Background
3D printing, one of the rapid prototyping technologies, is a technology for constructing an object by using an adhesive material such as powdered metal or plastic and the like in a layer-by-layer printing manner based on a digital model file. 3D printing is typically achieved using digital technology material printers. The method is often used for manufacturing models in the fields of mold manufacturing, industrial design and the like, and is gradually used for directly manufacturing some products, and parts printed by the technology are already available. The technology has applications in jewelry, footwear, industrial design, construction, engineering and construction (AEC), automotive, aerospace, dental and medical industries, education, geographic information systems, civil engineering, firearms, and other fields.
The common printer used in daily life can print planar articles designed by a computer, the working principle of the 3D printer is basically the same as that of the common printer, only the printing materials are different, the printing materials of the common printer are ink and paper, the 3D printer is internally provided with different printing materials such as metal, ceramic, plastic, sand and the like, the printing materials are actual raw materials, after the printer is connected with the computer, the printing materials can be overlapped layer by layer through computer control, and finally, a blueprint on the computer is changed into an actual object. Colloquially, a 3D printer is a device that can "print" out real 3D objects, such as printing a robot, printing a toy car, printing various models, even food, and so on. The generic name "printer" refers to the technical principle of a common printer, since the process of layered processing is very similar to inkjet printing. This printing technique is called a 3D stereoscopic printing technique.
There are many different techniques for 3D printing. They differ in the way the building components are built up in different layers, in the way the materials are available. Common materials for 3D printing include nylon glass fiber, durable nylon materials, gypsum materials, aluminum materials, titanium alloys, stainless steel, silver plating, gold plating and rubber materials.
The Fused Deposition Modeling (FDM) rapid prototyping process is a method of heating and melting various wires (such as engineering plastics ABS, polycarbonate PC, etc.) without using laser as a forming energy source, and then performing the Deposition molding, which is abbreviated as FDM. FDM has its inherent advantages and disadvantages compared to other molding techniques. The advantages are that: high forming precision, good hardness of the printing model and multiple colors. The disadvantages are as follows: the surface of the molded article was rough. FDM has unique advantages over conventional fabrication methods. First, relatively fine mechanical parts can be manufactured. Secondly, the mass-produced printed article can reduce the production cost to a certain extent.
According to the theory of FDM forming technology, almost all melt processable polymeric materials can be formed with FDM, and there are many wires for FDM forming technology, for example: ABS, PLA, PA, PC, PS, HIPS, TPU, PEEK, and the like. PVC is one of five general plastics in the world, has the advantages of low price, easy obtainment, good chemical stability, acid and alkali corrosion resistance, weather resistance, impact resistance, electrical insulation property and the like, and is widely applied in many fields. However, due to the instability of the ink at high temperature, the ink is not easy to extrude into filaments, and is not popularized in the field of 3D printing application.
Disclosure of Invention
In view of the above, the invention provides a 3D printing polyvinyl chloride polymer modified wire and a preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the 3D printing polyvinyl chloride high-molecular modified wire is composed of the following raw materials in parts by weight:
40-50 parts of polyvinyl chloride resin
10-20 parts of styrene thermoplastic elastomer
35-45 parts of inorganic filler
10-20 parts of heat stabilizer
0.8-1.6 parts of coupling agent
0.2-0.4 of lubricant.
Preferably, the polyvinyl chloride resin is composed of a polymerization degree of 700-850 and a polymerization degree of 1000-1100 polyvinyl chloride resin.
Preferably, the styrenic thermoplastic elastomer comprises at least one of an ethylenic thermoplastic elastomer selected from the group consisting of a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, and a hydrogenated styrene-isoprene-styrene block copolymer.
Preferably, the inorganic filler comprises one or a mixture of more of calcium carbonate, graphite, mica, silica, titanium dioxide, talcum powder, silicon nitride and barium sulfate.
Preferably, the heat stabilizer is a zinc-based heat stabilizer and a tin-based heat stabilizer.
Preferably, the coupling agent comprises at least one of silane coupling agent, maleic anhydride and aluminate coupling agent.
Preferably, the lubricant comprises at least one of sulphur, stearic acid and a stearate.
The preparation method of the 3D printing polyvinyl chloride polymer modified wire is characterized by comprising the following steps:
(1) heating and stirring a heat stabilizer, a coupling agent and a lubricant to 150 ℃, stirring at 60 r/min and 8-10 ℃/min, and stirring for 30 min;
(2) putting the styrene thermoplastic elastomer, the polyvinyl chloride resin and the inorganic filler into a high-speed mixer at the rotating speed of 400 rpm, heating to 90-100 ℃, stirring for 30min, adjusting the rotating speed to 500-800 rpm, adding the mixture obtained in the step (1), heating to 120-130 ℃, transferring to a cooling mixer, and cooling to 30-60 ℃;
(3) adding a double-screw extrusion granulator, wherein the four-section temperature of a machine barrel is respectively as follows: the temperature of the first zone is 100-110 ℃, the temperature of the second zone is 110-120 ℃, the temperature of the third zone is 120-130 ℃, the temperature of the fourth zone is 120-130 ℃, the temperature of the die head is 125-130 ℃, and the rotating speed of the screw is 50-80 rpm; plasticizing and granulating the material by an extruder, and cooling to 40-50 ℃;
(4) extruding the granules of step (3) through a single screw extruder into strands suitable for 3D printing.
The invention has the beneficial effects that: the heat stabilizer, the coupling agent and the lubricant are heated and stirred for pretreatment to form the colloidal additive composition, so that the interface of the polyvinyl chloride resin and the styrene thermoplastic elastomer is easy to bond, the valence bond strength between atoms is improved, and the compatibility and the interface adhesive force with a matrix are improved, so that the heat stability and the flowability of the polyvinyl chloride are improved. The wire rod that single screw rod extruded after the granulation was extruded through twin-screw multiple temperature section, the save time is long, when 3D printed, warp and wire drawing and self-decomposition basically can not take place to with the condition of printing the bottom plate bonding insecure when printing. The invention does not use heavy metal toxic additives, is safe and environment-friendly, has low cost and can be put into the household market.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the 3D printing polyvinyl chloride polymer modified wire is mainly prepared from the following raw materials in parts by weight: polyvinyl chloride resin 20 with polymerization degree of 700-850, polyvinyl chloride resin 30 with polymerization degree of 1000-1100, styrene-butadiene-styrene block copolymer 20, silicon dioxide 20, talcum powder 15, zinc-based heat stabilizer 15, maleic anhydride 1.5 and sodium stearate 0.3.
The preparation method of the 3D printing polyvinyl chloride polymer modified wire is characterized by comprising the following steps:
(1) heating and stirring zinc-based heat stabilizer, maleic anhydride and sodium stearate to 150 ℃, stirring at 60 r/min and 8-10 ℃/min, and stirring for 30 min;
(2) putting the styrene-butadiene-styrene block copolymer, the polyvinyl chloride resin, the silicon dioxide and the talcum powder into a high-speed mixer, heating to 100 ℃ at the rotating speed of 400 rpm, stirring for 30min, regulating the rotating speed to 600 rpm, adding the mixture obtained in the step (1), heating to 120 ℃, transferring into a cooling mixer, and cooling to 30-60 ℃;
(3) adding a double-screw extrusion granulator, wherein the four-section temperature of a machine barrel is respectively as follows: the temperature of the first zone is 100-110 ℃, the temperature of the second zone is 110-120 ℃, the temperature of the third zone is 120-130 ℃, the temperature of the fourth zone is 120-130 ℃, the temperature of the die head is 125-130 ℃, and the rotating speed of the screw is 50-80 rpm; plasticizing and granulating the material by an extruder, and cooling to 40-50 ℃;
(4) the pellets of step (3) were extruded through a single screw into strands of 1.75 mm.
The impact strength is 140J/m, the thermal deformation temperature is 81 ℃, the melt index is 9g/10min, and the dimensional shrinkage of the wire rod is less than 0.5 percent when the wire rod is subjected to a performance test on a 3D printer.
Example 2:
the 3D printing polyvinyl chloride polymer modified wire is mainly prepared from the following raw materials in parts by weight: 30 portions of polyvinyl chloride resin with the polymerization degree of 700-850, 20 portions of polyvinyl chloride resin with the polymerization degree of 1000-1100, 20 portions of styrene-butadiene-styrene block copolymer, 20 portions of silicon dioxide, 15 portions of talcum powder, 15 portions of zinc-based heat stabilizer, 1.5 portions of maleic anhydride and 0.3 portion of sodium stearate.
The preparation method of the 3D printing polyvinyl chloride polymer modified wire is characterized by comprising the following steps:
(1) heating and stirring zinc-based heat stabilizer, maleic anhydride and sodium stearate to 150 ℃, stirring at 60 r/min and 8-10 ℃/min, and stirring for 30 min;
(2) putting the styrene-butadiene-styrene block copolymer, the polyvinyl chloride resin, the silicon dioxide and the talcum powder into a high-speed mixer, heating to 100 ℃ at the rotating speed of 400 rpm, stirring for 30min, regulating the rotating speed to 600 rpm, adding the mixture obtained in the step (1), heating to 120 ℃, transferring into a cooling mixer, and cooling to 30-60 ℃;
(3) adding a double-screw extrusion granulator, wherein the four-section temperature of a machine barrel is respectively as follows: the temperature of the first zone is 100-110 ℃, the temperature of the second zone is 110-120 ℃, the temperature of the third zone is 120-130 ℃, the temperature of the fourth zone is 120-130 ℃, the temperature of the die head is 125-130 ℃, and the rotating speed of the screw is 50-80 rpm; plasticizing and granulating the material by an extruder, and cooling to 40-50 ℃;
(4) the pellets of step (3) were extruded through a single screw into strands of 1.75 mm.
The impact strength is 145J/m, the thermal deformation temperature is 85 ℃, the melt index is 9g/10min, and the dimensional shrinkage of the wire rod is less than 0.5 percent when the wire rod is subjected to a performance test on a 3D printer.
Example 3:
the 3D printing polyvinyl chloride polymer modified wire is mainly prepared from the following raw materials in parts by weight: 30 portions of polyvinyl chloride resin with the polymerization degree of 700-850, 20 portions of polyvinyl chloride resin with the polymerization degree of 1000-1100, 10 portions of styrene-butadiene-styrene block copolymer, 10 portions of hydrogenated styrene-isoprene-styrene block copolymer, 20 portions of silicon nitride, 15 portions of talcum powder, 10 portions of zinc-based heat stabilizer, 5 portions of octyl tin mercaptide, 1 portion of silane coupling agent, 0.5 portion of maleic anhydride and 0.3 portion of sodium stearate.
The preparation method of the 3D printing polyvinyl chloride polymer modified wire is characterized by comprising the following steps:
(1) heating and stirring zinc-based heat stabilizer, octyl tin mercaptide, silane coupling agent, maleic anhydride and sodium stearate to 150 ℃, stirring at 60 revolutions per minute and at 8-10 ℃/minute, and stirring for 30 min;
(2) putting styrene-butadiene-styrene block copolymer, hydrogenated styrene-isoprene-styrene block copolymer, polyvinyl chloride resin, silicon nitride and talcum powder into a high-speed mixer, heating to 100 ℃ at the rotating speed of 400 rpm, stirring for 30min, regulating the rotating speed to 600 rpm, adding the mixture obtained in the step (1), heating to 120 ℃, transferring into a cooling mixer, and cooling to 30-60 ℃;
(3) adding a double-screw extrusion granulator, wherein the four-section temperature of a machine barrel is respectively as follows: the temperature of the first zone is 100-110 ℃, the temperature of the second zone is 110-120 ℃, the temperature of the third zone is 120-130 ℃, the temperature of the fourth zone is 120-130 ℃, the temperature of the die head is 125-130 ℃, and the rotating speed of the screw is 50-80 rpm; plasticizing and granulating the material by an extruder, and cooling to 40-50 ℃;
(4) the pellets of step (3) were extruded through a single screw into strands of 1.75 mm.
The impact strength is 145J/m, the thermal deformation temperature is 82 ℃, the melt index is 9g/10min, and the dimensional shrinkage of the wire rod is less than 0.4 percent when the wire rod is subjected to a performance test on a 3D printer.
Example 4:
the 3D printing polyvinyl chloride polymer modified wire is mainly prepared from the following raw materials in parts by weight: 30 portions of polyvinyl chloride resin with the polymerization degree of 700-850, 20 portions of polyvinyl chloride resin with the polymerization degree of 1000-1100, 10 portions of styrene-butadiene-styrene block copolymer, 10 portions of hydrogenated styrene-isoprene-styrene block copolymer, 20 portions of silicon nitride, 15 portions of talcum powder, 10 portions of zinc-based heat stabilizer, 5 portions of octyl tin mercaptide, 1 portion of silane coupling agent, 0.5 portion of maleic anhydride and 0.3 portion of sodium stearate.
The preparation method of the 3D printing polyvinyl chloride polymer modified wire is characterized by comprising the following steps:
(1) heating and stirring zinc-based heat stabilizer, octyl tin mercaptide, silane coupling agent, maleic anhydride and sodium stearate to 150 ℃, stirring at 60 revolutions per minute and at 8-10 ℃/minute, and stirring for 30 min;
(2) putting styrene-butadiene-styrene block copolymer, hydrogenated styrene-isoprene-styrene block copolymer, polyvinyl chloride resin, silicon nitride and talcum powder into a high-speed mixer, heating to 100 ℃ at the rotating speed of 400 rpm, stirring for 30min, regulating the rotating speed to 600 rpm, adding the mixture obtained in the step (1), heating to 120 ℃, transferring into a cooling mixer, and cooling to 30-60 ℃;
(3) adding a double-screw extrusion granulator, wherein the four-section temperature of a machine barrel is respectively as follows: the temperature of the first zone is 100-110 ℃, the temperature of the second zone is 110-120 ℃, the temperature of the third zone is 120-130 ℃, the temperature of the fourth zone is 120-130 ℃, the temperature of the die head is 125-130 ℃, and the rotating speed of the screw is 50-80 rpm; plasticizing and granulating the material by an extruder, and cooling to 40-50 ℃;
(4) the pellets of step (3) were extruded into 3mm strands by means of a single screw extruder.
The impact strength is 150J/m, the thermal deformation temperature is 81 ℃, the melt index is 9g/10min, and the dimensional shrinkage of the wire rod is less than 0.4 percent when the wire rod is subjected to a performance test on a 3D printer.
Example 5:
the 3D printing polyvinyl chloride polymer modified wire is mainly prepared from the following raw materials in parts by weight: polyvinyl chloride resin 30 with polymerization degree of 700-850, polyvinyl chloride resin 20 with polymerization degree of 1000-1100, styrene-butadiene-styrene block copolymer 15, hydrogenated styrene-isoprene-styrene block copolymer 10, silicon nitride 10, mica 10, talcum powder 15, zinc-based heat stabilizer 10, octyl tin mercaptide 5, silane coupling agent 1, maleic anhydride 0.5 and sodium stearate 0.3.
The preparation method of the 3D printing polyvinyl chloride polymer modified wire is characterized by comprising the following steps:
(1) heating and stirring zinc-based heat stabilizer, octyl tin mercaptide, silane coupling agent, maleic anhydride and sodium stearate to 150 ℃, stirring at 60 revolutions per minute and at 8-10 ℃/minute, and stirring for 30 min;
(2) putting styrene-butadiene-styrene block copolymer, hydrogenated styrene-isoprene-styrene block copolymer, polyvinyl chloride resin, mica, silicon nitride and talcum powder into a high-speed mixer, heating to 100 ℃ at the rotating speed of 400 rpm, stirring for 30min, regulating the rotating speed to 600 rpm, adding the mixture obtained in the step (1), heating to 120 ℃, transferring into a cooling mixer, and cooling to 30-60 ℃;
(3) adding a double-screw extrusion granulator, wherein the four-section temperature of a machine barrel is respectively as follows: the temperature of the first zone is 100-110 ℃, the temperature of the second zone is 110-120 ℃, the temperature of the third zone is 120-130 ℃, the temperature of the fourth zone is 120-130 ℃, the temperature of the die head is 125-130 ℃, and the rotating speed of the screw is 50-80 rpm; plasticizing and granulating the material by an extruder, and cooling to 40-50 ℃;
(4) the pellets of step (3) were extruded into 3mm strands by means of a single screw extruder.
The impact strength is 150J/m, the thermal deformation temperature is 83 ℃, the melt index is 9g/10min, and the dimensional shrinkage of the wire rod is less than 0.4 percent when the wire rod is subjected to a performance test on a 3D printer.
It is to be understood that the foregoing description is only exemplary and illustrative of the present invention as set forth in the claims and is not intended to be limiting thereof. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.