CN103980484A - Heat-conductive high-molecular-weight nylon powder for 3D printing and preparation method thereof - Google Patents
Heat-conductive high-molecular-weight nylon powder for 3D printing and preparation method thereof Download PDFInfo
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Abstract
The invention provides a heat-conductive high-molecular-weight nylon powder composition which is characterized in that the powder composition is prepared through a polymerization reaction from raw materials comprising, by weight, 100 parts of lactam monomer, 1-50 parts of graphite, 0.005-1 part of an alkaline catalyst, 0.01-2 parts of an activator and 0.1-1 part of an anti-oxidant agent, wherein the lactam monomer is selected from one or more of caprolactam, decalactam and dodecalactam. The invention also provides a preparation method of the heat-conductive nylon powder composition and an application thereof. The molecular weight of the heat-conductive nylon powder can be adjusted in a range from 50000 to 1200000 and the particle size of the heat-conductive nylon powder can be controlled in a range from 20 to 100 microns with a uniform distribution. The powder can be used for 3D printing with stability of a product size being good and a thermal conductivity performance being high and can satisfy requirement of heat-conductive composite materials having high performance and complex structure in the technical fields of heat energy utilization, chemical heat exchange and the like.
Description
Technical field
The present invention relates to a kind of heat-conducting polymer amount nylon powder and preparation method thereof, be specifically related to high molecular weight nylon powder 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 of taking 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 material and generate the technology of 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.
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 producing the energy of being launched by laser in the target area of parts.When 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 enforcement laser radiation, powder is preheating to the slightly temperature lower than its fusing point, then under the effect that strikes off rod, powder is paved; Laser beam carries out sintering selectively according to point 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.Connecting by one computer that the manipulation light of CAD/CAM system scans to form parts " thin slice " controls laser energy and launches and be confined to selected target area part.Irradiate after the first layer " thin slice " that forms parts at powdered material, 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, be mainly used in foundry industry for above feature SLS method, and can be used for directly making fast mould.
Exploitation is adapted to the starting material of above-mentioned 3D printing technique, has become the emphasis of current various countries research.
Pure nylon material powder body material, dimensional stability and the thermotolerance of goods prepared by use 3D printing technique are all not so good.
Summary of the invention
For overcoming above-mentioned defect, the object of the present invention is to provide a kind of heat-conducting polymer nylon powder composite material, product size good stability, thermal conductivity is high.
One of object of the present invention is to provide the heat-conducting polymer amount nylon powder body material that a kind of 3D of can be used for prints.
Two of object of the present invention is by lactam monomers anionoid polymerization, prepares the nylon powder of heat-conducting polymer amount, thereby a kind of preparation method of heat-conducting polymer amount nylon powder of the 3D of can be used for printing is provided.
The present invention utilizes anionoid polymerization principle, under the condition existing, makes lactam monomers in Graphite Powder 99 generation home position polymerization reaction at basic catalyst, prepares heat conduction nylon powder.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 the conduction of heat in interface, reduce interface resistance, also utilize the transmission of stress in interface, thereby the heat conductivility of the heat conduction nylon powder composite material of preparation is obviously improved, and stronger interface interaction has also significantly improved mechanical property and the thermostability of heat conduction nylon composite materials simultaneously.Powder prepared by this method, tool molecular weight is high, the feature of good heat conductivity.Heat conduction nylon powder prepared by the present invention, nylon molecular weight can regulate and control at 5-120 ten thousand, and diameter of particle is controlled in 20-100 micrometer range, and size distribution homogeneous.Product size good stability of the present invention, thermal conductivity is high, can meet the demand of field to high-performance and baroque heat-conductive composite material such as heat energy utilization and chemical industry heat exchange.The nylon powder of high molecular 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 heat-conducting polymer amount nylon composite granule composition, is characterized in that, described powder composition is obtained through polyreaction by the raw material of following weight part, taking the weight part of lactam monomers as benchmark, wherein:
The described lactan lactan of selecting oneself, ten lactan, one or more in laurolactam.
According to the present invention, described powder composition is after mixing, to carry out original position melt polymerization by above-mentioned raw materials to obtain.
According to the present invention, in described powder, the viscosity-average molecular weight of nylon is 5～1,200,000, and high molecular is conducive to the raising of the performances such as product mechanics, and particle diameter is 20～100 microns, and this particle size range is beneficial to 3D complete processing.
According to the present invention, the molecular weight of described nylon is preferably 10-100 ten thousand, or 15-60 ten thousand, and 25-60 ten thousand can also be 35-45 ten thousand.
According to the present invention, the particle diameter of described nylon powder is preferably 30-90 micron, or 40-80 micron, can also be 50-70 micron.
According to the present invention, described activator is selected from benzene 2, one or more that 4-vulcabond (TDI), lek are received in glue, hexamethylene diisocyanate (HDI), '-diphenylmethane diisocyanate (MDI), poly methylene poly phenyl poly isocyanate (PAPI), triphenylmethane triisocyanate (JQ-1 glue) and diphenyl carbonate.
According to the present invention, described basic catalyst is selected from one or more in sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium ethylate and sodium methylate.
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 particle diameter of described graphite is 0.2～50 micron, and preferably 0.5-30 micron, or 1-20 micron, can also be 5-10 micron.
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, 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.
According to the present invention, the preferred add-on of described basic catalyst is 0.007-0.8, can also be 0.05-0.5,0.1-0.2 weight part.
According to the present invention, the preferred add-on of described oxidation inhibitor is: 0.2-0.8 weight part can also be 0.3-0.5 weight part.
According to the present invention, the preferred add-on of described activator is 0.1-1.5 weight part, and 0.2-1 weight part can also be 0.5-0.8 weight part.
The present invention also provides the preparation method of above-mentioned heat-conducting polymer amount nylon composite granule composition, it is characterized in that, described method comprises:
(1) taking the weight part of lactam monomers as benchmark, the graphite of the lactam monomers of 100 weight parts and 1～50 weight part is joined in container, under vacuum state, dewater;
(2) add the basic catalyst of 0.005～1 weight part and the oxidation inhibitor of 0.1～1 weight part, continue to vacuumize, be warming up to 130～140 DEG C, insulation reaction 10～30 minutes;
(3) then, add the activator of 0.01～2 weight part, be stirred to and mix, pour into and be equipped with in the container that is preheated to 150～170 DEG C of solid particulates, after insulation vigorous stirring for some time, be down to room temperature,
(4) by sorting method, obtaining molecular weight is 5～1,200,000, and particle diameter is the heat conduction nylon composite granule of 20～100 microns.
According to the present invention, preferably, described method specifically comprises:
(1) taking the weight part of lactam monomers as benchmark, the graphite of the lactam monomers of 100 weight parts and 1～50 weight part being joined in container, is to vacuumize at 90～120 DEG C in temperature, under vacuum state, dewaters;
(2) in the time of the pressure <400Pa of the system shown in vacuumometer, remove vacuum, add the basic catalyst of 0.005～1 weight part and the oxidation inhibitor of 0.1～1 weight part, continue to vacuumize, be warming up to 130～140 DEG C, in the time of the shown system pressure <400Pa of vacuumometer, insulation reaction 10～30 minutes;
(3) then, add the activator of 0.01～2 weight part, be stirred to and mix, pour into and be equipped with in the container that is preheated to 150～170 DEG C of solid particulates, insulation vigorous stirring, after 10～30 minutes, is down to room temperature (as 25 DEG C～30 DEG C) naturally,
(4) by sorting method, obtaining molecular weight is 5～1,200,000, and particle diameter is the heat conduction nylon composite granule of 20～100 microns.
In aforesaid method, use solid particulate will contribute to lactam monomers in molecular weight propagation process, the nylon powder of the high molecular of formation can not occur mutually bonding.In the sorting method of step (4), can sub-elect solid particulate, thereby this particle is reused simultaneously.
According to the present invention, the particle diameter of described solid particulate is 1～50 micron.
Magnetic material powders such as described solid particulate chosen from Fe, nickel, cobalt or be selected from one or more in quartz sand, silica dioxide granule and Machine-made Sand.
According to the present invention, the size separation equipment using in step (4) is selected from the one in Magnet Separater, suction type aspirator and cycle winnowing device.
The present invention also provides the application of above-mentioned high molecular weight nylon composite granule composition, it is characterized in that, described composition is applied to 3D printing technique, and wherein, described nylon powder is selected from the nylon composite granule composition of the invention described above.
The present invention also provides a kind of 3D Method of printing, it is characterized in that, uses nylon composite granule composition of the present invention as printed material.
According to the present invention, 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 entirety and adjacent each layer of other each layer of boning, 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 composite granule composition of the present invention.
Heat conduction nylon powder of the present invention, be to carry out in-situ polymerization through lactan at graphite surface, under the existence of hot particle, form the nylon powder of high molecular, be applied to 3D and print, work performance, thermostability, thermal conductivity are better, and product mechanical property and the heat conductivility of preparation are all better.
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 made according to ordinary skill knowledge and customary means, all should be within the scope of the present invention.
Comparative example:
Taking the weight part of caprolactam monomer as benchmark, by the caprolactam monomer of 100 weight parts, be to vacuumize at 90 DEG C in temperature, under vacuum state, dewater, in the time of the pressure <400Pa of the system shown in vacuumometer, remove vacuum, add the sodium hydroxide of 0.005 weight part, continue to vacuumize, be warming up to 130 DEG C, in the time of the pressure <400Pa of the shown system of vacuumometer, insulation reaction 10 minutes, add 0.06 weight part to benzene 2, 4-vulcabond, be stirred to and mix, pour in the mould that is preheating to 170 degree, be incubated after 30 minutes, naturally be cooled to 25 degree, then through pulverize at low temperature, preparing particle diameter is the heat conduction nylon composite granule of 20-30 micron, gained composite granule is printed for 3D, its preparation process:
(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 entirety and adjacent each layer of other each layer of boning, thereby obtain three-dimensional article.The thermal characteristics of 3D printed product and mechanical property are in table 1.
Embodiment 1
Taking the weight part of caprolactam monomer as benchmark, the crystalline flake graphite that is 5 microns by the particle diameter of the caprolactam monomer of 100 weight parts and 1 weight part joins in container, be to vacuumize at 90 DEG C in temperature, under vacuum state, dewater, in the time of the pressure <400Pa of the system shown in vacuumometer, remove vacuum, add the sodium hydroxide of 0.005 weight part and the antioxidant 1010 of 0.1 weight part, continue to vacuumize, be warming up to 130 DEG C, in the time of the pressure <400Pa of the shown system of vacuumometer, insulation reaction 10 minutes, add 0.01 weight part to benzene 2, 4-vulcabond, be stirred to and mix, pour into and be equipped with that to be preheated to the particle diameter of 160 DEG C be in the container of quartz sand of 1 micron, insulation vigorous stirring 10 minutes, naturally be cooled to 25 DEG C, afterwards by using suction type aspirator sorting method, obtaining viscosity-average molecular weight is 1,200,000, particle diameter is the heat conduction nylon composite granule of 20-30 micron, gained composite granule is printed for 3D, its preparation process:
(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 entirety and adjacent each layer of other each layer of boning, thereby obtain three-dimensional article.The thermal characteristics of 3D printed product and mechanical property are in table 1.
Embodiment 2
Taking the weight part of caprolactam monomer as benchmark, the expanded graphite that is 0.5 micron by the particle diameter of the caprolactam monomer of 100 weight parts and 10 weight parts joins in container, be to vacuumize at 100 DEG C in temperature, under vacuum state, dewater, in the time of the pressure <400Pa of the system shown in vacuumometer, remove vacuum, add the potassium hydroxide of 0.007 weight part and the oxidation inhibitor 1096 of 0.5 weight part, continue to vacuumize, be warming up to 135 DEG C, in the time of the pressure <400Pa of the shown system of vacuumometer, insulation reaction 10 minutes, add the lek of 0.15 weight part to receive glue, after being stirred to and mixing, pour into and be equipped with that to be preheated to the particle diameter of 165 DEG C be the iron of 10 microns, nickel, in the container of cobalt magnetic substance powder, insulation vigorous stirring is after 10 minutes, naturally be cooled to 25 DEG C, insulation vigorous stirring 10 minutes, naturally be cooled to 25 DEG C, afterwards by using Magnet Separater sorting method, obtaining viscosity-average molecular weight is 600,000, particle diameter is the heat conduction nylon composite granule of 30-50 micron.The preparation process of 3D product is identical with the 3D product preparation method in embodiment 1.The thermal characteristics of 3D printed product and mechanical property are in table 1.
Embodiment 3
Taking the weight part of ten lactam monomers as benchmark, the aphanitic graphite that is 10 microns by the particle diameter of ten lactam monomers of 100 weight parts and 50 weight parts joins in container, be to vacuumize at 120 DEG C in temperature, under vacuum state, dewater, in the time of the pressure <400Pa of the system shown in vacuumometer, remove vacuum, add the magnesium hydroxide of 1 weight part and the irgasfos 168 of 1 weight part, continue to vacuumize, be warming up to 140 DEG C, in the time of the pressure <400Pa of the shown system of vacuumometer, insulation reaction 20 minutes, add the hexamethylene diisocyanate of 2 weight parts, after being stirred to and mixing, pour into and be equipped with that to be preheated to the particle diameter of 180 DEG C be in the container of Machine-made Sand of 20 microns, insulation vigorous stirring is after 20 minutes, naturally be cooled to 25 DEG C, afterwards by using cycle winnowing device sorting method, obtaining viscosity-average molecular weight is 450,000, particle diameter is the heat conduction nylon composite granule of 40-60 micron.The preparation process of 3D product is identical with the 3D product preparation method in embodiment 1.The thermal characteristics of 3D printed product and mechanical property are in table 1.
Embodiment 4
Taking the weight part of ten lactam monomers as benchmark, the electrographite that is 1 micron by the particle diameter of ten lactam monomers of 100 weight parts and 25 weight parts joins in container, be to vacuumize at 110 DEG C in temperature, under vacuum state, dewater, in the time of the pressure <400Pa of the system shown in vacuumometer, remove vacuum, add the sodium ethylate of 0.1 weight part and the antioxidant 1010 of 0.3 weight part, continue to vacuumize, while being warming up to the pressure <400Pa of 135 DEG C and the shown system of vacuumometer, insulation reaction 30 minutes, add the '-diphenylmethane diisocyanate of 1 weight part, be stirred to and mix, pour into and be equipped with that to be preheated to the particle diameter of 170 DEG C be in the container of quartz sand of 15 microns, insulation vigorous stirring is after 30 minutes, naturally be cooled to 25 DEG C, afterwards by using cycle winnowing device sorting method, obtaining viscosity-average molecular weight is 350,000, particle diameter is the heat conduction nylon composite granule of 50-70 micron.The preparation process of 3D product is identical with the 3D product preparation method in embodiment 1.The thermal characteristics of 3D printed product and mechanical property are in table 1.
Embodiment 5
Taking the weight part of laurolactam monomer as benchmark, the electrographite that is 0.2 micron by the particle diameter of the laurolactam monomer of 100 weight parts and 30 weight parts joins in container, be to vacuumize at 100 DEG C in temperature, under vacuum state, dewater, in the time of the pressure <400Pa of the system shown in vacuumometer, remove vacuum, add the sodium methylate of 0.05 weight part and the oxidation inhibitor 1096 of 0.8 weight part, continue to vacuumize, be warming up to 135 DEG C, in the time of the pressure <400Pa of the shown system of vacuumometer, insulation reaction 15 minutes, add the poly methylene poly phenyl poly isocyanate of 0.5 weight part, be stirred to and mix, pour into and be equipped with that to be preheated to the particle diameter of 170 DEG C be in the container of silica dioxide granule of 10 microns, insulation vigorous stirring is after 20 minutes, naturally be cooled to 25 DEG C, afterwards by using cycle winnowing device sorting method, sticky must molecular weight be all 250,000, particle diameter is the heat conduction nylon composite granule of 60-80 micron.The preparation process of 3D product is identical with the 3D product preparation method in embodiment 1.The thermal characteristics of 3D printed product and mechanical property are in table 1.
Embodiment 6
Taking the weight part of laurolactam monomer as benchmark, the crystalline flake graphite that is 30 microns by the particle diameter of the laurolactam monomer of 100 weight parts and 40 weight parts joins in container, be to vacuumize at 115 DEG C in temperature, under vacuum state, dewater, in the time of the pressure <400Pa of the system shown in vacuumometer, remove vacuum, add the sodium hydroxide of 0.5 weight part and the irgasfos 168 of 0.1 weight part, continue to vacuumize, be warming up to 130 DEG C, in the time of the pressure <400Pa of the shown system of vacuumometer, insulation reaction 30 minutes, add the triphenylmethane triisocyanate of 0.2 weight part, be stirred to and mix, pour into and be equipped with that to be preheated to the particle diameter of 165 DEG C be in the container of silica dioxide granule of 20 microns, insulation vigorous stirring is after 15 minutes, naturally be cooled to 25 DEG C, afterwards by using cycle winnowing device sorting method, obtaining viscosity-average molecular weight is 150,000, particle diameter is the heat conduction nylon composite granule of 70-90 micron.The preparation process of 3D product is identical with the 3D product preparation method in embodiment 1.The thermal characteristics of 3D printed product and mechanical property are in table 1.
Embodiment 7
Taking the weight part of caprolactam monomer as benchmark, the aphanitic graphite that is 50 microns by the particle diameter of the caprolactam monomer of 100 weight parts and 35 weight parts joins in container, be to vacuumize at 120 DEG C in temperature, under vacuum state, dewater, in the time of the pressure <400Pa of the system shown in vacuumometer, remove vacuum, add the sodium hydroxide of 0.2 weight part and the antioxidant 1010 of 1 weight part, continue to vacuumize, be warming up to 140 DEG C, in the time of the pressure <400Pa of the shown system of vacuumometer, insulation reaction 20 minutes, add the diphenyl carbonate of 0.8 weight part, be stirred to and mix, pour into and be equipped with that to be preheated to the particle diameter of 170 DEG C be the iron of 50 microns, nickel, in the container of cobalt magnetic substance powder, and be incubated 170 DEG C of vigorous stirring, naturally be cooled to 25 DEG C, afterwards by using Magnet Separater sorting method, obtaining viscosity-average molecular weight is 100,000, particle diameter is the heat conduction nylon composite granule of 80-100 micron.The preparation process of 3D product is identical with the 3D product preparation method in embodiment 1.The thermal characteristics of 3D printed product and mechanical property are in table 1.
Thermal characteristics and the mechanical property of table 13D printed product
Claims (10)
1. a heat-conducting polymer amount nylon composite granule composition, is characterized in that, described powder composition is obtained through polyreaction by the raw material of following weight part, taking the weight part of lactam monomers as benchmark, wherein:
The described lactan lactan of selecting oneself, ten lactan, one or more in laurolactam.
2. according to the composition of claim 1, it is characterized in that, described powder body material is after mixing, to carry out original position melt polymerization by above-mentioned raw materials to obtain.
3. according to the composition of claim 1 or 2, it is characterized in that, in described powder, the viscosity-average molecular weight of nylon is 5～1,200,000, is preferably 10-100 ten thousand, or 15-60 ten thousand, and 25-60 ten thousand can also be 35-45 ten thousand.
Preferably, particle diameter is 20～100 microns, and more 30-90 micron, or 40-80 micron can also be 50-70 micron.
4. according to the composition of claims 1 to 3 any one, it is characterized in that, described activator is selected from benzene 2, one or more that 4-vulcabond (TDI), lek are received in glue, hexamethylene diisocyanate (HDI), '-diphenylmethane diisocyanate (MDI), poly methylene poly phenyl poly isocyanate (PAPI), triphenylmethane triisocyanate (JQ-1 glue) and diphenyl carbonate.Preferably, the preferred add-on of described activator is 0.1-1.5, and 0.2-1 can also be 0.5-0.8.
Preferably, described basic catalyst is selected from one or more in sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium ethylate and sodium methylate.Preferably, the preferred add-on of described basic catalyst is 0.007-0.8, can also be 0.05-0.5 weight part, 0.1-0.2 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.Preferably, the preferred add-on of described oxidation inhibitor is: 0.2-0.8 can also be 0.3-0.5 weight part.
Preferably, described graphite is selected from one or more in crystalline flake graphite, expanded graphite, aphanitic graphite and electrographite.
Preferably, the particle diameter of described graphite is 0.2～50 micron, and preferably 0.5-30 micron, or 1-20 micron, can also be 5-10 micron.
More 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. the preparation method of the heat-conducting polymer amount nylon composite granule composition of claim 1-4 any one, is characterized in that, described method comprises:
(1) taking the weight part of lactam monomers as benchmark, the graphite of the lactam monomers of 100 weight parts and 1～50 weight part is joined in container, under vacuum state, dewater;
(2) then add the basic catalyst of 0.005～1 weight part and the oxidation inhibitor of 0.1～1 weight part, continue to vacuumize, be warming up to 130～140 DEG C, insulation reaction 10～30 minutes;
(3) then, add the activator of 0.01～2 weight part, be stirred to and mix, pour into and be equipped with in the container that is preheated to 150～170 DEG C of solid particulates, after insulation vigorous stirring for some time, be down to room temperature,
(4) by sorting method, obtaining molecular weight is 5～1,200,000, and particle diameter is the heat conduction nylon composite granule of 20～100 microns.
6. according to the preparation method of claim 5, it is characterized in that, described method comprises:
(1) taking the weight part of lactam monomers as benchmark, the graphite of the lactam monomers of 100 weight parts and 1～50 weight part being joined in container, is to vacuumize at 90～120 DEG C in temperature, under vacuum state, dewaters;
(2) in the time of the pressure <400Pa of the system shown in vacuumometer, remove vacuum, add the basic catalyst of 0.005～1 weight part and the oxidation inhibitor of 0.1～1 weight part, continue to vacuumize, be warming up to 130～140 DEG C, in the time of the shown system pressure <400Pa of vacuumometer, insulation reaction 10～30 minutes;
(3) then, add the activator of 0.01～2 weight part, be stirred to and mix, pour into and be equipped with in the container that is preheated to 150～170 DEG C of solid particulates, insulation vigorous stirring, after 10～30 minutes, is down to room temperature (as 25 DEG C～30 DEG C) naturally,
(4) by sorting method, obtaining molecular weight is 5～1,200,000, and particle diameter is the heat conduction nylon composite granule of 20～100 microns.
7. according to the preparation method of claim 5 or 6, it is characterized in that, the particle diameter of described solid particulate is 1～50 micron.
Preferably, the magnetic material powder such as described solid particulate chosen from Fe, nickel, cobalt or be selected from one or more in quartz sand, silica dioxide granule and Machine-made Sand.
According to the present invention, the size separation equipment using in step (4) is selected from the one in Magnet Separater, suction type aspirator and cycle winnowing device.
8. the application of the high molecular weight nylon powder composition of claim 1-4 any one, is characterized in that, described composition is applied to 3D printing technique.
9. a 3D Method of printing, is characterized in that, right to use requires the nylon powder composition of 1-4 any one as printed material.
Preferably, described Method of printing comprises the steps:
(1) the nylon powder composition of claim 1-4 any one 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 entirety and adjacent each layer bonding two outer each layer, thus acquisition three-dimensional article.
10. a three-dimensional article, is characterized in that, described three-dimensional article comprises the nylon powder composition of claim 1-4 any one.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410181764.5A CN103980484B (en) | 2014-04-30 | 2014-04-30 | A kind of heat-conducting polymer amount nylon powder body that can be applicable to 3D printing 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410181764.5A CN103980484B (en) | 2014-04-30 | 2014-04-30 | A kind of heat-conducting polymer amount nylon powder body that can be applicable to 3D printing and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103980484A true CN103980484A (en) | 2014-08-13 |
| CN103980484B CN103980484B (en) | 2016-09-21 |
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| 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 |
| 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 |
| CN110831400A (en) * | 2019-10-08 | 2020-02-21 | 裕克施乐塑料制品（太仓）有限公司 | Three-layer integrated efficient high-strength heat conducting fin and preparation method thereof |
| CN111372975A (en) * | 2017-09-22 | 2020-07-03 | 剑桥实业有限公司 | Treatment of polymer particles |
| CN113454143A (en) * | 2019-02-13 | 2021-09-28 | 阿科玛法国公司 | Salted monomer powder and its use in a powder agglomeration process |
| CN115654029A (en) * | 2022-10-31 | 2023-01-31 | 泰尔重工股份有限公司 | Universal coupling end face tooth and manufacturing method thereof and universal coupling |
| CN113454143B (en) * | 2019-02-13 | 2024-06-04 | 阿科玛法国公司 | Salified monomer powder and its use in a powder agglomeration process |
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| CN103013102A (en) * | 2012-12-12 | 2013-04-03 | 中国科学院宁波材料技术与工程研究所 | LED (Light-Emitting Diode) heat radiator and preparation method thereof |
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| CN103012775A (en) * | 2012-12-03 | 2013-04-03 | 合肥杰事杰新材料股份有限公司 | Cast nylon 6 composite and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN105711094A (en) * | 2016-03-15 | 2016-06-29 | 东华大学 | Three-dimensional printing method |
| CN111372975A (en) * | 2017-09-22 | 2020-07-03 | 剑桥实业有限公司 | Treatment of polymer particles |
| CN111372975B (en) * | 2017-09-22 | 2024-03-29 | 剑桥实业有限公司 | Treatment of polymer particles |
| 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 |
| CN113454143A (en) * | 2019-02-13 | 2021-09-28 | 阿科玛法国公司 | Salted monomer powder and its use in a powder agglomeration process |
| CN113454143B (en) * | 2019-02-13 | 2024-06-04 | 阿科玛法国公司 | Salified monomer powder and its use in a powder agglomeration process |
| CN110831400A (en) * | 2019-10-08 | 2020-02-21 | 裕克施乐塑料制品（太仓）有限公司 | Three-layer integrated efficient high-strength heat conducting fin and preparation method thereof |
| CN115654029A (en) * | 2022-10-31 | 2023-01-31 | 泰尔重工股份有限公司 | Universal coupling end face tooth and manufacturing method thereof and universal coupling |
| CN115654029B (en) * | 2022-10-31 | 2024-01-23 | 泰尔重工股份有限公司 | Universal coupling end face tooth, manufacturing method thereof and universal coupling |
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