CN111117144B - Modified regenerated ABS (acrylonitrile butadiene styrene) nano composite material and preparation method thereof - Google Patents

Modified regenerated ABS (acrylonitrile butadiene styrene) nano composite material and preparation method thereof Download PDF

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CN111117144B
CN111117144B CN202010054210.4A CN202010054210A CN111117144B CN 111117144 B CN111117144 B CN 111117144B CN 202010054210 A CN202010054210 A CN 202010054210A CN 111117144 B CN111117144 B CN 111117144B
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abs
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composite material
regenerated
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CN111117144A (en
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李道华
何绍芬
杨钰莹
唐鹏
熊菊
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Chongqing Chemical Research Institute Co ltd
Chongqing Chemical Research Institute Materials Technology Co ltd
Chongqing Kezhiyuan Technology Co ltd
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Neijiang Normal University
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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
    • 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
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Abstract

The invention discloses a modified and regenerated acrylonitrile-butadiene-styrene copolymer resin (ABS) nano composite material and a preparation method thereof, belonging to the technical field of nano composite materials. The ABS plastic is prepared from recovered ABS as a main raw material, a new ABS material as an auxiliary material, a filler, a toughening agent, a coupling agent, a cross-linking agent, a plasticizer, a lubricant, a compatilizer and an antioxidant. The preparation method comprises the following steps: and (3) fully mixing the main raw materials and the auxiliary materials, then melting and blending, tabletting and crushing to obtain the modified regenerated ABS nano composite material. Compared with the recovered ABS material, the modified and regenerated ABS nanocomposite material prepared by the invention has the advantages that the tensile strength is improved by more than 20%, the bending strength is improved by more than 55%, the impact strength is improved by more than 45%, and the modified and regenerated ABS nanocomposite material can be reused for production and application, so that the utilization rate of waste ABS materials is greatly improved, the cost is saved, the composite material is safe and environment-friendly, and the composite material has a great popularization and application value.

Description

Modified regenerated ABS (acrylonitrile butadiene styrene) nano composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of nano composite materials, and particularly relates to a modified regenerated ABS nano composite material and a preparation method thereof.
Background
The nano composite material is prepared with resin, rubber, ceramic, metal and other matrix as continuous phase, nano metal, semiconductor, rigid particle, other inorganic particle, fiber, carbon nanotube and other material as dispersed phase, and through proper preparation process, the modifier is dispersed homogeneously in the matrix to form one composite system containing nano material.
Nano calcium carbonate (CaCO) 3 ) Due to the superfine of the nano particles, the crystal structure and the surface electronic structure of the nano particles are changed, so that the quantum size effect, the small size effect, the surface effect and the macroscopic quantum effect which are not possessed by common calcium carbonate are generated, the nano particles can be used as plastic fillers, the production cost can be reduced, the toughening and reinforcing effects are realized, the bending strength, the bending elastic modulus, the thermal deformation temperature and the dimensional stability of plastics can be improved, the plastic hysteresis heat is endowed, and the market additional value of ABS is improved. The nanometer pulvis Talci contains hydrous magnesium silicate of pulvis Talci as main ingredient, and has molecular formula of Mg 3 [Si 4 O 10 ](OH) 2 . The talcum powder has the advantages of anti-sticking property, flow aid property, fire resistance, insulativity, high melting point, inactive chemical property, strong adsorption force and the like, can increase the stability of the shape of a product, increase the tensile strength, the shear strength, the bending strength and the pressure strength, reduce the deformation, the elongation and the thermal expansion coefficient, and has the characteristics of high whiteness, uniform granularity, strong dispersibility and the like.
The carbon fiber is a novel fiber material of high-strength and high-modulus fiber with the carbon content of more than 95 percent. It is made up by stacking organic fibres of flake graphite microcrystals along the axial direction of fibre, and making carbonization and graphitization treatment so as to obtain the invented microcrystal graphite material. The carbon fiber is flexible outside and rigid inside, has lighter weight than metal aluminum, higher strength than steel, corrosion resistance and high modulus, and is an important material in national defense, military industry and civil use.
ABS is a terpolymer of acrylonitrile, butadiene and styrene. The plastic ABS resin is the polymer with the largest output and the most extensive application at present, organically integrates various performances of PB, PAN and PS, and has excellent mechanical properties of toughness, hardness and rigidity balance. China becomes a large country for ABS production and consumption, the phenomenon that the capacity is seriously larger than the demand appears in the domestic ABS field, so that the recycling rate of the waste ABS plastics is very low, the waste ABS plastics are difficult to degrade in the natural environment due to very strong corrosion resistance, and the waste plastics which are not recycled and recycled are degraded in the natural environment to generate harmful substances forbidden by the international standard and cause pollution which is difficult to estimate to the current ecological environment of China. Therefore, the recycling of the waste ABS plastic also becomes a worldwide problem.
Disclosure of Invention
In view of this, the present invention provides a modified regenerated ABS nanocomposite and a method for preparing the same.
In order to achieve the above purpose, the inventor of the present invention has long studied and largely practiced to provide the technical solution of the present invention, and the specific implementation process is as follows;
1. a modified regenerated ABS nano composite material consists of main raw materials and auxiliary materials; the main raw material is recovered acrylonitrile-butadiene-styrene copolymer resin (ABS); the auxiliary materials are ABS new material, filler, toughening agent, coupling agent, cross-linking agent, plasticizer, lubricant, compatilizer and antioxidant;
the filler is modified nano calcium carbonate, modified carbon fiber and modified talcum powder; the toughening agent is styrene-butadiene-styrene block copolymer (SBS);
the weight parts of the recovered ABS, the new ABS material, the modified nano calcium carbonate, the modified carbon fiber, the modified talcum powder, the SBS, the coupling agent, the crosslinking agent, the plasticizer, the lubricant, the compatilizer and the antioxidant are as follows (100-10).
Preferably, the modified nano calcium carbonate, the modified carbon fiber and the modified talcum powder are all prepared by surface modification of nano calcium carbonate, carbon fiber and talcum powder.
Preferably, the coupling agent is gamma-aminopropyltriethoxysilane (KH-550); the cross-linking agent is dicumyl peroxide (DCP); the plasticizer is Dibutyl Phthalate (DPB); the lubricant is solid paraffin; the compatilizer is maleic anhydride grafted polyethylene (PE-g-MAH); the antioxidant is pentaerythritol tetrakis [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], namely antioxidant 1010.
Preferably, the modification method of the modified nano calcium carbonate comprises the following steps: adding a mixed solution of anhydrous ethanol and a titanate coupling agent into nano calcium carbonate, stirring and reacting for 1h at the temperature of 80 ℃, filtering, washing and drying to obtain the nano calcium carbonate; the weight ratio of the absolute ethyl alcohol, the titanate coupling agent and the nano calcium carbonate is (mL: g) 100.
More preferably, the modification method of the modified nano calcium carbonate comprises the following steps: adding a mixed solution of absolute ethyl alcohol and a titanate coupling agent into nano calcium carbonate, placing the nano calcium carbonate in a constant temperature condition of 80 ℃, magnetically stirring the mixture for reaction for 1 hour, and filtering, washing and drying the mixture to obtain the nano calcium carbonate; the weight ratio of the absolute ethyl alcohol to the titanate coupling agent to the nano calcium carbonate is (mL: g: g) 100.
Preferably, the method for modifying the modified carbon fiber comprises the following steps: carbon fibers are mixed in a volume ratio of 1:1 for 2 hours, taking out, putting into a nitric acid solution with the concentration of 65-68 percent, sealing, reacting for 3 hours at the temperature of 60 ℃, taking out, washing with water, and drying to obtain the product.
More preferably, the method for modifying the modified carbon fiber comprises the following steps: nano-scale carbon fibers are mixed in a volume ratio of 1:1 for 2 hours, taking out, putting into a nitric acid solution with the concentration of 65-68 percent until the nitric acid solution can completely soak the carbon fiber, sealing by using a preservative film, putting into a constant-temperature water bath kettle at 60 ℃ for oxidation reaction for 3 hours, taking out, washing the oxidized carbon fiber in an ultrasonic cleaner by using distilled water, checking the pH value to be neutral by using a pH test paper, finishing, and drying in a drying oven at 90 ℃ to obtain the carbon fiber.
Preferably, the modification method of the modified talcum powder comprises the following steps: drying the talcum powder, adding the dried talcum powder into a mixed solution of absolute ethyl alcohol and a titanate coupling agent according to the volume ratio of 30.
More preferably, the modification method of the modified talcum powder comprises the following steps: drying nanoscale talcum powder in a forced air drying oven at 120 ℃, then adding the nanoscale talcum powder into a mixed solution of anhydrous ethanol and a titanate coupling agent according to the volume ratio of 30.
Preferably, the weight parts of the recovered ABS, the new ABS material, the modified nano calcium carbonate, the modified carbon fiber, the modified talcum powder, the SBS, the coupling agent, the cross-linking agent, the plasticizer, the lubricant, the compatilizer and the antioxidant are 100.
More preferably, the weight parts of the recovered ABS, the new ABS material, the modified nano calcium carbonate, the modified carbon fiber, the modified talcum powder, the SBS, the coupling agent, the cross-linking agent, the plasticizer, the lubricant, the compatilizer and the antioxidant are as follows (100).
2. The preparation method of the modified regenerated ABS nano composite material comprises the following steps:
s1, cleaning and drying recovered ABS, and then mixing with a new ABS material to obtain a resin raw material;
s2, fully mixing the resin raw material, the filler, the toughening agent, the coupling agent, the cross-linking agent, the plasticizer, the lubricant, the compatilizer and the antioxidant, performing melt blending at the temperature of 155-190 ℃, then preparing into a sheet shape, and crushing to obtain the modified regenerated ABS nano composite material.
Preferably, in the step S2, a two-roll mill is used for melt blending and tabletting, and a crusher is used for crushing. When the double-roller open mill is used, the added materials are melted into the SBS matrix and then are continuously open milled for 10 minutes until the materials are uniformly mixed. The temperature of the front roller of the double-roller open mill is 190 ℃, and the temperature of the rear roller of the double-roller open mill is 155 ℃.
The invention has the beneficial effects that:
1) The modified regenerated ABS nano composite material is prepared by taking recycled ABS as a main raw material, adding modified nano calcium carbonate and modified talcum powder to improve the compatibility of the ABS, adding modified carbon fiber to improve the interface bonding force of the ABS, and adding a small amount of new ABS material, toughening agent, coupling agent, crosslinking agent, plasticizer, lubricant, compatilizer and antioxidant, so that the modified regenerated ABS nano composite material with excellent mechanical properties is prepared;
2) The preparation process of the modified and regenerated ABS nanocomposite material is simple, the tensile strength of the prepared modified and regenerated ABS nanocomposite material is improved by more than 20% compared with that of a recycled ABS material, the bending strength is improved by more than 55%, the impact strength is improved by more than 45%, and the modified and regenerated ABS nanocomposite material can be reused in production and application, so that the utilization rate of waste ABS materials is greatly improved, and the modified and regenerated ABS nanocomposite material has the advantages of cost saving, safety and environmental friendliness, and has a great popularization and application value.
Drawings
FIGS. 1 to 6 are XRD patterns of modified recycled ABS nanocomposites obtained in examples 1 to 6 of the present invention, respectively;
FIGS. 7 to 12 are SEM images of modified recycled ABS nanocomposites obtained in examples 1 to 6 of the present invention, respectively;
FIGS. 13 to 18 are FT-IR diagrams of modified recycled ABS nanocomposites obtained in examples 1 to 6 of the present invention, respectively;
FIGS. 19 to 24 are TG-DTA graphs of modified recycled ABS nanocomposites obtained in examples 1 to 6 of the present invention, respectively.
Detailed Description
The present invention is further illustrated by the following examples so that those skilled in the art may better understand the invention and practice it, but the examples are not intended to limit the invention.
Example 1
The preparation method of the modified regenerated ABS nano composite material comprises the following steps:
s1, cleaning and drying 100g of recovered ABS, and mixing with 10g of new ABS material to obtain a resin raw material;
s2, fully mixing a resin raw material, 4G of modified nano calcium carbonate, 7G of modified carbon fiber, 9G of modified talcum powder, 10G of SBS, 2G of KH-550, 1G of DCP, 2G of DBP, 2G of solid paraffin, 2G of PE-G-MAH and 1G of antioxidant 1010, carrying out melt blending in a double-roll mill at the temperature of 155-190 ℃, then preparing into sheets, and crushing into particles to obtain the modified and regenerated ABS nano composite material.
Example 2
This example was the same as example 1 except that 7g of the modified carbon fiber was replaced with 11g and 9g of the modified talc was replaced with 5 g.
Example 3
In this example, the procedure was repeated except that 9g of modified talc was replaced with 7g of talc, and the examples were the same as those in example 1.
Example 4
The same procedure as in example 1 was repeated, except that 4g of modified nano calcium carbonate was replaced with 2g,7g of modified carbon fiber and 9g of modified talc was replaced with 5g and 1g, respectively.
Example 5
This example was the same as example 1 except that 4g of modified nano calcium carbonate was replaced with 6g,7g of modified carbon fiber and 9g of modified talc was replaced with 13g and 5 g.
Example 6
This example was identical to example 1, except that 4g of the modified nano-calcium carbonate was replaced with 6g of the modified carbon fiber (7g) and with 11g of the modified talc (9 g) and 7g of the modified talc (9 g) were used.
Example 7
This example was the same as example 1 except that 4g of modified nanocalcium carbonate was replaced with 8g and 7g of modified carbon fiber was replaced with 13 g.
Example 8
The same as example 1 was repeated, except that 4g of modified nano calcium carbonate was replaced with 10g and 7g of modified carbon fiber was replaced with 13 g.
Example 9
The examples were carried out in the same manner as example 1 except that in this example, 4g of modified nano calcium carbonate was replaced with 8g of,7g of modified carbon fiber and 9g of modified talc was replaced with 1 g.
Example 10
This example was the same as example 1 except that 7g of the modified carbon fiber was replaced with 13g and 9g of the modified talc powder was replaced with 3 g.
Comparative example 1
The same as example 1 was repeated except that in this example, the modified nano calcium carbonate was replaced with unmodified nano calcium carbonate, the modified carbon fibers were replaced with unmodified carbon fibers, and the modified talc powder was replaced with unmodified talc powder.
Comparative example 2
The process is the same as that of example 1 except that the modified nano calcium carbonate is replaced by unmodified nano calcium carbonate.
Comparative example 3
This example was the same as example 1 except that the modified carbon fiber was replaced with an unmodified carbon fiber.
Comparative example 4
In this example, the procedure was repeated in the same manner as in example 1 except that the modified talc powder was replaced with an unmodified talc powder.
1) Mechanical Property test
The modified recycled ABS nanocomposites prepared in examples 1-10 and comparative examples 1-4 and the recovered ABS material were subjected to mechanical property tests, and the method and test results are as follows.
The examples 1 to 10 and the comparative examples 1 to 4, as well as the recovered ABS material, were injection molded in an injection molding machine. The specific operation is as follows: before injection molding, the temperature of each section of the injection molding machine is set to about 140 ℃ for preheating for half an hour, and then the temperature of the injection molding machine is set according to the temperature parameters in the table 1. And (3) keeping the temperature for 10min after the temperature is raised to the set temperature, and then pouring the granulated and formed material into an injection molding machine for injection molding to obtain samples prepared in each embodiment and the comparative embodiment.
TABLE 1 temperatures of various sections of the injection molding machine
Segment of A segment of Two segment Three sections Four sections
Set temperature 200℃ 210℃ 220℃ 210℃
(1) Tensile Property test
The tensile property of the sample is tested by using a universal testing machine, and the tensile strength is the capability of resisting permanent deformation and damage of the material under the action of an external force. The specific operation is as follows: firstly, software SANS test software is opened, online is carried out, and the universal testing machine is preheated for 10min. Clicking a new experiment, selecting a tensile strength option, fixing a test sample on a universal testing machine, and setting the tensile rate to be 2mm/min. After zero clearing, the extensometer is clicked to start the experiment. The samples were subjected to tensile strength testing, 5 data were tested per set of samples, and the average value thereof was calculated.
(2) Bending property test
The bending properties of the samples were tested using a universal testing machine, with the bending strength being the maximum stress that the material can withstand when it breaks under a bending load or reaches a specified deflection. The flexural modulus is the strain resulting from bending stress versus bending.
The specific operation is as follows: firstly, the test software SANS is opened, online is carried out, and the universal testing machine is preheated for 10min. Clicking a new experiment, selecting a bending strength test option, fixing a test sample on a testing machine, setting the experiment span to be 64mm and the experiment speed to be 2mm/min, and starting the experiment after zero clearing. The samples were subjected to flexural strength and flexural modulus tests, 5 data per set of samples were tested, and the average value thereof was calculated.
(3) Impact testing
And (3) preparing the modified nano composite material sample into a test sample meeting the test requirement by comparing with a standard test sample strip, measuring the length, the width and the thickness of the sample strip by using a vernier caliper, and recording related data. And placing the sample strip to be tested in an electric notch sampling machine for notch treatment, wherein the notch depth is 2.00mm +/-0.05 mm, and then testing the impact strength. Before testing, the impact tester is used for carrying out idle swinging, and the idle swinging value is recorded. And (4) placing a sample strip on the impact tester, placing the pendulum bob at a specified position, resetting the dial, starting an impact test button, and recording a test value. Each group of patterns was measured in parallel five times and averaged. Sample actual value = read value-free run value. The mechanical property test results are shown in Table 2, wherein A 0 For the recovered ABS material without any treatment, A 1 ～A 10 Corresponding to examples 1 to 10, B, respectively 1 ～B 4 Corresponding to comparative examples 1 to 4, respectively.
Table 2 mechanical properties test data for nanocomposites
Sample numbering Tensile Strength (/ MPa) Flexural Strength (/ MPa) Impact toughness (/ kJ.m) -2 )
A 0 34.040 43.790 11.150
A 1 51.779 76.005 20.667
A 2 48.560 72.433 20.405
A 3 45.229 75.960 19.137
A 4 42.097 75.370 19.950
A 5 43.070 71.898 18.433
A 6 44.200 72.702 20.005
A 7 43.040 70.880 19.743
A 8 40.700 71.040 20.993
A 9 43.177 69.526 17.867
A 10 41.210 69.584 16.250
B1 33.218 59.547 11.700
B2 42.250 65.883 13.750
B3 39.07 71.048 12.467
B4 42.960 65.691 11.853
From the analysis in Table 2, it can be seen that the bending strength of the modified recycled ABS nanocomposite is comparable to that of the modified recycled ABS nanocompositeThe recycled ABS material is obviously improved, the bending strength of the nano composite materials prepared in the examples 1 to 10 is integrally greater than that of the nano composite materials prepared in the comparative examples 1 to 4, the integral bending strength improvement rate of the examples 1 to 10 is more than 55%, and the best bending strength improvement effect is A 1 The bending strength of the modified recycled ABS nanocomposite prepared in example 1 is improved by 73.6%. Test detection and analysis show that the bending strength is mainly influenced by the carbon fiber, because the surface of the carbon fiber after surface modification treatment generates functional groups, and the functional groups can generate chemical reaction when being combined with a resin interface, so that the binding force between the surface of the carbon fiber and the resin is enhanced, and mechanical binding is generated due to the physical form of the surface of the carbon fiber.
The tensile strength of the modified regenerated ABS nanocomposite material is obviously improved compared with that of the recycled ABS material, the tensile strength of the nanocomposite materials prepared in the examples 1-10 is integrally higher than that of the nanocomposite materials prepared in the comparative examples 1-4, the improvement rate of the overall tensile strength of the examples 1-10 is more than 20%, and the best improvement effect of the tensile strength is A 1 The tensile strength of the modified recycled ABS nanocomposite prepared in example 1 is improved by 52.1%. According to test analysis, the tensile strength is mainly influenced by the talcum powder, because two different functional groups exist on the surface of the modified talcum powder subjected to surface modification treatment, one is an inotropic group and the other is an organophilic group, and molecular chain entanglement is easily formed in the process of chemical reaction with the ABS material. Therefore, the compatibility of the modified talcum powder and the ABS resin has a certain limit, when the added modified talcum powder is too much, the modified talcum powder cannot be well combined with the ABS matrix, and the modified talcum powder cannot be well dispersed in the ABS matrix, so the tensile strength of the composite material can be reduced by adding the excessive modified talcum powder.
The impact strength of the modified regenerated ABS nano composite material is obviously improved compared with that of the recycled ABS material, the impact strength of the nano composite materials prepared in the embodiments 1 to 10 is integrally higher than that of the nano composite materials prepared in the comparative embodiments 1 to 4, the improvement rate of the overall impact strength of the embodiments 1 to 10 is more than 45%, and the best improvement effect of the impact strength is that A 8 Prepared as in example 8The impact strength of the modified recycled ABS nanocomposite material is improved by 88%, and the impact strength of the modified recycled ABS nanocomposite material prepared in the group A1, namely the embodiment 1, is also improved by 85%. Through test and analysis, the impact strength is mainly determined by nano CaCO 3 Due to the surface-modified nano CaCO 3 Compared with the ABS material which is not treated by the surface modifier, the compatibility with the ABS material is obviously improved, and when the nano CaCO is added 3 When appropriate, inorganic nano CaCO 3 Can be well dispersed in an ABS matrix and well combined with ABS so as to improve the impact property of the modified composite material.
In summary, comprehensive analysis of various mechanical property tests shows that the modified recycled ABS nanocomposite prepared in example 1 has the best mechanical properties.
2) X-ray diffraction (XRD) detection analysis
The modified regenerated ABS nanocomposites with better comprehensive mechanical properties, namely the number A, prepared in examples 1-6 1 ～A 6 XRD testing was performed on the group and recovered ABS materials, with the following methods and results:
preparing an injection molded sample into a sample block for a test sample with the length of 20mm +/-5 mm by using a file, then placing the sample in a test piece concave part, placing a sample-carrying test piece in a scanning port of an instrument, closing a safety door of the instrument, and starting the test after setting experimental parameters. And starting the experiment, and automatically acquiring data by the computer to obtain a text file of the test data. Setting experimental parameters: the starting angle is 10 degrees, the ending angle is 70 degrees, the stepping angle is 0.05 degrees, the sampling time is 0.5 second, the tube voltage is 40kV, and the tube current is 30mA. The detection results are shown in fig. 1 to 6.
From the comprehensive analysis of fig. 1 to 6, the position of the strongest peak appeared in the spectrogram of the modified and regenerated ABS nanocomposite was approximately the same as that of the recovered ABS plastic, and the characteristic peak of the recovered ABS appeared at 2 θ =21.453 °. As can be seen from the figure, the modified and regenerated ABS nanocomposite material has other obvious characteristic peaks besides the characteristic peak of ABS, which shows that the inorganic filler after modification treatment is dispersed in the composite material, and the modified and regenerated ABS nanocomposite material A 1 ～A 6 The strength of the groupThis is improved because the addition of the inorganic filler reduces the crystallization properties of the modified ABS nanocomposite. In conclusion, the addition of the inorganic filler increases the number of diffraction peaks and reduces the crystallization performance of the modified ABS nano composite material, and the modified carbon fibers, the modified nano calcium carbonate, the modified talcum powder and other additives are well dispersed in the ABS matrix material.
3) Scanning Electron Microscope (SEM) detection analysis
The modified regenerated ABS nano composite materials with better comprehensive mechanical properties, namely the number A, prepared in the examples 1 to 6 1 ～A 6 SEM test of the ABS material and the method and the result are as follows:
cutting off a fracture surface of an injection molded sample about 2mm away from a fracture opening of impact fracture by using a knife to serve as a test sample, performing gold plating treatment on the test sample, placing the sample in a scanning electron microscope for scanning after the treatment is finished, setting parameters, adjusting an observation opening, selecting a proper position, and observing the appearance of the fracture surface under the electron microscope. Experimental parameters: the high voltage was set to 10kV, the magnification was set to 1.5kX, the working distance was set to 10mm, and the electron beam intensity was set to 10. The detection results are shown in fig. 7 to 12.
Because ABS under normal temperature belongs to brittle fracture, so the surface of the section of the waste ABS plastic is relatively smooth, the section lines are relatively regular, basically no folds exist, and the waste ABS plastic expands towards one direction. From the comprehensive observation and analysis of fig. 7 to 12, it can be known that the fracture surface cracks of the modified composite material are increased obviously, and more granular and rod-like structures appear, and the inorganic nano particles have small diameter and large specific surface area, so that the inorganic nano particles can be fully adsorbed and bonded with the matrix and can be uniformly dispersed in the matrix, thereby proving that the nano calcium carbonate, the nano carbon fiber and the nano talcum powder can be uniformly distributed in the ABS resin. It can be observed from the figure that the modified composite material has more obvious fracture surface cracks, more concave-convex parts, disordered distribution, expansion towards all directions and no fixed rule, and the function of the nano carbon fiber in the ABS matrix material for transferring stress is explained, so that the tensile strength of the matrix material is improved, and the composite material is not easy to break under the action of external force.
4) Infrared Spectroscopy (FT-IR) detection analysis
The modified regenerated ABS nano composite materials with better comprehensive mechanical properties, namely the number A, prepared in the examples 1 to 6 1 ～A 6 The FT-IR test was performed on the combined and recovered ABS material, with the following method and results:
grinding an injection-molded sample into powder, placing a small amount of sample powder into an agate mortar, adding equal amount of potassium bromide powder, and tabletting after full grinding. And opening and preheating the infrared spectrometer, and carrying out infrared spectrum test on a sample of the infrared spectrometer. The detection results are shown in FIGS. 13 to 18.
From the comprehensive analysis of FIGS. 13-18, it can be seen that the modified recycled ABS nanocomposite and the recycled ABS plastic have the same absorption wave number, and both the modified recycled ABS nanocomposite and the recycled ABS plastic are 3000cm -1 -3500cm -1 The characteristic absorption peaks appear on the left and right sides, and the light transmittance of the modified regenerated ABS nano composite material is obviously lower than that of recycled ABS due to the addition of three inorganic fillers of modified carbon fiber, modified nano calcium carbonate and modified talcum powder in the ABS matrix. Compared with the waste ABS, the modified and regenerated ABS nano composite material has slight difference in peak area, which shows that the molecular structure of the modified and regenerated ABS nano composite material is changed, and the functional group is changed, thereby influencing the mechanical property of the composite material.
5) Thermogravimetric-differential thermal (TG-DTA) test
The modified regenerated ABS nano composite materials with better comprehensive mechanical properties, namely the number A, prepared in the examples 1 to 6 1 ～A 6 The TG-DTA test of the ABS materials is carried out, and the method and the result are as follows:
grinding an injection-molded sample into powder, weighing 3mg of sample powder by using an electronic balance, placing the sample powder in a ceramic crucible, and hanging the quartz crucible in a hearth by using tweezers. Opening a microcomputer differential thermal balance and preheating for 20 minutes, using an empty crucible for comparison, placing the empty crucible on the left side of a supporting rod of the balance, placing the crucible containing a sample to be tested on the right side of the supporting rod, lowering a furnace body, opening matched software, and starting testing after setting experimental parameters. The test results are shown in FIGS. 19 to 24.
The decomposition temperature of the waste ABS plastic is 320 ℃, and the waste ABS plastic is completely decomposed at about 550 ℃. From the comprehensive analysis of fig. 19 to 24, it can be seen that the decomposition starting temperature of the modified and regenerated ABS nanocomposite is about 350 ℃, the thermogravimetric curve decreases rapidly between 350 ℃ and 460 ℃, the decomposition rate increases, the curve tends to be stable around 600 ℃, and the decomposition is almost completed around 650 ℃. From the above comprehensive analysis, it can be known that modified carbon fiber and modified nano CaCO are filled in the waste ABS plastic 3 The thermal decomposition temperature of the modified regenerated ABS nano composite material obtained by the modified talcum powder is increased to a certain extent, which shows that the thermal property of the modified regenerated ABS nano composite material is improved, and the modified regenerated ABS nano composite material can play a role in flame retardance in a certain temperature range.
6) Density test
The modified regenerated ABS nano composite materials with better comprehensive mechanical properties, namely the number A, prepared in the examples 1 to 6 1 ～A 6 The density test was carried out on the group and recovered ABS material, the method and the results are as follows:
the injection molded samples were subjected to density testing using a density balance, and each set of experiments was tested in parallel 3 times to find the average value. The experimental steps are as follows: open density balance → clear → test in scale dish → test in basket → click on "calculate" button → record data. The test results are shown in table 3.
TABLE 3 sample Density
Sample (I) ρ1 ρ2 ρ3 Average density
A1 1.057 1.056 1.056 1.056
A2 1.055 1.053 1.054 1.054
A3 1.052 1.053 1.054 1.053
A4 1.043 1.041 1.04 1.041
A5 1.112 1.111 1.111 1.111
A6 1.113 1.11 1.11 1.111
From the comprehensive analysis in table 3, the densities of the modified and regenerated ABS nanocomposites are similar, which proves that the various additives are uniformly distributed in the composite.
7) Melt flow rate test
The modified regenerated ABS nano composite materials with better comprehensive mechanical properties, namely the number A, prepared in the examples 1 to 6 1 ～A 6 The melt flow rate test was performed on the combined and recycled ABS material, the method and results were as follows:
the injection molded samples were cut to a size that allowed passage through the melt flow rate meter funnel and all specimens were tested using the melt flow rate meter. Testing parameters: the test temperature was 220 ℃ with a time interval of 0.05s. Even at a temperature of 220 deg.c. The test results are shown in table 4.
TABLE 4 melt flow Rate
Sample (I) MFR(g/10min)
Recovery of ABS 45.6
A 1 55.176
A 2 53.664
A 3 53.532
A 4 54.072
A 5 53.943
A 6 52.86
It can be seen from the comprehensive analysis in table 4 that the melt flow rate of the modified recycled ABS nanocomposite is increased compared to the melt flow rate of the recycled ABS raw material, because the modified nano calcium carbonate and the modified nano talc powder are added to the modified recycled ABS nanocomposite, the intermolecular forces of ABS are weakened, the rheological properties and processability of the blend are improved, and the product molding is facilitated. And the improvement of the fluidity enables the internal stress of the blend to be released quickly, and the warping phenomenon caused by cooling shrinkage is reduced.
8) Vicat temperature test
The modified regenerated ABS nano composite materials with better comprehensive mechanical properties, namely the number A, prepared in the examples 1 to 6 1 ～A 6 The melt flow rate test was performed on the combined and recycled ABS material, the method and results were as follows:
the injection molded sample is made into a test sample which is 10mm +/-5 mm long and 4mm +/-1 mm wide and meets the test requirement, and the test is carried out by using a microcard temperature tester.
The micro-card softening temperature reflects the heat resistance of the material, the micro-card softening temperature of the recovered ABS is about 80 ℃ by checking data, and experiments show that A 1 ～A 6 The micro-calorie temperature of the modified regenerated ABS nano composite material is 84.6 ℃ on average, the micro-calorie softening temperature of the composite material is increased by 4.6 ℃, because the modified carbon fiber has the effect of improving the heat resistance, the modified carbon fiber and the ABS matrix have stronger interface bonding effect, the thermal motion of the ABS chain segment is limited by the addition of the modified carbon fiber, and the softening temperature of the composite material is increased.
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 (3)

1. A modified regenerated ABS nano composite material is characterized by comprising main raw materials and auxiliary materials; the main raw material is recovered acrylonitrile-butadiene-styrene copolymer resin, namely ABS; the auxiliary materials are ABS new material, filler, toughening agent, coupling agent, cross-linking agent, plasticizer, lubricant, compatilizer and antioxidant;
the filler is modified nano calcium carbonate, modified carbon fiber and modified talcum powder; the toughening agent is styrene-butadiene-styrene block copolymer (SBS); the coupling agent is gamma-aminopropyl triethoxysilane (KH-550); the cross-linking agent is dicumyl peroxide (DCP); the plasticizer is dibutyl phthalate (DBP); the lubricant is solid paraffin; the compatilizer is maleic anhydride grafted polyethylene (PE-g-MAH); the antioxidant is pentaerythritol tetrakis [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], namely antioxidant 1010;
the modified nano calcium carbonate is prepared by the following modification method: adding a mixed solution of anhydrous ethanol and a titanate coupling agent into nano calcium carbonate, stirring and reacting for 1h at the temperature of 80 ℃, filtering, washing and drying to obtain the nano calcium carbonate; the absolute ethyl alcohol and titanate coupling agent are 100 in terms of mL: g;
the modified carbon fiber is prepared by the following modification method: soaking 2h in a mixed solution of ethanol and acetone in a volume ratio of 1:1, taking out, then putting into a nitric acid solution with a concentration of 65-68%, sealing, then placing at 60 ℃ for reaction at 3h, taking out, washing with water, and drying to obtain the carbon fiber composite material;
the modified talcum powder is prepared by the following modification method: drying the talcum powder, adding the dried talcum powder into a mixed solution of absolute ethyl alcohol and a titanate coupling agent according to the volume ratio of 30;
the weight parts of the recovered ABS, the new ABS material, the modified nano calcium carbonate, the modified carbon fiber, the modified talcum powder, the SBS, the coupling agent, the crosslinking agent, the plasticizer, the lubricant, the compatilizer and the antioxidant are as follows (100).
2. The preparation method of the modified regenerated ABS nano composite material as claimed in claim 1, characterized by comprising the following steps:
s1, cleaning and drying recovered ABS, and then mixing with a new ABS material to obtain a resin raw material;
s2, fully mixing the resin raw material, the filler, the toughening agent, the coupling agent, the cross-linking agent, the plasticizer, the lubricant, the compatilizer and the antioxidant, carrying out melt blending at the temperature of 155 to 190 ℃, then making into a sheet shape, and crushing to obtain the modified regenerated ABS nano composite material.
3. The method for preparing the modified recycled ABS nanocomposite material as claimed in claim 2, wherein in the step S2, a two-roll mill is used for melt blending and tabletting, and a crusher is used for crushing.
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