CN114276566B - Nylon powder and preparation method and application thereof - Google Patents
Nylon powder and preparation method and application thereof Download PDFInfo
- Publication number
- CN114276566B CN114276566B CN202111590512.4A CN202111590512A CN114276566B CN 114276566 B CN114276566 B CN 114276566B CN 202111590512 A CN202111590512 A CN 202111590512A CN 114276566 B CN114276566 B CN 114276566B
- Authority
- CN
- China
- Prior art keywords
- temperature
- nylon
- suspension
- powder
- nylon powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004677 Nylon Substances 0.000 title claims abstract description 82
- 229920001778 nylon Polymers 0.000 title claims abstract description 82
- 239000000843 powder Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 52
- 239000000725 suspension Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 14
- 238000000110 selective laser sintering Methods 0.000 claims description 11
- 238000010146 3D printing Methods 0.000 claims description 4
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000299 Nylon 12 Polymers 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 35
- 238000009826 distribution Methods 0.000 abstract description 19
- 238000005516 engineering process Methods 0.000 abstract description 14
- 239000002904 solvent Substances 0.000 description 21
- 239000011347 resin Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002226 simultaneous effect Effects 0.000 description 2
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Landscapes
- Polyamides (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses nylon powder and a preparation method and application thereof, wherein the preparation method of the nylon powder comprises the following steps: the temperature of the nylon hot solution is reduced to T 1 Performing a first nucleation-growth to form a first suspension; raising the temperature of the first suspension to T 2 Then cooling to T 3 Performing a second nucleation-growth to obtain a second suspension; wherein T is 2 ‑T 1 ≤15℃，T 2 ‑T 3 The temperature is less than or equal to 15 ℃; continuing to cool the second suspension to form a precipitate; and (3) carrying out post-treatment on the precipitate to obtain nylon powder. The nylon powder prepared by the method has the advantages of narrow particle size distribution, large apparent density and high yield, and can well meet the use of SLS technology.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to nylon powder and a preparation method and application thereof.
Background
The selective laser sintering technology, namely SLS (Selective Laser Sintering) technology, is a typical 3D printing technology, utilizes a layered manufacturing idea, utilizes a discrete-stacking principle to stack materials layer by layer to manufacture an emerging manufacturing technology of a solid object, embodies the close combination of an information network technology, an advanced material technology and a digital manufacturing technology, and is an important component of intelligent manufacturing. Through the rapid development for many years, the SLS technology is widely applied to various fields of automobiles, household appliances, aerospace, medical biology and the like, and is one of the 3D printing technologies with mature application at present.
At present, most of selective laser sintering nylon powder is prepared by adopting a solvent precipitation method, namely nylon resin is dissolved in a proper solvent, and the powder is separated out by a cooling crystallization mode. However, although the existing nylon powder prepared by the common solvent precipitation method can easily meet the particle size requirement of the SLS technology, the prepared powder has the particle size (D50) of less than 60 mu m, the apparent density of the powder is not less than 420g/L, the particle size distribution width (D90-D10) basically exceeds 50 mu m, the performance requirement of laser sintering is difficult to meet, meanwhile, the preparation method requires very high temperature control precision, the fluctuation of the temperature easily causes the fluctuation of the particle size distribution width to be larger, and the later powder often needs sieving treatment, so that the yield is lower. Therefore, nylon powder prepared by adopting the existing solvent precipitation technology still cannot well meet the requirements of the selective laser sintering technology in terms of cost and performance.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a preparation method of nylon powder, which can prepare nylon powder with narrow particle size distribution, large apparent density and high yield.
Meanwhile, the invention also provides nylon powder and application thereof.
Specifically, the invention adopts the following technical scheme:
the first aspect of the present invention provides a method for preparing nylon powder, comprising the steps of:
the temperature of the nylon hot solution is reduced to T 1 Performing a first nucleation-growth to form a first suspension;
raising the temperature of the first suspension to T 2 Then cooling to T 3 Performing a second formingCore-growth to obtain a second suspension; wherein T is 2 -T 1 ≤15℃，T 2 -T 3 ≤15℃；
Continuing to cool the second suspension to form a precipitate; and (3) carrying out post-treatment on the precipitate to obtain nylon powder.
The invention adopts the crystallization process of twice nucleation-growth, and the temperature interval of the twice nucleation-growth is not more than 15 ℃, so that most nylon molecules can be nucleated and grown in the same temperature interval, the particle size of the powder can be intensively distributed in a certain narrower range, and the nylon powder with narrow particle size distribution is obtained. After the first nucleation-growth, the temperature is slightly increased, and the nylon powder with small particle size and oversized particle size is skillfully redissolved, so that the particle sizes of the powder are intensively distributed. Meanwhile, the temperature interval of the two nucleation-growth is not more than 15 ℃, so that the control precision requirement on temperature points in the actual operation process is relatively loose, the fault tolerance of the powder particle size distribution is improved, and the stability of the powder particle size distribution is improved.
In some embodiments of the invention, T 2 -T 1 ≤10℃，T 2 -T 3 ≤10℃。
In some embodiments of the invention, the nylon hot solution has a temperature of 135 to 160 ℃.
In some preferred embodiments, the nylon thermal solution is obtained by dissolving a nylon resin in a solvent under a protective atmosphere and at an elevated temperature.
More specifically, the preparation method of the nylon hot solution comprises the steps of mixing nylon resin and a solvent, and heating the obtained mixture to 135-160 ℃ under a protective atmosphere to dissolve the nylon resin to obtain the nylon hot solution. In the preparation process of the nylon hot solution, protective gas can be introduced to apply pressure to the mixture of the nylon resin and the solvent, or the mixture of the nylon resin and the solvent is heated in a closed container at the same time, and the dissolution of the nylon resin in the solvent is promoted by the pressure generated in the heating process.
In some embodiments of the invention, the dissolution time is 30 to 120 minutes. The dissolution process is generally kept at a constant temperature.
In some embodiments of the invention, the nylon resin comprises at least one of nylon 6, nylon 610, nylon 66, nylon 11, nylon 12, nylon 1010, nylon 1012, nylon 1212.
In some embodiments of the invention, the solvent comprises at least one of methanol, ethanol, DMF, DMA, water; preferably, the solvent is a mixed solvent, and contains a main solvent and an auxiliary solvent, wherein the main solvent comprises at least one of methanol, ethanol, DMF and DMA, and the auxiliary solvent comprises water. The proportion of the auxiliary solvent in the mixed solvent is 0.1-10wt%.
In some embodiments of the invention, the weight ratio of nylon resin to solvent is 1:5 to 20.
In some embodiments of the invention, the nylon hot solution contains an antioxidant. By adding an antioxidant, the nylon resin is prevented from being oxidized during the various subsequent processes of dissolution, nucleation-growth. The weight ratio of the antioxidant to the nylon is 1:10 to 10000.
Preferably, the antioxidant comprises at least one of antioxidant 168, antioxidant 1098, antioxidant 1010 and antioxidant 1076.
Preferably, the shielding gas includes at least one of nitrogen, argon and helium, and in actual operation, the shielding gas is a high-purity gas.
It should be appreciated that a nylon hot solution can be obtained by other methods and solvents in the art in addition to the above-listed methods, solvent types, and ratios, as long as the nylon resin can be dissolved in the solvent to form a uniform solution.
In some embodiments of the invention, the T 1 118-123 ℃. Preferably, the nylon hot solution is cooled to T through two stages 1 Wherein the first stage is cooled to 128-132 ℃, and the second stage is cooled from 128-132 ℃ to T 1 (118～123℃)。
In some embodiments of the invention, the first stage has a cooling rate of 1 to 5 ℃/min. Cooling to 128-132 deg.c, maintaining for 1-30 min and the second stage.
In some embodiments of the invention, the second stage is performed at a cooling rate of 0.5 to 3 ℃/min, and the second stage is performed for 1 to 30min to obtain the first suspension.
In actual operation, the solution can be cooled by indirect cold-heat exchange (such as coil heat exchange), and the cooling rate is adjusted by controlling the temperature of the cooling medium.
In some embodiments of the invention, the T 2 128-132 ℃.
In some embodiments of the invention, the temperature of the first suspension is raised to T 2 The process of (2) can be realized as follows: cooling the first suspension by indirect heat exchange (such as coil heat exchange), heating the first suspension, and regulating cooling rate and heating rate of heat exchange to increase temperature of the first suspension to T 2 . Preferably, the temperature of the cooling medium for cold-heat exchange is set to 115 to 120℃and the first suspension is heated at a rate of 0.1 to 0.5℃per minute, thereby raising the temperature of the first suspension to T 2 。
In practical operation, the nylon hot solution and the first suspension are generally contained in a certain reaction container (such as an autoclave), a coil pipe can be arranged in the reaction container so as to exchange heat with the coil pipe, and the reaction container is arranged in a heating device (such as an autoclave jacket) so as to realize simultaneous cooling and heating and easily realize accurate control of temperature.
For example, when the temperature is lowered by means of coil heat exchange and the heating is performed by means of an autoclave jacket, the temperature of the coil heat exchange can be maintained at 115 to 120℃during the second nucleation-growth process while the suspension is raised to 123 to 125℃by means of the autoclave jacket at a rate of 0.1 to 0.5℃per minute, at which time the autoclave temperature is raised to 128 to 132℃by adjusting the rate of lowering the temperature of the coil heat exchange. The cooling rate and the heating rate are reasonably regulated, and particularly, the cooling effect of the heat exchange of the coil of the autoclave effectively keeps the compactness of the powder through the simultaneous effect of the heat exchange of the coil and the jacket, and meanwhile, the nylon powder with small particle size and oversized particle size is skillfully redissolved through the heating effect of the jacket, so that the particle size of the powder is intensively distributed.
In some embodiments of the invention, the T 3 118-123 ℃, T is as follows 3 And T is 1 May be the same or different.
In some embodiments of the invention, the method comprises the step of 2 Cooling to T 3 At a rate of 0.1-3 ℃/min, at T 3 Keeping the temperature for 1-30 min.
In some embodiments of the invention, the step of cooling the second suspension to form a precipitate is more specifically to reduce the temperature of the second suspension to 108-110 ℃ to form a precipitate.
Preferably, the cooling process of the second suspension comprises two stages, wherein the first stage is to cool the second suspension to 113-115 ℃ at a cooling rate of 0.05-0.2 ℃/min, and then to cool the second suspension to 108-110 ℃ at a cooling rate of 0.02-0.12 ℃/min.
In some embodiments of the invention, the post-treatment step includes reducing the temperature of the precipitate-containing suspension to 20-50 ℃ (the rate of reduction may be set to 10-50 ℃/h, or other suitable rate), followed by solid-liquid separation, drying, and the like.
In general, during the preparation process, the temperature of the nylon hot solution was varied as follows: reducing the temperature from 135 ℃ to 160 ℃ to 128 ℃ to 132 ℃ at a rate of 1 ℃ to 5 ℃ per minute, and reducing the temperature to 118 ℃ to 123 ℃ at a rate of 0.5 ℃ to 3 ℃ per minute after keeping the temperature constant for 1 to 30 minutes 1 ) Keeping the temperature for 1-30 min; then heating to 128-132 deg.C (T) 2 ) Then the temperature is reduced to 118-123 ℃ at a speed of 0.1-3 ℃/min 3 ) Keeping the temperature for 1-30 min; then the temperature is reduced to 113-115 ℃ at the speed of 0.05-0.2 ℃/min, and then the temperature is reduced to 108-110 ℃ at the speed of 0.02-0.12 ℃/min; finally, the temperature is reduced to 20-50 ℃.
In a second aspect, the present invention provides a nylon powder produced by the above method. The average particle diameter of the nylon powder is 50-60 mu m, the particle diameter distribution (D90-D10) is less than 50 mu m, and the loose packed density is more than 420g/L.
A third aspect of the invention is to provide the use of the nylon powder in SLS 3D (selective laser sintering 3D) printing.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of the nylon powder, the crystallization process of twice nucleation and growth is adopted in the same temperature interval, so that most of nylon molecules nucleate and grow in the same interval, the particle size of the powder is intensively distributed in a certain narrower range, and as the temperature interval is not more than 15 ℃, preferably not more than 10 ℃, the control accuracy requirement of temperature points is loose, the fault tolerance of the particle size distribution of the powder is improved, and the stability of the particle size distribution of the powder is improved; meanwhile, the cooling rate and the heating rate are reasonably regulated in the process, particularly, the cooling effect of the heat exchange of the coil pipe of the autoclave effectively keeps the compactness of the powder through the simultaneous effect of the heat exchange of the coil pipe and the jacket, and meanwhile, the nylon powder with small particle size and oversized particle size is skillfully redissolved through the heating effect of the jacket, so that the particle size of the powder is concentrated and distributed.
The particle size of the nylon powder obtained by the preparation method disclosed by the invention is totally distributed within the range of 30-120 mu m, meets the requirements of a laser sintering technology on the powder, does not need screening treatment after crystallization, removes the residual loss in the process, basically and completely becomes a powder product, shortens the production process flow, improves the production efficiency and also improves the yield of the powder.
In the preparation method, the solvent only comprises water and an organic solvent, and the water can be recycled, so that the mixed solvent after crystallization can be recycled only by simple distillation, and the production cost is reduced.
Drawings
FIG. 1 is a graph showing the temperature change during the preparation of nylon powder;
FIG. 2 is a particle size distribution diagram of the nylon powder of example 1;
FIG. 3 is a particle size distribution diagram of the nylon powder of example 2;
FIG. 4 is a particle size distribution diagram of the nylon powder of example 3;
fig. 5 is a particle size distribution diagram of the nylon powder of comparative example 1.
Detailed Description
The invention provides a preparation method of nylon powder with narrow particle size distribution suitable for SLS 3D printing, which comprises the steps of dissolving nylon resin and a proper amount of antioxidant in a mixed solvent of an autoclave under the protection of inert gas, then completing a crystallization process of primary nucleation-growth in a two-stage cooling mode by heat exchange of a coil, then completing a crystallization process of secondary nucleation-growth by the simultaneous action of temperature rising of a coil and a jacket, finally realizing powder morphology optimization and precipitation endpoint by two-stage slow cooling, and obtaining nylon powder with good dispersibility through aftertreatment. The temperature change of the solution during the preparation is shown in fig. 1.
The technical scheme of the invention is further described below with reference to specific examples. The starting materials used in the examples below, unless otherwise specified, are all commercially available from conventional sources; the processes used, unless otherwise specified, are all conventional in the art.
Example 1
600g of nylon 1012 resin, 3750ml of ethanol, 200g of water and 1.8g of antioxidant 1098 are added into an autoclave, high-purity nitrogen is replaced for 20min and then pressurized to 1MPa, and then the mixture is heated to 145 ℃ and kept at a constant temperature for 90min while stirring to dissolve the materials. Then carrying out two-stage cooling through heat exchange of a coil pipe, wherein the cooling rate in the first stage is 3 ℃/min to 130 ℃, and the temperature is kept for 10min; the second stage cooling rate is 1 ℃/min to 120 ℃ and the temperature is kept constant for 10min. Then maintaining the temperature of the coil heat exchange at 120 ℃, simultaneously heating the suspension to 123 ℃ through an autoclave jacket at a rate of 0.2 ℃/min, at the moment, heating the autoclave to 130 ℃ by adjusting the cooling rate of the coil heat exchange, and then adjusting the coil heat exchange to cool the suspension to 120 ℃ at a cooling rate of 0.4 ℃/min, and keeping the temperature constant for 5min. And then regulating heat exchange of a coil pipe, reducing the temperature of the suspension to 115 ℃ at a cooling rate of 0.16 ℃/min, reducing the temperature of the suspension to 110 ℃ at a cooling rate of 0.12 ℃/min, after powder precipitation is finished, reducing the temperature of the suspension to below 50 ℃ at a cooling rate of 30 ℃/h, and performing post treatment to obtain nylon powder with good dispersibility.
The particle size distribution of the nylon powder was tested as follows: d10:40.00 μm, D50:55.15 μm, D90:76.42 μm, bulk density 463g/L, angle of repose 28℃as shown in FIG. 2.
Example 2
600g of nylon 12 resin, 3750ml of ethanol, 200g of water and 1.8g of antioxidant 1098 are added into an autoclave, high-purity nitrogen is replaced for 20min and then pressurized to 1MPa, and then the mixture is heated to 145 ℃ while stirring and kept at a constant temperature for 90min to dissolve the materials. Then carrying out two-stage cooling through heat exchange of a coil pipe, wherein the cooling rate in the first stage is 3 ℃/min to 131 ℃, and the temperature is kept for 10min; the second stage cooling rate is 1 ℃/min to 119 ℃, and the temperature is kept constant for 10min. Then maintaining the temperature of the coil heat exchange at 120 ℃, simultaneously heating the suspension to 123 ℃ through an autoclave jacket at a rate of 0.2 ℃/min, at the moment, heating the autoclave to 131 ℃ by adjusting the cooling rate of the coil heat exchange, and then adjusting the coil heat exchange to cool the suspension to 119 ℃ at a cooling rate of 0.4 ℃/min, and keeping the temperature constant for 5min. And then regulating heat exchange of a coil pipe, reducing the temperature of the suspension to 115 ℃ at a cooling rate of 0.16 ℃/min, reducing the temperature of the suspension to 110 ℃ at a cooling rate of 0.12 ℃/min, after powder precipitation is finished, reducing the temperature of the suspension to below 50 ℃ at a cooling rate of 30 ℃/h, and performing post treatment to obtain nylon powder with good dispersibility.
The particle size distribution of the nylon powder was tested as follows: d10:37.10 μm, D50:53.51 μm, D90:76.66 μm, bulk density 452g/L, angle of repose 28℃as shown in FIG. 3.
Example 3
600g of nylon 1012 resin, 3750ml of ethanol, 200g of water and 1.8g of antioxidant 1098 are added into an autoclave, high-purity nitrogen is replaced for 20min and then pressurized to 1MPa, and then the mixture is heated to 145 ℃ and kept at a constant temperature for 90min while stirring to dissolve the materials. Then carrying out two-stage cooling through heat exchange of a coil pipe, wherein the cooling rate in the first stage is 3 ℃/min to 129 ℃, and the temperature is kept for 10min; the second stage cooling rate is 1 ℃/min to 119 ℃, and the temperature is kept constant for 10min. Then maintaining the temperature of the coil heat exchange at 120 ℃, simultaneously heating the suspension to 123 ℃ through an autoclave jacket at a rate of 0.2 ℃/min, at the moment, heating the autoclave to 131 ℃ by adjusting the cooling rate of the coil heat exchange, and then adjusting the coil heat exchange to cool the suspension to 119 ℃ at a cooling rate of 0.4 ℃/min, and keeping the temperature constant for 5min. And then regulating heat exchange of a coil pipe, reducing the temperature of the suspension to 115 ℃ at a cooling rate of 0.16 ℃/min, reducing the temperature of the suspension to 110 ℃ at a cooling rate of 0.12 ℃/min, after powder precipitation is finished, reducing the temperature of the suspension to below 50 ℃ at a cooling rate of 30 ℃/h, and performing post treatment to obtain nylon powder with good dispersibility.
The particle size distribution of the nylon powder was tested as follows: d10:35.56 μm, D50:52.90 μm, D90:78.05 μm, bulk density 445g/L, angle of repose 28℃as shown in FIG. 4.
Comparative example 1
600g of nylon 1012 particles, 3750ml of ethanol, 200g of water and 1.8g of antioxidant 1098 are added into an autoclave, high-purity nitrogen is replaced for 20min, and then the mixture is heated to 145 ℃ with stirring and kept at a constant temperature for 90min to dissolve the materials. Then cooling, wherein the cooling rate in the first stage is 0.5 ℃/min to 123 ℃; the second stage cooling rate is 0.1 ℃/min to 108 ℃, and then cooling to normal temperature rapidly. And obtaining nylon powder after post-treatment such as filtration, drying and the like.
The particle size distribution of the nylon powder was tested as follows: d10:36.16 μm, D50:57.67 μm, D90:90.57 μm, a bulk density of 356g/L and an angle of repose of 34℃as shown in FIG. 5.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (3)
1. A preparation method of nylon powder is characterized in that: the method comprises the following steps:
the temperature of the nylon hot solution is reduced to T1, and the first nucleation-growth is carried out to form a first suspension;
raising the temperature of the first suspension to T2, then cooling to T3, and carrying out nucleation-growth for the second time to obtain a second suspension; wherein T2-T1 is less than or equal to 15 ℃, and T2-T3 is less than or equal to 15 ℃;
continuing to cool the second suspension to form a precipitate; post-processing the precipitate to obtain nylon powder;
the nylon hot solution is cooled to T1 through two stages, wherein the first stage is cooled to 128-132 ℃ and the second stage is cooled to T1 from 128-132 ℃;
the process of raising the temperature of the first suspension to T2 is achieved as follows: cooling the first suspension by indirect cold and heat exchange, and heating the first suspension at the same time, and adjusting the cooling rate and heating rate of the cold and heat exchange to increase the temperature of the first suspension to T2;
the temperature of the nylon hot solution is 135-160 ℃;
the temperature of T1 is 118-123 ℃;
the temperature of T2 is 128-132 ℃;
the temperature of T3 is 118-123 ℃;
the step of cooling the second suspension to form a precipitate comprises the following steps: the temperature of the second suspension is reduced to 108-110 ℃ to form a precipitate;
the nylon is selected from any one of nylon 1012 and nylon 12.
2. A nylon powder, characterized in that: the nylon powder is prepared by the preparation method of claim 1.
3. Use of the nylon powder of claim 2 for selective laser sintering 3D printing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111590512.4A CN114276566B (en) | 2021-12-23 | 2021-12-23 | Nylon powder and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111590512.4A CN114276566B (en) | 2021-12-23 | 2021-12-23 | Nylon powder and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114276566A CN114276566A (en) | 2022-04-05 |
| CN114276566B true CN114276566B (en) | 2023-11-28 |
Family
ID=80874533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111590512.4A Active CN114276566B (en) | 2021-12-23 | 2021-12-23 | Nylon powder and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114276566B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5932687A (en) * | 1997-03-05 | 1999-08-03 | Huels Aktiengesellschaft | Preparation of precipitated polyamide powders of narrow particle size distribution and low porosity |
| CN101570059A (en) * | 2008-03-19 | 2009-11-04 | 赢创德固赛有限责任公司 | Copolyamide powder and its production, its use in a moulding method and object made of this copolyamide powder |
| CA2736448A1 (en) * | 2010-04-07 | 2011-10-07 | Evonik Goldschmidt Gmbh | Polyamide 1010 powder and its use in personal care products |
| CN102399371A (en) * | 2011-10-17 | 2012-04-04 | 湖南华曙高科技有限责任公司 | Preparation method of polyamide powder for selective laser sintering |
| CN104385608A (en) * | 2014-09-30 | 2015-03-04 | 湖南华曙高科技有限责任公司 | Polyamide powder for laser sintering and preparation method thereof |
| CN104497323A (en) * | 2014-12-17 | 2015-04-08 | 湖南华曙高科技有限责任公司 | Preparation method of nylon powder for selective laser sintering |
| CN105778128A (en) * | 2016-05-11 | 2016-07-20 | 广东银禧科技股份有限公司 | Method for improving Tf-Tc difference value of polyamide material and polyamide material |
| DE102015016131A1 (en) * | 2015-12-14 | 2017-06-14 | Evonik Degussa Gmbh | Polymer composition for selective sintering processes |
| CN107236295A (en) * | 2017-05-19 | 2017-10-10 | 湖南华曙高科技有限责任公司 | A kind of selective laser sintering polyamide 610 dusty material and preparation method |
| CN110684213A (en) * | 2018-07-06 | 2020-01-14 | 绿点高新科技股份有限公司 | Method for producing polyamide powder and composition for producing polyamide powder |
| CN110885456A (en) * | 2019-12-13 | 2020-03-17 | 万华化学集团股份有限公司 | Nylon powder with narrow particle size distribution, preparation method thereof and application thereof in 3D printing |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6402810B1 (en) * | 2016-07-22 | 2018-10-10 | 株式会社リコー | Three-dimensional modeling resin powder, three-dimensional model manufacturing apparatus, and three-dimensional model manufacturing method |
-
2021
- 2021-12-23 CN CN202111590512.4A patent/CN114276566B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5932687A (en) * | 1997-03-05 | 1999-08-03 | Huels Aktiengesellschaft | Preparation of precipitated polyamide powders of narrow particle size distribution and low porosity |
| CN101570059A (en) * | 2008-03-19 | 2009-11-04 | 赢创德固赛有限责任公司 | Copolyamide powder and its production, its use in a moulding method and object made of this copolyamide powder |
| CA2736448A1 (en) * | 2010-04-07 | 2011-10-07 | Evonik Goldschmidt Gmbh | Polyamide 1010 powder and its use in personal care products |
| CN102399371A (en) * | 2011-10-17 | 2012-04-04 | 湖南华曙高科技有限责任公司 | Preparation method of polyamide powder for selective laser sintering |
| CN104385608A (en) * | 2014-09-30 | 2015-03-04 | 湖南华曙高科技有限责任公司 | Polyamide powder for laser sintering and preparation method thereof |
| CN104497323A (en) * | 2014-12-17 | 2015-04-08 | 湖南华曙高科技有限责任公司 | Preparation method of nylon powder for selective laser sintering |
| DE102015016131A1 (en) * | 2015-12-14 | 2017-06-14 | Evonik Degussa Gmbh | Polymer composition for selective sintering processes |
| CN105778128A (en) * | 2016-05-11 | 2016-07-20 | 广东银禧科技股份有限公司 | Method for improving Tf-Tc difference value of polyamide material and polyamide material |
| CN107236295A (en) * | 2017-05-19 | 2017-10-10 | 湖南华曙高科技有限责任公司 | A kind of selective laser sintering polyamide 610 dusty material and preparation method |
| CN110684213A (en) * | 2018-07-06 | 2020-01-14 | 绿点高新科技股份有限公司 | Method for producing polyamide powder and composition for producing polyamide powder |
| CN110885456A (en) * | 2019-12-13 | 2020-03-17 | 万华化学集团股份有限公司 | Nylon powder with narrow particle size distribution, preparation method thereof and application thereof in 3D printing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114276566A (en) | 2022-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110735073A (en) | high-quality 6-series aluminum alloy extruded casting blank and preparation method thereof | |
| CN101837267B (en) | Synthesis process of diamond with square crystals | |
| CN110791686A (en) | Aluminum alloy powder material for additive manufacturing, and preparation method and application thereof | |
| EP4001452A1 (en) | Amorphous nanocrystalline soft magnetic material, preparation method therefor and use thereof, amorphous ribbon material, amorphous nanocrystalline ribbon material, and amorphous nanocrystalline magnetic sheet | |
| US20220205071A1 (en) | Fe-based amorphous alloy containing subnanometer-scale ordered clusters, and preparation method and nanocrystalline alloy derivative thereof | |
| CN112593106B (en) | Laser additive manufacturing method capable of conveniently obtaining fine equiaxed grains | |
| CN110273176B (en) | Method for preparing large-area copper Cu (111) single crystal | |
| CN103012937B (en) | Preparation method of polyethylene casting film | |
| CN114276566B (en) | Nylon powder and preparation method and application thereof | |
| CN116332645A (en) | Molybdenum oxide tantalum target material and preparation method and application thereof | |
| CN112063976B (en) | Ultrahigh-purity copper target material and grain control method thereof | |
| CN103045926A (en) | TiB2/Si-Al electronic packaging composite material and preparation method of TiB2/Si-Al electronic packaging composite material | |
| CN108928822B (en) | Method for preparing molybdenum carbide by gaseous reduction of molybdenum oxide | |
| CN117123143B (en) | Method for synthesizing special-shaped dodecahedron diamond | |
| CN109942953B (en) | Thermal degradation polypropylene gradient phase change heat storage material and preparation method thereof | |
| CN110241420A (en) | A kind of cemented carbide material and hard alloy exemplar | |
| CN115975209A (en) | Method for synthesizing MOFs material in all solid phases | |
| CN114990391A (en) | Creep-resistant Al-Mg alloy for selective laser melting and preparation method thereof | |
| CN115142137A (en) | Novel optical coating material and preparation method thereof | |
| CN113681027A (en) | Method for preparing high-strength-ductility-product additive manufacturing alloy based on TWIP effect | |
| CN112281216A (en) | Preparation method of TASGG magneto-optical crystal | |
| CN1513756A (en) | Preparation method of hexagonal phase nano-aluminium nitride powder | |
| CN104741615A (en) | Super-fine grain twin-peak copper preparing method | |
| CN114535590B (en) | Method for preparing cobalt powder from cobalt carbonate | |
| CN115417452B (en) | Method for producing zinc arsenide by improved fusion synthesis method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |