MATERIAL FOR 3D PRINTING, PROCESS FOR PREPARING THE SAME AND ARTICLE THEREOF

Abstract

The present invention provides a composition for 3D printing, a process for preparing the same and an article thereof. By the solidifying method of UV irradiation, 3D printing is implemented. During said implementation, there is no need of high temperature heating, thus energy consumption is reduced, and there is no need for special solvent, thus harm to the environment is reduced. Meanwhile, the present invention uses micro-nano powder as the main material and polymer resin as adhesive, and at the same time, adds irradiation sensitizer. After electron beam irradiation, the polymer resin forms three-dimensional crosslinked network, thereby the strength, heat resistance and chemical resistance are improved after resin adhesion. Additionally, the present invention, by the addition of UV crosslinking agent, and by UV irradiation, cross-links the unsaturated resin after extrusion in 3D printing to form three-dimensional network structure, thus greatly improves the heat resistance, chemical resistance and mechanical strength of the shaping material, and makes the unsaturated resin have broader application prospects in 3D printing material.

Claims

1. A composition for 3D printing comprising the following components: photosensitive monomer: 100 parts by weight, photoinitiator: 1 to 3 parts by weight, micro-nano powder: 1 to 30 parts by weight, crosslinking agent: 1 to 30 parts by weight, toughening agent: 1 to 10 parts by weight, and pigment: 5 to 10 parts by weight; wherein the photosensitive monomer is monofunctional acrylate which is in liquid state at room temperature.

2. The composition according to claim 1, wherein the monofunctional acrylate which is in liquid state at room temperature is one or more selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, benzyl methacrylate, lauryl methacrylate and acrylate derivatives; preferably, the photoinitiator is alkylphenones, the alkylphenone is one or more selected from the group consisting of α,α-diethoxyacetophenone, α-hydroxyalkylphenone, and α-aminoalkylphenone; the micro-nano powder refers to a particulate matter having a particle size between 1 nm and 100 μm, preferably, the micro-nano powder is one or more selected from the group consisting of inorganic micro-nano powder and organic-inorganic hybrid micro-nano powder, preferably, the inorganic micro-nano powder is one or more selected from the group consisting of metal particles, metal oxide particles, non-metallic particles, silver halide particles, carbonate particles, and phosphate particles, preferably, the organic-inorganic hybrid micro-nano powder has a shell structure or an asymmetric structure; further preferably, the micro-nano powder has a particle size between 50 nm and 10 μm; preferably, the micro-nano powder is a micro-nano powder modified by a surface modifier; and preferably, the surface modifier is one or more selected from the group consisting of dopamine and silane coupling agents such as KH550, KH560, KH570, KH792 or DL602.

3. The composition according to claim 1, wherein the crosslinking agent is a multifunctional acrylate; preferably, the multifunctional acrylate is one or more selected from the group consisting of bifunctional crosslinking agents (such as diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, etc.), and trifunctional crosslinking agents (such as trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, etc.); preferably, the toughening agent is a liquid polysulfide rubber; and preferably, the pigment is an inorganic color pigment, more preferably, the inorganic color pigment is one or more selected from the group consisting of chromate pigments (such as lead chrome yellow, molybdenum chrome orange, etc.), cadmium pigments (such as cadmium yellow, cadmium red, etc.), iron pigments (such as iron yellow, iron red, etc.), green pigments (such as chrome green, chromium oxide green, etc.) and blue pigments (such as iron blue, ultramarine, etc.).

4. A process for preparing the composition for 3D printing according to claim 1, comprising the steps of mixing the various components; preferably, specifically comprising the following steps: 1) mixing 100 parts by weight of a photosensitive monomer, 1 to 30 parts by weight of a micro-nano powder, 1 to 30 parts by weight of a crosslinking agent and 5 to 10 parts by weight of a pigment; and 2) mixing the mixture obtained in step 1) with 5 to 10 parts by weight of a toughening agent, and 1 to 3 parts by weight of a photoinitiator; wherein, preferably, both of the mixing operations are carried out at room temperature (20 to 40° C.); preferably, the mixing in step 1) is carried out sufficiently by mechanical stirring at a rotational speed of 1000 to 4000 rpm for 1 to 2 hours; and preferably, step 2) is the step of sufficiently mixing for 1 to 2 hours at a rotational speed of 1000 to 4000 rpm under dark condition.

5. A high filling level micro-nano powder/polymer composite material for 3D printing using a micro-nano powder as the main raw material and a polymer resin as adhesive, having the following raw materials and their contents (parts by weight): micro-nano powder: 90 to 70 parts, polymer resin: 10 to 30 parts, and irradiation sensitizer: 0.05 to 0.2 parts; wherein, preferably, the composite material is prepared by a process comprising the mixing of raw materials and extrusion pelletization by a screw extruder; preferably, the micro-nano powder refers to a particulate matter having a particle size between 1 nm and 100 μm; preferably, the micro-nano powder is an inorganic micro-nano powder; and more preferably, the inorganic micro-nano powder is one or more selected from the group consisting of metal powder, metal oxide powder, non-metallic powder, silver halide powder, 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 one or more selected from the group consisting of dopamine and silane coupling agents such as KH550, KH560, KH570, KH792 or DL602; preferably, the polymer resin is a thermoplastic resin; more preferably, the thermoplastic resin is one or more selected from the group consisting of polyolefins (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-styrene block copolymer (SIS), butadiene-styrene transparent impact resin (K resin), and polyacrylate; preferably, the selected polymer resin has a melt index of at least greater than 10; and preferably, the radiation sensitizer is one or more selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, trimethallyl isocyanurate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, triallyl 1,3,5-benzenetricarboxylate, diallyl isocyanate, dially isophthalate, bismaleimide, triethylene glycol dimethacrylate, and diethylene glycol dimethacrylate.

6. The high filling level micro-nano powder/polymer composite material for 3D printing according to claim 5, characterized in that the raw materials further comprise: Antioxidant: 0.01-0.02 parts; preferably, the antioxidant is a hindered phenolic antioxidant and/or a phosphite auxiliary antioxidant; more preferably it is one or more selected from the group consisting of antioxidant 1010: pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]; antioxidant 1096: IRGANOX B-1096; coordinated compound of main antioxidant 1098: 3,3′-bis(3,5-di-tert-butyl-4-hydroxyphenyl)-N,N′-hexamethylenedipropionamide with phosphite antioxidant; and antioxidant 168: tris [2,4-di-tert-butylphenyl] phosphite; preferably, the raw materials of the material and their contents (parts by weight) are: micro-nano powder: 90 to 70 parts, polymer resin: 10 to 30 parts, irradiation sensitizer: 0.05 to 0.2 parts, and antioxidant: 0.01 to 0.02 parts.

7. A process for preparing the high filling level micro-nano powder/polymer composite material for 3D printing according to claim 5, comprising the steps of mixing of raw materials and extrusion pelletization by a screw extruder; preferably, specifically comprising: 1) modifying the micro-nano powder; 2) mixing the various raw materials; and 3) extruding and pelletizing by a screw extruder; wherein, preferably, the above step 1) specifically comprises subjecting 100 parts by weight of the micro-nano powder to surface modification with 5 to 20 parts of the surface modifier in solution; preferably, the step 2) is specifically: uniformly mixing 10 to 30 parts by weight of a polymer resin, 90 to 70 parts of modified micro-nano powder, 0.05 to 0.2 parts of a radiation sensitizer, and 0.01 to 0.02 parts of an antioxidant at room temperature, and feeding the mixture to a twin-screw extruder having an aspect ratio of 36 for extrusion pelletization, wherein the rotational speed of the extruder is 20 to 100 r/min, the temperature ranges of the various sections of the extruder are: feeding section 150 to 170° C., melting section 190 to 200° C., mixing section 190 to 200° C., exhaust section 170 to 190° C., and homogenization section 160 to 180° C.; preferably, the step specifically comprises: feeding the pellets of the composite material to the head of the 3D printer, heating and melting the pellets in the head, moving the head along the sectional profile and the filling path of the part while at the same time extruding the melted material, rapidly solidifying the melted material after extrusion under computer control and irradiating it using electron beam, to crosslink the material, and forming shape by accumulation layer by layer; and more preferably, the electron accelerator energy is 0.3 to 5 MeV, the power is 50 to 150 KW, and the irradiation dose is 5 to 20 KGy.

8. A UV radiation crosslinked polymer composition for 3D printing comprising the following main components: unsaturated resin: 100 parts by weight, and UV crosslinking agent: 0.5 to 5 parts by weight, wherein the unsaturated resin is selected from monofunctional or multifunctional ethylenically unsaturated polymers having a molecular weight of from 3,000 to 100,000, and having a melting point (or softening flow temperature) between 100 and 350° C.; wherein the UV crosslinking agent is a C3 or higher compound containing two or more terminal mercapto groups; preferably, the monofunctional or multifunctional ethylenically unsaturated polymer is one or more selected from the group consisting of polyolefins (such as PE, PP, PVC, PS, PB, etc.), polyalkynes (such as polyacetylene, polypropyne, etc.), unsaturated polyamides, unsaturated polycarbonates, unsaturated polyesters, ABS resins, and bicomponent or multicomponent copolymers of polyunsaturated olefins (such as butadiene, isoprene, etc.) and other olefinic monomers (such as styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS) and butadiene-styrene transparent impact resin (K resin)); and preferably, the UV crosslinking agent includes, but is not limited to, pentaerythritol tetramercaptoacetate, 4′,4-dimercaptodiphenyl sulfide, 2,5-dimercaptothiadiazole, trithiocyanuric acid or their homologues and derivatives, as well as combinations of the above compounds in any ratio.

9. The UV radiation crosslinked polymer composition according to claim 8, characterized in that the composition further comprises an aid for enhancing the printing effect without affecting its main function, specifically including: Antioxidant: 0.1-0.5 parts by weight, Powder: 1-20 parts by weight, Pigment: 0-10 parts by weight, and other aids: 0-5 parts by weight; preferably, the antioxidant is one or more selected from the group consisting of antioxidant 1010, antioxidant 1096, coordinated compound of main antioxidant 1098 and phosphite antioxidant and antioxidant 168, wherein, antioxidant 1010 refers to: pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]; antioxidant 1096 refers to: IRGANOX B-1096; main antioxidant 1098 refers to: 3,3′-bis(3,5-di-tert-butyl-4-hydroxyphenyl)-N,N′-hexamethylenedipropionamide; and antioxidant 168 refers to: tris [2,4-di-tert-butylphenyl] phosphite; the powder is preferably a particulate material having a particle size between 1 nm and 100 μm (also referred to as micro-nano particles); preferably, the powder is one or more selected from the group consisting of inorganic micro-nano particles, organic polymer micro-nano particles and organic-inorganic hybrid micro-nano particles; preferably, the inorganic micro-nano particles are one or more selected from the group consisting of metal micro-nano particles (such as silver, gold, iron, platinum particles, etc.), metal oxide micro-nano particles (such as Fe.sub.3O.sub.4, TiO.sub.2, Cu.sub.2O, ZnO, CdS particles, etc.), non-metallic micro-nano particles (such as carbon, silicon particles, etc.), silver halide micro-nano particles (such as AgCl, AgBr particles, etc.), carbonate micro-nano particles (such as CaCO.sub.3, BaCO.sub.3 particles, etc.) and phosphate micro-nano particles (such as LiFePO.sub.4 particles, etc.); preferably, the organic polymer micro-nano particles are one or more selected from the group consisting of polystyrene, polypropylene, polytetrafluoroethylene, ABS, epoxy resins, and other micro-nano particles; preferably, the organic-inorganic hybrid micro-nano particles have one or more of a core-shell structure or an asymmetric structure, such as PS @ Fe.sub.3O.sub.4, PS @ Dopa @ Ag, etc.; preferably, the pigment is an inorganic color pigment; the inorganic color pigment is preferably one or more selected from the group consisting of chromate pigments (such as lead chrome yellow, molybdenum chrome orange, etc.), cadmium pigments (such as cadmium yellow, cadmium red, etc.), iron pigments (such as iron yellow, iron red, etc.), green pigments (such as chrome green, chromium oxide green, etc.) and blue pigments (such as iron blue, ultramarine, etc.); and preferably, the other aid is an aid suitable for composition for 3D printing, such as inhibitor (mainly for preventing the material from being ineffective due to polymerization during storage and transportation), etc.

10. A UV radiation crosslinked polymer material for 3D printing, which is prepared from the UV radiation crosslinked polymer composition for 3D printing according to claim 8; wherein, preferably, the material is prepared by a process comprising the following steps: uniformly mixing 100 parts by weight of an unsaturated resin, 0.5 to 5 parts by weight of a UV crosslinking agent and optionally 0.1 to 0.5 parts by weight of an antioxidant, 1 to 20 parts by weight of a powder, 0 to 10 parts by weight of a pigment and 0-5 parts by weight of other aids, and extruding into filaments; preferably, the mixing is carried out with a single screw extruder.

11. A process for preparing the UV radiation crosslinked polymer material for 3D printing according to claim 3, comprising the following steps: uniformly mixing 100 parts by weight of an unsaturated resin, 0.5 to 5 parts by weight of a UV crosslinking agent and optionally 0.1 to 0.5 parts by weight of an antioxidant, 1 to 20 parts by weight of a powder, 0 to 10 parts by weight of a pigment and 0 to 5 parts by weight of other aids, and extruding into filaments; preferably, characterized in that the process comprises following the steps: uniformly mixing 100 parts by weight of an unsaturated resin, 0.5 to 5 parts by weight of a UV crosslinking agent, 0.1 to 0.5 parts by weight of an antioxidant, 1 to 20 parts by weight of a powder, 0 to 10 parts by weight of a pigment and 0-5 parts by weight of other aids with a single screw extruder, and extruding into filaments.

12. -14. (canceled)

Description

EXAMPLE 1.1

A 3D Printing Article A

[0127] 1) 100 parts by weight of methyl methacrylate, 10 parts of nano CaCO.sub.3 powder, 10 parts of diethylene glycol dimethacrylate and 5 parts of iron blue were mixed at a rotational speed of 2000 rpm for 1 hour at room temperature;

[0128] 2) the mixture obtained in step 1) was mixed with 1 part of liquid polysulfide rubber and 1 part of α,α-diethoxyacetophenone at a rotational speed of 2000 rpm for 1 hour at room temperature under dark condition; and

[0129] 3) the mixture obtained in step 2) was printed using a PROJET 1200 type SLA 3D printer through CAD program control, and solidified by UV at room temperature to form shape, to thereby obtain article A.

[0130] The article A was blue. The addition of nano CaCO.sub.3 powder endowed the article with excellent dimensional stability, and significantly improved strength and toughness.

EXAMPLE 1.2

A 3D Printing Article B

[0131] 1) 100 parts by weight of ethyl methacrylate, 15 parts of nano Ag powder, 10 parts of diethylene glycol dimethacrylate and 5 parts of iron blue were mixed at a rotational speed of 2000 rpm for 1 hour at room temperature;

[0132] 2) the mixture obtained in step 1) was mixed with 5 parts of liquid polysulfide rubber and 2 parts of α-hydroxyalkylphenone at a rotational speed of 2000 rpm for 1 hour at room temperature under dark condition; and

[0133] 3) the mixture obtained in step 2) was printed using a PROJET 1200 type SLA 3D printer through CAD program control, and solidified by UV at room temperature to form shape, to thereby obtain article B.

[0134] The article B was blue. The addition of nano Ag powder endowed the article with improved dimensional stability, strength and toughness, and at the same time, with excellent electrical conductivity. Highly conductive article having special shape could be printed according to need.

EXAMPLE 1.3

A 3D Printing Article C

[0135] 1) 100 parts by weight of methyl methacrylate, 20 parts of nano Fe.sub.3O.sub.4 powder, 10 parts of diethylene glycol dimethacrylate and 10 parts of chrome green were mixed at a rotational speed of 2000 rpm for 1 hour at room temperature;

[0136] 2) the mixture obtained in step 1) was mixed with 10 parts of liquid polysulfide rubber and 3 parts of a-hydroxyalkylphenone at a rotational speed of 2000 rpm for 1 hour at room temperature under dark condition; and

[0137] 3) the mixture obtained in step 2) was printed using a PROJET 1200 type SLA 3D printer through CAD program control, and solidified by UV at room temperature to form shape, to thereby obtain article C.

[0138] The article C was green. The addition of nano Fe.sub.3O.sub.4 powder endowed the article with improved dimensional stability, strength and toughness, and at the same time with response to the magnetic field.

EXAMPLE 1.4

A 3D Printing Room Temperature UV Solidifying Material

[0139] 1) 100 parts by weight of methyl methacrylate, 30 parts of micron Al.sub.2O.sub.3 powder, 20 parts of triethylene glycol dimethacrylate, and 10 parts of iron yellow were mixed at a rotational speed of 2000 rpm for 1 hour at room temperature;

[0140] 2) the mixture obtained in step 1) was mixed with 1 part of liquid polysulfide rubber and 2 parts of a-hydroxyalkylphenone at a rotational speed of 2000 rpm for 1 hour at room temperature under dark condition; and

[0141] 3) the mixture obtained in step 2) was printed using a PROJET 1200 type SLA 3D printer through CAD program control, and solidified by UV at room temperature to form shape, to thereby obtain article D.

[0142] The article D was yellow. The addition of micron Al.sub.2O.sub.3 powder endowed the article with improved dimensional stability, strength and toughness, and at the same time with good thermal conductivity, thus enabled the article to be applied to fields of heat conduction and electronic packaging.

EXAMPLE 1.5

A 3D Printing Article E

[0143] 1) 100 parts by weight of propyl methacrylate, 10 parts of a micron montmorillonite powder, 20 parts of trimethylolpropane trimethacrylate, and 5 parts of iron yellow were mixed at a rotational speed of 2000 rpm for 1 hour at room temperature;

[0144] 2) the mixture obtained in step 1) was mixed with 5 parts of liquid polysulfide rubber and 1 part of α-aminoalkylphenone at a rotational speed of 2000 rpm for 1 hour at room temperature under dark condition; and

[0145] 3) the mixture obtained in step 2) was printed using a PROJET 1200 type SLA 3D printer through CAD program control, and solidified by UV at room temperature to form shape, to thereby obtain article E.

[0146] The article E was yellow. The addition of micron montmorillonite powder endowed the article with significantly improved impact resistance, fatigue resistance and gas barrier properties.

EXAMPLE 1.6

A 3D Printing Article F

[0147] 1) 100 parts by weight of benzyl methacrylate, 15 parts of a micron ZrO.sub.2 powder, 30 parts of trimethylolpropane triacrylate, and 10 parts of cadmium red were mixed at a rotational speed of 2000 rpm for 1 hour at room temperature;

[0148] 2) the mixture obtained in step 1) was mixed with 10 parts of liquid polysulfide rubber and 2 parts of α,α-diethoxyacetophenone at a rotational speed of 2000 rpm for 1 hour at room temperature under dark condition; and

[0149] 3) the mixture obtained in step 2) was printed using a PROJET 1200 type SLA 3D printer through CAD program control, and solidified by UV at room temperature to form shape, to thereby obtain article F.

[0150] The article F was red. The addition of micron ZrO.sub.2 powder endowed the article with significantly improved fire resistance, thus enabled the product to be applied to printing of special refractory material.

EXAMPLE 2.1

A High Filling Level Micro-Nano Powder/Polymer Composite Material for 3D Printing

[0151] 1) 100 parts by weight of 500 nm Ag powder and 5 parts of dopamine were homogeneously mixed in 200 parts of Tris buffer (pH 8.5), reacted for 24 hours, washed several times and then dried at 70° C.; and

[0152] 2) 10 parts by weight of PE (melt index: 11.5), 90 parts of modified Ag powder, 0.05 parts of irradiation sensitizer triallyl cyanurate, and 0.02 parts of antioxidant 1010 were homogeneously mixed at room temperature, and fed into a twin-screw extruder having an aspect ratio of 36 for extrusion pelletization (recorded as pellets A), wherein the rotational speed of the extruder was 20 r/min, and the temperature ranges of the various sections of the extruder were: feeding section 150-170° C., melting section 190-200° C., mixing section 190-200° C., exhaust section 170-190° C., and homogenization section 160-180° C.

EXAMPLE 2.2

A 3D Printing Article Prepared From the Composite Material of Example 2.1

[0153] The pellets A obtained in Example 2.1 were added to the head of the 3D printer, and heated and melted in the head, the head was moved along the sectional profile and the filling path of the part while at the same time the melted material was extruded, by utilizing the hot meltability and adhesion of the material, it was rapidly solidified after extrusion under computer control, and irradiation was carried out using electron beam (electron accelerator energy of 0.5 MeV, power of 50 KW, and irradiation dose of 5 KGy), so that the material was crosslinked, and formed shape by accumulation layer by layer.

[0154] The obtained 3D printing article had excellent hardness, dimensional stability and electrical conductivity.

EXAMPLE 2.3

A High Filling Level Micro-Nano Powder/Polymer Composite Material for 3D Printing

[0155] 1) 100 parts by weight of 500 nm Al.sub.2O.sub.3 powder and 10 parts of silane coupling agent KH550 were homogeneously mixed in 200 parts of water, reacted for 24 hours at 60° C., washed several times and then dried at 70° C.; and

[0156] 2) 15 parts by weight of PP (melt index: 12.2), 85 parts of modified Al.sub.2O.sub.3 powder, 0.1 parts of irradiation sensitizer triallyl isocyanurate, and 0.01 parts of antioxidant 1096 were homogeneously mixed at room temperature, and fed into a twin-screw extruder having an aspect ratio of 36 for extrusion pelletization (recorded as pellets B), wherein the rotational speed of the extruder was 40 r/min, and the temperature ranges of the various sections of the extruder were: feeding section 150-170° C., melting section 190-200° C., mixing section 190-200° C., exhaust section 170-190° C., and homogenization section 160-180° C.

EXAMPLE 2.4

A 3D Printing Article Prepared From the Composite Material of Example 2.3

[0157] The pellets B obtained in Example 2.3 were added to the head of the 3D printer, and heated and melted in the head, the head was moved along the sectional profile and the filling path of the part while at the same time the melted material was extruded, by utilizing the hot meltability and adhesion of the material, it was rapidly solidified after extrusion under computer control, and irradiation was carried out using electron beam (electron accelerator energy of 0.75 MeV, power of 75 KW, and irradiation dose of 10 KGy), so that the material was crosslinked, and formed shape by accumulation layer by layer.

[0158] The obtained 3D printing article had excellent mechanical strength, dimensional stability and thermal conductivity.

EXAMPLE 2.5

A High Filling Level Micro-Nano Powder/Polymer Composite Material for 3D Printing

[0159] 1) 100 parts by weight of 1μm CaCO.sub.3 powder and 15 parts of silane coupling agent KH560 were homogeneously mixed in 200 parts of water, reacted for 24 hours at 60° C., washed several times and then dried at 70° C.; and

[0160] 2) 20 parts by weight of PA (melt index: 10.5), 80 parts of modified CaCO.sub.3 powder, 0.2 parts of irradiation sensitizer trimethylolpropane trimethacrylate, and 0.01 parts of antioxidant 1098 were homogeneously mixed at room temperature, and fed into a twin-screw extruder having an aspect ratio of 36 for extrusion pelletization (recorded as pellets C), wherein the rotational speed of the extruder was 60 r/min, and the temperature ranges of the various sections of the extruder were: feeding section 150-170° C., melting section 190-200° C., mixing section 190-200° C., exhaust section 170-190° C., and homogenization section 160-180° C.

EXAMPLE 2.6

A 3D Printing Article Prepared From The Composite Material of Example 2.5

[0161] The pellets C obtained in Example 2.5 were added to the head of the 3D printer, and heated and melted in the head, the head was moved along the sectional profile and the filling path of the part while at the same time the melted material was extruded, by utilizing the hot meltability and adhesion of the material, it was rapidly solidified after extrusion under computer control, and irradiation was carried out using electron beam (electron accelerator energy of 1 MeV, power of 100 KW, and irradiation dose of 15 KGy), so that the material was crosslinked, and formed shape by accumulation layer by layer.

[0162] The obtained 3D printing article had excellent mechanical strength, dimensional stability and heat resistance.

EXAMPLE 2.7

A High Filling Level Micro-Nano Powder/Polymer Composite Material for 3D Printing

[0163] 1) 100 parts by weight of 4 μm ZrO.sub.2 powder and 20 parts of silane coupling agent KH570 were homogeneously mixed in 200 parts of water, reacted for 24 hours at 60° C., washed several times and then dried at 70° C.; and

[0164] 2) 25 parts by weight of PC (melt index: 15), 75 parts of modified ZrO.sub.2 powder, 0.05 parts of irradiation sensitizer trimethylolpropane trimethacrylate, and 0.01 parts of antioxidant 168 were homogeneously mixed at room temperature, and fed into a twin-screw extruder having an aspect ratio of 36 for extrusion pelletization (recorded as pellets D), wherein the rotational speed of the extruder was 80 r/min, and the temperature ranges of the various sections of the extruder were: feeding section 150-170° C., melting section 190-200° C., mixing section 190-200° C., exhaust section 170-190° C., and homogenization section 160-180° C.

EXAMPLE 2.8

A 3D Printing Article Prepared From the Composite Material of Example 2.7

[0165] The pellets D obtained in Example 2.7 were added to the head of the 3D printer, and heated and melted in the head, the head was moved along the sectional profile and the filling path of the part while at the same time the melted material was extruded, by utilizing the hot meltability and adhesion of the material, it was rapidly solidified after extrusion under computer control, and irradiation was carried out using electron beam (electron accelerator energy of 1.5 MeV, power of 125 KW, and irradiation dose of 20 KGy), so that the material was crosslinked, and formed shape by accumulation layer by layer.

[0166] The obtained 3D printing article had excellent mechanical strength, dimensional stability, heat resistance and wear resistance.

EXAMPLE 2.9

A High Filling Level Micro-Nano Powder/Polymer Composite Material for 3D Printing

[0167] 1) 100 parts by weight of a 10 μm montmorillonite powder and 20 parts of a silane coupling agent KH792 were homogeneously mixed in 200 parts of water, reacted for 24 hours at 60° C., washed several times and then dried at 70° C.; and

[0168] 2) 30 parts by weight of EVA (melt index: 20.3), 70 parts of modified montmorillonite powder, 0.05 parts of irradiation sensitizer trimethylolpropane trimethacrylate, and 0.02 parts of antioxidant 168 were homogeneously mixed at room temperature, and fed into a twin-screw extruder having an aspect ratio of 36 for extrusion pelletization (recorded as pellets E), wherein the rotational speed of the extruder was 100 r/min, and the temperature ranges of the various sections of the extruder were: feeding section 150-170° C., melting section 190-200° C., mixing section 190-200° C., exhaust section 170-190° C., and homogenization section 160-180° C.

EXAMPLE 2.10

A 3D Printing Article Prepared From the Composite Material of Example 2.9

[0169] The pellets E obtained in Example 2.9 were added to the head of the 3D printer, and heated and melted in the head, the head was moved along the sectional profile and the filling path of the part while at the same time the melted material was extruded, by utilizing the hot meltability and adhesion of the material, it was rapidly solidified after extrusion under computer control, and irradiation was carried out using electron beam (electron accelerator energy of 2 MeV, power of 150 KW, and irradiation dose of 5 KGy), so that the material was crosslinked, and formed shape by accumulation layer by layer.

[0170] The obtained 3D printing article had excellent mechanical strength, dimensional stability and flame retardancy.

EXAMPLE 2.11

A High Filling Level Micro-Nano Powder/Polymer Composite Material for 3D Printing

[0171] 1) 100 parts by weight of 10 μm of laponite powder and 15 parts of silane coupling agent DL602 were homogeneously mixed in 200 parts of water, reacted for 24 hours at 60° C., washed several times and then dried at 70° C.; and

[0172] 2) 10 parts by weight of ABS (melt index: 14.5), 90 parts of modified laponite powder, 0.05 parts of irradiation sensitizer trimethylolpropane trimethacrylate, and 0.02 parts of antioxidant 168 were homogeneously mixed at room temperature, and fed into a twin-screw extruder having an aspect ratio of 36 for extrusion pelletization (recorded as pellets F), wherein the rotational speed of the extruder was 100 r/min, and the temperature ranges of the various sections of the extruder were: feeding section 150-170° C., melting section 190-200° C., mixing section 190-200° C., exhaust section 170-190° C., and homogenization section 160-180° C.

EXAMPLE 2.12

A 3D Printing Article Prepared From the Composite Material of Example 2.11

[0173] The pellets F obtained in Example 2.11 were added to the head of the 3D printer, and heated and melted in the head, the head was moved along the sectional profile and the filling path of the part while at the same time the melted material was extruded, by utilizing the hot meltability and adhesion of the material, it was rapidly solidified after extrusion under computer control, and irradiation was carried out using electron beam (electron accelerator energy of 2 MeV, power of 150 KW, and irradiation dose of 5 KGy), so that the material was crosslinked, and formed shape by accumulation layer by layer. The obtained 3D printing article had excellent mechanical strength, dimensional stability and flame retardancy.

EXAMPLE 2.13

A High Filling Level Micro-Nano Powder/Polymer Composite Material for 3D Printing

[0174] 10 parts by weight of ABS (melt index: 14.5), 90 parts of laponite powder, 0.05 parts of irradiation sensitizer trimethylolpropane trimethacrylate, and 0.02 parts of antioxidant 168 were homogeneously mixed at room temperature, and fed into a twin-screw extruder having an aspect ratio of 36 for extrusion pelletization (recorded as pellets F1), wherein the rotational speed of the extruder was 100 r/min, and the temperature ranges of the various sections of the extruder were: feeding section 150-170° C., melting section 190-200° C., mixing section 190-200° C., exhaust section 170-190° C., and homogenization section 160-180° C.

EXAMPLE 2.14

A 3D Printing Article Prepared From the Composite Material of Example 2.13

[0175] The pellets F1 obtained in Example 2.13 were added to the head of the 3D printer, and heated and melted in the head, the head was moved along the sectional profile and the filling path of the part while at the same time the melted material was extruded, by utilizing the hot meltability and adhesion of the material, it was rapidly solidified after extrusion under computer control, and irradiation was carried out using electron beam (electron accelerator energy of 2 MeV, power of 150 KW, and irradiation dose of 5 KGy), so that the material was crosslinked, and formed shape by accumulation layer by layer.

[0176] The obtained 3D printing article had excellent mechanical strength (slightly lower than the article of Example 12), dimensional stability and flame retardancy.

EXAMPLE 3.1

A 3D Printing Article A Prepared From UV Radiation Crosslinked Polymer Composition for 3D Printing and Material Prepared Therefrom

[0177] 1) 100 parts by weight of PE (molecular weight: 8500), 0.5 parts of trimethylolpropane tris (3-mercaptopropionate), 0.1 parts of an antioxidant 1010, 5 parts of micron calcium carbonate powder, and 1 part of lead chrome yellow were homogeneously mixed with a single screw extruder, and extruded into filaments having a diameter of 2.0 mm with the diameter error within 5%, the single screw extruder had a screw diameter of 70mm and an aspect ratio of 20:1, the extruder temperatures were successively set as 150-165° C., 165-175° C., 175-185° C., and 185-200° C., and the die temperature was 200-205° C.

[0178] 2) The filaments obtained in step 1) were sent to the head through the filament feeding device of UPRINT 3D printer, and heated and melted in the head, the head was moved along the sectional profile and the filling path of the part while at the same time the melted material was extruded, by utilizing the hot meltability and adhesion of the material, it was rapidly solidified after extrusion under computer control, and irradiation was carried out using UV having a wavelength of 337 nm, so that the material was crosslinked, and formed shape by accumulation layer by layer, to thereby obtain article A.

[0179] The article A was yellow, and had excellent heat resistance, chemical resistance and mechanical strength as compared with common PE printed article.

EXAMPLE 3.2

A 3D Printing Article B Prepared From UV Radiation Crosslinked Polymer Composition for 3D Printing and Material Prepared Therefrom

[0180] 1) 100 parts by weight of an unsaturated polyester (PET copolymerized with maleic anhydride, having a molecular weight of 8000), 1 part of trimethylolpropane tris (3-mercaptopropionate), 0.2 parts of an antioxidant 1010, and 10 parts of nano carbon powder were homogeneously mixed with a single screw extruder, and extruded into filaments having a diameter of 2.0 mm with the diameter error within 5%, the single screw extruder had a screw diameter of 70 mm and an aspect ratio of 20:1, the extruder temperatures were successively set as: 185-195° C., 190-200° C., 195-205° C., 200-210° C., and 195-205° C., and the die temperature was 215-225° C..

[0181] 2) The filaments obtained in step 1) were sent to the head through the filament feeding device of UPRINT 3D printer, and heated and melted in the head, the head was moved along the sectional profile and the filling path of the part while at the same time the melted material was extruded, by utilizing the hot meltability and adhesion of the material, it was rapidly solidified after extrusion under computer control, and irradiation was carried out using UV having a wavelength of 337 nm, so that the material was crosslinked, and formed shape by accumulation layer by layer, to thereby obtain article B.

[0182] The article B was red, and had excellent heat resistance, chemical resistance and mechanical strength as compared with common PET printed product, and meanwhile the addition of nano carbon endowed the article with excellent electrical conductivity.

EXAMPLE 3.3

A 3D Printing Article C Prepared From UV Radiation Crosslinked Polymer Composition for 3D Printing and Material Prepared Therefrom

[0183] 1) 100 parts by weight of PB (molecular weight: 4000), 2 parts of trimethylolpropane trimethacrylate, 0.3 parts of antioxidant 1096, 15 parts of nano Fe.sub.3O.sub.4 powder, and 3 parts of iron yellow were homogeneously mixed with a single screw extruder, and extruded into filaments having a diameter of 2.0 mm with the diameter error within 5%, the single screw extruder had a screw diameter of 70 mm and an aspect ratio of 20:1, the extruder temperatures were successively set as: 185-195° C., 190-200° C., 195-205° C., 200-210° C., and 195-205° C., and the die temperature was 215-225° C..

[0184] 2) The filaments obtained in step 1) were sent to the head through the filament feeding device of UPRINT 3D printer, and heated and melted in the head, the head was moved along the sectional profile and the filling path of the part while at the same time the melted material was extruded, by utilizing the hot meltability and adhesion of the material, it was rapidly solidified after extrusion under computer control, and irradiation was carried out using UV having a wavelength of 337 nm, so that the material was crosslinked, and formed shape by accumulation layer by layer, to thereby obtain article C.

[0185] The article C was yellow, and had excellent heat resistance, chemical resistance and mechanical strength as compared with common PB printed product, and meanwhile the addition of nano Fe.sub.3O.sub.4 endowed the article with response to magnetic field.

EXAMPLE 3.4

A 3D Printing Article D Prepared From UV Radiation Crosslinked Polymer Composition for 3D Printing and Material Prepared Therefrom

[0186] 1) 100 parts by weight of an unsaturated resin (copolymer of 70% of methacrylate and 30% of butadiene, having a molecular weight of 10,000), 3 parts of pentaerythritol tetrakis(2-mercaptoacetate), 0.4 parts of an antioxidant 1096, 20 parts of micron Al.sub.2O.sub.3 powder, and 4 parts of chrome green were homogeneously mixed with a single screw extruder, and extruded into filaments having a diameter of 2.0 mm with the diameter error within 5%, the single screw extruder had a screw diameter of 70 mm and an aspect ratio of 20:1, the extruder temperatures were successively set as:185-195° C., 190-200° C., 195-205° C., 200-210° C., and 195-205° C., and the die temperature was 215-225° C..

[0187] 2) The filaments obtained in step 1) were sent to the head through the filament feeding device of UPRINT 3D printer, and heated and melted in the head, the head was moved along the sectional profile and the filling path of the part while at the same time the melted material was extruded, by utilizing the hot meltability and adhesion of the material, it was rapidly solidified after extrusion under computer control, and irradiation was carried out using UV having a wavelength of 337 nm, so that the material was crosslinked, and formed shape by accumulation layer by layer, to thereby obtain article D.

[0188] The article D was green, and had excellent heat resistance, chemical resistance and mechanical strength as compared with common polyacrylate printed product, and meanwhile the addition of micron Al.sub.2O.sub.3 powder endowed the article with excellent heat conductivity.

EXAMPLE 3.5

A 3D Printing Article E Prepared From UV Radiation Crosslinked Polymer Composition for 3D Printing and Material Prepared Therefrom

[0189] 1) 100 parts by weight of ABS (molecular weight: about 10,000), 0.5 parts of pentaerythritol tetrakis(2-mercaptoacetate), 0.5 parts of antioxidant 168, 20 parts of micron montmorillonite powder, and 5 parts of iron blue were homogeneously mixed with a single screw extruder, and extruded into filaments having a diameter of 2.0 mm with the diameter error within 5%, the single screw extruder had a screw diameter of 70 mm and an aspect ratio of 20:1, the extruder temperatures were successively set as: 245-255° C., 255-265° C., 265-275° C., 275-285° C., and 285-300° C., and the die temperature was 300-325° C.

[0190] 2) The filaments obtained in step 1) were sent to the head through the filament feeding device of UPRINT 3D printer, and heated and melted in the head, the head was moved along the sectional profile and the filling path of the part while at the same time the melted material was extruded, by utilizing the hot meltability and adhesion of the material, it was rapidly solidified after extrusion under computer control, and irradiation was carried out using UV having a wavelength of 254 nm, so that the material was crosslinked, and formed shape by accumulation layer by layer, to thereby obtain article E.

[0191] The article E was blue, and had excellent heat resistance, chemical resistance and mechanical strength as compared with common ABS printed product, and meanwhile the addition of micron montmorillonite endowed the article with excellent gas barrier property.