CN1246367C - Method for preparing high tap density polyamide powder of controll able average partical size - Google Patents
Method for preparing high tap density polyamide powder of controll able average partical size Download PDFInfo
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- CN1246367C CN1246367C CN 200410088820 CN200410088820A CN1246367C CN 1246367 C CN1246367 C CN 1246367C CN 200410088820 CN200410088820 CN 200410088820 CN 200410088820 A CN200410088820 A CN 200410088820A CN 1246367 C CN1246367 C CN 1246367C
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- polymeric amide
- soluble polymers
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- water soluble
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- 239000000843 powder Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000004952 Polyamide Substances 0.000 title claims abstract description 10
- 229920002647 polyamide Polymers 0.000 title claims abstract description 10
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 3
- 150000001408 amides Chemical class 0.000 claims description 45
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 29
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 20
- -1 polyoxyethylene Polymers 0.000 claims description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 229920006122 polyamide resin Polymers 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229920000141 poly(maleic anhydride) Polymers 0.000 claims description 4
- 238000010008 shearing Methods 0.000 claims description 4
- 229920005601 base polymer Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 238000009825 accumulation Methods 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract 2
- 230000008018 melting Effects 0.000 abstract 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 10
- 239000002202 Polyethylene glycol Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 229920001223 polyethylene glycol Polymers 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005315 distribution function Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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Abstract
The present invention relates to a preparation method of high stacking density polyamide powder with controllable average particle diameter, which belongs to the field of powder preparation. The preparation method disclosed in the present invention comprises various water soluble polymers used in the method. The method comprises the following specific preparation steps: firstly, a blended substance is obtained by uniformly mixing polyamide particles and the water soluble polymers in a mixer or a screw extruding machine at the temperature higher than the melting point of the polyamide particles and the melting point of the water soluble polymers; secondly, the obtained blended substance is placed in water to remove the water soluble polymers in the blended substance, and the polyamide powder with the powder stacking density higher than 485 g/L is obtained after water washing and drying. The polyamide powder prepared with the method of the present invention has the characteristics of controllable particle diameter, regular shape and high stacking density. The present invention has the advantages of environmental friendliness of the preparation process, simple and convenient production process, low energy consumption, low production cost and recycle of the water soluble polymers in use.
Description
Technical field
The invention provides the method that controlled being used to of a kind of particle diameter prepares high-bulk-density polymeric amide powder, the Silon physical efficiency that makes is enough in coating and sintered article raw material.
Background technology
Polyamide powder has the chemical proofing and the favorable mechanical performance of height, is widely used in coating, sintered article raw material, solid lubricant, makeup substrate etc.The traditional preparation process method of polymeric amide powder comprises following several: solution deposit, emulsion method, direct polymerization method and mechanical crushing method (pulverize at low temperature, section method and comminution by gas stream) etc.Wherein solution deposit need expend a large amount of organic solvents, and operational condition is generally High Temperature High Pressure, the technical qualification complexity, and the powder porosity is bigger; The diameter of particle scope that emulsion method obtains is bigger, and introduces dispersion agent impurity easily; The powder of direct polymerization method preparation is the porous spheroid, and porosity is higher equally; Mechanical crushing method need expend a large amount of liquid nitrogen, and tooling cost and energy consumption are all very high, and is difficult to obtain the even regular powder than small particle size.
In order to overcome the limitation of above-mentioned various preparation Silon body methods, can utilize the polymer blending technology, water-soluble polymers and polymeric amide are carried out blend in certain proportion with under the shearing rate, polymeric amide dispersed phase drop with homogeneous in mixture is existed, water is removed water-soluble polymer dissolves then, obtains regular spheric polymeric amide powder.
Summary of the invention
The objective of the invention is to utilize the polymer blending technology to prepare that particle diameter is controlled, the regular spherical polymeric amide powder of high-bulk-density, and be applied on coating, the sintered article raw material.
When two kinds of polymkeric substance in the proper ratio after the blend, enough little as interfacial tension, the component that content is lower can be with micron-sized size dispersion in another component.Simultaneously, keep minimum energy state in order to make co-mixing system, it is regular spherical that disperse phase will be.Along with the reduction of disperse phase massfraction, the size of disperse phase will be more and more littler; The increase of mixing equipment middle shear rate can more effectively strengthen the broken of dispersed phase component and disperse, and reduces dispersed phase size.
The invention is characterized in: the mixture of polymeric amide and water-soluble polymers under the temperature of both fusing points that is higher than them in milling device or screw extrusion press melt blending, and make polymeric amide become disperse phase uniformly therein; Described water-soluble polymers is following a kind of or their blend in several: polyoxyethylene glycol, polyoxyethylene, polyacrylamide, polyvinyl alcohol, polymaleic anhydride and ether of cellulose base polymer; The shearing rate by regulating ratio between polymeric amide and the water-soluble polymers and mixing equipment and the kind of water-soluble polymers obtain the polyamide powder of different median sizes and size distribution.
The present invention utilizes polymer blending dispersive principle to prepare the polymeric amide powder, and it is easy to have production process, the advantage that energy consumption and production cost are low, and environmentally friendly and used water-soluble polymers can reclaim and reuse.Utilize this technology, not only can conveniently control the median size of polymeric amide powder, can access simultaneously tap density high be regular spheric polymeric amide powder.
The method for preparing the polymeric amide powder of the present invention, concrete steps are:
The first step: with mass ratio be 1: 5～1: 1 polyamide resin and water-soluble polymers mixture be higher than them both separately under the temperature of fusing point in milling device or screw extrusion press melt blending, and make polyamide resin become the uniform disperse phase of particle diameter therein;
Second step: the blend that the first step is obtained places the water dissolving and removes wherein water-soluble polymers as external phase, obtain the polymeric amide powder of powder accumulation density greater than 485g/l after washing, drying, described polymeric amide forms in following any mode:
(1) form from the lactan that has at least 6 carbon atoms,
(2) form from the p-aminocarboxylic acid that has at least 6 carbon atoms,
(3) form from diamines and the dicarboxylic acid that respectively carries at least 6 carbon atoms,
(4) form from above-mentioned each monomeric copolyamide.
Employed water-soluble polymers comprises polyoxyethylene glycol (PEG) among the present invention; Polyoxyethylene (PEO); Polyacrylamide (PAM); Polyvinyl alcohol (PVA); Polymaleic anhydride (PMA); The ether of cellulose base polymer; Or the blend of above-mentioned polymkeric substance.The shearing rate by regulating ratio between polyamide resin and the water-soluble polymers and mixing equipment and the kind of water-soluble polymers obtain the polyamide powder of different median sizes and size distribution.
Example subsequently is to be used for illustrating the present invention, limits the invention never in any form.Size distribution is determined by screening and the scattering of light in laser beam (Malvern Mastersizer).
Used to give a definition:
D
0.1(μ m): the integration size distribution that records with laser diffractometry, diameter is in the particle below the diameter value of giving and accounts for 10% in this distribution,
D
0.5(μ m): the same, diameter is in the following particle of described diameter value and accounts for 50%,
D
0.9(μ m): the same, diameter is in the following particle of described diameter value and accounts for 90%,
D[4,3]: the particle diameter mean value that from volume distributed median, obtains with laser diffractometry,
Width: the D of integral distribution function
0.9And D
0.1Between poor.
Embodiment
Following example only is used to explain operating process of the present invention and prescription, and is not used for limiting scope of the present invention.
Embodiment 1:
1. the polymeric amide-12 and the polyoxyethylene glycol that with mass ratio are 1: 5 are pre-mixed evenly, utilize twin screw extruder to carry out blend then under the condition of 200 ℃ and 104 rev/mins and extrude;
2. with resulting blend cooling, water is removed water-soluble polyethylene glycol dissolving wherein, obtains the polymeric amide powder;
3. the polymeric amide powder of gained is washed and drying the powder that obtains having following feature:
D
0.1(μm)＝5μm
D
0.5(μm)＝20μm
D
0.9(μm)＝52μm
D[4，3]＝20μm
Width=47 μ m
Tap density: 492g/L
Embodiment 2:
1. the polymeric amide-12 and the polyoxyethylene glycol that with mass ratio are 1: 4 are pre-mixed evenly, utilize twin screw extruder to carry out blend then under the condition of 200 ℃ and 104 rev/mins and extrude;
2. with resulting blend cooling, water is removed water-soluble polyethylene glycol dissolving wherein, obtains the polymeric amide powder;
3. the polymeric amide powder of gained is washed and drying the powder that obtains having following feature:
D
0.1(μm)＝12μm
D
0.5(μm)＝31μm
D
0.9(μm)＝76μm
D[4，3]＝34μm
Width=64 μ m
Tap density: 490g/L
Embodiment 3:
1. the polymeric amide-12 and the polyoxyethylene glycol that with mass ratio are 1: 3 are pre-mixed evenly, utilize twin screw extruder to carry out blend then under the condition of 200 ℃ and 104 rev/mins and extrude;
2. with resulting blend cooling, water is removed water-soluble polyethylene glycol dissolving wherein, obtains the polymeric amide powder;
3. the polymeric amide powder of gained is washed and drying the powder that obtains having following feature:
D0.1(μm)＝25μm
D0.5(μm)＝44μm
D0.9(μm)＝90μm
D[4，3]＝49μm
Width=65 μ m
Tap density: 495g/L
Embodiment 4:
1. the polymeric amide-12 and the polyoxyethylene glycol that with mass ratio are 1: 2 are pre-mixed evenly, utilize twin screw extruder to carry out blend then under the condition of 200 ℃ and 104 rev/mins and extrude;
2. with resulting blend cooling, water is removed water-soluble polyethylene glycol dissolving wherein, obtains the polymeric amide powder;
3. the polymeric amide powder of gained is washed and drying the powder that obtains having following feature:
D0.1(μm)＝33μm
D0.5(μm)＝60μm
D0.9(μm)＝120μm
D[4，3]＝65μm
Width=87 μ m
Tap density: 489g/L
Embodiment 5:
1. the polymeric amide-12 and the polyoxyethylene glycol that with mass ratio are 1: 3 are pre-mixed evenly, utilize twin screw extruder to carry out blend then under the condition of 200 ℃ and 40 rev/mins and extrude;
2. with resulting blend cooling, water is removed water-soluble polyethylene glycol dissolving wherein, obtains the polymeric amide powder;
3. the polymeric amide powder of gained is washed and drying the powder that obtains having following feature:
D0.1(μm)＝40μm
D0.5(μm)＝80μm
D0.9(μm)＝148μm
D[4，3]＝88μm
Width=92 μ m
Tap density: 490g/L
Embodiment 6:
1. the polymeric amide-12 and the polyoxyethylene glycol that with mass ratio are 1: 3 are pre-mixed evenly, utilize twin screw extruder to carry out blend then under the condition of 200 ℃ and 70 rev/mins and extrude;
2. with resulting blend cooling, water is removed water-soluble polyethylene glycol dissolving wherein, obtains the polymeric amide powder;
3. the polymeric amide powder of gained is washed and drying the powder that obtains having following feature:
D0.1(μm)＝32μm
D0.5(μm)＝51μm
D0.9(μm)＝98μm
D[4，3]＝53μm
Width=66 μ m
Tap density: 488g/L
Embodiment 7:
1. the polymeric amide-12 and the polyoxyethylene glycol that with mass ratio are 1: 3 are pre-mixed evenly, utilize twin screw extruder to carry out blend then under the condition of 200 ℃ and 90 rev/mins and extrude;
2. with resulting blend cooling, water is removed water-soluble polyethylene glycol dissolving wherein, obtains the polymeric amide powder;
3. the polymeric amide powder of gained is washed and drying the powder that obtains having following feature:
D0.1(μm)＝35μm
D0.5(μm)＝56μm
D0.9(μm)＝102μm
D[4，3]＝61μm
Width=67 μ m
Tap density: 492g/L
Embodiment 8:
1. the polymeric amide-12 and the polyoxyethylene glycol that with mass ratio are 1: 3 are pre-mixed evenly, utilize twin screw extruder to carry out blend then under the condition of 200 ℃ and 130 rev/mins and extrude;
2. with resulting blend cooling, water is removed water-soluble polyethylene glycol dissolving wherein, obtains the polymeric amide powder;
3. the polymeric amide powder of gained is washed and drying the powder that obtains having following feature:
D0.1(μm)＝15μm
D0.5(μm)＝33μm
D0.9(μm)＝89μm
D[4，3]＝35μm
Width=74 μ m
Tap density: 496g/L
Embodiment 9:
1. the polymeric amide-12 and the polyoxyethylene glycol that with mass ratio are 1: 3 are pre-mixed evenly, utilize twin screw extruder to carry out blend then under the condition of 200 ℃ and 165 rev/mins and extrude;
2. with resulting blend cooling, water is removed water-soluble polyethylene glycol dissolving wherein, obtains the polymeric amide powder;
3. the polymeric amide powder of gained is washed and drying the powder that obtains having following feature:
D0.1(μm)＝11μm
D0.5(μm)＝25μm
D0.9(μm)＝72μm
D[4，3]＝27μm
Width=61 μ m
Tap density: 493g/L
Embodiment 10:
With the polymeric amide-12 among the polymeric amide-6 replacement embodiment 1, temperature is 260 ℃, and other technology is constant, obtains having the polymeric amide powder of following feature:
D0.1(μm)＝6μm
D0.5(μm)＝15μm
D0.9(μm)＝50μm
D[4，3]＝21μm
Width=44 μ m
Tap density: 503g/L
Embodiment 11:
With the polymeric amide-12 among the polymeric amide-66 replacement embodiment 1, temperature is 280 ℃, and other technology is constant, obtains having the polymeric amide powder of following feature:
D0.1(μm)＝4μm
D0.5(μm)＝18μm
D0.9(μm)＝55μm
D[4，3]＝22μm
Width=54 μ m
Tap density: 502g/L
Embodiment 12:
With the polymeric amide-12 among the polymeric amide-11 replacement embodiment 1, temperature is 210 ℃, and other technology is constant, obtains having the polymeric amide powder of following feature:
D0.1(μm)＝9μm
D0.5(μm)＝16μm
D0.9(μm)＝55μm
D[4，3]＝24μm
Width=46 μ m
Tap density: 497g/L
Embodiment 13:
With the polyoxyethylene glycol among the polyoxyethylene replacement embodiment 3, temperature is 220 ℃, and other technology is constant, obtains having the polymeric amide powder of following feature:
D0.1(μm)＝20μm
D0.5(μm)＝40μm
D0.9(μm)＝80μm
D[4，3]＝45μm
Width=60 μ m
Tap density: 490g/L
Embodiment 14:
With the polyoxyethylene glycol among the polyacrylamide replacement embodiment 3, temperature is 210 ℃, and other technology is constant, obtains having the polymeric amide powder of following feature:
D0.1(μm)＝12μm
D0.5(μm)＝30μm
D0.9(μm)＝75μm
D[4，3]＝32μm
Width=63 μ m
Tap density: 510g/L
Embodiment 15:
With the polyoxyethylene glycol among the polyvinyl alcohol replacement embodiment 3, temperature is 210 ℃, and other technology is constant, obtains having the polymeric amide powder of following feature:
D0.1(μm)＝0.3μm
D0.5(μm)＝4μm
D0.9(μm)＝13μm
D[4，3]＝6μm
Width=12.7 μ m
Tap density: 515g/L.
Claims (3)
1. the method for a median size controllable preparation high-bulk-density polymeric amide powder is characterized in that this method may further comprise the steps successively:
The first step: with mass ratio be 1: 5～1: 1 polyamide resin and water-soluble polymers mixture be higher than them both separately under the temperature of fusing point in milling device or screw extrusion press melt blending, and make polyamide resin become the uniform disperse phase of particle diameter therein;
Second step: the blend that the first step is obtained places the water dissolving and removes wherein water-soluble polymers as external phase, obtain the polymeric amide powder of powder accumulation density greater than 485g/l after washing, drying, described polymeric amide forms in following any mode:
(1) form from the lactan that has at least 6 carbon atoms,
(2) form from the p-aminocarboxylic acid that has at least 6 carbon atoms,
(3) form from diamines and the dicarboxylic acid that respectively carries at least 6 carbon atoms,
(4) form from above-mentioned each monomeric copolyamide.
2. the method for median size controllable preparation high-bulk-density polymeric amide powder according to claim 1, it is characterized in that described water-soluble polymers is following a kind of or their blend in several: polyoxyethylene glycol, polyoxyethylene, polyacrylamide, polyvinyl alcohol, polymaleic anhydride and ether of cellulose base polymer.
3. the method for median size controllable preparation high-bulk-density polymeric amide powder according to claim 1, it is characterized in that the shearing rate by regulating ratio between polyamide resin and the water-soluble polymers and mixing equipment and the kind of water-soluble polymers obtain the polyamide powder of different median sizes and size distribution.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410088820 CN1246367C (en) | 2004-11-05 | 2004-11-05 | Method for preparing high tap density polyamide powder of controll able average partical size |
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|---|---|---|---|
| CN 200410088820 CN1246367C (en) | 2004-11-05 | 2004-11-05 | Method for preparing high tap density polyamide powder of controll able average partical size |
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| CN1246367C true CN1246367C (en) | 2006-03-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101077910B (en) | 2006-05-23 | 2010-06-09 | 上海杰事杰新材料股份有限公司 | Method for preparing particle diameter controllable high molecular weight nylon micro-sphere |
| CN103665839B (en) * | 2012-09-14 | 2017-02-08 | 合肥杰事杰新材料股份有限公司 | Polyamide microspheres and preparation method thereof |
| JP7007818B2 (en) * | 2017-06-16 | 2022-02-10 | ダイセル・エボニック株式会社 | Method of manufacturing resin particles |
| JP6909065B2 (en) * | 2017-06-16 | 2021-07-28 | ダイセル・エボニック株式会社 | A water-soluble matrix, a preformed body containing resin particles, and a method for producing resin particles. |
| WO2020005200A1 (en) | 2018-06-25 | 2020-01-02 | Hewlett-Packard Development Company, L.P. | Three-dimensional printing |
| CN110437473B (en) * | 2019-08-19 | 2022-07-12 | 万华化学集团股份有限公司 | Polymer powder surface treatment method |
| CN113337105B (en) * | 2020-03-02 | 2022-09-23 | 中国科学院化学研究所 | Polymer powder and preparation method thereof |
| CN113354942B (en) * | 2020-03-02 | 2022-10-18 | 中国科学院化学研究所 | Polymer powder and preparation method thereof |
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