; After temperature is 285 DEG C of insulations 60 minutes, evacuation, the pressure in reactor is reduced to 0.3Pa, and continues 4 hours under this pressure; Stop stirring, it is filled with nitrogen in reactor, the pressure in reactor is made to be increased to 0.2～0.5MPa by 0.3Pa, open the outlet valve discharging of reactor to container, being stirred vigorously 100 minutes, centrifugation, dry, prepared relative viscosity is 16, particle diameter is identical with embodiment 1 in its 3D product preparation method of composite heat-conducting nylon powder body of 50-70 micron, and printed product performance test is in Table 1.
Embodiment 4
The high temperature resistant atent solvent phenyl silicone oil of 300 weight portions is joined in reactor, by the nylon salt of 100 weight portions in whipping process, the dodecanedioic acid of 15 weight portions, stirring is to mix homogeneously, in reactor, add acetic acid that weight portion is 0.5, weight portion be 0.8 N-vinylcaprolactam and the antioxidant 1096 of 0.8 weight portion, stirring is to mix homogeneously; Reactor is carried out inflated with nitrogen and evacuation processes to discharge the air in reactor; Then in reactor, it is filled with nitrogen, makes the initial pressure in reactor maintain between 0.2～0.5MPa; By 25 DEG C, the temperature of reactor was uniformly heating in 110 minutes temperature is 200～210 DEG C, and is incubated 50 minutes, maintains between 1.5～2MPa by the pressure in reactor simultaneously; Continue reacting by heating still afterwards, make the temperature of reactor be 200～210 DEG C by temperature in 130 minutes and be warming up to 280～285 DEG C, during this period, at the uniform velocity discharge gas reactor, reduce pressure in reactor to 1.01MPa; After temperature is 280 DEG C of insulations 50 minutes, evacuation, the pressure in reactor is reduced to 0.3Pa, and continues 3 hours under this pressure; Stop stirring, it is filled with nitrogen in reactor, the pressure in reactor is made to be increased to 0.2～0.5MPa by 0.3Pa, open the outlet valve discharging of reactor to container, being stirred vigorously 30 minutes, centrifugation, dry, prepared relative viscosity is 4, particle diameter is identical with embodiment 1 in its 3D product preparation method of composite heat-conducting nylon powder body of 20-40 micron, and printed product performance test is in Table 1.
Table 1 the performance test results
Claims (16)
1. a highly viscous nylon composite granule compositions, it is characterised in that described powder composition carries out slurry polymerization after mixing by the raw material of following weight portion and obtains, with the weight portion of amidic-salt for benchmark, wherein:
One or more in nylon salt, NYLON610 salt and nylon 612 salt of described amidic-salt, the relative viscosity of described nylon powder body is 4-20, and the particle diameter of described nylon powder body is 20～100 microns,
The preparation method of described highly viscous nylon composite granule comprises the steps:
(1) the high temperature resistant atent solvent of 100～600 weight portions is joined in reactor, by the amidic-salt of 100 weight portions in whipping process, the molecular weight regulator of 5～30 weight portions, stirring is to mix homogeneously, in reactor, add strand stabilizer that weight portion is 0.01～1, weight portion be 0.02～0.8 catalyst and the antioxidant of 0.1～1 weight portion, stirring is to mix homogeneously;
(2) temperature of reactor carrying out at least two sections of intensifications, being first uniformly heating to temperature within a certain period of time by room temperature is 180～220 DEG C, maintains between 1.5～2MPa by the pressure in reactor simultaneously; Continuing reacting by heating still afterwards, making the temperature of reactor be 180～220 DEG C by temperature within a period of time, to be warming up to temperature be 280～285 DEG C, and reduces pressure in reactor to 1.01MPa; After temperature is 270～285 DEG C of insulations 30～60 minutes, evacuation, the pressure in reactor is reduced to 0.3Pa, and continues 1～4 hour under this pressure;
(3) opening the outlet valve discharging of reactor to container, be stirred vigorously 10～100 minutes, centrifugation, dry, prepared relative viscosity is 4～20, and particle diameter is at the highly viscous nylon composite granule of 20-100 micron. .
2. compositions according to claim 1, it is characterised in that the relative viscosity of described nylon powder body is 5-18.
3. compositions according to claim 2, it is characterised in that the relative viscosity of described nylon powder body is 6-16.
4. compositions according to claim 3, it is characterised in that the particle diameter of described nylon powder body is 30-90 micron.
5. compositions according to claim 4, it is characterised in that the particle diameter of described nylon powder body is 40-80 micron.
6. compositions according to claim 5, it is characterised in that the particle diameter of described nylon powder body is 50-70 micron.
7. the compositions according to any one of claim 1-2, it is characterised in that described molecular weight regulator is selected from one or both in adipic acid and dodecanedioic acid;
Described strand stabilizer is selected from one or both in benzoic acid and acetic acid;
Described catalyst is selected from one or both in ortho phosphorous acid and N-vinylcaprolactam;
Described antioxidant is selected from antioxidant 1010: four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester; Antioxidant 1096:IRGANOXB-1096; Antioxidant 1098:(N, N'-pair-(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.
8. compositions according to claim 7, it is characterised in that
The addition of described molecular weight regulator is 10-25 weight portion;
The addition of described strand stabilizer is 0.1-0.8 weight portion;
The addition of described catalyst is 0.1-0.6 weight portion;
The addition of described antioxidant is 0.2-0.8 weight portion.
9. compositions according to claim 8, it is characterised in that
The addition of described molecular weight regulator is 15-20 weight portion;
The addition of described strand stabilizer is 0.3-0.5 weight portion;
The addition of described catalyst is 0.2-0.5 weight portion;
The addition of described antioxidant is 0.3-0.5 weight portion.
10. the preparation method of the highly viscous nylon composite granule of an any one of claim 1-9, it is characterised in that described method comprises the steps:
(1) the high temperature resistant atent solvent of 100～600 weight portions is joined in reactor, by the amidic-salt of 100 weight portions in whipping process, the molecular weight regulator of 5～30 weight portions, stirring is to mix homogeneously, in reactor, add strand stabilizer that weight portion is 0.01～1, weight portion be 0.02～0.8 catalyst and the antioxidant of 0.1～1 weight portion, stirring is to mix homogeneously;
(2) temperature of reactor carrying out at least two sections of intensifications, being first uniformly heating to temperature within a certain period of time by room temperature is 180～220 DEG C, maintains between 1.5～2MPa by the pressure in reactor simultaneously;Continuing reacting by heating still afterwards, making the temperature of reactor be 180～220 DEG C by temperature within a period of time, to be warming up to temperature be 280～285 DEG C, and reduces pressure in reactor to 1.01MPa; After temperature is 270～285 DEG C of insulations 30～60 minutes, evacuation, the pressure in reactor is reduced to 0.3Pa, and continues 1～4 hour under this pressure;
(3) opening the outlet valve discharging of reactor to container, be stirred vigorously 10～100 minutes, centrifugation, dry, prepared relative viscosity is 4～20, and particle diameter is at the highly viscous nylon composite granule of 20-100 micron.
11. preparation method according to claim 10, it is characterised in that described method comprises the steps:
(1) the high temperature resistant atent solvent of 100～600 weight portions is joined in reactor, under agitation, molecular weight regulator by the amidic-salt of 100 weight portions, 5～30 weight portions, stirring is to mix homogeneously, in reactor, add strand stabilizer that weight portion is 0.01～1, weight portion be 0.02～0.5 catalyst and the antioxidant of 0.1～1 weight portion, stirring is to mix homogeneously;
(2) reactor is carried out inflated with nitrogen and evacuation processes to discharge the air in reactor; Then in reactor, it is filled with nitrogen, makes the initial pressure in reactor maintain between 0.2～0.5MPa;
(3) by 25 DEG C, the temperature of reactor being uniformly heating in 90～120 minutes temperature is 180～220 DEG C, and is incubated 30～60 minutes, maintains between 1.5～2MPa by the pressure in reactor simultaneously; Then proceed to reacting by heating still so that the temperature of reactor was 180～220 DEG C by temperature in 120～180 minutes, and to be warming up to temperature be 280～285 DEG C, during this period, at the uniform velocity discharge gas reactor, reduce pressure in reactor to 1.01MPa; After temperature is 270～285 DEG C of insulations 30～60 minutes, evacuation, the pressure in reactor is reduced to 0.3Pa, and continues 1～4 hour under this pressure;
(4) stirring is stopped, it is filled with nitrogen in reactor, the pressure in reactor is made to be increased to 0.2～0.5MPa by 0.3Pa, open the outlet valve discharging of reactor to container, it is stirred vigorously 10～100 minutes, centrifugation, dry, prepared relative viscosity is 4～20, and particle diameter is at the highly viscous nylon composite granule of 20-100 micron.
12. the preparation method according to claim 10 or 11, it is characterised in that one or more in silicone oil or phenyl silicone oil of described high temperature resistant atent solvent.
13. the application of the highly viscous nylon composite granule compositions of any one of claim 1-9, it is characterised in that described nylon powder composition is applied to 3D printing technique.
14. a 3D Method of printing, it is characterised in that use the highly viscous nylon composite granule compositions of any one of claim 1-9 as printed material.
15. 3D Method of printing according to claim 14, it is characterised in that described method comprises the steps:
(1) the nylon composite granule compositions of any one of claim 1-9 is deposited on carrier surface, and coverage goal region;
(2) described nylon composite granule compositions is flattened, form a smooth surface;
(3) on energetic beam illumination to target area, described powder body will be made to form an integral layer; With
(4) step (1)～(3) are repeated, to form each layer outside overall with neighboring layers bonding two, thus obtaining three-dimensional article.
16. a three-dimensional article, it is characterised in that described three-dimensional article includes the highly viscous nylon composite granule compositions of any one of claim 1-9.
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| CN201410182347.2A CN103980485B (en) | 2014-04-30 | 2014-04-30 | A kind of highly viscous nylon powder body that can be used for 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 |
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| KR20080013645A (en) * | 2006-08-08 | 2008-02-13 | 이준채 | The fiber coating my manufacturing method which uses the nonferrous metal it will be able to intercept the electromagnetic waves and that use method |
| CN102477219B (en) * | 2010-11-29 | 2014-04-16 | 上海杰事杰新材料(集团)股份有限公司 | High-temperature resistant semi-aromatic nylon and its preparation method |
| CN102604381B (en) * | 2012-03-30 | 2013-10-23 | 金发科技股份有限公司 | Polyamide composite material and preparation method and application thereof |
| 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 |
| CN103467978B (en) * | 2013-09-23 | 2016-06-29 | 湖南工业大学 | A kind of carrying roller multiple elements design modified nylon 6 composites and preparation method thereof |
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