CN115322524A - Polyester elastomer powder for selective laser sintering and preparation method thereof - Google Patents

Polyester elastomer powder for selective laser sintering and preparation method thereof Download PDF

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CN115322524A
CN115322524A CN202211025815.6A CN202211025815A CN115322524A CN 115322524 A CN115322524 A CN 115322524A CN 202211025815 A CN202211025815 A CN 202211025815A CN 115322524 A CN115322524 A CN 115322524A
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polyester elastomer
percent
powder
selective laser
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夏和生
周玲娟
费国霞
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Nanjing Mo Branch 3d Technology Co ltd
Jiangsu Jitri Advanced Polymer Materials Research Institute Co Ltd
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Nanjing Mo Branch 3d Technology Co ltd
Jiangsu Jitri Advanced Polymer Materials Research Institute Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y70/00Materials specially adapted for additive manufacturing
    • B33Y70/10Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • C08K2003/0812Aluminium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds
    • C08K2003/321Phosphates
    • C08K2003/324Alkali metal phosphate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Civil Engineering (AREA)
  • Composite Materials (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The invention discloses polyester elastomer powder for selective laser sintering and a preparation method thereof, which relate to the technical field of additive manufacturing and comprise the following raw materials in percentage by weight: 80 to 90 percent of thermoplastic polyester elastomer resin, 5 to 15 percent of vinyl elastomer, 0.1 to 1 percent of anti-hydrolysis agent, 0.1 to 1 percent of toughening agent, 0.1 to 1 percent of anti-sticking agent, 0.1 to 1 percent of dispersing agent, 0.1 to 1 percent of antioxidant, 0.1 to 1 percent of flame retardant, 0.1 to 1 percent of light absorbent and 0.1 to 1 percent of flow assistant. The invention has the advantages of ingenious design, reasonable components and reasonable manufacturing method, is suitable for popularization, overcomes the defects of poor hydrolytic resistance and low flame retardant grade of the thermoplastic polyester elastomer, ensures that the flame retardant property of the obtained material reaches UL 94V-0 grade, has good mechanical property and water resistance, does not influence too many mechanical properties of the material by adding the hydrolytic resistance agent and the light absorption agent, and is suitable for popularization and use.

Description

Polyester elastomer powder for selective laser sintering and preparation method thereof
Technical Field
The invention relates to the technical field of additive manufacturing, in particular to polyester elastomer powder for selective laser sintering and a preparation method thereof.
Background
The selective laser sintering technology can prepare products with any complex structure within the allowable size range, and is very effective for sample design and test in the research process and even small-batch manufacturing in the production process, but compared with the traditional process, the manufacturing method has some influences on precision and mechanical properties, and in many fields, particularly when manufacturing selective laser display samples, users pay great attention to the surface quality and the size precision of selective laser sintering products.
At present, the main polymer materials for selective laser sintering are PA, PC, TPU, PP and the like, and the laser energy absorption efficiency is a very important index when the materials are sintered by laser. The laser absorption rate of the material is low, the required laser energy is high, so that the loss of the laser energy is inevitably caused, the energy waste is caused by the output of the overhigh laser energy, the service life of the laser is influenced, and the service life of the 3D printer is shortened. The invention provides polyester elastomer powder for selective laser sintering and a preparation method thereof, which can have good laser energy absorption rate, reduce the laser energy required by sintering and simultaneously obtain good performance of a sintered product.
Disclosure of Invention
The invention aims to provide polyester elastomer powder for selective laser sintering and a preparation method thereof, the material has good laser energy absorption rate, and sintered products can obtain good mechanical properties under the condition of low laser energy density.
In order to achieve the purpose, the invention adopts the following technical scheme:
the polyester elastomer powder for selective laser sintering comprises the following raw materials in percentage by weight: 80 to 90 percent of thermoplastic polyester elastomer resin, 5 to 15 percent of vinyl elastomer, 0.1 to 1 percent of anti-hydrolysis agent, 0.1 to 1 percent of toughening agent, 0.1 to 1 percent of anti-sticking agent, 0.1 to 1 percent of dispersing agent, 0.1 to 1 percent of antioxidant, 0.1 to 1 percent of flame retardant, 0.1 to 1 percent of light absorbent and 0.1 to 1 percent of flow assistant.
Preferably, the feed comprises the following raw materials in percentage by weight: 80% of thermoplastic polyester elastomer resin, 15% of vinyl elastomer, 0.5% of hydrolysis resistant agent, 1% of toughening agent, 1% of anti-sticking agent, 0.3% of dispersing agent, 0.4% of antioxidant, 0.3% of flame retardant, 0.5% of light absorbent and 1% of flow aid.
Preferably, the feed comprises the following raw materials in percentage by weight: 85% of thermoplastic polyester elastomer resin, 10% of vinyl elastomer, 0.5% of hydrolysis resistant agent, 1% of toughening agent, 1% of anti-sticking agent, 0.3% of dispersing agent, 0.4% of antioxidant, 0.3% of flame retardant, 0.5% of light absorbent and 1% of flow aid.
Preferably, the feed comprises the following raw materials in percentage by weight: 90% of thermoplastic polyester elastomer resin, 5% of vinyl elastomer, 0.5% of hydrolysis resistant agent, 1% of toughening agent, 1% of anti-sticking agent, 0.3% of dispersing agent, 0.4% of antioxidant, 0.3% of flame retardant, 0.5% of light absorbent and 1% of flow aid.
Preferably, the flow aid comprises one or more of methyl siloxane and chlorinated siloxane.
Preferably, the toughening agent is one or more of a polysulfide rubber and a urethane prepolymer.
Preferably, the dispersant is one or more of sodium tripolyphosphate and sodium dodecyl sulfate.
Preferably, the anti-sticking agent is zinc stearate; the antioxidant is one or more of tea polyphenol and tert-butyl p-hydroxyanisole; the flame retardant is silicone polymer and/or organic silicon micro powder.
Preferably, the light absorbing agent comprises aluminum powder and carbon powder, and the weight ratio of the aluminum powder to the carbon powder is 2:1; the hydrolysis resistant agent is carbodiimide, bis-carbodiimide or polycarbodiimide.
A preparation method of polyester elastomer powder for selective laser sintering comprises the following steps:
the method comprises the following steps: adding thermoplastic polyester elastomer resin, vinyl elastomer, hydrolysis resistant agent and toughening agent into a high-speed mixer, and mixing for 20-25 min at 25-40 ℃; sequentially adding a dispersing agent, an antioxidant, a flame retardant, a light absorbing agent and a flow aid, mixing for 15-20min at 25-40 ℃, melting, extruding and granulating by an extruder to obtain polyester elastomer granules;
step two: carrying out deep cooling crushing on polyester elastomer granules to obtain powder particles;
step three: drying the powder particles;
step four: and uniformly mixing and stirring the dried powder particles and the anti-sticking agent to obtain the polyester elastomer powder for selective laser sintering.
The polyester elastomer powder for selective laser sintering overcomes the defects of poor hydrolysis resistance and low flame retardant grade of a thermoplastic polyester elastomer, the flame retardant property of the obtained material reaches UL 94V-0 grade, and meanwhile, the mechanical property and the water resistance are good, and compared with a comparative example, the fact that the mechanical property of too many materials is not influenced by adding the hydrolysis resistance agent and the light absorption agent is found. The invention has the advantages of ingenious design, reasonable components, reasonable preparation method and suitability for popularization.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.
Example one
Adding 800g of thermoplastic polyester elastomer resin, 150g of vinyl elastomer, 5g of carbodiimide and 10g of polysulfide rubber into a high-speed mixer, mixing for 25min at 30 ℃, then sequentially adding 3g of sodium tripolyphosphate, 4g of tea polyphenol, 3g of silicone polymer, 3.33g of aluminum powder, 1.67g of carbon powder and 10g of methyl siloxane, mixing for 20min at 30 ℃, and carrying out melting, extrusion and granulation to obtain polyester elastomer granules;
and (3) performing awakening, deep cooling and crushing on the obtained polyester elastomer granules to obtain powder particles, then drying the powder particles, adding 10g of zinc stearate, mixing and uniformly stirring to obtain the polyester elastomer powder for selective laser sintering.
Example two
Adding 850g of thermoplastic polyester elastomer resin, 100g of vinyl elastomer, 5g of bis-carbodiimide and 10g of polysulfide rubber into a high-speed mixer, and mixing for 25min at the temperature of 30 ℃; then adding 3g of lauryl sodium sulfate, 4g of tert-butyl p-hydroxyanisole, 3g of organic silicon micro powder, 3.33g of aluminum powder, 1.67g of carbon powder and 10g of methyl siloxane in sequence, mixing for 20min at 30 ℃, and obtaining polyester elastomer granules through melting, extrusion and granulation;
and (3) performing awakening, deep cooling and crushing on the obtained polyester elastomer granules to obtain powder particles, then drying the powder particles, adding 10g of zinc stearate, mixing and stirring uniformly to obtain the polyester elastomer powder for selective laser sintering.
EXAMPLE III
Adding 900g of thermoplastic polyester elastomer resin, 50g of vinyl elastomer, 5g of carbodiimide and 10g of polysulfide rubber into a high-speed mixer, and mixing for 25min at 30 ℃; then adding 3g of sodium dodecyl sulfate, 4g of tert-butyl p-hydroxyanisole, 3g of silicone polymer, 3.33g of aluminum powder, 1.67g of carbon powder and 10g of chlorinated siloxane in sequence, mixing for 20min at 30 ℃, and obtaining polyester elastomer granules through melting, extrusion and granulation;
and (3) performing awakening, deep cooling and crushing on the obtained polyester elastomer granules to obtain powder particles, then drying the powder particles, adding 10g of zinc stearate, mixing and uniformly stirring to obtain the polyester elastomer powder for selective laser sintering.
Comparative example 1
Adding 855g of thermoplastic polyester elastomer resin, 100g of vinyl elastomer and 10g of polysulfide rubber into a high-speed mixer, and mixing for 25min at the temperature of 30 ℃; then, sequentially adding 3g of sodium tripolyphosphate, 4g of tea polyphenol, 3g of silicone polymer, 3.33g of aluminum powder, 1.67g of carbon powder and 10g of methyl siloxane, mixing for 20min at 30 ℃, and carrying out melting, extrusion and granulation to obtain polyester elastomer granules;
and (3) performing awakening, deep cooling and crushing on the obtained polyester elastomer granules to obtain powder particles, then drying the powder particles, adding 10g of zinc stearate, mixing and uniformly stirring to obtain the polyester elastomer powder for selective laser sintering.
Comparative example No. two
Adding 855g of thermoplastic polyester elastomer resin, 100g of vinyl elastomer, 5g of carbodiimide and 10g of polysulfide rubber into a high-speed mixer, and mixing for 25min at 30 ℃; then, sequentially adding 3g of sodium tripolyphosphate, 4g of tea polyphenol, 3g of silicone polymer and 10g of methyl siloxane, mixing for 20min at 30 ℃, and carrying out melting, extrusion and granulation to obtain polyester elastomer granules;
and (3) performing awakening, deep cooling and crushing on the obtained polyester elastomer granules to obtain powder particles, then drying the powder particles, adding 10g of zinc stearate, mixing and uniformly stirring to obtain the polyester elastomer powder for selective laser sintering.
Experiment of
The polyester elastomer powders in the above examples and comparative examples were respectively used for laser sintering, the sintering laser energy density was calculated, and the hardness, tensile strength and flame retardancy of the sintered product were examined. The tensile strength is tested according to ISO 527-1,2 standard; the flame retardant property is tested according to UL94 plastic combustion performance test standard and GB/T2408 standard, and the test result is as follows:
TABLE 1
Figure BDA0003815497390000051
The polyester elastomer powder for selective laser sintering provided by the invention overcomes the defects of poor hydrolysis resistance and low flame retardant grade of a thermoplastic polyester elastomer as shown in Table 1, the flame retardant property of the obtained material reaches UL 94V-0 grade, and meanwhile, the mechanical property and the water resistance are good, and compared with a comparative example, the mechanical property of too many materials cannot be influenced by increasing an hydrolysis resistant agent and a light absorbing agent; by not adding a light absorber in comparative example two, the laser energy density required for sintering is much greater.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (10)

1. The polyester elastomer powder for selective laser sintering is characterized by comprising the following raw materials in percentage by weight: 80 to 90 percent of thermoplastic polyester elastomer resin, 5 to 15 percent of vinyl elastomer, 0.1 to 1 percent of anti-hydrolysis agent, 0.1 to 1 percent of toughening agent, 0.1 to 1 percent of anti-sticking agent, 0.1 to 1 percent of dispersing agent, 0.1 to 1 percent of antioxidant, 0.1 to 1 percent of flame retardant, 0.1 to 1 percent of light absorbent and 0.1 to 1 percent of flow assistant.
2. The polyester elastomer powder for selective laser sintering according to claim 1, comprising the following raw materials in percentage by weight: 80% of thermoplastic polyester elastomer resin, 15% of vinyl elastomer, 0.5% of hydrolysis resistant agent, 1% of toughening agent, 1% of anti-sticking agent, 0.3% of dispersing agent, 0.4% of antioxidant, 0.3% of flame retardant, 0.5% of light absorbent and 1% of flow aid.
3. The polyester elastomer powder for selective laser sintering according to claim 1, comprising the following raw materials in percentage by weight: 85% of thermoplastic polyester elastomer resin, 10% of vinyl elastomer, 0.5% of hydrolysis resistant agent, 1% of toughening agent, 1% of anti-sticking agent, 0.3% of dispersing agent, 0.4% of antioxidant, 0.3% of flame retardant, 0.5% of light absorbent and 1% of flow aid.
4. The polyester elastomer powder for selective laser sintering according to claim 1, comprising the following raw materials in percentage by weight: 90% of thermoplastic polyester elastomer resin, 5% of vinyl elastomer, 0.5% of anti-hydrolysis agent, 1% of toughening agent, 1% of anti-sticking agent, 0.3% of dispersing agent, 0.4% of antioxidant, 0.3% of flame retardant, 0.5% of light absorbent and 1% of flow aid.
5. The polyester elastomer powder for selective laser sintering according to claim 1, wherein the flow aid comprises one or more of methyl siloxane and chlorinated siloxane.
6. The polyester elastomer powder for selective laser sintering of claim 1, wherein the toughening agent is one or more of a polysulfide rubber and a urethane prepolymer.
7. The polyester elastomer powder for selective laser sintering according to claim 1, wherein the dispersant is one or more of sodium tripolyphosphate and sodium lauryl sulfate.
8. The polyester elastomer powder for selective laser sintering according to claim 1, wherein the anti-sticking agent is zinc stearate; the antioxidant is one or more of tea polyphenol and tert-butyl p-hydroxyanisole; the flame retardant is silicone polymer and/or organic silicon micro powder.
9. The polyester elastomer powder for selective laser sintering according to claim 1, wherein the light absorber comprises aluminum powder and carbon powder, and the weight ratio of the aluminum powder to the carbon powder is 2:1; the hydrolysis resistant agent is carbodiimide, bis-carbodiimide or polycarbodiimide.
10. A method for preparing the polyester elastomer powder for selective laser sintering according to any one of claims 1 to 9, comprising the steps of:
the method comprises the following steps: adding thermoplastic polyester elastomer resin, vinyl elastomer, hydrolysis resistant agent and toughening agent into a high-speed mixer, and mixing for 20-25 min at 25-40 ℃; sequentially adding a dispersing agent, an antioxidant, a flame retardant, a light absorbing agent and a flow aid, mixing for 15-20min at 25-40 ℃, melting, extruding and granulating by an extruder to obtain polyester elastomer granules;
step two: carrying out deep cooling crushing on polyester elastomer granules to obtain powder particles;
step three: drying the powder particles;
step four: and uniformly mixing and stirring the dried powder particles and the anti-sticking agent to obtain the polyester elastomer powder for selective laser sintering.
CN202211025815.6A 2022-08-25 2022-08-25 Polyester elastomer powder for selective laser sintering and preparation method thereof Pending CN115322524A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1200806C (en) * 1997-03-18 2005-05-11 Dsmip财产有限公司 Laser sinterable thermoplastic power
CN104908143A (en) * 2015-03-23 2015-09-16 济南大学 Preparation method for laser sintering 3D (three-dimensional) printing rapid prototyping alumina powder
CN105985632A (en) * 2015-10-28 2016-10-05 合肥学院 Powder material for selective laser sintering and preparation method thereof
CN111154135A (en) * 2020-01-13 2020-05-15 苏州申赛新材料有限公司 3D printing foaming product and preparation process thereof
CN112111095A (en) * 2020-09-25 2020-12-22 中北大学 Composite wax powder material suitable for selective laser sintering process
CN112440472A (en) * 2020-10-28 2021-03-05 湖南华曙高科技有限责任公司 Method for low-temperature sintering of high-molecular composite powder material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1200806C (en) * 1997-03-18 2005-05-11 Dsmip财产有限公司 Laser sinterable thermoplastic power
CN104908143A (en) * 2015-03-23 2015-09-16 济南大学 Preparation method for laser sintering 3D (three-dimensional) printing rapid prototyping alumina powder
CN105985632A (en) * 2015-10-28 2016-10-05 合肥学院 Powder material for selective laser sintering and preparation method thereof
CN111154135A (en) * 2020-01-13 2020-05-15 苏州申赛新材料有限公司 3D printing foaming product and preparation process thereof
CN112111095A (en) * 2020-09-25 2020-12-22 中北大学 Composite wax powder material suitable for selective laser sintering process
CN112440472A (en) * 2020-10-28 2021-03-05 湖南华曙高科技有限责任公司 Method for low-temperature sintering of high-molecular composite powder material

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