AES engineering plastic 3D printing consumable and preparation method thereof

Abstract

The invention particularly relates to an AES engineering plastic 3D printing consumable and a preparation method thereof. The 3D printing consumable is prepared from the following raw materials in parts by weight: 60 to 70 parts of AES resin, 10 to 15 parts of siloxane copolymerized polycarbonate, 8 to 12 parts of acrylic modified silicon resin, 8 to 12 parts of compatilizer, 5 to 15 parts of flame retardant, 4 to 10 parts of inorganic filler, 1 to 3 parts of silane coupling agent, 0.5 to 5 parts of antioxidant and 0.5 to 5 parts of functional additive. The AES engineering plastic 3D printing consumable material is prepared through the synergistic effect of the AES resin, the siloxane copolymerized polycarbonate, the acrylic acid modified silicon resin, the compatilizer, the flame retardant and other raw materials, has good printing precision, interlayer binding force and heat resistance, and can meet the requirements of 3D printing of high-precision and high-strength parts. The preparation method is stable in process, convenient to operate and control, high in production efficiency and beneficial to industrial production.

Description

Technical Field

[0001] This invention relates to the field of polymer materials and their molding and processing technology, specifically to an AES engineering plastic 3D printing consumable and its preparation method. Background Technology

[0002] 3D printing, as a rapid prototyping technology, has been widely used in aerospace, automotive manufacturing, medical devices, and construction due to its ability to quickly manufacture complex shapes. 3D printing consumables, as one of the core elements of 3D printing technology, directly affect the quality and application range of printed products. With the rapid development of 3D printing technology, the requirements for printing materials are becoming increasingly stringent.

[0003] AES resin is an engineering plastic copolymerized from acrylonitrile, ethylene-propylene-diolefin terpolymer, and styrene. Due to its excellent physical properties, processability, and chemical stability, AES engineering plastics have broad application prospects in the field of 3D printing. However, existing AES engineering plastics may suffer from problems such as low printing accuracy, weak interlayer bonding, and poor heat resistance during 3D printing, making it difficult to meet the requirements of some high-end applications. Therefore, developing a high-performance AES engineering plastic 3D printing consumable is of great significance. Summary of the Invention

[0004] The purpose of this invention is to address the shortcomings of the prior art by providing an AES engineering plastic 3D printing consumable and its preparation method. The 3D consumable possesses excellent printing accuracy, interlayer bonding strength, and heat resistance, meeting the requirements for high-precision, high-strength 3D printed components. The preparation method is stable, easy to operate and control, and conducive to industrial production.

[0005] The objective of this invention is achieved through the following technical solution: an AES engineering plastic 3D printing consumable, comprising the following raw materials in parts by weight: 60-70 parts of AES resin, 10-15 parts of siloxane copolymer polycarbonate, 8-12 parts of acrylic modified silicone resin, 8-12 parts of compatibilizer, 5-15 parts of flame retardant, 4-10 parts of inorganic filler, 1-3 parts of silane coupling agent, 0.5-5 parts of antioxidant, and 0.5-5 parts of functional additives.

[0006] Furthermore, the compatibilizer is at least one of maleic anhydride-grafted polyolefin elastomer, EPDM-grafted maleic anhydride, and styrene-maleic anhydride copolymer.

[0007] Furthermore, the flame retardant is at least one of cage-type polysilsesquioxane, aluminum hypophosphite, and zinc borate.

[0008] Furthermore, the flame retardant is composed of cage-type polysilsesquioxane, aluminum hypophosphite, and zinc borate in a weight ratio of 1-3:2-5:1-3. This invention reduces the environmental pollution caused by brominated flame retardants by compounding cage-type polysilsesquioxane, aluminum hypophosphite, and zinc borate into a halogen-free composite flame retardant, and effectively improves the flame retardant performance of AES engineering plastic 3D printing consumables.

[0009] Furthermore, the antioxidant is at least one of hindered phenolic antioxidants, phosphite antioxidants, and thioester antioxidants.

[0010] Furthermore, the inorganic filler is at least one of talc, calcium carbonate, nano-alumina, and nano-silica.

[0011] Furthermore, the silane coupling agent is at least one selected from γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane.

[0012] Furthermore, the functional additive is at least one of polyethylene wax, polytetrafluoroethylene wax, stearate, and silicone oil.

[0013] The 3D printing consumables of this invention, using AES resin as a base material, provide excellent mechanical properties and weather resistance. Combined with raw materials such as siloxane copolymer polycarbonate, acrylic-modified silicone resin, compatibilizers, and flame retardants, the 3D printing consumables exhibit good printing accuracy, interlayer bonding strength, heat resistance, and flame retardancy, thus enhancing their application performance. The siloxane segments, acrylic-modified silicone resin, and other raw materials work together to effectively improve the material's heat resistance and interlayer bonding strength, and help reduce printing warpage.

[0014] This invention also provides a method for preparing AES engineering plastic 3D printing consumables, comprising the following steps:

[0015] (1) Mix the raw materials evenly according to the proportion to obtain the mixture;

[0016] (2) The obtained mixture is added to an extruder for melt extrusion to obtain AES engineering plastic wire;

[0017] (3) Cool and cut the AES engineering plastic filament to obtain AES engineering plastic 3D printing consumables.

[0018] Furthermore, in step (1), AES resin, siloxane copolycarbonate, and compatibilizer are added to a mixer and stirred at 1000-1400 rpm for 5-10 minutes; then the remaining raw materials are added to the mixer and stirred at 500-1000 rpm for 5-15 minutes to obtain a mixture.

[0019] Furthermore, in step (1), the inorganic filler and the silane coupling agent are pre-mixed in a solvent, then the solvent is removed, and then the mixture is added to a mixer. The solvent is preferably, but not limited to, anhydrous ethanol.

[0020] Furthermore, in step (2), the extruder is a twin-screw extruder, and the heating temperatures of each zone of the extruder are: zone 1 180-190℃, zone 2 200-220℃, zone 3 210-220℃, and zone 4 190-200℃; the screw speed is 200-500 rpm.

[0021] The beneficial effects of this invention are as follows: By synergistically combining AES resin, siloxane copolymerized polycarbonate, acrylic-modified silicone resin, compatibilizers, flame retardants, and other raw materials, this invention prepares AES engineering plastic 3D printing consumables, which possess excellent printing accuracy, interlayer bonding strength, and heat resistance, meeting the requirements for high-precision, high-strength 3D printed parts. The preparation method of this invention is stable, easy to operate and control, and has high production efficiency, facilitating industrial production. Detailed Implementation

[0022] To facilitate understanding by those skilled in the art, the present invention will be further described below with reference to embodiments. The content mentioned in the embodiments is not intended to limit the present invention.

[0023] In some embodiments of the present invention, an AES engineering plastic 3D printing consumable comprises the following raw materials in parts by weight: 60-70 parts of AES resin, 10-15 parts of siloxane copolymer polycarbonate, 8-12 parts of acrylic modified silicone resin, 8-12 parts of compatibilizer, 5-15 parts of flame retardant, 4-10 parts of inorganic filler, 1-3 parts of silane coupling agent, 0.5-5 parts of antioxidant, and 0.5-5 parts of functional additives.

[0024] In some embodiments of the present invention, the melt flow rate (MFR) of AES resin is 8-15 g / 10 min, and the test conditions are 220°C and 2.16 kg.

[0025] In some embodiments of the present invention, at least one of maleic anhydride-grafted polyolefin elastomer, ethylene propylene diene monomer (EPDM) rubber-grafted maleic anhydride, and styrene-maleic anhydride copolymer is used.

[0026] In some embodiments of the present invention, the flame retardant is at least one of cage-type polysilsesquioxane, aluminum hypophosphite, and zinc borate.

[0027] In some embodiments of the present invention, the flame retardant is composed of cage-type polysilsesquioxane, aluminum hypophosphite and zinc borate in a weight ratio of 1-3:2-5:1-3.

[0028] In some embodiments of the present invention, the antioxidant is at least one of hindered phenolic antioxidants, phosphite antioxidants, and thioester antioxidants.

[0029] In some embodiments of the present invention, the inorganic filler is at least one selected from talc, calcium carbonate, nano-alumina, and nano-silica. The particle size of the inorganic filler is 50-100 nm.

[0030] In some embodiments of the present invention, the functional additive is at least one selected from polyethylene wax, polytetrafluoroethylene wax, stearate, and silicone oil. The stearate is calcium stearate, zinc stearate, or magnesium stearate, etc.

[0031] In some embodiments of the present invention, a method for preparing an AES engineering plastic 3D printing consumable includes the following steps:

[0032] (1) Add AES resin, siloxane copolycarbonate and compatibilizer to a mixer and stir at 1000-1400 rpm for 5-10 min; then add the remaining raw materials to the mixer and stir at 500-1000 rpm for 5-15 min to obtain a mixture; AES resin and siloxane copolycarbonate are pre-dried to reduce the moisture content to less than 0.05%;

[0033] (2) The obtained mixture is added to an extruder for melt extrusion to obtain AES engineering plastic wire;

[0034] (3) Cool and cut the AES engineering plastic filament to obtain AES engineering plastic 3D printing consumables.

[0035] Furthermore, in step (1), the inorganic filler and silane coupling agent are added to anhydrous ethanol and stirred for 20-60 minutes. The amount of anhydrous ethanol added is 1.5-4 times the sum of the mass of the inorganic filler and the coupling agent. The anhydrous ethanol is removed by heating to obtain the inorganic filler treated with silane coupling agent.

[0036] Furthermore, in step (2), the extruder is a twin-screw extruder, and the heating temperatures of each zone of the extruder are: zone 1 180-190℃, zone 2 200-220℃, zone 3 210-220℃, and zone 4 190-200℃; the screw speed is 200-500 rpm.

[0037] Example 1

[0038] In this embodiment, an AES engineering plastic 3D printing consumable includes the following raw materials in parts by weight: 65 parts AES resin, 12 parts siloxane copolymer polycarbonate, 10 parts acrylic modified silicone resin, 8 parts compatibilizer, 8 parts flame retardant, 5 parts inorganic filler, 3 parts γ-aminopropyltriethoxysilane, 2 parts antioxidant, and 2 parts functional additives.

[0039] In this embodiment, the AES used is Ningbo Longyang LYP AES-590. The siloxane copolymer polycarbonate is SABIC PC EXL9330. The acrylic-modified silicone resin is Hubei Longsheng Sihai SH-024.

[0040] Furthermore, the compatibilizer is a maleic anhydride-grafted polyolefin elastomer, specifically the Dow GR216 maleic anhydride-grafted polyolefin elastomer. The flame retardant is composed of epoxycyclohexylethyl cage-like polysilsesquioxane, aluminum hypophosphite, and zinc borate in a weight ratio of 2:3:2.

[0041] Furthermore, the antioxidant is composed of antioxidant 1076 and antioxidant 168 in a 1:1 weight ratio. The inorganic filler is composed of talc powder and nano-alumina in a 1:1 weight ratio, and the particle size of the inorganic filler is 50-100 nm. The functional additive is composed of polytetrafluoroethylene wax and dimethyl silicone oil in a 2:1 weight ratio. The polytetrafluoroethylene wax uses DuPont MP1400 powder.

[0042] In this embodiment, a method for preparing an AES engineering plastic 3D printing consumable includes the following steps:

[0043] (1) Add AES resin, siloxane copolycarbonate and compatibilizer to a mixer and stir at 1200 rpm for 10 min; then add the remaining raw materials to the mixer and stir at 500 rpm for 10 min to obtain a mixture;

[0044] (2) The obtained mixture is added to an extruder for melt extrusion to obtain AES engineering plastic wire;

[0045] (3) Cool and cut the AES engineering plastic filament to obtain AES engineering plastic 3D printing consumables. The diameter of the AES engineering plastic 3D printing consumables is 1.75mm ± 0.05mm.

[0046] Furthermore, in step (1), the inorganic filler and silane coupling agent are added to anhydrous ethanol and stirred for 30 minutes. The amount of anhydrous ethanol added is twice the sum of the mass of the inorganic filler and the coupling agent. The anhydrous ethanol is removed by heating to obtain the inorganic filler treated with silane coupling agent.

[0047] Furthermore, in step (2), the extruder is a twin-screw extruder, and the heating temperatures of each zone of the extruder are: zone 1 185℃, zone 2 205℃, zone 3 210℃, and zone 4 190℃; the screw speed is 400 rpm.

[0048] Furthermore, in step (3), the AES engineering plastic wire is air-cooled, first at 50°C for 30 minutes, then at 30°C for 30 minutes, with a wind speed of 3 m / s, and then cooled to room temperature.

[0049] Example 2

[0050] In this embodiment, an AES engineering plastic 3D printing consumable includes the following raw materials in parts by weight: 61 parts AES resin, 14 parts siloxane copolymer polycarbonate, 10 parts acrylic modified silicone resin, 10 parts compatibilizer, 8 parts flame retardant, 5 parts inorganic filler, 3 parts γ-aminopropyltriethoxysilane, 2 parts antioxidant, and 2 parts functional additives.

[0051] Furthermore, the compatibilizer is composed of maleic anhydride-grafted polyolefin elastomer and styrene-maleic anhydride copolymer in a weight ratio of 2:1. The maleic anhydride-grafted polyolefin elastomer is Dow Chemical's GR216 maleic anhydride-grafted polyolefin elastomer; the styrene-maleic anhydride copolymer is CrayValley's SMA3000P-1.

[0052] Furthermore, the flame retardant is composed of epoxycyclohexylethyl cage-like polysilsesquioxane, aluminum hypophosphite, and zinc borate in a weight ratio of 2:3:1. The inorganic filler is talc. The functional additive is composed of polytetrafluoroethylene wax and dimethyl silicone oil in a weight ratio of 2:1.

[0053] In this embodiment, a method for preparing an AES engineering plastic 3D printing consumable includes the following steps:

[0054] (1) Add AES resin, siloxane copolycarbonate and compatibilizer to a mixer and stir at 1200 rpm for 10 min; then add the remaining raw materials to the mixer and stir at 500 rpm for 10 min to obtain a mixture;

[0055] (2) The obtained mixture is added to an extruder for melt extrusion to obtain AES engineering plastic wire;

[0056] (3) Cool and cut the AES engineering plastic filament to obtain AES engineering plastic 3D printing consumables.

[0057] The rest of this embodiment is the same as that in Embodiment 1.

[0058] Example 3

[0059] In this embodiment, an AES engineering plastic 3D printing consumable includes the following raw materials in parts by weight: 70 parts AES resin, 10 parts siloxane copolymer polycarbonate, 8 parts acrylic modified silicone resin, 8 parts compatibilizer, 7 parts flame retardant, 5 parts inorganic filler, 3 parts γ-aminopropyltriethoxysilane, 2 parts antioxidant, and 2 parts functional additives.

[0060] Furthermore, the compatibilizer is a maleic anhydride-grafted polyolefin elastomer. The flame retardant is composed of epoxy cyclohexylethyl cage-like polysilsesquioxane, aluminum hypophosphite, and zinc borate in a weight ratio of 2:3:2. The inorganic filler is composed of talc and nano-silica in a weight ratio of 1:1. The functional additive is composed of polytetrafluoroethylene wax and dimethyl silicone oil in a weight ratio of 2:1.

[0061] In this embodiment, a method for preparing an AES engineering plastic 3D printing consumable includes the following steps:

[0062] (1) Add AES resin, siloxane copolycarbonate and compatibilizer to a mixer and stir at 1200 rpm for 10 min; then add the remaining raw materials to the mixer and stir at 500 rpm for 10 min to obtain a mixture;

[0063] (2) The obtained mixture is added to an extruder for melt extrusion to obtain AES engineering plastic wire;

[0064] (3) Cool and cut the AES engineering plastic filament to obtain AES engineering plastic 3D printing consumables.

[0065] The rest of this embodiment is the same as that in Embodiment 1.

[0066] Comparative Example 1

[0067] The difference between this comparative example and Example 1 is that the AES engineering plastic 3D printing consumable in this comparative example does not contain siloxane copolycarbonate, but is replaced by an equal amount of AES resin. The rest of this example is the same as that in Example 1.

[0068] Comparative Example 2

[0069] The difference between this comparative example and Example 1 is that the AES engineering plastic 3D printing consumable acrylic modified silicone resin in this comparative example does not contain acrylic modified silicone resin. The rest of this example is the same as Example 1.

[0070] Comparative Example 3

[0071] The difference between this comparative example and Example 1 is that the AES engineering plastic 3D printing consumable in this comparative example uses an equal amount of aluminum hypophosphite instead of the flame retardant in Example 1. The rest of this example is the same as Example 1.

[0072] 3D printing samples were prepared using the 3D printing consumables obtained in Example 1 and Comparative Examples 1-3. Performance tests were conducted on the samples prepared in Example 1 and Comparative Examples 1-3, and the test results are shown in Table 1 below:

[0073] project Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Melt index (g / 10min) 12.2 12.9 13.3 11.7 Tensile strength (MPa) 49.6 43.5 45.3 47.1 Interlayer bonding strength (MPa) 39.2 32.3 35.1 37.6 Heat distortion temperature (°C) 97 91 93 94 Shrinkage rate (MD, %) 0.26 0.41 0.32 0.37 Shrinkage rate (TD, %) 0.43 0.56 0.51 0.54 Flame retardancy rating V-0 V-0 V-0 V-1

[0074] The melt flow index test was conducted according to GB / T 3682-2000, with test conditions of 220℃ and 2.16kg. Tensile strength was tested according to ISO 527, with a loading rate of 50mm / min. Heat distortion temperature was tested according to GB / T 1634.2-2019, with a sample size of 80*10*4*mm and a test condition of 0.45MPa. Flame retardancy testing primarily used the UL94 standard, with a thickness of 3.2mm. The interlayer bonding strength test method was as follows: a 3D printing sample was printed using 3D printing filament with a layer thickness of 0.2mm. The nozzle temperature was 220℃, the heated bed temperature was 70℃, and the printing speed was 50mm / s. An A-shaped dumbbell-shaped tensile specimen was cut according to ISO 527, and the tensile strength in the Z-axis direction was tested, thus determining the interlayer bonding strength. The method for determining warpage performance parameters is as follows: 3D printing filament is printed into a product with dimensions of 150mm×300mm×3mm. After being placed at 23℃ and 50% RH for 24h, the shrinkage rate in the MD and TD directions is calculated respectively.

[0075] In summary, this invention prepares AES engineering plastic 3D printing consumables by compounding AES resin, siloxane copolymer polycarbonate, acrylic modified silicone resin with compatibilizers, flame retardants, and other raw materials. The synergistic effect of each raw material gives the prepared AES engineering plastic 3D printing consumables good printing accuracy, interlayer bonding strength, heat resistance, and flame retardancy, which can meet the needs of 3D printing high-precision, high-strength parts.

[0076] The specific embodiments described above are further illustrations of the technical solution and beneficial effects of the present invention, and are not intended to limit the implementation methods. For those skilled in the art, any obvious substitutions without departing from the concept of the present invention are within the protection scope of the present invention.

Claims

1. An AES engineering plastic 3D printing consumable, characterized in that: The raw materials include the following parts by weight: 60-70 parts AES resin, 10-15 parts siloxane copolymer polycarbonate, 8-12 parts acrylic modified silicone resin, 8-12 parts compatibilizer, 5-15 parts flame retardant, 4-10 parts inorganic filler, 1-3 parts silane coupling agent, 0.5-5 parts antioxidant, and 0.5-5 parts functional additives.

2. The AES engineering plastic 3D printing consumable according to claim 1, characterized in that: The compatibilizer is at least one of maleic anhydride-grafted polyolefin elastomer, EPDM-grafted maleic anhydride, and styrene-maleic anhydride copolymer.

3. The AES engineering plastic 3D printing consumable according to claim 1, characterized in that: The flame retardant is at least one of cage-type polysilsesquioxane, aluminum hypophosphite, and zinc borate.

4. The AES engineering plastic 3D printing consumable according to claim 1, characterized in that: The flame retardant is composed of cage-type polysilsesquioxane, aluminum hypophosphite and zinc borate in a weight ratio of 1-3:2-5:1-3.

5. The AES engineering plastic 3D printing consumable according to claim 1, characterized in that: The antioxidant is at least one of hindered phenolic antioxidants, phosphite antioxidants, and thioester antioxidants.

6. The AES engineering plastic 3D printing consumable according to claim 1, characterized in that: The inorganic filler is at least one of talc, calcium carbonate, nano alumina, and nano silica.

7. The AES engineering plastic 3D printing consumable according to claim 1, characterized in that: The functional additive is at least one of polyethylene wax, polytetrafluoroethylene wax, stearate, and silicone oil.

8. The method for preparing AES engineering plastic 3D printing consumables as described in any one of claims 1-7, characterized in that: Includes the following steps: (1) Mix the raw materials evenly according to the proportion to obtain the mixture; (2) The obtained mixture is added to an extruder for melt extrusion to obtain AES engineering plastic wire; (3) Cool and cut the AES engineering plastic filament to obtain AES engineering plastic 3D printing consumables.

9. The method for preparing AES engineering plastic 3D printing consumables according to claim 8, characterized in that: In step (1), AES resin, siloxane copolycarbonate and compatibilizer are added to a mixer and stirred at 1000-1400 rpm for 5-10 minutes; then the remaining raw materials are added to the mixer and stirred at 500-1000 rpm for 5-15 minutes to obtain a mixture.

10. The method for preparing AES engineering plastic 3D printing consumables according to claim 8, characterized in that: In step (2), the extruder is a twin-screw extruder, and the heating temperatures of each zone of the extruder are: zone 1 180-190℃, zone 2 200-220℃, zone 3 210-220℃, and zone 4 190-200℃; the screw speed is 200-500 rpm.