CN110698807A - Recycled plastic for 3D printing and preparation method thereof - Google Patents
Recycled plastic for 3D printing and preparation method thereof Download PDFInfo
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Abstract
The invention relates to recycled and regenerated plastic for 3D printing, which is prepared from 60-70 parts of recycled and regenerated plastic, 5-20 parts of glass fiber, 3-10 parts of graphene, 1-10 parts of a toughening agent, 2-3 parts of a dispersing agent, 1-15 parts of biochar, 1-5 parts of a compatilizer, 0.1-2 parts of a chain extender, 0.5-1 part of a lubricant, 0.1-5 parts of a foaming agent and 1-8 parts of other additives. In addition, the EVA can also comprise 10-60 parts, and the content of VA in the EVA is 20-55%. The graphene-like material is one of silicon alkene, germanium alkene and molybdenum disulfide which are subjected to surface active treatment. The chain extender is one or more of pyromellitic anhydride, dicumyl peroxide and acrylonitrile-butadiene-styrene copolymer grafted oxazoline. The recycled and regenerated plastic is one or more of ABS, polypropylene and PET.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to recycled and regenerated plastic for 3D printing and a preparation method thereof.
Technical Field
Polypropylene (PP) is a semicrystalline thermoplastic resin, usually a translucent colorless solid, odorless and nontoxic. The composite material has the characteristics of good mechanical property, good thermal stability, excellent forming and processing properties, relatively low price and the like, and is widely applied to the fields of automobiles, household appliances, electronics and electricity and the like. However, unmodified PP has the disadvantages of low tensile strength, poor impact resistance, flammability, etc., which limits its further applications.
To solve this problem, the industry often uses blending polypropylene with other types of resins and additives to improve the properties of the material. The glass fiber reinforced composite material is a composite material prepared by taking a polymer as a matrix and glass fiber as a reinforcing material. Research shows that the strength of the material can be greatly enhanced by adding the fiber material into the polypropylene, and the heat distortion temperature of the polypropylene material can be improved. However, the polypropylene composite material for battery cases has poorer flame retardant property after the glass fiber is added. When the polypropylene is used in the fields of household appliances, electronic products and the like, certain mechanical properties and higher flame retardant property are required. Therefore, how to improve the rigidity of the polypropylene and make the polypropylene have excellent flame retardant property, toughness and heat conductivity has great application value.
ABS resin is thermoplastic engineering plastic developed in 40 years of 20 th century, and is ternary graft copolymer comprising acrylonitrile (A), butadiene (B) and styrene (S). ABS resin is the plastic with the largest output and the most extensive application at present, and the price is cheaper. With the rapid development of the plastic industry and the continuous expansion of the industrialization scale, the environmental pollution caused by respective wastes of PP, ABS and PET is more and more serious, and the damage and loss of the wastes to the ecological environment and the economic development become social problems to be solved urgently. The PP, ABS and PET wastes or waste materials are added and recycled and then are blended to obtain the high polymer recycled alloy plastic with excellent performance and low price, and the high polymer recycled alloy plastic has good practical value and prospect in the aspects of electronic appliances, automobiles, mechanical parts, daily necessities and the like. However, since the PP, ABS and PET wastes or waste materials are different in source and are used, the properties of the PP, ABS and PET wastes or waste materials are greatly reduced compared with those of new materials, and the PP, ABS and PET wastes or waste materials are difficult to be directly used for engineering plastics, so that the PP, ABS and PET wastes or waste materials need to be subjected to optimized modification treatment to obtain high-performance alloy materials with practical values for recycling
The prior art with publication number CN104629307A discloses a flame-retardant recycled plastic prepared from recycled PC and ABS, which comprises the following components in percentage by mass: 30-60% of PC recycled material, 20-40% of ABS recycled material, 5-10% of glass fiber, 5-10% of main flame retardant, 2-4% of auxiliary flame retardant, 0.5-2% of anti-aging agent, 0.1-1% of chain extender, 1-3% of toughening compatilizer, 0.1-0.5% of antioxidant and 0.5-1% of lubricant, wherein the PC recycled material and the ABS recycled material are used as base materials, and a proper amount of auxiliary agents such as anti-aging agent, chain extender, toughening compatilizer and the like are added in modes such as glass fiber reinforcement, main flame retardant and auxiliary flame retardant synergistic flame retardant modification, so that the obtained recycled plastic has good mechanical property and flame retardant property, and is good in processing property and strong in weather resistance, and the cost can be obviously reduced when the recycled plastic is applied to the aspects of electronic appliances, automobile industry.
Therefore, if the waste plastics can be recycled by a simple method, the cost can be saved, and the environment can be protected. In the era of low carbon and environmental protection advocated worldwide, the recycling of waste plastics is widely supported by governments and recognized by knowledgeable persons, and considerable economic and environmental benefits can be obtained.
On the other hand, 3D printing has gained increasing attention in recent years as a new additive manufacturing technology. The 3D printing is based on a digital model, and the objects with different topological structures are manufactured by using materials such as thermoplastic resin, photosensitive resin, powdered metal, ceramic and the like in a layer-by-layer printing mode. Compared with the traditional manufacturing mode, 3D printing does not need a die, and objects with very complex structures and individuation can be prepared, so that various requirements can be met. Currently, 3D printing has been used in the fields of medical and medical engineering, electronics, aerospace, construction industry, etc. Depending on the printing technique and the printing material, the 3D printing can be mainly classified into a Fused Deposition Method (FDM), a selective laser sintering method (SLS), a stereolithography method (SLA), an inkjet printing method (3DP), and the like. Among many 3D printing technologies, the FDM technology has the advantages of simple printing principle, low technical threshold, abundant raw materials, and relatively inexpensive equipment, and is therefore always the focus of research. FDM technology requires that the material be processed into wires of a defined diameter, after which objects of any topology are prepared using the melt-solidification principle. With almost thirty years of development, FDM technology is now becoming mature.
3D printing technology itself is not complicated, but available consumables are a difficulty, and in recent years, attention is paid to 3D printing materials suitable for FDM.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention not only solves the problem of reduced toughness, impact strength, tensile strength at break and other properties of the recycled plastic, provides the recycled plastic with good compatibility and high impact strength and tensile strength at break, but also overcomes the thermal shrinkage of the recycled plastic in the 3D printing and forming process, and provides the recycled plastic for 3D printing and the preparation method thereof, so that the printed product has stable shape and high forming rate. Through chain extension tackifying treatment on the recycled plastic, the interfacial compatibility of the biochar and the synergistic enhancement of the biochar/graphene, the flame retardance, rigidity and notch impact strength of the recycled and regenerated plastic are effectively improved, and the method is realized through the following technical scheme:
the recycled and regenerated plastic for 3D printing comprises 60-70 parts of recycled and regenerated plastic, 5-20 parts of glass fiber, 3-10 parts of graphene, 1-10 parts of a toughening agent, 2-3 parts of a dispersing agent, 1-15 parts of biochar, 1-5 parts of a compatilizer, 0.1-2 parts of a chain extender, 0.5-1 part of a lubricant, 0.1-5 parts of a foaming agent and 1-8 parts of other additives.
Preferably, the EVA also comprises 10-60 parts of EVA, and the content of the VA in the EVA is 20-55%.
Preferably, the flame-retardant coating also comprises 8-12 parts of a flame-retardant composition. The flame retardant composition comprises a flame retardant and a synergistic flame retardant, wherein the flame retardant is a phosphorus-containing halogen-free flame retardant, and the synergistic flame retardant is a mixture of antimony trioxide and silicon stannate.
Wherein the mass ratio of the flame retardant to the synergistic flame retardant is 5:2, and the mass ratio of the antimony trioxide to the silicon stannate is 1: 1.
Preferably, the graphene-like is one of surface-active-treated silicon, germanium alkene and molybdenum disulfide.
Preferably, the chain extender is one or more of pyromellitic anhydride, dicumyl peroxide and acrylonitrile-butadiene-styrene copolymer grafted oxazoline.
Preferably, the chain extender comprises the following components in parts by weight: 5-12 parts of pyromellitic anhydride, 6-15 parts of dicumyl peroxide and 7-18 parts of acrylonitrile-butadiene-styrene copolymer grafted oxazoline.
Preferably, the foaming agent is a physical foaming agent or a chemical foaming agent, and the physical foaming agent is n-pentane, n-hexane, n-heptane or petroleum ether; the chemical foaming agent is azodicarbonamide or sodium dodecyl sulfate.
Preferably, the recycled and regenerated plastic is one or more of ABS, polypropylene and PET.
Preferably, the other additive is at least one of a stabilizer, an antistatic agent, an antioxidant, an ultraviolet absorber, a filler and a pigment.
The invention has the following beneficial effects:
firstly, the graphene-like material provided by the invention plays a role of a nucleating agent, and improves the crystallization behavior of the recycled plastic matrix resin in the regeneration process so as to improve the mechanical property of the recycled plastic matrix resin.
Secondly, the surface of the biochar after carbonization treatment does not contain hydrophilic groups, so that the compatibility with recycled plastic matrix resin is effectively improved, the biochar is easy to disperse in the process of processing and forming, and the biochar can play a role of a lubricant for other additive components.
Thirdly, the biochar disclosed by the invention has a rich pore structure and a high specific surface area, mechanical meshing action can be generated among other recycled plastic matrix resins, the biochar and graphene-like can play a role in enhancing as an enhancing phase, the problems existing in glass fiber filling and enhancing are solved, and the mechanical properties and flame retardant properties of the recycled regenerated plastic, such as impact strength, breaking tensile strength and the like, are improved.
Fourthly, the recycled plastics with different components can be compatible into homogenized composite plastics, the range of 3D printing consumables is widened, high-quality recycling of waste plastics is realized, and the method has economic and environmental benefits.
Detailed Description
The present invention will be further described with reference to specific examples for better illustrating the objects, technical solutions and advantages of the present invention, but the scope of the present invention is not limited to the following examples.
The recycled and regenerated plastic for 3D printing comprises 60-70 parts of recycled and regenerated plastic, 5-20 parts of glass fiber, 3-10 parts of graphene, 1-10 parts of a toughening agent, 2-3 parts of a dispersing agent, 1-15 parts of biochar, 1-5 parts of a compatilizer, 0.1-2 parts of a chain extender, 0.5-1 part of a lubricant, 0.1-5 parts of a foaming agent and 1-8 parts of other additives. Wherein:
1) the modified graphene is active graphene powder treated by a surface treating agent. Preferably, the surface treating agent is a surfactant and a coupling agent, the surfactant is at least one of sodium dodecyl benzene sulfonate, sodium fatty alcohol acyl sulfate, polysiloxane and polyvinyl alcohol, and the coupling agent is at least one of vinyl, epoxy, amino and amide silane coupling agents
2) The toughening agent is at least one of maleic anhydride grafted ethylene-octene copolymer, acrylic acid grafted ethylene-octene copolymer, maleic anhydride grafted ethylene propylene diene monomer, maleic anhydride grafted polypropylene, glycidyl methacrylate grafted ethylene-octene copolymer and maleic anhydride grafted SEBS.
3) The dispersant is at least one of white oil, calcium stearate, zinc stearate and silicone powder.
4) The compatilizer is styrene-maleic anhydride copolymer, maleic anhydride grafted acrylonitrile-butadiene-styrene copolymer, glycidyl methacrylate grafted styrene-acrylonitrile copolymer, glycidyl methacrylate grafted ABS, glycidyl methacrylate grafted SBS and glycidyl methacrylate grafted SEBS, and the grafting rate is 1-6%.
5) The lubricant is modified ethylene di-fatty acid amide and pentaerythritol stearyl fatty acid.
6) The other additive is at least one of nucleating agent, stabilizer, antistatic agent, ultraviolet absorbent, filler and pigment. Nucleating agents, stabilizers, antistatic agents, ultraviolet absorbers, fillers, pigments, which are conventionally used in the art, are suitable for the present invention, and can be selectively added as needed by those skilled in the art.
In a specific embodiment, the graphene-like material is one of surface-active-treated silicon, germanium, and molybdenum disulfide, and preferably molybdenum disulfide.
In a specific embodiment, the chain extender is one or more of pyromellitic anhydride, dicumyl peroxide, and acrylonitrile-butadiene-styrene copolymer grafted oxazoline. As a more preferable embodiment, the chain extender comprises the following components in parts by weight: 5-12 parts of pyromellitic anhydride, 6-15 parts of dicumyl peroxide and 7-18 parts of acrylonitrile-butadiene-styrene copolymer grafted oxazoline.
In particular embodiments, the blowing agent is a physical blowing agent or a chemical blowing agent, the physical blowing agent being n-pentane, n-hexane, n-heptane, or petroleum ether; the chemical foaming agent is azodicarbonamide or sodium dodecyl sulfate.
In a specific embodiment, the recycled and regenerated plastic is one or more of ABS, polypropylene and PET.
The biochar in the present invention is not particularly limited, but is preferably biochar made of plant fibers (e.g., straw), which can be produced according to the existing methods or commercially available.
The invention is further illustrated by the following examples:
example 1
The recycled plastic for 3D printing of the embodiment is composed of 60 recycled plastic, 5 parts of glass fiber, 3 parts of molybdenum disulfide, 3 parts of maleic anhydride grafted ethylene-octene copolymer, 2 parts of zinc stearate, 3 parts of biochar, 1 part of styrene-maleic anhydride copolymer, 0.5 part of chain extender, 0.5 part of modified ethylene bis-fatty amide, 0.1 part of azodicarbonamide, and 1 part of antioxidant, 1 part of stabilizer and ultraviolet absorber mixture. Wherein, the recycled and regenerated plastic consists of ABS, polypropylene and PET. The chain extender comprises the following components in parts by weight: 5-12 parts of pyromellitic anhydride, 6-15 parts of dicumyl peroxide and 7-18 parts of acrylonitrile-butadiene-styrene copolymer grafted oxazoline.
The specific surface area of the biochar in the embodiment is 300-500m2。
The method for recycling the recycled plastic for 3D printing comprises the following steps:
step one, molybdenum disulfide surface active treatment: adding molybdenum disulfide slurry with the particle size of 4-8 microns into a reaction kettle, stirring, heating to 60-85 ℃, respectively adding a surfactant and a coupling agent into the reaction kettle for surface treatment, stirring for 3-4 hours to obtain molybdenum disulfide subjected to surface activity treatment, and finally washing and drying to obtain dried molybdenum disulfide for later use; wherein, the weight percentage of the molybdenum disulfide solid content in the molybdenum disulfide slurry is 5-15%, the addition amount of the surfactant is 1-3.0% of the weight percentage of the molybdenum disulfide solid content, and the addition amount of the coupling agent is 1-2.5% of the weight percentage of the molybdenum disulfide solid content.
Step two, the step of preparing the recycled plastic comprises the following steps:
(1) plasticizing recovered plastic powder consisting of ABS, polypropylene and PET by adopting a screw extruder, conveying the plasticized recovered plastic powder into a high-temperature melt reaction kettle, adding a chain extender, setting the temperature of the reaction kettle at 210-230 ℃ and the pressure at 1.8-2.2MPa, and homogenizing and chain extending to obtain the recovered plastic composite melt.
(2) And (3) conveying the recycled plastic composite melt obtained in the step (2) to a filter for filtration, feeding the filter into a double-screw extruder for extrusion and granulation to obtain recycled regenerated plastic for later use.
Step three, the step of blending and pre-foaming the recycled plastic to obtain the 3D printing material comprises the following steps:
(1) the preparation method comprises the steps of putting a mixture of maleic anhydride grafted ethylene-octene copolymer, zinc stearate, styrene-maleic anhydride copolymer, modified ethylene bis fatty amide, azodicarbonamide, an antioxidant, a stabilizer and an ultraviolet absorbent into a low-speed mixer according to a ratio, mixing for 1-5 minutes, putting recycled plastic into the low-speed mixer, and mixing for at least 2 minutes, wherein the rotating speed of the low-speed mixer is 90 revolutions per minute to obtain the modified ethylene-octene copolymer.
(2) And (2) blending the recycled plastic obtained in the step (1) from a main feeding port of a double-screw extruder, adding the modified molybdenum disulfide obtained in the step (I), the surface coupling treated glass fiber and the biochar from a side feeding port of the double-screw extruder, setting the extrusion temperature to be 180-230 ℃, and performing melt extrusion and granulation to obtain the wire master batch.
(3) And adding the wire master batch into a single-screw extruder for processing and cooling, and then drawing and controlling the wire diameter of the wire by a tractor to obtain the 3D printing wire.
Example 2
The recycled and regenerated plastic for 3D printing of the embodiment is prepared from 70 parts of recycled and regenerated plastic, 20 parts of glass fiber, 10 parts of molybdenum disulfide, 10 parts of acrylic acid grafted ethylene-octene copolymer, 3 parts of calcium stearate, 1-15 parts of biochar, 5 parts of maleic anhydride grafted acrylonitrile-butadiene-styrene copolymer, 2 parts of chain extender, 1 part of pentaerythritol hard fatty acid, 5 parts of azodicarbonamide, 30 parts of EVA (new material) with the VA content of 40%, 2 parts of antioxidant, 3 parts of stabilizer and nucleating agent mixture. Wherein:
the diameter of the biological carbon is 50-500nm, the specific surface area is 900-2. The recycled and regenerated plastic consists of ABS, polypropylene and PET.
Recycled plastic for 3D printing was then prepared according to the preparation method of example 1.
Example 3
The recycled and regenerated plastic for 3D printing in the embodiment is a mixture formed by mixing 65 parts of recycled and regenerated plastic, 10 parts of glass fiber, 8 parts of molybdenum disulfide, 6 parts of maleic anhydride grafted polypropylene, 3 parts of zinc stearate, 10 parts of charcoal, 3 parts of ABS grafted with glycidyl methacrylate, 1 part of chain extender, 1 part of pentaerythritol stearic acid, 2 parts of azodicarbonamide and 10 parts of EVA (reclaimed material), wherein the content of VA is 35%, and the mass parts of antioxidant, 5 parts of stabilizer, nucleating agent and compatilizer are 25%, 25% and 50%.
The aperture of the biochar in the embodiment is 150-300nm, and the specific surface area is 1100-1300m2. The recycled and regenerated plastic consists of ABS, polypropylene and PET.
Recycled plastic for 3D printing was then prepared according to the preparation method of example 1.
Comparative example
In this example, the recycled plastic of this example had the following composition: 60 parts of recycled plastic, 5 parts of glass fiber, 3 parts of maleic anhydride grafted ethylene-octene copolymer, 2 parts of zinc stearate, 1 part of styrene-maleic anhydride copolymer, 0.5 part of modified ethylene bis fatty amide, and a mixture of 1 part of antioxidant, 1 part of stabilizer and ultraviolet absorbent. Wherein the recycled plastic consists of ABS, polypropylene and PET, and is prepared by referring to the step (three) of example 1.
Performance detection
The pellets prepared in the above examples and comparative examples were dried in a 90 ℃ forced air oven for 8 hours and then the dried pellets were injection molded on an injection molding machine to obtain corresponding test specimens. The test method comprises the following steps:
tensile strength: testing according to GBT 1040.3-2006 standard;
notched izod impact strength: testing according to the national standard GB/T1843.2-1996;
the fused finger test conditions were tested according to the IS01133:2011 standard.
TABLE-Properties of recycled Plastic for 3D printing
Test results show that the graphene-like and biochar disclosed by the invention have a strong reinforcing effect on recycled plastics, and the impact strength and the tensile strength of the recycled and regenerated plastics are enhanced; the recycled plastic with different components has good compatibility and can be compatible into homogenized composite plastic, so that the melt fluidity of the recycled and regenerated plastic is enhanced, the extrusion speed is stable, the thermal stability of a product is enhanced, the contractibility is reduced, the method is beneficial to printing parts with high precision by using an FDM technology, and the application field of the recycled and regenerated plastic is widened.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. The recycled and regenerated plastic for 3D printing is characterized in that a 3D printing material comprises 60-70 parts of recycled and regenerated plastic, 5-20 parts of glass fiber, 3-10 parts of graphene, 1-10 parts of toughening agent, 2-3 parts of dispersing agent, 1-15 parts of biochar, 1-5 parts of compatilizer, 0.1-2 parts of chain extender, 0.5-1 part of lubricant, 0.1-5 parts of foaming agent and 1-8 parts of other additives.
2. Recycled plastic for 3D printing according to claim 1, characterized in that: the EVA material also comprises 10-60 parts of EVA, and the content of the EVA containing VA is 20-55%.
3. The recycled plastic for 3D printing as claimed in claim 1, further comprising 8 to 12 parts of a flame retardant composition.
4. The recycled plastic for 3D printing as claimed in claim 1, wherein the graphene-like material is one of surface-activated silicon, germanium, molybdenum disulfide.
5. The recycled plastic for 3D printing as claimed in claim 1, wherein the chain extender is one or more of pyromellitic anhydride, dicumyl peroxide, acrylonitrile-butadiene-styrene copolymer grafted oxazoline.
6. The recycled plastic for 3D printing as claimed in claim 5, wherein the chain extender comprises the following components in parts by weight: 5-12 parts of pyromellitic anhydride, 6-15 parts of dicumyl peroxide and 7-18 parts of acrylonitrile-butadiene-styrene copolymer grafted oxazoline.
7. The recycled plastic for 3D printing as claimed in any one of claims 1 to 6, wherein the foaming agent is a physical foaming agent or a chemical foaming agent, and the physical foaming agent is n-pentane, n-hexane, n-heptane or petroleum ether; the chemical foaming agent is azodicarbonamide or sodium dodecyl sulfate.
8. The recycled plastic for 3D printing according to any one of claims 1 to 6, wherein the recycled plastic is one or more of ABS, polypropylene and PET.
9. The recycled plastic for 3D printing as claimed in any one of claims 1 to 6, wherein the other additive is at least one of a stabilizer, an antistatic agent, an antioxidant, an ultraviolet absorber, a filler and a pigment.
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