CN115785439A - Nylon powder and continuous preparation method thereof - Google Patents
Nylon powder and continuous preparation method thereof Download PDFInfo
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- CN115785439A CN115785439A CN202211569751.6A CN202211569751A CN115785439A CN 115785439 A CN115785439 A CN 115785439A CN 202211569751 A CN202211569751 A CN 202211569751A CN 115785439 A CN115785439 A CN 115785439A
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- 239000004677 Nylon Substances 0.000 title claims abstract description 92
- 229920001778 nylon Polymers 0.000 title claims abstract description 92
- 239000000843 powder Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title description 10
- 238000003756 stirring Methods 0.000 claims abstract description 100
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 64
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000011347 resin Substances 0.000 claims abstract description 52
- 229920005989 resin Polymers 0.000 claims abstract description 52
- 239000002904 solvent Substances 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 33
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 239000012046 mixed solvent Substances 0.000 claims abstract description 15
- 229920000299 Nylon 12 Polymers 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 150000001408 amides Chemical class 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000009826 distribution Methods 0.000 claims abstract description 8
- 239000004135 Bone phosphate Substances 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 25
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical group C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 34
- 239000000047 product Substances 0.000 description 18
- 239000002994 raw material Substances 0.000 description 14
- 102220042174 rs141655687 Human genes 0.000 description 14
- 102220076495 rs200649587 Human genes 0.000 description 14
- 102220043159 rs587780996 Human genes 0.000 description 14
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 235000011037 adipic acid Nutrition 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 2
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- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
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- 238000005315 distribution function Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
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Abstract
The invention provides a method for continuously preparing nylon powder, which comprises the following steps: (1) Rapidly heating nylon 12 resin in a solvent until the nylon 12 resin is dissolved, and then cooling to 120-125 ℃; (2) Transferring the reaction materials into a first stirring tank, and controlling the temperature in the first stirring tank to be 116-118 ℃; (3) Transferring the reaction material in the first stirring tank into a second stirring tank, and controlling the temperature in the second stirring tank to be 112-114 ℃; (4) Transferring the reaction material in the second stirring tank into a third stirring tank, controlling the temperature in the third stirring tank to be 65-75 ℃, and performing solid-liquid separation and drying on the reaction product to obtain nylon powder; wherein the solvent is a mixed solvent consisting of an alcohol solvent and an amide solvent; the nylon 12 resin is polymerized by laurolactam, dibasic acid and tribasic acid. According to the invention, through the control of process conditions and the selection of nylon resin, the reaction materials can be rapidly cooled, nucleated and largely precipitated, and the nylon powder with narrow distribution is obtained.
Description
Technical Field
The invention belongs to the technical field of nylon powder preparation, and particularly relates to a process method for continuously preparing nylon powder.
Background
The nylon powder is widely applied to the technical fields of powder coating, 3D printing and the like by virtue of excellent chemical resistance, mechanical properties and the like. In the prior art, the preparation method of the nylon powder mainly comprises two methods of solvent precipitation and cryogenic grinding, wherein the nylon powder prepared by the solvent precipitation method has more regular particles and higher sphericity, and is beneficial to obtaining higher bulk density of the nylon powder.
In the existing solvent precipitation method, industrial ethanol is generally used as a solvent, for example, in the method described in CN1197082A, after mixing nylon resin with ethanol and heating to dissolve, the precipitation of nylon powder in the solution is divided into two stages, the first stage is reduced to nucleation without producing a large amount of precipitate, and the second stage is reduced to supersaturation until the powder is completely precipitated, so as to obtain the nylon powder finally. The reactor of the method is mostly in a kettle type, and the preparation process is mostly in a batch process, so that the nylon powder is easy to generate large difference on the specification parameters such as the particle size and the shape of the powder in different production batches, and the production capacity is small, so that the large-scale use of the nylon powder is limited.
In the method for preparing nylon powder by using the solvent precipitation method, the reaction system needs to be cooled at different cooling rates in different stages in the cooling and precipitation process of the nylon powder, the temperature of a jacket needs to be cooled at the same cooling rate, and the temperature difference between the jacket and a reaction material needs to be ensured within a proper range. The design complexity is greatly increased by continuous production according to a similar process. Based on the prior art known at present, the continuous solvent precipitation process of nylon powder has a great difficulty.
Therefore, there is a need for an improved continuous process for preparing nylon powder, which simplifies the production process and has high production efficiency and can obtain nylon powder with narrow particle size distribution.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention enables reaction materials to be rapidly cooled, nucleated and largely precipitated by controlling process conditions and selecting nylon resin, so as to obtain nylon powder with narrower particle size distribution.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
the present invention provides in a first aspect a process for the continuous preparation of nylon powder comprising the steps of:
(1) Rapidly heating nylon 12 resin in a solvent until the nylon 12 resin is dissolved, and then cooling to 120-125 ℃ to obtain a reaction material;
(2) Transferring the reaction materials into a first stirring tank, and controlling the temperature in the first stirring tank to be 116-118 ℃;
(3) Transferring the reaction material in the first stirring tank into a second stirring tank, and controlling the temperature in the second stirring tank to be 112-114 ℃;
(4) Transferring the reaction material in the second stirring tank into a third stirring tank, controlling the temperature in the third stirring tank to be 65-75 ℃, and then carrying out solid-liquid separation and drying on the reaction product to obtain nylon powder;
in the step (1), the solvent is a mixed solvent consisting of an alcohol solvent and an amide solvent;
the nylon 12 resin is prepared by polymerizing laurolactam, dibasic acid and tribasic acid, wherein the dosage ratio of the laurolactam to the tribasic acid in the polymerization process is (0.1-0.3), for example, 100.
In some embodiments, the ratio of laurolactam to the diacid used during the polymerization of the nylon 12 resin is 100 (0.25-0.7), such as 100.
In a particular embodiment of the process according to the invention, in step (1), the triacid is selected from one or more of tricarballylic acid, hydroxypropatrioic acid, trimesic acid or 1,2, 4-trimellitic acid, preferably trimesic acid.
In some specific embodiments, the mass ratio of the alcohol solvent to the amide solvent in the solvent in step (1) is 100: (5 to 15), such as 100; the amide solvent is selected from one or more of N-methylformamide, N-methylacetamide, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone; the alcohol solvent is aliphatic alcohol with 1-3 carbon atoms. In some more specific embodiments, the alcoholic solvent may be selected from industrial ethanol and the amide solvent may be selected from N, N-dimethylformamide (abbreviated as "DMF").
In the specific implementation mode of the method, in the step (1), the nylon 12 resin is firstly melted under the heating condition to obtain a melt state, and then is mixed with the heated solvent to obtain a reaction material; in particular, the two materials may be circulated in the loop reactor at a certain feed rate for thorough mixing. Then, the mixed materials can be rapidly cooled by a shell and tube heat exchanger to obtain reaction materials.
In step (2) of the method of the present invention, the reaction material enters the first stirring tank, and reacts under the stirring action thereof, and in some specific embodiments, the stirring speed in the first stirring tank may be 70 to 90rpm, such as 75rpm,80rpm; the reaction pressure in the first stirring tank is controlled to 365 to 395KPa, for example, 370KPa,380KPa,385KPa and 390KPa, by ethanol release.
In step (3) of the method of the present invention, the reacted material in the first stirring tank enters a second stirring tank for reaction, and in some embodiments, the stirring speed in the second stirring tank may be 110 to 130rpm, for example, 115rpm,120rpm; and controlling the reaction pressure in the second stirring tank to be 320-345 KPa, such as 330KPa and 340KPa, by ethanol discharge.
In step (4) of the method of the present invention, the reaction material in the second stirring tank is transferred to a third stirring tank, and in some embodiments, the stirring speed in the third stirring tank may be 40 to 60rpm, for example, 50rpm; and the temperature in the third stirring tank is rapidly reduced to 65-75 ℃ through ethanol vaporization and jacket heat transfer.
In some specific embodiments, jackets are arranged outside the first stirring tank and the second stirring tank to remove reaction heat in the stirring tanks; the jacket outside the third stirring tank is filled with cooling water with the water temperature of 15 ℃ so as to rapidly reduce the temperature in the third stirring tank. The residence time of the reaction materials in the first stirring tank, the second stirring tank and the third stirring tank is 10-30 min, such as 15min and 20min.
The invention provides in a second aspect a nylon powder prepared by the method, said nylon powder having a median diameter (D50) of from 50 to 80 μm, for example, 60 μm,75 μm,80 μm; in some preferred embodiments, the nylon powder has a median diameter (D50) of 50 to 65 μm, e.g., 55 μm,60 μm,62 μm.
The nylon powder has a particle size distribution width (i.e., D90-D10) of 40 to 90 μm, e.g., 50 μm,60 μm,70 μm,80 μm; in some preferred embodiments, the nylon powder has a particle size distribution width of 45 to 55 μm, e.g., 50 μm,52 μm.
By adopting the technical scheme, the method has the following technical effects:
the method takes a triacid component nylon resin containing a certain proportion of trifunctional groups as a matrix, and takes a composition obtained by compounding a good solvent and fatty alcohol as a solvent; meanwhile, the method of the invention obviously narrows the temperature interval between the nucleation temperature and a large amount of precipitation temperature in the cooling precipitation process by controlling the temperature and pressure conditions in each preparation process, thereby simplifying the production process and realizing the continuous preparation of the nylon powder.
Drawings
FIG. 1: a specific process flow diagram for the continuous preparation of nylon powder is used in the examples of the present invention;
the system comprises a circulation flow reactor 1, a shell and tube heat exchanger 2, a first stirring tank 3, a second stirring tank 4, a third stirring tank 5, a centrifugal machine 6, a centrifugal machine 7 and a dryer.
Detailed Description
In order to facilitate understanding of the present invention, the present invention will be further described with reference to examples. It should be understood that the following examples are only for better understanding of the present invention and are not intended to limit the present invention to the following examples.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The specific experimental procedures or conditions are not shown in the examples, and the procedures or conditions may be performed according to the procedures or conditions of the corresponding conventional experimental procedures in the art. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The raw material source information of each of the following examples and comparative examples is as follows;
laurolactam: purchasing Wanhua chemistry;
adipic acid: purchasing Henan magic horses;
trimesic acid: purchased from alatin;
n, N-Dimethylformamide (DMF): purchased from peru.
The following test methods were used to prepare the products of the following examples and comparative examples:
d10 (μm), D50 (μm), D90 (μm): integral particle size distribution measured by laser diffraction method;
width of particle size distribution: the difference between the distribution functions D90 and D10 is integrated, i.e., (D90-D10).
The following examples specifically adopt the continuous preparation process shown in fig. 1, specifically, nylon resin and a solvent are mixed in a loop reactor 1, and conveyed to a tubular heat exchanger 2 through a pipeline for rapid cooling to obtain a reaction material; and then conveying the reaction materials into a first stirring tank 3 for reaction, and conveying the reacted materials into a second stirring tank 4 and a third stirring tank 5 in sequence for continuous reaction. And carrying out solid-liquid separation on a reaction product obtained after the reaction in the third stirring tank 5 through a centrifugal machine 6, and finally drying in a dryer 7 to obtain a nylon powder product.
Comparative example 1
At a 1m 3 Adding 300kg of laurolactam, 15kg of water and 2.1kg of adipic acid into the stirring container, heating to 270 ℃, then carrying out polymerization and staying for 3h, decompressing the system to normal pressure, vacuumizing for 1h at 250 ℃ (the vacuum degree is maintained below-85 KPa), cooling the system to 220 ℃, discharging,Water cooling and dicing to obtain nylon resin 1; relative viscosity of nylon resin 1: 1.62.
(1) The obtained nylon resin 1 is used as a resin raw material, heated to 200 ℃ by a hot oil jacket and changed into a melt state, and fed at a feeding speed of 5 kg/h; meanwhile, industrial ethanol is used as a solvent, and after the industrial ethanol is heated to 180 ℃, the industrial ethanol is fed at a feeding speed of 20 kg/h;
mixing the nylon resin 1 in the melt state with industrial ethanol in a loop reactor (circulating for more than 10 times), and then rapidly cooling to 120 ℃ through a tubular heat exchanger to obtain a reaction material;
(2) The reaction materials enter a first stirring tank, the stirring speed in the first stirring tank is 75rpm, the reaction pressure is controlled to be about 393KPa through ethanol discharge, and the reaction temperature is 118 ℃; the reaction materials stay in the stirring tank for 30min;
(3) The materials in the first stirring tank enter a second stirring tank through a pipeline, the stirring speed in the second stirring tank is 120rpm, the reaction pressure is controlled to be about 345KPa through ethanol discharge, and the reaction temperature is 114 ℃; the reaction materials stay in the stirring tank for 30min;
(4) The materials in the second stirring tank enter a third stirring tank through a pipeline, the stirring speed in the third stirring tank is 50rpm, the temperature in the third stirring tank is rapidly reduced to 75 ℃ through ethanol vaporization and jacket heat transfer, and the reaction materials stay in the stirring tank for 30min; and then carrying out solid-liquid separation on the reaction product after reaction by a centrifugal machine, and drying by a dryer to obtain a nylon powder product.
D10=15 μm, D50=87 μm, D90=143 μm of the nylon powder product obtained above were detected; (D90-D10) =128 μm.
Comparative example 2
This comparative example prepared nylon powder with reference to the process of comparative example 1, differing from the process of comparative example 1 in that:
in the step (1), industrial ethanol and DMF are used as a mixed solvent (mass ratio is 100;
the reaction pressure of the first stirring tank in the step (2) is 391KPa;
the reaction pressure of the second stirring tank in the step (3) is 342KPa.
The nylon powder product prepared by the comparative example has D10=23 μm, D50=81 μm and D90=136 μm; (D90-D10) =113 μm.
Comparative example 3
At a 1m 3 Adding 300kg of laurolactam, 15kg of water, 1.65kg of adipic acid and 0.3kg of trimesic acid into the stirring container, heating to 270 ℃, then polymerizing and staying for 3 hours, decompressing the system to normal pressure, vacuumizing for 1 hour at 250 ℃ (the vacuum degree is maintained below-85 KPa), discharging after the system is cooled to 220 ℃, cooling by water and pelletizing to obtain nylon resin 2; the relative viscosity of nylon resin 2 was 1.63.
The method of reference comparative example 1, in which nylon powder was prepared using nylon resin 2 as a resin raw material, was different from the method of comparative example 1 in that:
the reaction pressure of the first stirring tank in the step (2) is 392KPa;
the reaction pressure of the second stirring tank in the step (3) was 341KPa.
The nylon powder product prepared by this comparative example was tested to have D10=25 μm, D50=81 μm, and D90=132 μm; (D90-D10) =107 μm.
Example 1
This example prepared nylon powder by the method of comparative example 1, differing from the method of comparative example 1 in that:
in the step (1), nylon resin 2 is used as a resin raw material, and industrial ethanol and DMF are used as a mixed solvent (mass ratio is 100;
the reaction pressure of the first stirring tank in the step (2) is 395KPa;
the reaction pressure of the second stirring tank in the step (3) was 345KPa.
The nylon powder product prepared in this example was found to have D10=32 μm, D50=76 μm, and D90=118 μm; (D90-D10) =86 μm.
Example 2
This example prepared nylon powder by the method of comparative example 1, differing from the method of comparative example 1 in that:
in the step (1), nylon resin 2 is used as a resin raw material, and industrial ethanol and DMF are used as a mixed solvent (mass ratio is 100;
the reaction pressure of the first stirring tank in the step (2) is 392KPa;
the reaction pressure of the second stirring tank in the step (3) is 342KPa.
The nylon powder product prepared in this example was tested for D10=32 μm, D50=76 μm, D90=109 μm; (D90-D10) =77 μm.
Example 3
This example prepared nylon powder by the method of comparative example 1, differing from the method of comparative example 1 in that:
in the step (1), nylon resin 2 is used as a resin raw material, and industrial ethanol and DMF are used as a mixed solvent (mass ratio is 100;
the reaction pressure of the first stirring tank in the step (2) is 393KPa;
the reaction pressure of the second stirring tank in the step (3) is 343KPa.
The nylon powder product prepared in this example was tested for D10=31 μm, D50=71 μm, D90=115 μm; (D90-D10) =84 μm.
Example 4
At one 1m 3 Adding 300kg of laurolactam, 15kg of water, 1.2kg of adipic acid and 0.6kg of trimesic acid into the stirring container, heating to 270 ℃, then polymerizing and staying for 3h, decompressing the system to normal pressure, vacuumizing for 1h at 250 ℃ (the vacuum degree is maintained below-85 KPa), cooling the system to 220 ℃, discharging, cooling by water, and pelletizing to obtain nylon resin 3; the relative viscosity of nylon resin 3 was 1.61.
Nylon powder was prepared by referring to the method of comparative example 1, which is different from the method of comparative example 1 in that:
in the step (1), the prepared nylon resin 3 is used as a resin raw material, and industrial ethanol and DMF are used as a mixed solvent (the mass ratio is 100;
the reaction pressure of the first stirring tank in the step (2) is 392KPa;
the reaction pressure of the second stirring tank in the step (3) was 341KPa.
The nylon powder product prepared in this example was found to have D10=35 μm, D50=67 μm, and D90=103 μm; (D90-D10) =68 μm.
Example 5
At one 1m 3 Adding 300kg of laurolactam, 15kg of water, 0.75kg of adipic acid and 0.9kg of trimesic acid into the stirring container, heating to 270 ℃, then polymerizing and staying for 3h, decompressing the system to normal pressure, vacuumizing for 1h at 250 ℃ (the vacuum degree is maintained below-85 KPa), cooling the system to 220 ℃, discharging, cooling by water, and pelletizing to obtain nylon resin 4; the relative viscosity of the nylon resin 4 was 1.64.
Nylon powder was prepared by referring to the method of comparative example 1, which is different from the method of comparative example 1 in that:
in the step (1), the prepared nylon resin 4 is used as a resin raw material, and industrial ethanol and DMF are used as a mixed solvent (mass ratio is 100;
the reaction pressure of the first stirring tank in the step (2) is 391KPa;
the reaction pressure of the second stirring tank in the step (3) is 343KPa.
The nylon powder product prepared in this example was tested for D10=31 μm, D50=65 μm, D90=108 μm; (D90-D10) =77 μm.
Example 6
This example prepared nylon powder by the method of comparative example 1, differing from the method of comparative example 1 in that:
in the step (1), nylon resin 3 is used as a resin raw material, and industrial ethanol and DMF are used as a mixed solvent (mass ratio is 100;
in the step (2), the reaction pressure of the first stirring tank is 378KPa, and the reaction temperature is 117 ℃;
the reaction pressure of the second stirring tank in the step (3) is 342KPa.
The nylon powder product prepared in this example was tested for D10=31 μm, D50=56 μm, D90=84 μm; (D90-D10) =53 μm.
Example 7
This example prepared nylon powder by the method of comparative example 1, differing from the method of comparative example 1 in that:
in the step (1), nylon resin 3 is used as a resin raw material, and industrial ethanol and DMF are used as a mixed solvent (mass ratio is 100;
in the step (2), the reaction pressure of the first stirring tank is 380KPa, and the reaction temperature is 117 ℃;
the reaction pressure of the second stirring tank in the step (3) is 342KPa.
The nylon powder product prepared in this example was found to have D10=32 μm, D50=55 μm, and D90=83 μm; (D90-D10) =51 μm.
Example 8
This example prepared nylon powder by the method of comparative example 1, differing from the method of comparative example 1 in that:
in the step (1), nylon resin 3 is used as a resin raw material, and industrial ethanol and DMF are used as a mixed solvent (mass ratio is 100;
in the step (2), the reaction pressure of the first stirring tank is 368KPa, and the reaction temperature is 116 ℃;
the reaction pressure of the second stirring tank in the step (3) was 341KPa.
The nylon powder product prepared in this example was tested for D10=31 μm, D50=61 μm, D90=91 μm; (D90-D10) =60 μm.
Example 9
This example prepared nylon powder by the method of comparative example 1, differing from the method of comparative example 1 in that:
in the step (1), nylon resin 3 is used as a resin raw material, and industrial ethanol and DMF are used as a mixed solvent (mass ratio is 100;
in the step (2), the reaction pressure of the first stirring tank is 375KPa, and the reaction temperature is 117 ℃;
the reaction pressure of the second stirring tank in the step (3) is 335KPa, and the reaction temperature is 113 ℃.
The nylon powder product prepared in this example was tested for D10=35 μm, D50=52 μm, D90=79 μm; (D90-D10) =44 μm.
Example 10
This example prepared nylon powder by the method of comparative example 1, differing from the method of comparative example 1 in that:
in the step (1), nylon resin 3 is used as a resin raw material, and industrial ethanol and DMF are used as a mixed solvent (mass ratio is 100;
in the step (2), the reaction pressure of the first stirring tank is 377KPa, and the reaction temperature is 117 ℃;
in the step (3), the reaction pressure of the second stirring tank is 330KPa, and the reaction temperature is 113 ℃.
The nylon powder product prepared in this example was tested for D10=34 μm, D50=54 μm, D90=77 μm; (D90-D10) =43 μm.
Example 11
This example prepared nylon powder by the method of comparative example 1, differing from the method of comparative example 1 in that:
in the step (1), nylon resin 3 is used as a resin raw material, and industrial ethanol and DMF are used as a mixed solvent (mass ratio is 100;
in the step (2), the reaction pressure of the first stirring tank is 380KPa, and the reaction temperature is 117 ℃;
the reaction pressure of the second stirring tank in the step (3) is 320KPa, and the reaction temperature is 112 ℃.
The nylon powder product prepared in this example was found to have D10=32 μm, D50=55 μm, and D90=87 μm; (D90-D10) =55 μm.
Claims (10)
1. A method for continuously preparing nylon powder is characterized by comprising the following steps:
(1) Rapidly heating nylon 12 resin in a solvent until the nylon 12 resin is dissolved, and then cooling to 120-125 ℃ to obtain a reaction material;
(2) Transferring the reaction materials into a first stirring tank, and controlling the temperature in the first stirring tank to be 116-118 ℃;
(3) Transferring the reaction material in the first stirring tank into a second stirring tank, and controlling the temperature in the second stirring tank to be 112-114 ℃;
(4) Transferring the reaction material in the second stirring tank into a third stirring tank, controlling the temperature in the third stirring tank to be 65-75 ℃, and then carrying out solid-liquid separation and drying on the reaction product to obtain nylon powder;
in the step (1), the solvent is a mixed solvent composed of an alcohol solvent and an amide solvent;
the nylon 12 resin is prepared by polymerizing laurolactam, dibasic acid and tribasic acid, wherein the dosage ratio of the laurolactam to the tribasic acid in the polymerization process is 100 (0.1-0.3).
2. The process according to claim 1, wherein in step (1), the triacid is selected from one or more of tricarballylic acid, hydroxypropatriic acid, trimesic acid or 1,2, 4-trimellitic acid, preferably trimesic acid.
3. The method according to claim 1, wherein the mass ratio of the alcohol solvent to the amide solvent in the solvent in step (1) is 100: (5-15).
4. The method according to claim 3, wherein the amide solvent is selected from one or more of N-methylformamide, N-methylacetamide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone;
the alcohol solvent is selected from aliphatic alcohol with 1-3 carbon atoms.
5. The method according to claim 4, wherein the alcoholic solvent is selected from industrial ethanol and the amide solvent is selected from N, N-dimethylformamide.
6. The method as claimed in any one of claims 1 to 5, wherein the ratio of the amount of the laurolactam to the dibasic acid used in the polymerization of the nylon 12 resin is 100 (0.25 to 0.7).
7. The method according to any one of claims 1 to 6, wherein the pressure of the first agitation tank is controlled to 365 to 395KPa;
the pressure of the second stirring tank is controlled to be 320-345 KPa.
8. The method according to claim 7, wherein the residence time of the reaction materials in the first, second and third stirred tanks is 10-30 min.
9. A nylon powder produced by the process according to any one of claims 1 to 8, wherein the nylon powder has a median diameter (D50) of 50 to 80 μm, preferably 50 to 65 μm.
10. Nylon powder according to claim 9, characterized in that the nylon powder has a particle size distribution width of 40-90 μm, preferably 45-55 μm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115851113A (en) * | 2022-12-09 | 2023-03-28 | 万华化学集团股份有限公司 | Nylon powder coating and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157762A (en) * | 2007-09-13 | 2008-04-09 | 郑州大学 | Method for preparing nylon powder by employing DMF |
| CN101970557A (en) * | 2008-03-14 | 2011-02-09 | 威士伯采购公司 | Powder compositions and methods of manufacturing articles therefrom |
| CN106675010A (en) * | 2015-11-06 | 2017-05-17 | 中国石油化工股份有限公司 | Nylon resin powder for selective laser sintering, and preparation method thereof |
| 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 |
-
2022
- 2022-12-08 CN CN202211569751.6A patent/CN115785439A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157762A (en) * | 2007-09-13 | 2008-04-09 | 郑州大学 | Method for preparing nylon powder by employing DMF |
| CN101970557A (en) * | 2008-03-14 | 2011-02-09 | 威士伯采购公司 | Powder compositions and methods of manufacturing articles therefrom |
| CN106675010A (en) * | 2015-11-06 | 2017-05-17 | 中国石油化工股份有限公司 | Nylon resin powder for selective laser sintering, and preparation method thereof |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 袁宗伟: "溶剂法制备粒径分布集中的 PA12 球形微粉", 《工程塑料应用》, vol. 46, no. 6, pages 75 - 78 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115851113A (en) * | 2022-12-09 | 2023-03-28 | 万华化学集团股份有限公司 | Nylon powder coating and preparation method and application thereof |
| CN115851113B (en) * | 2022-12-09 | 2023-08-11 | 万华化学集团股份有限公司 | Nylon powder coating and preparation method and application thereof |
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