WO2022007361A1 - 3d printing powder and preparation method therefor - Google Patents

3d printing powder and preparation method therefor Download PDF

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WO2022007361A1
WO2022007361A1 PCT/CN2020/140811 CN2020140811W WO2022007361A1 WO 2022007361 A1 WO2022007361 A1 WO 2022007361A1 CN 2020140811 W CN2020140811 W CN 2020140811W WO 2022007361 A1 WO2022007361 A1 WO 2022007361A1
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polyamide
flame retardant
printing powder
solution
printing
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PCT/CN2020/140811
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French (fr)
Chinese (zh)
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常欢
叶南飚
李成
周沃华
刘鑫鑫
朱秀梅
苏榆钧
唐磊
黄险波
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金发科技股份有限公司
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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
    • 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
    • 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
    • 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
    • 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
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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

Definitions

  • the invention relates to the technical field of green polymer materials, in particular to a 3D printing powder and a preparation method thereof.
  • 3D printing technology Compared with traditional technology, 3D printing technology has strong designability, simple process, low energy consumption, suitable for customized production, and can greatly shorten the production cycle from design to parts. field is widely used.
  • 3D printing powders of different material types have been developed.
  • polymer 3D printing powder materials the research and application of polyamide 3D printing powder is one of the important research fields.
  • the methods for preparing polyamide 3D printing powder are mainly cryogenic pulverization combined with grinding.
  • Patent CN107151441A, patent CN108017905A and other patents use cryogenic pulverization method to crush polyamide particles to obtain polyamide 3D printing powder with smaller particle size, but the powder particles obtained by this technology have poor particle shape uniformity and poor powder fluidity. And if it needs to achieve functionality, it can only be modified by blending with functional additives, which has the defect of uneven mixing, which affects the performance stability of the parts.
  • the fluidity of 3D printing powder is different from that of resin, and the fluidity of powder directly affects the uniformity of powder spreading or the stability of powder feeding.
  • the powder fluidity is too poor, which is easy to cause uneven thickness of the powder layer and uneven melting amount in the scanning area, resulting in uneven internal structure of the part and affecting the forming quality; while the powder with high fluidity is easy to fluidize, deposit evenly, and use the powder
  • the high rate is conducive to improving the dimensional accuracy and uniform densification of the surface of the 3D printed parts.
  • the fluidity of the powder is not only related to the particle size, but also related to the surface friction of the powder particles and the degree of unevenness (roundness). Only 3D printing powders with uniform particle size, uniform surface friction and roundness have good powder fluidity.
  • the purpose of the present invention is to provide a flame retardant functional 3D printing powder and a preparation method thereof.
  • the flame retardant is uniformly distributed in the 3D printing powder resin, and the 3D printing parts prepared by using it have better flame retardant performance and mechanical properties. performance; and the powder particles are round and smooth, and the powder has good fluidity.
  • Another object of the present invention is to provide a method for preparing the above flame retardant functional 3D printing powder.
  • a 3D printing powder is characterized in that, by weight, it comprises the following components:
  • the particle size of the flame retardant is dispersed in the polyamide resin matrix in the form of less than 10 microns, and the particle size distribution range of the 3D printing powder is d(0.1) ⁇ 15 microns and d(0.9) ⁇ 125 microns.
  • the fluidity is ⁇ 10s/50g, and the bulk density is 0.45-0.65g/cm 3 .
  • the distribution of flame retardants in polyamide was detected by the following method: 3D printing powder was prepared into splines by 3D printing, and a section of the strips was cut and soaked in solution for 24 hours to dissolve the flame retardant on the surface of the splines, but not. The polyamide was dissolved, and then the cross-sectional morphology of the splines was observed with a scanning electron microscope; the test and characterization were carried out in combination with energy spectrum elemental analysis.
  • bromine-based flame retardants can be treated with toluene and xylene solutions; phosphorus-based flame retardants can be treated with polar solvents such as chloroform and dichloromethane or strong alkaline water; siloxane-based flame retardants can be treated with isopropanol .
  • the material is injection-molded into a spline by laser sintering, and a section of the cut spline is placed in a solution (the flame retardant can be dissolved, but the polyamide resin matrix cannot be dissolved.
  • the flame retardant can be dissolved, but the polyamide resin matrix cannot be dissolved.
  • the organic hypophosphite as an example, using a strong alkaline aqueous solution After soaking for 24 hours, the cross-sectional morphology of the splines was observed with a scanning electron microscope, and the energy spectrum of the observed area was analyzed. The energy spectrum showed no phosphorus elements, indicating that the flame retardant was completely etched and washed out, and the cross-sectional morphology was The distribution pattern of the holes in is the distribution pattern of the flame retardant. The holes are uniform and the diameter is less than 5 microns, indicating that the flame retardants are uniformly distributed and have no agglomeration and precipitation; It shows that the distribution of flame retardants does not have a
  • the flame retardants selected below are soluble in the compound solvent of the present invention.
  • the flame retardant is selected from one or more of bromine-based flame retardants, phosphorus-based flame retardants, and silicon-based flame retardants.
  • the brominated flame retardant is selected from brominated polystyrene, brominated polyphenylene ether, brominated bisphenol A epoxy resin, brominated styrene-maleic anhydride copolymer, brominated epoxy resin, brominated At least one of phenoxy resin, decabromodiphenyl ether, decabromodiphenyl, brominated polycarbonate, perbromotricyclopentadecane, and brominated aromatic cross-linked polymer;
  • the phosphorus-based flame retardant is selected from aryl phosphate monophosphate, aryl phosphate diphosphate, dimethyl alkyl phosphate, triphenyl phosphate, tricresyl phosphate, tris(xylylene) phosphate, propylene At least one of benzene-based phosphates, butylbenzene-based phosphates, organic hypophosphites, and cyclic phosphates;
  • the silicon-based flame retardant is selected from at least one of polydimethylsiloxane, polymethylhydrogensiloxane, and branched-chain polysiloxane.
  • the trade names of straight-chain polysiloxanes are such as RM4-7105, RM4-7501, RM4-7081, RM1-9641, etc. (different end capping substances); the trade names of branched polysiloxanes are such as XC -99-B5654 etc.
  • the protrusions and roundness of the 3D printing powder surface can also be seen by scanning electron microscopy (generally 100-300 microns or higher).
  • the particle size distribution range of the 3D printing powder obtained by the method of the present invention is d(0.1) ⁇ 15 microns and d(0.9) ⁇ 125 microns.
  • the test method for the particle size range is to test in accordance with the standard GB/T 19077-2016.
  • d(0.1) ⁇ 15 microns means that 10% of the 3D printing powders have a particle size smaller than 15 microns
  • d(0.9) ⁇ 125 microns means that 90% of the 3D printing powders have a particle size smaller than 125 microns.
  • the powder fluidity of the 3D printing powder obtained by the method of the present invention is ⁇ 10s/50g.
  • the fluidity of 3D printing powders was tested using a powder flow meter.
  • the bulk density of the 3D printing powder obtained by the method of the present invention is 0.45-0.65 g/cm 3 .
  • the test method of bulk density is to use the self-weight of the resin to freely drop the sample into a container of known volume from a specified height, and measure the mass of the resin per unit volume, that is, to obtain the size of the bulk density.
  • the particle size and bulk density of the 3D printing powder affect the melting process of the material during the 3D printing process. Too low bulk density and too large particle size will lead to longer 3D printing time (especially prolonging the high temperature melting time of 3D printing powder); too high bulk density and too small particle size will lead to 3D printing process.
  • the 3D printing powder is not heated uniformly, which affects the performance of the part.
  • the particle size of the flame retardant is dispersed in the polyamide resin matrix in the form of less than 5 microns, and the particle size distribution range of the 3D printing powder is d(0.1) ⁇ 25 microns and d(0.9) ⁇ 105 Micron, the powder fluidity is ⁇ 9s/50g, and the bulk density is 0.5-0.6g/cm 3 .
  • the polyamide resin is at least one of aliphatic polyamide and semi-aromatic polyamide; the aliphatic polyamide is selected from PA6, PA66, PA12, PA1010, PA1012, PA11, PA610, PA69, PA1212 At least one of the semi-aromatic polyamides is selected from at least one of PA5T, PA6T610, PA6T6I, PA6T1010, PA10T, PA10T10I, PA10T1010, PA10T1012, and PA10T6T. Examples of specific embodiments of the present invention include PA12, PA66, and PA10T.
  • the above-mentioned preparation method of 3D printing powder includes the following steps:
  • the compound solvent in parts by weight, includes 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; during the precipitation process, the flame retardant function The weight ratio of the polyamide solution to deionized water is 1:5-1:50.
  • the decolorization treatment process includes adding an adsorbent, heating the solution to 60°C - maintaining the reflux temperature of the compound solvent for 0.5-2 hours, and then cooling down to below 50°C and filtering.
  • the adsorbent is selected from at least one of activated carbon and activated clay.
  • step (A) the solution is heated to a temperature of 100° C. to the reflux temperature of the solution.
  • step (C) when the 3D printing powder is precipitated, the temperature of deionized water is in the range of 20-60° C.
  • the polyamide raw material is derived from at least one of new polyamide material, polyamide recycled material and polyamide waste material.
  • the new polyamide material is newly synthesized and contains more than or equal to 99wt% of polyamide resin;
  • the polyamide recycled material is the polyamide obtained by processing polyamide waste through a recycling process, which contains more than or equal to 99wt% of polyamide resin;
  • Polyamide wastes are discarded polyamide products, wherein the content of polyamide resin ranges from 25 to 90 wt%.
  • the present invention has the following beneficial effects:
  • the invention overcomes the defects of the existing 3D printing powder preparation technology, and provides a flame-retardant functional 3D printing powder and a preparation method thereof.
  • the 3D printing powder of the present invention is different from the material obtained by blending and modification.
  • the flame retardant has a small particle size and a uniform distribution in the resin matrix of the 3D printing powder without agglomeration (the particle size is less than 10 microns, preferably less than 5 microns),
  • the 3D printing powder has a round shape and good fluidity, and the parts printed with it are flat and have excellent flame retardant properties.
  • the present 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 or new polyamide material.
  • the method can integrate the purification of polyamide waste and the preparation of 3D printing powder.
  • the polyamide solution is sprayed into the water by spraying, which can realize the precipitation of polyamide with sufficient, uniform particle size, roundness and no bumps, and the particle size distribution range of the 3D printing powder can be made d(0.1 without screening. ) ⁇ 15 microns and d(0.9) ⁇ 125 microns, the powder fluidity is ⁇ 10s/50g, and the bulk density is 0.45-0.65g/cm 3 .
  • Figure 1 Scanning electron microscope photo of 3D printing powder with rounded surface according to Example 1 of the present invention, with rounded shape and strong uniformity.
  • Figure 2 SEM photos of commercially available 3D printing powders, with uneven particle size and different shapes, with many surface bumps.
  • Figure 3 Scanning electron microscope photo of the 33D printing powder in the comparative example, the particle size is uneven, the shape is different, and the surface is uneven.
  • Figure 4 The morphology of the 3D printing powder prepared by the 3D printing method of Example 1 of the present invention after etching treatment, the flame retardant is uniformly distributed, and there is no phenomenon of agglomeration and precipitation.
  • Figure 5 The 3D printing powder prepared by the blending method (Comparative Example 3), the morphology of the spline prepared by the 3D printing method after etching treatment, the flame retardant distribution is uneven, and there is obvious agglomeration.
  • the sources of raw materials used in the present invention are as follows:
  • Polyamide waste PA12 It comes from recycled materials such as plumbing pipes and peripheral parts of automobile engines, and contains a small amount of toner. Theoretically, the PA12 content is about 95%-97%.
  • Polyamide waste PA66 Recycling material from gears, bearings and other parts in mechanical equipment, containing glass fiber reinforcement, the theoretical PA66 content is about 65%-70%.
  • Polyamide waste PA10T Recycling material from parts around the engine, containing glass fiber reinforcement, the theoretical PA10T content is 60-70%.
  • PA12 new material Arkema, P201TL;
  • Phenol industrial grade
  • Flame retardant A OP1230, phosphorus flame retardant
  • Flame Retardant B Cyclic Phosphate
  • Flame retardant D RM4-7105, linear polysiloxane flame retardant
  • Flame retardant E XC-99-B5654, branched chain polysiloxane flame retardant.
  • 3D printing powder bulk density test Using the self-weight of the resin, drop the sample freely into a container of known volume from a specified height, and measure the mass of the resin per unit volume to obtain the bulk density (test standard GB /T 20316.2-2006).
  • Example 2 The difference between Example 2 and Example 1 is that the flame retardant B is added together with the activated carbon.
  • Example 3 The difference between Example 3 and Example 1 is that the flame retardant is C.
  • Example 4 The difference between Example 4 and Example 1 is that the flame retardant is D.
  • 100g polyamide waste PA66 was added to the compound solvent (80g phenol/160g toluene), heated to a temperature of 105°C and stirred until dissolved, then added 10g activated carbon, kept stirring for 0.5 hours, cooled to 40°C and filtered to obtain a clear polyamide solution 10g flame retardant E is added to the polyamide clear solution, stirred until fully dissolved, to obtain functional polyamide solution; then the functional polyamide solution is sprayed into 4000g deionized water (deionized water temperature is maintained at 30- 40°C), the polyamide flame retardant modified 3D printing powder was precipitated; after drying, weighed, and then other properties were tested.
  • compound solvent 80g phenol/160g toluene
  • PA12 reclaimed material 100g was added to the compound solvent (100g phenol/200g toluene), heated to a temperature of 100°C and stirred to dissolve, then 10g of activated carbon was added, kept stirring for 0.5 hours, cooled to 40°C and filtered to obtain a clear polyamide solution; Add 15g of flame retardant E to the polyamide clear solution, stir until fully dissolved to obtain a functional polyamide solution; then spray the functional polyamide solution into 4000g of deionized water (the deionized water temperature is maintained at 40-50 °C), the polyamide flame retardant modified 3D printing powder was precipitated; after drying, weighed, and then tested other properties.
  • compound solvent 100g phenol/200g toluene
  • Example 9 The difference between Example 9 and Example 1 is that in step (A), the solution is heated to a temperature of 110°C and stirred until dissolved, and the temperature of deionized water is maintained at 50-60°C.
  • 100g of polyamide waste PA12 was added to the compound solvent (100g phenol/200g toluene), heated to a temperature of 100°C and stirred until dissolved, then added 10g of activated carbon, kept stirring for 0.5 hours, cooled to 40°C and filtered to obtain a clear polyamide solution ;
  • the sieving machine conducts classification and collection, and selects flame-retardant 3D printing powder with a particle size in the range of 120-400 mesh.
  • polyamide waste PA12 into the compound solvent (100g phenol/200g toluene), heat to a temperature of 100°C and stir until dissolved, then add 10g activated carbon, keep stirring for 0.5 hours, cool to 40°C and filter to obtain a clear polyamide solution ; Then pass the polyamide clear solution into 4000g of deionized water to separate out and recover polyamide PA12.
  • the dried recycled polyamide PA12 and 10g of flame retardant A were extruded and granulated through a twin-screw extruder (screw length-diameter ratio was 45:1, the first zone was 170°C, the second zone was 180°C, the third zone was 190°C, and the fourth zone was 190°C.
  • the medium and low temperature is frozen to below -120°C, so as to achieve embrittlement and easy pulverization, and then the frozen pellets are put into the cavity of the low-temperature pulverizer, and the impeller rotates at high speed for pulverization; Flame retardant 3D printing powder with particle size in the range of 120-400 mesh.
  • Table 1 The performance test results of the 3D printing powders of the examples and comparative examples
  • the 3D printing powder obtained by other methods has a flame retardant hole particle size > 5 microns in the matrix, and has low fluidity.
  • the uneven particle size distribution also leads to a low bulk density.

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Abstract

A flame-retardant functional modified 3D printing powder, comprising the following components in parts by weight: 100 parts of polyamide, and 1-30 parts of flame retardant; said flame retardant being dispersed in a polyamide resin matrix in the form of particles sized less than 10 micrometers, and the 3D printing powder having uniform particle size distribution, good fluidity and appropriate bulk density. The 3D printing powder is prepared by a solution method: dissolving resins of new polyamide material, waste material and recycled material in a phenol/toluene-based solvent system; obtaining a polyamide clear solution by means of decolorization (a required step to treat the polyamide waste material), filtering and purification; adding the flame retardant into the polyamide clear solution to fully dissolve the flame retardant; finally, by using a spraying method to spray the solution into deionized water, obtaining the modified 3D printing powder having regular particles, uniform particle size and good fluidity.

Description

一种3D打印粉末及其制备方法A kind of 3D printing powder and preparation method thereof 技术领域technical field
本发明涉及绿色高分子材料技术领域，特别是涉及一种3D打印粉末及其制备方法。The invention relates to the technical field of green polymer materials, in particular to a 3D printing powder and a preparation method thereof.
背景技术Background technique
3D打印技术与传统技术相比，可设计性强，工序简单，能耗低，适合定制化生产，可大大缩短从设计到制件的生产周期，因此目前在医疗、艺术等个性化需求较强的领域被广泛应用。针对不同应用领域，开发了不同材料种类的3D打印粉末。在高分子3D打印粉末材料中，聚酰胺3D打印粉末的研究和应用是重要的研究领域之一。Compared with traditional technology, 3D printing technology has strong designability, simple process, low energy consumption, suitable for customized production, and can greatly shorten the production cycle from design to parts. field is widely used. For different application fields, 3D printing powders of different material types have been developed. Among polymer 3D printing powder materials, the research and application of polyamide 3D printing powder is one of the important research fields.
目前，制备聚酰胺3D打印粉末的方法主要为深冷粉碎法结合研磨法。专利CN107151441A、专利CN108017905A等专利利用深冷粉碎法，对聚酰胺颗粒料进行破碎获得粒径较小的聚酰胺3D打印粉末，但是该技术获得的粉末颗粒形状均一度差，粉体流动性差。并且如需实现功能性，只能通过与功能性添加剂共混改性，存在混合不均的缺陷，对制件性能稳定性造成影响。At present, the methods for preparing polyamide 3D printing powder are mainly cryogenic pulverization combined with grinding. Patent CN107151441A, patent CN108017905A and other patents use cryogenic pulverization method to crush polyamide particles to obtain polyamide 3D printing powder with smaller particle size, but the powder particles obtained by this technology have poor particle shape uniformity and poor powder fluidity. And if it needs to achieve functionality, it can only be modified by blending with functional additives, which has the defect of uneven mixing, which affects the performance stability of the parts.
现有聚酰胺3D打印粉末通常使用的都是以纯聚酰胺树脂原材料，基于聚酰胺废料回收提纯过程与制备3D打印粉末过程一体化的技术鲜有报道。Existing polyamide 3D printing powders are usually made of pure polyamide resin as raw materials, and there are few reports on the integration of polyamide waste recycling and purification processes with the preparation of 3D printing powders.
3D打印粉末的流动性与树脂流动性不同，粉体的流动性直接影响铺粉的均匀性或送粉的稳定性。粉末流动性太差，易造成粉层厚度不均，扫描区域内的熔化量不均，导致制件内部结构不均，影响成形质量；而高流动性的粉末易于流化，沉积均匀，粉末利用率高，有利于提高3D打印成形件的尺寸精度和表面均匀致密化。粉末的流动性不仅与粒径有关，而且与粉末颗粒表面摩擦性、凹凸程度(圆润)有关，只有粒径均一、表面摩擦力均一、圆润的3D打印粉末才具有良好的粉末流动性。The fluidity of 3D printing powder is different from that of resin, and the fluidity of powder directly affects the uniformity of powder spreading or the stability of powder feeding. The powder fluidity is too poor, which is easy to cause uneven thickness of the powder layer and uneven melting amount in the scanning area, resulting in uneven internal structure of the part and affecting the forming quality; while the powder with high fluidity is easy to fluidize, deposit evenly, and use the powder The high rate is conducive to improving the dimensional accuracy and uniform densification of the surface of the 3D printed parts. The fluidity of the powder is not only related to the particle size, but also related to the surface friction of the powder particles and the degree of unevenness (roundness). Only 3D printing powders with uniform particle size, uniform surface friction and roundness have good powder fluidity.
现有技术中，难以实现3D打印粉末中阻燃剂均匀分散。即使采用粒径小于5微米的阻燃剂颗粒也难以得满足上述需求，因为这些阻燃剂在熔融过程中会发生团聚和析出，造成树脂基体中的阻燃剂分布不均。如果通过扫描电镜观察制件中有比阻燃剂颗粒自身粒径大很多的颗粒或空洞，则说明阻燃剂有团聚和析出。In the prior art, it is difficult to achieve uniform dispersion of the flame retardant in the 3D printing powder. Even if flame retardant particles with a particle size of less than 5 microns are used, it is difficult to meet the above requirements, because these flame retardants will agglomerate and precipitate during the melting process, resulting in uneven distribution of flame retardants in the resin matrix. If there are particles or voids that are much larger than the particle size of the flame retardant particles themselves through scanning electron microscopy, it means that the flame retardant has agglomeration and precipitation.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于，提供一种阻燃功能性3D打印粉末及其制备方法，阻燃剂在3D打印粉末树脂中分布均匀，使用其制备的3D打印制件具有更优良的阻燃性能和力学性能；并且粉末颗粒圆润表面光滑，粉体流动性好。The purpose of the present invention is to provide a flame retardant functional 3D printing powder and a preparation method thereof. The flame retardant is uniformly distributed in the 3D printing powder resin, and the 3D printing parts prepared by using it have better flame retardant performance and mechanical properties. performance; and the powder particles are round and smooth, and the powder has good fluidity.
本发明的另一目的在于，提供上述阻燃功能性3D打印粉末的制备方法。Another object of the present invention is to provide a method for preparing the above flame retardant functional 3D printing powder.
本发明是通过以下技术方案实现的：The present invention is achieved through the following technical solutions:
一种3D打印粉末，其特征在于，按重量份计，包括以下组分：A 3D printing powder is characterized in that, by weight, it comprises the following components:
聚酰胺        100份；100 parts of polyamide;
阻燃剂        1-30份；Flame retardant 1-30 copies;
所述的阻燃剂的粒径均以小于10微米的形态分散于聚酰胺树脂基体中，3D打印粉末的粒径分布范围是d(0.1)＜15微米且d(0.9)＜125微米，粉体流动性为≤10s/50g，堆积密度0.45-0.65g/cm 3。 The particle size of the flame retardant is dispersed in the polyamide resin matrix in the form of less than 10 microns, and the particle size distribution range of the 3D printing powder is d(0.1)<15 microns and d(0.9)<125 microns. The fluidity is ≤10s/50g, and the bulk density is 0.45-0.65g/cm 3 .
阻燃剂在聚酰胺中分布是通过以下方法检测：将3D打印粉末以3D打印方式制备成样条，截取样条中的一段置于溶液中浸泡24小时溶解样条表面的阻燃剂但是不溶解聚酰胺，之后用扫描电子显微镜观察样条截面形貌；结合能谱元素分析进行测试表征。The distribution of flame retardants in polyamide was detected by the following method: 3D printing powder was prepared into splines by 3D printing, and a section of the strips was cut and soaked in solution for 24 hours to dissolve the flame retardant on the surface of the splines, but not. The polyamide was dissolved, and then the cross-sectional morphology of the splines was observed with a scanning electron microscope; the test and characterization were carried out in combination with energy spectrum elemental analysis.
如溴系阻燃剂可采用甲苯、二甲苯溶液处理；磷系阻燃剂可以采用氯仿、二氯甲烷等极性溶剂或强碱水处理；硅氧烷类阻燃剂可采用异丙醇处理。For example, bromine-based flame retardants can be treated with toluene and xylene solutions; phosphorus-based flame retardants can be treated with polar solvents such as chloroform and dichloromethane or strong alkaline water; siloxane-based flame retardants can be treated with isopropanol .
具体的，将材料以激光烧结方式注塑成样条，截取样条中的一段置于溶液(可以溶解阻燃剂，但是不能溶解聚酰胺树脂基体。以有机次磷酸盐为例，用强碱水溶液即可)中浸泡处理24小时，之后用扫描电子显微镜观察样条截面形貌，并分析所观察区域的能谱，能谱中显示无磷元素说明阻燃剂刻蚀洗出完全，截面形貌中的孔洞分布形态即为阻燃剂的分布形态，孔洞均匀且直径小于5微米说明阻燃剂分布均匀且没有发生团聚和析出；如果部分区域有阻燃剂溶解后的孔洞且直径大于20微米说明阻燃剂分布不均有团聚和析出的情况。Specifically, the material is injection-molded into a spline by laser sintering, and a section of the cut spline is placed in a solution (the flame retardant can be dissolved, but the polyamide resin matrix cannot be dissolved. Taking the organic hypophosphite as an example, using a strong alkaline aqueous solution After soaking for 24 hours, the cross-sectional morphology of the splines was observed with a scanning electron microscope, and the energy spectrum of the observed area was analyzed. The energy spectrum showed no phosphorus elements, indicating that the flame retardant was completely etched and washed out, and the cross-sectional morphology was The distribution pattern of the holes in is the distribution pattern of the flame retardant. The holes are uniform and the diameter is less than 5 microns, indicating that the flame retardants are uniformly distributed and have no agglomeration and precipitation; It shows that the distribution of flame retardants does not have agglomeration and precipitation.
以下所选取的阻燃剂可溶于本发明复配溶剂中。The flame retardants selected below are soluble in the compound solvent of the present invention.
所述的阻燃剂选自溴系阻燃剂、磷系阻燃剂、硅系阻燃剂中的一种或几种。The flame retardant is selected from one or more of bromine-based flame retardants, phosphorus-based flame retardants, and silicon-based flame retardants.
所述的溴系阻燃剂选自溴化聚苯乙烯、溴化聚苯醚、溴化双酚A型环氧树脂、溴化苯乙烯-马来酸酐共聚物、溴化环氧树脂、溴化苯氧基树脂、十溴二苯醚、十溴代联苯、溴化聚碳酸酯、全溴三环十五烷、溴化芳香族交联聚合物中的至少一种；The brominated flame retardant is selected from brominated polystyrene, brominated polyphenylene ether, brominated bisphenol A epoxy resin, brominated styrene-maleic anhydride copolymer, brominated epoxy resin, brominated At least one of phenoxy resin, decabromodiphenyl ether, decabromodiphenyl, brominated polycarbonate, perbromotricyclopentadecane, and brominated aromatic cross-linked polymer;
所述的磷系阻燃剂选自单磷酸芳基磷酸酯、双磷酸芳基磷酸酯、烷基磷酸二甲酯、磷酸三苯酯、磷酸三甲苯酯、磷酸三(二甲苯)酯、丙苯系磷酸酯、丁苯系磷酸酯、有机次磷酸盐、环状磷酸酯中的至少一种；The phosphorus-based flame retardant is selected from aryl phosphate monophosphate, aryl phosphate diphosphate, dimethyl alkyl phosphate, triphenyl phosphate, tricresyl phosphate, tris(xylylene) phosphate, propylene At least one of benzene-based phosphates, butylbenzene-based phosphates, organic hypophosphites, and cyclic phosphates;
所述的硅系阻燃剂选自聚二甲基硅氧烷、聚甲基氢硅氧烷、支链型聚硅氧烷中的至少一种。The silicon-based flame retardant is selected from at least one of polydimethylsiloxane, polymethylhydrogensiloxane, and branched-chain polysiloxane.
可选的，直链型聚硅氧烷的商品牌号如RM4-7105、RM4-7501、RM4-7081、RM1-9641 等(不同封端物质)；支链型聚硅氧烷的商品牌号如XC-99-B5654等。Optionally, the trade names of straight-chain polysiloxanes are such as RM4-7105, RM4-7501, RM4-7081, RM1-9641, etc. (different end capping substances); the trade names of branched polysiloxanes are such as XC -99-B5654 etc.
通过扫描电镜显微镜(一般100-300微米或更高精度)也可以看到3D打印粉末表面的突起、圆润度情况。The protrusions and roundness of the 3D printing powder surface can also be seen by scanning electron microscopy (generally 100-300 microns or higher).
通过本发明方法得到的3D打印粉末的粒径分布范围是d(0.1)＜15微米且d(0.9)＜125微米。粒径范围的测试方法为按照标准GB/T 19077-2016进行测试。d(0.1)＜15微米表示10％的3D打印粉末的粒径小于15微米，d(0.9)＜125微米表示90％的3D打印粉末的粒径小于125微米。The particle size distribution range of the 3D printing powder obtained by the method of the present invention is d(0.1)<15 microns and d(0.9)<125 microns. The test method for the particle size range is to test in accordance with the standard GB/T 19077-2016. d(0.1)<15 microns means that 10% of the 3D printing powders have a particle size smaller than 15 microns, and d(0.9)<125 microns means that 90% of the 3D printing powders have a particle size smaller than 125 microns.
通过本发明方法得到的所述的3D打印粉末的粉体流动性为≤10s/50g。3D打印粉末流动性使用粉体流动仪测试。The powder fluidity of the 3D printing powder obtained by the method of the present invention is ≤10s/50g. The fluidity of 3D printing powders was tested using a powder flow meter.
通过本发明方法得到的所述3D打印粉末的堆积密度0.45-0.65g/cm 3。堆积密度的测试方法为利用树脂的自重，将试样从规定的高度自由落入已知容积的容器中，测量单位体积的树脂的质量，即得到堆积密度的大小。3D打印粉末的粒径与堆积密度影响着3D打印过程中材料的熔融过程。过低的堆积密度与过大的粒径会导致3D打印耗时更长(特别是延长3D打印粉末的受高温熔融时长)；过高的堆积密度与过小的粒径会导致3D打印过程中3D打印粉末受热不均匀，使制件性能受到影响。 The bulk density of the 3D printing powder obtained by the method of the present invention is 0.45-0.65 g/cm 3 . The test method of bulk density is to use the self-weight of the resin to freely drop the sample into a container of known volume from a specified height, and measure the mass of the resin per unit volume, that is, to obtain the size of the bulk density. The particle size and bulk density of the 3D printing powder affect the melting process of the material during the 3D printing process. Too low bulk density and too large particle size will lead to longer 3D printing time (especially prolonging the high temperature melting time of 3D printing powder); too high bulk density and too small particle size will lead to 3D printing process. The 3D printing powder is not heated uniformly, which affects the performance of the part.
优选的，所述的阻燃剂的粒径均以小于5微米的形态分散于聚酰胺树脂基体中，3D打印粉末的粒径分布范围是d(0.1)＜25微米且d(0.9)＜105微米，粉体流动性为≤9s/50g，堆积密度0.5-0.6g/cm 3。 Preferably, the particle size of the flame retardant is dispersed in the polyamide resin matrix in the form of less than 5 microns, and the particle size distribution range of the 3D printing powder is d(0.1)<25 microns and d(0.9)<105 Micron, the powder fluidity is ≤9s/50g, and the bulk density is 0.5-0.6g/cm 3 .
通过本发明的方法，可以处理绝大部分种类的聚酰胺，经过实验，以下聚酰胺都可以通过本发明的方法制备得到上述性能的3D打印粉末。所述的聚酰胺树脂为脂肪族聚酰胺、半芳香族聚酰胺中的至少一种；所述的脂肪族聚酰胺选自PA6、PA66、PA12、PA1010、PA1012、PA11、PA610、PA69、PA1212中的至少一种；所述的半芳香族聚酰胺选自PA5T、PA6T610、PA6T6I、PA6T1010、PA10T、PA10T10I、PA10T1010、PA10T1012、PA10T6T中的至少一种。本发明具体实施方式举例PA12、PA66、PA10T。By the method of the present invention, most kinds of polyamides can be processed. After experiments, the following polyamides can be prepared by the method of the present 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 PA6, PA66, PA12, PA1010, PA1012, PA11, PA610, PA69, PA1212 At least one of the semi-aromatic polyamides is selected from at least one of PA5T, PA6T610, PA6T6I, PA6T1010, PA10T, PA10T10I, PA10T1010, PA10T1012, and PA10T6T. Examples of specific embodiments of the present invention include PA12, PA66, and PA10T.
上述的3D打印粉末的制备方法，包括以下步骤：The above-mentioned preparation method of 3D printing powder includes the following steps:
(A)将聚酰胺原料加入复配溶剂中，加热达到50℃至溶液回流的温度并搅拌至溶解(如有不溶物，增加过滤工序将不溶物滤除；如溶液颜色较深，则增加脱色处理工序)，得到聚酰胺澄清溶液；(A) adding the polyamide raw material to the compound solvent, heating to a temperature of 50° C. to the reflux temperature of the solution and stirring to dissolve (if there is insoluble matter, increase the filtration process to filter out the insoluble matter; if the color of the solution is darker, then increase the decolorization treatment procedure) to obtain a clear solution of polyamide;
(B)将阻燃剂加入聚酰胺澄清溶液中，搅拌至溶解，得到阻燃功能性聚酰胺溶液；(B) adding the flame retardant to the polyamide clear solution, stirring until dissolved, to obtain a flame retardant functional polyamide solution;
(C)将阻燃功能性聚酰胺溶液以喷雾方式喷入去离子水中，析出3D打印粉末，期间，去 离子水的温度为0-80℃范围内；(C) spraying the flame-retardant functional polyamide solution into deionized water by spraying to precipitate 3D printing powder, during which the temperature of deionized water is in the range of 0-80 °C;
所述的复配溶剂，按重量份计，包括10-30份苯酚、15-40份甲苯；聚酰胺原料与复配溶剂重量比为1:10-1:2；析出过程中，阻燃功能性聚酰胺溶液与去离子水的重量比为1:5-1:50。The compound solvent, in parts by weight, includes 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; during the precipitation process, the flame retardant function The weight ratio of the polyamide solution to deionized water is 1:5-1:50.
具体的，脱色处理工序为加入吸附剂，将溶液升温至60℃-复配溶剂回流温度保持0.5-2小时，再降温至低于50℃后过滤。Specifically, the decolorization treatment process includes adding an adsorbent, heating the solution to 60°C - maintaining the reflux temperature of the compound solvent for 0.5-2 hours, and then cooling down to below 50°C and filtering.
所述的吸附剂选自活性炭、活性白土中的至少一种。The adsorbent is selected from at least one of activated carbon and activated clay.
优选的，步骤(A)将溶液加热达到100℃至溶液回流温度，步骤(C)中，析出3D打印粉末时，去离子水的温度为20-60℃范围内。通过控制此步骤中去离子的温度来控制聚酰胺与光稳定剂的析出与结晶速率，能够进一步缩小光稳定剂在树脂基体中的粒径分布，同时使3D打印粉末颗粒更圆润、粒径分布更窄。Preferably, in step (A), the solution is heated to a temperature of 100° C. to the reflux temperature of the solution. In step (C), when the 3D printing powder is precipitated, the temperature of deionized water is in the range of 20-60° C. By controlling the temperature of deionization in this step to control the precipitation and crystallization rates of polyamide and light stabilizer, the particle size distribution of the light stabilizer in the resin matrix can be further reduced, and the 3D printing powder particles can be more rounded and particle size distribution. Narrower.
所述的聚酰胺原料来源于聚酰胺新料、聚酰胺回收料、聚酰胺废料中的至少一种。聚酰胺新料是新合成得到的，其中含有大于等于99wt％的聚酰胺树脂；聚酰胺回收料是将聚酰胺废料通过回收工艺处理得到的聚酰胺，其中含有大于等于99wt％的聚酰胺树脂；聚酰胺废料为报废丢弃的聚酰胺制品，其中聚酰胺树脂含量范围是25-90wt％。The polyamide raw material is derived from at least one of new polyamide material, polyamide recycled material and polyamide waste material. The new polyamide material is newly synthesized and contains more than or equal to 99wt% of polyamide resin; the polyamide recycled material is the polyamide obtained by processing polyamide waste through a recycling process, which contains more than or equal to 99wt% of polyamide resin; Polyamide wastes are discarded polyamide products, wherein the content of polyamide resin ranges from 25 to 90 wt%.
本发明与现有技术相比，具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明克服了现有3D打印粉末制备技术的缺陷，提供了一种阻燃功能性3D打印粉末及其制备方法。本发明的3D打印粉末不同于共混改性获得的材料，阻燃剂在3D打印粉末的树脂基体中粒径细小且分布均一不聚团(粒径均小于10微米，优选小于5微米)、3D打印粉末形状圆润流动性较好，利用其打印获得的制件平整，阻燃性能优秀。本发明还提供了该3D打印粉末的制备方法，该阻燃功能性3D打印粉末可以来源于聚酰胺废料也可以来源于聚酰胺新料。本方法可一体化完成聚酰胺废料的提纯和3D打印粉末制备过程。工艺的最后步骤采用喷雾的方式将聚酰胺溶液喷到水中，这样可以实现聚酰胺充分、粒径均一、圆润无凹凸的析出，无需筛选即可使得3D打印粉末的粒径分布范围是d(0.1)＜15微米且d(0.9)＜125微米，粉体流动性为≤10s/50g，堆积密度0.45-0.65g/cm 3。 The invention overcomes the defects of the existing 3D printing powder preparation technology, and provides a flame-retardant functional 3D printing powder and a preparation method thereof. The 3D printing powder of the present invention is different from the material obtained by blending and modification. The flame retardant has a small particle size and a uniform distribution in the resin matrix of the 3D printing powder without agglomeration (the particle size is less than 10 microns, preferably less than 5 microns), The 3D printing powder has a round shape and good fluidity, and the parts printed with it are flat and have excellent flame retardant properties. The present 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 or new polyamide material. The method can integrate the purification of polyamide waste and the preparation of 3D printing powder. In the last step of the process, the polyamide solution is sprayed into the water by spraying, which can realize the precipitation of polyamide with sufficient, uniform particle size, roundness and no bumps, and the particle size distribution range of the 3D printing powder can be made d(0.1 without screening. )<15 microns and d(0.9)<125 microns, the powder fluidity is ≤10s/50g, and the bulk density is 0.45-0.65g/cm 3 .
附图说明Description of drawings
图1：本发明实施例1的表面圆润的3D打印粉末扫描电镜照片，形状圆润均一性强。Figure 1: Scanning electron microscope photo of 3D printing powder with rounded surface according to Example 1 of the present invention, with rounded shape and strong uniformity.
图2：市售3D打印粉末扫描电镜照片，颗粒粒径不均，形状各异表面凹凸多。Figure 2: SEM photos of commercially available 3D printing powders, with uneven particle size and different shapes, with many surface bumps.
图3：对比例33D打印粉末扫描电镜照片，颗粒粒径不均，形状各异表面凹凸多。Figure 3: Scanning electron microscope photo of the 33D printing powder in the comparative example, the particle size is uneven, the shape is different, and the surface is uneven.
图4：本发明实施例1的3D打印粉末利用3D打印方式制备的样条经刻蚀处理后的形貌， 阻燃剂分布均匀，无团聚和析出的现象。Figure 4: The morphology of the 3D printing powder prepared by the 3D printing method of Example 1 of the present invention after etching treatment, the flame retardant is uniformly distributed, and there is no phenomenon of agglomeration and precipitation.
图5：通过共混方法制备得到的3D打印粉末(对比例3)，利用3D打印方式制备的样条经刻蚀处理后的形貌，阻燃剂分布不均，有明显的团聚现象。Figure 5: The 3D printing powder prepared by the blending method (Comparative Example 3), the morphology of the spline prepared by the 3D printing method after etching treatment, the flame retardant distribution is uneven, and there is obvious agglomeration.
具体实施方式detailed description
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。The present invention will be described in detail below with reference to specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that, for those skilled in the art, several modifications and improvements can be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.
本发明所用原料来源如下：The sources of raw materials used in the present invention are as follows:
聚酰胺废料PA12：来自水暖管道、汽车发动机周边零件等回收料，含有少量色粉，理论上PA12含量约为95％-97％。Polyamide waste PA12: It comes from recycled materials such as plumbing pipes and peripheral parts of automobile engines, and contains a small amount of toner. Theoretically, the PA12 content is about 95%-97%.
聚酰胺废料PA66：来自机械设备中齿轮、轴承等零部件的回收料，含有玻纤增强，理论上PA66含量约为65％-70％。Polyamide waste PA66: Recycling material from gears, bearings and other parts in mechanical equipment, containing glass fiber reinforcement, the theoretical PA66 content is about 65%-70%.
聚酰胺废料PA10T：来自发动机周边零部件回收料，含有玻纤增强，理论上PA10T含量为60-70％。Polyamide waste PA10T: Recycling material from parts around the engine, containing glass fiber reinforcement, the theoretical PA10T content is 60-70%.
PA12新料：阿科玛，P201TL；PA12 new material: Arkema, P201TL;
PA12回收料：自制，将上述聚酰胺废料PA12粉碎，加入3倍聚酰胺废料重量的复配溶剂(重量比苯酚：甲苯＝1:1)，加热至80℃搅拌溶解，降温至30℃后过滤得到聚酰胺溶液；再将聚酰胺溶液加入去离子水中，分离掉液体得到PA12回收料。PA12 recycled material: self-made, pulverize the above-mentioned polyamide waste PA12, add a compound solvent (weight ratio phenol:toluene=1:1) of 3 times the weight of the polyamide waste, heat to 80 ° C, stir and dissolve, cool to 30 ° C and filter after A polyamide solution is obtained; then the polyamide solution is added to deionized water, and the liquid is separated to obtain a PA12 recycled material.
苯酚：工业纯；Phenol: industrial grade;
甲苯：工业纯；Toluene: industrial grade;
阻燃剂A：OP1230，磷系阻燃剂；Flame retardant A: OP1230, phosphorus flame retardant;
阻燃剂B：环状磷酸酯；Flame Retardant B: Cyclic Phosphate;
阻燃剂C：十溴二苯乙烷；Flame Retardant C: Decabromodiphenylethane;
阻燃剂D：RM4-7105，直链型聚硅氧烷阻燃剂；Flame retardant D: RM4-7105, linear polysiloxane flame retardant;
阻燃剂E：XC-99-B5654，支链型聚硅氧烷阻燃剂。Flame retardant E: XC-99-B5654, branched chain polysiloxane flame retardant.
各项性能测试方法Various performance test methods
(1)考察3D打印粉末中阻燃剂的分布：将实施例和对比例3D打印粉末通过3D打印成样条后参照说明书列举的方法处理样条的一面，再进行SEM形貌分析测试。具体的，将样条固定在样品台并黏在导电胶上，表面镀金作为导电层，置于样品舱中抽真空，并调整电流电 压，观察样品形貌，统计得到光稳定剂孔洞粒径。扫描至20微米-500微米之间。(1) Investigate the distribution of flame retardants in the 3D printing powder: After 3D printing the 3D printing powders of the examples and comparative examples into splines, treat one side of the splines according to the method listed in the manual, and then conduct SEM morphology analysis and test. Specifically, the spline was fixed on the sample stage and adhered to the conductive adhesive, and the surface was plated with gold as a conductive layer, placed in the sample chamber and evacuated, and the current and voltage were adjusted, the morphology of the sample was observed, and the particle size of the light stabilizer holes was obtained by statistics. Scan to between 20 microns and 500 microns.
(3)3D打印粉末流动性测试：使用粉体流动仪，按照使用方法测试。(3) 3D printing powder flowability test: use a powder flowmeter and test according to the usage method.
(4)3D打印粉末粒径测试：按照标准GB/T 19077-2016进行测试。(4) 3D printing powder particle size test: test according to the standard GB/T 19077-2016.
(5)3D打印粉末堆积密度测试：利用树脂的自重，将试样从规定的高度自由落入已知容积的容器中，测量单位体积的树脂的质量，即得到堆积密度的大小(测试标准GB/T 20316.2-2006)。(5) 3D printing powder bulk density test: Using the self-weight of the resin, drop the sample freely into a container of known volume from a specified height, and measure the mass of the resin per unit volume to obtain the bulk density (test standard GB /T 20316.2-2006).
(6)通过SEM考察3D打印粉末外观：将试样固定在样品台并黏在导电胶上，表面镀金作为导电层，置于样品舱中抽真空，并调整电流电压，观察样品形貌，扫描至20微米-500微米之间。(6) Investigate the appearance of 3D printing powder by SEM: fix the sample on the sample stage and stick it on the conductive adhesive, the surface is plated with gold as a conductive layer, place it in the sample chamber to vacuumize, adjust the current and voltage, observe the sample morphology, scan to between 20 microns and 500 microns.
实施例1：Example 1:
将100g聚酰胺废料PA12加入复配溶剂(100g苯酚/200g甲苯)中，加热至温度80℃搅拌至溶解，再加入10g活性炭，保温搅拌0.5小时，降温至40℃后过滤，得到聚酰胺澄清溶液；将10g阻燃剂A加入聚酰胺澄清溶液中，搅拌至充分溶解，得到功能性聚酰胺溶液；再将功能性聚酰胺溶液以喷雾方式喷入4000g去离子水中(去离子水温度维持0-10℃)，析出聚酰胺阻燃改性3D打印粉末；干燥后称量，再进行其他性能的测试。Add 100g of polyamide waste PA12 into the compound solvent (100g phenol/200g toluene), heat to a temperature of 80°C and stir until dissolved, add 10g activated carbon, keep stirring for 0.5 hours, cool to 40°C and filter to obtain a clear polyamide solution 10g flame retardant A is added in the polyamide clear solution, stirred until fully dissolved, to obtain functional polyamide solution; then the functional polyamide solution is sprayed into 4000g deionized water (the deionized water temperature is maintained at 0- 10°C), the polyamide flame retardant modified 3D printing powder was precipitated; after drying, weighed, and then other properties were tested.
实施例2：Example 2:
实施例2与实施例1的区别在于，阻燃剂B与活性炭一同加入。The difference between Example 2 and Example 1 is that the flame retardant B is added together with the activated carbon.
实施例3：Example 3:
实施例3与实施例1的区别在于，阻燃剂为C。The difference between Example 3 and Example 1 is that the flame retardant is C.
实施例4：Example 4:
实施例4与实施例1的区别在于，阻燃剂为D。The difference between Example 4 and Example 1 is that the flame retardant is D.
实施例5：Example 5:
将100g聚酰胺废料PA10T加入复配溶剂(100g苯酚/200g甲苯)中，加热至温度100℃搅拌至溶解，再加入10g活性炭，升温至120℃，保温搅拌0.5小时，降温至40℃后过滤，得到聚酰胺澄清溶液；将10g阻燃剂E加入聚酰胺澄清溶液中，搅拌至充分溶解，得到功能性聚酰胺溶液；再将功能性聚酰胺溶液以喷雾方式喷入4000g去离子水中(去离子水温度维持20-30℃)，析出聚酰胺阻燃改性3D打印粉末；干燥后称量，再进行其他性能的测试。100g of polyamide waste PA10T was added to the compound solvent (100g phenol/200g toluene), heated to a temperature of 100°C and stirred until dissolved, then added 10g of activated carbon, heated to 120°C, kept stirring for 0.5 hours, cooled to 40°C and filtered, A polyamide clear solution was obtained; 10 g of flame retardant E was added to the polyamide clear solution, stirred until fully dissolved to obtain a functional polyamide solution; and then the functional polyamide solution was sprayed into 4000 g of deionized water (deionized water). The water temperature is maintained at 20-30 °C), and the polyamide flame retardant modified 3D printing powder is precipitated; after drying, weigh and test other properties.
实施例6：Example 6:
将100g聚酰胺废料PA66加入复配溶剂(80g苯酚/160g甲苯)中，加热至温度105℃搅拌至溶解，再加入10g活性炭，保温搅拌0.5小时，降温至40℃后过滤，得到聚酰胺澄清 溶液；将10g阻燃剂E加入聚酰胺澄清溶液中，搅拌至充分溶解，得到功能性聚酰胺溶液；再将功能性聚酰胺溶液以喷雾方式喷入4000g去离子水中(去离子水温度维持30-40℃)，析出聚酰胺阻燃改性3D打印粉末；干燥后称量，再进行其他性能的测试。100g polyamide waste PA66 was added to the compound solvent (80g phenol/160g toluene), heated to a temperature of 105°C and stirred until dissolved, then added 10g activated carbon, kept stirring for 0.5 hours, cooled to 40°C and filtered to obtain a clear polyamide solution 10g flame retardant E is added to the polyamide clear solution, stirred until fully dissolved, to obtain functional polyamide solution; then the functional polyamide solution is sprayed into 4000g deionized water (deionized water temperature is maintained at 30- 40°C), the polyamide flame retardant modified 3D printing powder was precipitated; after drying, weighed, and then other properties were tested.
实施例7：Example 7:
将100g PA12新料加入复配溶剂(100g苯酚/200g甲苯)中，加热至温度110℃搅拌至溶解，保温搅拌1小时，降温至40℃后过滤，得到聚酰胺澄清溶液；将20g阻燃剂E加入聚酰胺澄清溶液中，搅拌至充分溶解，得到功能性聚酰胺溶液；再将功能性聚酰胺溶液以喷雾方式喷入4000g去离子水中(去离子水温度维持50-60℃)，析出聚酰胺阻燃改性3D打印粉末；干燥后称量，再进行其他性能的测试。Add 100g of PA12 new material to the compound solvent (100g phenol/200g toluene), heat to a temperature of 110°C and stir to dissolve, keep stirring for 1 hour, cool down to 40°C and filter to obtain a clear polyamide solution; add 20g of flame retardants E is added to the clear polyamide solution, stirred until fully dissolved to obtain a functional polyamide solution; then the functional polyamide solution is sprayed into 4000 g of deionized water (the temperature of deionized water is maintained at 50-60 ° C), and the polymer is precipitated. Amide flame retardant modified 3D printing powder; weighed after drying, and then tested for other properties.
实施例8：Example 8:
将100g PA12回收料加入复配溶剂(100g苯酚/200g甲苯)中，加热至温度100℃搅拌至溶解，再加入10g活性炭，保温搅拌0.5小时，降温至40℃后过滤，得到聚酰胺澄清溶液；将15g阻燃剂E加入聚酰胺澄清溶液中，搅拌至充分溶解，得到功能性聚酰胺溶液；再将功能性聚酰胺溶液以喷雾方式喷入4000g去离子水中(去离子水温度维持40-50℃)，析出聚酰胺阻燃改性3D打印粉末；干燥后称量，再进行其他性能的测试。100g of PA12 reclaimed material was added to the compound solvent (100g phenol/200g toluene), heated to a temperature of 100°C and stirred to dissolve, then 10g of activated carbon was added, kept stirring for 0.5 hours, cooled to 40°C and filtered to obtain a clear polyamide solution; Add 15g of flame retardant E to the polyamide clear solution, stir until fully dissolved to obtain a functional polyamide solution; then spray the functional polyamide solution into 4000g of deionized water (the deionized water temperature is maintained at 40-50 ℃), the polyamide flame retardant modified 3D printing powder was precipitated; after drying, weighed, and then tested other properties.
实施例9：Example 9:
实施例9与实施例1的区别在于，步骤(A)中将溶液加热至温度110℃搅拌至溶解，去离子水温度维持50-60℃。The difference between Example 9 and Example 1 is that in step (A), the solution is heated to a temperature of 110°C and stirred until dissolved, and the temperature of deionized water is maintained at 50-60°C.
对比例1：Comparative Example 1:
将100g聚酰胺废料PA12加入复配溶剂(100g苯酚/200g甲苯)中，加热至温度100℃搅拌至溶解，再加入10g活性炭，保温搅拌0.5小时，降温至40℃后过滤，得到聚酰胺澄清溶液；将10g阻燃剂A加入聚酰胺澄清溶液中，搅拌至充分溶解，得到功能性聚酰胺溶液；在10分钟内向功能性聚酰胺溶液加入4000g去离子水，析出聚酰胺阻燃改性颗粒；干燥后将粒料在液氮中低温冷冻至-120℃以下，使之实现脆化易粉碎状态，再将冷冻好的粒料投入低温粉碎机腔体内，通过叶轮高速旋转进行粉碎加工；由气流筛分机进行分级并收集，选择粒度在120～400目范围内的阻燃3D打印粉末。100g of polyamide waste PA12 was added to the compound solvent (100g phenol/200g toluene), heated to a temperature of 100°C and stirred until dissolved, then added 10g of activated carbon, kept stirring for 0.5 hours, cooled to 40°C and filtered to obtain a clear polyamide solution ; Add 10 g of flame retardant A to the clear polyamide solution, stir until fully dissolved, and obtain a functional polyamide solution; add 4000 g of deionized water to the functional polyamide solution within 10 minutes to separate out polyamide flame retardant modified particles; After drying, freeze the pellets in liquid nitrogen at low temperature to below -120°C to achieve embrittlement and easy pulverization, and then put the frozen pellets into the cavity of the low-temperature pulverizer, and the impeller rotates at high speed for pulverization; The sieving machine conducts classification and collection, and selects flame-retardant 3D printing powder with a particle size in the range of 120-400 mesh.
对比例2：Comparative Example 2:
将100g聚酰胺废料PA12加入1500g的复合溶剂中(甲酸15％、盐酸10％、乙酸35％、水40％)，在80℃下搅拌溶解4h，后离心分离(转速为4000R/min)的到清液，再清液中投入10g阻燃剂A，搅拌均匀，再将溶液通入1500g的去离子水中，析出PA12沉淀，沉淀， 去离子水洗涤PA12颗粒至pH呈中性，干燥后将粒料在液氮中低温冷冻至-120℃以下，使之实现脆化易粉碎状态，再将冷冻好的粒料投入低温粉碎机腔体内，通过叶轮高速旋转进行粉碎加工；由气流筛分机进行分级并收集，选择粒度在120～400目范围内的阻燃3D打印粉末。Add 100g of polyamide waste PA12 to 1500g of composite solvent (formic acid 15%, hydrochloric acid 10%, acetic acid 35%, water 40%), stir and dissolve at 80°C for 4h, and then centrifuge (rotation speed is 4000R/min) to Add 10 g of flame retardant A into the clear liquid, stir evenly, and then pour the solution into 1500 g of deionized water to precipitate PA12, precipitate, and wash the PA12 particles with deionized water until the pH is neutral. The material is frozen at low temperature in liquid nitrogen to below -120°C, so as to achieve embrittlement and easy crushing. Then, the frozen pellets are put into the cavity of the low-temperature crusher, and the impeller rotates at high speed for crushing processing; And collect, select the flame retardant 3D printing powder with particle size in the range of 120-400 mesh.
对比例3：Comparative Example 3:
将100g聚酰胺废料PA12加入复配溶剂(100g苯酚/200g甲苯)中，加热至温度100℃搅拌至溶解，再加入10g活性炭，保温搅拌0.5小时，降温至40℃后过滤，得到聚酰胺澄清溶液；再将聚酰胺澄清溶液通入4000g去离子水中，析出回收聚酰胺PA12。将干燥后的回收聚酰胺PA12与10g阻燃剂A通过双螺杆挤出机挤出造粒(螺杆长径比为45：1，一区170℃，二区180℃，三区190℃，四区205℃，五区215℃，六区225℃，七区235℃，八区240℃，九区245℃，机头温度240℃，转速为350转/分)，再将粒料在液氮中低温冷冻至-120℃以下，使之实现脆化易粉碎状态，再将冷冻好的粒料投入低温粉碎机腔体内，通过叶轮高速旋转进行粉碎加工；由气流筛分机进行分级并收集，选择粒度在120～400目范围内的阻燃3D打印粉末。Add 100g of polyamide waste PA12 into the compound solvent (100g phenol/200g toluene), heat to a temperature of 100°C and stir until dissolved, then add 10g activated carbon, keep stirring for 0.5 hours, cool to 40°C and filter to obtain a clear polyamide solution ; Then pass the polyamide clear solution into 4000g of deionized water to separate out and recover polyamide PA12. The dried recycled polyamide PA12 and 10g of flame retardant A were extruded and granulated through a twin-screw extruder (screw length-diameter ratio was 45:1, the first zone was 170°C, the second zone was 180°C, the third zone was 190°C, and the fourth zone was 190°C. Zone 205°C, zone 5 215°C, zone 6 225°C, zone 7 235°C, zone 8 240°C, zone 9 245°C, head temperature 240°C, rotating speed 350 rpm), then put the pellets in liquid nitrogen The medium and low temperature is frozen to below -120°C, so as to achieve embrittlement and easy pulverization, and then the frozen pellets are put into the cavity of the low-temperature pulverizer, and the impeller rotates at high speed for pulverization; Flame retardant 3D printing powder with particle size in the range of 120-400 mesh.
表1：实施例和对比例3D打印粉末各项性能测试结果Table 1: The performance test results of the 3D printing powders of the examples and comparative examples
Figure PCTCN2020140811-appb-000001
Figure PCTCN2020140811-appb-000001
续表1：Continued from Table 1:
Figure PCTCN2020140811-appb-000002
Figure PCTCN2020140811-appb-000002
从对比例1-3可知，通过其他方法得到的3D打印粉末，其基体中的阻燃剂孔洞粒径＞5微米，并且流动性低，粒径分布不均匀也导致了堆积密度较低。From Comparative Examples 1-3, it can be seen that the 3D printing powder obtained by other methods has a flame retardant hole particle size > 5 microns in the matrix, and has low fluidity. The uneven particle size distribution also leads to a low bulk density.

Claims (11)

  1. 一种3D打印粉末，其特征在于，按重量份计，包括以下组分：A 3D printing powder is characterized in that, by weight, it comprises the following components:
    聚酰胺        100份；100 parts of polyamide;
    阻燃剂        1-30份；Flame retardant 1-30 copies;
    所述的阻燃剂的粒径均以小于10微米的形态分散于聚酰胺树脂基体中，3D打印粉末的粒径分布范围是d(0.1)＜15微米且d(0.9)＜125微米，粉体流动性为≤10s/50g，堆积密度0.45-0.65g/cm 3。 The particle size of the flame retardant is dispersed in the polyamide resin matrix in the form of less than 10 microns, and the particle size distribution range of the 3D printing powder is d(0.1)<15 microns and d(0.9)<125 microns. The fluidity is ≤10s/50g, and the bulk density is 0.45-0.65g/cm 3 .
  2. 根据权利要求1所述的3D打印粉末，其特征在于，所述的阻燃剂选自溴系阻燃剂、磷系阻燃剂、硅系阻燃剂中的一种或几种。The 3D printing powder according to claim 1, wherein the flame retardant is selected from one or more of bromine-based flame retardants, phosphorus-based flame retardants, and silicon-based flame retardants.
  3. 根据权利要求2所述的3D打印粉末，其特征在于，所述的溴系阻燃剂选自溴化聚苯乙烯、溴化聚苯醚、溴化双酚A型环氧树脂、溴化苯乙烯-马来酸酐共聚物、溴化环氧树脂、溴化苯氧基树脂、十溴二苯醚、十溴代联苯、溴化聚碳酸酯、全溴三环十五烷、溴化芳香族交联聚合物中的至少一种；所述的磷系阻燃剂选自单磷酸芳基磷酸酯、双磷酸芳基磷酸酯、烷基磷酸二甲酯、磷酸三苯酯、磷酸三甲苯酯、磷酸三(二甲苯)酯、丙苯系磷酸酯、丁苯系磷酸酯、有机次磷酸盐、环状磷酸酯中的至少一种；所述的硅系阻燃剂选自聚二甲基硅氧烷、聚甲基氢硅氧烷、支链型聚硅氧烷中的至少一种。The 3D printing powder according to claim 2, wherein the brominated flame retardant is selected from the group consisting of brominated polystyrene, brominated polyphenylene ether, brominated bisphenol A epoxy resin, brominated benzene Ethylene-maleic anhydride copolymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromodiphenyl, brominated polycarbonate, perbromotricyclopentadecane, brominated aromatic At least one of the family of cross-linked polymers; the phosphorus-based flame retardant is selected from aryl phosphate monophosphate, aryl phosphate diphosphate, dimethyl alkyl phosphate, triphenyl phosphate, trimethyl phosphate At least one of ester, tris(xylylene) phosphate, propylbenzene-based phosphate, butylbenzene-based phosphate, organic hypophosphite, and cyclic phosphate; the silicon-based flame retardant is selected from polydimethylene At least one of polysiloxane, polymethyl hydrogen siloxane and branched-chain polysiloxane.
  4. 根据权利要求2或3所述的3D打印粉末，其特征在于，阻燃剂在聚酰胺中分布是通过以下方法检测：将3D打印粉末以3D打印方式制备成样条，截取样条中的一段置于溶液中浸泡24小时溶解样条表面的阻燃剂但是不溶解聚酰胺(溴系阻燃剂可采用甲苯、二甲苯溶液处理；磷系阻燃剂采用氯仿、二氯甲烷等极性溶剂或强碱水处理；硅氧烷类阻燃剂采用异丙醇处理)，之后用扫描电子显微镜观察样条截面形貌；结合能谱元素分析进行测试表征。The 3D printing powder according to claim 2 or 3, wherein the distribution of the flame retardant in the polyamide is detected by the following method: the 3D printing powder is prepared into a spline by 3D printing, and a section of the spline is cut off. Soak in the solution for 24 hours to dissolve the flame retardant on the surface of the spline but not the polyamide (bromine-based flame retardants can be treated with toluene and xylene solutions; phosphorus-based flame retardants can be treated with polar solvents such as chloroform and dichloromethane) or strong alkaline water treatment; siloxane flame retardants are treated with isopropanol), and then the cross-sectional morphology of the splines was observed with a scanning electron microscope; combined with energy spectrum elemental analysis to test and characterize.
  5. 根据权利要求1所述的3D打印粉末，其特征在于，所述的聚酰胺选自脂肪族聚酰胺、半芳香族聚酰胺中的至少一种；所述的脂肪族聚酰胺选自PA6、PA66、PA12、PA1010、PA1012、PA11、PA610、PA69、PA1212中的至少一种；所述的半芳香族聚酰胺选自PA5T、PA6T610、PA6T6I、PA6T1010、PA10T、PA10T10I、PA10T1010、PA10T1012、PA10T6T中的至少一种。The 3D printing powder according to claim 1, wherein the polyamide is selected from at least one of aliphatic polyamide and semi-aromatic polyamide; the aliphatic polyamide is selected from PA6, PA66 , PA12, PA1010, PA1012, PA11, PA610, PA69, PA1212 at least one; the semi-aromatic polyamide is selected from at least one of PA5T, PA6T610, PA6T6I, PA6T1010, PA10T, PA10T10I, PA10T1010, PA10T1012, PA10T6T A sort of.
  6. 根据权利要求1-5任一项所述的3D打印粉末，其特征在于，所述的阻燃剂的粒径均以小于5微米的形态分散于聚酰胺树脂基体中，3D打印粉末的粒径分布范围是d(0.1)＜25微米且d(0.9)＜105微米，粉体流动性为≤9s/50g，堆积密度0.5-0.6g/cm 3。 The 3D printing powder according to any one of claims 1-5, wherein the particle size of the flame retardant is dispersed in the polyamide resin matrix in the form of less than 5 microns, and the particle size of the 3D printing powder is The distribution range is d(0.1)<25 microns and d(0.9)<105 microns, the powder fluidity is ≤9s/50g, and the bulk density is 0.5-0.6g/cm 3 .
  7. 权利要求1-6任一项所述的3D打印粉末的制备方法，其特征在于，包括以下步骤：The method for preparing 3D printing powder according to any one of claims 1-6, characterized in that, it comprises the following steps:
    (A)将聚酰胺原料加入复配溶剂中，加热达到50℃至溶液回流的温度并搅拌至溶解(如有 不溶物，增加过滤工序将不溶物滤除；如溶液颜色较深，则增加脱色处理工序)，得到聚酰胺澄清溶液；(A) adding the polyamide raw material to the compound solvent, heating to a temperature of 50° C. to the reflux temperature of the solution and stirring to dissolve (if there is insoluble matter, increase the filtration process to filter out the insoluble matter; if the color of the solution is darker, increase the decolorization treatment procedure) to obtain a clear solution of polyamide;
    (B)将阻燃剂加入聚酰胺澄清溶液中，搅拌至溶解，得到阻燃功能性聚酰胺溶液；(B) adding the flame retardant to the polyamide clear solution, stirring until dissolved, to obtain a flame retardant functional polyamide solution;
    (C)将阻燃功能性聚酰胺溶液以喷雾方式喷入去离子水中，析出3D打印粉末，期间，去离子水的温度为0-80℃范围内；(C) spraying the flame retardant functional polyamide solution into deionized water by spraying to precipitate 3D printing powder, during which the temperature of the deionized water is in the range of 0-80°C;
    所述的复配溶剂，按重量份计，包括10-30份苯酚、15-40份甲苯；聚酰胺原料与复配溶剂重量比为1:10-1:2；析出过程中，阻燃功能性聚酰胺溶液与去离子水的重量比为1:5-1:50。The compound solvent, in parts by weight, includes 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; during the precipitation process, the flame retardant function The weight ratio of the polyamide solution to deionized water is 1:5-1:50.
  8. 根据权利要求7所述的3D打印粉末的制备方法，其特征在于，脱色处理工序为加入吸附剂，将溶液升温达到50℃至复配溶剂回流温度保持0.5-2小时，再降温至低于50℃后过滤。The preparation method of 3D printing powder according to claim 7, characterized in that, the decolorization treatment process is adding adsorbent, heating the solution to 50° C. to the reflux temperature of the compound solvent for 0.5-2 hours, and then cooling down to less than 50° C. filter after ℃.
  9. 据权利要求8所述的3D打印粉末的制备方法，其特征在于，所述的吸附剂选自活性炭、活性白土中的至少一种。The method for preparing 3D printing powder according to claim 8, wherein the adsorbent is selected from at least one of activated carbon and activated clay.
  10. 根据权利要求6所述的3D打印粉末的制备方法，其特征在于，步骤(A)将溶液加热达到100℃至溶液回流温度，步骤(C)中，析出3D打印粉末时，去离子水的温度为20-60℃范围内。The method for preparing 3D printing powder according to claim 6, wherein in step (A), the solution is heated to 100° C. to the reflux temperature of the solution, and in step (C), when the 3D printing powder is precipitated, the temperature of deionized water is in the range of 20-60°C.
  11. 根据权利要求7所述的3D打印粉末的制备方法，其特征在于，所述的聚酰胺原料来源于聚酰胺新料、聚酰胺回收料、聚酰胺废料中的至少一种；聚酰胺新料是新合成得到的，其中含有大于等于99wt％的聚酰胺树脂；聚酰胺回收料是将聚酰胺废料通过回收工艺处理得到的聚酰胺，其中含有大于等于99wt％的聚酰胺树脂；聚酰胺废料为报废丢弃的聚酰胺制品，其中聚酰胺树脂含量范围是25-90wt％。The method for preparing 3D printing powder according to claim 7, wherein the polyamide raw material is derived from at least one of new polyamide material, polyamide recycled material, and polyamide waste; and the new polyamide material is Newly synthesized, which contains more than or equal to 99wt% of polyamide resin; polyamide recycling material is polyamide obtained by processing polyamide waste through recycling process, which contains more than or equal to 99wt% of polyamide resin; polyamide waste is scrapped Discarded polyamide articles, wherein the polyamide resin content is in the range of 25-90 wt%.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114276675A (en) * 2022-01-26 2022-04-05 福州大学 Nylon 12 composite material for MJR3D printing and preparation method thereof
IT202200011264A1 (en) * 2022-05-27 2023-11-27 Innovatech3D S R L Sb METHOD FOR RECYCLING A POWDERED WASTE MATERIAL RESULTING FROM THREE-DIMENSIONAL PRINTING

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
CN113402474B (en) * 2021-06-15 2022-06-10 杭州捷尔思阻燃化工有限公司 Preparation method and application of melamine cyanurate

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
CN111909509A (en) * 2020-07-06 2020-11-10 金发科技股份有限公司 3D printing powder and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
CN111909509A (en) * 2020-07-06 2020-11-10 金发科技股份有限公司 3D printing powder and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114276675A (en) * 2022-01-26 2022-04-05 福州大学 Nylon 12 composite material for MJR3D printing and preparation method thereof
CN114276675B (en) * 2022-01-26 2022-12-23 福州大学 Nylon 12 composite material for MQR 3D printing and preparation method thereof
IT202200011264A1 (en) * 2022-05-27 2023-11-27 Innovatech3D S R L Sb METHOD FOR RECYCLING A POWDERED WASTE MATERIAL RESULTING FROM THREE-DIMENSIONAL PRINTING

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