CN112457624A - Modified regenerated ABS (acrylonitrile-butadiene-styrene) nano composite material as well as preparation method and application thereof - Google Patents
Modified regenerated ABS (acrylonitrile-butadiene-styrene) nano composite material as well as preparation method and application thereof Download PDFInfo
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 184
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 title claims abstract description 144
- 239000000463 material Substances 0.000 title claims abstract description 80
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 14
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- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 35
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical class O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 33
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- PGPMOHVQAHACIX-UHFFFAOYSA-N [3-propanoyloxy-2,2-bis(propanoyloxymethyl)propyl] propanoate Chemical group CCC(=O)OCC(COC(=O)CC)(COC(=O)CC)COC(=O)CC PGPMOHVQAHACIX-UHFFFAOYSA-N 0.000 claims description 6
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical group CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical class C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
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- 101001095088 Homo sapiens Melanoma antigen preferentially expressed in tumors Proteins 0.000 description 4
- 102100037020 Melanoma antigen preferentially expressed in tumors Human genes 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- 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
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
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Abstract
The invention discloses a modified regenerated ABS (acrylonitrile-butadiene-styrene) nano composite material as well as a preparation method and application thereof, belonging to the technical field of regenerated ABS composite materials. The composite material comprises a dispersed phase and auxiliary materials, wherein the dispersed phase is uniformly dispersed in a base material by taking recycled ABS as the base material, and the auxiliary materials are used for improving the mechanical property of the base material. The preparation method comprises the following steps: pretreating recovered ABS, mixing with dispersed phase and adjuvants, melt-extruding the mixture in an extruder, cooling, granulating, oven drying, and making into wire with diameter of 1.75 mm. Compared with the recycled ABS material, the modified recycled ABS nanocomposite material prepared by the invention has the advantages of improved tensile strength, elongation at break, impact strength, bending modulus and light transmittance, good flexibility and mechanical property, smooth printing, no odor, smooth and uniform surface, stable size, difficult shrinkage and the like when being used for 3D printing.
Description
Technical Field
The invention belongs to the technical field of regenerated ABS composite materials, and particularly relates to a modified regenerated ABS nano composite material and a preparation method and application thereof.
Background
ABS is a blend or ternary blend of acrylonitrile, butadiene and styrene, wherein the acrylonitrile enables the mixture to have good heat resistance, chemical resistance and high surface strength; the butadiene enables the mixture to have better impact strength and low-temperature strength recovery; the styrene imparts molding, gloss and rigidity to the blend. The ABS plastic has excellent performance, so that the ABS plastic can be widely used in four fields of automobiles, office appliances, coating, household appliances and the like. In the automotive field: many parts on automobiles are made of ABS plastic, such as instrument panels, bumpers, steering wheels, etc.; there are also a number of uses for ABS plastics in the office appliance sector such as: telephone housings, various office machine housings; coating: in the aspect of indoor or outdoor decoration, the plastic has the advantages of easy compression, easy processing, low cost and the like, and is used for a coating process; household appliance aspect: parts, housings, building materials and the like of household appliances use plastics in large quantities. China belongs to a large population country, the damage repair and replacement speed of automobiles, household appliances, office appliances, coating and other frequently used articles is high, the quantity of the generated waste ABS is very large, and great harm and resource waste are caused to the environment. Therefore, an efficient, environment-friendly and sustainable development method is urgently needed for treating and recycling the ABS material.
The 3D printing adopts an additive manufacturing method, a digital model is obtained through computer modeling or prototype scanning, then the digital model is decomposed into multilayer two-dimensional section data, and then the data are printed layer by layer. In the Fused Deposition Modeling (FDM) technique, which is commonly used in the 3D printing technique, ABS wires are heated and fused, and selectively coated on a hot bed to form a cross section until a three-dimensional configuration is formed. ABS is used as a common traditional engineering plastic, has excellent performance, and is more diversified and more widely used along with the research. The prepared structural product is the basic application of ABS for 3D printing, is widely used in medical treatment and life, and has the performance gradually approaching that of injection molding parts along with the deep research on component formula and printing process. The ABS has good mechanical property and thermal property, aiming at a large amount of waste ABS plastics on the current market, a melt blending method and a high polymer material modification principle are adopted, the recovered ABS plastics are used as raw materials, the recovered ABS plastics are modified or compounded with inorganic nano materials, elastomers, fibers and the like, various additives such as coupling agents, toughening agents, filling agents, anti-aging agents and the like are respectively added, and the novel environment-friendly nano composite material is prepared by a plastic processing technology through processing modes such as hot pressing, melt extrusion, injection molding and the like, can effectively improve the mechanical property, the thermal property and the like of the regenerated ABS composite material, realizes the further optimization of the performance of the recovered ABS nano composite material, and can be used for manufacturing a 3D printing material.
Disclosure of Invention
In view of the above, the present invention aims to provide a modified regenerated ABS nanocomposite, and a preparation method and an application thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a modified regenerated ABS nano composite material comprises a continuous phase taking recovered acrylonitrile-butadiene-styrene copolymer (ABS) as a base material, a dispersed phase uniformly dispersed in the base material and auxiliary materials for improving the mechanical property of the base material;
the weight ratio of the continuous phase, the dispersed phase and the auxiliary materials is 100: 3-14: 40-56;
the composite material has tensile strength of 32.36-38.85 MPa, elongation at break of 4.79-5.68% and impact strength of 16.23kJ/m2～18.14kJ/m2The bending strength is 43.62 MPa-55.74 MPa, and the bending modulus is 900.73 MPa-2282.8 Mpa, the light transmittance of the composite material reaches more than 80%;
the dispersed phase is modified inorganic nano particles;
the auxiliary materials are ABS new material, coupling agent, toughening agent, antioxidant, lubricant and colorant.
Preferably, the modified inorganic nanoparticles are modified nano silicon carbide, modified talcum powder and modified nano titanium dioxide.
Preferably, the weight ratio of the waste ABS, the modified nano silicon carbide, the modified talcum powder, the modified nano titanium dioxide, the new ABS material, the coupling agent, the toughening agent, the antioxidant, the lubricant and the colorant is 100: 1-12: 1:20: 6-18: 11-12: 1-2.
Preferably, the modified nano silicon carbide and the modified nano titanium dioxide are modified by silane, and the modified talcum powder is subjected to surface activation treatment by titanate.
Preferably, the method for performing modification treatment on the modified nano silicon carbide and the modified nano titanium dioxide by using silane comprises the following steps: adding silicon carbide or titanium dioxide into 2% silane solution, stirring for 0.5h, drying, and ball milling.
The modification treatment method of the modified nano silicon carbide comprises the following specific steps: adding silicon carbide into the prepared 2% silane solution, stirring for 0.5h by using a magnetic stirrer, putting into an oven, drying at the temperature of 80 ℃, taking out the dried nano silicon carbide, putting into a ball mill, adjusting the rotating speed of the ball mill to 200r/min, and ball-milling for 2 h.
The modification treatment method of the modified nano titanium dioxide comprises the following specific steps: adding titanium dioxide into the prepared 2% silane solution, stirring in a magnetic stirrer for 0.5h, then placing in an oven to adjust the temperature to 80 ℃, drying for 3h, taking out, placing in a ball mill, adjusting the rotating speed of the ball mill to 200r/min, and ball-milling for 2 h.
Preferably, the method for carrying out surface activation treatment on the modified talcum powder by titanate comprises the following steps: and adding the dried talcum powder into a 2% titanate solution, heating and stirring for 2 hours, drying, and grinding.
The surface activation treatment method of the modified talcum powder specifically comprises the following steps: drying talcum powder for about 2h at 120 ℃, preparing a 2% solution by titanate (NDZ-101) diluted by absolute ethyl alcohol, pouring the solution into the talcum powder, stirring for 2h by a magnetic stirrer, heating and stirring until most of the absolute ethyl alcohol is volatilized, drying the stirred talcum powder for 2h at 100 ℃ in a drying oven, taking out the dried talcum powder, and grinding to obtain the modified talcum powder.
Preferably, the coupling agent is a silane coupling agent (KH-550) and a modified styrene-butadiene-styrene block copolymer (SBS), the toughening agent is Dibutyl Phthalate (DPB) and modified POE, the antioxidant is pentaerythritol tetrapropionate (1010), the lubricant is common paraffin, and the colorant is carbon black.
More preferably, the weight ratio of the waste ABS, the modified nano silicon carbide, the modified talcum powder, the modified nano titanium dioxide, the new ABS material, the KH-550, the modified SBS, the DPB, the modified POE, the pentaerythritol tetrapropionate, the common paraffin and the carbon black is 100: 1-12: 1:1:20: 1-2: 5-16: 1-2: 10: 1-2.
More preferably, the weight ratio of the waste ABS, the modified nano silicon carbide, the modified talcum powder, the modified nano titanium dioxide, the new ABS material, the KH-550, the modified SBS, the DPB, the POE, the pentaerythritol tetrapropionate, the common paraffin and the carbon black is 100:7:1:1:20:1.5:12:2:10:1.5:2: 1.
Preferably, the modified SBS or POE modification treatment method comprises the following steps: respectively and uniformly mixing SBS or POE with maleic anhydride grafted polyethylene, melting and mixing, adding dicumyl peroxide for grafting, melting and extruding, granulating and drying.
The modification treatment method of the POE comprises the following specific steps: weighing POE, maleic anhydride grafted polyethylene and a dicumyl peroxide cross-linking agent according to the proportion of MAPE to DCP being 100:2:0.5, uniformly mixing the POE and the maleic anhydride grafted polyethylene by a kneading machine, adding dicumyl peroxide for grafting when carrying out melt mixing in a double-screw extruder, carrying out melt extrusion, carrying out granulation by a granulator after extrusion, drying the obtained granules for 1h at 60 ℃ by using a blast dryer, and sealing and storing the obtained granules for later use; the SBS modification treatment method specifically comprises the following steps: weighing SBS, maleic anhydride grafted polyethylene and a dicumyl peroxide cross-linking agent according to the proportion of SBS, MAPE and DCP being 100:4:0.3, uniformly mixing SBS and maleic anhydride grafted polyethylene through a kneading machine, adding dicumyl peroxide for grafting and then melt-extruding when carrying out melt mixing in a double-screw extruder, carrying out grain cutting through a grain cutting machine after extruding, drying obtained grains for 1h at 70 ℃ through a blast dryer, and obtaining the modified SBS rubber which is sealed and stored for later use.
The POE and the SBS have good ageing resistance, fluidity and elasticity, and the modified POE and the modified SBS can further enhance the ageing resistance and the impact strength of the ABS plastic and improve the dispersion effect of the inorganic filler in the ABS.
2. The preparation method of the modified regenerated ABS nano composite material comprises the following steps:
cleaning, drying and removing scrap iron from recovered ABS, and then mixing with a dispersion phase and auxiliary materials to obtain a mixture;
and putting the mixture into an extruder for melt extrusion, cooling, granulating and drying to obtain the modified regenerated ABS nano composite material.
More preferably, the preparation method of the modified regenerated ABS nano composite material comprises the following steps:
putting the recovered ABS plastic into a proper amount of cleaning solution for cleaning, measuring the pH value of the cleaning solution by using pH test paper for many times during the cleaning period, keeping the pH value of the cleaning solution at about 9, adding proper sodium bicarbonate when the pH value is less than 9, and cleaning for about 10 min; washing and recovering the ABS plastic for many times by using distilled water until residual medicines are washed away; putting the cleaned recovered ABS plastic into a forced air drying oven, setting the drying temperature to be 70 ℃, and drying for 2 hours; after the recovered ABS plastic is dried, adsorbing and recovering metal in the ABS plastic by using a magnet;
mixing the treated recovered ABS with modified nano-silicon carbide, modified talcum powder, modified nano-titanium dioxide, new ABS material, KH-550, modified SBS, DPB, modified POE, 1010, common paraffin and carbon black;
putting the mixed materials into an extruder for melt extrusion, cooling by water, and granulating by a granulator; drying the composite material for 2 hours at 70 ℃ in a blast drier to obtain the modified regenerated ABS nano composite material.
Drying the modified regenerated ABS nano composite material granules, and preparing the wires with the diameter of 1.75mm by using a high-precision 3D printing consumable extruder.
3. The modified regenerated ABS nano composite material is applied as a 3D printing material.
The invention has the beneficial effects that:
1) the modified regenerated ABS nano composite material of the invention takes a recovered ABS resin matrix as a continuous phase, takes modified nano silicon carbide, modified nano titanium dioxide and modified talcum powder as a dispersed phase, and properly adds a small amount of new ABS material and modified organic nano materials of POE and SBS, and is characterized in that various additives are prepared into the modified regenerated ABS nano composite material by a melt blending method, wherein, the silicon carbide is modified, so that the modified silicon carbide has the chemical property of organic groups, the modified silicon carbide is more uniformly dispersed in the ABS, the aging resistance, high temperature resistance and strength of the ABS composite material are enhanced, the talcum powder is subjected to surface modification, so as to improve the surface activity of the talcum powder, and the talcum powder is better mixed with the ABS, thereby improving the high temperature creep resistance, impact resistance and surface scratch resistance of the ABS composite material, and carrying out surface modification treatment on the titanium dioxide, the surface energy of titanium dioxide particles is reduced, the surface activity of the titanium dioxide particles is improved, the affinity of the titanium dioxide and ABS is improved, and the aging resistance, the antibacterial property and the ultraviolet resistance of the ABS composite material are improved;
2) the preparation method of the modified regenerated ABS nano composite material is simple to operate, and compared with the recycled ABS material, the tensile strength of the prepared modified regenerated ABS nano composite material is increased by the following range: 2.4-22.9%, the elongation at break is increased by the following range: 8.6% -28.8%, and the impact strength promotion range is as follows: 45.6% -62.7%, the increase range of the bending strength is as follows: 5.5% -34.9%, the increase of flexural modulus is: 17.7% -198.4%;
3) the modified regenerated ABS nano composite material has good application performances such as flexibility and mechanical property, can be used as a 3D printing material, can be used for 3D printing, is smooth in printing and odorless, and has the advantages of smooth surface, attractive appearance, uniformity, stable size, difficulty in shrinkage and the like, so that the modified regenerated ABS nano composite material has wide application value.
Drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
FIG. 1 is a template diagram of a modified recycled ABS nanocomposite material of the present invention;
FIGS. 2-7 are graphs of the infrared spectra (FT-IR) of modified recycled ABS nanocomposites of the present invention;
FIGS. 8 to 14 are X-ray diffraction (XRD) patterns of modified recycled ABS nanocomposites according to the present invention;
FIGS. 15-21 are Scanning Electron Microscope (SEM) images of modified recycled ABS nanocomposites of the present invention;
FIG. 22 is a flexural modulus plot of a modified recycled ABS nanocomposite of the present invention;
FIG. 23 is a plot of the flexural strength of a modified recycled ABS nanocomposite of the present invention;
FIG. 24 is a graph of the impact strength of a modified recycled ABS nanocomposite of the present invention;
FIGS. 25 to 31 are differential thermal-thermogravimetric (TG-DTA) graphs of modified recycled ABS nanocomposites of the present invention.
Detailed Description
The present invention is further described with reference to the following drawings and specific examples so that those skilled in the art can better understand the present invention and can practice the present invention, but the examples are not intended to limit the present invention.
Example 1
The preparation method of the modified regenerated ABS nanocomposite material of the embodiment comprises the following steps:
s1, placing the recovered ABS plastic into a proper amount of cleaning solution for cleaning, measuring the pH value of the cleaning solution by using pH test paper for many times during the cleaning period, keeping the pH value of the cleaning solution at about 9, adding proper sodium bicarbonate when the pH value is less than 9, and cleaning for about 10 min; washing and recovering the ABS plastic for many times by using distilled water until residual medicines are washed away; putting the cleaned recovered ABS plastic into a forced air drying oven, setting the drying temperature to be 70 ℃, and drying for 2 hours; after the recovered ABS plastic is dried, adsorbing and recovering metal in the ABS plastic by using a magnet;
s2, adding silicon carbide into the prepared 2% silane solution, stirring for 0.5h by using a magnetic stirrer, putting into an oven, drying at the temperature of 80 ℃, taking out the dried nano silicon carbide, putting into a ball mill, adjusting the rotating speed of the ball mill to 200r/min, and ball-milling for 2h to obtain the modified nano silicon carbide; adding titanium dioxide into a prepared 2% silane solution, stirring in a magnetic stirrer for 0.5h, then placing in an oven to adjust the temperature to 80 ℃, drying for 3h, taking out, placing in a ball mill, adjusting the rotating speed of the ball mill to 200r/min, and ball-milling for 2h to obtain modified nano titanium dioxide; drying talcum powder for about 2h at 120 ℃, preparing a 2% solution by titanate (NDZ-101) diluted by absolute ethyl alcohol, pouring the solution into the talcum powder, stirring for 2h by a magnetic stirrer, heating and stirring until most of the absolute ethyl alcohol is volatilized, drying the stirred talcum powder for 2h in a drying oven at 100 ℃, taking out the dried talcum powder, and grinding to obtain the modified talcum powder;
s3, weighing POE, maleic anhydride grafted polyethylene and a dicumyl peroxide cross-linking agent according to the proportion of POE, MAPE and DCP being 100:2:0.5, uniformly mixing the POE and the maleic anhydride grafted polyethylene through a kneading machine, adding dicumyl peroxide during melting and mixing in a double-screw extruder, performing melt extrusion after grafting, performing granulation through a granulator after extrusion, and drying the obtained granules at 60 ℃ for 1h by using a blast dryer to obtain the modified POE rubber; weighing SBS, maleic anhydride grafted polyethylene and a dicumyl peroxide cross-linking agent according to the proportion of MAPE to DCP being 100:4:0.3, uniformly mixing SBS and maleic anhydride grafted polyethylene through a kneading machine, adding dicumyl peroxide for grafting when carrying out melt mixing in a double-screw extruder, carrying out melt extrusion, carrying out grain cutting through a grain cutting machine after extrusion, and drying the obtained grains for 1h at 70 ℃ by using a blast dryer to obtain modified SBS rubber;
s4, mixing 300g of the treated recovered ABS plastic with 21g of modified nano-silicon carbide, 3g of modified talcum powder, 3g of modified nano-titanium dioxide, 60g of new ABS material, KH-5504.5 g, 36g of modified SBS, 6 DPB6g, 30g of modified POE, 10104.5 g of common paraffin and 3g of carbon black;
and stirring the mixed materials by a kneading machine for 30min to uniformly mix the materials, setting the temperature of each section of the extruder according to the temperature parameters in the table 1, putting the mixed materials into the extruder for melting and extruding, cooling by water, and granulating by a granulator. Drying the mixture for 2 hours at 70 ℃ in a blast drier to obtain the granules of the modified regenerated ABS nano composite material.
TABLE 1 set temperature of extruder
Example 2
This example was carried out under the same conditions as in example 1 except that KH-550 was replaced with 3g, SBS was replaced with 18g, modified nano-silicon carbide was replaced with 3g, 1010 was replaced with 3g, ordinary paraffin was replaced with 3g, and carbon black was replaced with 6 g.
Example 3
This example was carried out under the same conditions as in example 1 except that KH-550 was replaced with 3g, SBS was replaced with 24g, modified nano-silicon carbide was replaced with 9g, 1010 was replaced with 3g, ordinary paraffin was replaced with 3g, and carbon black was replaced with 6 g.
Example 4
This example was carried out under the same conditions as in example 1 except that SBS was replaced with 30g, the modified nano-sized silicon carbide was replaced with 15g, the normal paraffin was replaced with 3g, and the carbon black was replaced with 6 g.
Example 5
This example was carried out under the same conditions as in example 1 except that KH-550 was replaced with 6g, SBS was replaced with 42g, modified nano-silicon carbide was replaced with 27g, and 1010 was replaced with 6 g.
Example 6
This example was carried out under the same conditions as in example 1 except that KH-550 was replaced with 6g, SBS was replaced with 48g, modified nano-silicon carbide was replaced with 33g, and 1010 was replaced with 6 g.
Detection and analysis
1) Sample preparation of modified regenerated ABS nanocomposite
The new PE100g was poured into the feed inlet of the injection molding machine several times to clean the injection molding machine until pure PE material was injected by the injection molding machine, and the modified regenerated ABS pellets extruded and pelletized by the extruder in example 1 were poured into the feed inlet of the injection molding machine several times. In a manual mode, the material is automatically stored and seated through a starting motor; in a semi-automatic mode, after a series of operations such as closing the safety door, injecting, opening the safety door, taking out a workpiece and the like, the modified regenerated ABS nanocomposite module is successfully prepared, wherein the temperature settings of all sections of the injection molding machine are shown in table 2, and the modified regenerated ABS nanocomposite template is shown in fig. 1.
TABLE 2 injection molding machine set temperature
2) Structural characterization analysis
Infrared Spectroscopy (FT-IR) detection and analysis
Samples of the modified recycled ABS plastics obtained in examples 1 to 6 and the recovered ABS plastics were filed with powder using a file, and the same mass of KBr powder was put in and sufficiently ground into powder, and the measurement was carried out by an instrument, and the results are shown in FIGS. 2 to 7.
In the figure, A0 represents a recovered ABS plastic, and A1 to A6 represent modified recycled ABS plastics obtained in examples 1 to 6.
From the analysis in FIGS. 2-7, it can be seen that the modified recycled ABS nanocomposite has the same absorption wave number as the recycled ABS plastic, and the modified recycled ABS nanocomposite and the recycled ABS have absorption wave numbers of 3000cm-1～3500cm-1Characteristic absorption appears from left to rightThe light transmittance of the modified regenerated ABS nano composite material is higher than that of the recovered ABS, so that the added toughening agent and the modified POE elastomer are well dispersed in the modified regenerated ABS nano composite material. The absorption peaks of the modified recycled ABS nanocomposite and the absorption peaks of the recycled ABS in fig. 6 and 7 overlap, because both the modified POE elastomer and the ABS as graft polymers exhibit high elasticity, so that the milled modified recycled ABS nanocomposite sample powder causes a phenomenon of non-uniform particle size, resulting in non-uniform distribution of plastic powder in the glass sheet.
X-ray diffraction (XRD) detection and analysis
The recovered ABS plastic and the modified regenerated ABS nano composite materials prepared in the embodiments 1 to 6 are respectively used for filing powder by a file, the filed powder is uniformly poured into the concave part on a glass slide, if overflow occurs, the glass slide can be used for flattening, and the redundant powder is carefully removed so as not to influence the precision of the experiment. The sample is placed in an X-ray diffractometer for detection and analysis, and the result is shown in FIGS. 8-14.
Fig. 14 is an XRD pattern of the recovered ABS plastic, from which analysis shows that only characteristic peaks of ABS and no other characteristic peaks appear at 21.453 °, fig. 8 to 13 are XRD patterns of the modified recycled ABS nanocomposites obtained in examples 1 to 6, respectively, and from fig. 8 to 13, from which analysis shows that characteristic peaks of modified nano-silicon carbide, modified nano-titanium dioxide and modified talc appear at 35.264 °, 44.698 ° and 59.257 °, respectively, thus proving that the modified inorganic nano-filler has been uniformly dispersed in the composite. In examples 1 to 6, the peak heights of the ABS diffraction peaks were all less than the peak height of the recovered ABS, because the modified POE elastomer and the modified SBS rubber have the characteristics of low crystallinity and good fluidity, the crystallinity of the prepared modified recycled ABS nanocomposite was reduced.
Scanning Electron Microscope (SEM) detection and analysis
The recovered ABS material and the modified regenerated ABS nanocomposite samples obtained in examples 1 to 6 were granulated to have a width of about 0.5cm, a length of 0.8cm and a height of 0.3 cm. And (3) carrying out gold plating treatment on the section part of the sample by using an ion sputtering instrument, and setting experiment parameters: the high pressure is: 20kV, the magnification is: 1.0kx, working distance: 10mm, electron beam intensity: 10. then, the shape of the cross section was observed, and the results are shown in FIGS. 15 to 21.
FIG. 21 is an SEM image of the impact on the cross section of the recycled ABS, and it can be analyzed that the recycled ABS has a relatively smooth cross section without fine voids, and the grain trend of the cross section is relatively regular and extends in one direction, which is a brittle fracture. FIGS. 15 to 20 are SEM images of the impact cross sections of the modified recycled ABS plastics obtained in examples 1 to 6, respectively, and the SEM images are analyzed. The sections of fig. 15 and 16 are smooth and the section lines are regular, and the added modified nano silicon carbide is dispersed in the ABS, so that the brittle section formed by the rigidity of the recovered ABS is increased. The fracture lines in fig. 17 to 20 have all directions and no regularity, and the modified SBS rubber and the modified POE elastomer are dispersed in the ABS composite material to increase the toughness thereof, so that the sample absorbs energy when receiving impact, thereby causing unevenness of the cross section.
3) Analysis of mechanical Properties
The modules of the modified recycled ABS nanocomposites obtained in examples 1 to 6 were subjected to tensile, flexural, impact and flexural modulus measurements.
Specifically, tensile property detection and analysis: opening a universal testing machine for preheating for 10min, moving a working piston for 2 times, then opening a computer to click software to select the stretching function of the test plastic module on line, finally testing 5 samples of each type according to actual setting parameters, wherein the length is 115mm, the thickness is 4mm, the width is 100mm, the speed is 2mm/min, the data is recorded, and the average value is obtained; and (3) detecting and analyzing the bending property: starting a universal tester, preheating for 10min, connecting a computer, setting parameters, and setting the length, width, thickness and experimental span of the nanocomposite sample to be 8.0cm, 1.0cm, 0.4cm and 6.0cm in sequence. Treating a sample: cutting the samples into 8.0cm long samples by a cutting machine, measuring 5 samples in each group, recording data, and calculating an average value; impact performance detection and analysis: and (3) sample treatment, namely cutting the sample mould into 8.0cm pieces by using a cutting machine, wherein the width of the sample mould is 1.0cm, the thickness of the sample mould is 0.4cm, and polishing the surface of the sample mould by using polishing paper. The results are shown in table 3, fig. 22, fig. 23 and fig. 24.
TABLE 3 mechanical Properties of recycled ABS plastics and modified recycled ABS plastics
From the analysis in table 3, it can be seen that the tensile strength of the modified recycled ABS nanocomposite is 32.36 Mpa-38.85 Mpa, which is improved compared with the tensile strength of recycled ABS, and the increase range is: 2.4 to 22.9 percent. The tensile strength is mainly influenced by talcum powder, the talcum powder is nano inorganic particles treated by a surface modifier, the surface modifier has two different functional groups, the groups which are hydrophilic to inorganic particles are easy to chemically react with the surfaces of the inorganic particles, and the groups which are hydrophilic to organic substances can chemically react with ABS resin or form entanglement of molecular chains. The talcum powder treated by the carbonate coupling agent is better dispersed in the ABS resin, so that the mechanical property of the ABS resin is improved.
With the addition of the modified silicon carbide, the modified titanium dioxide and the talcum powder, the elongation at break is increased to a certain extent compared with that of recovered ABS, and the modified POE elastomer has good fluidity, so that the dispersion conditions of the modified nano silicon carbide, the modified talcum powder and the modified nano titanium dioxide in the recovered ABS plastic in the inorganic filler are improved, the modified nano silicon carbide with high strength can be better dispersed in the recovered ABS, and the rigidity of the modified regenerated ABS nano composite material is improved.
In FIGS. 22, 23 and 24, A0 represents the recovered ABS plastic, and A1 to A6 represent the modified recycled ABS plastics obtained in examples 1 to 6.
Fig. 22 is a flexural modulus graph, and as can be seen from the data analysis in fig. 22 and table 3, the flexural modulus of the modified recycled ABS nanocomposite is 900.73Mpa to 2282.8Mpa, and the flexural modulus of the modified recycled ABS nanocomposite is increased compared to the flexural modulus of the recycled ABS, and the increase in flexural modulus is: 17.7% -198.4%, and shows the trend of decreasing first, then increasing second and then decreasing; FIG. 23 is a bending strength graph, and from the analysis in FIG. 23 and Table 3, the modified recycled ABS nanocomposite has a bending strength of 43.62MPa to 55.74MPa, which is greater than that of recycled ABS, and the increase is: 5.5 to 34.9 percent, and the trend is increasing first and then decreasing. From the comprehensive analysis of fig. 22 and 23, it can be seen that with the addition of the modified nano-silicon carbide and the modified SBS, the bending strength of the modified recycled ABS nanocomposite prepared in example 1 is 55.74MPa, which is 34.9% higher than that of recycled ABS; the flexural modulus is 1693.71Mpa, which is improved by 121.37% compared with the recovered ABS.
FIG. 24 is a bar graph of the impact strength of the modified recycled ABS nanocomposite, and the data analysis in FIG. 24 and Table 3 shows that the impact strength of the modified recycled ABS nanocomposite is 16.23kJ/m2～18.14kJ/m2And the impact strength is higher than that of recovered ABS, and the lifting amplitude of the impact strength is as follows: 45.6 to 62.7 percent, the trend is first increasing and then decreasing, wherein the impact strength of the modified regenerated ABS nano composite material prepared in example 1 is improved by 62.7 percent compared with that of recycled ABS. With the gradual increase of the modified SBS rubber and the addition of the modified POE elastomer, the modified SBS and the modified POE have low cohesive energy, narrow relative molar mass distribution and strong shear sensitivity, so that the impact strength of the modified and regenerated ABS nano composite material is improved.
4) Differential thermal-thermogravimetric (TG-DTA) analysis
The recovered ABS plastic and the modified regenerated ABS nanocomposite samples prepared in examples 1 to 6 were ground into powder, 10mg of the sample was weighed into a crucible, the crucible with the sample was placed into the right pan of a differential thermal balance, and the left pan of the differential thermal balance was placed into an empty crucible as a reference. Before differential thermal analysis, the thermogravimetric analyzer is preheated for about 30min, the initial temperature of the experiment is set to be 25 ℃, the heating rate is set to be 20 ℃/min, and the termination temperature of the experiment is set to be 800 ℃. Examples 1-6 one sample from each set was taken for thermogravimetric-differential thermal analysis. The results are shown in FIGS. 25 to 31.
In the figure, the abscissa A represents the temperature, FIG. 31 is a differential thermal-thermogravimetric analysis chart of the recovered ABS plastic, and FIGS. 25 to 30 are differential thermal-thermogravimetric analysis charts of the modified recycled ABS nanocomposites obtained in examples 1 to 6. As can be seen from the analysis in FIG. 31, the decomposition temperature of the recovered ABS plastic starts at about 280 ℃, the thermogravimetric curve rapidly decreases in the range from 280 ℃ to 450 ℃, and the temperature at which the ABS plastic is completely decomposed is about 540 ℃ as seen from the differential thermal curve. From the analysis of FIGS. 25 to 30, the decomposition temperature of the modified and regenerated ABS nanocomposite was about 350 deg.C, the thermogravimetric curve of the modified and regenerated ABS nanocomposite decreased rapidly between 350 deg.C and 480 deg.C, and the complete decomposition temperature of the modified and regenerated ABS nanocomposite was about 600 deg.C from the differential thermal curve. The thermal property of the modified regenerated ABS nano composite material is proved to be obviously improved, so that the modified regenerated ABS nano composite material can play a role in flame retardance within a certain temperature range.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. A modified regenerated ABS (acrylonitrile-butadiene-styrene copolymer) nano composite material is characterized by comprising a continuous phase taking recovered ABS as a base material, a dispersed phase uniformly dispersed in the base material and auxiliary materials for improving the mechanical property of the base material;
the mass ratio of the continuous phase, the dispersed phase and the auxiliary materials is 100: 3-14: 40-56;
the composite material has tensile strength of 32.36-38.85 MPa, elongation at break of 4.79-5.68% and impact strength of 16.23kJ/m2～18.14kJ/m2The bending strength is 43.62-55.74 Mpa, the bending modulus is 900.73-2282.8 Mpa, and the light transmittance of the composite material is more than 80%;
the dispersed phase is modified inorganic nano particles;
the auxiliary materials are ABS new material, coupling agent, toughening agent, antioxidant, lubricant and colorant.
2. The modified recycled ABS nanocomposite as claimed in claim 1, wherein the modified inorganic nanoparticles are modified nano-silicon carbide, modified talc powder and modified nano-titanium dioxide.
3. The modified recycled ABS nanocomposite material as claimed in claim 2, wherein the weight ratio of the recycled ABS, the modified nano silicon carbide, the modified talcum powder, the modified nano titanium dioxide, the ABS new material, the coupling agent, the toughening agent, the antioxidant, the lubricant and the colorant is 100: 1-12: 1:1:20: 6-18: 11-12: 1-2.
4. The modified recycled ABS nanocomposite as claimed in claim 2, wherein the modified nano silicon carbide and the modified nano titanium dioxide are modified by silane, and the modified talc is surface-activated by titanate.
5. The modified recycled ABS nanocomposite as claimed in claim 3, wherein the coupling agents are silane coupling agent (KH-550) and modified styrene-butadiene-styrene block copolymer (SBS), the toughening agent is Dibutyl Phthalate (DPB) and modified polyolefin elastomer (POE), the antioxidant is pentaerythritol tetrapropionate, the lubricant is normal paraffin, and the colorant is carbon black.
6. The modified and regenerated ABS nanocomposite material as claimed in claim 5, wherein the mass ratio of the recycled ABS, the modified nano silicon carbide, the modified talcum powder, the modified nano titanium dioxide, the new ABS material, the KH-550, the modified SBS, the DPB, the modified POE, the pentaerythritol tetrapropionate, the common paraffin and the carbon black is 100: 1-12: 1:1:20: 1-2: 5-16: 1-2: 10: 1-2.
7. The modified recycled ABS nanocomposite as claimed in claim 6, wherein the weight ratio of the recycled ABS, the modified nano silicon carbide, the modified talcum powder, the modified nano titanium dioxide, the ABS virgin material, the KH-550, the modified SBS, the DPB, the modified POE, the pentaerythritol tetrapropionate, the common paraffin wax and the carbon black is 100:7:1:1:20:1.5:12:2:10:1.5:2: 1.
8. The modified recycled ABS nanocomposite as claimed in claim 5, wherein the modified SBS or POE is prepared by the following steps: respectively and uniformly mixing SBS or POE with maleic anhydride grafted polyethylene, melting and mixing, adding dicumyl peroxide for grafting, melting and extruding, granulating and drying.
9. The method for preparing the modified recycled ABS nanocomposite as claimed in any one of claims 1 to 8, comprising the steps of:
cleaning, drying and removing scrap iron from recovered ABS, and then mixing with a dispersion phase and auxiliary materials to obtain a mixture;
putting the mixture into an extruder for melt extrusion, cooling, granulating and drying to obtain modified regenerated ABS nano composite material granules;
drying the modified regenerated ABS nano composite material granules, and preparing the wires with the diameter of 1.75mm by using a high-precision 3D printing consumable extruder.
10. Use of the modified recycled ABS nanocomposite according to any one of claims 1 to 8 as 3D printing material.
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