CN110437473B - Polymer powder surface treatment method - Google Patents
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Abstract
The invention relates to surface treatment of polymer powder, which takes the polymer powder as a raw material and comprises the following steps: step 1: heating and uniformly mixing a water-soluble polymer, an aqueous phase medium, a defoaming agent and an optional amino cyclodextrin derivative to obtain a treatment solution, wherein the number average molecular weight of the water-soluble polymer is 20000-150000 g/mol; step 2: mixing the polymer powder and the treatment solution, and uniformly mixing to obtain a solid-liquid mixture containing powder; and step 3: and (3) carrying out solid-liquid separation and drying on the mixture obtained in the step (2) to obtain the treated thermoplastic polymer powder. The powder roughness is reduced by the adsorption of the water-soluble polymer to a high surface energy area of the powder, high-temperature and high-pressure treatment is not needed, and the method is simple and safe. The treated powder can be used in the fields of powder coating, 3D printing, cosmetics, additives, medicines and the like.
Description
Technical Field
The invention belongs to the technical field of polymer powder, and particularly relates to a surface treatment method of polymer powder.
Background
The development of modern high technology and new material industries, technical progress of traditional industries and product upgrade require many polymer powder raw materials. Because the powder has fine particle size, large specific surface area and more surface particles, the interaction force between the surface particles and the internal particles is different, and the mechanical activation or mechanochemical action in the preparation process of the powder makes the particles on the surface of the powder have higher energy (surface energy) and activity than the particles in the powder. Therefore, the surface properties of the powder determine the special properties of the powder, such as low sintering temperature, high strength of the sintered body, good filling and reinforcing properties, unique dispersibility, rheological properties and the like.
The methods for preparing polymer powder mainly include low-temperature mechanical pulverization method and solvent precipitation method. The low-temperature mechanical pulverization method utilizes the characteristic that a high polymer material has an embrittlement temperature, and pulverizes the high polymer material into micron-sized powder under a low-temperature condition. Common polymer materials such as polystyrene, polypropylene, polycarbonate, polyolefin, ethylene-vinyl acetate resin, polyamide, etc. can be prepared into powder materials by adopting a low-temperature mechanical pulverization method. The low-temperature grinding method has the advantages that the process is simple, continuous production can be realized, the prepared particles are disordered in shape and wide in particle size distribution, the powder is subjected to screening treatment sometimes, and unqualified powder is subjected to repeated reprocessing.
Powder shape, surface energy, flowability are critical to polymer powder applications. For example, in selective laser sintering, the spherical powder sintered model has improved performance in all aspects. According to Frenkel model (Viscous Flow of Crystalline metals under the Action of Surface tension. the Journal of Physics,1945.9(5): p.385-391.), the Surface tension of the powder is also one of the keys to improving sintering properties.
At present, some methods for treating the surface of polymer powder have been reported. For example, CN108407299A discloses a method for rounding irregular polymer powder, wherein the polymer powder is heated to form melt droplets and spontaneously retracts under the action of interfacial tension, thereby rounding the irregular polymer powder. Efficient processing of high temperature polymer powders is difficult due to the boiling point of the medium. CN107022100A discloses a polymer powder treatment process for powder bed melting process, the polymer powder being coated with hydrophobic substances of alkanes, alkenes and mixtures thereof. The coating of hydrophobic substances reduces the surface tension and affects the sintering. CN106633114A discloses a spheroidizing method of polyetheretherketone 3D printing powder, using a gyroscope to make the fluid flow to wash the polyetheretherketone material. However, the method has strict requirements on equipment and operation, and the process needs a corresponding solvent.
In conclusion, in the prior art, the treatment of the surface of the polymer powder is focused on the spheroidization of the powder, so that the purpose of improving the flow is achieved, and the surface characteristics are not regulated and controlled; on the other hand, the treatment is limited to different powder materials and requires high temperatures or special solvents. The treatment method which is easy to operate and general has value for expanding the application of the powder.
Disclosure of Invention
In view of the problems of the prior art, the present invention provides a method for surface treatment of polymer powder with good operability, which realizes surface treatment of powder by adsorption of water-soluble polymer in a high surface energy region of powder, and has the advantages of no need of high temperature and high pressure treatment, and simple and safe method.
The purpose of the invention is realized by the following technical scheme, wherein the parts of the raw materials are parts by mass except for special description.
In one aspect of the present invention, there is provided a polymer powder surface treatment method, comprising the steps of:
step 1: heating and uniformly mixing a water-soluble polymer, an aqueous phase medium, a defoaming agent and an optional amino cyclodextrin derivative to obtain a treatment solution; the heating and mixing temperature is 60-95 ℃;
step 2: mixing the polymer powder and the treatment solution, and uniformly mixing to obtain a solid-liquid mixture containing powder; the mixing treatment time is 10-60 min, preferably 15-30 min; the mixing treatment temperature is 25-50 ℃;
and 3, step 3: carrying out solid-liquid separation and drying on the mixture obtained in the step 2 to obtain treated polymer powder; solid-liquid separation is carried out by means of screen filtration or centrifugal separation and the like; the drying mode can be vacuum drying or normal pressure drying, and the like, and preferably vacuum drying is carried out; the drying temperature is 60-100 ℃, and preferably 70-90 ℃; the drying time is 1-5 h.
In the method, the dosage of each component is as follows:
polymer powder (b): 2 to 50 parts by mass, preferably 10 to 20 parts by mass;
water-soluble polymer: 0.4 to 5 parts by mass, preferably 0.8 to 2 parts by mass;
aqueous phase medium: 100 parts by mass;
amino cyclodextrin derivatives: 0-2 parts by mass;
defoaming agent: 0.01 to 0.1 part by mass;
wherein the number average molecular weight of the water-soluble polymer is 20000g/mol to 150000g/mol, preferably 50000g/mol to 120000 g/mol.
In the method, the aqueous phase medium is water, a small molecular alcohol and/or an ether aqueous solution; the molecular weight of the micromolecular alcohol or ether is less than 200g/mol, and the micromolecular alcohol or ether is selected from one or more of methanol, ethanol, glycol, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monopropyl ether, and preferably from one or more of methanol, ethanol and ethylene glycol monoethyl ether; the small molecular alcohol and/or ether accounts for 0-8 wt%, preferably 1-5 wt% of the aqueous medium.
In the method of the present invention, the particle size of the polymer powder is in the range of 10 to 300. mu.m, preferably 50 to 150. mu.m. The polymer powder is thermoplastic polymer powder, and the thermoplastic polymer can be selected from thermoplastic polyurethane elastomer, polyamide, polyvinyl chloride, polycarbonate, polyester, polyether ether ketone, polyphenylene sulfide, polyphenylene oxide and polypropylene, preferably thermoplastic polyurethane elastomer and polypropylene; the polymer powder may be obtained by pulverization or the like.
In the method of the present invention, the water-soluble polymer has a number average molecular weight of 20000g/mol to 150000g/mol, preferably 50000g/mol to 120000g/mol, and is selected from polyvinyl alcohol, hydroxypropyl cellulose, hydroxyethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, and polyethylene oxide, preferably selected from polyvinyl alcohol and hydroxyethyl cellulose. Wherein the alcoholysis degree range of the polyvinyl alcohol is 85-95 percent; the viscosity range of the 2wt% aqueous solution of the hydroxypropyl cellulose and the hydroxyethyl cellulose is 50-400 mPa.s. The water-soluble polymer generates a small amount of adsorption through intermolecular force on the surface of powder (micron level), and particularly adsorbs a sharp area on the surface of the powder (higher surface energy and easier adsorption), so that the surface of the powder is wrapped, and the surface roughness of the powder is reduced.
In the method of the invention, the defoaming agent is one or more of polyether modified silicone defoaming agent and silicone defoaming agent, such as BYK-019 and BYK-024.
In the method, the amido cyclodextrin derivative is substituted at 6-position, and the structural formula is as follows:
wherein the substituent R is a linear alkylene group having 2 to 6 carbon atoms; the cyclodextrin is selected from the group consisting of alpha-cyclodextrin, beta-cyclodextrin, and gamma-cyclodextrin.
The preparation method of the amino cyclodextrin derivative can refer to CN104031179B and the literature report of YangDong (research on the interaction between the preparation of several cyclodextrin derivatives and the subject and object, 2016, Tianjin science and technology university), the cyclodextrin with the structure has partial hydrophilicity and can play a role in adjusting viscosity, and on the other hand, the dried cyclodextrin component can be agglomerated on the surface to play a role in blocking and lubricating powder.
In a second aspect of the invention, there is provided a polymer powder obtained by treating according to the above process.
In a third aspect of the invention, there is provided the use of the polymer powder treated according to the above method in powder coatings, 3D printing, cosmetics, additives, pharmaceuticals and the like.
The invention has the following beneficial effects:
(1) the water-soluble polymer adsorbs a high surface energy area of polymer powder, so that the roughness of the powder can be reduced, high-temperature and high-pressure treatment is not required, and the method is simple and universal.
(2) The surface characteristics of the polymer powder can be adjusted by the water-soluble polymer, and the application effect of the powder is improved.
(3) The method has wide application range, is not limited by the types of polymers, and has small influence on the properties of the material.
Drawings
FIGS. 1 to 7 are scanning electron micrographs of examples 1 to 7, respectively;
FIGS. 8 to 9 are scanning electron micrographs of comparative examples 1 to 2, respectively.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and ordinary skill in the art without departing from the spirit of the method of the invention described above.
And (3) performance testing:
powder morphology: a scanning electron microscope is used.
Powder particle size distribution: measured using a laser particle size distribution instrument model BT-9300 ST.
Powder flowability: measured using an england rich raman FT4 powder rheometer.
In the examples, the raw material sources are as follows:
polyvinyl alcohol, Shandong Youso chemical technology Co., Ltd
Defoaming agents BYK-019 and BYK-024: bike chemical technology consultancy (Shanghai) Co., Ltd
Polypropylene powder: cryogenic grinding self-made
Polycarbonate powder: self-made by crushing
Thermoplastic polyurethane powder: cryogenic grinding self-made
Polyvinylpyrrolidone: chemical reagents of national drug group Limited
Hydroxyethyl cellulose: chemical reagents of national drug group Co Ltd
Beta-cyclodextrin: chemical reagents of national drug group Co Ltd
Sodium hydroxide: chemical reagents of national drug group Co Ltd
P-toluenesulfonyl chloride: chemical reagents of national drug group Limited
Potassium carbonate: chemical reagents of national drug group Co Ltd
Ethylene diamine: chemical reagents of national drug group Co Ltd
Dimethylformamide (b): chemical reagents of national drug group Co Ltd
Acetone: chemical reagents of national drug group Co Ltd
Example 1
Dissolving 30g of beta-cyclodextrin in 600ml of deionized water, adding 18g of NaOH solution (0.75mol/L), stirring and reacting for 30min under ice bath, adding 6g of paratoluensulfonyl chloride in batches, continuously stirring and reacting for 5h at the temperature of 0-5 ℃, performing suction filtration to obtain a light yellow clear solution, adjusting the pH to 6-7 by using 2mol/L hydrochloric acid, separating out a white precipitate, refrigerating overnight, performing suction filtration and recrystallization twice, and drying to obtain 6-OTs-beta-CD.
Taking 0.83g of potassium carbonate and 2ml of ethylenediamine, putting the mixture into a 100ml three-neck round-bottom flask, adding 15ml of DMF as a solvent, stirring for 2h at room temperature, adding 7.8g of 6-OTs-beta-CD dissolved in 15ml of DMF, heating to 80 ℃, and stirring for reaction for 24h under the protection of nitrogen. After the reaction liquid is cooled, pouring the reaction liquid into 200ml of acetone for precipitation, and obtaining light yellow solid ethylenediamine-beta-cyclodextrin after suction filtration and drying.
Heating and uniformly mixing 100 parts by mass of water, 2 parts by mass of ethylenediamine-beta-cyclodextrin, 1 part by mass of polyvinyl alcohol (the number average molecular weight is 50000g/mol, the alcoholysis degree is 85%), and 0.1 part by mass of defoaming agent BYK-019 at 95 ℃ to obtain a treatment solution;
mixing 10 parts by mass of D50Polypropylene powder of 50 μm was mixed with the aforementioned treatment solution and mixed at 25 ℃ for 15min, followed by solid-liquid separation using a mesh and vacuum drying at 100 ℃ for 2h to obtain polymer microsphere powder.
Example 2
Heating and uniformly mixing 100 parts by mass of an aqueous medium (1 wt% methanol aqueous solution), 0.4 part by mass of polyvinylpyrrolidone with the average molecular weight of 150000g/mol and 0.01 part by mass of defoaming agent BYK-019 at 90 ℃ to obtain a treatment solution;
2 parts by mass of D50Thermoplastic polyurethane powder of 300 μm was mixed with the above treatment solution and treated by mixing at 35 ℃ for 10min, after solid-liquid separation using centrifugation, vacuum-dried at 60 ℃ for 4.5h to obtain polymer microsphere powder.
Example 3
Heating and uniformly mixing 100 parts by mass of an aqueous medium (8 wt% ethanol aqueous solution), 5 parts by mass of hydroxyethyl cellulose (the number average molecular weight is 20000g/mol, the viscosity of 2wt% aqueous solution is 50mPa.s) and 0.1 part by mass of a defoaming agent BYK-024 at 60 ℃ to obtain a treatment solution;
50 parts by mass of D5010 μm thermoplastic polyurethane powderMixing the powder with the above solution, mixing at 50 deg.C for 60min, performing solid-liquid separation with a screen, and drying at 90 deg.C under normal pressure for 2 hr to obtain polymer microsphere powder.
Example 4
Heating and uniformly mixing 100 parts by mass of an aqueous medium (2 wt% of ethylene glycol monoethyl ether aqueous solution), 0.8 part by mass of polyvinyl alcohol (the number average molecular weight is 120000g/mol, and the alcoholysis degree is 90%), and 0.05 part by mass of a defoaming agent BYK-024 at 80 ℃ to obtain a treatment solution;
20 parts by mass of D50Polypropylene powder of 150 μm was mixed with the above treatment solution and treated by mixing at 40 ℃ for 30min, after solid-liquid separation using centrifugation, vacuum-dried at 80 ℃ for 4h to obtain polymer microsphere powder.
Example 5
Heating and uniformly mixing 100 parts by mass of an aqueous medium (6 wt% tetrahydrofuran aqueous solution), 1 part by mass of polyvinylpyrrolidone (with the number average molecular weight of 100000g/mol) and 0.05 part by mass of a defoaming agent BYK-019 at 90 ℃ to obtain a treatment solution;
mixing 30 parts by mass of D50Thermoplastic polyurethane powder of 300 μm was mixed with the above treatment solution and mixed at 50 ℃ for 40min, solid-liquid separated using centrifugation, and vacuum dried at 70 ℃ for 4h to obtain polymer microsphere powder.
Example 6
Heating and uniformly mixing 100 parts by mass of an aqueous medium (5 wt% ethanol aqueous solution), 2 parts by mass of hydroxyethyl cellulose (the number average molecular weight is 77000g/mol, the viscosity of the 2wt% aqueous solution is 400mPa.s) and 0.1 part by mass of a defoaming agent BYK-024 at 95 ℃ to obtain a treatment solution;
40 parts by mass of D50Thermoplastic polyurethane powder of 10 μm was mixed with the above treatment solution and subjected to mixing treatment at 35 ℃ for 50min, solid-liquid separated using a mesh, and then vacuum-dried at 60 ℃ for 5 hours to obtain polymer microsphere powder.
Example 7
Heating and uniformly mixing 100 parts by mass of water, 3 parts by mass of polyvinyl alcohol (the number average molecular weight is 130000g/mol, the alcoholysis degree is 95%) and 0.05 part by mass of defoaming agent BYK-019 at 80 ℃ to obtain a treatment solution;
25 parts by mass of D50Polycarbonate powder of 200 μm was mixed with the above treatment solution, and mixed at 40 ℃ for 60min, subjected to solid-liquid separation using a sieve, and then vacuum-dried at 100 ℃ for 1h to obtain polymer microsphere powder.
Comparative example 1
A commercially available thermoplastic polyurethane powder FS 1092A-TPU.
Comparative example 2
Commercially available polypropylene powder Luvosint 8824 WT.
TABLE 1 powder Properties before and after treatment of examples and comparative examples
Claims (18)
1. A polymer powder treatment process comprising the steps of:
step 1: heating and uniformly mixing a water-soluble polymer, a water-phase medium, a defoaming agent and an optional amino cyclodextrin derivative to obtain a treatment solution; the aqueous medium is an aqueous solution of micromolecule alcohol and/or ether, and the micromolecule alcohol and/or ether accounts for 1-8 wt% of the aqueous medium;
the number average molecular weight of the water-soluble polymer is 20000 g/mol-150000 g/mol, and the water-soluble polymer is selected from polyvinyl alcohol, hydroxypropyl cellulose, hydroxyethyl cellulose, polyacrylamide, polyvinylpyrrolidone and polyethylene oxide; wherein the alcoholysis degree of the polyvinyl alcohol is 85-95%;
step 2: mixing the polymer powder and the treatment solution, and uniformly mixing to obtain a solid-liquid mixture containing powder; wherein the particle size range of the polymer powder is 10-300 mu m, and the polymer powder is thermoplastic polymer powder; the mixing treatment temperature is 25-50 ℃;
and step 3: and (3) performing solid-liquid separation and drying on the mixture obtained in the step (2) to obtain the treated polymer powder.
2. The method of claim 1, wherein the water-soluble polymer has a number average molecular weight of 50000g/mol to 120000 g/mol.
3. The process of claim 1, wherein the components are used in amounts of:
polymer powder (b): 2-50 parts by mass;
water-soluble polymer: 0.4-5 parts by mass;
aqueous phase medium: 100 parts by mass;
amino cyclodextrin derivatives: 0-2 parts by mass;
defoaming agent: 0.01 to 0.1 parts by mass.
4. The method according to claim 3, wherein the polymer powder is used in an amount of 10 to 20 parts by mass and the water-soluble polymer is used in an amount of 0.8 to 2 parts by mass.
5. The process according to any one of claims 1 to 4, wherein the small molecule alcohol or ether has a molecular weight of less than 200 g/mol;
the small molecular alcohol and/or ether accounts for 1-5 wt% of the aqueous medium.
6. The method according to claim 5, wherein the small molecule alcohol or ether is selected from one or more of methanol, ethanol, ethylene glycol, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monopropyl ether.
7. The method according to claim 6, wherein the small molecule alcohol or ether is selected from one or more of methanol, ethanol, and ethylene glycol monoethyl ether.
8. The process according to any one of claims 1 to 4, characterized in that the polymer powder is chosen from thermoplastic polyurethane elastomers, polyamides, polyvinyl chloride, polycarbonates, polyesters, polyetheretherketones, polyphenylene sulfides, polyphenylene oxides, polypropylene.
9. The process according to claim 8, wherein the polymer powder has a particle size in the range of 50 to 150 μm;
the polymer powder is selected from thermoplastic polyurethane elastomer and polypropylene.
10. The process according to any one of claims 1 to 4, wherein the hydroxypropyl cellulose, hydroxyethyl cellulose, has a viscosity in the range of 50 to 400mPa.s in a 2wt% aqueous solution.
11. The treatment method according to claim 10, wherein the water-soluble polymer is selected from polyvinyl alcohol, hydroxyethyl cellulose.
12. The process according to any one of claims 1 to 4, wherein the defoaming agent is selected from polyether modified silicone defoaming agents, silicone defoaming agents.
13. The process of claim 12 wherein the defoaming agent is selected from BYK-019 and BYK-024.
14. The process of any one of claims 1 to 4, wherein the amino cyclodextrin derivative is 6-substituted and has the formula:
wherein, the substituent R is a linear alkylene with 2-6 carbon atoms; said cyclodextrin is selected fromα-cyclodextrin, a,β-cyclodextrins andγ-cyclodextrin.
15. The treatment method according to any one of claims 1 to 4, wherein the heating and mixing temperature in step 1 is 60 to 95 ℃;
and/or: in the step 2, the mixing treatment time is 10-60 min;
and/or: in the step 3, the drying temperature is 60-100 ℃; the drying time is 1-5 h.
16. The treatment method according to claim 15, wherein the mixing treatment time in the step 2 is 15 to 30 min; and/or: in the step 3, the drying temperature is 70-90 ℃.
17. A polymer powder obtained by the process according to any one of claims 1 to 16.
18. The polymer powder of claim 17 for applications including powder coatings, 3D printing, cosmetics, additives.
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