CN108948500B - Preparation method of polyethylene mixture containing polyurethane modified powder rubber for 3D printing - Google Patents
Preparation method of polyethylene mixture containing polyurethane modified powder rubber for 3D printing Download PDFInfo
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- CN108948500B CN108948500B CN201810964801.8A CN201810964801A CN108948500B CN 108948500 B CN108948500 B CN 108948500B CN 201810964801 A CN201810964801 A CN 201810964801A CN 108948500 B CN108948500 B CN 108948500B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
The invention discloses a preparation method of a polyethylene mixture containing polyurethane modified powdered rubber for 3D printing, which comprises the following steps: adding fluorinated graphene and polyurethane into perfluoroalkane to obtain a polyurethane solution; uniformly mixing nitrile latex, soft water, a polyurethane solution, an anti-aging agent, a demulsifier, a separant and a coagulant, heating to 60-90 ℃, stirring, washing, dehydrating and drying to obtain nitrile rubber; uniformly mixing nitrile rubber, polyethylene, a silane coupling agent, phenolic resin and montmorillonite, and granulating in a double-screw extruder at 150-200 ℃ to obtain a powder mixed material for 3D printing. The mixed material has excellent tensile yield stress, tensile breaking stress and other properties.
Description
Technical Field
The invention relates to a preparation method of a 3D printing material, in particular to a preparation method of a polyethylene mixture containing polyurethane modified powdered rubber for 3D printing.
Background
The 3D printing is a manufacturing method for forming three-dimensional complex structural parts by adding materials point by point, line by line and plane by plane. On the one hand, it can be applied to the manufacture of almost any type of material; on the other hand, it will drive the development of material technology by creating a large number of new materials that are suitable for their unique process characteristics. Thermoplastic high molecular polymers are easy to extrude, blow mold and inject, so that the thermoplastic high molecular polymers become the most developed type in 3D printing high molecular materials, and the materials comprise various engineering plastics and biological plastics, and are generally in thread-shaped consumables during the preparation of the printing materials.
The 3D printing technology is applied to rubber products, and the rubber products are structurally and raw materials used by the rubber products are required to meet the requirements of the 3D printing technology. Most of rubber products use single mixed materials, various compounding agents and fillers are used for obtaining necessary physical and mechanical properties and physical and chemical properties, and meanwhile, a vulcanization process is required, so that the raw materials required by the 3D printing technology can be realized by only integrating the vulcanization process into modified materials used by the 3D printing technology.
The high-density polyethylene is a nonpolar thermoplastic resin with high crystallinity, has good heat resistance and cold resistance, good chemical stability, higher rigidity and toughness and good mechanical strength. The dielectric property and the environmental stress cracking resistance are also better. The hardness, tensile strength and creep property are better than those of low-density polyethylene; the wear resistance, the electrical insulation, the toughness and the cold resistance are all good, but are slightly inferior to the low-density insulation; the ageing resistance is poor, the environmental cracking resistance is inferior to that of low density polyethylene, and the thermal oxidation in particular reduces the performance. Therefore, modification treatment is required for 3D printing materials.
CN103980590A a toughened high density polyethylene, comprising: high density polyethylene and toughening master batch. The toughening master batch is prepared from an ethylene propylene elastomer, a styrene-butadiene elastomer, a diluent, a crosslinking inhibitor and a free radical polymerization initiator. The invention also relates to a method for preparing the toughened high-density polyethylene, the toughened master batch, a method for preparing the toughened master batch, application of the toughened master batch in toughened high-density polyethylene, application of the toughened high-density polyethylene in 3D printing and a 3D printing method. CN104177566A polypyrrole conductive composite material for 3D printing and its preparation method. The preparation method of the composite material comprises the following steps: mixing polyvinylpyrrolidone with ethanol, adding p-toluenesulfonic acid, stirring at room temperature, sequentially adding ammonium persulfate and hydroxyethyl acrylate, stirring at room temperature, adding polypyrrole particles, heating, stirring, and cooling to obtain the polypyrrole conductive composite material for 3D printing. Wherein the content of polypyrrole is 45-50%, the content of hydroxyethyl acrylate is 5-20%, the content of polyvinylpyrrolidone is 10-20%, the content of ethanol is 10-30%, the content of p-toluenesulfonic acid is 1-2%, and the content of ammonium persulfate is 1-2%. CN103992548A A3D prints modified low density polyethylene material, its part by weight composition is as follows: 80-95 parts of low-density polyethylene, 1-10 parts of inorganic nanoparticle filler, 1-5 parts of coupling agent, 5-10 parts of toughening agent and 1-5 parts of antioxidant; the modified low-density polyethylene material disclosed by the invention has good melt viscosity, fluidity, heat resistance and wear resistance, so that the low-density polyethylene nano composite material is more in line with the characteristics of a 3D printing material, and has a wide application prospect in a 3D printing technology. CN103992548A A3D prints modified low density polyethylene material, its part by weight composition is as follows: 80-95 parts of low-density polyethylene, 1-10 parts of inorganic nanoparticle filler, 1-5 parts of coupling agent, 5-10 parts of toughening agent and 1-5 parts of antioxidant; the modified low-density polyethylene material disclosed by the invention has good melt viscosity, fluidity, heat resistance and wear resistance, so that the low-density polyethylene nano composite material is more in line with the characteristics of a 3D printing material, and has a wide application prospect in a 3D printing technology. CN103936392A A preparation method of 3D printing inorganic powder molding material, characterized in that the method comprises the following steps: mixing 10-30% of acetone, 62-85% of powder material and 2-10% of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, and grinding for 1-2 h at the rotating speed of 500-1000 r/min to obtain pretreated powder material; preparation of a molding material: adding 40-65% of acetone according to mass percentage concentration, adding 2-8% of polyvinyl formal, stirring for dissolving, adding 30-55% of pretreated powder material, stirring and mixing uniformly, putting into a grinding machine, mixing and grinding for 6-9 h at normal temperature at the rotating speed of 500-1000 r/min, and then spray drying to obtain the 3D printing inorganic powder molding material. The material can be directly molded without spraying a binder when being heated to 190-210 ℃ and the pressure is within the range of 1-10 MPa, and has the advantages of simple preparation process, easily controlled conditions, low production cost and easy industrial production. CN103833258A glue for 3D printer and its preparation method, the glue is prepared from (by weight parts) deionized water 55-75, ethylene glycol 12-18, isopropanol 15-20, triethanolamine 10-13, nonylphenol polyoxyethylene ether 3-6, polyvinyl alcohol 3-6, and industrial dye 0-5 by stirring, standing, deoxidizing, filtering, etc. The glue provided by the invention reduces the curing time of the printed object, enhances the dissolution of polyvinyl alcohol by using the isopropanol, strengthens the viscosity between layers, enhances the tensile strength and hardness of the printed object, reduces the time for curing and hardening by hot air, improves the efficiency and reduces the energy consumption. The method is simple and has strong operability. CN103819164A powder for a 3D printer and a preparation method thereof, wherein the powder is prepared by grinding and mixing 55-80% of gypsum, 1-10% of anhydrite, 1-10% of barium sulfate, 10-20% of polyvinyl alcohol, 1-5% of fumed silica and 1-5% of lecithin by weight percentage. The invention can effectively improve the precision of the printed object and the precision of the printed size, and avoid the problems of increased printer faults, blocked printing head and the like caused by the flying of powder. CN103980593A modified high-density polyethylene 3D printing molding material with high toughness, which comprises the following components in parts by weight: 60 parts of high-density polyethylene, 10-50 parts of talcum powder, 20-25 parts of calcium carbonate, 10-50 parts of wollastonite, 10-15 parts of carbon nano tube, 0.1-0.5 part of antioxidant and 0.1-0.5 part of silane coupling agent. The modified high-density polyethylene material has high tensile strength and better impact toughness, can improve the application value of the high-density polyethylene, expands the application field of the high-density polyethylene material, and enables the high-density polyethylene material to better accord with the characteristics of a 3D printing material. The material is not only environment-friendly, but also low in cost, and has important industrial application value. CN103980595A A3D prints modified ultra high molecular weight polyethylene material, its part by weight composition is as follows: 80-95 parts of ultrahigh molecular weight polyethylene, 30-40 parts of low density polyethylene, 10-15 parts of carbon nano tube, 1-10 parts of inorganic filler, 1-5 parts of modifier, 0.1-0.5 part of antioxidant and 0.1-0.5 part of coupling agent; the modified UHMWPE material disclosed by the invention has good melt flowability, heat resistance and wear resistance, so that the ultrahigh molecular weight polyethylene is more in line with the characteristics of a 3D printing material, and the modified UHMWPE material has a wide application prospect in a 3D printing technology. CN106009351A A3D prints and uses the high molecular polymer material, by paraffin hydrocarbon oil, o-cresol formaldehyde epoxy resin, talc powder, polydimethylsiloxane, oxidized polyethylene wax, triethylene glycol diisocaprylate, tributyl citrate, dibasic lead phthalate, talc powder, polystyrene resin, benzoin dimethyl ether, graphite fiber, polystyrene resin, cotton seed oil polyphenylene ethylene, graphene, tartaric acid, barium stearate, polyamide resin composition, the material prepared has higher tensile strength and tensile modulus, and has kept good toughness, its elongation at break and impact strength, etc. performance index are good; not only has quite high toughness, but also has higher heat resistance and good service performance. CN105732915A A high molecular polymer material for 3D printing, which is composed of urethane acrylate, epoxy resin, ethyl cellulose, polyethylene wax, wollastonite powder, hydrogenated rosin alcohol, epoxy acrylate, 2-hydroxy-4-methoxybenzophenone, trioctyl trimellitate, dipropylene glycol diacrylate, benzidine, polyoxyethylene laurate, nano nickel oxide, polybutyl acrylate, trimesic acid, isodecyl acrylate, barium stearate and calcium stearate, the prepared material has high tensile strength and tensile modulus, retains good toughness, and has good performance indexes such as breaking elongation and impact strength; not only has quite high toughness, but also has higher heat resistance and good service performance.
JPH11176248(a) improves radiation resistance and obtains sufficient durability at a relatively high temperature by forming an insulating layer of low density polyethylene produced by a single-site catalyst as a base resin. The polyethylene includes ethylene copolymers such as ethylene alpha-olefin copolymers. An oxidizing agent, an ultraviolet absorber, and various processing aids for improving moldability may be appropriately added to improve the heat resistance and radiation resistance of the composition. KR101506704(B1) the present invention relates to a method for manufacturing a porous scaffold of high density polyethylene, and more particularly, to a three-dimensional printing which can accurately form a three-dimensional shape for facial transplantation to achieve the desired formation of a porous scaffold, and can freely adjust even the size and shape of pores. The porous scaffold is based on 3D printing high-density polyethylene, and comprises a 3D printing composite material formed by porous support and mixing the high-density polyethylene and bioactive substances in a porous structure; and performing surface plasma treatment on one side of the porous support formed on the surface treatment layer. JPS62127226(a), JPH0624769(B2) describe a 3D printed material for baby bottle nipples based on high density polyethylene.
Accordingly, there is a need for improvements in the art.
Disclosure of Invention
The invention aims to provide a preparation method of a polyethylene mixture containing polyurethane modified powdered rubber for 3D printing, which has excellent performance.
In order to solve the technical problem, the invention provides a preparation method of a polyethylene mixture containing polyurethane modified powdered rubber for 3D printing, which comprises the following steps:
1) and preparing a polyurethane solution:
adding fluorinated graphene into perfluoroalkane serving as a solvent, performing ultrasonic treatment at room temperature (10-30 ℃) for 15-20 h, then adding polyurethane, and stirring at 20-100 ℃ for 12-24 h (so that the polyurethane is dissolved in the perfluoroalkane) to obtain a polyurethane solution;
the feed-liquid ratio of the fluorinated graphene to the perfluoroalkane is 0.1-0.6 g/ml, and the feed-liquid ratio of the polyurethane to the perfluoroalkane is 1-30 g/ml;
2) and preparing powdered nitrile rubber: adding 100 parts of nitrile latex, 50-80 parts of soft water and 90-110 parts of polyurethane solution (prepared in step 1) into a container (a coagulation kettle), uniformly stirring (stirring for 30 min-1 h), adding 0.1-0.6 part of anti-aging agent, uniformly stirring (stirring for 5-20 min), adding 50-100 parts of demulsifier at 0-10 ℃ (coagulation temperature), uniformly stirring (stirring for 30 min-1 h), adding 10-30 parts of separant and 10-40 parts of coagulant, heating to 60-90 ℃, stirring for 1-3 h, washing, dehydrating and drying to obtain nitrile rubber (powder);
in the step 2), the butyronitrile latex is taken as 100 parts;
3) uniformly mixing (high-speed blending, namely blending for 20-50 minutes at a rotating speed of 100-200 rpm) 5-10 parts of nitrile rubber (powder), 100 parts of polyethylene, 0.2-0.5 part of silane coupling agent, 0.1-0.5 part of phenolic resin (phenolic resin serving as a compatibilizer) and 0.1-0.5 part of montmorillonite (montmorillonite serving as a reinforcing effect), and granulating in a double-screw extruder at 150-200 ℃ to prepare a powder mixed material for 3D printing (namely a polyethylene mixture containing polyurethane modified powder rubber for 3D printing);
in the step 3), the polyethylene is taken as 100 parts;
the above parts are all parts by mass.
As an improvement of the process for the preparation of the polyurethane modified powder rubber containing polyethylene mixture for 3D printing of the present invention:
the polyurethane is Waterborne Polyurethane (WPU);
the number of layers of the fluorinated graphene is less than or equal to 20, the thickness of the fluorinated graphene is 0.8-5.0 nm, the particle size of the fluorinated graphene is 2.0-5.0 mu m, and the fluorine content of the fluorinated graphene is 20-40 wt.%;
the perfluoroalkane is perfluorohexane, perfluorocyclohexane or perfluoroheptane;
the anti-aging agent is 1076 or DLTP;
the demulsifier is a saturated NaCl aqueous solution (saturated NaCl salt solution);
the separant is a compound composed of a fatty acid soap compound, a stearate compound and a carbonate compound according to the mass ratio of 1:1: 1-1: 2: 3; the fatty acid soap compound is fatty acid potassium, the stearate compound is zinc stearate, and the carbonate compound is calcium carbonate;
the coagulant is a divalent salt; the divalent salt is magnesium sulfate and calcium chloride;
the polyethylene is high density polyethylene (HMA-025, etc.);
the silane coupling agent is Si69 coupling agent, and the phenolic resin is phenolic resin 2401 and phenolic resin 2402.
In the present invention: nitrile latex, i.e., latex prepared by emulsion polymerization of butadiene and acrylonitrile, such as XNBRL-830 nitrile latex (total solid content: 44 + -1%) manufactured by Shanghai Jinlang rubber and plastic science and technology Limited; the hardness of the soft water is 0mg/l-60 mg/l; in the step 2), the washing is repeated 3-5 times by using soft water, and the dehydration is realized by centrifugation, and the drying is carried out for 8-20 hours at the temperature of 80-120 ℃.
The preparation method of the polyethylene mixture containing the polyurethane modified powdered rubber for 3D printing has the technical advantages that:
the high-density polyethylene has good heat resistance, rigidity and toughness, is mixed with polymers such as powdered rubber, polyurethane and the like, has the original characteristics and excellent comprehensive performance, and is suitable for 3D printing materials. The addition production process of the polyurethane and the powdered rubber is simple and easy to operate. The performance of the prepared mixture is as follows: the mass flow rate (g/10min) of the melt is 0.20-0.40, the tensile yield stress is more than or equal to 9.0MPa, the tensile fracture stress is more than or equal to 10.0MPa, and the brittle temperature is-125 to-140 ℃.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
The term "part" as used herein means a part by mass. The anti-aging agent, the demulsifier, the coagulant and the separant are all general aids in the rubber field, and can be of the types commonly used in the rubber field.
The raw materials of the invention can be obtained by conventional commercial methods:
the number of layers of the fluorinated graphene is less than or equal to 20, the thickness of the fluorinated graphene is 0.8-5.0 nm, the particle size of the fluorinated graphene is 2.0-5.0 microns, and the fluorine content is 20-40 wt.%; such as available from Shandong Yamama electro-optic materials, Inc.;
the butyronitrile latex, namely the latex prepared by polymerizing butadiene and acrylonitrile emulsion, is XNBRL-830 butyronitrile latex (the total solid content is 44 +/-1 percent) produced by Shanghai Jinlang rubber and plastic science and technology Limited company;
the polyethylene is high density polyethylene (HMA-025);
the hardness of the soft water is 0mg/l-60 mg/l;
the polyurethane is Waterborne Polyurethane (WPU), such as WPU-KDJS-XX of Jiangxi Keding chemical materials Co.
The following examples used the same fluorinated graphene, nitrile latex, polyethylene, and polyurethane as described above as starting materials.
The test methods of the following examples and comparative examples were examined as follows:
tensile yield strength: GB/T1040-92; elongation at break: GB/T1040-92; melt flow rate: GB/3682-.
Example 1a process for the preparation of a polyethylene blend containing a polyurethane modified powdered rubber for 3D printing, the following steps being carried out in sequence:
1) and preparing a polyurethane solution:
according to the feed-liquid ratio of 0.2g/ml of fluorinated graphene to perfluorohexane and the feed-liquid ratio of 10g/ml of polyurethane to perfluorohexane;
adding fluorinated graphene into perfluorohexane, performing ultrasonic treatment at room temperature for 15h (200w), then adding polyurethane, and stirring at 20 ℃ for 12h to dissolve the polyurethane into the perfluorohexane to prepare a polyurethane solution;
2) and preparing powdered nitrile rubber:
adding 100 parts of butyronitrile latex, 60 parts of soft water and 90 parts of polyurethane solution into a condensation kettle, stirring for 30min, adding 0.2 part of anti-aging agent 1076, stirring for 5min, adding 50 parts of saturated NaCl salt solution (serving as a demulsifier) at the condensation temperature of 10 ℃, stirring for 40min, adding 10 parts of isolating agent (a mixture of potassium fatty acid, zinc stearate and calcium carbonate in a mass ratio of 1:1: 1), adding 20 parts of magnesium sulfate, heating to 70 ℃, stirring for 2 hours, washing (repeatedly washing with soft water for 3-5 times), dehydrating (centrifugally dehydrating), and drying (drying at 100-120 ℃ for 20 hours) to obtain the powdery butyronitrile rubber.
3) The powder glue mixture for 3D printing comprises: 5 parts of powdered nitrile rubber, 100 parts of polyethylene, 0.2 part of Si69, 0.3 part of phenolic resin 2401 and 0.5 part of montmorillonite are blended at a high speed (blending is carried out for 20-50 minutes at the rotating speed of 100-200 rpm), and granulation is carried out in a double-screw extruder at the temperature of 150 ℃ to prepare a powder mixed material for 3D printing, namely, a polyethylene mixture containing polyurethane modified powdered rubber for 3D printing.
The performance of the prepared mixture is as follows: the melt mass flow rate (g/10min) is 0.25, the tensile yield stress is 9.5MPa, the tensile fracture stress is 11.2MPa, and the brittle temperature is-130 ℃.
Comparative example 1-1, the use of fluorinated graphene in step 1) of example 1 was eliminated, and the remainder was identical to example 1.
The performance of the prepared mixture is as follows: the melt mass flow rate (g/10min) is 0.20, the tensile yield stress is 8.5MPa, the tensile fracture stress is 9.3MPa, and the brittle temperature is-113 ℃.
Comparative examples 1-2, the use of polyurethane in step 1) of example 1 was eliminated and the solution obtained in step 1) was used instead of the polyurethane solution used in step 2), with the same volume; the rest is equivalent to embodiment 1.
The performance of the prepared mixture is as follows: the melt mass flow rate (g/10min) is 0.15, the tensile yield stress is 6.9MPa, the tensile fracture stress is 7.5MPa, and the brittle temperature is-80 ℃.
Comparative examples 1 to 3, step 1) of example 1 was omitted and the polyurethane solution in step 2) was changed to perfluorohexane with the same volume usage; the rest is equivalent to embodiment 1.
The performance of the prepared mixture is as follows: the melt mass flow rate (g/10min) is 0.15, the tensile yield stress is 6.0MPa, the tensile fracture stress is 6.4MPa, and the brittle temperature is-70 ℃.
Comparative examples 1-4, the use of demulsifier in step 2) of example 1 was eliminated, and the remainder was identical to example 1.
The particles of the nitrile rubber prepared in the step 2) are not uniform, and even powdery nitrile rubber cannot be prepared; thereby making it impossible to efficiently perform the subsequent steps.
Comparative examples 1-5, eliminating the use of release agent from step 2) of example 1; the rest is equivalent to embodiment 1.
The particles of the nitrile rubber prepared in the step 2) are unstable, so that the nitrile rubber is easy to form lumps due to violent polymerization, and the prepared nitrile rubber cannot be effectively subjected to subsequent steps.
Comparative examples 1 to 6, the use of montmorillonite in step 3) of example 1 was eliminated, and the remainder was the same as in example 1.
The tensile yield stress of the prepared mixture is 8.6MPa, and the tensile breaking stress is 10.1 MPa.
Comparative examples 1 to 7, the use of the silane coupling agent Si69 in step 3) of example 1 was eliminated, and the remainder was identical to example 1.
The tensile yield stress of the prepared mixture is 8.4MPa, and the tensile breaking stress is 9.8 MPa.
Example 2a process for the preparation of a polyethylene blend containing a polyurethane modified powdered rubber for 3D printing, the following steps are performed in order:
1) and preparing a polyurethane solution:
according to the feed-liquid ratio of 0.3g/ml of fluorinated graphene to perfluorocyclohexane and the feed-liquid ratio of 15g/ml of polyurethane to perfluorocyclohexane;
adding fluorinated graphene into perfluorocyclohexane, performing ultrasonic treatment at room temperature for 20 hours, then adding polyurethane, and stirring at 50 ℃ for 20 hours to dissolve the polyurethane into the perfluorocyclohexane to obtain a polyurethane solution.
2) And preparing powdered nitrile rubber:
adding 100 parts of butyronitrile latex, 80 parts of soft water and 100 parts of polyurethane solution into a condensation kettle, stirring for 1 hour, adding 0.6 part of antioxidant DLTP, stirring for 5 minutes, adding 70 parts of saturated NaCl salt solution at the condensation temperature of 0 ℃, stirring for 1 hour, adding 30 parts of separant (prepared by mixing potassium fatty acid, zinc stearate and calcium carbonate in a mass ratio of 1:2: 2), adding 10 parts of calcium chloride, heating to 70 ℃, stirring for 1.5 hours, washing, dehydrating and drying to obtain the powdery butyronitrile rubber.
3) The powder glue mixture for 3D printing comprises: 10 parts of powdered nitrile rubber, 100 parts of polyethylene, 0.3 part of Si69, 0.2 part of phenolic resin 2402 and 0.5 part of montmorillonite are mixed at a high speed and granulated in a double-screw extruder at 180 ℃ to prepare the powder mixed material for 3D printing.
The performance of the prepared mixture is as follows: the melt mass flow rate (g/10min) is 0.30, the tensile yield stress is 10.2MPa, the tensile fracture stress is 11.1MPa, and the brittle temperature is-135 ℃.
Example 3a process for the preparation of a polyethylene blend containing a polyurethane modified powdered rubber for 3D printing, the following steps are performed in order:
1) and preparing a polyurethane solution:
according to the feed-liquid ratio of 0.3g/ml of fluorinated graphene to perfluoroheptane and 5g/ml of polyurethane to perfluoroheptane;
adding fluorinated graphene into perfluoroheptane, performing ultrasonic treatment at room temperature for 18h, then adding polyurethane, and stirring at 50 ℃ for 15h to dissolve the polyurethane into the perfluoroheptane to obtain a polyurethane solution.
2) And preparing powdered nitrile rubber:
adding 100 parts of butyronitrile latex, 60 parts of soft water and 100 parts of polyurethane solution into a condensation kettle, stirring for 50min, adding 0.3 part of anti-aging agent 1076, stirring for 5min, adding 70 parts of saturated NaCl salt solution at the condensation temperature of 5 ℃, stirring for 30min, adding 20 parts of isolating agent (prepared by mixing potassium fatty acid, zinc stearate and calcium carbonate in a mass ratio of 1:2: 3), adding 20 parts of magnesium sulfate, heating to 90 ℃, stirring for 3 hours, washing, dehydrating and drying to obtain the powdery butyronitrile rubber.
3) The powder glue mixture for 3D printing comprises: high-speed blending 6 parts of powdered nitrile rubber, 100 parts of polyethylene, 0.2 part of Si69, 0.5 part of phenolic resin 2401 and 0.3 part of montmorillonite, and granulating in a double-screw extruder at 180 ℃ to obtain the powder mixed material for 3D printing.
The performance of the prepared mixture is as follows: the melt mass flow rate (g/10min) is 0.23, the tensile yield stress is 9.6MPa, the tensile fracture stress is 11.6MPa, and the brittle temperature is-130 ℃.
Example 4a process for the preparation of a polyethylene blend containing a polyurethane modified powdered rubber for 3D printing, the following steps being performed in order:
1) and preparing a polyurethane solution:
according to the feed-liquid ratio of 0.3g/ml of fluorinated graphene to perfluorohexane and the feed-liquid ratio of 30g/ml of polyurethane to perfluorohexane;
adding fluorinated graphene into perfluorohexane, performing ultrasonic treatment at room temperature for 20h, then adding polyurethane, and stirring at 50 ℃ for 20h to dissolve the polyurethane in the perfluorohexane to obtain a polyurethane solution.
2) And preparing powdered nitrile rubber:
adding 100 parts of butyronitrile latex, 60 parts of soft water and 100 parts of polyurethane solution into a condensation kettle, stirring for 1 hour, adding 0.4 part of antioxidant DLTP, stirring for 5 minutes, adding 80 parts of saturated NaCl salt solution at the condensation temperature of 5 ℃, stirring for 1 hour, adding 10 parts of separant (mixed by potassium fatty acid, zinc stearate and calcium carbonate in a mass ratio of 1:1: 1), adding 20 parts of calcium chloride, heating to 70 ℃, stirring for 2 hours, washing, dehydrating and drying to obtain the powdery butyronitrile rubber.
3) The powder glue mixture for 3D printing comprises: 8 parts of powdered nitrile rubber, 100 parts of polyethylene, 0.2 part of Si69, 0.5 part of phenolic resin 2402 and 0.3 part of montmorillonite are mixed at a high speed and granulated in a double-screw extruder at 180 ℃ to prepare the powder mixed material for 3D printing.
The performance of the prepared mixture is as follows: the melt mass flow rate (g/10min) is 0.30, the tensile yield stress is 9.6MPa, the tensile fracture stress is 12.5MPa, and the brittle temperature is-132 ℃.
Example 5a process for the preparation of a polyethylene blend containing a polyurethane modified powdered rubber for 3D printing, the following steps are performed in order:
1) and preparing a polyurethane solution:
according to the feed-liquid ratio of 0.3g/ml of fluorinated graphene to perfluorohexane and 20g/ml of polyurethane to perfluorohexane;
adding fluorinated graphene into perfluorohexane, performing ultrasonic treatment at room temperature for 15h, then adding polyurethane, and stirring at 100 ℃ for 24h to dissolve the polyurethane in the perfluorohexane to obtain a polyurethane solution.
2) And preparing powdered nitrile rubber:
adding 100 parts of butyronitrile latex, 60 parts of soft water and 100 parts of polyurethane solution into a condensation kettle, stirring for 1 hour, adding 0.2 part of anti-aging agent 1076, stirring for 5 minutes, adding 80 parts of saturated NaCl salt solution at the condensation temperature of 0 ℃, stirring for 1 hour, adding 10 parts of isolating agent (prepared by mixing potassium fatty acid, zinc stearate and calcium carbonate in a mass ratio of 1:2: 2), adding 40 parts of magnesium sulfate, heating to 90 ℃, stirring for 3 hours, washing, dehydrating and drying to obtain the powdery butyronitrile rubber.
3) The powder glue mixture for 3D printing comprises: mixing 7 parts of powdered nitrile butadiene rubber, 100 parts of polyethylene, 0.5 part of Si69, 0.1 part of phenolic resin 2402 and 0.1 part of montmorillonite at a high speed, and granulating in a double-screw extruder at 180 ℃ to obtain the powder mixed material for 3D printing.
The performance of the prepared mixture is as follows: the melt mass flow rate (g/10min) is 0.33, the tensile yield stress is 12.8MPa, the tensile fracture stress is 10.7MPa, and the brittle temperature is-130 ℃.
Example 6a process for the preparation of a polyethylene blend containing a polyurethane modified powdered rubber for 3D printing, the following steps being performed in order:
1) and preparing a polyurethane solution:
according to the feed-liquid ratio of 0.3g/ml of fluorinated graphene to perfluoroheptane and 10g/ml of polyurethane to perfluoroheptane;
adding fluorinated graphene into perfluoroheptane, performing ultrasonic treatment at room temperature for 20h, then adding polyurethane, and stirring at 20 ℃ for 24h to dissolve the polyurethane into the perfluoroheptane, thereby obtaining a polyurethane solution.
2) And preparing powdered nitrile rubber:
adding 100 parts of butyronitrile latex, 80 parts of soft water and 100 parts of polyurethane solution into a condensation kettle, stirring for 30min, adding 0.2 part of antioxidant DLTP, stirring for 5min, adding 100 parts of saturated NaCl salt solution at the condensation temperature of 0 ℃, stirring for 1 hour, adding 30 parts of separant (mixing fatty acid potassium, zinc stearate and calcium carbonate in a mass ratio of 1:2: 3), adding 10 parts of calcium chloride, heating to 60 ℃, stirring for 2 hours, washing, dehydrating and drying to obtain the powdery butyronitrile rubber.
3) The powder glue mixture for 3D printing comprises: 6 parts of powdered nitrile rubber, 100 parts of polyethylene, 0.3 part of Si69, 0.2 part of phenolic resin 2401 and 0.1 part of montmorillonite are mixed at a high speed and granulated in a double-screw extruder at 150 ℃ to prepare the powder mixed material for 3D printing.
The performance of the prepared mixture is as follows: the melt mass flow rate (g/10min) is 0.32, the tensile yield stress is 10.7MPa, the tensile fracture stress is 11.4MPa, and the brittle temperature is-128 ℃.
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (4)
1. The preparation method of the polyethylene mixture containing the polyurethane modified powder rubber for 3D printing is characterized by comprising the following steps:
1) and preparing a polyurethane solution:
adding fluorinated graphene into perfluoroalkane serving as a solvent, performing ultrasonic treatment for 15-20 hours at room temperature, then adding polyurethane, and stirring for 12-24 hours at 20-100 ℃ to obtain a polyurethane solution;
the feed-liquid ratio of the fluorinated graphene to the perfluoroalkane is 0.1-0.6 g/ml, and the feed-liquid ratio of the polyurethane to the perfluoroalkane is 1-30 g/ml;
the polyurethane is water-based polyurethane; the number of layers of the fluorinated graphene is less than or equal to 20, the thickness of the fluorinated graphene is 0.8-5.0 nm, the particle size of the fluorinated graphene is 2.0-5.0 mu m, and the fluorine content of the fluorinated graphene is 20-40 wt.%;
the perfluoroalkane is perfluorohexane, perfluorocyclohexane or perfluoroheptane;
2) and preparing powdered nitrile rubber: adding 100 parts of nitrile latex, 50-80 parts of soft water and 90-110 parts of polyurethane solution into a container, uniformly stirring, adding 0.1-0.6 part of anti-aging agent, uniformly stirring, adding 50-100 parts of demulsifier at 0-10 ℃, uniformly stirring, adding 10-30 parts of separant and 10-40 parts of coagulant, heating to 60-90 ℃, stirring for 1-3 hours, washing, dehydrating and drying to obtain powdered nitrile rubber;
the anti-aging agent is 1076 or DLTP, the demulsifier is a saturated NaCl aqueous solution, the separant is a compound consisting of a fatty acid soap compound, a stearate compound and a carbonate compound according to the mass ratio of 1:1: 1-1: 2:3, and the coagulant is divalent salt
3) Uniformly mixing 5-10 parts of powdered nitrile butadiene rubber, 100 parts of polyethylene, 0.2-0.5 part of silane coupling agent, 0.1-0.5 part of phenolic resin and 0.1-0.5 part of montmorillonite, and granulating in a double-screw extruder at 150-200 ℃ to prepare a powder mixed material for 3D printing;
the polyethylene is high density polyethylene;
the above parts are all parts by mass.
2. The method of preparing a polyurethane modified powdered rubber-containing polyethylene mixture for 3D printing as claimed in claim 1, wherein: the fatty acid soap compound is fatty acid potassium, the stearate compound is zinc stearate, and the carbonate compound is calcium carbonate; the divalent salt is magnesium sulfate and calcium chloride.
3. The method for preparing a polyurethane modified powder rubber-containing polyethylene mixture for 3D printing according to claim 2, wherein in the step 3): the silane coupling agent is Si69 coupling agent, and the phenolic resin is phenolic resin 2401 and phenolic resin 2402.
4. The method of preparing a polyurethane modified powdered rubber-containing polyethylene mixture for 3D printing according to claim 1, characterized by the following steps in sequence:
1) and preparing a polyurethane solution:
according to the feed-liquid ratio of 0.2g/ml of fluorinated graphene to perfluorohexane and the feed-liquid ratio of 10g/ml of polyurethane to perfluorohexane;
adding fluorinated graphene into perfluorohexane, performing ultrasonic treatment at room temperature for 15h at 200w, then adding polyurethane, and stirring at 20 ℃ for 12h to dissolve the polyurethane into the perfluorohexane to prepare a polyurethane solution;
2) and preparing powdered nitrile rubber:
adding 100 parts of nitrile latex, 60 parts of soft water and 90 parts of polyurethane solution into a condensation kettle, stirring for 30min, adding 0.2 part of anti-aging agent 1076, stirring for 5min, adding 50 parts of saturated NaCl salt solution at the condensation temperature of 10 ℃, stirring for 40min, then adding 10 parts of isolating agent, adding 20 parts of magnesium sulfate, heating to 70 ℃, stirring for 2 hours, washing, dehydrating and drying to obtain powder nitrile rubber;
the separant is a mixture consisting of potassium fatty acid, zinc stearate and calcium carbonate in a mass ratio of = 1:1: 1;
the washing is repeated washing with soft water for 3-5 times;
the dehydration is centrifugal dehydration;
drying for 20 hours at 100-120 ℃;
3) the powder glue mixture for 3D printing comprises: 5 parts of powdered nitrile rubber, 100 parts of polyethylene, 0.2 part of Si69, 0.3 part of phenolic resin 2401 and 0.5 part of montmorillonite are blended at a high speed, wherein the high speed blending is carried out for 20-50 minutes at the rotating speed of 100-200 rpm, and then granulation is carried out in a double-screw extruder at 150 ℃ to prepare the polyethylene mixture containing the polyurethane modified powdered rubber for 3D printing.
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