CN114276566A - Nylon powder and preparation method and application thereof - Google Patents
Nylon powder and preparation method and application thereof Download PDFInfo
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- CN114276566A CN114276566A CN202111590512.4A CN202111590512A CN114276566A CN 114276566 A CN114276566 A CN 114276566A CN 202111590512 A CN202111590512 A CN 202111590512A CN 114276566 A CN114276566 A CN 114276566A
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- 239000004677 Nylon Substances 0.000 title claims abstract description 88
- 229920001778 nylon Polymers 0.000 title claims abstract description 88
- 239000000843 powder Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 51
- 239000000725 suspension Substances 0.000 claims abstract description 47
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 238000000110 selective laser sintering Methods 0.000 claims description 11
- 238000010146 3D printing Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 abstract description 24
- 238000009826 distribution Methods 0.000 abstract description 18
- 239000002904 solvent Substances 0.000 description 21
- 239000011347 resin Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 14
- 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
- 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
- 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
- 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
- 230000001681 protective effect Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 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
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- 239000012046 mixed solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-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
- 229920000299 Nylon 12 Polymers 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000000149 argon plasma sintering Methods 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
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006467 substitution reaction Methods 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 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
- 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
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 230000002226 simultaneous effect Effects 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
Images
Classifications
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- 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
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: reducing the temperature of the hot nylon solution to T1Carrying out first nucleation-growth to form a first suspension; increasing the temperature of the first suspension to T2Then cooling to T3Carrying out second nucleation-growth to obtain a second suspension; wherein, T2‑T1≤15℃，T2‑T3Less than or equal to 15 ℃; continuously cooling the second suspension to form a precipitate; and carrying out post-treatment on the precipitate to obtain nylon powder. The nylon powder prepared by the invention has narrow particle size distribution, large apparent density, high yield and good performanceThereby meeting the SLS technical use.
Description
Technical Field
The invention relates to the technical field of high polymer materials, and particularly relates 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, and the technology applies a layered manufacturing idea, and utilizes a discrete-stacking principle to stack materials layer by layer to manufacture a new 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 part of intelligent manufacturing. Through rapid development for many years, the SLS technology has been widely applied to various fields such as automobiles, household appliances, aerospace, medical biology and the like, and is one of the more mature 3D printing technologies currently applied.
At present, most of the nylon powder prepared by selective laser sintering is prepared by a solvent precipitation method, wherein nylon resin is dissolved in a proper solvent, and the powder is separated out by a cooling crystallization mode. However, although the nylon powder prepared by the conventional 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 microns, the apparent density of the powder is not less than 420g/L, the particle size distribution width (D90-D10) basically exceeds 50 microns, and the performance requirement of laser sintering is difficult to meet. Therefore, the nylon powder prepared by the existing solvent precipitation technology still cannot well meet the requirements of the selective laser sintering technology in cost and performance.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a preparation method of nylon powder, which can prepare the 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 invention provides a preparation method of nylon powder, which comprises the following steps:
reducing the temperature of the hot nylon solution to T1Carrying out first nucleation-growth to form a first suspension;
increasing the temperature of the first suspension to T2Then cooling to T3Carrying out second nucleation-growth to obtain a second suspension; wherein, T2-T1≤15℃，T2-T3≤15℃；
Continuously cooling the second suspension to form a precipitate; and 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 twice nucleation-growth is not more than 15 ℃, so that most of 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 narrow range, and the nylon powder with narrow particle size distribution can be obtained. After the first nucleation-growth, the temperature is slightly raised, so that the nylon powder with small grain size and over-large grain size is skillfully dissolved again, and the grain size of the powder is intensively distributed. Meanwhile, the temperature interval of the two nucleation-growth processes is not more than 15 ℃, so that the requirement on the control precision of the temperature point in the actual operation process is looser, the fault tolerance rate 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, T2-T1≤10℃，T2-T3≤10℃。
In some embodiments of the present invention, the temperature of the hot nylon solution is 135-160 ℃.
In some preferred embodiments, the hot nylon solution is obtained by dissolving a nylon resin in a solvent under a protective atmosphere at an elevated temperature.
More specifically, the preparation method of the nylon hot solution comprises the steps of mixing nylon resin with a solvent, heating the obtained mixture to 135-160 ℃ in a protective atmosphere, and dissolving the nylon resin to obtain the nylon hot solution. In the preparation process of the hot nylon 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 time for dissolution is 30 to 120 minutes. The temperature is generally kept constant during the dissolution process.
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 comprises 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 0.1-10 wt%.
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 hot nylon solution contains an antioxidant. By adding the antioxidant, the nylon resin can be prevented from being oxidized in the processes of dissolution, nucleation-growth and subsequent various procedures. 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 protective gas comprises at least one of nitrogen, argon and helium, and in practical operation, the protective gas is high-purity gas.
It should be understood that the hot nylon solution can be obtained by other methods and solvents in the art besides the above-mentioned methods, kinds and proportions of the solvents, 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 is1Is 118 to 123 ℃. Preferably, the nylon hot solution is cooled to T through two stages1Wherein the temperature is reduced to 128-132 ℃ in the first stage and reduced to T from 128-132 ℃ in the second stage1(118～123℃)。
In some embodiments of the present invention, the temperature reduction rate of the first stage is 1-5 ℃/min. Cooling to 128-132 deg.C, and keeping the temperature for 1-30 min.
In some embodiments of the invention, the cooling rate of the second stage is 0.5-3 ℃/min, and the temperature of the second stage is kept for 1-30 min to obtain the first suspension.
In actual operation, the solution can be cooled by indirect heat exchange (such as coil heat exchange), and the cooling rate can be adjusted by controlling the temperature of the cooling medium.
In some embodiments of the invention, the T is2Is 128 to 132 ℃.
In some embodiments of the invention, the temperature of the first suspension is increased to T2The process of (2) can be implemented as follows: cooling the first suspension by indirect heat exchange (such as coil heat exchange), heating the first suspension, and adjusting the cooling rate and the heating rate of the heat exchange to raise the temperature of the first suspension to T2. Preferably, the temperature of the cooling medium for heat exchange is set to 115-120 ℃, and the first suspension is heated at a rate of 0.1-0.5 ℃/min, so that the temperature of the first suspension is raised to T2。
In practical operation, the hot nylon solution and the first suspension are generally contained in a certain reaction vessel (such as an autoclave), a coil can be arranged in the reaction vessel to perform coil heat exchange, and the reaction vessel is arranged in a heating device (such as an autoclave jacket), so that simultaneous cooling and heating can be realized, and accurate temperature control can be easily realized.
For example, when the temperature is reduced by adopting a coil heat exchange mode and heated by adopting an autoclave jacket, the heat exchange temperature of the coil can be kept at 115-120 ℃ in the second nucleation-growth process, and meanwhile, the suspension is heated to 123-125 ℃ by the autoclave jacket at the speed of 0.1-0.5 ℃/min, and at the moment, the temperature of the autoclave is increased to 128-132 ℃ by adjusting the temperature reduction speed of the coil heat exchange. By reasonably adjusting the cooling rate and the heating rate, particularly by the simultaneous action of the coil heat exchange and the jacket of the high-pressure kettle, the cooling effect of the coil heat exchange effectively keeps the compactness of the powder, and the heating and heating effect of the jacket skillfully re-dissolves the nylon powder with small grain size and overlarge grain size, so that the grain sizes of the powder are intensively distributed.
In some embodiments of the invention, the T is3At 118-123 ℃, T3And T1May be the same or different.
In some embodiments of the invention, T is2Cooling to T3The rate of (A) is 0.1 to 3 ℃/min at T3Keeping the temperature for 1-30 min.
In some embodiments of the present invention, the step of reducing the temperature of the second suspension to form a precipitate is more specifically to reduce the temperature of the second suspension to 108 to 110 ℃ to form a precipitate.
Preferably, the cooling process of the second suspension comprises two stages, wherein in the first stage, the temperature of the second suspension is reduced to 113-115 ℃ at a cooling rate of 0.05-0.2 ℃/min, and then is reduced to 108-110 ℃ at a cooling rate of 0.02-0.12 ℃/min.
In some embodiments of the present invention, the post-treatment step includes reducing the temperature of the suspension containing the precipitate to 20-50 ℃ (the temperature reduction rate can be set to 10-50 ℃/h, or other suitable rate), and then performing solid-liquid separation, drying, and the like.
In general, during the preparation process, the temperature of the hot nylon solution was varied as follows: reducing the temperature from 135-160 ℃ to 128-132 ℃ at a rate of 1-5 ℃/min, keeping the temperature for 1-30 min, and then cooling to 0.5-3 DEG CThe rate of the reaction is reduced to 118-123 ℃ (T)1) Keeping the temperature constant for 1-30 min; then heating to 128-132 ℃ (T)2) Then, the temperature is decreased to 118-123 deg.C (T) at a rate of 0.1-3 deg.C/min3) Keeping the temperature constant for 1-30 min; then reducing the temperature to 113-115 ℃ at the rate of 0.05-0.2 ℃/min, and then reducing the temperature to 108-110 ℃ at the rate of 0.02-0.12 ℃/min; finally, the temperature is reduced to 20-50 ℃.
In a second aspect of the present invention, there is provided a nylon powder obtained by the above process. The average particle size of the nylon powder is 50-60 mu m, the particle size distribution (D90-D10) is less than 50 mu m, and the apparent density is more than 420 g/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:
the preparation method of the nylon powder adopts twice nucleation-growth crystallization processes in the same temperature interval so as to achieve that most nylon molecules nucleate and grow in the same interval, so that the particle size of the powder is intensively distributed in a certain narrow range, and the control precision requirement of the temperature point is loose because the temperature interval is not more than 15 ℃, preferably not more than 10 ℃, so that the fault tolerance rate 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 temperature reduction rate and the temperature rise rate are reasonably adjusted in the process, particularly, the temperature reduction effect of the coil heat exchange effectively keeps the compactness of the powder through the simultaneous effect of the coil heat exchange and the jacket of the high-pressure kettle, and meanwhile, the heating and temperature rise effect of the jacket skillfully re-dissolves the nylon powder with small grain size and overlarge grain size, so that the grain sizes of the powder are intensively distributed.
The particle size of the nylon powder obtained by the preparation method is totally distributed within the range of 30-120 mu m, the requirement of a laser sintering technology on the powder is met, screening treatment is not needed after crystallization, residual loss in the process is eliminated, the nylon powder is basically and completely made into a powder product, the production process flow is shortened, the production efficiency is improved, and meanwhile, the yield of the powder is also improved.
In the preparation method, the solvent only comprises two types of water and 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 temperature changes in 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 is characterized in that nylon resin and a proper amount of antioxidant are dissolved in a mixed solvent of an autoclave under the protection of inert gas, then the obtained solution completes a crystallization process of primary nucleation-growth in a two-section cooling mode through coil heat exchange, then completes a crystallization process of secondary nucleation-growth by utilizing the simultaneous action of coil cooling and jacket heating, finally realizes the morphology optimization and precipitation endpoint of the powder through two-section slow cooling, and obtains the nylon powder with good dispersibility through post-treatment. The temperature change of the solution during the preparation process is shown in fig. 1.
The technical solution of the present invention is further described below with reference to specific examples. The starting materials used in the following examples, unless otherwise specified, are available from conventional commercial sources; the processes used, unless otherwise specified, are conventional in the art.
Example 1
Adding 600g of nylon 1012 resin, 3750ml of ethanol, 200g of water and 1.8g of antioxidant 1098 into an autoclave, replacing for 20min by high-purity nitrogen, pressurizing to 1MPa, heating to 145 ℃ while stirring, and keeping the temperature for 90min to dissolve the materials. Then carrying out two-stage cooling by coil heat exchange, wherein the first-stage cooling rate is 3 ℃/min to 130 ℃, and keeping the temperature for 10 min; the second stage cooling rate is 1 deg.C/min to 120 deg.C, and the temperature is kept for 10 min. Then keeping the heat exchange temperature of the coil pipe at 120 ℃, simultaneously heating the suspension to 123 ℃ through a high-pressure kettle jacket at the speed of 0.2 ℃/min, then heating the high-pressure kettle to 130 ℃ by adjusting the cooling rate of the coil pipe heat exchange, then adjusting the coil pipe heat exchange to reduce the temperature of the suspension to 120 ℃ at the cooling rate of 0.4 ℃/min, and keeping the temperature for 5 min. And then regulating coil heat exchange to reduce the temperature of the suspension to 115 ℃ at a cooling rate of 0.16 ℃/min, then reducing the temperature of the suspension to 110 ℃ at a cooling rate of 0.12 ℃/min, finishing powder precipitation, finally reducing the temperature of the suspension to below 50 ℃ at a cooling rate of 30 ℃/h, and carrying out post-treatment to obtain the nylon powder with good dispersibility.
The particle size distribution of the nylon powder was tested to be: d10: 40.00 μm, D50: 55.15 μm, D90: 76.42 μm, a loose packed density of 463g/L, and an angle of repose of 28 ℃ as shown in FIG. 2.
Example 2
Adding 600g of nylon 12 resin, 3750ml of ethanol, 200g of water and 1.8g of antioxidant 1098 into an autoclave, replacing for 20min by high-purity nitrogen, pressurizing to 1MPa, heating to 145 ℃ while stirring, and keeping the temperature for 90min to dissolve the materials. Then, carrying out two-stage cooling through coil heat exchange, wherein the first-stage cooling rate is 3 ℃/min to 131 ℃, and keeping the temperature for 10 min; the second stage cooling rate is 1 deg.C/min to 119 deg.C, and the temperature is kept for 10 min. Then keeping the coil heat exchange temperature at 120 ℃, simultaneously heating the suspension to 123 ℃ through a high-pressure kettle jacket at the speed of 0.2 ℃/min, then heating the high-pressure kettle to 131 ℃ by adjusting the cooling rate of the coil heat exchange, then adjusting the coil heat exchange to reduce the temperature of the suspension to 119 ℃ at the cooling rate of 0.4 ℃/min, and keeping the temperature for 5 min. And then regulating coil heat exchange to reduce the temperature of the suspension to 115 ℃ at a cooling rate of 0.16 ℃/min, then reducing the temperature of the suspension to 110 ℃ at a cooling rate of 0.12 ℃/min, finishing powder precipitation, finally reducing the temperature of the suspension to below 50 ℃ at a cooling rate of 30 ℃/h, and carrying out post-treatment to obtain the nylon powder with good dispersibility.
The particle size distribution of the nylon powder was tested to be: d10: 37.10 μm, D50: 53.51 μm, D90: 76.66 μm, a loose packed density of 452g/L, an angle of repose of 28 ℃ as shown in FIG. 3.
Example 3
Adding 600g of nylon 1012 resin, 3750ml of ethanol, 200g of water and 1.8g of antioxidant 1098 into an autoclave, replacing for 20min by high-purity nitrogen, pressurizing to 1MPa, heating to 145 ℃ while stirring, and keeping the temperature for 90min to dissolve the materials. Then, carrying out two-stage cooling through coil heat exchange, wherein the first-stage cooling rate is 3 ℃/min to 129 ℃, and keeping the temperature for 10 min; the second stage cooling rate is 1 deg.C/min to 119 deg.C, and the temperature is kept for 10 min. Then keeping the coil heat exchange temperature at 120 ℃, simultaneously heating the suspension to 123 ℃ through a high-pressure kettle jacket at the speed of 0.2 ℃/min, then heating the high-pressure kettle to 131 ℃ by adjusting the cooling rate of the coil heat exchange, then adjusting the coil heat exchange to reduce the temperature of the suspension to 119 ℃ at the cooling rate of 0.4 ℃/min, and keeping the temperature for 5 min. And then regulating coil heat exchange to reduce the temperature of the suspension to 115 ℃ at a cooling rate of 0.16 ℃/min, then reducing the temperature of the suspension to 110 ℃ at a cooling rate of 0.12 ℃/min, finishing powder precipitation, finally reducing the temperature of the suspension to below 50 ℃ at a cooling rate of 30 ℃/h, and carrying out post-treatment to obtain the nylon powder with good dispersibility.
The particle size distribution of the nylon powder was tested to be: d10: 35.56 μm, D50: 52.90 μm, D90: 78.05 μm, a loose packed density of 445g/L, an angle of repose of 28 ℃ as shown in FIG. 4.
Comparative example 1
Adding 600g of nylon 1012 granules, 3750ml of ethanol, 200g of water and 1.8g of antioxidant 1098 into an autoclave, replacing with high-purity nitrogen for 20min, heating to 145 ℃ while stirring, and keeping the temperature for 90min to dissolve the materials. Then cooling, wherein the first-stage cooling rate is 0.5 ℃/min to 123 ℃; the second stage cooling rate is 0.1 deg.c/min-108 deg.c, and the temperature is then cooled fast to normal temperature. And carrying out post-treatment such as filtration and drying to obtain nylon powder.
The particle size distribution of the nylon powder was tested to be: d10: 36.16 μm, D50: 57.67 μm, D90: 90.57 μm, a loose packed density of 356g/L, and an angle of repose of 34 ℃ as shown in FIG. 5.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of nylon powder is characterized by comprising the following steps: the method comprises the following steps:
reducing the temperature of the hot nylon solution to T1Carrying out first nucleation-growth to form a first suspension;
increasing the temperature of the first suspension to T2Then cooling to T3Carrying out second nucleation-growth to obtain a second suspension; wherein, T2-T1≤15℃，T2-T3≤15℃；
Continuously cooling the second suspension to form a precipitate; and carrying out post-treatment on the precipitate to obtain nylon powder.
2. The method for producing nylon powder according to claim 1, characterized in that: the temperature of the nylon hot solution is 135-160 ℃.
3. The method for producing nylon powder according to claim 1, characterized in that: the T is1Is 118 to 123 ℃.
4. The method for producing nylon powder according to claim 3, characterized in that: the nylon hot solution is cooled to T in two stages1Wherein the temperature is reduced to 128-132 ℃ in the first stage and reduced to T from 128-132 ℃ in the second stage1。
5. The method for producing nylon powder according to claim 3, characterized in that: the T is2Is 128 to 132 ℃.
6. The method for producing nylon powder according to claim 5, characterized in that: increasing the temperature of the first suspension to T2The process of (2) is realized as follows:the first suspension is cooled in an indirect heat exchange mode, the first suspension is heated at the same time, and the cooling rate and the heating rate of the heat exchange are adjusted to increase the temperature of the first suspension to T2。
7. The method for producing nylon powder according to claim 1, characterized in that: the T is3Is 118 to 123 ℃.
8. The method for producing nylon powder according to claim 1, characterized in that: the step of cooling the second suspension to form a precipitate is as follows: and reducing the temperature of the second suspension to 108-110 ℃ to form a precipitate.
9. A nylon powder characterized by: the nylon powder is prepared by the preparation method of any one of claims 1 to 8.
10. Use of the nylon powder of claim 9 in selective laser sintering 3D printing.
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