CN111171345A - Preparation method of polyamide microspheres - Google Patents
Preparation method of polyamide microspheres Download PDFInfo
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 61
- 229920002647 polyamide Polymers 0.000 title claims abstract description 61
- 239000004005 microsphere Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000001816 cooling Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 34
- 238000000110 selective laser sintering Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 15
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 15
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 239000004677 Nylon Substances 0.000 claims description 33
- 229920001778 nylon Polymers 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 229920003081 Povidone K 30 Polymers 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 229920000299 Nylon 12 Polymers 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 3
- 229920000571 Nylon 11 Polymers 0.000 claims description 2
- 229920002292 Nylon 6 Polymers 0.000 claims description 2
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 2
- 229920003082 Povidone K 90 Polymers 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 17
- 239000002245 particle Substances 0.000 abstract description 12
- 238000009826 distribution Methods 0.000 abstract description 8
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- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 239000006184 cosolvent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/14—Powdering or granulating by precipitation from solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/141—Processes of additive manufacturing using only solid materials
- B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
- C08J2435/06—Copolymers with vinyl aromatic monomers
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Abstract
The invention discloses a preparation method of polyamide microspheres. The preparation method of the polyamide microsphere comprises the following steps: 1) adding polyamide, polyvinylpyrrolidone and a solvent into a reaction kettle, and heating for dissolving; 2) firstly, cooling to the temperature of the first stage at a cooling rate of 0.4-1 ℃/min, then cooling to the temperature of the second stage at a cooling rate of 0.05-0.3 ℃/min, and then cooling to 45 ℃ or below, wherein the precipitated precipitate is polyamide microspheres; wherein in the step 1), the heating and dissolving temperature is 135-160 ℃; in the step 2), the temperature of the first stage is 5-15 ℃ higher than that of the second stage, and the temperature of the second stage is the precipitation temperature. The polyamide microsphere prepared by the method has the characteristics of narrow particle size distribution, large apparent density and good flow property, and is particularly suitable for the selective laser sintering technology.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method of polyamide microspheres.
Background
The Selective Laser Sintering technology, namely an SLS (Selective Laser Sintering) technology, is a typical 3D printing technology, and the technology directly sinters and forms solid powder raw materials into solid parts by using a discrete-accumulation principle and using Laser as a heat source and computer control by using a layered manufacturing idea, and has the advantages of efficient utilization of materials, high manufacturing efficiency and the like. 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.
The polyamide powder is used as a typical thermoplastic semi-crystalline polymer material, has excellent mechanical property, good thermal property and low melt viscosity, is very suitable for being used as a forming material of an SLS (selective laser sintering) process, and can be used for preparing a sintered part with high density and high strength after SLS sintering.
The prior polyamide powdering method mainly comprises a solvent precipitation method and a cryogenic grinding method. The cryogenic grinding method is to utilize a grinder to cool and grind in liquid nitrogen, the method has simple process, but needs cryogenic equipment, needs a large amount of cryogenic carriers in the production process, and the grains obtained by grinding have irregular shapes, are difficult to obtain spherical particles, have wide particle size range, are difficult to meet the requirements of SLS technology on powder morphology, flowability and the like, and can be seen in CN102898941A and CN 1473877A. At present, the selective laser sintering polyamide powder is mostly prepared by a solvent precipitation method, wherein polyamide is dissolved in a proper solvent, and the powder is separated out by a cooling crystallization mode. However, although the conventional solvent precipitation technology, such as CN1197082A, can easily meet the particle size requirement of the SLS technology, the particle morphology or porosity or incompactness still cannot meet the requirements of the SLS technology on powder flowability and apparent density, although the solvent can be modified by adding an organic auxiliary cosolvent to improve the powder morphology, and a certain amount of butanone is added to ethanol, the solvent is difficult to separate and recover in the actual production process, the production cost is increased, the powder is easily yellowed, and the powder use performance is affected, so the polyamide powder prepared by the conventional solvent precipitation technology cannot well meet the requirements of the selective laser sintering technology.
Disclosure of Invention
The invention aims to solve the problems of irregular appearance and small apparent density of polyamide powder produced by the existing solvent precipitation method and enable the polyamide powder to better meet the use requirement of an SLS (selective laser sintering) technology. The spherical or spheroidal polyamide powders prepared by this process are particularly suitable for selective laser sintering techniques.
The invention has the following inventive concept: the polyamide microspheres are prepared by an improved solvent precipitation method, and a process of micro powder nucleation-precipitation is realized by adopting a dissolution-cooling-precipitation mode and adopting two-stage procedure cooling.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of polyamide microspheres. The preparation method of the polyamide microsphere comprises the following steps:
1) adding polyamide, polyvinylpyrrolidone (PVP) and a solvent into a reaction kettle, and heating for dissolving;
2) firstly, cooling to the temperature of the first stage at the cooling rate of 0.4-1 ℃/min, then cooling to the temperature of the second stage at the cooling rate of 0.05-0.3 ℃/min, and then cooling to 45 ℃ or below, wherein the precipitated precipitate is polyamide microspheres;
wherein, in the step 1), the temperature for heating and dissolving is 135-160 ℃; in the step 2), the temperature of the first stage is 5-15 ℃ higher than that of the second stage, and the temperature of the second stage is the precipitation temperature.
Preferably, in step 1) of the preparation method, the mass ratio of the polyamide to the solvent is 1: (5-20); further preferably, the mass ratio of polyamide to solvent is 1: (5.2-10.3).
Preferably, in step 1) of the preparation method, the mass ratio of the polyamide to the polyvinylpyrrolidone is (1-200): 1; more preferably, the mass ratio of the polyamide to the polyvinylpyrrolidone is (50-100): 1.
preferably, in step 1) of this preparation method, the polyamide is selected from at least one of nylon 6, nylon 610, nylon 66, nylon 11, nylon 12, nylon 1010, nylon 1012, and nylon 1212.
Preferably, in step 1) of the preparation method, the polyvinylpyrrolidone is at least one selected from the group consisting of PVP-K15, PVP-K30, PVP-K60 and PVP-K90.
Preferably, in step 1) of the preparation method, the solvent consists of 0.1-10% of auxiliary solvent and the balance of main solvent by mass percent; more preferably, the solvent consists of 3 to 7 mass percent of auxiliary solvent and the balance of main solvent.
Preferably, in the solvent of step 1), the main solvent is at least one selected from methanol, ethanol, isopropanol, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMA), tetrahydrofuran, acetone, and dimethyl sulfoxide; further preferably, the main solvent is at least one selected from methanol, ethanol, N-dimethylformamide and N, N-dimethylacetamide; most preferably, the primary solvent is ethanol.
Preferably, in the solvent of step 1), the auxiliary solvent is water.
In some preferred embodiments of the present invention, an aqueous solution of ethanol is selected as the solvent in step 1).
Preferably, in the preparation method, the heating and dissolving of the step 1) are carried out under the protection of protective gas.
Preferably, the protective gas in step 1) is at least one selected from nitrogen, argon and helium. In some preferred embodiments of the present invention, nitrogen is introduced into the reactor as the shielding gas.
Preferably, in step 1) of the preparation method, the pressure of the reaction kettle is 0.8MPa to 1.2MPa after the protective gas is introduced.
Preferably, in step 1) of the preparation method, the temperature for heating and dissolving is 145-155 ℃.
Preferably, in the step 1) of the preparation method, the heating and dissolving are carried out for 30-120 min at constant temperature; further preferably, the heating and dissolving process is carried out at a constant temperature for 90-120 min.
Preferably, in step 2) of this preparation method, the precipitation temperature is from 100 ℃ to 120 ℃. In some preferred embodiments of the invention, the precipitation temperature is from 108 ℃ to 115 ℃.
In step 2) of the preparation method, the temperature reduction is divided into two stages of procedure temperature reduction. Wherein the cooling rate of the first stage is preferably 0.4 ℃/min to 0.6 ℃/min, and most preferably 0.5 ℃/min; the cooling rate in the second stage is preferably 0.08 ℃/min to 0.12 ℃/min, most preferably 0.1 ℃/min.
Preferably, in step 2) of the preparation method, the temperature is then reduced to 45 ℃ or below, in particular to 45 ℃ to normal temperature, such as 45 ℃ to 25 ℃.
In step 2) of this production method, the cooling rate to 45 ℃ or less is preferably 0.8 ℃/min to 1.5 ℃/min, and more preferably 1 ℃/min.
Preferably, the preparation method further comprises a post-treatment step of filtering and drying the precipitate in the step 2).
The polyamide microspheres prepared by the preparation method are spherical or spheroidal.
The invention provides a polyamide microsphere. The polyamide microsphere is prepared by the preparation method.
The invention also provides the application of the polyamide microsphere in selective laser sintering, and the polyamide microsphere is prepared by the preparation method.
Specifically, the polyamide microspheres are applied to a forming material for selective laser sintering.
The invention has the beneficial effects that:
the polyamide microsphere prepared by the method has the characteristics of narrow particle size distribution, large apparent density and good flow property, and is particularly suitable for the selective laser sintering technology.
Specifically, compared with the prior art, the invention has the following advantages:
firstly, in the preparation method of the polyamide microsphere, polyamide is dissolved and precipitated in a water mixed solvent containing PVP, intermolecular hydrogen bonds are formed by C ═ O groups of the PVP and N-H groups of the polyamide in the process to help to shape the polyamide to obtain a spherical shape, two-stage program cooling enables PVP and polyamide molecular chains to be converted from a free winding state into a state that the polyamide molecular chains are wrapped by the PVP to form spheres, the rapid cooling in the first stage is favorable for particle nucleation, and the slow cooling in the second stage enables the molecules to have enough time to grow on crystal nuclei to shape the spheres, so that the spherical shape shaping capacity of the PVP is more effectively exerted, the spherical or spheroidal polyamide micropowder is prepared, and the problem of irregular powder shape in the prior art is solved.
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.
Finally, the polyamide microspheres prepared by the method have the advantages of regular shape, good powder flowability, large apparent density and the like, and meet the requirements of selective laser sintering technology on sintering powder.
Drawings
FIG. 1 is a scanning electron micrograph of nylon microspheres prepared in example 1;
FIG. 2 is a scanning electron micrograph of the nylon microsphere prepared in comparative example 1.
Detailed Description
The invention provides a preparation method of polyamide microspheres, which is characterized in that polyamide and a proper amount of dispersant polyvinylpyrrolidone are dissolved in a mixed solvent of an autoclave under protective gas in a dissolving-cooling-precipitating manner, and then the nucleation-precipitation process of micropowder is realized by adopting two-stage procedure cooling, and finally spherical or spheroidal polyamide micropowder with good dispersibility is obtained.
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or apparatus used in the examples and comparative examples were obtained from conventional commercial sources unless otherwise specified. Unless otherwise indicated, the testing or testing methods are conventional in the art.
Example 1
Adding 600g of nylon 1012 granules, 3750mL of ethanol, 200g of water and 6g of PVP-K30 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 cooling, wherein the first-stage cooling rate is 0.5 ℃/min to 123 ℃; the second stage cooling rate is 0.1 ℃/min to 108 ℃, and then the temperature is rapidly reduced to 45 ℃ at the cooling rate of 1 ℃/min. And carrying out post-treatment such as filtration and drying to obtain nylon powder.
FIG. 1 is a scanning electron micrograph of the nylon microsphere prepared in this example. As can be seen from FIG. 1, the nylon powder prepared in this example has a nearly spherical morphology. The particle size distribution of the nylon powder was tested to be: d10: 31.98 μm, D50: 58.69 μm, D90: 81.03 μm. The bulk density of the nylon powder was 435g/L, and the angle of repose was 28 ℃.
Example 2
Adding 600g of nylon 1012 granules, 3750mL of ethanol, 200g of water and 12g of PVP-K60 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 cooling, wherein the first-stage cooling rate is 0.5 ℃/min to 123 ℃; the second stage cooling rate is 0.1 ℃/min to 108 ℃, and then the temperature is rapidly reduced to 45 ℃ at the cooling rate of 1 ℃/min. After post-treatment such as filtration and drying, nylon powder is obtained, and the shape of the powder is similar to a sphere.
The particle size distribution of the nylon powder was tested to be: d10: 36.74 μm, D50: 57.40 μm, D90: 83.32 μm. The bulk density of the nylon powder was 460g/L and the angle of repose was 27 °.
Example 3
Adding 600g of nylon 12 granules, 6000mL of ethanol, 200g of water and 12g of PVP-K15 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 cooling, wherein the first-stage cooling rate is 0.5 ℃/min to 125 ℃; the second stage cooling rate is 0.1 ℃/min to 110 ℃, and then the second stage cooling rate is 1 ℃/min to 40 ℃. After post-treatment such as filtration and drying, nylon powder is obtained, and the shape of the powder is similar to a sphere.
The particle size distribution of the nylon powder was tested to be: d10: 26.91 μm, D50: 53.74 μm, D90: 81.80 μm. The bulk density of the nylon powder was 421g/L, and the angle of repose was 30 ℃.
Example 4
Adding 600g of nylon 12 granules, 6000mL of ethanol, 200g of water and 12g of PVP-K30 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 cooling, wherein the first-stage cooling rate is 0.5 ℃/min to 125 ℃; the second stage cooling rate is 0.1 ℃/min to 110 ℃, and then the second stage cooling rate is 1 ℃/min to 40 ℃. After post-treatment such as filtration and drying, nylon powder is obtained, and the shape of the powder is similar to a sphere.
The particle size distribution of the nylon powder was tested to be: d10: 36.65 μm, D50: 59.43 μm, D90: 85.76 μm. The bulk density of the nylon powder was 443g/L, and the angle of repose was 28 °.
Example 5
Adding 600g of nylon 610 granules, 7500mL of ethanol, 200g of water and 6g of PVP-K60 into an autoclave, replacing for 20min by high-purity nitrogen, pressurizing to 1MPa, heating to 155 ℃ while stirring, and keeping the temperature for 120min to dissolve the materials. Then cooling, wherein the first-stage cooling rate is 0.5 ℃/min to 128 ℃; the second stage cooling rate is 0.1 ℃/min to 115 ℃, and then the second stage cooling rate is 1 ℃/min to 25 ℃. After post-treatment such as filtration and drying, nylon powder is obtained, and the shape of the powder is similar to a sphere.
The particle size distribution of the nylon powder was tested to be: d10: 42.58 μm, D50: 63.07 μm, D90: 98.79 μm. The bulk density of the nylon powder was 498g/L and the angle of repose was 27 ℃.
Comparative example 1
Adding 600g of nylon 1012 granules, 3750mL of ethanol, 200g of water and 6g of PVP-K30 into an autoclave, replacing for 20min by high-purity nitrogen, pressurizing to 1MPa, heating to 145 ℃ while stirring, keeping the constant temperature for 90min to dissolve the materials, and rapidly cooling to 25 ℃ at the cooling rate of 1 ℃/min. And carrying out post-treatment such as filtration and drying to obtain nylon powder.
FIG. 2 is a scanning electron micrograph of the nylon microsphere prepared in this example. As can be seen from FIG. 2, the nylon powder prepared in this example has irregular morphology. The particle size distribution of the nylon powder was tested to be: d10: 40.32 μm, D50: 72.10 μm, D90: 116.37 μm. The bulk density of the nylon powder was 322g/L, and the angle of repose was 33 ℃.
The test results show that the polyamide microspheres prepared by the method have the advantages of regular shape, good powder fluidity, large apparent density and the like, and meet the requirements of selective laser sintering technology on sintering powder.
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 polyamide microspheres is characterized by comprising the following steps: the method comprises the following steps:
1) adding polyamide, polyvinylpyrrolidone and a solvent into a reaction kettle, and heating for dissolving;
2) firstly, cooling to the temperature of the first stage at the cooling rate of 0.4-1 ℃/min, then cooling to the temperature of the second stage at the cooling rate of 0.05-0.3 ℃/min, and then cooling to 45 ℃ or below, wherein the precipitated precipitate is polyamide microspheres;
in the step 1), the temperature for heating and dissolving is 135-160 ℃;
in the step 2), the temperature of the first stage is 5-15 ℃ higher than that of the second stage, and the temperature of the second stage is the precipitation temperature.
2. The method for preparing polyamide microspheres according to claim 1, wherein the method comprises the following steps: in the step 1), the mass ratio of polyamide to solvent is 1: (5-20); the mass ratio of polyamide to polyvinylpyrrolidone is (1-200): 1.
3. the method for preparing polyamide microspheres according to claim 1 or 2, wherein: in the step 1), the polyamide is selected from at least one of nylon 6, nylon 610, nylon 66, nylon 11, nylon 12, nylon 1010, nylon 1012 and nylon 1212.
4. The method for preparing polyamide microspheres according to claim 1 or 2, wherein: in the step 1), the polyvinylpyrrolidone is at least one selected from PVP-K15, PVP-K30, PVP-K60 and PVP-K90.
5. The method for preparing polyamide microspheres according to claim 1 or 2, wherein: in the step 1), the solvent consists of 0.1-10% of auxiliary solvent and the balance of main solvent by mass percent; the main solvent is at least one selected from methanol, ethanol, isopropanol, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, acetone and dimethyl sulfoxide; the auxiliary solvent is water.
6. The method for preparing polyamide microspheres according to claim 1, wherein the method comprises the following steps: the heating and dissolving of the step 1) are carried out under the protection of protective gas; the protective gas is at least one of nitrogen, argon and helium.
7. The method for preparing polyamide microspheres according to claim 6, wherein the method comprises the following steps: in the step 1), the heating and dissolving are carried out for 30-120 min at constant temperature.
8. The method for preparing polyamide microspheres according to claim 1, wherein the method comprises the following steps: in the step 2), the precipitation temperature is 100-120 ℃.
9. Polyamide microspheres, characterized in that: is prepared by the preparation method of any one of claims 1 to 8.
10. The application of polyamide microspheres in selective laser sintering is characterized in that: the polyamide microsphere is prepared by the preparation method of any one of claims 1 to 8.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112300415A (en) * | 2020-11-19 | 2021-02-02 | 广东聚石科技研究有限公司 | Spherical nylon powder and preparation method and application thereof |
| CN112619202A (en) * | 2020-12-24 | 2021-04-09 | 晨光生物科技集团股份有限公司 | Industrial method for preparing food-grade lutein |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN105440663A (en) * | 2014-08-07 | 2016-03-30 | 中国科学院理化技术研究所 | Preparation method of nylon micro powder for selective laser sintering |
| CN105694068A (en) * | 2016-04-22 | 2016-06-22 | 广东银禧科技股份有限公司 | Polyamide powder and preparation method thereof |
| CN106674553A (en) * | 2015-11-11 | 2017-05-17 | 中国科学院理化技术研究所 | Polyamide porous microsphere and preparation method thereof |
| CN108203542A (en) * | 2016-12-16 | 2018-06-26 | 中国石油化工股份有限公司 | A kind of preparation method of selective laser sintering nylon powder |
| CN113337105A (en) * | 2020-03-02 | 2021-09-03 | 中国科学院化学研究所 | Polymer powder and preparation method thereof |
-
2019
- 2019-12-31 CN CN201911406719.4A patent/CN111171345A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105440663A (en) * | 2014-08-07 | 2016-03-30 | 中国科学院理化技术研究所 | Preparation method of nylon micro powder for selective laser sintering |
| 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 |
| CN106674553A (en) * | 2015-11-11 | 2017-05-17 | 中国科学院理化技术研究所 | Polyamide porous microsphere and preparation method thereof |
| CN105694068A (en) * | 2016-04-22 | 2016-06-22 | 广东银禧科技股份有限公司 | Polyamide powder and preparation method thereof |
| CN108203542A (en) * | 2016-12-16 | 2018-06-26 | 中国石油化工股份有限公司 | A kind of preparation method of selective laser sintering nylon powder |
| CN113337105A (en) * | 2020-03-02 | 2021-09-03 | 中国科学院化学研究所 | Polymer powder and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 郝超伟等: "PVP 对Nylon6形貌及结晶行为影响的研究", 《光谱学与光谱分析》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112300415A (en) * | 2020-11-19 | 2021-02-02 | 广东聚石科技研究有限公司 | Spherical nylon powder and preparation method and application thereof |
| CN112619202A (en) * | 2020-12-24 | 2021-04-09 | 晨光生物科技集团股份有限公司 | Industrial method for preparing food-grade lutein |
| CN112619202B (en) * | 2020-12-24 | 2022-04-12 | 晨光生物科技集团股份有限公司 | Industrial method for preparing food-grade lutein |
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