CN111909509B - 3D printing powder and preparation method thereof - Google Patents
3D printing powder and preparation method thereof Download PDFInfo
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- CN111909509B CN111909509B CN202010641684.9A CN202010641684A CN111909509B CN 111909509 B CN111909509 B CN 111909509B CN 202010641684 A CN202010641684 A CN 202010641684A CN 111909509 B CN111909509 B CN 111909509B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
Abstract
The invention discloses flame-retardant functional modified 3D printing powder which comprises the following components in parts by weight: 100 parts of polyamide; 1-30 parts of a flame retardant; the particle size of the flame retardant is dispersed in a polyamide resin matrix in a form of less than 10 microns, and meanwhile, the 3D printing powder is uniform in particle size distribution, good in flowability and proper in bulk density. The 3D printing powder is prepared by a solution method, resin of a new polyamide material, resin of a waste polyamide material and resin of a reclaimed polyamide material are dissolved in a solvent system mainly containing phenol/toluene, a polyamide clear solution is obtained through decolorization (a step required for processing the polyamide waste material), filtration and purification, a flame retardant is added into the polyamide clear solution to fully dissolve the flame retardant, and finally the solution is sprayed into deionized water by a spraying method to obtain the modified 3D printing powder with regular particles, uniform particle size and good fluidity.
Description
Technical Field
The invention relates to the technical field of green high polymer materials, in particular to 3D printing powder and a preparation method thereof.
Background
Compared with the traditional technology, the 3D printing technology has the advantages of strong designability, simple process, low energy consumption, suitability for customized production and capability of greatly shortening the production period from design to finished piece, so that the 3D printing technology is widely applied to the fields with strong personalized requirements such as medical treatment, art and the like at present. For different application fields, 3D printing powders of different material types have been developed. In the polymer 3D printing powder material, the research and application of polyamide 3D printing powder are one of important research fields.
At present, the method for preparing polyamide 3D printing powder mainly comprises a cryogenic grinding method and a grinding method. Patent CN107151441A and patent CN108017905A use cryogenic grinding method to crush polyamide granules to obtain polyamide 3D printing powder with small particle size, but the powder obtained by the technology has poor uniformity of particle shape and poor powder flowability. If the functionality is needed to be realized, the modified polyurethane can only be blended with functional additives for modification, so that the defect of uneven mixing exists, and the performance stability of a finished piece is influenced.
The existing polyamide 3D printing powder is generally made of pure polyamide resin raw materials, and the technology based on integration of a polyamide waste recovery and purification process and a 3D printing powder preparation process is rarely reported.
The flowability of 3D printing powder is different from the flowability of resin, and the flowability of powder directly influences the uniformity of powder laying or the stability of powder feeding. The flowability of the powder is too poor, so that the thickness of a powder layer is uneven, the melting amount in a scanning area is uneven, the internal structure of a workpiece is uneven, and the forming quality is influenced; and the high-fluidity powder is easy to fluidize, uniform in deposition and high in powder utilization rate, and is beneficial to improving the dimensional accuracy and surface uniform densification of a 3D printing forming part. The flowability of the powder is not only related to the particle size, but also to the surface friction and the degree of roughness (rounding) of the powder particles, and only 3D printing powder having uniform particle size and uniform surface friction has good powder flowability.
In the prior art, the flame retardant is difficult to uniformly disperse in the 3D printing powder. Even with flame retardant particles having a particle size of less than 5 microns, it is difficult to meet the above requirements because these flame retardants agglomerate and precipitate during melting, resulting in uneven distribution of the flame retardant in the resin matrix. If the particles or cavities with the particle size much larger than that of the flame retardant particles are observed in the finished product through a scanning electron microscope, the agglomeration and precipitation of the flame retardant are indicated.
Disclosure of Invention
The invention aims to provide flame-retardant functional 3D printing powder and a preparation method thereof, wherein a flame retardant is uniformly distributed in 3D printing powder resin, and a 3D printing product prepared by using the flame retardant has better flame retardant property and mechanical property; and the powder particles have smooth surfaces and good powder flowability.
Another object of the present invention is to provide a method for preparing the flame retardant functional 3D printing powder.
The invention is realized by the following technical scheme:
the 3D printing powder is characterized by comprising the following components in parts by weight:
100 parts of polyamide;
1-30 parts of a flame retardant;
the particle size of the flame retardant is dispersed in a polyamide resin matrix in a form of less than 10 microns, the particle size distribution range of the 3D printing powder is D (0.1) < 15 microns and D (0.9) < 125 microns, the powder flowability is less than or equal to 10s/50g, and the bulk density is 0.45-0.65g/cm3。
The distribution of the flame retardant in the polyamide is determined by the following method: preparing 3D printing powder into sample strips in a 3D printing mode, cutting one section of the sample strips, placing the sample strips in a solution, soaking for 24 hours to dissolve the flame retardant on the surfaces of the sample strips but not dissolve polyamide, and observing the cross section appearance of the sample strips by using a scanning electron microscope; and testing and characterizing by combining spectral element analysis.
For example, the bromine flame retardant can be treated by toluene and xylene solution; the phosphorus flame retardant can be treated by polar solvents such as chloroform, dichloromethane and the like or strong alkaline water; the siloxane-based flame retardant may be treated with isopropyl alcohol.
Specifically, the material is injected into a sample strip in a laser sintering mode, one section of the sample strip is cut and placed in a solution (capable of dissolving a flame retardant but incapable of dissolving a polyamide resin matrix, taking organic hypophosphite as an example, and only using a strong alkali aqueous solution) for soaking treatment for 24 hours, then a scanning electron microscope is used for observing the section morphology of the sample strip, and an energy spectrum of an observed area is analyzed, phosphorus-free elements are displayed in the energy spectrum to indicate that the flame retardant is completely etched and washed out, the distribution morphology of holes in the section morphology is the distribution morphology of the flame retardant, and the uniform holes and the diameter of the holes of less than 5 micrometers indicate that the flame retardant is uniformly distributed and does not agglomerate and precipitate; if the partial area has holes after the flame retardant is dissolved and the diameter is more than 20 microns, the condition that the flame retardant is agglomerated and separated out due to uneven distribution is shown.
The flame retardant selected below can be dissolved in the compound solvent of the invention.
The flame retardant is selected from one or more of a brominated flame retardant, a phosphorus flame retardant and a silicon flame retardant.
The brominated flame retardant is selected from at least one of brominated polystyrene, brominated polyphenylene oxide, brominated bisphenol A epoxy resin, brominated styrene-maleic anhydride copolymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perbromo tricyclopentadecane and brominated aromatic cross-linked polymer;
the phosphorus flame retardant is selected from at least one of aryl phosphate monophosphate, aryl phosphate diphosphate, alkyl dimethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, propylbenzene phosphate, butylbenzene phosphate, organic hypophosphite and cyclic phosphate;
the silicon flame retardant is at least one selected from polydimethylsiloxane, polymethylhydrosiloxane and branched polysiloxane.
Alternatively, linear polysiloxanes are available under the trade designations RM4-7105, RM4-7501, RM4-7081, RM1-9641, and the like (different endcapping materials); the branched polysiloxane is available under the trade name XC-99-B5654.
The protrusion and the roundness of the surface of the 3D printing powder can be seen through a scanning electron microscope (generally 100-300 microns or higher precision).
The particle size distribution range of the 3D printing powder obtained by the method of the invention is D (0.1) < 15 microns and D (0.9) < 125 microns. The particle size range was tested according to standard GB/T19077-. D (0.1) < 15 microns means that 10% of the 3D printing powder has a particle size of less than 15 microns, and D (0.9) < 125 microns means that 90% of the 3D printing powder has a particle size of less than 125 microns.
The powder flowability of the 3D printing powder obtained by the method is less than or equal to 10s/50 g. The 3D printed powder flowability was tested using a powder flow meter.
The bulk density of the 3D printing powder obtained by the method of the invention is 0.45-0.65g/cm3. The bulk density is measured by freely dropping a sample from a specified height into a container with a known volume by using the self weight of the resin, and measuring the mass of the resin per unit volume. The particle size and the bulk density of the 3D printing powder influence the melting process of the material during the 3D printing process. Too low bulk density and too large particle size can result in longer 3D printing time (especially extending the length of time that the 3D printing powder is melted by high temperature); too high bulk density and too small particle size can cause 3D printing powder to be heated unevenly during 3D printing, so that the performance of a workpiece is affected.
Preferably, the particle sizes of the flame retardants are all dispersed in the polyamide resin matrix in a form of less than 5 microns, the particle size distribution range of the 3D printing powder is D (0.1) < 25 microns and D (0.9) < 105 microns, the powder flowability is less than or equal to 9s/50g, and the bulk density is 0.5-0.6g/cm3。
By the process of the invention, a large majority of polyamide types can be processed, and through experiments, the following polyamides can be prepared by the process of the invention to obtain 3D printing powders with the above properties. The polyamide resin is at least one of aliphatic polyamide and semi-aromatic polyamide; the aliphatic polyamide is selected from at least one of PA6, PA66, PA12, PA1010, PA1012, PA11, PA610, PA69 and PA 1212; the semi-aromatic polyamide is selected from at least one of PA5T, PA6T610, PA6T6I, PA6T1010, PA10T, PA10T10I, PA10T1010, PA10T1012 and PA10T 6T. Specific embodiments of the present invention are exemplified by PA12, PA66, and PA 10T.
The preparation method of the 3D printing powder comprises the following steps:
(A) adding polyamide raw materials into a compound solvent, heating to 50 ℃ to the reflux temperature of the solution, and stirring until the polyamide raw materials are dissolved (if insoluble substances exist, a filtering process is added to filter the insoluble substances, and if the solution is darker in color, a decoloring process is added), so as to obtain a polyamide clear solution;
(B) adding a flame retardant into the polyamide clarified solution, and stirring until the flame retardant is dissolved to obtain a flame-retardant functional polyamide solution;
(C) spraying the flame-retardant functional polyamide solution into deionized water in a spraying manner, and separating out 3D printing powder, wherein the temperature of the deionized water is within the range of 0-80 ℃;
the compound solvent comprises, by weight, 10-30 parts of phenol and 15-40 parts of toluene; the weight ratio of the polyamide raw material to the compound solvent is 1:10-1: 2; in the precipitation process, the weight ratio of the flame-retardant functional polyamide solution to the deionized water is 1:5-1: 50.
Specifically, the decoloring treatment process comprises the steps of adding an adsorbent, heating the solution to 60 ℃ to the reflux temperature of the compound solvent, keeping the reflux temperature for 0.5 to 2 hours, cooling to a temperature lower than 50 ℃, and filtering.
The adsorbent is selected from at least one of activated carbon and activated clay.
Preferably, the solution is heated to 100 ℃ in step (a) to the reflux temperature of the solution, and the temperature of the deionized water is in the range of 20-60 ℃ when the 3D printing powder is precipitated in step (C). The separation and crystallization rates of the polyamide and the light stabilizer are controlled by controlling the temperature of deionization in the step, so that the particle size distribution of the light stabilizer in a resin matrix can be further reduced, and the 3D printing powder particles are more rounded and have narrower particle size distribution.
The polyamide raw material is at least one of a new polyamide material, a recycled polyamide material and a waste polyamide material. The novel polyamide material is newly synthesized, and contains more than or equal to 99wt% of polyamide resin; the polyamide reclaimed material is polyamide obtained by treating polyamide waste through a recovery process, and contains more than or equal to 99wt% of polyamide resin; the polyamide waste is discarded polyamide articles, wherein the polyamide resin content is in the range of 25-90 wt%.
Compared with the prior art, the invention has the following beneficial effects:
the invention overcomes the defects of the existing 3D printing powder preparation technology and provides flame-retardant functional 3D printing powder and a preparation method thereof. The 3D printing powder is different from a material obtained by blending modification, the flame retardant has fine particle size, uniform distribution and no agglomeration (the particle size is less than 10 micrometers, preferably less than 5 micrometers) in a resin matrix of the 3D printing powder, the 3D printing powder has good rounded shape and fluidity, a workpiece obtained by printing the powder is flat, and the flame retardant property is excellent. The invention also provides a preparation method of the 3D printing powder, and the flame-retardant functional 3D printing powder can be derived from polyamide waste materials or new polyamide materials. The method can integrally complete the purification of the polyamide waste and the preparation process of the 3D printing powder. The final step of the process adopts a spraying mode to spray the polyamide solution into water, so that full, uniform and smooth precipitation without unevenness of polyamide can be realized, the particle size distribution range of 3D printing powder can be D (0.1) < 15 microns and D (0.9) < 125 microns without screening, the powder flowability is less than or equal to 10s/50g, and the bulk density is 0.45-0.65g/cm3。
Drawings
FIG. 1: the scanning electron microscope photo of the 3D printing powder with round and smooth surface in the embodiment 1 of the invention has round and smooth shape and strong uniformity.
FIG. 2: the commercially available 3D printed powder has scanning electron micrographs that the particle size is not uniform and the surface is uneven due to the shape.
FIG. 3: comparative example 33D A scanning electron micrograph of the powder printed, and the particles had uneven particle diameters and many irregularities on the surfaces of the particles having different shapes.
FIG. 4: the 3D printing powder prepared by the 3D printing method provided by the embodiment 1 of the invention has the appearance after etching treatment of the sample strip, and the flame retardant is uniformly distributed without agglomeration and precipitation.
FIG. 5: the 3D printing powder (comparative example 3) prepared by the blending method has the appearance that a sample strip prepared by the 3D printing method is subjected to etching treatment, the distribution of the flame retardant is uneven, and the agglomeration phenomenon is obvious.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The raw materials used in the invention are as follows:
polyamide scrap PA 12: recycled materials from water heating pipelines, automobile engine peripheral parts and the like contain a small amount of toner, and the content of PA12 is about 95-97% theoretically.
Polyamide scrap PA 66: recycled materials from parts such as gears and bearings in mechanical equipment contain glass fiber reinforcement, and theoretically, the content of PA66 is about 65% -70%.
Polyamide waste PA 10T: recycled material from engine peripheral components, containing glass fiber reinforcement, theoretically having a PA10T content of 60-70%.
PA12 New Material: arkema, P201 TL;
PA12 reclaimed material: self-making, namely crushing the polyamide waste PA12, adding a compound solvent (the weight ratio of phenol to toluene =1: 1) which is 3 times of the weight of the polyamide waste, heating to 80 ℃, stirring for dissolving, cooling to 30 ℃, and filtering to obtain a polyamide solution; and adding the polyamide solution into deionized water, and separating liquid to obtain a PA12 reclaimed material.
Phenol: the method is industrial pure;
toluene: the method is industrial pure;
flame retardant A: OP1230, a phosphorus based flame retardant;
and (3) a flame retardant B: a cyclic phosphate ester;
and (3) a flame retardant C: decabromodiphenylethane;
and (3) a flame retardant D: RM4-7105, straight-chain polysiloxane flame retardant;
and (3) a flame retardant E: XC-99-B5654, a branched chain type polysiloxane flame retardant.
Method for testing various performances
(1) Investigating the distribution of the flame retardant in the 3D printing powder: the example and comparative 3D-printed powders were 3D-printed into splines and one side of the splines was treated according to the methods listed in the specification and then subjected to SEM topography testing. Specifically, a sample strip is fixed on a sample table and adhered to a conductive adhesive, gold is plated on the surface of the sample strip to serve as a conductive layer, the sample strip is placed in a sample cabin and vacuumized, the current and voltage are adjusted, the appearance of the sample is observed, and the particle size of a hole of the light stabilizer is obtained through statistics. Scanning to between 20 microns and 500 microns.
(3) 3D printing powder flowability test: the powder flow meter was used and the test was performed according to the method of use.
(4) 3D printing powder particle size test: the test was performed according to the standard GB/T19077-2016.
(5) 3D printing powder bulk density test: the weight of the resin is used to freely drop the sample from a specified height into a container with a known volume, and the mass of the resin per unit volume is measured to obtain the bulk density (test standard GB/T20316.2-2006).
(6) Examine the 3D printed powder appearance by SEM: fixing a sample on a sample table, adhering the sample on a conductive adhesive, plating gold on the surface of the sample to be used as a conductive layer, placing the sample in a sample cabin for vacuumizing, adjusting current and voltage, observing the appearance of the sample, and scanning the sample to 20-500 micrometers.
Example 1:
adding 100g of polyamide waste PA12 into a compound solvent (100 g of phenol/200 g of toluene), heating to 80 ℃, stirring until the polyamide waste PA12 is dissolved, adding 10g of activated carbon, keeping the temperature, stirring for 0.5 hour, cooling to 40 ℃, and filtering to obtain a polyamide clear solution; adding 10g of flame retardant A into the polyamide clarified solution, and stirring until the flame retardant A is fully dissolved to obtain a functional polyamide solution; spraying the functional polyamide solution into 4000g of deionized water (the temperature of the deionized water is maintained at 0-10 ℃) in a spraying manner, and precipitating polyamide flame-retardant modified 3D printing powder; after drying, weighing and testing other properties.
Example 2:
example 2 differs from example 1 in that the flame retardant B is added together with the activated carbon.
Example 3:
example 3 differs from example 1 in that the flame retardant is C.
Example 4:
example 4 differs from example 1 in that the flame retardant is D.
Example 5:
adding 100g of polyamide waste PA10T into a compound solvent (100 g of phenol/200 g of toluene), heating to 100 ℃, stirring until the polyamide waste PA10T is dissolved, adding 10g of activated carbon, heating to 120 ℃, keeping the temperature, stirring for 0.5 hour, cooling to 40 ℃, and filtering to obtain a polyamide clear solution; adding 10g of flame retardant E into the polyamide clarified solution, and stirring until the flame retardant E is fully dissolved to obtain a functional polyamide solution; spraying the functional polyamide solution into 4000g of deionized water (the temperature of the deionized water is maintained at 20-30 ℃) in a spraying manner, and precipitating polyamide flame-retardant modified 3D printing powder; after drying, weighing and testing other properties.
Example 6:
adding 100g of polyamide waste PA66 into a compound solvent (80 g of phenol/160 g of toluene), heating to 105 ℃, stirring until the polyamide waste PA66 is dissolved, adding 10g of activated carbon, keeping the temperature, stirring for 0.5 hour, cooling to 40 ℃, and filtering to obtain a polyamide clear solution; adding 10g of flame retardant E into the polyamide clarified solution, and stirring until the flame retardant E is fully dissolved to obtain a functional polyamide solution; spraying the functional polyamide solution into 4000g of deionized water (the temperature of the deionized water is maintained at 30-40 ℃) in a spraying manner, and precipitating polyamide flame-retardant modified 3D printing powder; after drying, weighing and testing other properties.
Example 7:
adding 100g of PA12 new material into a compound solvent (100 g of phenol/200 g of toluene), heating to 110 ℃, stirring until the PA12 new material is dissolved, keeping the temperature and stirring for 1 hour, cooling to 40 ℃, and filtering to obtain a polyamide clear solution; adding 20g of flame retardant E into the polyamide clarified solution, and stirring until the flame retardant E is fully dissolved to obtain a functional polyamide solution; spraying the functional polyamide solution into 4000g of deionized water (the temperature of the deionized water is kept between 50 and 60 ℃) in a spraying manner, and precipitating polyamide flame-retardant modified 3D printing powder; after drying, weighing and testing other properties.
Example 8:
adding 100g of PA12 reclaimed materials into a compound solvent (100 g of phenol/200 g of toluene), heating to 100 ℃, stirring until the PA12 reclaimed materials are dissolved, adding 10g of activated carbon, keeping the temperature, stirring for 0.5 hour, cooling to 40 ℃, and filtering to obtain a polyamide clear solution; adding 15g of flame retardant E into the polyamide clarified solution, and stirring until the flame retardant E is fully dissolved to obtain a functional polyamide solution; spraying the functional polyamide solution into 4000g of deionized water (the temperature of the deionized water is maintained at 40-50 ℃) in a spraying manner, and precipitating polyamide flame-retardant modified 3D printing powder; after drying, weighing and testing other properties.
Example 9:
example 9 differs from example 1 in that in step (a) the solution is heated to a temperature of 110 ℃ and stirred until dissolved, the temperature of the deionised water being maintained at 50-60 ℃.
Comparative example 1:
adding 100g of polyamide waste PA12 into a compound solvent (100 g of phenol/200 g of toluene), heating to 100 ℃, stirring until the polyamide waste PA12 is dissolved, adding 10g of activated carbon, stirring for 0.5 hour under heat preservation, cooling to 40 ℃, and filtering to obtain a polyamide clear solution; adding 10g of flame retardant A into the polyamide clarified solution, and stirring until the flame retardant A is fully dissolved to obtain a functional polyamide solution; 4000g of deionized water is added into the functional polyamide solution within 10 minutes, and polyamide flame-retardant modified particles are separated out; after drying, freezing the granules in liquid nitrogen at low temperature to below-120 ℃ to realize an embrittled and easily-crushed state, putting the frozen granules into a cavity of a low-temperature crusher, and crushing by high-speed rotation of an impeller; classifying and collecting by an airflow screening machine, and selecting flame-retardant 3D printing powder with the granularity of 120-400 meshes.
Comparative example 2:
adding 100g of polyamide waste PA12 into 1500g of composite solvent (15% of formic acid, 10% of hydrochloric acid, 35% of acetic acid and 40% of water), stirring and dissolving for 4h at 80 ℃, then centrifugally separating (at the rotation speed of 4000R/min) to obtain clear liquid, adding 10g of flame retardant A into the clear liquid, stirring uniformly, introducing the solution into 1500g of deionized water, separating out PA12 precipitate, precipitating, washing PA12 particles with the deionized water until the pH is neutral, freezing the particles in liquid nitrogen at low temperature to below-120 ℃ after drying to realize an embrittled and easily-crushed state, then putting the frozen particles into a low-temperature crusher cavity, and crushing and processing through high-speed rotation of an impeller; classifying and collecting by an airflow screening machine, and selecting flame-retardant 3D printing powder with the granularity of 120-400 meshes.
Comparative example 3:
adding 100g of polyamide waste PA12 into a compound solvent (100 g of phenol/200 g of toluene), heating to 100 ℃, stirring until the polyamide waste PA12 is dissolved, adding 10g of activated carbon, stirring for 0.5 hour under heat preservation, cooling to 40 ℃, and filtering to obtain a polyamide clear solution; and introducing the polyamide clear solution into 4000g of deionized water, and precipitating and recovering polyamide PA 12. Extruding and granulating the dried recovered polyamide PA12 and 10g of flame retardant A by a double-screw extruder (the length-diameter ratio of a screw is 45: 1, the first region is 170 ℃, the second region is 180 ℃, the third region is 190 ℃, the fourth region is 205 ℃, the fifth region is 215 ℃, the sixth region is 225 ℃, the seventh region is 235 ℃, the eighth region is 240 ℃, the ninth region is 245 ℃, the temperature of a machine head is 240 ℃, and the rotating speed is 350 r/min), freezing the granules in liquid nitrogen at low and medium temperatures to below-120 ℃ to realize an embrittling and easily-crushing state, putting the frozen granules into a cavity of a low-temperature crusher, and crushing by high-speed rotation of an impeller; classifying and collecting by an airflow screening machine, and selecting flame-retardant 3D printing powder with the granularity of 120-400 meshes.
Table 1: examples and comparative example 3D printing powders the results of various performance tests
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| Particle size of fire retardant pores, micron | <10 | <10 | <10 | <10 | <5 | <5 |
| 3D printing powder fluidity test, s/50g | 9.2 | 9.5 | 9.2 | 9.4 | 8.8 | 8.4 |
| 3D printing powder particle size test D (0.1), micrometer | 11.1 | 12.0 | 12.1 | 14.8 | 24.2 | 23.4 |
| 3D printing powder particle size test D (0.9), micrometer | 120.3 | 123.5 | 124.7 | 122.8 | 100.2 | 103.9 |
| 3D printing powder bulk Density test, g/cm3 | 0.47 | 0.48 | 0.47 | 0.50 | 0.54 | 0.55 |
Continuing with Table 1:
| example 7 | Example 8 | Example 9 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Particle size of fire retardant pores, micron | <5 | <5 | <5 | >10 | >10 | >10 |
| 3D printing powder fluidity test, s/50g | 7.9 | 8.2 | 8.1 | 14.4 | 12.5 | 18.7 |
| 3D printing powder particle size test D (0.1), micrometer | 22.0 | 23.6 | 24.1 | 50.5 | 39.5 | 68.8 |
| 3D printing powder particle size test D (0.9), micrometer | 101.4 | 102.8 | 98.5 | 471.1 | 350.2 | 442.7 |
| 3D printing powder bulk Density test, g/cm3 | 0.54 | 0.57 | 0.60 | 0.42 | 0.43 | 0.42 |
From comparative examples 1-3, it is known that 3D printing powders obtained by other methods have flame retardant pores with a particle size > 5 μm in the matrix and also have a low flowability and a non-uniform particle size distribution resulting in a low bulk density.
Claims (10)
1. A preparation method of 3D printing powder is characterized by comprising the following steps:
(A) adding a polyamide raw material into a compound solvent, heating to 50 ℃ to the reflux temperature of the solution, stirring until the solution is dissolved, and adding a filtering procedure to filter out insoluble substances if the insoluble substances exist; if the solution is darker in color, adding a decoloring treatment procedure to obtain a polyamide clear solution;
(B) adding a flame retardant into the polyamide clarified solution, and stirring until the flame retardant is dissolved to obtain a flame-retardant functional polyamide solution;
(C) spraying the flame-retardant functional polyamide solution into deionized water in a spraying manner, and separating out 3D printing powder, wherein the temperature of the deionized water is within the range of 0-80 ℃;
the compound solvent comprises, by weight, 10-30 parts of phenol and 15-40 parts of toluene; the weight ratio of the polyamide raw material to the compound solvent is 1:10-1: 2; in the precipitation process, the weight ratio of the flame-retardant functional polyamide solution to the deionized water is 1:5-1: 50;
the obtained 3D printing powder comprises the following components in parts by weight:
100 parts of polyamide;
1-30 parts of a flame retardant;
the particle size of the flame retardant is dispersed in a polyamide resin matrix in a form of less than 10 microns, the particle size distribution range of the 3D printing powder is D (0.1) < 15 microns and D (0.9) < 125 microns, the powder flowability is less than or equal to 10s/50g, and the bulk density is 0.45-0.65g/cm3。
2. The method for preparing 3D printing powder according to claim 1, wherein the decoloring treatment step is to add an adsorbent, heat the solution to 50 ℃ to the reflux temperature of the compound solvent for 0.5-2 hours, cool the solution to less than 50 ℃ and filter the solution.
3. The method of preparing a 3D printing powder according to claim 2, wherein the adsorbent is selected from at least one of activated carbon and activated clay.
4. The method of preparing a 3D printing powder according to claim 1, wherein the solution is heated to 100 ℃ to the solution reflux temperature in step (a), and the temperature of the deionized water is in the range of 20-60 ℃ when the 3D printing powder is precipitated in step (C).
5. The method for preparing 3D printing powder according to claim 1, wherein the polyamide raw material is derived from at least one of a new polyamide material, a recycled polyamide material, and a waste polyamide material; the novel polyamide material is newly synthesized, and contains more than or equal to 99wt% of polyamide resin; the polyamide reclaimed material is polyamide obtained by treating polyamide waste through a recovery process, and contains more than or equal to 99wt% of polyamide resin; the polyamide waste is discarded polyamide articles, wherein the polyamide resin content is in the range of 25-90 wt%.
6. 3D printing powder obtainable by the process for preparing a 3D printing powder according to any one of claims 1 to 5,
the flame retardant is selected from one or more of a brominated flame retardant, a phosphorus flame retardant and a silicon flame retardant.
7. The 3D printing powder of claim 6, wherein the brominated flame retardant is selected from at least one of brominated polystyrene, brominated polyphenylene oxide, brominated bisphenol a epoxy resin, brominated styrene-maleic anhydride copolymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perbromotricyclopentadecane, brominated aromatic cross-linked polymer; the phosphorus flame retardant is selected from at least one of aryl phosphate monophosphate, aryl phosphate diphosphate, alkyl dimethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, propylbenzene phosphate, butylbenzene phosphate, organic hypophosphite and cyclic phosphate; the silicon flame retardant is at least one selected from polydimethylsiloxane, polymethylhydrosiloxane and branched polysiloxane.
8. The 3D printing powder according to claim 6, wherein the distribution of flame retardant in the polyamide is detected by: preparing 3D printing powder into sample strips in a 3D printing mode, cutting one section of the sample strips, placing the sample strips in a solution, soaking for 24 hours to dissolve the flame retardant on the surfaces of the sample strips but not polyamide, wherein a bromine flame retardant is treated by toluene and xylene solution, a phosphorus flame retardant is treated by chloroform and dichloromethane polar solvent or strong alkali water, and a siloxane flame retardant is treated by isopropanol; then observing the section morphology of the sample band by using a scanning electron microscope; and testing and characterizing by combining spectral element analysis.
9. The 3D printing powder according to claim 6, wherein the polyamide is selected from at least one of aliphatic polyamides, semi-aromatic polyamides; the aliphatic polyamide is selected from at least one of PA6, PA66, PA12, PA1010, PA1012, PA11, PA610, PA69 and PA 1212; the semi-aromatic polyamide is selected from at least one of PA5T, PA6T610, PA6T6I, PA6T1010, PA10T, PA10T10I, PA10T1010, PA10T1012 and PA10T 6T.
10. The 3D printing powder according to any one of claims 6 to 9, wherein the particle sizes of the flame retardants are dispersed in the polyamide resin matrix in a form of less than 5 microns, the particle size distribution range of the 3D printing powder is D (0.1) < 25 microns and D (0.9) < 105 microns, the powder flowability is less than or equal to 9s/50g, and the bulk density is 0.5-0.6g/cm3。
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| CN112940189B (en) * | 2021-03-04 | 2023-01-10 | 深圳市创想三维科技股份有限公司 | Flame-retardant photosensitive resin composition and preparation method and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2005010087A1 (en) * | 2003-07-25 | 2005-02-03 | Degussa Ag | Powdery composition of a polymer and a flameproofing agent containing ammonium polyphosphate, method for the production thereof, and moulded body produced from said powder |
| CN104910614A (en) * | 2015-06-23 | 2015-09-16 | 青岛科技大学 | Low-warpage nylon powder composite material for 3D printing and preparation method thereof |
| CN104910613A (en) * | 2015-06-23 | 2015-09-16 | 青岛科技大学 | 3D printing weather-resistant nylon powder composite material and preparation method thereof |
| CN106832906A (en) * | 2017-03-02 | 2017-06-13 | 张家港市五湖新材料技术开发有限公司 | A kind of high flame retardant nylon composite materials for 3D printing |
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| CN107151442A (en) * | 2017-05-26 | 2017-09-12 | 褚建英 | A kind of laser sintering rapid forming nylon composite materials and preparation method thereof |
| CN111909509B (en) * | 2020-07-06 | 2022-02-18 | 金发科技股份有限公司 | 3D printing powder and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2005010087A1 (en) * | 2003-07-25 | 2005-02-03 | Degussa Ag | Powdery composition of a polymer and a flameproofing agent containing ammonium polyphosphate, method for the production thereof, and moulded body produced from said powder |
| CN104910614A (en) * | 2015-06-23 | 2015-09-16 | 青岛科技大学 | Low-warpage nylon powder composite material for 3D printing and preparation method thereof |
| CN104910613A (en) * | 2015-06-23 | 2015-09-16 | 青岛科技大学 | 3D printing weather-resistant nylon powder composite material and preparation method thereof |
| CN106832906A (en) * | 2017-03-02 | 2017-06-13 | 张家港市五湖新材料技术开发有限公司 | A kind of high flame retardant nylon composite materials for 3D printing |
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