CN103980592B - A kind of high filler loading capacity micro nano powder/polymer composites for 3D printing and preparation method thereof and goods - Google Patents

Abstract

The invention relates to a high-filling micro-nano powder/polymer composite material for 3D printing and its preparation method and product. The raw materials of the material include: polymer 10-30 parts by weight, micro-nano powder 90- 70 parts by weight, 0.05-0.2 parts by weight of radiation sensitizer, and 0.01-0.02 parts by weight of antioxidant. The present invention uses micro-nano powder as the main material, and polymer resin as the binder, which is printed and shaped by 3D printing, and a radiation sensitizer is added at the same time, and the polymer resin forms a three-dimensional crosslinked network after being irradiated by electron beams. , Improve the strength, heat resistance and chemical corrosion resistance after resin bonding. The high filling amount of micro-nano powder endows the molding material with excellent mechanical properties. In addition, according to changes in the environment and needs of the product, the type of micro-nano powder can be changed to obtain materials with special functions, such as excellent electrical conductivity, thermal conductivity, flame retardancy and impact resistance, etc.

Description

A high-filling micro-nano powder/polymer composite material for 3D printing and its preparation method and product

technical field

The present invention relates to a material for 3D printing and its preparation method and product, in particular to a high-filling micro-nano powder/polymer composite material for 3D printing and its preparation method and product.

Background technique

3D printing is an emerging rapid prototyping technology. Through computer modeling, 3D model programs are set, and materials such as metal, ceramic powder or polymer are controlled by computer digital software programs by means of laser sintering, heating melting, and ultraviolet curing. The layers are built up and bonded to form a solid product. In simple terms, 3D printing can be regarded as the superposition of 2D printing technology in space. Using materials such as solid powder or polymer melt as printing "ink", through computer modeling and design, the precision and size of the product can be precisely controlled. Compared with the traditional molding technology, this printing technology does not require complicated molds and processes, the equipment is compact, the program is controlled by a computer, and the operation is simple. Therefore, it has received more and more attention, and it is gradually used in biology, medicine, construction, aviation, etc. The field has opened up a broad application space, especially suitable for hollow parts with small batches, individualization and complex structures.

Currently, the most commonly used polymer materials for 3D printing are nylon, ABS, polycarbonate, and polyphenylene sulfone, etc. These materials require high temperature when molding, not only the molding speed is slow, but also the finished product has excellent properties such as strength and toughness. Poor. In contrast, the development of other 3D printing materials is very rare, which also limits the practicability and universality of 3D printing. Therefore, it is very important to develop new 3D printing materials to make up for the deficiencies of the above materials.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies of the above-mentioned prior art and provide a high-filling micro-nano powder/polymer composite material for 3D printing.

Another object of the present invention is to provide a method for preparing the above-mentioned composite material.

Another object of the present invention is to provide a product prepared from the above-mentioned high-filling micro-nano powder/polymer composite material for 3D printing, which has high strength and special functions.

The fourth object of the present invention is to provide a method for preparing the above-mentioned product.

The fifth object of the present invention is to provide a use of the above-mentioned composite material.

To achieve the above object, the present invention adopts the following technical solutions:

A high-filling micro-nano powder/polymer composite material for 3D printing, the material uses the micro-nano powder as the main raw material, polymer resin as the binder, the raw material of the material and its content (weight parts) include:

90-70 parts of micro-nano powder,

10-30 parts of polymer resin,

Radiation sensitizer 0.05-0.2 part.

According to the present invention, the composite material is prepared by a method including mixing of raw materials and extruding and granulating with a screw extruder.

The micro-nano powder in the present invention refers to particulate matter with a particle diameter between 1 nanometer and 100 micrometers. Preferably, the micro-nano powder is an inorganic micro-nano powder; more preferably, the inorganic micro-nano powder is selected from metal elemental powder, metal oxide powder, non-metal elemental powder, silver halide powder , one or more of carbonate powder, phosphate powder, silicate powder and clay powder. Preferably, the particle size of the micro-nano powder is between 50 nm and 10 μm.

Preferably, the micro-nano powder is a micro-nano powder modified by a surface modifier.

Preferably, the surface modifier is selected from one or more of dopamine and silane coupling agents, such as KH550, KH560, KH570, KH792 or DL602.

According to the present invention, said polymer resin is a thermoplastic resin. Described thermoplastic resin is selected from polyolefin (PE, PP, PVC, PS), polyamide (PA), polycarbonate (PC), polyoxymethylene (POM), ethylene-vinyl acetate copolymer (EVA), polyester ( PET, PBT, PCL, PLA), acrylonitrile-styrene-butadiene copolymer (ABS), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-benzene One or more of ethylene block copolymer (SIS), styrene-butadiene transparent impact resin (K resin), polyacrylate.

According to the invention, the polymeric resin selected has a melt index greater than at least 10.

According to the present invention, the radiation sensitizer is selected from triallyl cyanurate, triallyl isocyanurate, trimethacryl isocyanate, trimethylolpropane trimethacrylate, three Methylolpropane Triacrylate, Triallyl Trimellitate, Diallyl Isocyanate, Dipropylene Isophthalate, Bismaleimide, Triethylene Glycol Dimethacrylate, Dimethyl One or more of diethylene glycol acrylate.

According to the present invention, also include in the described raw material:

Antioxidant 0.01-0.02 part.

According to the present invention, the antioxidant is hindered phenolic antioxidant and/or phosphite auxiliary antioxidant. Preferably, selected from antioxidant 1010: tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester; antioxidant 1096: IRGANOXB-1096; primary antioxidant 1098 : (N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine) and phosphite antioxidant intercompatibility; and antioxidant Agent 168: one or more of tris[2,4-di-tert-butylphenyl]phosphite.

According to the present invention, the raw material of described material and content (weight part) thereof are:

90-70 parts of micro-nano powder,

10-30 parts of polymer resin,

Radiation sensitizer 0.05-0.2 part,

Antioxidant 0.01-0.02 part.

The present invention also provides the following technical solutions:

The preparation method of the high-filling micro-nano powder/polymer composite material for 3D printing includes the steps of mixing raw materials and extruding and granulating with a screw extruder.

According to the present invention, the method specifically includes:

1) Modification of micro-nano powder;

2) mixing of each raw material;

3) Extrude and granulate with a screw extruder.

According to the present invention, the above step 1) is specifically: surface modifying 100 parts by weight of the micro-nano powder with 5-20 parts of the surface modifying agent in a solution.

According to the present invention, the step 2) is specifically: 10-30 parts by weight of polymer resin, 90-70 parts of modified micro-nano powder, 0.05-0.2 parts of radiation sensitizer, 0.01- 0.02 parts of antioxidant are mixed evenly at room temperature, and sent to a twin-screw extruder with an aspect ratio of 36 for extrusion and granulation. The extruder speed is 20-100r/min, and the temperature range of each section of the extruder It is: feeding section 150-170°C, melting section 190-200°C, mixing section 190-200°C, exhaust section 170-190°C, homogenizing section 160-180°C.

The present invention also provides following technical scheme:

A product, which is produced by 3D printing from the above-mentioned high-filling micro-nano powder/polymer composite material for 3D printing.

The preparation method of the above product includes the step of 3D printing the above-mentioned high-filling micro-nano powder/polymer composite material for 3D printing.

According to the present invention, the steps specifically include:

The pellets of the composite material are added to the nozzle of the 3D printer, heated and melted in the nozzle, the nozzle moves along the section profile of the part and the filling trajectory, and at the same time extrudes the molten material, which solidifies rapidly after extrusion under computer control, and Irradiation with electron beams cross-links the material and builds up the shape in layers.

According to the present invention, the irradiation parameters are specifically: the energy of the electron accelerator is 0.3-5 MeV, the power is 50-150KW, and the irradiation dose is 5-20KGy.

A use of the above-mentioned high-filling micro-nano powder/polymer composite material for 3D printing, which is used for 3D printing.

The outstanding features of the present invention are:

1. The micro-nano powder in the composite material of the present invention has been chemically modified to effectively enhance the interaction between the powder and the polymer resin.

2. In the preparation process of the composite material of the present invention, the polymer resin forms a three-dimensional cross-linked network through electron irradiation technology, which improves the thermal stability and chemical corrosion resistance of the resin, and further improves the performance of the composite material.

3. The composite material of the present invention has many of the above-mentioned excellent properties, and is especially suitable as a material for 3D printing. The prepared product has excellent hardness, dimensional stability, and heat resistance. According to the difference of filling micro-nano powder, at the same time It can have special functions such as electrical conductivity, thermal conductivity, flame retardancy, wear resistance, and gas barrier properties.

detailed description

The present invention will be further described in detail through specific embodiments below, but it should not be understood that the scope of the present invention is limited to the following examples. Without departing from the above-mentioned method idea of the present invention, various replacements or changes made according to common technical knowledge and customary means in this field shall be included in the scope of the present invention.

Example 1

A high-filling micro-nano powder/polymer composite material for 3D printing

1) Mix 100 parts by weight of 500nmAg powder and 5 parts of dopamine in 200 parts of Tris buffer (pH8.5), react for 24 hours, and dry at 70°C after repeated washing.

2) 10 parts by weight of PE (melt index 11.5), 90 parts of modified Ag powder, 0.05 parts of radiation sensitizer triallyl cyanurate, 0.02 parts of antioxidant 1010 in Mix uniformly at room temperature, and send into a twin-screw extruder with an aspect ratio of 36 for extrusion and granulation (referred to as pellet A). Among them, the extruder speed is 20r/min, and the temperature range of each section of the extruder is: feeding section 150-170°C, melting section 190-200°C, mixing section 190-200°C, exhaust section 170-190°C, The homogenization section is 160-180°C.

Example 2

A kind of 3D printing product that the composite material of embodiment 1 makes

The pellet A obtained in Example 1 is added to the nozzle of the 3D printer, heated and melted in the nozzle, the nozzle moves along the section profile of the part and the filling track, and the molten material is extruded at the same time, utilizing the thermal melting and bonding properties of the material It is solidified rapidly after extrusion under computer control, and irradiated with electron beams (electron accelerator energy is 0.5MeV, power is 50KW, and irradiation dose is 5KGy), so that the material is cross-linked and formed layer by layer.

The resulting 3D printed articles have excellent hardness, dimensional stability and electrical conductivity.

Example 3

A high-filling micro-nano powder/polymer composite material for 3D printing

1) Mix 100 parts by weight of 500nm Al ₂ O ₃ powder and 10 parts of silane coupling agent KH550 in 200 parts of water, react at 60°C for 24 hours, wash several times and then dry at 70°C.

2) 15 parts by weight of PP (melt index 12.2), 85 parts of modified Al ₂ O ₃ powder, 0.1 part of radiation sensitizer triallyl isocyanurate, 0.01 part of anti- The oxygen agent 1096 was uniformly mixed at room temperature, and then sent to a twin-screw extruder with an aspect ratio of 36 for extrusion and granulation (referred to as pellet B). Among them, the speed of the extruder is 40r/min, and the temperature range of each section of the extruder is: feeding section 150-170°C, melting section 190-200°C, mixing section 190-200°C, exhaust section 170-190°C, The homogenization section is 160-180°C.

Example 4

A kind of 3D printing product that the composite material of embodiment 3 makes

The pellet B obtained in Example 3 is added to the nozzle of the 3D printer, heated and melted in the nozzle, the nozzle moves along the section profile of the part and the filling track, and the molten material is extruded at the same time, utilizing the thermal melting and bonding properties of the material It is solidified rapidly after extrusion under computer control, and irradiated with electron beams (electron accelerator energy is 0.75MeV, power is 75KW, and radiation dose is 10KGy), so that the material is cross-linked and formed layer by layer.

The resulting 3D printed articles have excellent mechanical strength, dimensional stability and thermal conductivity.

Example 5

A high-filling micro-nano powder polymer composite material for 3D printing

1) Mix 100 parts by weight of 1 μm CaCO ₃ powder and 15 parts of silane coupling agent KH560 in 200 parts of water, react at 60°C for 24 hours, wash several times and dry at 70°C.

2) 20 parts by weight of PA (melt index 10.5), 80 parts _of modified CaCO Powder, 0.2 part of radiation sensitizer trimethylolpropane trimethacrylate, 0.01 part of antioxidant Agent 1098 was mixed uniformly at room temperature, and then sent to a twin-screw extruder with an aspect ratio of 36 for extrusion and granulation (referred to as pellet C). Among them, the extruder speed is 60r/min, and the temperature range of each section of the extruder is: feeding section 150-170°C, melting section 190-200°C, mixing section 190-200°C, exhaust section 170-190°C, The homogenization section is 160-180°C.

Example 6

A kind of 3D printing product that the composite material of embodiment 5 makes

The pellet C obtained in Example 5 is added to the nozzle of the 3D printer, heated and melted in the nozzle, the nozzle moves along the section profile of the part and the filling track, and the molten material is extruded at the same time, utilizing the thermal melting and bonding properties of the material It is solidified rapidly after extrusion under computer control, and irradiated with electron beams (electron accelerator energy is 1MeV, power is 100KW, and irradiation dose is 15KGy), so that the material is cross-linked and formed layer by layer.

The resulting 3D printed articles have excellent mechanical strength, dimensional stability and heat resistance.

Example 7

A high-filling micro-nano powder polymer composite material for 3D printing

1) Mix 100 parts by weight of 4μm ZrO ₂ powder and 20 parts of silane coupling agent KH570 in 200 parts of water, react at 60°C for 24 hours, wash several times and dry at 70°C.

₂ ) 25 parts by weight of PC (melt index 15), 75 parts of modified ZrO powder, 0.05 part of radiation sensitizer trimethylolpropane trimethacrylate, 0.01 part of antioxidant Agent 168 was uniformly mixed at room temperature, and sent into a twin-screw extruder with an aspect ratio of 36 for extrusion and granulation (referred to as pellet D). Among them, the speed of the extruder is 80r/min, and the temperature range of each section of the extruder is: feeding section 150-170°C, melting section 190-200°C, mixing section 190-200°C, exhaust section 170-190°C, The homogenization section is 160-180°C.

Example 8

A kind of 3D printing product that the composite material of embodiment 7 makes

The pellet D obtained in Example 7 is added to the nozzle of the 3D printer, heated and melted in the nozzle, the nozzle moves along the section profile of the part and the filling track, and the molten material is extruded at the same time, utilizing the thermal melting and bonding properties of the material After being extruded under computer control, it is rapidly solidified, and irradiated with electron beams (electron accelerator energy is 1.5MeV, power is 125KW, and radiation dose is 20KGy), so that the material is cross-linked and layered into layers.

The obtained 3D printed products have excellent mechanical strength, dimensional stability, heat resistance and wear resistance.

Example 9

A high-filling micro-nano powder polymer composite material for 3D printing

1) Mix 100 parts by weight of 10 μm montmorillonite powder and 20 parts of silane coupling agent KH792 in 200 parts of water, react at 60°C for 24 hours, wash several times and dry at 70°C.

2) With 30 parts by weight of EVA (melt index 20.3), 70 parts of modified montmorillonite powder, 0.05 part of radiation sensitizer trimethylolpropane trimethacrylate, 0.02 part of anti- The oxygen agent 168 was uniformly mixed at room temperature, and sent into a twin-screw extruder with an aspect ratio of 36 for extrusion and granulation (referred to as pellet E). Among them, the speed of the extruder is 100r/min, and the temperature range of each section of the extruder is: feeding section 150-170°C, melting section 190-200°C, mixing section 190-200°C, exhaust section 170-190°C, The homogenization section is 160-180°C.

Example 10

A kind of 3D printing product that the composite material of embodiment 9 makes

The pellet E obtained in Example 9 is added to the nozzle of the 3D printer, heated and melted in the nozzle, the nozzle moves along the section profile of the part and the filling track, and the molten material is extruded at the same time, utilizing the thermal melting and bonding properties of the material It is solidified rapidly after extrusion under computer control, and irradiated with electron beams (electron accelerator energy is 2MeV, power is 150KW, and irradiation dose is 5KGy), so that the material is cross-linked and formed layer by layer.

The resulting 3D printed articles have excellent mechanical strength, dimensional stability and flame retardancy.

Example 11

A high-filling micro-nano powder polymer composite material for 3D printing

1) Mix 100 parts by weight of 10 μm lithium powder and 15 parts of silane coupling agent DL602 in 200 parts of water, react at 60°C for 24 hours, wash several times and then dry at 70°C.

2) 10 parts by weight of ABS (melt index 14.5), 90 parts of modified lithium powder, 0.05 part of radiation sensitizer trimethylolpropane trimethacrylate, 0.02 part of anti The oxygen agent 168 was uniformly mixed at room temperature, and sent into a twin-screw extruder with an aspect ratio of 36 for extrusion and granulation (referred to as pellet F). Among them, the speed of the extruder is 100r/min, and the temperature range of each section of the extruder is: feeding section 150-170°C, melting section 190-200°C, mixing section 190-200°C, exhaust section 170-190°C, The homogenization section is 160-180°C.

Example 12

A kind of 3D printing product that the composite material of embodiment 11 makes

The pellets F obtained in Example 11 are added to the nozzle of the 3D printer, heated and melted in the nozzle, and the nozzle moves along the cross-sectional profile of the part and the filling track, and at the same time extrudes the melted material, utilizing the heat-melting and bonding properties of the material It is solidified rapidly after extrusion under computer control, and irradiated with electron beams (electron accelerator energy is 2MeV, power is 150KW, and irradiation dose is 5KGy), so that the material is cross-linked and formed layer by layer.

The resulting 3D printed articles have excellent mechanical strength, dimensional stability and flame retardancy.

Example 13

A high-filling micro-nano powder polymer composite material for 3D printing

With 10 parts by weight of ABS (melt index 14.5), 90 parts of lithium powder, 0.05 parts of radiation sensitizer trimethylolpropane trimethacrylate, 0.02 parts of antioxidant 168 at room temperature Mix evenly, send into the twin-screw extruder that length-to-diameter ratio is 36 extrusion granulation (recorded as pellet F1). Among them, the speed of the extruder is 100r/min, and the temperature range of each section of the extruder is: feeding section 150-170°C, melting section 190-200°C, mixing section 190-200°C, exhaust section 170-190°C, The homogenization section is 160-180°C.

Example 14

A kind of 3D printing product that the composite material of embodiment 13 makes

The pellets F obtained in Example 11 are added to the nozzle of the 3D printer, heated and melted in the nozzle, and the nozzle moves along the cross-sectional profile of the part and the filling track, and at the same time extrudes the melted material, utilizing the heat-melting and bonding properties of the material It is solidified rapidly after extrusion under computer control, and irradiated with electron beams (electron accelerator energy is 2MeV, power is 150KW, and irradiation dose is 5KGy), so that the material is cross-linked and formed layer by layer.

The obtained 3D printed product has excellent mechanical strength (slightly lower than that of the product of Example 12), dimensional stability and flame retardancy.

Claims (21)

1. A product, which is made by 3D printing of a high-filling micro-nano powder/polymer composite material for 3D printing; The high-filling micro-nano powder/polymer composite material for 3D printing uses micro-nano powder as the main raw material, and polymer resin as the binder. The raw materials and contents of the material include: 90-70 parts by weight of micro-nano powder, 10-30 parts by weight of polymer resin, Radiation sensitizer 0.05-0.2 weight part. 2. The product according to claim 1, characterized in that the composite material is produced by a method comprising mixing of raw materials and extruding and granulating with a screw extruder. 3. The product according to claim 1 or 2, characterized in that, the micro-nano powder refers to a particle size between 1 nanometer and 100 microns; the micro-nano powder is an inorganic micro-powder Nano powder. 4. The product according to claim 3, wherein the inorganic micro-nano powder is selected from metal elemental powder, metal oxide powder, non-metal elemental powder, silver halide powder, carbonate powder One or more of powder, phosphate powder, silicate powder and clay powder; the particle size of the micro-nano powder is between 50nm and 10μm. 5. The product according to claim 3, wherein the micro-nano powder is a micro-nano powder modified by a surface modifier. 6. The product according to claim 5, wherein the surface modifier is selected from one or more of dopamine and silane coupling agents, and the silane coupling agent is selected from KH550, KH560, KH570, KH792 or DL602. 7. The product according to claim 1 or 2, wherein the polymer resin is a thermoplastic resin; the thermoplastic resin is selected from polyolefin, polyamide, polycarbonate, polyoxymethylene, ethylene-vinyl acetate Copolymer, polyester, acrylonitrile-styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene transparent One or more of impact-resistant resin and polyacrylate. 8. The article of claim 7, wherein the polyolefin is selected from PE, PP or PVC, and the polyester is selected from PET, PBT, PCL or PLA. 9. The article of claim 1 or 2, wherein the selected polymeric resin has a melt index greater than at least 10. 10. The product according to claim 1 or 2, wherein the radiation sensitizer is selected from triallyl cyanurate, triallyl isocyanurate, trimethacryl isocyanate , trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, triallyl trimesate, diallyl isocyanate, dipropylene isophthalate, bismaleimide , one or more of triethylene glycol dimethacrylate, diethylene glycol dimethacrylate. 11. The product according to claim 1 or 2, characterized in that, the raw materials also include: Antioxidant 0.01-0.02 parts. 12. The product according to claim 11, wherein the antioxidant is a hindered phenolic antioxidant and/or a phosphite auxiliary antioxidant. 13. The product according to claim 12, wherein the antioxidant is selected from antioxidant 1010: tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] Pentaerythritol ester; Antioxidant 1096: IRGANOXB-1096; Primary antioxidant 1098: (N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanedi Amine) and phosphite antioxidant intercomplexes; and antioxidant 168: one or more of tris[2,4-di-tert-butylphenyl]phosphite. 14. The product according to claim 1 or 2, characterized in that, the raw materials and contents thereof are: 15. The method for preparing the product according to any one of claims 1 to 14, wherein the high-filling micro-nano powder/polymer composite material for 3D printing is prepared by a method comprising the following steps: The steps of mixing raw materials and extruding and granulating with a screw extruder. 16. The preparation method according to claim 15, characterized in that, the preparation method of the material specifically comprises: 1) Modification of micro-nano powder; 2) Mixing of each raw material; 3) Extrude and granulate with a screw extruder. 17. The preparation method according to claim 16, characterized in that the above step 1) is specifically: surface modifying 100 parts by weight of the micro-nano powder with 5-20 parts of a surface modifier in a solution sex; The steps 2) and 3) are specifically: 10-30 parts by weight of polymer resin, 90-70 parts of modified micro-nano powder, 0.05-0.2 parts of radiation sensitizer, 0.01-0.02 The antioxidant of one part is mixed evenly at room temperature, and is sent into the twin-screw extruder that aspect ratio is 36 to extrude granulation, and extruder rotating speed is 20-100r/min, and the temperature range of each section of extruder is : The feeding section is 150-170°C, the melting section is 190-200°C, the mixing section is 190-200°C, the exhaust section is 170-190°C, and the homogenization section is 160-180°C. 18. The preparation method of the product according to any one of claims 1-14, comprising the step of 3D printing the high-filling micro-nano powder/polymer composite material for 3D printing. 19. The preparation method according to claim 18, wherein said steps specifically comprise: The pellets of the composite material are added to the nozzle of the 3D printer, heated and melted in the nozzle, the nozzle moves along the section profile of the part and the filling trajectory, and at the same time extrudes the molten material, which solidifies rapidly after extrusion under computer control, and Irradiation with electron beams cross-links the material and builds up the shape in layers. 20. The preparation method according to claim 19, characterized in that the parameters of the irradiation are specifically: electron accelerator energy of 0.3-5 MeV, power of 50-150KW, and irradiation dose of 5-20KGy. 21. Use of the high-filling micro-nano powder/polymer composite material for 3D printing in the article according to any one of claims 1 to 14, which is used for 3D printing.