CN103992473A - Heat-conduction high-viscosity nylon powder applicable to 3D printing and preparation method thereof - Google Patents
Heat-conduction high-viscosity nylon powder applicable to 3D printing and preparation method thereof Download PDFInfo
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Abstract
A heat-conduction high-viscosity nylon powder applicable to 3D printing is characterized by being prepared from raw materials by employing a polymerization reaction. Based on the weight proportions of an amide salt, the raw materials comprise, in parts by weight, 100 parts of the amide salt, 1-50 parts of graphite, 0.02-0.8 part of a catalyst, 5-30 parts of a molecular-weight controlling agent, 0.01-1 part of a molecular-chain stabilizing agent and 0.1-1 part of an anti-oxidant. The invention also provides a preparation method and application of the above composition. The prepared heat-conduction nylon powder has the relative viscosity of 4-20, and is adjustable in the particle size of 20-100 mu m and narrow in distribution. The prepared heat-conduction nylon powder is applicable to 3D printing, and products thereof are good in dimensional stability and high in heat conduction performance, and are capable of satisfying demands on high-performance complex-structure heat-conduction composite material in the fields of thermal energy utilization, chemical engineering heat exchange and the like.
Description
Technical field
The present invention relates to high sticky nylon powder of a kind of heat conduction and preparation method thereof, be specifically related to sticky nylon powder of height of a kind of 3D of can be used for printing and preparation method thereof.
Background technology
3D printing technique claims again lamination manufacturing technology, is a kind of emerging technology in rapid shaping field, and it is a kind ofly to take digital model file as basis, uses powdery metal or the plastics etc. can jointing material, carrys out the technology of constructed object by the mode of successively printing.Ultimate principle is lamination manufacture, successively increases the technology that material generates 3D solid.At present, 3D printing technique is mainly applied to the fields such as product prototype, mould manufacture and artistic creation, jewelry-making, substitutes the retrofit technique that these tradition rely on.In addition, 3D printing technique is applied to the fields such as medical science, biotechnology, building, clothes, aviation gradually, for wide space has been opened up in innovation.
3D printing technique mainly comprises the techniques such as SLA, FDM, SLS, LOM.Wherein fusion sediment forming technique (FDM) and selective laser sintering (SLS) technology all can be used thermoplastics as basic 3D printed material.
3D printing technique mainly comprises the techniques such as SLA, FDM, SLS, LOM.Wherein fusion sediment forming technique (FDM) and selective laser sintering (SLS) technology all can be used thermoplastics as basic 3D printed material.
Conventionally SLS technology and equipment adopt transmitting focusing in the laser of the energy of target area.Partial melting or softening powdered material under the effect of the energy of being launched by laser in producing the target area of parts.During operation, the quantity of irradiated laser energy that powder connects should be enough to form fast part sheets, thereby target sublimity must be heated before implementing laser radiation, powder is preheating to slightly lower than the temperature of its fusing point, then under the effect that strikes off rod, powder is paved; Laser beam carries out sintering selectively according to minute layer cross section information under computer control, carries out lower one deck sintering after one deck completes again, and after whole sintering are complete, removes unnecessary powder, can obtain a part sintering.
Particularly, SLS equipment comprises and a kind ofly before powder bed is exposed to laser energy, on target surface, deposits that one deck is smooth, the device of the powdered material of level.The computer that scans to form parts " thin slice " by a manipulation light that connects CAD/CAM system is controlled laser energy and is launched and be confined to selected target area part.At powdered material, irradiate after the first layer " thin slice " that forms parts, the second layer of powdered material is deposited in target area.The laser of being handled by CAD/CAM program rescans the part only exposing in target area, obtains the second layer " thin slice " of parts.Constantly repeat the method and form complete parts until parts build up " a slice connects a slice ".
Because the various performances of sinterable powder are guaranteeing that selective laser sintering method has very important effect in there is an action pane.That is to say, under high temperature to a certain degree, make polymer beads that softening phenomenon occurs and be reduced to bottom line, make powder can be stored in the targeted environment of being heated and don't initiation particle generation melting phenomenon, until energy is concentrated and offered the particle being heated fast by the laser beam scanning afterwards.
Because SLS forming method has manufacturing process simple, the features such as degree of flexibility is high, material range of choice is wide, material price is cheap, and cost is low, material use efficiency is high, and shaping speed is fast, for above feature SLS method, be mainly used in foundry industry, and can be used for directly making fast mould.
The polymer materials that 3D forming technique is more conventional is in the market vinyl cyanide one divinyl one styrene copolymer (ABS), poly(lactic acid) (PLA), nylon (PA) and polycarbonate (PC), and wherein nylon is the printing starting material of current consumption maximum.The nylon of exploitation performance is adapted to above-mentioned 3D printing technique, has wide and market outlook and strategic importance.
Summary of the invention
The inventor finds, pure low sticky nylon powder body material is used 3D to print technique, the goods of preparation, and dimensional stability and thermotolerance are all not so good.For overcoming above-mentioned deficiency, the invention provides the high sticky nylon powder composite material of heat conduction, product size good stability, thermal conductivity is high.
One of object of the present invention is to provide the high sticky nylon powder composition of heat conduction that a kind of 3D of can be used for prints.
Two of object of the present invention is that amide salt and graphite are carried out to in-situ polymerization, prepares the nylon powder of heat-conducting polymer amount, thus the high preparation method who glues nylon powder of the heat conduction that provides a kind of 3D of can be used for to print.
The present invention utilizes in-situ polymerization principle, under the condition existing, makes amide salt in Graphite Powder 99 generation home position polymerization reaction at catalyzer, prepares nylon powder.Powder prepared by this method, tool molecular weight is high, the feature of good heat conductivity.The sticky nylon powder of height prepared by the present invention is applicable to 3D and prints technique.
The present invention is achieved through the following technical solutions:
The high sticky nylon composite granule composition of heat conduction, is characterized in that, described composition is obtained through polyreaction by the raw material of following weight part, and the weight part of amide salt of take is benchmark, and wherein said raw material comprises:
According to the present invention, one or more in nylon salt, NYLON610 salt and nylon 612 salt of described amide salt.
According to the present invention, described powder raw material carries out home position polymerization reaction and obtains after mixing.
According to the present invention, the relative viscosity of the sticky nylon powder of described height is 4-20, preferred 5-18, and more preferably 6-15, can also be 8-10.
According to the present invention, the particle diameter of described nylon powder is 20～100 microns, and this particle size range is beneficial to 3D complete processing.Particle diameter is preferably 30-90 micron, or 40-80 micron, can also be 50-70 micron.
According to the present invention, the particle diameter of described graphite is 0.2～50 micron, preferred 1-40 micron, and more preferably 5-30 micron, can also be 10-20 micron.
According to the present invention, described graphite is selected from one or more in crystalline flake graphite, expanded graphite, aphanitic graphite and electrographite.Preferably, the add-on of described graphite is 5-45 weight part, can also be 10-40 weight part, or 20-35 weight part.
According to the present invention, select oneself one or both in diacid and dodecanedioic acid of described molecular weight regulator.Preferably, the add-on of described molecular weight regulator is 10-25 weight part, more preferably 15-20 weight part.
According to the present invention, described molecular chain stablizer is selected from one or both in phenylformic acid and acetic acid.Preferably, the add-on of described molecular chain stablizer is 0.1-0.8 weight part, can also be 0.3-0.5 weight part.
According to the present invention, described catalyzer is selected from one or both in ortho phosphorous acid and N-ethanoyl hexanolactam.Preferably, the add-on of described catalyzer is 0.1-0.6 weight part, can also be 0.2-0.5 weight part.
According to the present invention, described oxidation inhibitor is selected from antioxidant 1010: four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Oxidation inhibitor 1096:IRGANOX B-1096; Oxidation inhibitor 1098:(N, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine) and phosphite ester kind antioxidant interworking thing; Irgasfos 168: one or more in three [2.4-di-tert-butyl-phenyl] phosphorous acid ester.Oxidation inhibitor can prevent that, in 3D print procedure, Yin Gaowen causes the decomposition of nylon.
Preferably, the add-on of described oxidation inhibitor is 0.2-0.8 weight part, can also be 0.3-0.5 weight part.
The present invention also provides the preparation method of the high sticky nylon composite granule composition of a kind of heat conduction, it is characterized in that, described method comprises the steps:
(1) the high temperature resistant inert solvent of 100～600 weight parts is joined in reactor, in whipping process by the amide salt of 100 weight parts, the graphite of 1～50 weight part, the molecular weight regulator of 5～30 weight parts, after being stirred to and mixing, after adding weight part is 0.01～1 molecular chain stablizer, weight part is 0.02～0.8 catalyzer and the oxidation inhibitor of 0.1～1 weight part in reactor, be stirred to and mixing;
(2) temperature of reactor is carried out at least two sections of intensifications, first by room temperature, being evenly warming up within a certain period of time temperature is 180～220 ℃, the pressure in reactor is maintained between 1.5～2MPa simultaneously; Continue afterwards reacting by heating still, the temperature that makes reactor is 180～220 ℃ by temperature within for some time, and to be warming up to temperature be 280～285 ℃, and reduce pressure in reactor to 1.01MPa; In temperature, be 270～285 ℃ of insulations after 30～60 minutes, vacuumize, the pressure drop in reactor is low to moderate to 0.3Pa, and under this pressure, continues 1～4 hour;
(3) the bleeder valve discharging of opening reactor to container, vigorous stirring 10～100 minutes, centrifugation, dry, making relative viscosity is 4～20, particle diameter is at the composite heat-conducting nylon powder of 20-100 micron.
According to the present invention, described method specifically comprises the steps:
(1) the high temperature resistant inert solvent of 100～600 weight parts is joined in reactor, in whipping process by the amide salt of 100 weight parts, the graphite of 1～50 weight part, the molecular weight regulator of 5～30 weight parts, after being stirred to and mixing, after adding weight part is 0.01～1 molecular chain stablizer, weight part is 0.02～0.8 catalyzer and the oxidation inhibitor of 0.1～1 weight part in reactor, be stirred to and mixing;
(2) reactor carried out to inflated with nitrogen and vacuumize the air of processing with in discharge reactor; Then in reactor, be filled with nitrogen, the initial pressure in reactor is maintained between 0.2～0.5MPa;
(3) temperature of reactor being evenly warming up to temperature in 90～120 minutes by 25 ℃ is 180～220 ℃, and is incubated 30～60 minutes, the pressure in reactor is maintained between 1.5～2MPa simultaneously; Continue afterwards reacting by heating still, the temperature that makes reactor was 180～220 ℃ by temperature in 120～180 minutes, and to be warming up to temperature be 280～285 ℃, during this period, at the uniform velocity discharges gas reactor, reduces pressure in reactor to 1.01MPa; In temperature, be 270～285 ℃ of insulations after 30～60 minutes, vacuumize, the pressure drop in reactor is low to moderate to 0.3Pa, and under this pressure, continues 1～4 hour;
(4) stop stirring, in reactor, be filled with nitrogen, make the pressure in reactor be increased to 0.2～0.5MPa by 0.3Pa, open the bleeder valve discharging of reactor to container, vigorous stirring 10～100 minutes, centrifugation, dry, making relative viscosity is 4～20, particle diameter is at the composite heat-conducting nylon powder of 20-100 micron.
According to the present invention, described high temperature resistant inert solvent is selected from silicone oil or phenyl silicone oil.
The present invention also provides the application of above-mentioned nylon powder composition, it is characterized in that, described nylon powder composition is applied to 3D printing technique, and wherein, described nylon powder is selected from the nylon powder of the invention described above.
The present invention also provides a kind of 3D Method of printing, it is characterized in that, uses nylon powder of the present invention as printed material.
According to the present invention, described Method of printing comprises the steps:
(1) nylon powder composition of the present invention is deposited on carrier surface, and coverage goal region;
(2) described nylon powder composition is flattened, formed a smooth surface;
(3) energy-beam is irradiated on target area, makes described powder form an integral layer; With
(4) repeating step (1)～(3), to form other each layer whole and adjacent each layer of bonding, thereby obtain three-dimensional article.
The present invention also provides a kind of three-dimensional article, it is characterized in that, described three-dimensional article comprises nylon powder composition of the present invention.
The present invention is the principle of utilizing home position polymerization reaction, by graphite and amide salt etc. is carried out to home position polymerization reaction, prepares heat conduction nylon powder composite material in high boiling solvent.Owing to being home position polymerization reaction, graphite is uniformly dispersed in nylon matrix, interfacial interaction power between graphite and nylon matrix is strong, be conducive to heat in the conduction of interface, reduce interface resistance, also utilize stress in the transmission of interface, thereby the heat conductivility of heat conduction nylon powder composition is obviously improved, and stronger interface interaction has also significantly improved mechanical property and the thermostability of heat conduction nylon composite materials simultaneously.Heat conduction nylon powder prepared by the present invention, relatively sticky 4-20, particle diameter is adjustable in 20-100 micron.The goods that the present invention makes can be used for 3D to be printed, its product size good stability, and thermal conductivity is high, can meet the demands of field to high-performance and baroque heat-conductive composite material such as heat energy utilization and chemical industry heat exchange.
Embodiment
Below by embodiment, the present invention is described in further detail, but this should be interpreted as to scope of the present invention only limits to following example.In the situation that not departing from aforesaid method thought of the present invention, various replacements or the change according to ordinary skill knowledge and customary means, made, all should be within the scope of the present invention.
Comparative example 1:
Common nylon powder, particle diameter 30-50 μ m, the material that relative viscosity is 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, formed a smooth surface;
(3) energy-beam is irradiated on target area, makes described powder form an integral layer; With
(4) repeating step (1)～(3), to form other each layer whole and adjacent each layer of bonding, thereby obtain three-dimensional article, and its product performance are in Table 1.
Embodiment 1
The high temperature resistant inert solvent silicone oil of 100 weight parts is joined in reactor, in whipping process by the nylon salt of 100 weight parts, the particle diameter of 1 weight part is 0.2 micron of crystalline flake graphite, the hexanodioic acid of 5 weight parts, after being stirred to and mixing, after adding weight part is 0.01 phenylformic acid, weight part is 0.02 ortho phosphorous acid and the antioxidant 1010 of 0.1 weight part in reactor, be stirred to and mixing; Reactor is carried out inflated with nitrogen and vacuumizes processing to discharge the air in reactor; Then in reactor, be filled with nitrogen, the initial pressure in reactor is maintained between 0.2～0.5MPa; The temperature of reactor was evenly warming up to temperature in 90 minutes by 25 ℃ be 180～190 ℃, and be incubated 30 minutes, the pressure in reactor maintained between 1.5～2MPa simultaneously; Continue afterwards reacting by heating still, make the temperature of reactor by temperature, be 180～190 ℃ in 180 minutes and be warming up to 280～285 ℃, during this period, at the uniform velocity discharge gas reactor, reduce pressure in reactor to 1.01MPa; In temperature, be 270 ℃ of insulations after 30 minutes, vacuumize, the pressure drop in reactor is low to moderate to 0.3Pa, and under this pressure, continues 1 hour; Stop stirring, in reactor, be filled with nitrogen, make the pressure in reactor be increased to 0.2～0.5MPa by 0.3Pa, open the bleeder valve discharging of reactor to container, vigorous stirring 10 minutes, centrifugation, dry, making relative viscosity is 20, particle diameter is at the composite heat-conducting nylon powder of 80-100 micron.
Above-mentioned nylon powder is carried out to 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, formed a smooth surface;
(3) energy-beam is irradiated on target area, makes described powder form an integral layer; With
(4) repeating step (1)～(3), to form other each layer whole and adjacent each layer of bonding, thereby obtain three-dimensional article, and thermal characteristics and mechanical performance data are in Table 1.
Embodiment 2
The high temperature resistant inert solvent phenyl silicone oil of 100 weight parts is joined in reactor, in whipping process by the NYLON610 salt of 100 weight parts, the particle diameter of 10 weight parts is the expanded graphite of 5 microns, the dodecanedioic acid of 10 weight parts, after being stirred to and mixing, after adding weight part is 0.1 acetic acid, weight part is 0.1 N-ethanoyl hexanolactam and the oxidation inhibitor 1096 of 0.5 weight part in reactor, be stirred to and mixing; Reactor is carried out inflated with nitrogen and vacuumizes processing to discharge the air in reactor; Then in reactor, be filled with nitrogen, the initial pressure in reactor is maintained between 0.2～0.5MPa; The temperature of reactor was evenly warming up to temperature in 100 minutes by 25 ℃ be 190～200 ℃, and be incubated 40 minutes, the pressure in reactor maintained between 1.5～2MPa simultaneously; Continue afterwards reacting by heating still, make the temperature of reactor by temperature, be 190～200 ℃ in 140 minutes and be warming up to 280～285 ℃, during this period, at the uniform velocity discharge gas reactor, reduce pressure in reactor to 1.01MPa; In temperature, be 280 ℃ of insulations after 40 minutes, vacuumize, the pressure drop in reactor is low to moderate to 0.3Pa, and under this pressure, continues 2 hours; Stop stirring, in reactor, be filled with nitrogen, make the pressure in reactor be increased to 0.2～0.5MPa by 0.3Pa, open the bleeder valve discharging of reactor to container, vigorous stirring 30 minutes, centrifugation, dry, making relative viscosity is 15, particle diameter is at the composite heat-conducting nylon powder of 60-80 micron, and it is identical with embodiment 1 that its 3D prints article process, and thermal characteristics and mechanical performance data are in Table 1.
Embodiment 3
The high temperature resistant inert solvent silicone oil of 600 weight parts is joined in reactor, in whipping process by the nylon 612 salt of 100 weight parts, the particle diameter of 50 weight parts is the aphanitic graphite of 50 microns, the hexanodioic acid of 30 weight parts, after being stirred to and mixing, after adding weight part is 1 phenylformic acid, weight part is 0.5 ortho phosphorous acid and the irgasfos 168 of 1 weight part in reactor, be stirred to and mixing; Reactor is carried out inflated with nitrogen and vacuumizes processing to discharge the air in reactor; Then in reactor, be filled with nitrogen, the initial pressure in reactor is maintained between 0.2～0.5MPa; The temperature of reactor was evenly warming up to temperature in 120 minutes by 25 ℃ be 210～220 ℃, and be incubated 60 minutes, the pressure in reactor maintained between 1.5～2MPa simultaneously; Continue afterwards reacting by heating still, make the temperature of reactor by temperature, be 210～220 ℃ in 120 minutes and be warming up to 280～285 ℃, during this period, at the uniform velocity discharge gas reactor, reduce pressure in reactor to 1.01MPa; In temperature, be 285 ℃ of insulations after 60 minutes, vacuumize, the pressure drop in reactor is low to moderate to 0.3Pa, and under this pressure, continues 4 hours; Stop stirring, in reactor, be filled with nitrogen, make the pressure in reactor be increased to 0.2～0.5MPa by 0.3Pa, open the bleeder valve discharging of reactor to container, vigorous stirring 100 minutes, centrifugation, dry, making relative viscosity is 10, particle diameter is at the composite heat-conducting nylon powder of 50-70 micron, and it is identical with embodiment 1 that its 3D prints article process, and thermal characteristics and mechanical performance data are in Table 1.
Embodiment 4
The high temperature resistant inert solvent phenyl silicone oil of 300 weight parts is joined in reactor, in whipping process by the nylon salt of 100 weight parts, the particle diameter of 15 weight parts is the electrographite of 10 microns, the dodecanedioic acid of 15 weight parts, after being stirred to and mixing, after adding weight part is 0.5 acetic acid, weight part is 0.8 N-ethanoyl hexanolactam and the oxidation inhibitor 1096 of 0.8 weight part in reactor, be stirred to and mixing; Reactor is carried out inflated with nitrogen and vacuumizes processing to discharge the air in reactor; Then in reactor, be filled with nitrogen, the initial pressure in reactor is maintained between 0.2～0.5MPa; The temperature of reactor was evenly warming up to temperature in 110 minutes by 25 ℃ be 200～210 ℃, and be incubated 50 minutes, the pressure in reactor maintained between 1.5～2MPa simultaneously; Continue afterwards reacting by heating still, make the temperature of reactor by temperature, be 200～210 ℃ in 130 minutes and be warming up to 280～285 ℃, during this period, at the uniform velocity discharge gas reactor, reduce pressure in reactor to 1.01MPa; In temperature, be 280 ℃ of insulations after 50 minutes, vacuumize, the pressure drop in reactor is low to moderate to 0.3Pa, and under this pressure, continues 3 hours; Stop stirring, in reactor, be filled with nitrogen, make the pressure in reactor be increased to 0.2～0.5MPa by 0.3Pa, open the bleeder valve discharging of reactor to container, vigorous stirring 30 minutes, centrifugation, dry, making relative viscosity is 4, particle diameter is at the composite heat-conducting nylon powder of 20-40 micron, and it is identical with embodiment 1 that its 3D prints article process, and thermal characteristics and mechanical performance data are in Table 1.
Table 1 performance data and testing method
Claims (10)
1. the high sticky nylon composite granule composition of heat conduction, is characterized in that, described composition is obtained through polyreaction by the raw material of following weight part, and the weight part of amide salt of take is benchmark, and wherein said raw material comprises:
2. according to the composition of claim 1, it is characterized in that, preferably, one or more in nylon salt, NYLON610 salt and nylon 612 salt of described amide salt.
Preferably, described powder raw material carries out home position polymerization reaction and obtains after mixing.
3. according to the composition of claim 1 or 2, it is characterized in that, the relative viscosity of described nylon powder is 4-20, preferred 5-18, and more preferably 6-15, can also be 8-10.
Preferably, the particle diameter of described nylon powder is 20～100 microns, and more preferably 30-90 micron, or 40-80 micron can also be 50-70 micron.
4. according to the composition of claim 1-3 any one, it is characterized in that, the particle diameter of described graphite is 0.2～50 micron, preferred 1-40 micron, and more preferably 5-30 micron, can also be 10-20 micron.
Preferably, described graphite is selected from one or more in crystalline flake graphite, expanded graphite, aphanitic graphite and electrographite.
Also preferably, the add-on of described graphite is 5-45 weight part, can also be 10-40 weight part, or 20-35 weight part.
5. according to the composition of claim 1-4 any one, it is characterized in that select oneself one or both in diacid and dodecanedioic acid of described molecular weight regulator.Preferably, the add-on of described molecular weight regulator is 10-25 weight part, more preferably 15-20 weight part.
Preferably, described molecular chain stablizer is selected from one or both in phenylformic acid and acetic acid.Also preferably, the add-on of described molecular chain stablizer is 0.1-0.8 weight part, can also be 0.3-0.5 weight part.
Preferably, described catalyzer is selected from one or both in ortho phosphorous acid and N-ethanoyl hexanolactam.Also preferably, the add-on of described catalyzer is 0.1-0.6 weight part, can also be 0.2-0.5 weight part.
Preferably, described oxidation inhibitor is selected from antioxidant 1010: four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Oxidation inhibitor 1096:IRGANOX B-1096; Oxidation inhibitor 1098:(N, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine) and phosphite ester kind antioxidant interworking thing; Irgasfos 168: one or more in three [2.4-di-tert-butyl-phenyl] phosphorous acid ester.Also preferably, the add-on of described oxidation inhibitor is 0.2-0.8 weight part, can also be 0.3-0.5 weight part.
6. a preparation method for the high sticky nylon composite granule composition of the heat conduction of claim 1-5 any one, is characterized in that, described method comprises the steps:
(1) the high temperature resistant inert solvent of 100～600 weight parts is joined in reactor, in whipping process by the amide salt of 100 weight parts, the graphite of 1～50 part, the molecular weight regulator of 5～30 weight parts, after being stirred to and mixing, after adding weight part is 0.01～1 molecular chain stablizer, weight part is 0.02～0.8 catalyzer and the oxidation inhibitor of 0.1～1 weight part in reactor, be stirred to and mixing;
(2) temperature of reactor is carried out at least two sections of intensifications, first by room temperature, being evenly warming up within a certain period of time temperature is 180～220 ℃, the pressure in reactor is maintained between 1.5～2MPa simultaneously; Continue afterwards reacting by heating still, the temperature that makes reactor is 180～220 ℃ by temperature within for some time, and to be warming up to temperature be 280～285 ℃, and reduce pressure in reactor to 1.01MPa; In temperature, be 270～285 ℃ of insulations after 30～60 minutes, vacuumize, the pressure drop in reactor is low to moderate to 0.3Pa, and under this pressure, continues 1～4 hour;
(3) the bleeder valve discharging of opening reactor to container, vigorous stirring 10～100 minutes, centrifugation, dry, making relative viscosity is 4～20, particle diameter is at the composite heat-conducting nylon powder of 20-100 micron.
7. according to the preparation method of claim 6, it is characterized in that, described method comprises the steps:
(1) the high temperature resistant inert solvent of 100～600 weight parts is joined in reactor, in whipping process by the amide salt of 100 weight parts, the graphite of 1～50 part, the molecular weight regulator of 5～30 weight parts, after being stirred to and mixing, after adding weight part is 0.01～1 molecular chain stablizer, weight part is 0.02～0.8 catalyzer and the oxidation inhibitor of 0.1～1 weight part in reactor, be stirred to and mixing;
(2) reactor carried out to inflated with nitrogen and vacuumize the air of processing with in discharge reactor; Then in reactor, be filled with nitrogen, the initial pressure in reactor is maintained between 0.2～0.5MPa;
(3) temperature of reactor being evenly warming up to temperature in 90～120 minutes by 25 ℃ is 180～220 ℃, and is incubated 30～60 minutes, the pressure in reactor is maintained between 1.5～2MPa simultaneously; Continue afterwards reacting by heating still, the temperature that makes reactor was 180～220 ℃ by temperature in 120～180 minutes, and to be warming up to temperature be 280～285 ℃, during this period, at the uniform velocity discharges gas reactor, reduces pressure in reactor to 1.01MPa; In temperature, be 270～285 ℃ of insulations after 30～60 minutes, vacuumize, the pressure drop in reactor is low to moderate to 0.3Pa, and under this pressure, continues 1～4 hour;
(4) stop stirring, in reactor, be filled with nitrogen, make the pressure in reactor be increased to 0.2～0.5MPa by 0.3Pa, open the bleeder valve discharging of reactor to container, vigorous stirring 10～100 minutes, centrifugation, dry, making relative viscosity is 4～20, particle diameter is at the composite heat-conducting nylon powder of 20-100 micron.
Preferably, described high temperature resistant inert solvent is selected from silicone oil or phenyl silicone oil.
8. the application of the high sticky nylon composite granule composition of the heat conduction of claim 1-5 any one, is characterized in that, described nylon powder composition is applied to 3D printing technique.
9. a 3D Method of printing, is characterized in that, right to use requires the high sticky nylon composite granule composition of the heat conduction of 1-5 any one as printed material.
Preferably, described Method of printing comprises the steps:
(1) nylon composite granule composition of the present invention is deposited on carrier surface, and coverage goal region;
(2) described nylon composite granule composition is flattened, formed a smooth surface;
(3) energy-beam is irradiated on target area, makes described powder form an integral layer; With
(4) repeating step (1)～(3), to form two outer each layers whole and adjacent each layer of bonding, thereby obtain three-dimensional article.
10. a three-dimensional article, is characterized in that, described three-dimensional article comprises the high sticky nylon composite granule composition of the heat conduction of claim 1-5 any one.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410181731.0A CN103992473B (en) | 2014-04-30 | 2014-04-30 | The heat conduction height that a kind of 3D of can be used for prints glues nylon powder body and preparation method thereof |
| US15/507,662 US11472929B2 (en) | 2014-04-30 | 2015-04-24 | Nylon powder composition for 3D printing, and preparation method and application thereof |
| PCT/CN2015/077350 WO2015165361A1 (en) | 2014-04-30 | 2015-04-24 | Nylon powder composition for 3d printing, and preparation method and use thereof |
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|---|---|---|---|
| CN201410181731.0A CN103992473B (en) | 2014-04-30 | 2014-04-30 | The heat conduction height that a kind of 3D of can be used for prints glues nylon powder body and preparation method thereof |
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| CN103992473A true CN103992473A (en) | 2014-08-20 |
| CN103992473B CN103992473B (en) | 2016-09-21 |
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Cited By (9)
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| CN104910616A (en) * | 2015-06-30 | 2015-09-16 | 广东银禧科技股份有限公司 | Low-temperature nylon powder material for selective laser sintering and preparation method thereof |
| WO2015165361A1 (en) * | 2014-04-30 | 2015-11-05 | 中国科学院化学研究所 | Nylon powder composition for 3d printing, and preparation method and use thereof |
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| CN105711094A (en) * | 2016-03-15 | 2016-06-29 | 东华大学 | Three-dimensional printing method |
| CN109593355A (en) * | 2018-11-09 | 2019-04-09 | 湖南华曙高科技有限责任公司 | Nylon polymer dusty material and preparation method thereof |
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| CN113874417A (en) * | 2019-07-15 | 2021-12-31 | 惠普发展公司，有限责任合伙企业 | Three-dimensional printing |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102477219A (en) * | 2010-11-29 | 2012-05-30 | 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 |
| CN102604381A (en) * | 2012-03-30 | 2012-07-25 | 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 |
| CN103467978A (en) * | 2013-09-23 | 2013-12-25 | 湖南工业大学 | Multi-component compound modified nylon 6 composite material for carrier roller and preparation method thereof |
-
2014
- 2014-04-30 CN CN201410181731.0A patent/CN103992473B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102477219A (en) * | 2010-11-29 | 2012-05-30 | 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 |
| CN102604381A (en) * | 2012-03-30 | 2012-07-25 | 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 |
| CN103467978A (en) * | 2013-09-23 | 2013-12-25 | 湖南工业大学 | Multi-component compound modified nylon 6 composite material for carrier roller and preparation method thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015165361A1 (en) * | 2014-04-30 | 2015-11-05 | 中国科学院化学研究所 | Nylon powder composition for 3d printing, and preparation method and use thereof |
| CN104910616A (en) * | 2015-06-30 | 2015-09-16 | 广东银禧科技股份有限公司 | Low-temperature nylon powder material for selective laser sintering and preparation method thereof |
| WO2017000923A1 (en) * | 2015-06-30 | 2017-01-05 | 广东银禧科技股份有限公司 | Low-temperature nylon powder material for selective laser sintering and preparation method therefor |
| CN104910616B (en) * | 2015-06-30 | 2017-07-21 | 广东银禧科技股份有限公司 | It is a kind of for low temperature nylon powder material of selective laser sintering and preparation method thereof |
| CN105150540A (en) * | 2015-09-28 | 2015-12-16 | 常州大学 | Printing applicability evaluation method for fuse deposition molding three-dimensional printing materials |
| CN105711094A (en) * | 2016-03-15 | 2016-06-29 | 东华大学 | Three-dimensional printing method |
| CN109593355A (en) * | 2018-11-09 | 2019-04-09 | 湖南华曙高科技有限责任公司 | Nylon polymer dusty material and preparation method thereof |
| CN109593355B (en) * | 2018-11-09 | 2022-01-14 | 湖南华曙高科技有限责任公司 | Nylon polymer powder material and preparation method thereof |
| CN109897177B (en) * | 2019-02-27 | 2021-04-06 | 中国科学院福建物质结构研究所 | Workpiece with multi-scale three-dimensional heat conduction network and preparation method thereof |
| WO2020244523A1 (en) * | 2019-06-06 | 2020-12-10 | 南京工程学院 | Method for preparing nylon powder and use thereof |
| CN113874417A (en) * | 2019-07-15 | 2021-12-31 | 惠普发展公司，有限责任合伙企业 | Three-dimensional printing |
| CN112679727A (en) * | 2020-11-19 | 2021-04-20 | 裕克施乐塑料制品（太仓）有限公司 | Heat-conducting powder with three-layer structure for SLS (selective laser sintering), and preparation and use methods thereof |
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