A recycled abs composite and a method for producing the same

Abstract

The present application belongs to the technical field of composite material recycling and preparation, and relates to a regenerated ABS composite material and a preparation method thereof. The present application composites waste ABS, ASA and AS, improves the chemical resistance and heat resistance of the material through the addition of ASA, and can also maintain a certain mechanical strength of the material, is conducive to maintaining the performance decline of the ABS material in the electroplating process, and composites the AS material, improves the fluidity of the composite, is conducive to reducing the internal stress in the material processing process, improves the electroplating effect, and reflects the content of acrylonitrile in the ABS composite material system, which is conducive to enhancing the adhesion of the electroplated layer.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of composite material recycling and preparation, and relates to a regenerated ABS composite material and a preparation method thereof. BACKGROUND

[0002] Acrylonitrile-butadiene-styrene copolymer (ABS) is a high polymer material with excellent comprehensive performance, which includes butadiene rubber (PB) in its composition. The component is easy to be eroded, and can obtain good bonding force with the plating layer after electroplating, thereby giving ABS material good metallic luster. The ABS material after electroplating has good corrosion resistance, metallic luster, and aesthetic advantages, and is widely used in various fields.

[0003] However, for waste ABS, although there is electroplatable regenerated ABS at present, it still does not meet the requirements of electroplated ABS. The main reason is that the butadiene rubber (PB) in acrylonitrile-butadiene-styrene copolymer (ABS) parts is aged and the content is reduced in the life cycle of use, waste and recycling of the ABS, and various pollutants in the environment enter the recycling process of waste ABS, resulting in that the electroplating effect is far from the effect of electroplated ABS.

[0004] At present, the electroplating technology of ABS mainly modifies the original material, and there is no electroplated waste ABS recycling technology. In addition, the butadiene rubber phase in waste ABS is aged due to long-term use, and the ABS has experienced different use and waste processes in its life cycle. Compared with the original ABS material, the ABS has a very serious impurity pollution problem. At present, there is no recycling and preparation method for electroplated waste ABS, and the existing regenerated ABS material often has the problems of pitting, bubbles and poor adhesion during electroplating.

[0005] Chinese patent application file (publication number: CN112341750A) discloses a high black matte ASA composite material and a preparation method and application thereof, which comprises the following components by mass percentage: ASA powder 5-36%; ABS resin 5-82.1%; AS resin 10-56.1%; matte agent 1-5%; high blackness color powder 0.1-1%; antioxidant 0.3-1%; processing aid 0.1-1%; the high blackness color powder is a complex of inorganic black powder and organic black powder; the mass ratio of inorganic black powder to organic black powder in the complex is (10-30):(21-120). The blackness value of the ASA composite material disclosed in the application can be controlled in the range of less than 26.2, but the technical solution does not design an electroplated ABS technology solution.

[0006] A Chinese patent application (publication number: CN111875897A) discloses a high-temperature-resistant, electroplating-grade ABS resin and its preparation method. The resin comprises the following components by weight: 10-20 parts ABS resin, 25-35 parts ABS high-rubber powder, 40-55 parts highly branched styrene-acrylonitrile copolymer, 10-15 parts heat-resistant agent, 0.1-10 parts kaolin, and 0.5-2 parts other additives. By controlling the ABS rubber content, blending large and small rubber particles, and introducing kaolin filler, the high-temperature, electroplating-grade ABS resin is obtained. This high-temperature, electroplating-grade ABS resin exhibits excellent high-temperature resistance and electroplating adhesion, reducing the failure rate of electroplated parts in hot-cold cycling tests, thus meeting the requirements for electroplating-grade ABS in the automotive, home appliance, and machinery sectors. This invention prepares ABS material by physically blending SAN and high-rubber powder. The butadiene rubber content is controlled by adjusting the ratio of SAN and high-rubber powder to achieve the electroplating effect. However, it is completely different from the waste ABS material recycling technology, and the technical problems to be faced and solved are inconsistent.

[0007] A Chinese patent application (publication number: CN104530635A) discloses an ABS material for electroplating, its preparation method, and its application. The ABS material comprises the following components, by weight: 30-60 parts by weight of conventional emulsion-based ABS resin, 15-40 parts by weight of high-flow emulsion-based ABS resin, 2-10 parts by weight of bulk-based ABS resin, 8-15 parts by weight of high-rubber powder, 6-12 parts by weight of heat-resistant agent, 0.2-0.6 parts by weight of antioxidant, and 0.5-1.5 parts by weight of lubricant. The electroplating ABS material provided herein improves material fluidity and processability by adding high-flow emulsion-based ABS resin and bulk-based ABS resin, reducing internal stress in injection-molded parts, achieving better electroplating bonding strength, and increasing the electroplating yield rate. The electroplating ABS material of this invention combines emulsion-based ABS and bulk-based ABS for blending and modification. However, the rubber particles in the bulk-based ABS are larger, making them difficult to corrode during electroplating, which can affect the electroplating effect. Summary of the Invention

[0008] The purpose of the present invention is to address the above-mentioned problems existing in the prior art and to provide a recycled ABS composite material with good physical properties and electroplating adhesion properties.

[0009] The object of the present invention can be achieved by the following technical scheme: a recycled ABS composite material, the composite material comprising the following raw materials in parts by mass: 68.0 to 84.5 parts of recycled ABS slices, 10.0 to 20.0 parts of recycled ASA slices, 5.0 to 10.0 parts of recycled AS slices, 0.3 to 1.0 parts of an anti-hydrolysis agent, 0.1 to 0.5 parts of a lubricant, and 0.1 to 0.5 parts of an antioxidant.

[0010] In the above-mentioned regenerated ABS composite material, the recycled ABS chip, the recycled ASA chip and the recycled AS chip are obtained by recycling treatment of waste ABS chip, waste ASA chip and waste AS chip respectively.

[0011] The advantages of the ternary composite of waste ABS, ASA and AS mainly lie in that the addition of ASA and AS can improve the chemical resistance of waste ABS material, avoid sharp decline in chemical corrosion resistance during electroplating, and increase the content of acrylonitrile in waste ABS material, which is beneficial to enhancing the adhesion of the electroplated layer. Compared with the addition of pure AS, the addition of ASA and AS in waste ABS is beneficial to maintaining the impact performance of waste ABS material. The addition of pure AS can cause sharp decline in the impact performance of ABS material, while the addition of ASA instead of part of AS in ABS can maintain good impact performance of ABS, which is beneficial to maintaining the mechanical properties of the electroplated material.

[0012] Preferably, the waste ABS chip is prepared by recycling at least one of waste ABS pipes, ABS plates and ABS coils.

[0013] Further preferably, the waste ABS chip is prepared by recycling emulsion ABS parts, and the impact strength is greater than or equal to 18 kj / m 2 .

[0014] Preferably, the waste ASA chip is prepared by recycling at least one of waste ASA plates and ASA fittings.

[0015] Preferably, the waste AS chip is prepared by recycling at least one of waste AS refrigerator drawers and AS water filter pot shells.

[0016] In the above-mentioned regenerated ABS composite material, the recycling treatment includes collection, sorting, crushing, flotation, cleaning, impurity removal, drying and homogenization treatment.

[0017] In the above-mentioned regenerated ABS composite material, the recycling treatment specifically includes the following steps:

[0018] S1, classifying the collected waste plastic parts according to color, aging degree and surface coating condition, removing parts with severe surface aging and abnormal color, and removing labels, coatings and foreign matters on the sorted waste plastic parts by using a sanding machine to obtain preliminarily impurity-removed waste plastic parts;

[0019] S2, then feeding the waste plastic parts into a crusher for crushing, and screening through the screen in the crushing chamber and the screen in the discharge chamber of the crusher to obtain waste plastic chip rough material with secondary impurity filtration and uniform size;

[0020] S3, the waste plastic chip raw material is conveyed to a salt water tank by a conveying auger, and plastic impurities are removed by flotation, and then conveyed to a vertical dehydrator, under the action of centrifugal force, the salt water on the surface of the waste plastic chip raw material is separated, and the impurities remaining on the surface of the chip are further removed under the action of centrifugal friction, to obtain further purified waste plastic chip raw material;

[0021] S4, the waste plastic chip raw material is sent to a clean water tank, the density of ABS, ASA and AS plastic is greater than that of water, which will sink to the bottom of the water, and other impurities with a density less than water will float on the water surface, then the impurities floating on the water surface are removed, the waste plastic chip at the bottom is conveyed to a second vertical dehydrator by a bottom auger, and is treated by two centrifugal dehydrations, and is blown into a homogenizing tank by hot air for homogenization treatment, to obtain pure and uniform waste plastic chip.

[0022] As preferred, the diameter of the chip after crushing is 1-30 mm. The crusher includes double-layer screens, the screen aperture of the crushing chamber is 10-30 mm, and the plastic is crushed to a size less than the screen aperture, and then falls through the screen aperture of the crushing chamber into the discharge chamber; the screen aperture of the discharge chamber is 1-30 mm, the plastic crushing pieces from the screen of the crushing chamber slide through the screen plate of the discharge chamber to the discharge port, and the impurities such as plastic powder, soil, sand, iron filings and the like are screened out during the sliding process; at the same time, washing water is introduced into the crushing chamber and the discharge chamber from the top of the crusher during crushing, and the double action of crushing friction and washing water effectively removes the pollutants on the surface of the waste plastic material.

[0023] Further preferably, the screen aperture of the crushing chamber of the crusher must be greater than that of the discharge chamber.

[0024] As preferred, the top of the conveying auger is connected with clean water, and the top clean water will wash and separate the powder and impurities in the waste plastic chip when the material is upwardly conveyed.

[0025] As preferred, the vertical dehydrator is a centrifugal separator with a spiral rotating shaft and a screen cylinder, and the dehydration rotation speed is 1000-3000 rpm.

[0026] As preferred, the screen cylinder of the vertical dehydrator has a screen aperture of 0-5 mm, which must be smaller than that of the discharge chamber.

[0027] As preferred, the clean water tank has a bottom stirring paddle for stirring the waste plastic chip in the clean water, so that the impurities in the waste plastic chip can better float up.

[0028] In the above-mentioned regenerated ABS composite material, the salt water density in the flotation process is 1.05-1.10 g / cm 3 .

[0029] The significant advantage of the waste plastic product recycling of the present application lies in that impurity removal schemes are arranged at each link of the recycling and pretreatment process, ensuring that the recycled waste ABS chips, waste ASA chips and waste AS chips are clean and free of impurities; the entire pretreatment process is a continuous and automated process, which is convenient to operate and has high efficiency, and can realize the recycling of waste ABS chips, waste ASA chips and waste AS chips required by electroplating.

[0030] In the above-mentioned regenerated ABS composite material, the anti-hydrolysis agent is at least one of monomeric carbodiimide and polymeric carbodiimide. After long-term use and multiple processing, the internal polybutadiene rubber molecular structure of the waste ABS material is oxidatively cleaved and broken, resulting in carbonyl groups, causing yellowing and performance degradation. The physical regeneration process of the waste ABS needs to be carried out under hot melt conditions, which can induce the intensification of the yellowing reaction. However, the addition of the anti-hydrolysis agent in the present application can react with small molecular substances generated by polymer decomposition to form stable compounds without side effects, thereby slowing down the polymer degradation process.

[0031] In the above-mentioned regenerated ABS composite material, the lubricant is at least one of stearic acid, calcium stearate, paraffin, polyethylene wax, oxidized polyethylene wax, pentaerythritol stearate, N,N'-ethylene bis-stearamide, and silicone powder.

[0032] Preferably, the lubricant is at least one of N,N'-ethylene bis-stearamide and silicone powder.

[0033] Preferably, the antioxidant is at least one of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 1098, antioxidant 1035, antioxidant 697, antioxidant BHT 264, and antioxidant DLTP.

[0034] The present application also provides a preparation method of the above-mentioned regenerated ABS composite material, which comprises the following steps:

[0035] S1, configuring the above-mentioned raw materials;

[0036] S2, uniformly mixing the recycled ABS chips, recycled ASA chips, recycled AS chips, anti-hydrolysis agent, lubricant, and antioxidant, and then feeding them into a single-screw extruder for melt extrusion and granulation.

[0037] In the above-mentioned preparation method of the regenerated ABS composite material, the motor frequency of the single-screw extruder is 30-40 Hz, and the temperature is 180-230℃.

[0038] As preferred, the single screw extruder has 9 temperature control zones, wherein the temperature of temperature control zones 1-2 is 180-220 DEG C, the temperature of temperature control zones 3-4 is 200-230 DEG C, the temperature of temperature control zones 5-6 is 200-220 DEG C, and the temperature of temperature control zones 7-9 is 210-230 DEG C.

[0039] Compared with the prior art, the present application has the following beneficial effects:

[0040] 1. The waste plastic parts of the present application are recycled and sorted by a recycling and sorting, pretreatment process, formula and standardized granulation equipment and process integration scheme, and the waste ABS parts, waste ASA parts and waste AS parts are recycled and treated respectively, wherein the impurities affecting the electroplating effect in the waste plastic materials are removed layer by layer by the recycling and sorting, pretreatment process and standardized granulation equipment and process, completely avoiding the influence of impurities in the waste plastic recycling on the electroplating effect.

[0041] 2. The waste ABS, ASA and AS are compounded in the present application, the chemical resistance and heat resistance of the material are improved by adding ASA, and the material can also maintain a certain mechanical strength, which is beneficial to maintaining the performance decline of ABS material in the electroplating process, and the flowability of the composite is improved by compounding AS material, which is beneficial to reducing the internal stress in the material processing process, improving the electroplating effect, and reflecting the content of acrylonitrile in the ABS composite material system, which is beneficial to enhancing the adhesion of the electroplated layer.

[0042] 3. The present application uses monomeric carbodiimide and polymeric carbodiimide as hydrolysis-resistant agent, which is beneficial to inhibiting the thermal oxidative cracking of the waste ABS material in the standardization granulation process, maintaining good physical properties of the material, and improving the mechanical strength of the electroplated parts. DETAILED DESCRIPTION

[0043] The following are specific embodiments of the present application, which further describe the technical solutions of the present application, but the present application is not limited to these embodiments.

[0044] Raw material source: the hydrolysis-resistant agent is Shanghai Langyi. 210.

[0045] The lubricant is Hangzhou Kaijie Plastic Silicone Powder KJ-B120.

[0046] The antioxidant is BASF antioxidant Irganox 1076.

[0047] Examples 1-5:

[0048] S1, the collected waste ABS, ASA, AS plastic parts are classified according to color, aging degree, surface coating, and the parts with serious surface aging and abnormal color are removed, and the labels, coatings and foreign matters on the surface of the sorted waste plastic parts are removed by sanding machine to obtain the waste plastic parts with preliminary impurities removed;

[0049] S2, then the waste plastic parts are sent into the crusher for crushing, and are screened through the screen in the crushing chamber and the screen in the discharge chamber to obtain the waste plastic chip rough material with secondary impurity filtering and uniform size;

[0050] The crusher adopts double-layer screen, the screen aperture of the crushing chamber is 20mm, and when the plastic is crushed to a size smaller than the screen aperture, it will pass through the screen aperture of the crushing chamber and fall into the discharge chamber; the screen aperture of the discharge chamber is 10mm, the plastic crushed pieces from the screen of the crushing chamber slide to the discharge port through the screen plate of the discharge chamber, and the impurities such as plastic powder, soil, sand, iron filings and the like are screened out in the sliding process; at the same time, washing water is introduced into the crushing chamber and the discharge chamber from the top of the crusher during crushing, and through the dual action of crushing friction and washing water, the pollutants on the surface of the waste plastic material are effectively removed;

[0051] S3, the waste plastic chip rough material is conveyed to the brine tank through the conveying auger, the density of the brine is 1.10g / cm 3 , the plastic impurities are removed by flotation, and then the waste plastic chip rough material is conveyed to the vertical dehydrator, under the centrifugal action, the brine on the surface of the waste plastic chip rough material is separated, and the impurities remaining on the surface of the chip are further removed under the centrifugal friction action, to obtain the further purified waste plastic chip rough material;

[0052] The vertical dehydrator is a centrifugal separator with a spiral rotating shaft and a screen cylinder, and the dehydration rotation speed is 1000-3000rpm; the screen cylinder aperture of the vertical dehydrator is 3mm.

[0053] S4, the waste plastic chip rough material is sent to the clean water tank, the densities of ABS, ASA and AS plastic are greater than that of water, which will sink to the bottom, and other impurities with density less than water will float on the water surface, then the impurities floating on the water surface are removed, the waste plastic chips at the bottom are conveyed to the second vertical dehydrator through the bottom auger, and are treated by two centrifugal dehydrations, and are blown into the homogenizing tank by hot air to obtain the pure and uniform recycled ABS, ASA and AS plastic chips.

[0054] S5, the raw materials are configured according to Table 1;

[0055] S6, the recycled ABS chip, recycled ASA chip, recycled AS chip, hydrolysis resistance agent, lubricant, antioxidant are uniformly mixed, and then fed into a single screw extruder for melt extrusion granulation; the motor frequency of the single screw extruder is 35 Hz, and the temperature is 180-230 DEG C; the single screw extruder has 9 temperature control zones, wherein the temperature of temperature control zone 1-2 is 180 DEG C, the temperature of temperature control zone 3-4 is 200 DEG C, the temperature of temperature control zone 5-6 is 210 DEG C, and the temperature of temperature control zone 7-9 is 230 DEG C.

[0056] Comparative examples 1-5:

[0057] The difference between example 1-5 is that the raw material configuration is shown in table 2.

[0058] Table 1: raw material configuration of example 1-5

[0059]

[0060] Table 2: raw material configuration of comparative examples 1-5

[0061]

[0062] The melt index of the recycled ABS composite material prepared in example 1-5 and comparative examples 1-5 is detected at 220 DEG C, 10 kg, the IZOD notch impact at 23 DEG C, and the application evaluation of the recycled ABS composite material color plate after electroplating is carried out.

[0063] Table 3: performance test results of recycled ABS composite material prepared in example 1-5 and comparative examples 1-5

[0064]

[0065]

[0066] The product physical properties of the application are characterized according to the melt index and IZOD notch impact of ISO standard, wherein the appearance requirements: the effective plating layer surface is not allowed to have defects such as bubbles, protrusions, pits and peeling, and the surface gloss is uniform and beautiful; the plating adhesion experiment is carried out according to the national standard GB / T 9286.

[0067] From the above results, the melt index of example 1-5 is 15-25 g / cm 3Between, impact strength is all in 17 and above, close to the performance of original ABS material, appearance inspection is all no defect, 65 DEG C / 65 humidity, appearance is all no change, and grid experiment no coating peeling, it is explained that under the temperature and humidity, it has good electroplating adhesion, simultaneously under high and low temperature test of -40~80 DEG C, appearance is no change, grid experiment no coating peeling, material electroplating performance has good high and low temperature resistance.

[0068] The embodiments of the present application do not exhaust the technical scope of the point of protection claimed by the present application, and the new technical solutions formed by the same or multiple technical features in the technical solutions of the embodiments are also within the scope of protection claimed by the present application; meanwhile, in all the enumerated or non-enumerated embodiments of the present application, each parameter in the same embodiment only represents one example (i.e. one feasible solution) of the technical solution, and there is no strict cooperation and limitation relationship between each parameter, wherein each parameter can be replaced by each other without violating the axiom and the statement of the present application, except for the special declaration.

[0069] The technical means disclosed by the present application is not limited to the technical means disclosed by the above technical means, and also includes the technical solutions composed of any combination of the above technical features. The above is the specific embodiment of the present application, and it should be pointed out that for ordinary skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements are also considered as the protection scope of the present application.

[0070] The specific embodiments described herein are merely illustrative of the present application. Those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar ways to replace, but will not deviate from the spirit of the present application or exceed the scope defined by the appended claims.

Claims

1. A recycled ABS composite material, characterized in that: The composite material is composed of the following raw materials in parts by mass: 68.0 to 84.5 parts of recycled ABS slices, 10.0 to 20.0 parts of recycled ASA slices, 5.0 to 10.0 parts of recycled AS slices, 0.3 to 1.0 parts of an anti-hydrolysis agent, 0.1 to 0.5 parts of a lubricant, and 0.1 to 0.5 parts of an antioxidant; The anti-hydrolysis agent is a polymeric carbodiimide; The recycled ABS slices, recycled ASA slices and recycled AS slices are obtained by recycling waste ABS slices, waste ASA slices and waste AS slices respectively; Recycling includes collection, sorting, crushing, flotation, cleaning, impurity removal, drying and homogenization; The recycling process specifically includes the following steps: S1. Classify the collected waste plastic parts by color, degree of aging, and surface coating, remove parts with severe surface aging or abnormal color, and use a sander to remove labels, coatings, and foreign matter from the surfaces of the sorted waste plastic parts to obtain preliminarily cleaned waste plastic parts; S2, then the waste plastic parts are sent to the crusher for crushing, and screened by the crushing indoor screen and the discharging indoor screen of the crusher to obtain waste plastic chips with secondary impurities filtered and uniform size; S3, the waste plastic chips are transported to the brine tank through the conveying auger, and the plastic foreign matter is removed by flotation, and then transported to the vertical dehydrator to obtain further purified waste plastic chips; S4. The waste plastic slices are sent to the clean water tank, and then the impurities floating on the water surface are removed. The waste plastic slices at the bottom are transported to the second vertical dehydrator through the bottom auger, and are subjected to two centrifugal dehydration treatments. The hot air is blown into the homogenization tank for homogenization treatment to obtain pure and uniform waste plastic slices.

2. A recycled ABS composite material according to claim 1, characterized in that: The diameter of the slices after crushing is 1 to 30 mm.

3. The recycled ABS composite material according to claim 1, characterized in that: The density of brine during flotation is 1.05-1.10 g / cm 3 .

4. The recycled ABS composite material according to claim 1, characterized in that: The lubricant is at least one of stearic acid, calcium stearate, paraffin, polyethylene wax, oxidized polyethylene wax, pentaerythritol stearate, N,N'-ethylene bisstearamide, and silicone powder.

5. A method for preparing the recycled ABS composite material according to claim 1, characterized in that: The method comprises the following steps: S1. Prepare the raw materials according to claim 1; S2. Evenly mix the recycled ABS slices, recycled ASA slices, recycled AS slices, anti-hydrolysis agent, lubricant, and antioxidant, and then feed them into a single-screw extruder for melt extrusion and granulation.

6. The method for preparing a recycled ABS composite material according to claim 5, characterized in that: The motor frequency of the single-screw extruder is 30-40 Hz and the temperature is 180-230°C.

7. The method for preparing a recycled ABS composite material according to claim 5 or 6, characterized in that: The single-screw extruder has 9 temperature control zones, among which the temperature of temperature control zones 1 to 2 is 180 to 220°C, the temperature of temperature control zones 3 to 4 is 200 to 230°C, the temperature of temperature control zones 5 to 6 is 200 to 220°C, and the temperature of temperature control zones 7 to 9 is 210 to 230°C.

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