CN115636959A - Spherical polymer powder material for selective laser sintering and preparation method thereof - Google Patents
Spherical polymer powder material for selective laser sintering and preparation method thereof Download PDFInfo
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- CN115636959A CN115636959A CN202211367776.8A CN202211367776A CN115636959A CN 115636959 A CN115636959 A CN 115636959A CN 202211367776 A CN202211367776 A CN 202211367776A CN 115636959 A CN115636959 A CN 115636959A
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Abstract
The application discloses a spherical polymer powder material for selective laser sintering, which comprises, by mass, 3-13 parts of a polymer, 45-65 parts of a diluent and 32-52 parts of a dispersing agent, wherein the polymer is a homopolymer or a copolymer of polypropylene, and the dispersing agent is selected from 1, 3-propylene glycol, 1, 3-butanediol and 1, 4-butanediol. The application also discloses a preparation method of the spherical polymer powder material for selective laser sintering. The invention prepares polymer powder under normal pressure, has high sphericity, narrow particle size distribution, simple preparation process, recyclable solvent and good industrial prospect.
Description
Technical Field
The application belongs to the technical field of high polymer materials, and particularly relates to a spherical polymer powder material for selective laser sintering and a preparation method thereof.
Background
Selective Laser Sintering (SLS) is one of additive manufacturing techniques, and powder can be naturally sintered and molded layer by layer through layer-by-layer manufacturing and layer-by-layer superposition. The powder in the sintering area is heated to enable the particle boundaries to be fused and bonded together, while the powder in the non-sintering area is still in a loose state and plays a role of supporting the next layer of sintering, so that a supporting material and a mold are not needed, the limitation of the shape complexity of a formed product is avoided, and the method becomes one of the additive manufacturing technologies which are applied most.
The selection of molding materials is an important link of the SLS technology, and directly influences the molding speed of the sintering process and the precision and performance of the molded part. The material applied to SLS technology comprises metal powder material, polymer powder material and ceramic powder material, wherein the polymer powder material has lower melting temperature, the sintering power and the forming temperature are much lower than those of the metal and ceramic powder materials, the surface tension is small, the phenomenon of spheroidization cannot occur in the sintering process like the metal powder, larger pores cannot be generated in a sintered part to cause the density reduction of the sintered part, the good mechanical property can be ensured, and the polymer powder becomes the SLS forming material which is most widely applied at present. The polypropylene is one of five general-purpose plastics, has excellent heat resistance, chemical stability and processing fluidity and is low in price, so that the preparation of the polypropylene powder for SLS technology is necessary.
The current methods for preparing the polypropylene powder for SLS mainly comprise a solvent precipitation method and a cryogenic grinding method. The solvent precipitation method needs to be dissolved under the conditions of high pressure and high temperature, and has high requirements on equipment. In patent CN107383593B, solvents such as xylene, toluene and diphenyl ether are selected to prepare polypropylene powder, but the selected solvents have great harm to the environment. The deep cooling pulverization method is also a common method for preparing the polypropylene powder for SLS, and patent CN104031319A describes that the polypropylene powder is prepared by the deep cooling pulverization method, the preparation process is simple, but the prepared powder has wide particle size distribution and irregular shape, and the forming precision of SLS sintered parts is seriously influenced. Therefore, it is required to develop a method for preparing polypropylene powder, which has simple preparation process, environmental friendliness, narrow particle size distribution and high sphericity.
Disclosure of Invention
The embodiment of the application aims to provide a spherical polymer powder material for selective laser sintering with narrow particle size distribution and high sphericity and a preparation method thereof, which can obtain polymer powder with good powder laying effect at a lower temperature so as to solve the technical problems related to the background technology.
In order to solve the technical problem, the present application is implemented as follows:
the spherical polymer powder material for selective laser sintering comprises, by mass, 3-13 parts of a polymer, 45-65 parts of a diluent and 32-52 parts of a dispersing agent, wherein the polymer is a homopolymer or a copolymer of polypropylene, and the dispersing agent is selected from 1, 3-propylene glycol, 1, 3-butanediol and 1, 4-butanediol.
In some embodiments, the diluent is dioctyl terephthalate, diisononyl phthalate, glycerol monooleate.
The application also discloses a preparation method of the spherical polymer powder material for selective laser sintering, which comprises the following steps:
adding 3-13 parts of polymer, 45-65 parts of diluent and 32-52 parts of dispersant into a reaction kettle according to a certain proportion by weight, heating and stirring at normal pressure, and fully and uniformly mixing to obtain a uniform solution;
keeping the temperature of the homogeneous solution for a certain time, and cooling according to a program to separate out a polymer from the homogeneous solution;
the precipitated polymer was sufficiently washed with ethanol and dried to obtain polymer powder.
In some embodiments, the heating and stirring under normal pressure sufficiently mixes the components uniformly, and the method includes:
the heating temperature is 130-160 ℃.
In some embodiments, the heating under normal pressure and stirring for thorough mixing comprises:
the stirring speed is 20-500rpm.
In some embodiments, the incubating the mixed solution for a certain time comprises:
the heat preservation time is 1-3h.
In some embodiments, the programmed temperature reduction phase separates the polymer from the mixed solution, including:
the cooling rate is 1-5 ℃/min.
In some embodiments, the drying results in a polymer powder comprising:
the drying temperature is 60-80 ℃.
Compared with the prior art, the method has the following technical effects:
(1) 1, 3-propylene glycol, 1, 3-butanediol and 1, 4-butanediol with high boiling point are selected as dispersing agents for use, on one hand, agglomeration caused by adhesion of polymer lean phase particles can be effectively prevented, on the other hand, the polymer lean phase particles have weak interaction with a diluent, and the interaction force between the polymer and the diluent can be adjusted, so that liquid-liquid phase separation can be generated when a uniform solution is cooled, the polymer lean phase can nucleate and grow up in a solution state under the condition, and the requirements of polymer powder on preparation conditions are reduced;
(2) 1, 3-propylene glycol, 1, 3-butanediol and 1, 4-butanediol with high boiling point are added as dispersing agents, so that the nucleation potential barrier of the polymer is effectively reduced, the polymer lean phase liquid drop is preferentially nucleated and grows around the dispersing agents, the nucleation rate of the polymer lean phase liquid drop is improved, the polymer lean phase liquid drop can begin to nucleate at the initial stage of cooling, the crystallinity and the sphericity of the powder are improved, and the polymer powder with narrow particle size distribution, high sphericity and good mechanical property is obtained;
(3) The polymer, the diluent and the dispersant can form a uniform solution at normal pressure after being heated, high pressure is not needed, the diluent and the dispersant completely separate phases at room temperature, and the solvent can be recycled.
Drawings
FIG. 1 is a microscopic topography of a spherical polymer powder material for selective laser sintering as provided in an embodiment of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some, but not all, of the embodiments of the present application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The terms first, second and the like in the description and in the claims of the present application are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It will be appreciated that the data so used may be interchanged under appropriate circumstances such that embodiments of the application are capable of operation in sequences other than those illustrated or described herein, and that the terms "first," "second," etc. are generally used in a generic sense and do not limit the number of terms, e.g., a first term can be one or more than one. In addition, "and/or" in the specification and claims means at least one of connected objects, a character "/", and generally means that the former and latter related objects are in an "or" relationship.
The spherical polymer powder material for selective laser sintering provided by the embodiments of the present application is described in detail by specific embodiments and application scenarios thereof in conjunction with the accompanying drawings.
The spherical polymer powder material for selective laser sintering comprises, by mass, 3-13 parts of a polymer, 45-65 parts of a diluent and 32-52 parts of a dispersing agent, wherein the polymer is a homopolymer or a copolymer of polypropylene, and the dispersing agent is selected from 1, 3-propylene glycol, 1, 3-butanediol and 1, 4-butanediol.
In some embodiments, the diluent is dioctyl terephthalate, diisononyl phthalate, glycerol monooleate.
The application also discloses a preparation method of the spherical polymer powder material for selective laser sintering, which comprises the following steps:
adding 3-13 parts of polymer, 45-65 parts of diluent and 32-52 parts of dispersant into a reaction kettle according to a certain proportion by mass, heating and stirring at the temperature of 130-160 ℃ at normal pressure, and fully and uniformly mixing at the stirring speed of 20-500rpm to obtain a uniform solution;
keeping the temperature of the homogeneous solution for 1-3h, and cooling at a cooling rate of 1-5 ℃/min according to a program to separate out the polymer from the homogeneous solution;
washing the precipitated polymer with ethanol, and drying at 60-80 deg.C to obtain polymer powder.
Referring again to fig. 1, the polymer powder prepared by the present application can be seen under a microscope to have a narrow particle size distribution and a high sphericity.
The following is a detailed description of a method for preparing a spherical polymer powder material for selective laser sintering disclosed in the present application with specific examples and comparative examples.
Example 1:
adding the copolymerization polypropylene/dioctyl terephthalate/1, 3-butanediol into a reaction kettle according to the mass ratio of 5/55/40, mixing to obtain a uniform solution at the temperature of 150 ℃ and the stirring speed of 200rpm, preserving the temperature for 3 hours, then cooling to 60 ℃ at the cooling speed of 5 ℃/min, taking out the mixture, fully washing with ethanol, and drying at 70 ℃ to obtain polymer powder.
Example 2:
adding the copolymerization polypropylene/diisononyl phthalate/1, 3-butanediol into a reaction kettle according to the mass ratio of 7/65/28, mixing to obtain a uniform solution at the temperature of 140 ℃ and the stirring speed of 300rpm, keeping the temperature for 2 hours, then cooling to 60 ℃ at the cooling speed of 5 ℃/min, taking out the mixture, fully washing with ethanol, and drying at 80 ℃ to obtain polymer powder.
Example 3:
adding the homo-polypropylene/dioctyl terephthalate/1, 4-butanediol into a reaction kettle according to the mass ratio of 7/60/33, uniformly mixing at the temperature of 150 ℃ and the stirring speed of 300rpm, then preserving heat for 2 hours, then cooling to 60 ℃ at the cooling speed of 3 ℃/min, taking out the mixture, fully washing with ethanol, and drying at 70 ℃ to obtain polymer powder.
Example 4:
adding the copolymerized polypropylene/diisononyl phthalate/1, 3-propylene glycol into a reaction kettle according to the mass ratio of 5/65/28, uniformly mixing at 145 ℃ and the stirring speed of 200rpm, keeping the temperature for 1h, then cooling to 60 ℃ at the cooling speed of 5 ℃/min, taking out the mixture, fully washing with ethanol, and drying at 80 ℃ to obtain polymer powder.
Example 5:
adding the homo-polypropylene/glycerol monooleate/1, 4-butanediol into a reaction kettle according to the mass ratio of 7/65/28, uniformly mixing at 155 ℃ and the stirring speed of 300rpm, keeping the temperature for 2h, then cooling to 60 ℃ at the cooling speed of 5 ℃/min, taking out the mixture, fully washing with ethanol, and drying at 80 ℃ to obtain polymer powder.
Comparative example 1:
adding the co-polypropylene/dioctyl terephthalate into a reaction kettle according to the mass ratio of 5/95, mixing to obtain a uniform solution at the temperature of 150 ℃ and the stirring speed of 200rpm, preserving heat for 3 hours, then cooling to 60 ℃ at the cooling speed of 5 ℃/min, taking out the mixture, fully washing with ethanol, and drying at 70 ℃ to obtain polymer powder.
The results of the tests carried out on the polymer powders obtained in examples 1 to 5 and on the polymer powder obtained in comparative example 1 are shown in Table 1.
TABLE 1 Polymer powder test data for comparative example 1 and examples 1-4
As can be seen from Table 1, the polymer powders obtained in examples 1 to 5 of the present application have a narrower particle size distribution, a higher sphericity, and a higher crystallinity and a higher bulk density than those obtained in comparative example 1.
Compared with the prior art, the method has the following technical effects:
(1) 1, 3-propylene glycol, 1, 3-butanediol and 1, 4-butanediol with high boiling points are selected as a dispersing agent for use, so that on one hand, the polymer lean phase particles can be effectively prevented from being adhered to cause agglomeration, on the other hand, the polymer lean phase particles have weak interaction with a diluent, the interaction force between the polymer and the diluent can be adjusted, the homogeneous solution can be subjected to liquid-liquid phase separation when being cooled, the polymer lean phase can nucleate and grow under the condition in a solution state, and the requirements of polymer powder on preparation conditions are reduced;
(2) 1, 3-propylene glycol, 1, 3-butanediol and 1, 4-butanediol with high boiling point are added as dispersing agents, so that the nucleation potential barrier of the polymer is effectively reduced, the polymer lean phase liquid drop is preferentially nucleated and grows around the dispersing agents, the nucleation rate of the polymer lean phase liquid drop is improved, the polymer lean phase liquid drop can begin to nucleate at the initial stage of cooling, the crystallinity and the sphericity of the powder are improved, and the polymer powder with narrow particle size distribution, high sphericity and good mechanical property is obtained;
(3) The polymer, the diluent and the dispersant can form a uniform solution at normal pressure after being heated, high pressure is not needed, the diluent and the dispersant completely separate phases at room temperature, and the solvent can be recycled.
While the present embodiments have been described with reference to the accompanying drawings, it is to be understood that the present embodiments are not limited to those precise embodiments, which are intended to be illustrative rather than restrictive, and that various changes and modifications may be effected therein by one skilled in the art without departing from the scope of the appended claims.
Claims (8)
1. The spherical polymer powder material for selective laser sintering is characterized by comprising 3-13 parts of polymer, 45-65 parts of diluent and 32-52 parts of dispersing agent by mass, wherein the polymer is a homopolymer or a copolymer of polypropylene, and the dispersing agent is selected from 1, 3-propylene glycol, 1, 3-butanediol and 1, 4-butanediol.
2. Spherical polymer powder material for selective laser sintering according to claim 1, characterized in that the diluent is dioctyl terephthalate, diisononyl phthalate, glycerol monooleate.
3. A method for preparing a spherical polymer powder material for selective laser sintering according to any one of claims 1 or 2, comprising:
adding 3-13 parts of polymer, 45-65 parts of diluent and 32-52 parts of dispersant into a reaction kettle according to a certain proportion by mass, heating and stirring at normal pressure, and fully and uniformly mixing to obtain a uniform solution;
keeping the temperature of the homogeneous solution for a certain time, and cooling according to a program to separate out a polymer from the homogeneous solution;
the precipitated polymer was sufficiently washed with ethanol and dried to obtain polymer powder.
4. The preparation method according to claim 3, wherein the heating and stirring under normal pressure are carried out to mix the mixture fully and uniformly, and the method comprises the following steps:
the heating temperature is 130-160 ℃.
5. The preparation method according to claim 3, wherein the heating and stirring under normal pressure are carried out to mix the mixture fully and uniformly, and the method comprises the following steps:
the stirring speed is 20-500rpm.
6. The method for preparing the composite material according to claim 3, wherein the incubating the mixed solution for a certain period of time comprises:
the heat preservation time is 1-3h.
7. The method of claim 3, wherein the programmed temperature reduction phase separates the polymer from the mixed solution, comprising:
the cooling rate is 1-5 ℃/min.
8. The method according to claim 3, wherein said drying provides a polymer powder comprising:
the drying temperature is 60-80 ℃.
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